INDEX. Organizing Committee.. 3. Scientific Committee..3. General Information 5. Topic List. 7. Scientific Program 9. Abstract List..

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1 BOOK OF ABSTRACTS

2 INDEX Organizing Committee.. 3 Scientific Committee..3 General Information 5 Topic List. 7 Scientific Program 9 Abstract List..13 2

3 ORGANIZING COMMITTEE: Chairpersons: Jaume Soley, Sociedad Española de Química Industrial e Ingeniería Química (SEQUI) Santiago Esplugas, Universidad de Barcelona Vocals: José Costa López, Col.legi Oficial de Químics de Catalunya ANQUE Josep Mouriño, Col legi Oficial d Enginyers Industrials de Catalunya Pilar Navarro, EXPOQUIMIA Rosa Nomen, IQS Universidad Ramón Llull Luis Serrano, EXPOQUIMIA Assistants: Núria Basset Ana Justo Mireia Marcé SCIENTIFIC COMMITTEE: Chairpersons: Carme González Azón, Universitat de Barcelona Arturo Romero, Universidad Complutense de Madrid Vocals: Amorós, José Luís Universidad de Castellón Arauzo, Jesús ABENGOA Benítez, Javier Universidad de Extremadura Bilbao, Rafael Universidad de Zaragoza Bilbao, Javier Universidad del País Vasco Carrasco, Félix Universitat de Girona Cordero, Tomás Universidad de Málaga De Lucas, Antonio Universidad de Castilla y la Mancha Delgado, Sebastián Universidad de La Laguna Díaz, Mario Universidad de Oviedo Escudero, Juan Carlos Lipotec Fabregat, Azael Universitat Rovira i Virgili 3

4 Feyo de Azevedo, Sebastião University of Porto Galán, Miguel Ángel Universidad de Salamanca García Ochoa, Félix Universidad Complutense de Madrid Giménez, Jaume Universitat de Barcelona Gódia, Francesc Universitat Autònoma de Barcelona González Velasco, Juan Ramón Universidad del País Vasco Grossmann, Ignacio University Carnegie Mellon Irabien, Ángel Universidad de Cantabria Lema, Juan Universidad de Santiago de Compostela Lora, Jaime Universidad Politécnica de Valencia Marcilla, Antonio Universidad de Alicante Martín, Olga Universitat de Lleida Martín del Valle, Eva Universidad de Salamanca Mulet, Antonio Universidad Politécnica de Valencia Ortiz, Inmaculada Universidad de Cantabria Plesu, Valentín University Politehnica of Bucharest Puigjaner, Luís Universitat Politècnica de Catalunya Rodrigo, Manuel Andrés Universidad de Castilla La Mancha Rodríguez, Juan José Universidad Autónoma de Madrid Romero, Arturo Universidad Complutense de Madrid Sales, Diego Universidad de Cádiz Santamaría, Jesús Universidad de Zaragoza Santos, Aurora Universidad Complutense de Madrid Sastre, Ana María Universitat Politècnica de Catalunya Sotelo, José Luis Universidad Complutense de Madrid Van Grieken, Rafael ANECA Vicente, Manuel SEQUI 4

5 GENERAL INFORMATION: The Congress structure consists of Plenary Conferences and Round Tables, about topics of relevant interest in the field of Chemical Engineering, and Scientific Communications presented as Orals and Posters. The Inaugural Conference is held on the 30 th September 2014 with the lecture: Achieving more sustainable solutions through process intensification Dr. Rafiqul Gani (Technical University of Denmark) The Plenary Conferences that will be held during the Congress are in charge of distinguished specialists in their fields: Process Systems Engineering: Current and Future Contributions to Chemical Engineering Dr. Gintaras V. Reklaitis (Purdue University) Iron as an electron acceptor for biogeochemical transformations of pollutants in groundwater and soils Dr. Peter Jaffe (Princeton University) Nanoparticle Stabilized Emulsions for Catalytic upgrading of bio oil Dr. Daniel Resasco (University of Oklahoma) The engineering of the future Dr. José Antonio Garrido (Bilbao Metropoli 30) Chemical Engineering and Sustainable Development: Shaping our Future Dr. Adisa Azapagic (University of Manchester) At the Round Tables, experts from different subjects share their knowledge and opinions with the audience, explaining their points of view, answering any question related and discussing any controversial matter that could appear. The role of Chemical Engineering in a developing economy Chairperson: Dr. Eva Martín del Valle (Universidad de Salamanca) Participants: Dr. Ricardo Bravo (Aerisnet), Dr. Jesús Arauzo (Abengoa), Dr. José Antonio Garrido (Bilbao Metropoli 30) 5

6 Sustainable Chemical Engineering: Resources Optimization Chairpersons: Dr. Juan José Rodríguez (Universidad Autónoma de Madrid), Dr. Ángel Irabien (Universidad de Cantabria) Participants: Dr. Adisa Azapagic (University of Manchester), Dr. Fernando Cortabitarte (Acciona Desalacion), Dr. Juan Seijas (SENER) Situation of Chemical Engineering Education Chairperson: Dr. Jaume Giménez (Universidad de Barcelona), Dr. Arturo Romero (Universidad Complutense de Madrid) Participants: Dr. Rafael Van Grieken (ANECA), Dr. Juan Andrés Legarreta (UNIBASQ), Dr. Rosa Nomen (IQS) The Scientific Communications are presented as oral and poster presentations. The posters are exhibited during the whole congress in the reception area. Both poster and oral presentations have to be included into one of the topics determined by the Scientific Committee. 6

7 TOPIC LIST: 1. Chemical Engineering Fundamentals 1.1 Applied Thermodynamics, Fluid Dynamics, Heat Transfer Thermodynamics and Transport Properties Mixing, Rheology, Multiphase Flow and Fluid Flow Modelling 1.2 Separation Techniques Distillation, Absorption, Extraction Membrane Separation, Molecular Separation, Chromatography 1.3 Chemical Reaction Engineering Kinetics Catalysis Chemical Reactors 2. Chemical Engineering for Sustainable Development 2.1 Natural Resources Sustainability Energy, Water and Materials Green Chemistry and Engineering Life Cycle Assessment Renewable Raw Materials and Waste Valorization 2.2 Environmental Technology and Risk Analysis Process Safety Management Waste Minimization and Treatment Advanced Techniques for Effluent Treatment Hazardous Wastes and Soil Remediation 3. Applied Chemical Engineering 3.1. Food Engineering Food Technologies. Innovations in Food Processing Food Packaging Technologies and Food Storage Food Safety 3.2 Process and Product Engineering Molecular and Process Modelling, Simulation and Optimization, CAPE Process Intensification Supply Chain Management & Business Decision Support Product Design and Development Polymer and Solid Processing 7

8 3.3. Chemical Engineering Education New competences demanded from Chemical Engineers Education for entrepreneurship New Tools in Chemical Engineering Education 4. Emerging Technologies in Chemical Engineering 4.1 Materials and Particle Technology Carbon Materials Ceramics and Composites Emulsions Encapsulation. Materials for Packaging 4.2. Biotechnology and Biochemical Engineering Applied Biocatalysis Bioreactors, Separation Processes, Integrated Bioprocesses Biomedical Applications, Bioinformatics, Biomolecular Design 4.3. Biomedical and Pharmaceutical Engineering Design of Pharmaceutical Products and Processes Personal Care Products 4.4 Micro and Nanotechnology Nanomaterials Processing Nanomedicine and Drug Delivery Microdevices and Microreactors Plant on a chip 8

9 SCIENTIFIC PROGRAM Tuesday, 30 th September :00/ 13:30 13:30/ 16:15 16:15/ 17:00 17:00/ 18:30 EXPOQUIMIA Registration and Poster Set-up INAUGURAL LECTURE (Room 3.11) Achieving more sustainable solutions through process intensification Rafiqul Gani (DTU, Denmark) ROUND TABLE (Room 3.11) The role of Chemical Engineering in a developing economy Coordinator: Eva Martín del Valle (Universidad de Salamanca) Jesús Arauzo (Abengoa) - Ricardo Bravo (Aerisnet) - José Antonio Garrido (Bilbao Metropoli-30) Wednesday, 1 st October :00/ 09:30 09:30/ 10:00 10:00/ 10:30 10:30/ 11:00 11:00/ 11:15 11:15/ 12:00 ROOM 3.12 ROOM _002_O Effect of binder in the process of DME conversion to propylene using a ZSM-5 zeolite catalyst Paula Pérez-Uriarte 13_003_O Deactivation of bifunctional catalysts for the synthesis of dimethyl ether in a single stage María Ibáñez 13_004_O Self-condensation of Cyclohexanone using Amberlyst-15 as catalyst David Lorenzo 13_005_O Nanoestructured Co 3 O 4 catalysts development for chlorinated volatile organic compound oxidation Jonatan González-Prior 21_001_O Utilising carbon dioxide: integrating environmental sustainability considerations into process design Rosa M. Cuéllar-Franca 21_002_O Sustainable wet flue gas desulfurization: from lab-scale batch reactor to pilot scrubber Ricardo del Valle-Zermeño 21_005_O Anaerobic co-digestion of olive oil mill wastes and pig manure for the maximization of biogas production Sergio Martínez-Lozano 21_004_O ph dependence leaching tests: metal release from contaminated sediment in a potential carbon storage area M. Camino Martín-Torre Coffee Break and Poster Session PLENARY LECTURE (Room 3.11) Process Systems Engineering: Current and Future Contributions to Chemical Engineering Gintaras V. Reklaitis (Purdue University) 12:00/ 12:30 12:30/ 13:00 12_001_O Fiber characterization for CO 2 absorption Lucía Gómez-Coma 12_002_O Mathematical modeling and simulation of carbon dioxide capture using vacuum pressure swing adsorption Julià Sempere 21_003_O Microbial fuel cells for energetic valorization of waste streams Sara Mateo 21_006_O Influence of the emulsifier concentration on the physical stability and rheology of eco-friendly nanoemulsions Luis Trujillo-Cayado 9

10 13:00/ 13:30 13:30/ 15:15 15:15/ 15:45 15:45/ 16:15 16:15/ 17:00 12_003_O Biogas upgrading: siloxane removal by adsorption and regeneration by AOPs Alba Cabrera-Codony 11_001_O Going beyond linear dynamic viscoelasticity Pablo Ramírez 11_002_O Physicochemical characterization of the biodiesel production process using a molecular-based approach Fèlix Llovell Lunch Break and Poster Session 21_007_O Quartz coating to reduce its toxicity in ceramic compositions Eliseo Monfort 21_008_O Safety life cycle analysis applied to the engineering of safety valves in process plants Josep Basco 21_013_O Ionic liquid recovery in ionic liquid-based three phase partitioning (ILTPP) systems Enrique Álvarez-Guerra PLENARY LECTURE (Room 3.11) Iron as an electron acceptor for biogeochemical transformations of pollutants in groundwater and soils Peter Jaffe (University of Princeton) 17:00/ 18:30 ROUND TABLE (Room 3.11) Sustainable Chemical Engineering: Resources Optimization Coordinator: Ángel Irabién (U. de Cantabria) - Juan José Rodríguez (U. Autónoma de Madrid) Adisa Azapagic (U. of Manchester) - Fernando Cortabitarte (Acciona Agua) - Borja Zárraga (SENER) Thursday, 2 nd October :00/ 09:30 09:30/ 10:00 10:00/ 10:30 10:30/ 11:00 11:00/ 11:15 11:15/ 12:00 ROOM 3.12 ROOM _001_O Optimization using surrogate models based on a kriging interpolation: Application to the rigorous design of distillation columns Natalia Quirante 32_002_O Enhanced epsilon-constraint method through the integration of objective reduction and sampling techniques Janire Pascual 32_003_O Adaptive evolutionary optimization of complex processes using a kriging based genetic algorithm Ahmed Shokry 32_004_O Mathematical knowledge management to support decision making in process systems engineering Edrisi Muñoz 22_001_O Multiple bisorption-desorption cycles in a fixebed column to remove Pb(II) by treated olive tree pruning Alicia Ronda 22_002_O Enzymatic membrane reactors for antibiotics degradation in wastewaters: tetracycline as case study Ricardo Abejón 22_003_O Sonocatalytic Degradation of Rhodamine-B using Pilot-scale Triple Frequency Ultrasound Cavitation Reactor (TF-USCR) Shridharan Parthasarathy 22_004_O Remediation metallurgic industry wastewater using iron nanoparticles Blanca Calderón Coffee Break and Poster Session PLENARY LECTURE (Room 3.11) Nanoparticle-stabilized emulsions for catalytic upgrading of bio-oil Daniel Resasco (University of Oklahoma) 10

11 12:00/ 12:30 12:30/ 13:00 13:00/ 13:30 13:30/ 15:15 15:15/ 15:45 15:45/ 16:15 16:15/ 17:00 17:00/ 18:30 42_001_O Preparation of 3D Scaffolds by Microstereothermal lithography using New Bio Unsaturated Polyesters Filipa Gonçalves 42_002_O On the validation of superporous monolith, as stationary phase for immobilized metal affinity chromatography (IMAC) Montaña Elviro 42_003_O Exploring sulfur oxidizing biofilms in a gasphase flat plate bioreactor under controlled ph Lledó Prades 13_001_O Thermal safety of an exothermic liquid liquid reaction system Sebastien Leveneur 13_006_O Process optimization studies of NH3 SCR of NOx over Ba CeO2 MnOx mixed oxide catalyst by RSM Aligholi Niaei 21_010_O Electrochemical valorization of CO 2 : formate production using gas diffusion electrodes Andrés Del Castillo 21_012_O Multi objective optimization applied to the minimization of the environmental impact of water consumption in agriculture: a case study of wheat production in Spain Ángel Galán Martín 21_011_O Optimization of microalgae culture for biodiesel production Álvaro González Lunch Break and Poster Session 22_006_O Ozonation of the selected emerging contaminants deet and norptriptyline: kinetics and identification of by products Elena Rodríguez Paniagua 22_007_O Evaluation of the bacterial inactivation capacity in water of a new commercial Nano TiO 2 suspension Pilar Valero PLENARY LECTURE (Room 3.11) The engineering of the future José Antonio Garrido (Bilbao Metropoli 30) ROUND TABLE (Room 3.11) Situation of Chemical Engineering education Coordinator: Jaume Giménez (Universidad de Barcelona) Arturo Romero (U. Compl. de Madrid) Rafael Van Grieken (ANECA) Juan Andrés Legarreta (UNIBASQ) Rosa Nomen (IQS) 09:00/ 09:30 09:30/ 10:00 10:00/ 10:30 10:30/ 11:00 Friday, 3 rd October 2014 ROOM 3.12 ROOM _002_O Synthesis and chemisorption of thioacethyl functionalized C 60 fullerene derivatives on the gold surface Piotr Piotrowski 44_003_O Development of a multi analyte microelectrode array sensor for biofilm profiling Xavier Guimerà 44_004_O High throughput self driven electroosmotic micropump for blood plasma separation Jasmina Casals Terré 44_001_O Kinetics of the thermal degradation of poly(lactic acid) /montmorillonite nanocomposites driven by random chain scission Félix Carrasco 22_008_O Environmental application of weber blue agave fibers in textile dyestuffs removal Alejandra Alicia Peláez Cid 22_009_O Oxidation of priority and emerging pollutants by persulfate activated with zero valent iron Sergio Rodríguez 22_010_O Screening of heterogeneous catalysts for dark and photo Fenton's oxidation of actual pharmaceutical industry wastewaters Rui Martins 22_011_O Degradation and mineralization of pharmaceutical pollutants by catalytic ozonation: in situ ATR FTIR studies Shailesh S. Sable 11

12 11:00/ 11:15 11:15/ 12:00 12:00/ 12:30 12:30/ 13:00 13:00/ 15:15 Coffee Break and Poster Session PLENARY LECTURE (Room 3.11) Chemical Engineering and sustainable development: Shaping our future Adisa Azapagic (University of Manchester) 41_001_O Optimization of the encapsulation of ascorbic acid in chitosan nanoparticles Marina Cristià 41_002_O Novel transformation of lignite combustion ashes into ceramic microstructures Vayos Karayannis 31_001_O How high power ultrasound treatment on olive paste affects the virgin olive oil process yield Mohamed Aymen Bejaoui 31_002_O Oxidative Stability NATURAL milk mayonnaise Evaluation with Differential Scanning Calorimeter (DSC) Francisco Segovia Closure Cocktail and Posters Removal 12

13 ABSTRACT LIST 11_001_O 11_002_O 11_005_P 11_006_P 11_007_P 11_008_P 11_009_P 11_010_P 11_011_P 11_013_P 11_014_P 11_015_P 11_016_P GOING BEYOND LINEAR DYNAMIC VISCOELASTICITY JA Carmona, P Ramirez, N Calero, MC Garcia and J Muñoz. PHYSICOCHEMICAL CHARACTERIZATION OF THE BIODIESEL PRODUCTION PROCESS USING A MOLECULAR BASED APPROACH. F. Llovell, M.B. Oliveira, J.A.P. Coutinho, L. F. Vega STUDY OF PARTICLE CYCLE TIMES IN DRAFT TUBE CONICAL SPOUTED BEDS I. Estiati, H. Altzibar and M. Olazar ESTIMATION OF HANSEN SOLUBILITY PARAMETER OF AROMATIC COMPOUNDS BY GROUP CONTRIBUTION METHOD T. Sato, S. Araki, M. Morimoto, R Tanaka and H. Yamamoto MEASUREMENT OF GASSOLUBILITY OF OXYGEN FOR PURE AND MIXED SOLVENTS AND CORRERATION BY HANSEN SOLUBILITY PARAMETER T. Sato, Y. Hamada, M. Sumikawa, S. Araki and H. Yamamoto TEMPERATURE DEPENDENCE OF HANSEN SOLUBILITY PARAMETERS OF POLYETHYLENE GLYCOL Kana Miyatake, Takashi Sato, Sadao Araki, Yamamoto Hideki MAPPING BINARY LIQUID VAPOR OR LIQUID LIQUID VAPOR EQUILIBRIA REGIONS, INCLUDING THE DIFFERENT AZEOTROPIC BEHAVIOURS, AS A FUNCTION OF THE NRTL BINARY PARAMETERS J.A. Reyes Labarta, M.M. Olaya and A. Marcilla INFLUENCE OF CONCENTRATION ON THE RHEOLOGICAL BEHAVIOUR OF DIUTAN GUM SOLUTIONS M.C. García, M.C. Alfaro, and J. Muñoz. THERMODYNAMIC STUDY OF PVAc METHANOL DILUTED SOLUTIONS J. Camacho, D. Blanco, L.E. Martín, E. Díez, G. Ovejero APPLICATION OF THE DISPERSION MODEL AND COMPARISON WITH HYDRODYNAMIC PARAMETERS IN POROUS MEDIA COLUMN Boluda Botella, N., García Cortés, A.N., Cenador Marín, I., Hernández Teruel, M.J. and Acevedo Sempere, M. RHEOLOGICAL BEHAVIOUR, PHASE DIAGRAM AND MICELLE GEOMETRY OF NON IONIC SURFACTANT FATTY ALCOHOL ETHOXYLATES. A.I. García López, A. Reyes Requena, J. F. Rincón Romero and J.F. Martínez Gallegos DENSITIES, REFRACTIVE INDEX AND EXCESS MOLAR VOLUMES IN MIXTURES OF IMIDAZOLIUM BASED IONIC LIQUIS WITH WATER C. L. Bolívar, M. G. Montalbán, R. Trigo, G. Víllora ADVANCED INSTRUMENTATION TO DETERMINATE BINARY MIXTURES PHYSICAL PROPERTIES J. López, J. Ortega, I. Nuez, R. Ríos 13

14 11_017_P 11_018_P 12_001_O 12_002_O 12_003_O 12_004_P 12_006_P 12_008_P 12_009_P 12_010_P 12_012_P 12_013_P 12_015_P 12_016_P ACCURATE CALCULATION OF EXPANSION COEFFICIENTS AND THEIR IMPACT ON MULTI PROCESS SIMULATION Sánchez, M.; Florido, X.; Pérez, N.; Fernández, L.; Ríos, R. INFLUENCE OF IMPELLER SPEED ON BORAX CRYSTALLIZATION IN DUAL IMPELLER BATCH COOLING CRYSTALLIZER Antonija Kaćunić, Marija Ćosić, Nenad Kuzmanić FIBER CHARACTERIZATION FOR CO2 ABSORPTION L. Gomez Coma, A. Garea, A. Irabien, J.C Rouch, J.F. Lahitte and J.C. Remigy MATHEMATICAL MODELING AND SIMULATION OF CARBON DIOXIDE CAPTURE USING VACCUM PRESURE SWING ADSORPTION A. Gutiérrez, J. Menacho, E. Serra, R. Nomen and J. Sempere BIOGAS UPGRADING: SILOXANE REMOVAL BY ADSORPTION AND REGENERATION BY AOPs Alba Cabrera Codony, Rafael Gonzalez Olmos, Maria J. Martín CONTINUOUS ULTRASOUND EXTRACTION OF BORAGE POLYPHENOLS: DETERMINATION OF TOTAL POLYPHENOLS AND EFFECTIVE DIFFUSIVITY F. Segovia, M.P. Almajano DEVELOPMENT AND CHARACTERISATION OF A POLYMER INCLUSION CELLULOSE ACETATE MEMBRANE CONTAINING CALIX[4]RESORCINARENES AS A CARRIER FOR METAL ION TRANSPORT N. Benosmane, B. Boutemeur, M. Hamdi OXYGEN PERMEATION AND TRANSPORT PROPERTIES TEANSPORT PROPERTIES OF Ca0.2Sr0.8Ti1 xfexo3 d S. Araki, N. Yazumi, S. Hamakawa and H. Yamamoto INFLUENCE OF REACTION TIME AND CONCENTRATION OF ACID CATALYST FOR SILICA SOL ON MEMBRANE PERFORMANCE OF HYDROPHOBIC SILICA MEMBRANES D.Gondoh, S.Araki and H.Yamamoto ADSORPTION PROPERTIES OF GLUTARALDEHYDE CROSSLINKED POLY(VINYL ALCOHOL)/SODIUM ALGINATE POLYMER GEL FOR HAZARDOUS ORGANICS REMOVAL FROM WATER R. Okumura, S. Araki and H. Yamamoto PROCEDURE FOR AMYGDALIN ISOLATION FROM PLUM SEEDS Ivan M. Savic, Vesna D. Nikolic, Ivana M. Savic, Ljubisa B. Nikolic, Dragljub G. Gajic REUSE OF TEXTILE EFFLUENTS TREATED WITH PVDF ULTRAFILTRATION MEMBRANE V. Buscio, M. Crespi and C. Gutiérrez Bouzán NATURAL BIOACTIVE MICROPARTICLES FROM EUCALYPTUS LEAVES BY SUPERCRITICAL FLUID PROCESSES C. Chinnarasu; A. Montes; L. Casas; C. Mantell; C. Pereyra; E.J. Martinez de la Ossa BEHAVIOUR OF TERPENES, SESQUITERPENES AND OXYGENATED COMPOUNDS DURING THE ESSENTIAL OIL DETERPENATION PROCESS BY LIQUID LIQUID EXTRACTION, AT K C. E. C. Rodrigues, C. C. Koshima, D. Gonçalves 14

15 12_017_P ETHANOL DEHYDRATION WITH HEAVY ALCOHOLS: LL EQUILIBRIA OF THE SYSTEM WATER+ETHANOL+UNDECANOL AT 15ºC V. Gomis, N. Boluda, A. Font, M.D. Saquete, J. García Cano and J. Crichton 12_018_P LIQUID LIQUID PHASE EQUILIBRIUM DATA FOR THE WATER + 2 PROPANOL + 1 UNDECANOL SYSTEM V. Gomis, N. Boluda, A. Font, M.D. Saquete, J. García Cano and K. Davidson 12_019_P 12_020_P 12_021_P 12_022_P FRACTIONATION OF RECYCLED PULP SUSPENSIONS IN A HYDROCYCLONE Llop, M.F., Puig, J., Méndez, J.A., Pèlach, M.A PURE SILICA ZEOLITE ITQ 29 / POLY(1 TRIMETHYLSILYL 1 PROPYNE MIXED MATRIX MEMBRANES FOR CO2/N2 SEPARATION A. Fernández Barquín, C. Casado Coterillo, S. Valencia and A. Irabien REMOVAL PROCESS OF ARSENIC (V) IN AQUEOUS SOLUTION BY REVERSE OSMOSIS A. Abejón, A. Garea, A. Irabien POLY [2 (DIMETHYLAMINO)ETHYL METHACRYLATE]/ PUMICE COMPOSITE HYDROGEL: PREPARATION, CHARACTERIZATION AND APPLICATION IN RAPID ADSORPTION OF HUMIC ACID F. Taktak, Z. İlbay 12_023_P LIQUID LIQUID EQUILIBRIA FOR TERNARY MIXTURE OF [BMIM+][MESO4 ]+ N HEXANE + AN ORGANIC COMPOUND INVOLVED IN THE KINETIC RESOLUTION OF RAC 2 PENTANOL C.L. Bolívar, M.G. Montalbán, R.Trigo, R.C. Sosa and G.Víllora 12_024_P EVALUATION OF MOVING BED ADSORPTION PROCESSES FOR POST COMBUSTION CO 2 CAPTURE Bishan Meghani, Andrew Wright, Trevor Drage, Sean Rigby 12_025_P 12_026_P 12_027_P 12_028_P 12_029_P OPTIMIZATION OF ULTRASOUND ASSISTED EXTRACTION OF ACTIVE COMPONENTS FROM SATSUMA MANDARIN (CITRUS UNSHIU MARC.) LEAVES VIA RESPONSE SURFACE METHODOLOGY Ş. İ. Kırbaşlar, Z. İlbay and S. Şahin INFLUENCE OF MODELING IN A DISTILLATION PROCESS DESIGN WITH NEW EXPERIMENTAL METHOD. APPLICATION OF A MULTIPROPERTY MODEL WITH MULTIOBJECTIVE OPTIMIZATION Pérez, E.; Ortega, J.; Palomar, J.; Fernández; L. Florido, X. EXTRACTION OF CHLOROGENIC ACID SHELL COFFEE USING SUPER CRITICAL TECHNOLOGY AND EVALUATION OF ANTIOXIDANT ACTIVITY Yasmin Lopera, Zaida Lopera, Andres Ramirez, Juan Carlos Jaramillo REMOVAL OF NICKEL (II) FROM AQUEOUS SOLUTIONS BY MODIFIED GRAPHEN OXIDE Elif Caliskan Salihi, Jiabin Wang and Lidija Siller EFFECT OF PORE STRUCTURE AND DESORPTION PRESSURE ON ADSORPTION BREAKTHROUGH BEHAVIORS OF CARBON DIOXIDE/NITROGEN MIXTURE IN VARIOUS KINDS OF ZEOLITE PELLETS J. H. Moon, J. SIM, J. H. Park, Y. C. Park and B. M. Min 15

16 12_030_P 12_031_P 13_001_O 13_002_O 13_003_O 13_004_O 13_005_O 13_006_O 13_007_P 13_008_P 13_009_P 13_010_P 13_011_P 13_014_P DEVELOPEMENT OF COUNTRY SPECIFIC GREENHOUSE GAS EMSSION FACTOR FOR ENERGY SECTOR IN SOUTH KOREA J. H. Moon, J. S. Lee, G. H. Han, Y. C. Park, and B. M Min THE CATALYTIC CONVERSION OF PROPYLENE OXIDE TO PROPYLENE CARBONATE BY METAL ORGANIC POROUS MATERIALS H. KIM, J. H. Moon, D. H. Chun and Y. C. Park THERMAL SAFETY OF AN EXOTHERMIC LIQUID LIQUID REACTION SYSTEM H. Rakotondramaro, J. Zheng, J. Wärnå, L. Estel, B. Taouk, T. Salmi, C. Crua, S. Leveneur EFFECT OF BINDER IN THE PROCESS OF DME CONVERSION TO PROPYLENE USING A ZSM 5 ZEOLITE CATALYST P. Pérez Uriarte, A. Ateka, E. Epelde, M. Gamero, J. Bilbao, A.T. Aguayo DEACTIVATION OF BIFUNCIONAL CATALYSTS FOR THE SYNTHESIS OF DIMETHYL ETHER IN A SINGLE STAGE M. Ibáñez, A. Ateka, J. Albo, A.T. Aguayo, J. Ereña, P. Castaño SELF CONDENSATION OF CYCLOHEXANONE USING AMBERLYST 15 AS CATALYST D. Lorenzo, E. Simón, A. Santos, A. Romero NANOESTRUCTURED Co3O4 CATALYSTS DEVELOPMENT FOR CHLORINATED VOLATILE ORGANIC COMPOUND OXIDATION Jonatan González Prior, Maitane Gabilondo, Beatriz de Rivas, Rubén López Fonseca, Jose Ignacio Gutiérrez Ortiz PROCESS OPTIMIZATION STUDIES OF NH3 SCR OF NOx OVER Ba CeO2 MnOx MIXED OXIDE CATALYST BY RSM Aligholi Niaei, Seyed Mahdi Mousavia, Dariush Salari, Parvaneh Nakhostin Panahi EFFECT OF THE THERMAL TREATMENT AND THE METAL LOADING ON THE PROPERTIES OF METAL CONTAINING CATALYSTS MADE FROM HYDROTALCITE S. Garcés, S. Korili, A. Gil 2,5 DIMETHYLFURAN OXIDATION AND ITS INTERACTION WITH NO. Katiuska Alexandrino, Ángela Millera, Rafael Bilbao, María U. Alzueta ACTIVATION OF MELAMINE UREA FORMALDEHYDE ADHESIVES WITH OF HYDROPHILIC/HYDROPHOBIC HYPERBRANCHED POLY(AMIDOAMINE)S AND THEIR APPLICATION IN PARTICLEBOARDS FABRICATION S. Amirou, H.A. Essawy, A. Zerizer, A.Pizzi OXIDATION OF DIMETHOXYMETHANE UNDER HIGH PRESSURE CONDITIONS Lorena Marrodán, Eduardo Royo, Ángela Millera, Rafael Bilbao, María U. Alzueta THE OXIDATION PROCESS OF DIMETHYL CARBONATE AS FUEL ADDITIVE UNDER COMBUSTION CONDITONS María Abián, Pablo Salinas, Ángela Millera, Rafael Bilbao, María U. Alzueta H3PW12O40 ACID: A NOVEL AND RECYCLABLE HETEROPOLY ACID FOR THE MICROWAVE ACCELERATED OF SYNTHESIS OF 3, 5 DIARYL 1H PYRAZOLE Yamina Abdi, Chérifa Rabia, Maamar Hamdi, Baya Boutemeur 16

17 13_015_P 13_016_P 13_017_P 13_020_P 13_021_P 13_022_P 13_025_P 13_026_P 13_028_P 13_029_P 13_030_P 13_031_P 13_032_P 13_034_P 13_037_P COKE FORMATION AND GROWTH DURING ETHANOL STEAM REFORMING ON A Ni/La2O3 Al2O3CATALYST C. Montero, P. Castaño, B. Aramburu, J. Bilbao and A.G. Gayubo POLYCYCLIC AROMATIC HYDROCARBON (PAH) AND SOOT FORMATION IN THE PYROLYSIS OF OXYGENATED COMPOUNDS USED AS DIESEL FUEL ADDITIVES Fausto Viteri, Ángela Millera, Rafael Bilbao, María U. Alzueta EFFECT OF TEMPERATURE ON Ni/La2O3 Al2O3 CATALYST DEACTIVATION BY COKE DURING CRUDE BIO OIL STEAM REFORMING B. Aramburu, A. Remiro, B. Valle, J. Bilbao, A.G. Gayubo STEAM METHANE REFORMER MODELING AND OPTIMIZATION Mojtaba Sinaei Nobandegani, Farhad Shahraki, Tayebeh Darbandi THE EFFECT OF TEMPERATURE ON SLURRY HYDROCRACKING REACTION OF NAPHTHALENE Solmaz Akmaz and Pegah Amiri Caglayan MODIFIED HZSM 5 ZEOLITES FOR INTENSIFYING PROPYLENE PRODUCTION FROM ETHYLENE Eva Epelde, Paula Pérez Uriarte, Andrés T. Aguayo, Javier Bilbao, Ana G. Gayubo INFLUENCE OF WATER ON CATALYST STABILITY IN THE STEAM REFORMING OF DIMETHYL ETHER J. Vicente, J. Ereña, L. Oar Arteta, I. Sierra, J. Bilbao, A. G. Gayubo EFFECT OF TEMPERATURE AND METAL TYPE ON THE PERFORMANCE of ni and co CATALYSTS FOR ETHANOL steam REFORMING J. Vicente, A. G. Gayubo, J. Ereña, C. Montero, I. Sierra, J. Bilbao WATER GAS SHIFT REACTION UNDER SUB CRITICAL WATER CONDITION O. Yilmaz and N. Ayas Synthesis of SnO2/ZrO2 catalyst for supercritical water gasification of glucose N. Ayas, S. Yurtdas, M. Yurdakul APPLICATION OF MODEL FREE KINETICS TO THE STUDY OF SHALE DEVOLATILIZATION J. Foltin, G.N. Prado and A. C. L. Lisbôa PRODUCTION OF METHANOL FROM CARBON DIOXIDE OVER Cu2O/ZnO ELECTRODES J. Albo, L. Gomez, P. Castaño and A. Irabien KINETICS OF RICE HUSK CHAR GASIFICATION WITH CARBON DIOXIDE J. Alvarez, G. López, M. Amutio, M. Artetxe, I. Barbarias, A. Arregi, M. Olazar THERMOKINETIC ANALYSIS OF PYROLYSIS OF AQUATIC BIOMASS, LIGNITE COAL AND THEIR BLENDS Selim Ceylan, Yıldıray Topcu, Zeynep Ceylan FENTON LIKE OXIDATION OF ORANGE II WITH NATURAL ARGENTINIAN DIATOMITES N. Inchaurrondo, J. Chirinos, J. Font, P. Haure 17

18 13_038_P 13_039_P 21_001_O 21_002_O 21_003_O 21_004_O 21_005_O 21_006_O 21_007_O 21_008_O 21_010_O 21_011_O 21_012_O 21_013_O PREPARATION OF M Ag/ZSM 5 (M: Mn and Fe) BIMETAL NANOCATALYST FOR NH3 SCR OF NO Aligholi Niaei, Parvaneh Nakhostin Panahi, Darush Salari, Seyed Mahdi Mousavi THERMAL BEHAVIOUR AND KINETICS OF MACROALGA BIOMASS DURING PYROLYSIS Zeynep Ceylan, Selim Ceylan, Yıldıray Topcu UTILISING CARBON DIOXIDE: INTEGRATING ENVIRONMENTAL SUSTAINABILITY CONSIDERATIONS INTO PROCESS DESIGN Rosa M. Cuéllar Franca and Adisa Azapagic SUSTAINABLE WET FLUE GAS DESULFURIZATION: FROM LAB SCALE BATCH REACTOR TO PILOT SCRUBBER R. del Valle Zermeño, J. Aparicio, M. Guembe, J.Formosa, J.M. Chimenos MICROBIAL FUEL CELLS FOR ENERGETIC VALORIZATON OF WASTE STREAMS S. Mateo, J. Lobato, P. Cañizares, J. Villaseñor, M.A. Rodrigo, F.J. Fernández ph DEPENDENCE LEACHING TESTS: METAL RELEASE FROM CONTAMINATED SEDIMENT IN A POTENTIAL CARBON STORAGE AREA M. Camino Martín Torre, Iciar Muñoz, Alberto Coz, Berta Galán, Javier R. Viguri ANAEROBIC CO DIGESTION OF OLIVE OIL MILL WASTES AND PIG MANURE FOR THE MAXIMIZATION OF BIOGAS PRODUCTION E. Genescà. S. Martínez Lozano, E. Borràs, J. García Montaño, A. Surribas INFLUENCE OF THE EMULSIFIER CONCENTRATION ON THE PHYSICAL STABILITY AND RHEOLOGY OF ECO FRIENDLY NANOEMULSIONS L.A. Trujillo Cayado, J. Santos, M.C. Alfaro, N. Calero and J. Muñoz QUARTZ COATING TO REDUCE ITS TOXICITY IN CERAMIC COMPOSITIONS E. Monfort, A. Escrig, M.J. Ibáñez, G. Bonvicini, A. Salomoni, O. Creutzemberg, C. Ziemann SAFETY LIFE CYCLE ANALYSIS APPLIED TO THE ENGINEERING OF SAFETY VALVES IN PROCESS PLANTS Josep Basco ELECTROCHEMICAL VALORIZATION OF CO2: FORMATE PRODUCTION USING GAS DIFFUSION ELECTRODES A. Del Castillo, M. Alvarez Guerra, J. Solla Gullón, A. Sáez, V. Montiel, A. Irabien OPTIMIZATION OF MICROALGAE CULTURE FOR BIODIESEL PRODUCTION A. González Garcinuño, J.M. Sánchez Álvarez, E.M. del Valle1, M.A. Galán MULTI OBJECTIVE OPTIMIZATION APPLIED TO THE MINIMIZATION OF THE ENVIRONMENTAL IMPACT OF WATER CONSUMPTION IN AGRICULTURE: A CASE STUDY OF WHEAT PRODUCTION IN SPAIN Ángel Galán Martín, Gonzalo Guillén Gosálbez, Assumpció Antón, Laureano Jiménez IONIC LIQUID RECOVERY IN IONIC LIQUID BASED THREE PHASE PARTITIONING (ILTPP) SYSTEMS E. Alvarez Guerra, S.P.M. Ventura, J.A.P. Coutinho and A. Irabien 18

19 21_014_P 21_015_P 21_017_P 21_018_P 21_019_P 21_021_P 21_022_P 21_023_P 21_024_P 21_025_P 21_027_P 21_028_P 21_029_P 21_030_P BIO OIL PRODUCTION FROM HAZELNUT SHELLS VIA PYROLYSIS IN A FLUIDIZED BED REACTOR Josep O. Pou Ibar, Carles Colominas Guàrdia, Rubén Montserrat Trenchs PHYSICO CHEMICAL CHARACTERIZATION OF THE TWO PHASE OLIVE MILL SOLID WASTE FOR ITS USE IN THERMAL DEGRADATION PROCESSES A. Ronda, M. Calero, F. Corpas Iglesias, T. Cotes, F.J. Iglesias Godino, M.A. Martín Lara, C. Martínez ILFD PROJECT: LEACHATE TREATMENT FROM LANDFILL Joaquín Reina Hernández FROM THE BIOGAS TO VEHICLE FUEL BIOLIMP ENERGY PLANT FOR BIOMETHANE PRODUCTION Joaquín Reina Hernández TECHNO ECONOMIC ASSESSMENT OF THE PDO PRODUCTION FROM LIGNOCELULLOSIC MATERIALS H. A. Forero, V. Hernández, Carlos A. Cardona CATALYTIC CRACKING OF SCRAP TYRE PYROLYSIS OIL (STPO) IN FLUID CATALYTIC CRACKING UNITS (FCCU) OPERATING CONDITIONS E. Rodríguez, A. Ibarra, I. Hita, R. Palos, J. Bilbao, J.M. Arandes EVALUATION OF MEA DEGRADATION IN CO 2 CHEMICAL ABSORPTION PROCESS AT DIFFERENT CO 2 PARTIAL PRESSURES F. Vega, A. Sanna, B. Navarrete, M. Maroto Valer, M. Cano HYDRAULIC ROAD BINDERS USING FLY ASH BASED GEOPOLYMERS Y. Luna, L. Fernández, C. Leiva, A. Cornejo, C. Fernández Pereira PRODUCTION OF FERULOYL ESTERASE FROM VINE TRIMMING SHOOT AND CORNCOB Pérez Rodríguez, N., Moreira, C.D.,Torrado Agrasar, A., Belo, I., y Domínguez, J.M. ENZYMATIC RELEASE OF FERULIC ACID FROM VINE TRIMMING SHOOTS AND CORNCOB Pérez Rodríguez, N., Moreira, C.D.,Torrado Agrasar, A., Belo, I., y Domínguez, J.M. SIMPLIFIED MODELS FOR IONIC LIQUID RECOVERY IN IONIC LIQUID BASED THREE PHASE PARTITIONING (ILTPP) PROCESS E. Alvarez Guerra, P. Herrero and A. Irabien DEVELOPMENT OF FIREPROOF MORTARS COMPOSED BY BAGASSE COMBUSTION ASHES C. Leiva, C. Arenas, M. Rodríguez Galán, L.F. Vilches, A. Cornejo, Y.Luna, B. Alonso Fariñas RECYCLING OF COAL COMBUSTION BOTTOM ASH AND FGD GYPSUM IN CEMENT PRODUCTION M. Rodríguez Galán, C. Leiva, L. Caraballo, C. Arenas, L.F. Vilches, A. Cornejo, B. Alonso Fariñas, B. Navarrete ELECTRODIALYSIS POWERED BY PHOTOVOLTAIC SOLAR ENERGY: A SUSTAINABILITY ASSESSMENT C. Fernandez Gonzalez, A. Dominguez Ramos, R. Ibáñez and A. Irabien 19

20 21_031_P 21_032_P 21_033_P 21_034_P 21_035_P 21_036_P 21_038_P 21_039_P 21_040_P 21_041_P 21_042_P 21_043_P 21_044_P 21_045_P CONVERSION OF THE ORGANIC FRACTION OF THE MUNICIPAL SOLID WASTES INTO BIO ETHANOL F.J. Fernández, P. Cañizares CO 2 LEAKAGES FROM CCS IN SUB SEABED GEOLOGICAL FORMATIONS: HEAVY METAL RELEASE FROM MARINE SEDIMENT M. Camino Martín Torre, Iciar Muñoz, Berta Galán, Javier R. Viguri REDUCTION OF CO 2 TO CO IN VOLTAIC ARC TUBULAR REACTOR Carles Colominas Guàrdia, Josep O. Pou Ibar, Miguel Tabernero Oller SYNTHESIS, CHARACTERIZATION AND FUEL CELL PERFORMANCE OF PHOSPHORIC ACID DOPED POLYBENZIMIDAZOLE MEMBRANE Çağla Gül Tosun, Levent Akyalçin and Hasan Ferdi Gerçel SUSTAINABILITY EVALUATION OF MUNICIPAL SOLID WASTE INCINERATION USING A LIFE CYCLE ASSESSMENT APPROACH Maria Margallo, Ana Hernández, Rubén Aldaco, Angel Irabien EUROPEAN REGULATORY FRAMEWORK OF MSWI FLY AND BOTTOM ASH VALORIZATION Ana Hernández, María Margallo, Rubén Aldaco, Ángel Irabien BIOREFINERY DESIGN BASED ON MACAMBO (Theobroma bicolor) FRUIT A. A. González, J. A. Dávila, C. A. Cardona REDUCING SUGAR PRODUCTION FROM SEVEN AGROINDUSTRIAL COLOMBIAN WASTES J. A. Dávila, L. V. Daza, A. A. González, C. A. Cardona ASSESSING THE LIFE CYCLE ENVIRONMENTAL IMPACTS OF ELECTRICITY GENERATION IN TURKEY Burcin Atilgan and Adisa Azapagic CONTINUOUS PROCESS FOR THE ELECTROCHEMICAL REDUCTION OF INDIGO DYE X. Coma, V. Buscio, M. Crespi and C. Gutiérrez Bouzán TECHNO ECONOMIC EVALUATION OF THE PHB PRODUCTION FROM MILK WHEY AS FEEDSTOCK Catalina Alvarez C.; Juan Carlos Higuita V. ANALYSIS OF OPTIMAL CONDITIONS FOR THE GROWTH OF Chlorella vulgaris USING VINASSE AS SUBSTRATE Juan D. Garcia M; Catalina Álvarez C; Juan C. Higuita V. EMULSOR SCREEN PROCESSING OF SUBMICRON ECO FRIENDLY EMULSIONS J. Santos, L.A. Trujillo Cayado, N. Calero, M.C. Alfaro and J. Muñoz BIOCONVERSION OF HYDROLYZED BAGASSE SUGARCANE IN ETHANOL BY Spataspora arborariae UFMG HM19.1A Guadalupe Bustos V., Erika Vizcaino G., Nadia A. Rodríguez D., Alfredo Del Angel, Nubia R. Rodríguez D. 20

21 21_046_P 21_047_P 21_048_P 21_049_P 21_050_P 21_051_P 21_052_P 21_054_P 21_055_P 21_056_P 21_057_P 21_058_P KINETIC STUDY OF ETHANOL PRODUCTION BY Spataspora arborariae UFMG HM19.1A IN MEDIA HYDROLYZATE SUGARCANE BAGASSE DETOXIFIED Guadalupe Bustos V., Erika Vizcaino G., Nadia A. Rodríguez D., Alfredo Del Angel, Nubia R. Rodríguez D. DECOMPOSITION CHARACTERISTICS OF BIOMASS OAL POLYMER MIXTURES VIA PYROLYSIS Gamzenur Özsin, Murat Kılıç, Esin Apaydın Varol, Başak B. Uzun, Ayşe E. Pütün, Ersan Pütün EVOLVED GAS ANALYSIS (TG/FT IR/MS) AND REACTION KINETICS OF DIFFERENT OIL SEEDS DURING PYROLYSIS Gamzenur Özsin, Murat Kılıç, Ayşe E. Pütün CONVERSION OF FRUIT PULP INTO ENERGY RICH GAS PRODUCTS BY SUPERCRITICAL WATER GASIFICATION E. Demirel and N. Ayas ZSM 5 CATALYSIS IN PYROLYSIS REACTIONS Sahin F. MULTI OBJECTIVE OPTIMIZATION METHOD BASED ON INPUT OUTPUT MODELS TO MINIMIZE THE LIFE CYCLE GREENHOUSE GAS EMISSIONS OF THE EUROPEAN ECONOMY Daniel Cortés Borda, Antonio Ruiz Hernández, Gonzalo Guillén Gosálbez, Maria Llop, Roger Guimerà, Marta Sales Pardo ELECTROSYNTHESIS OF DIMETHYL CARBONATE FROM CO 2 AND METHANOL IN THE PRESENCE OF [bmim][br]: THE INFLUENCE OF THE ELECTROCHEMICAL CELL CONFIGURATION I. Garcia Herrero, A. del Castillo, M. Alvarez Guerra, A. Irabien ALLOCATION OF GHG EMISSIONS IN COMBINED HEAT AND POWER SYSTEMS IN PAPER INDUSTRY Aldrich, R., Llauró, F.X., Puig, J., Mutjé P., Pèlach, M.A ETHERIFICATION OF CRUDE GLYCEROL BY BENZYL ALCOHOL M. P. Pico, S. Rodríguez, A. Santos, A. Romero HYDROTHERMAL CARBONIZATION OF TWO PHASE OLIVE MILL WASTE: CHARACTERIZATION OF THE HTC CHAR AND DETERMINATION OF THE KINETICS FROM THE SOLID MASS YIELD V. Benavente, J. Gordon, E. Calabuig, A. Fullana PRODUCTION OF HYDROGEN FROM PLASTIC WASTE BY PYROLYSIS AND CATALYTIC STEAM REFORMING I. Barbarias, M. Artetxe, M. Amutio, G. Lopez, J. Alvarez, A. Arregi, M. Olazar HYDROGEN PRODUCTION BY STEAM REFORMING OF PYROLYSIS VOLATILE PRODUCTS OF PINE SAWDUST A. Arregi, M. Amutio, G. Lopez, M. Artetxe, J. Alvarez, I. Barbarias, M. Olazar 21

22 21_059_P 21_060_P 21_061_P 21_062_P 21_063_P 21_064_P 21_065_P 21_068_P 21_069_P 21_070_P 21_071_P 21_072_P 21_074_P 21_075_P 21_076_P BIOMASS AND HDPE COGASIFICATION IN A CONICAL SPOUTED BED REACTOR A. Erkiaga, J. Alvarez, G. Lopez, M. Artetxe, I. Barbarias, A. Arregi, M. Olazar OBTENTION OF HIGH BIOETHANOL CONCENTRATIONS FROM CORN RESIDUES Iria Ana Ares Peón, Belén Gómez, Gil Garrote, Juan Carlos Parajó A BIOREFINERY PROCESS BASED ON AUTOHYDROLYSIS VALORIZATION OF HARDWOOD Sandra Rivas, Carlos Vila, Valentin Santos, Juan Carlos Parajó DELIGNIFICATION OF AUTOHYDROLYZED WOOD BY ORGANOSOLV METHODS Carlos Vila, Sandra Rivas, Valentin Santos, Juan Carlos Parajó MULTI OBJECTIVE OPTIMIZATION APPLIED TO MINIMIZE THE ECONOMIC COST AND THE ENVIRONMENTAL IMPACT OF BUILDING INSULATION Joan Carreras, Abdallah el Badry, Dieter Boer, Gonzalo Guillén Gosálbez, Laureano Jiménez, Luisa F. Cabeza, Marc Medrano FAST GROWING BIOMASS VALORIZATION BY ENVIRONMENTALLY FRIENDLY PROCESSES Elena Domínguez, Fátima Vargas, Gil Garrote, Juan Carlos Parajó RENEWABLE BIOFUELS PRODUCTION FROM AGRICULTURAL RESIDUES Fátima Vargas, Elena Domínguez, Alejandro Rodríguez, Gil Garrote MULTI OBJECTIVE OPTIMIZATION OF INTERNATIONAL ECONOMIES VIA MULTI REGIONAL INPUT OUTPUT ANALYSIS: APPLICATION TO THE US ECONOMY J. Pascual González, G. Guillén Gosálbez and L. Jiménez CONVERSION OF LIGNOCELLULOSIC BIOMASS TO HEMICELLULOSE BASED SUSTAINABLE POLYMERIC MATERIALS VIA EXTRUSION Duygu Erdemir, Erinç Bahçegül, Merve Akkuş, Büşra Akınalan, Necati Özkan, Ufuk Bakir PROPERTIES OF UREA FORMALDEHYDE POLYMER COMPOSITE FILLED WITH THE STERILIZED MEDICAL WASTE F. Boran, S. Bayrak and E. Karadurmuş FURAN MANUFACTURE FROM LIGNOCELLULOSIC MATERIALS BY REACTION IN CATALYZED IONIC LIQUIDS Susana Peleteiro; Lucía Penín; Aloia Romaní; Gil Garrote and Juan Carlos Parajó POLYOLS PRODUCTION BY LIQUEFACTION OF PAULOWNIA WOOD Lucía Penín; Susana Peleteiro; Gil Garrote and Juan Carlos Parajó BIOFUEL PRODUCTION FROM STEAM EXPLOSION PREPREATED BIOMASS Romaní, Aloia; Peleteiro, Susana; Garrote, Gil; Ballesteros, Ignacio; Ballesteros, Mercedes and Parajó, Juan Carlos PAULOWNIA BIOREFINERY USING SEQUENTIAL NON ISOTHERMAL AUTOHYDROLYSIS STEPS Yolanda Álvarez, Elena Domínguez, Gil Garrote, Juan Carlos Parajó TEXTILE DYEING APPLYING PROTIC IONIC LIQUIDS M. Iglesias, R.S. Andrade, H. Mazzer, L. Cardozo 22

23 21_077_P 21_081_P 22_001_O 22_002_O 22_003_O 22_004_O 22_006_O 22_007_O 22_008_O 22_009_O 22_010_O 22_011_O 22_005_P INJECTION OF CO 2 IN WATER: THERMOPHYSICAL AND FLUID FLOW MODELLING USING AN ADVANCED EQUATION OF STATE AND CFD F. Llovell, J. Hermann, W. Chang, S. Guri, L. F. Vega UPGRADING OF LOW RANK COAL WITH HIGH MOISTURE J. H. Park, C. H. Lee, D. Shun, D. H. Bae, H. J. Ryu, J. H. Moon, J. S. Shin, G. Y. Kim, and J. Park MULTIPLE BISORPTION DESORPTION CYCLES IN A FIXE BED COLUMN TO REMOVE Pb(II) BY TREATED OLIVE TREE PRUNNING A. Ronda, G. Blázquez, G. Tenorio, A. Pérez, M.C. Trujillo, M. Calero ENZYMATIC MEMBRANE REACTORS FOR ANTIBIOTICS DEGRADATION IN WASTEWATERS: TETRACYCLINE AS CASE STUDY R. Abejón, M. de Cazes, M.P. Belleville and J. Sanchez Marcano SONOCATALYTIC DEGRADATION OF RHODAMINE B USING PILOT SCALE TRIPLE FREQUENCY ULTRASOUND CAVITATION REACTOR (TF USCR) S. Parthasarathy, S. Manickam, X.Y. Liew, Y.V. Lim, K.W. Choo, D.R. Bibi, R.L.Gomes REMEDIATION METALLURGIC INDUSTRY WASTEWATER USING IRON NANOPARTICLES B. Calderon and A. Fullana OZONATION OF THE SELECTED EMERGING CONTAMINANTS DEET AND NORPTRIPTYLINE: KINETICS AND IDENTIFICATION OF BY PRODUCTS E. Rodríguez, F.J. Benítez, J.L. Acero, F.J. Real, G. Roldán EVALUATION OF THE BACTERIAL INACTIVATION CAPACITY IN WATER OF A NEW COMMERCIAL NANO TIO2 SUSPENSION P. Valero, J. Torres, M.P. Ormad, R. Mosteo, J.L. Ovelleiro ENVIRONMENTAL APPLICATION OF WEBER BLUE AGAVE FIBERS IN TEXTILE DYESTUFFS REMOVAL A.A. Peláez Cid, A.R. Cárcamo Gómez, J. Vázquez Bautista, R. Radillo Ruíz OXIDATION OF PRIORITY AND EMERGING POLLUTANTS BY PERSULFATE ACTIVATED WITH ZERO VALENT IRON Sergio Rodriguez, Aurora Santos and Arturo Romero SCREENING OF HETEROGENEOUS CATALYSTS FOR DARK AND PHOTO FENTON'S OXIDATION OF ACTUAL PHARMACEUTICAL INDUSTRY WASTEWATERS R. C. Martins, A. C. Oliveira and R. M. Quinta Ferreira DEGRADATION AND MINERALIZATION OF PHARMACEUTICAL POLLUTANTS BY CATALYTIC OZONATION: IN SITU ATR FTIR STUDIES S.S. Sable, P. P. Ghute, F. Medina, R. B. Mane, C.V. Rode, D. Fahrnasova, A. Urakawa, S. Contreras EVOLUTION OF CONCENTRATION AND HUMAN RISK OVER TIME DUE TO PETROLEUM HYDROCARBONS IN SOIL J. Pinedo, R. Ibáñez, Á. Irabien 23

24 22_012_P 22_013_P 22_015_P 22_016_P 22_017_P 22_018_P 22_019_P 22_020_P 22_021_P 22_022_P 22_023_P 22_024_P 22_025_P ASSESSMENT OF FE FOULING ON LP UV LAMP SLEEVES A.Cruz, M. Li, C.Sans, S.Esplugas, Z. Qiang USE OF ACTIVATED PERSULFATE FOR THE REMEDIATION OF A BIODIESEL BLEND CONTAMINATED SOIL F. Pardo, J.M. Rosas, A. Santos, A. Romero ANALYSIS OF THE SPECIES GENERATED DURING THE FIRST STAGES OF PHENOL OXIDATION BY PHOTO FENTON REAGENT N. Villota, L.M. Camarero, J.M. Lomas and E. Fuentes ANALYSIS OF THE COLOR CHANGES DURING THE DEGRADATION OF PARACETAMOL WITH PHOTO FENTON REAGENT N. Villota, L.M. Camarero, J.M. Lomas and I. García REMOVAL OF BISPHENOL A FROM WASTEWATERS USING SLUDGE CARBON/TIO2 NANO COMPOSITES S. Athalathil, B. Erjavec, R. Kaplan, A. Fortuny, A. Pintar and A. Fabregat ORGANIC POLLUTANT DEGRADATION USING SYNTHETIC AND NATURAL METAL PHOSPHATE MATERIALS: A COMPARATIVE STUDY Y. Roumila, R. Bagtache, D. Meziani and K. Abdmeziem SUSTAINABLE WATER RESOURCE ENGINEERING THROUGH THE DEVELOPMENT AND APPLICATION OF NOVEL BIOANALYTICAL TOOLS S.Parthasarathy, C.A.Ortori, D.A. Barrett, R.L.Gomes STABILIZATION/SOLIDIFICATION OF A METALURGICAL WASTE USING COAL FLY ASH AND COAL SLAG BASED GEOPOLYMER. INFLUENCE OF SLAG PARTICLE SIZE Y. Luna, A. Cornejo, C. Leiva, C. Arenas, M. Rodriguez Galán TRATAMIENTO DE LOS POLVOS DE HORNO ELÉCTRICO DE ARCO PROCEDENTES DE LA FABICACION DE ACERO ESTRUCTURAL. PROCESO DE OBTENCIÓN DE ZINC Roca, A; Cruells, M; Cordova, K. DETERMINATION OF KINETICS PARAMETERS FOR COMPOSTING PROCESS OF THE ORGANIC FRACTION OF MUNICIPAL SOLID WASTE WITH SOURCE SEPARATION J. F. Saldarriaga, S. Upegui EVALUATION OF THE MICROBIOTA OF IMMATURE COMPOST AND MORAVIA SOIL FOR THE BIOREMEDIATION OF SOILS CONTAMINATED WITH CHLORPYRIFOS, MALATHION AND METHYL PARATHION S. Upegui, J. F. Saldarriaga EFFECT OF INITIAL ph IN THE DEGRADATION OF THE EMERGING CONTAMINANT METOPROLOL BY MEANS OF UVC/H2O2 V. Romero, E. Rodríguez, P. Marco, J. Giménez, S. Esplugas METOPROLOL REMOVAL BY CATALYST BICARBONATE ACTIVATED HYDROGEN PEROXIDE IN DRINKING WATER V. Romero, O. González, S. Minghao, S. Esplugas 24

25 22_026_P 22_028_P 22_029_P 22_030_P 22_031_P 22_032_P 22_033_P 22_035_P 22_036_P 22_037_P 22_038_P 22_039_P 22_040_P 22_041_P EXPLOITATION OF LIGNOCELLULOSIC RESIDUES GENERATED BY PAPER AND CITRUS INDUSTRIES BY COMPOSTING Jaime, P.; Domínguez, J.; Espinosa, E.; Palenzuela, M.V.; Rodríguez, A.; Rosal, A. ELIMINATION OF THE EMERGING CONTAMINANT METOPROLOL BY PHOTO FENTON PROCESS WITH SUCCESSIVE AND CONTINUOUS IRON (II) ADDITIONS P. Marco, V. Romero, A. Solé, J. Giménez, S. Esplugas REMOVAL OF SELECTED EMERGING CONTAMINANTS FROM DIFFERENT WATER MATRICES BY UF AND NF MEMBRANES E. Rodríguez, J.L. Acero, F.J. Benítez, F.J. Real, G. Roldán REMEMBRANE: RECOVERY OF REVERSE OSMOSIS MEMBRANE AT ITS END OF LIFE C. Pérez, F.X. Simón, J. García Montaño, S. Martínez Lozano STUDY OF THE INFLUENCE OF THE PRESENCE OF DISSOLVED SOLID IN THE REMOVAL OF CYANIDE IN WASTEWATER TREATMENT BY OZONE Pueyo N., Ormad M.P., Ovelleiro J.L. OPTIMIZATION ON THE STABILIZATION/SOLIDIFICATION TECHNIQUE OF ELECTROPLATING SLUDGE BY STATISTICAL ANALYSIS M.T. Montañés, R. Sánchez Tovar and A. Marín Torres CHLOROPHENOLS DEGRADATION BY BIOLOGICALLY ACTIVATED CARBON J. Chirinos, A. Fabregat, A. Fortuny, C. Bengoa, F. Stüber, J. Font USE OF IRON ORGANOMETALLIC COMPOUNDS IN THE DEPOLLUTION OF CONTAMINED SOILS BY METRIBUZIN A. Boucif, Z. Hank and S. Boutamine OPTIMIZATION OF PROCEDURE FOR REMOVAL OF COPPER(II) IONS FROM WATER Ivana M. Savic, Ivan M. Savic, Stanisa T. Stojiljkovic, Dragoljub G. Gajic PYROLYSIS OF ANAEROBIC DIGESTED PIG MANURE IN A FLUIDIZED BED Violeta Quispe, Javier Ábrego, María Benita Murillo, Gloria Gea and María Atienza Martínez CONTROL OF HAZARDOUS CHEMICAL SUBSTANCES IN TEXTILE MATERIALS R. Rodríguez, M.Vilaseca, M. Crespi and C. Gutiérrez Bouzán RESPIROMETRIC BIODEGRADABILITY ASSESSMENT OF DYE CONTAINING EFFLUENTS AFTER ELECTROCHEMICAL TREATMENT M. Vilaseca, V. López Grimau, C. Gutiérrez Bouzán and M. Crespi DENITRIFICATION IN AN UP FLOW STIRRED PACKED BED REACTOR (USPBR) USING BIOLOGICAL ACTIVATED CARBON Y. García Martínez, A. Fortunyand A. Fabregat METHODOLOGY FOR ECO EFFICIENT AND SAFE COMBUSTION OF GAS REFINERY J. Saavedra, V. Kafarov, L. Meriño, A. Sierra, M Gómez 25

26 22_042_P 22_043_P 22_044_P 22_045_P 22_046_P 22_047_P 22_048_P 22_049_P 22_050_P 22_051_P 22_052_P 22_053_P 22_054_P 22_055_P MICRORESPIROMETRY AS AN EFFECTIVE TECHNIQUE FOR MONITORING BIOMASS GROWTH AND ACTIVITY IN CHALCOPYRITE BIOLEACHING PROCESSES E. Benzal, E. Morral, X. Guimerà, X. Gamisans, M. Solé and A. D. Dorado ADSORBENTS PREPARATION FROM TEXTILE WASTE MATERIAL AND THEIR APPLICATION IN DYESTUFFS REMOVAL A.A. Peláez Cid, B.M. Espíndola Durán, J. Vázquez Bautista, R. Radillo Ruíz ALUMINA BASED CATALYSTS FOR PP CWAO OF AQUEOUS PHENOL SOLUTIONS C. García Figueruelo, M. Munoz, Z. M. de Pedro, A. Quintanilla, J.A. Casas, J.J. Rodriguez DECOLORIZATION OF BAKER S YEAST EFFLUENT BY ULTRASOUND Didem Ildırar, Serap Fındık EVALUATION OF A COMMERCIAL NANO TiO 2 SUSPENSION PHOTOCATALYTIC ACTIVITY IN THE 2,4 DICHLOROPHENOL OXIDATION S. Escuadra, M.P. Ormad, A.M. Laseras, J. Gomez and J.L. Ovelleiro SLOW PYROLYSIS KINETICS AND THERMOGRAVIMETRIC CHARACTERISTICS OF CRUDE OIL SLUDGE Murat Kılıç, Gamzenur Özsin, Esin Apaydın Varol, Ersan Pütün, Ayşe E. Pütün BIOSORPTIVE REMOVAL OF HEAVY METAL IONS ONTO GRASS WASTE Murat Kılıç, Gamzenur Özsin, Ayşe E. Pütün PYROLYSIS OF TEXTILE WASTES: INTEGRATED KINETIC STUDY AND EVOLVED GAS ANALYSIS Gamzenur Özsin and Ayşe E. Pütün ASSESSMENT OF IRON CHELATES EFFICIENCY FOR PHOTO FENTON AT NEUTRAL ph Antonella De Luca, Renato F. Dantas, Santiago Esplugas ADVANCED Co/Ce/H ZSM 5 CATALYSTS FOR THE DEEP OXIDATION OF CHLORINATED ORGANIC COMPOUNDS B. de Rivas, C. Sampedro, J. González Prior, R. López Fonseca and J.I. Gutiérrez Ortiz SORPTION OF PHOSPATE AND ZINC ONTO HEMATITE AND MAGNETITE AS A MECHANISM OF ATTENUATION OF CONTAMINATION IN AGRICULTURAL SOILS Maria Martínez, Vicens Martí and Javier. Giménez NICKEL REMOVAL FROM EXHAUSTED ELECTROPLATTING BATHS BY USING VEGETABLE WASTES María Martínez, Isabel Villaescusa, Nuria Fiol, Nuria Miralles and Antonio Florido INVESTIGATION OF ADSORPTIVE/CATALYTIC EFFECT ON THE REMOVAL OF MANGANESE FROM WATER Nihan Kaya DEGRADATION AND MINERALIZATION OF BISPHENOL A BY THE PHOTO FENTON PROCESS M. Navarro Jordà, M. Graells, M. Pérez Moya 26

27 22_056_P 22_057_P 22_058_P 22_059_P 22_061_P 22_062_P 22_063_P 22_064_P 22_065_P 22_066_P 22_067_P 22_068_P 22_069_P PHOTOCATALYTIC DEGRADATION OF METOPROLOL BY B DOPED TIO2: IDENTIFICATION OF INTERMEDIATES R.P. Cavalcante, R.F. Dantas, B. Bayarri, O. González, S.C. Oliveira, J. Giménez, S. Esplugas, Jr.A. Machulek COMPARATIVE PHOTOCATALYTIC DEGRADATION OF METOPROLOL PHARMACEUTICAL IN AQUEOUS SOLUTIONS BY USING TWO TYPES OF TIO2 PHOTOCATALYSTS: SCAVENGER STUDY R.P. Cavalcante, R.F. Dantas, B. Bayarri, O. González, S.C. Oliveira, J. Giménez, S. Esplugas, Jr.A. Machulek USING EXPERIMENTAL DESIGN TO OPTIMIZE BARLEY STRAW EFFLUENT DEGRADATION BY FENTON REAGENT Francesc Torrades, José Antonio García Hortal, Omar Folqués Martín TREATMENT OF SYNTHETIC MUNICIPAL WASTEWATER CONTAINING ANTIPYRINE BY SONOPHOTOCATALYSIS J.M. Monteagudo, A. Durán, A. Fernández, A. Carnicer, M.A. Alonso, J.M. Frades NOVEL COMPACT ANAEROBIC/AEROBIC REACTORS FOR THE REMOVAL OF AZO DYES IN WASTEWATER A.Giménez, J.Chirinos, Y.García, A. Fabregat, A. Fortuny, C. Bengoa, F. Stüber, J. Font WOOL DRY SCOURING J. Iglesias, Ll. Alerm, M. Tavares, S. Balsells, M. Jorba, L. Coderch, M. Martí PHOTOCATALYTIC OZONATION OF TRICLOPYR, AN HERBICIDE REFRACTORY TO OZONE R. R. Solís, F.J. Rivas, J.L. Pérez Bote PHOTOCATALYTIC OZONATION BY NITROGEN DOPED TITANIA OF HERBICIDES CLOPYRALID, PICLORAM AND TRICLOPYR R. R. Solís, F.J. Rivas, J.L. Pérez Bote WO3 MICROSPHERES FOR PHOTOCATALYTIC OZONATION OF DEET E. Mena, A. Rey, F.J. Beltrán, B. Acedo BORON DOPED TiO2 PHOTOCATALYSTS FOR SOLAR PHOTOCATALYTIC TREATMENTS OF SELECTED PESTICIDES D.H. Quiñones, A. Rey, P.M. Álvarez, E. Mena, F.J. Beltrán, G. Li Puma METHANE RECOVERY FROM ANAEROBIC BIOREACTOR EFFLUENTS BY DEGASSING MEMBRANE TECHNOLOGY M. Henares, M. Izquierdo, C. Gabaldón and V. Martínez Soria SINERGETIC EFFECT OF COUPLING DIELECTRIC BARRIER DISCHARGE AND PHOTOCATALYSIS IN THE VOC REMOVAL M. Henaresa, J. Palau, A.A. Assadi, A. Bouzaza, D. Wolbert, M. Izquierdoa, J.M. Peña Roja, V. Martínez Soria CU(II) REMOVAL FROM WATER BY AZOLLA SPECIES AS BIOSORBENTS M. Izquierdo, P. Brouwer and P. Marzal 27

28 22_070_P 22_071_P 22_074_P 22_075_P 22_076_P 22_077_P 22_078_P 22_079_P 22_080_P 22_081_P 22_082_P 22_083_P 22_084_P 22_085_P REMEDIATION OF A PAH CONTAMINATED SOIL BY OXIDATION WITH FENTON REAGENT AND SIMOULTANEOUS SOLUBILIZATION WITH SURFACTANTS M. Peluffo, F. Pardo, A. Santos, A. Romero NOVEL Fe(III) Al2O3 NANOCOMPOSITE AS FENTON LIKE CATALYST FOR THE CWHPO OF PHENOLIC WASTEWATERS C. di Luca, F. Ivorra, P. Massa and R. Fenoglio PRELIMINARY STUDY OF THE RECYCLING OF POLYURETHANE BY SPLIT PHASE GLYCOLYSIS TO RECOVER OF POLYOLS I. Duque Ingunza, R. López Fonseca, O. Martínez, I. Acillona, S. Arnaiz and J.I. Gutiérrez Ortiz ASSESSING THE PVC EFFLUENT TREATMENT USING A MEMBRANE BIOREACTOR PILOT L. Blanco, D. Hermosilla, A. Blanco, N. Swinnen, D. Prieto and C. Negro NEW CERAMICS USING RECYCLED INDUSTRIAL SECONDARY RESOURCES TOWARDS SUSTAINABLE DEVELOPMENT V. Karayannis CYANIDE REMOVAL FROM WATER BY ADVANCED OXIDATION PROCESSES BASED ON OZONE AND HYDROGEN PEROXIDE N. Miguel, N. Pueyo, A.Palomar, M.P. Ormad, J.L. Ovelleiro APPLICATION OF FORWARD OSMOSIS TO CHEMICAL WASHING EFFLUENTS FROM BEVERAGE INDUSTRY E. Gonga Roselló, M. F. López Pérez, J. Lora García, A. Abad Sempere CHEMICAL DURABILITY AND STRUCTURAL PROPERTIES OF PHOSPHATE GLASSES Y. Makhkhas, S. Krimi and E.H. Sayouty REMOVAL OF PHARMACEUTICAL COMPOUNDS, IBUPROFEN AND CLOFIBRIC ACID BY HETEROGENOUS PHOTO FENTON LIKE PROCESS WITH IN SITU H2O2 Pallavi P. Ghute, Shailesh S Sable, Francesc Medina, Sandra Contreras INFLUENCE OF VARIOUS INDUSTRIAL SOLVENTS ON THE ANAEROBIC BIODEGRADABILITY OF ETHANOL N. Vermorel, M. Izquierdo, C. Gabaldón, J.M. Penya Roja A SIMPLE MODEL OF A GAS LIQUID REACTOR FOR SEMIBATCH OZONATION OF WASTEWATERS M. Marce, S. Esplugas, S. Baig OPERATION OF AN ANMBR FOR WINERY WASTEWATER TREATMENT N. Basset; E. Santos; J. Dosta; A. Guastalli; J. Mata Álvarez COMBINATION OF ADVANCED OXIDATION PROCESSES AND BIOFILTRATION FOR RECLAMATION REVERSE OSMOSIS BRINE A. Justo, O. González, C. Sans ANAEROBIC CO DIGESTION OF FARM WASTES: ULTRA SOUNDS PRE TREATMENT ON LIGNOCELLULOSIC WASTES X. Fonoll, R. Roig, N. Basset, J. Dosta and J. Mata Alvarez 28

29 22_086_P 22_087_P 22_088_P 22_089_P INFLUENCE OF THE INOCULUM IN THE RESPIROMETRIC BIODEGRADABILITY OF OXIDIZED WATERS P.Ribao, S.Dominguez, M.J. Rivero, I. Ortiz INFLUENCE OF CERTAIN PARAMETERS OF CHINE CLAY ON ITS DUSTINESS A. López Lilao, M. Bruzi, V. Sanfelix, A. Gozalbo, G. Mallol, E. Monfort WATERREUSE: EL RETO DE LA REUTILIZACIÓN DE AGUA DE PROCESO EN LA INDUSTRIA. Pedro Trinidad, Pedro Muñoz, José Aguirre, Manuel Susarte y Miguel Octavio UNDERSTANDING THE EFFECT OF LEACHATE COMPOSITION ON ITS OXIDATION P. Oulego, S. Collado, A. Laca and M. Díaz 22_090_P 22_091_P 22_092_P 31_001_O 31_002_O 31_004_P 31_005_P 31_006_P USE OF CO CULTURES FOR THE SIMULTANEOUS BIODEGRADATION OF CYANIDE AND PHENOLIC COMPOUNS R. G. Combarros, S. Collado, A. Laca and M. Diaz ESTUDIO QUÍMICO FÍSICO DE NANO PARTÍCULAS DE Ce3+/Ce4+ MEDIANTE DERIVADOS NAFTALIMÍDICOS E. Martín, G. Pulido, F. Leganés y F. F. Piñas OXIDATION OF LEVOFLOXACIN BY PERMANGANATE IN WATER TREATMENT: KINETICS, MECHANISMS, AND ANTIBACTERIAL ACTIVITY VARIATION Ke Xu, Jiuhui Qu, Carme Sans, Santiago Esplugas, Zhimin Qiang HOW HIGH POWER ULTRASOUND TREATMENT ON OLIVE PASTE AFFECTS THE VIRGIN OLIVE OIL PROCESS YIELD. Mohaemed Aymen Bejaoui, Abraham Gila, Araceli Sánchez Ortiz, María Paz Aguilera Herrera, Gabriel Beltrán Maza, Antonio Jiménez Márquez OXIDATIVE STABILITY NATURAL MILK MAYONNAISE EVALUATION WITH DIFFERENTIAL SCANNING CALORIMETER (DSC) F. Segovia, X. Ramis, A. García, M.P. Almajano EFFECTS OF FLAX SHIVE COATING WITH PARAFFIN WAX ON THE PROPERTIES OF LIGHTWEIGHT FLAX SHIVES CEMENT COMPOSITE A Al Mohamadawi, K. Benhabib, A. Goullieux VEGETABLE OILS EXTRACTION PROCESS USING RENEWABLE SOLVENTS AS SUBSTITUTES TO THE HEXANE C. E. C. Rodrigues, M. C. Capellini, K. K. Aracava, S. L. B. Navarro, M. M. Sawada, N. K. Scharlack COMPARATIVE EVALUATION OF NEW PREBIOTIC INGREDIENTS FROM ORANGE PEEL WASTES Belén Gómez, Iria Ana Ares Peón, Beatriz Gullón, Remedios Yáñez, Juan Carlos Parajó, José Luis Alonso 29

30 31_007_P 31_008_P 31_009_P 31_010_P 31_012_P 31_013_P 31_014_P 31_015_P 32_001_O 32_002_O 32_003_O 32_004_O 32_005_P PRODUCTION OF FISH PROTEIN HYDROLYSATES ENRICHED IN ANGIOTENSIN CONVERTING ENZYME INHIBITORS BY MEMBRANE REACTOR F.J. Espejo Carpio, P.J. García Moreno, M. Marín Suárez, M.C. Almécija, A. Guadix and E.M. Guadix INFLUENCE OF TEMPERATURE AND TIME ON POLYUNSATURATED FATTY ACIDS CONCENTRATION BY LOW TEMPERATURE CRYSTALLIZATION G. De León González, R. Morales, F.J. Espejo Carpio, F. Camacho, A. Guadix, E.M. Guadix and M. Muñío EFFECT OF MICRONIZED NATURAL TALC ADDITION ON THE DISSOLUTION OF PROTEINS AND PECTIC CELL WALL POLYSACCHARIDES DURING INDUSTRIAL PROCESSING OF HOJIBLANCA OLIVE OIL Abir Sadkaoui, Antonio Jiménez, Rafael Pacheco, Gabriel Beltrán EFFECT OF MICRONIZED NATURAL TALC PHYSICO CHEMICAL CHARACTERISTICS AND DOSAGE ON THE BREAK DOWN OF OIL IN WATER EMULSIONS Abir Sadkaoui, Antonio Jiménez, Rafael Pacheco, Gabriel Beltrán INFLUENCE OF TEMPERATURE ON PHYSICAL PROPERTIES OF CANADIAN MAPLE SYRUP M. Iglesias, R.S. Andrade, A.C. Santos Silva OPTIMIZE OF HORIZONTAL CENTRIGUGE DECANTER PERFORMANCE TO AVOID OF FAT LOSS IN OLIVE POMACE USING ARTIFICIAL NEURAL NETWORKS. Estrella Funes, Yosra Allouche, Gabriel Beltrán, Antonio Jiménez STABILIZATION OF A NUT POWDER DISPERSIONS BY THICKENERS AND EMULSIFIERS Fábregas.A, Faulón.D, Santamaría. E, González.C and Gutiérrez, J.M ALGINATE BEADS CONTAINING COCOA EXTRACT TO ENRICH A GELATIN DESSERT Lupo, B; Riu, M; Maestro. A; Gutiérrez, J.M and González. C. OPTIMIZATION USING SURROGATE MODELS BASED ON A KRIGING INTERPOLATION: Application to the rigorous design of distillation columns N. Quirante, J. Javaloyes and J.A. Caballero ENHANCED EPSILON CONSTRAINT METHOD THROUGH THE INTEGRATION OF OBJECTIVE REDUCTION AND SAMPLING TECHNIQUES Pedro J. Copado Méndez, Carlos Pozo, Gonzalo Guillén Gosálbez, and Laureano Jiménez Esteller ADAPTIVE EVOLUTIONARY OPTIMIZATION OF COMPLEX PROCESSES USING A KRIGING BASED GENETIC ALGORITHM Ahmed Shokry, Kefah Hjaila, and Antonio Espuña MATHEMATICAL KNOWLEDGE MANAGEMENT TO SUPPORT DECISION MAKING IN PROCESS SYSTEMS ENGINEERING Edrisi Muñoz, Elisabet Capón García, Jose M. Laínez, Antonio Espuña, Luis Puigjaner EARLY FOAMING DETECTION IN A SWEETENING UNIT USING PCA Mahdieh Askrian, Estanislao Musulin, Raúl Benítez, Moisès Graells, Reza Zarghami 30

31 32_007_P 32_008_P 32_009_P ENERGY IMPROVEMENTS OF THE AMMONIA REFRIGERATION SYSTEM OF AMMONIA PRODUCTION Lj. Matijašević, I. Dejanović, E. Kristan, K. Huljev NOVEL TRIPLE RESPONSIVE HYDROGELS BASED ON 2 (DIMETHYLAMINO) ETHYL METHACRYLATE by COPOLYMERIZATION with 2 (N MORPHOLINO) ETHYL METHACRYLATE Fulya Taktak, Murat Yıldız, Cengiz Soykan and Hakan Sert APPLICATION OF RECOVERY STRESS ANALYSIS ON POLY(LACTIC ACID) MODIFIED BY REACTIVE EXTRUSION J. Cailloux, A. García, F. Carrasco, O.O. Santana, M.Ll. Maspoch 32_011_P 32_014_P 32_015_P 32_016_P 32_017_P 32_018_P 32_019_P 32_021_P 32_022_P 32_023_P CEMENT PLASTICIZING CHEMICAL ADMIXTURE COMPATIBILITY IN CONCRETE PRODUCTION A.Evren Arioz, B. Omer Arioz, A. O.Mete Kockar KINETIC AND THERMODYNAMIC STUDY OF NATURAL PHOSPHATE DISSOLUTION BY CALORIMETRY B. Belgacem,S. Leveneur, M. Chlendi, L. Estel, M. Bagane EFFECT OF FUEL COMPOSITION ON GAS EMISSIONS FROM FURNACE OIL REFINING INDUSTRY J. Saavedra, V. Kafarov, L. Meriño, A. carreño DYNAMIC MODELING AND SIMULATION OF CRUDE DISTILLATION UNIT T. Weng Khim, A.Hisyam and K. Ramesh SISTEMAS NEURO FUZZY PARA LA TOMA DE DECISIONES Y OPTIMIZACIÓN DEL PROCESO DE ELABORACIÓN DEL ACEITE DE OLIVA VIRGEN. A. Jiménez Márquez;G. Beltrán Maza;MP Aguilera Herrera ARTIFICIAL NEURONAL NETWORK FOR HORIZONTAL SOLID BOWL DECANTER CENTRIFUGE SIMULATOR TO THE VIRGIN OLIVE OIL ELABORATION PROCESS A. Jiménez Márquez; E. Belén Funes ; MP Aguilera Herrera ;G. Beltrán Maza ADEM SIMULATION FOR PARTICLE BREAKAGE BEHAVIOR Junya Kano and Shingo Ishihara, STUDY OF A TWO STAGE MEMBRANE SYSTEM FOR CO2 CAPTURE E. Rodríguez Fernández, A. Fernández Barquín, E. Santos, C. Casado Coterillo and A. Irabien LOGIC BASED ALGORITHMS FOR THE INTEGRATION OF DIFFERENT MODELS IN THE SYNTHESIS OF CHEMICAL PROCESSES: APPLICATION TO THE DESIGN OF A POWER UTILITY PLANT N. Quirante and J.A. Caballero. OPTIMIZATION OF CHEMICAL PROCESSES USING CHEMICAL SIMULATORS AND MACHINE LEARNING ALGORITHMS J. Javaloyes, N. Quirante, R. Ruiz Femenia and J. A. Caballero 31

32 32_024_P 32_026_P 32_027_P 33_001_P 33_002_P 33_003_P 33_004_P 33_005_P 33_006_P 33_007_P 33_008_P 33_009_P ANALYSIS OF THE IMPROVING IN CONVENTIONAL DISTILLATION COLUMNS TROUGH THE OPTIMAL DESIGN OF EQUIVALENT INTERNALLY HEAT INTEGRATED DISTILLATION COLUMNS Juan A. Reyes Labarta, J. Javaloyes, N. Quirante, and J. A. Caballero DETERMINING THE BEST POSSIBLE OPERATION PARAMETERS TO MINIMIZE WATER CONTENTS IN ORDER TO MAXIMIZE THE DESIRED MEA PRODUCT STREAM R. Naeem Al Hazmi CHARACTERIZATION OF POWDER COMPOUNDS BY USING EXPERIMENTAL AND MOLECULAR SIMULATION STUDIES Z. Ozturk, D.A. Kose, B. Ozturk and A. Asan TEACHING EXPERIENCES IN CHEMICAL ENGINEERING: EVALUATION, DESIGN AND SET UP OF VLE EXPERIMENTS OF AMINE BASED SOLVENTS FOR CCS CAPTURE F. Vega, M. Rodríguez, B. Navarrete, B. Alonso Fariñas DESIGN OF CONTROL ALGORITHMS FOR PREDETERMINED RESPONSE Barberà, E EL SISTEMA DE GESTIÓN DE LA CALIDAD: DESDE EL DISEÑO DE ASIGNATURAS HASTA LAS AUDITORÍAS. IMPLICACIÓN DE LOS ALUMNOS J. Giménez, M. Cruells, N. Escaja, J. Fernández, J.A. Garrido, M. Llauradó, A. Roca, L. Rodríguez, M.Ll. Sagristà, C. Navarro, J.O. Bernad, C. Escobar EL JUEGO DE ROL COMO HERRAMIENTA EN LA ENSEÑANZA DE LA INGENIERÍA QUÍMICA J. Giménez, M. Vicente INNOVATIVE TOOLS FOR DRIVING THE SELF LEARNING OF CHEMICAL ENGINEERING STUDENTS C. Negro, A. Blanco, E. Fuente, M.C. Monte, D. Hermosilla, A. Tijero, N. Merayo, I. Latour, L. Cortijo, H. Barndök, L. Blanco. SOFTWARE TO DESIGN LIQUID PHASE IDEAL REACTORS: CASES FOR TEACHING PURPOSES A. Durán, J.M. Monteagudo, C. Loarces DEGRADATION OF BOSCALID IN WASTE WATER BY AOP OZONATION AND HETEROGENEOUS PHOTOCATALYSIS. STUDY AND COMPARISON OF TREATMENTS C. Ayral, P. Destrac, C. Andriantsiferana, F. Benoit Marqui, M H.Manero, C. Julcour, H. Delmas BENEFITS OF ASPEN PLUS AND ASPEN HYSYS SOFTWARE FOR CHEMICAL ENGINEERING BACHELOR THESIS E. Díez, J.C. Domínguez, R. Miranda, I. Moraleja, M. Oliet, A. Rodríguez, V. Alonso, P. Yustos, J.M. Toledo, Y. Madrid, M.T. Pérez Corona, E. García Carpintero, M. Hipólito, E. Escriche, M. Collado THE INTEGRATION OF A MATHEMATICAL THERMODINAMIC MODEL IN THE SIMULATION OF A RECTIFICATION PROCESS BY A PACKED COLUMN. A PRACTICAL CASE AS A FORMATIVE TOOL Marrero, P.; Ríos, R.; de la Nuez, I.; Fernández, L, Ortega, J. 32

33 33_010_P 41_001_O 41_002_O PRODUCT ENGINEERING:EXPERIMENTAL DEVELOPMENT OF A WALL DECORATIVE PAINT Santamaría. E, Maestro. A, Gutiérrez, J.M and González. C. OPTIMIZATION OF THE ENCAPSULATION OF ASCORBIC ACID IN CHITOSAN NANOPARTICLES M. G. Cristia, L. P. Blanco, A. C. Balfagon NOVEL TRANSFORMATION OF LIGNITE COMBUSTION ASHES INTO CERAMIC MICROSTRUCTURES V. Karayannis, E. Katsika and A. Moutsatsou 41_003_P 41_004_P 41_008_P 41_009_P 41_010_P 41_011_P 41_012_P 41_013_P 41_014_P 41_015_P EFFECTIVE FRAGRANCE ENCAPSULATION BY RECYCABLE POROUS MATERIALS: PERSONAL CARE AND TEXTILE APPLICATIONS L.Ferrarons Filba, A. C. Balfagon, N. Marimon Margarit DEVELOPMENT OF EXPERIMENTAL AND NUMERICAL METHODS FOR SOLID OF RESIDENCE TIME DISTRIBUTION (RTD) A.Bellil, K. Benhabib, P. Coorevits, C. Marie, M. Hazi, A. Ould dris SYNTHESIS OF IRON TITANIUM CARBIDE POWDER FROM EGYPTIAN TITANIUM BEARING MATERIALS El Sadek, M. H.; Morsi, M. B.; El Barawy, K.; and El Didamony, H. A. SYNTHESIS AND PHYSICAL GELS of ph RESPONSIVE ZWITTERIONIC ABA TRIBLOCK COPOLYMER AND DRUG RELEASE STUDIES Fulya TAKTAK and Vural BÜTÜN EFFECTS OF CURING TIME ON MECHANICAL AND MICROSTRUCTURAL PROPERTIES OF FLY ASH BASED GEOPOLYMERS A.Evren Arioz, B. Omer Arioz, A. O.Mete Kockar EVALUATION OF DISPERSIBILITY SILICA PARTICLE WITH DIFFERENT SURFACE PROPERTIES USING HANSEN SOLUBILITY PARAMETERS T. Horiba, T. Sato, S, Araki and H. Yamamoto THERMODYNAMIC PARAMETERS OF CAFFEINE ADSORPTION FROM WATER ONTO CARBONACEOUS MATERIALS S. Álvarez, J.L. Sotelo, G. Ovejero, A. Rodríguez, J. García UNE NOUVELLE APPROCHE DE LA PRÉPARATION DU MATÉRIAU COMPOSITE (LiMn2O4/Pan) Harfouche Nesrine, Nessark Belkacem MEASUREMENT OF THE DISPERSION STATE OF PARTICLE FILLERS IN COMPOSITE MATERIALS BY DIELECTRIC CONSTANT Kizuku Kushimoto, Atsuko Simosaka, Yoshiyuki Shirakawa, Jusuke Hidaka CONTROL OF THE PARTICLE STRUCTURE IN THE FUNCTIONAL COATING FILM BY ELECTROSTATIC POWDER COATING Takuya Mitsunaga, Atsuko Shimosaka, Yoshiyuki Shirakawa, Jusuke Hidaka 33

34 41_016_P 41_017_P 41_018_P 41_020_P 41_021_P 41_022_P 42_001_O 42_002_O 42_003_O 42_004_P 42_006_P 42_007_P ADSORPTION OF HUMIC ACID FROM AQUEOUS SOLUTION BY POLYANILINE/CLINOPTILOLITE COMPOSITES Barış Kiriş, Merve Deniz, Ayça Bal, Serkan Emik, Satılmış Basan IMPROVING PERMEABILITY OF ULTRAFILTRATION PVDF MEMBRANES BY SURFACE TREATMENT WITH ATMOSPHERIC PLASMA M. F. López Pérez, J. Lora García, I. Png Gonzalez, Miguel Angel Peydro POLYPHENOLS ADSORPTION IN MESOPOROUS SILICA MATERIALS. RESEARCH OF THEIR APPLICATION AS SUNSCREENS Luna. D, Santamaría. E, Maestro.A, Gutiérrez, J.M and González. C PRODUCTION OF natural ADHESIVES WITH ACACIA MANGIUM BARK EXTRACTS FOR THE FABRICATION OF PELLETS AND BRIQUETTES Yasmin Lopera, Sebastián Tobón, Alex Sáez THERMAL, MECHANICAL AND AGING PROPERTIES OF LLDPE/WOOD AND PP/WOOD COMPOSITES Erdal Karadurmuş, Gamze Sultan Baş and Erol Sancaktar SCALE UP MODEL AND INFLUENCE OF THE PROCESS VARIABLES IN THE PREPARATION OF HIGHLY CONCENTRATED EMULSIONS Anna May Masnou, Jordi Ribó Besolí, Montserrat Porras, Alicia Maestro, Carme González, José María Gutiérrez PREPARATION OF 3D SCAFFOLDS BY MICROSTEREO THERMAL LITHOGRAPHY USING NEW BIO UNSATURATED POLYESTERS Filipa Gonçalves, Cátia Costa, Inês Fabela, Dina Farinha, Henrique Faneca, Pedro Simões, Paulo Bártolo, Arménio C. Serra, Jorge F. J. Coelho ON THE VALIDATION OF SUPERPOROUS MONOLITH, AS STATIONARY PHASE FOR INMOBILIZED METAL AFFINITY CHROMATOGRAPHY (IMAC). M. Elviro, E.M. Martín del Valle, M.A. Galán EXPLORING SULFUR OXIDIZING BIOFILMS IN A GAS PHASE FLAT PLATE BIOREACTOR UNDEr CONTROLLED ph Ll. Prades, X. Guimerà, D. Gabriel, A. D. Dorado and X. Gamisans BIOPROCESS DEVELOPMENT FOR THE PRODUCTION OF LONG CHAIN POLYUNSATURATED FATTY ACIDS (LC PUFA) Sergi Abad, Antoni Planas and Xavier Turon LIGNIN AS A POTENTIAL RAW MATERIAL FOR THE DESIGNING BIOREFINERIES. TECHNO ECONOMIC AND ENVIRONMENTAL ASSESSMENT J. C. Carvajal, V. Hernández, M.A. Rojas, E. Castro, C. A. Cardona BIOSURFACTANT PRODUCTION USING 2ND GENERATION FEEDSTOCKS M. Guillén, E. Genescà, B. Lechuga, N. Alcover, A. Surribas 34

35 42_008_P 42_009_P 42_010_P 42_012_P REACTIVITY OF THIOSEMICARBAZIDE ON DIVALENT COBALT(II) AND COPPER(II) IONS REVISITED: SYNTHESIS OF COMPLEXES, CHARACTERIZATION, CATALASE LIKE AND BIOLOGICAL ACTIVITIES O. Hamrani, Z. Hank and S. Boutamine GELATIN/HYALURONIC ACID/SODIUM ALGINATE/BONE ASH COMPOSITE FILMS WITH ENHANCED THERMAL AND MECHANICAL PROPERTIES Neslihan Alemdar MATHEMATICAL MODELING TO OPTIMIZE control strategies in AN INDUSTRIAL BIOTRICkLING FILTER FOR BIOGAS SWEETENING C. Canal, Ll. Prades, X. Gamisans and A.D. Dorado POLY(GLUTAMIC ACID) BIOSYNTHESIS UNDER HIGHLY OXYGENATED CONDITIONS Alejandra Hernandez Valencia, Jose R. Cascante Alpízar and Jordi J Bou 42_013_P OPTIMIZATION OF THE DETERGENCY OF STARCHY SOILS WITH α AMYLASE FROM B. LICHENIFORMIS SOLUTIONS IN CIP SYSTEMS Jurado, E.; Vicaria, J.M.; Martínez Gallegos, J.F.; Herrera Márquez, O., and García López A.I. 42_014_P 42_015_P 43_001_P 43_002_P 43_003_P 44_001_O 44_002_O MOLECULARLY IMPRINTED POLY(N ISOPROPYLACRYLAMIDE) THERMOSENSITIVE BASED CRYOGEL FOR IgG PURIFICATION Işık Perçin, Veyis Karakoç, Adil Denizli LIQUID LIQUID CENTRIFUGAL PROCESSES FOR INTENSIFIED TWO PHASE BIOCATALYTIC REACTIONS C.NIOI, D. RIBOUL, P. DESTRAC, C.GOURDON, J.S. CONDORET METHACRYLIC ACID BASED HYDROGELS AS PARACETAMOL CARRIER FOR CONTROLLED RELEASE SYSTEMS B. Ozkahraman and A. Bal DESIGN AND SYNTHESIS OF NEW SCHIFF BASES FROM ANTHRONE DERIVATIVES María de Lourdes Sansores Paredes, Rubén Marrero Carballo, Gumersindo Mirón López, Cristian Carrera Figueiras, Adriana Esparza Ruiz INVESTIGATION OF ANTIOXIDANT AND ANTIMICROBIAL ACTIVITY Poncirus trifoliata PEEL AND LEAVES FROM TURKEY Fatma Gülay Kırbaşlar, Mine Sarsağ Gümüş, Başaran Dülger, Gülen Türker, Zeliha Özsoy Güneş KINETICS OF THE THERMAL DEGRADATION OF POLY(LACTICACID)/ MONTMORILLONITE NANOCOMPOSITES DRIVEN BY RANDOM CHAIN SCISSION F. Carrasco, L.A. Pérez Maqueda, P.E. Sánchez Jiménez, O.O. Santana, M.Ll. Maspoch SYNTHESIS AND CHEMISORPTION OF THIOACETHYL FUNCTIONALIZED C60 FULLERENE DERIVATIVES ON THE GOLD SURFACE P. Piotrowski, J. Pawłowska, J. Pawłowski, R. Bilewicz and A. Kaim 35

36 44_003_O 44_004_O 44_005_P 44_007_P 44_008_P 44_009_P 44_010_P 44_011_P 44_012_P 44_013_P 44_014_P 44_015_P 44_016_P 44_017_P DEVELOPMENT OF A MULTI ANALYTE MICROELECTRODE ARRAY SENSOR FOR BIOFILM PROFILING X. Guimerà, A. Moya, A. D. Dorado, D. Gabriel, G. Gabriel and X. Gamisans HIGH THROUGHPUT SELF DRIVEN ELECTROOSMOTIC MICROPUMP FOR BLOOD PLASMA SEPARATION Mahdi Mohammadi, Hojjat Madadi, Jasmina Casals Terré SYNTHESIS OF A POLYOXOMETALATE BASED HYBRID MATERIAL APPLICATION IN PHOTOCATALYSIS D. Meziani, R. Bagtache, Y. Roumila and K. Abdmeziem ELECTROSPINNABILITY ZONES FOR THE GELATIN/WATER/ACETIC ACID SYSTEM: EFFECT OF ACID CONTENT ON THE SCAFFOLDS CYTOTOXICITY Marisa Erencia, Jorge Macanás, Fernando Carrillo INTERFACIAL TENSION INFLUENCE ON FRAGANCE MICROENCAPSULATION Óscar García, Carlos García, Manel J. Lis FRAGRANCE MICROENCAPSULATION. ASSESSMENT OF THE YIELD USING TGA Carlos García, Óscar García, Manel J. Lis FORMATION AND CHARACTERIZATION OF TiO2 ANODIC NANOSTRUCTURES OF HIGH SURFACE AREA R. Sánchez Tovar, R.M. Fernández Domene, D.M. García García, M.T. Montañés, J. García Antón SYNTHESIS OF N VINYLCAPROLACTAM BASED TERPOLYMERIC MICROGELS AND INVESTIGATION OF THEIR DRUG RELEASE PROPERTIES B. Özkahraman, I. Acar and G. Güçlü A NOVEL TUMOR TARGETED NANOPARTICLES BASED ON HYPERBRANCED POLYESTER: SYNTHESIS AND CHARACTERIZATION A. Bal, E. Cevher and S. Ozgumus COMPARATIVE STUDY OF CARBON NANOTUBES DISPERSION USING CHEMICAL FUNCTIONALIZATION AND SURFACTANTS FOR THERMICAL NANOFLUIDS C.Segarra, J.M.Tiscar and J.C.Jarque SURFACE IMPRINTED CELLULOSE NANOFIBERS Emel Tamahkar, Tülin Kutsal, Adil Denizli PLASMA ENHANCED CHEMICAL VAPOR DEPOSITION OF FLUORINATED COPOLYMER THIN FILMS FOR MECHANICALLY STRONG AND SUPERHYDROPHOBIC NANOCOATINGS Mustafa Karaman, Ezgi Yenice, Tuba Uçar VITAMIN C ADSORPTION IN MESOPOROUS MATERIALS. USE OF PH GATE FOR VITAMIN RELEASE. Montenegro. Z, Santamaría. E, Maestro.A, Gutiérrez, J.M and González. C PREPARATION AND CHARACTERIZATION OF PHOSPHATE GLASSES CONTAINING TRANSITION METAL Y. Makhkhas, S. Krimi and E.H. Sayouty 36

37 44_018_P SYNTHESIS OF SILICA NANOPARTICLES USED AS PROCOAGULANT AGENTS Anna May Masnou, Toni Escales Bordoy, Montserrat Porras, Alicia Maestro, Carme González, José María Gutiérrez 37

38 INDEX OF AUTHORS A Abad Sempere. A 22_078_P Antón. A 21_012_O Abad. S 42_004_P Aparicio. J 21_002_O Abdi. Y 13_014_P Apaydın-Varol. E 21_047_P Abdmeziem. K 22_018_P 44_005_P Aracava. K.K 31_005_P Abejón. A 12_021_P Araki. S 41_011_P 11_006_P 11_007_P Abejón. R 22_002_O 12_008_P 12_010_P 12_009_P Abián. M 13_011_P 11_008_P Ábrego. J 22_037_P Aramburu. B 13_015_P 13_017_P Acar. I 44_011_P Aramburu. B 13_017_P Acedo.B 22_065_P Arandes. J.M 21_021_P Acero. J.L 22_006_O 22_029_P Arenas. C 21_028_P 21_029_P 22_020_P Acevedo Sempere. M 11_013_P Ares-Peón. I. A 31_006_P 21_060_P Acillona. I 22_074_P Arnaiz. S 22_074_P Aguado. R 21_066_P Arregi. A 13_032_P 21_057_P 21_058_P Aguayo. A.T 13_003_O 13_022_P 21_059_P Aguilera Herrera. M.P 31_001_O 32_017_P 32_018_P Artetxe. M 13_032_P 21_057_P 21_058_P Akmaz. S 13_021_P 21_059_P Akyalçin. L 21_034_P Asan. A 32_027_P Albo. J 13_003_O 13_031_P Askrian. M 32_005_P Alcover. N 42_007_P Ateka. A 13_002_O 13_003_O Aldaco. R 21_035_P 21_036_P Athalathil. S 22_017_P Aldrich. R 21_054_P Atienza-Martínez. M 22_037_P Alemdar. N 42_009_P Atilgan. B 21_040_P Alerm. Ll 22_062_P Ayas. N 21_049_P 13_029_P 13_028_P Alexandrino. K 13_008_P Aymen Bejaoui. M 31_001_O Alfaro. M.C 11_010_P 21_044_P 21_006_O Ayral. C 33_007_P Allouche. Y 31_013_P Azapagic. A 21_001_O 21_040_P Almajano. M.P 12_004_P 31_002_O B Almajano. M.P 31_002_O Bae. D.H 21_081_P Al-Mohamadawi. A 31_004_P Bagane. M 32_014_P Alonso. J.L 31_006_P Bagtache. R 22_018_P 44_005_P Alonso. M.A 22_059_P Baig. S 22_082_P Alonso. V 33_008_P Bal. A 41_016_P 44_012_P 43_001_P Alonso-Fariñas. B 21_028_P 21_029_P 33_001_P Balfagon. A.C 41_001_O 41_003_P Altzibar. H 11_005_P Ballesteros. I 21_072_P 21_074_P Álvarez. C 21_042_P 21_043_P Ballesteros. M 21_074_P 21_066_P 21_072_P Alvarez. J 13_032_P 21_057_P 21_058_P Balsells. S 22_062_P 21_059_P Barbarias. I 13_032_P 21_057_P 21_058_P Álvarez. P.M 22_066_P 21_059_P Álvarez. S 41_012_P Barberà. E 33_002_P Álvarez. Y 21_075_P Barndök. H 33_005_P Alvarez-Guerra. E 21_013_O 21_027_P 21_010_O Barrett. D.A 22_019_P 21_052_P Bártolo. P 42_001_O Alzueta. M.U 13_008_P 13_010_P 13_011_P Basan. S 41_016_P 13_016_P Basco. J 21_008_O Amirou. S 13_009_P Basset. N 22_083_P 22_085_P Amutio. M 13_032_P 21_057_P 21_058_P Bayarri. B 22_056_P 22_057_P Andrade. R.S 21_076_P 31_012_P Bayrak. S 21_070_P Andriantsiferana. C 33_007_P Belén Funes. E 32_018_P Belgacem. B 32_014_P

39 Belleville. M.P 22_002_O Camarero. L.M 22_015_P 22_016_P Bellil. A 41_004_P Canal. C 42_010_P Belo. I 21_024_P 21_025_P Cano. M 21_022_P Beltrán Maza. G 31_001_O 32_017_P 32_018_P Cañizares. P 21_003_O 21_031_P Beltrán. F.J 22_065_P 22_066_P Capellini. M.C 31_005_P Beltrán. G 31_009_P 31_010_P 31_013_P Carmona. JA 11_001_O Benavente. V 21_056_P Carnicer. A 22_059_P Bengoa. C 22_033_P 22_061_P Carrasco. F 44_001_O 32_009_P Benhabib. K 31_004_P 41_004_P Carreño. A 32_015_P Benítez. F.J 22_029_P 22_006_O Carrera-Figueiras. C 43_002_P Benítez. R 32_005_P Carreras. J 21_063_P Benoit-Marqui. F 33_007_P Carrillo. F 44_007_P Benosmane. N 12_006_P Casado-Coterillo. C 12_020_P 32_021_P Benzal. E 22_042_P Casals-Terré. J 44_004_O Bernad. J.O 33_003_P Casas. J.A 22_044_P Bibi. D.R 22_003_O Casas. L 12_015_P Bilbao. J 13_002_O 13_015_P 13_017_P Cascante-Alpízar. J.R 42_012_P 13_025_P 13_026_P 21_021_P Castaño. P 13_003_O 13_015_P 13_031_P 13_022_P Cavalcante. R.P 22_056_P 22_057_P Bilbao. R 13_008_P 13_010_P 13_011_P Cenador Marín. I 11_013_P 13_016_P Cevher. E 44_012_P Blanco. L.P 41_001_O Ceylan. S 13_034_P 13_039_P Blázquez. G 22_001_O Ceylan. Z 13_034_P 13_039_P Boer. D 21_063_P Chang. C 21_077_P Bolívar. C.L 11_015_P 12_023_P Chimenos. J.M 21_002_O Boluda. N 12_017_P 12_018_P Chinnarasu. C 12_015_P Boluda-Botella. N 11_013_P Chirinos. J 13_037_P 22_033_P 22_061_P Bonvicini. G 21_007_O Chlendi. M 32_014_P Boran. F 21_070_P Choo. K.W 22_003_O Borràs. E 21_005_O Chun. D.H 12_031_P Bou. J.J 42_012_P Coderch. L 22_062_P Boucif. A 22_035_P Coelho. J.F. J 42_001_O Boutamine. S 42_008_P 22_035_P Collado. M 33_008_P Boutemeur. B 12_006_P 13_014_P Collado. S 22_089_P 22_090_P Brandão. W.R 12_011_P Colominas Guàrdia. C 21_014_P 21_033_P Brito. K.D 12_011_P Coma. X 21_041_P Brito. R.P 12_011_P Combarros. R.G 22_090_P Brouwer. P 22_069_P Condoret. J.S 42_015_P Bruzi. M 22_087_P Contreras. S 22_080_P 22_011_O Büntün. V 41_009_P Coorevits. P 41_004_P Buscio. V 12_013_P 21_041_P Copado Méndez. P.J 32_002_O Bustos. G 21_045_P 21_046_P Cordova. K 22_021_P C Cornejo. A 21_023_P 21_028_P 21_029_P Caballero. J.A 32_001_O 32_022_P 32_023_P 22_020_P 32_024_P Corpas-Iglesias. F 21_015_P Cabeza. L.F 21_063_P Cortés-Borda. D 21_051_P Cabrera-Codony. A 12_003_O Cortijo. L 33_005_P Caglayan. P.A 13_021_P Ćosić. M 11_018_P Cailloux. J 32_009_P Costa. C 42_001_O Calabuig. E 21_056_P Cotes. T 21_015_P Calderon. B 22_004_O Coutinho. J.A.P 21_013_O 11_002_O Calero. M 22_001_O 21_015_P Coz. A 21_004_O Calero. N 11_001_O 21_006_O 21_044_P Crespi. M 12_013_P 21_041_P 22_038_P Camacho. F 31_008_P 22_039_P Camacho. J 11_011_P Creutzemberg. O 21_007_O

40 Crichton. J 12_017_P Escales-Bordoy. T 44_018_P Cristia. M.G 41_001_O Escobar. C 33_003_P Crua. C 13_001_O Escriche. E 33_008_P Cruells. M 33_003_P 22_021_P Escrig. A 21_007_O Cruz. A 22_012_P Escuadra. S 22_046_P Cuéllar-Franca. R.M 21_001_O Esparza-Ruiz. A 43_002_P D Espejo-Carpio. F.J 31_007_P 31_008_P Dantas. R.F 22_050_P 22_056_P 22_057_P Espíndola Durán. B.M 22_043_P Darbandi. T 13_020_P Espinosa. E 22_026_P Davidson. K 12_018_P Esplugas. S 22_012_P 22_024_P 22_025_P Dávila. J.A 21_038_P 21_039_P 22_050_P 22_056_P 22_057_P Daza. L.V 21_039_P 22_028_P 22_082_P 22_092_P De Cazes. M 22_002_O Espuña. A 32_003_O 32_004_O De la Nuez. I 33_009_P Essawy. H.A 13_009_P De León-González. G 31_008_P Estel. L 13_001_O 32_014_P De Luca. A 22_050_P Estiati. I 11_005_P De Pedro. Z.M 22_044_P Evren Arioz. A 32_011_P 41_010_P de Rivas. B 13_005_O 22_051_P F Dejanović. I 32_007_P Fabela. I 42_001_O Del Angel. A 21_045_P 21_046_P Fábregas. A 31_014_P Del Castillo. A 21_010_O 21_052_P Fabregat. A 22_033_P 22_040_P 22_061_P Del Valle-Zermeño. R 21_002_O 22_017_P Demirel. E 21_049_P Fahrnasova. D 22_011_O Delmas. H 33_007_P Faneca. H 42_001_O Deniz. M 41_016_P Farinha. D 42_001_O Denizli. A 42_014_P 44_014_P Faulón. D 31_014_P Destrac. P 33_007_P 42_015_P Fenoglio. R 22_071_P Di Luca. C 22_071_P Fernández Pereira. C 21_023_P Díaz. M 22_090_P 22_089_P Fernández. A 22_059_P Díez. E 11_011_P 33_008_P Fernández. F.J 21_003_O 21_031_P Domínguez. E 21_064_P 21_065_P 21_075_P Fernández. J 33_003_P Domínguez. J 22_026_P Fernández. L 21_023_P 11_017_P 12_026_P Domínguez. J.C 33_008_P 33_009_P Domínguez. J.M 21_024_P 21_025_P Fernández-Barquín. A 12_020_P 32_021_P Dominguez. S 22_086_P Fernández-Domene. R.M44_010_P Dominguez-Ramos. A 21_030_P Fernandez-Gonzalez. C 21_030_P Dorado. A.D 42_003_O 42_010_P 22_042_P Ferrarons-Filba. L 41_003_P 44_003_O Figueirêdo. M.F 12_011_P Dosta. J 22_083_P 22_085_P Fındık. S 22_045_P Drage. T 12_024_P Fiol. N 22_053_P Dülger. B 43_003_P Florido. A 22_053_P Duque-Ingunza. I 22_074_P Florido. X 11_017_P 12_026_P Durán. A 22_059_P 33_006_P Folqués Martín.O 22_058_P E Foltin. J 13_030_P El Badry. A 21_063_P Fonoll. X 22_085_P El-Barawy. K 41_008_P Font. A 12_017_P 12_018_P El-Didamony. H.A 41_008_P Font. J 13_037_P 22_033_P 22_061_P El-Sadek. M.H 41_008_P Forero. H. A 21_019_P Elviro. M 42_002_O Formosa. J 21_002_O Emik. S 41_016_P Fortuny. A 22_033_P 22_061_P 22_017_P Epelde.E 13_002_O 13_022_P Fortunyand. A 22_040_P Erencia. M 44_007_P Frades. V 22_059_P Ereña. J 13_025_P 13_026_P 13_003_O Fuente. E 33_005_P Erjavec. B 22_017_P Fuentes. E 22_015_P Erkiaga. A 21_059_P Fullana. A 22_004_O 21_056_P Escaja. N 33_003_P

41 Funes. E 31_013_P Gomez. L 13_031_P G Gómez. M 22_041_P Gabaldón. C 22_081_P Gomez-Coma.L 12_001_O Gabilondo. M 13_005_O Gomis. V 12_017_P 12_018_P Gabriel. D 42_003_O 44_003_O Gonçalves. F 42_001_O Gabriel. G 44_003_O Gonçalves.D 12_016_P Gajic. D.G 12_012_P 22_036_P Gondoh. D 12_009_P Galán. B 21_032_P 21_004_O Gonga Roselló. E 22_078_P Galán. M.A 21_011_O 42_002_O González. A.A 21_038_P 21_039_P Galán-Martín. A 21_012_O González. C 31_014_P 31_015_P 44_018_P Gamero. M 13_002_O 44_016_P 41_022_P 41_018_P Gamisans. X 42_003_O 44_003_O 22_042_P 33_010_P 42_010_P González. O 22_025_P 22_084_P 22_057_P Garcés. S 13_007_P 22_056_P García Cortés. A.N 11_013_P González-Garcinuño. A 21_011_O García López. A.I 42_013_P Gonzalez-Olmos. R 12_003_O García Montaño. J 21_005_O González-Prior. J 22_051_P 13_005_O García. A 31_002_O 32_009_P Gordon. J 21_056_P García. C 44_008_P 44_009_P Goullieux. A 31_004_P García. I 22_016_P Gourdon. C 42_015_P García. J 41_012_P Gozalbo. A 22_087_P Garcia. J.D 21_043_P Graells. M 22_055_P 32_005_P García. M.C 11_010_P 11_001_O Guadix. A 31_007_P 31_008_P García. O 44_008_P 44_009_P Guadix. E.M 31_007_P 31_008_P García. Y 22_061_P Guastalli. A 22_083_P García-Antón. J 44_010_P Güçlü. G 44_011_P García-Cano. J 12_017_P 12_018_P Guembe. M 21_002_O García-Figueruelo. C 22_044_P Guillén-Gosálbez. G 32_002_O 21_068_P 21_063_P García-García. D.M 44_010_P 21_051_P 21_012_O Garcia-Herrero. I 21_052_P Guillén. M 42_007_P García-Hortal. J.A 22_058_P Guimerà. R 21_051_P García-López. A.I 11_014_P Guimerà. X 42_003_O 44_003_O 22_042_P García-Martínez. Y 22_040_P Gullón. B 31_006_P García-Montaño. J 22_030_P Guri. S 21_077_P García-Moreno. P.J 31_007_P Gutiérrez. A 12_002_O Garea. A 12_001_O 12_021_P Gutiérrez. J.M 31_015_P 31_014_P 44_018_P Garrido. J.A 33_003_P 44_016_P 41_022_P 41_018_P Garrote. G 21_060_P 21_064_P 21_074_P 33_010_P 21_065_P 21_075_P 21_071_P Gutiérrez-Bouzán. C 12_013_P 22_039_P 22_038_P 21_072_P 21_041_P Gayubo. A.G 13_022_P 13_015_P 13_017_P Gutiérrez-Ortiz. J.I 13_005_O 22_074_P 22_051_P 13_025_P 13_026_P Gea. G 22_037_P Hamada. Y 11_007_P Genescà. E 21_005_O 42_007_P Hamakawa. S 12_008_P Gerçel. H.F 21_034_P Hamdi. M 12_006_P 13_014_P Ghute. P. P 22_011_O 22_080_P Hamrani. O 42_008_P Gil. A 13_007_P Han. G.H 12_030_P Gila. A 31_001_O Hank. Z 42_008_P 22_035_P Giménez. A 22_061_P Harfouche. N 41_013_P Giménez. J 22_024_P 22_028_P 22_052_P Hassaine-Sadi. F 21_020_P 22_056_P 22_057_P 33_003_P Haure. P 13_037_P 33_004_P Hazi. M 41_004_P Gomes. R.L 22_003_O 22_019_P Hermann. J 21_077_P Gómez. B 21_060_P 31_006_P Hermosilla. D 22_075_P 33_005_P Gomez. J 22_046_P Hernández Teruel. M.J 11_013_P H

42 Hernández. A 21_035_P 21_036_P Karaman. M 44_015_P Hernández. V 21_019_P Karayannis. V 41_002_O 22_076_P Hernandez-Valencia. A 42_012_P Katsika. E 41_002_O Herrera-Márquez. O 42_013_P Kaya. N 22_054_P Herrero. P 21_027_P Kılıç. M 21_047_P 21_048_P Hidaka. J 41_014_P 41_015_P Kim. G.Y 21_081_P Hideki. Y 11_008_P Kim. H 12_031_P Higuita. J.C 21_042_P 21_043_P Kırbaşlar. F.G 43_003_P Hipólito. M 33_008_P Kırbaşlar. Ş.İ. 12_025_P hirakawa. Y 41_014_P Kiriş. B 41_016_P Hisyam. A 32_016_P Korili. S 13_007_P Hita. I 21_021_P Kose. D.A 32_027_P Hjaila. K 32_003_O Koshima. C. C 12_016_P Horiba. T 41_011_P Krimi. S 22_079_P 44_017_P Huljev. K 32_007_P Kristan. E 32_007_P I Kushimoto. K 41_014_P Ibáñez. M 13_003_O Kutsal. T 44_014_P Ibáñez. M.J 21_007_O Kuzmanić. N 11_018_P Ibáñez. R 21_030_P 22_005_P L Ibarra. A 21_021_P Laca. A 22_089_P 22_090_P Iglesias. J 22_062_P Lahitte. J.F 12_001_O Iglesias. M 21_076_P 31_012_P Laínez. J.M 32_004_O Iglesias-Godino. F.J 21_015_P Laseras. A.M 22_046_P İlbay. Z 12_025_P 12_022_P Latour. I 33_005_P Ildırar. D 22_045_P Lechuga. B 42_007_P Inchaurrondo. N 13_037_P Lee. H.C 21_081_P Irabien. A 12_001_O 12_020_P 12_021_P Lee. J.S 12_030_P 13_031_P 21_010_O 21_013_O Leganés. F 22_091_P 21_027_P 21_030_P 21_035_P Leiva. C 21_023_P 21_028_P 21_029_P 21_036_P 21_052_P 22_005_P 22_020_P 32_021_P Leveneur. S 13_001_O 32_014_P Ishihara. S 32_019_P Li Puma. G 22_066_P Ivorra. F 22_071_P Li. M 22_012_P Izquierdo. M 22_069_P 22_081_P Liew. X.Y 22_003_O J Lim. Y.V 22_003_O Jaime. P 22_026_P Lis. M.J 44_008_P 44_009_P Jaramillo. J.C 12_027_P Lisbôa. A.C.L 13_030_P Jarque. J.C 44_013_P Llauradó. M 33_003_P Javaloyes. J 32_001_O 32_023_P 32_024_P Llauró. F.X 21_054_P Jiménez Esteller. L 32_002_O Llop. M 12_019_P 21_051_P Jiménez Márquez. A 31_001_O 32_017_P 32_018_P Llovell. F 11_002_O 21_077_P Jiménez. A 31_009_P 31_010_P 31_013_P Loarces. C 33_006_P Jiménez. L 21_012_O 21_063_P 21_068_P Lobato. J 21_003_O Jorba. M 22_062_P Lomas. J.M 22_015_P 22_016_P Jurado. E 42_013_P Lopera. Y 12_027_P 41_020_P Justo. Ana 22_084_P Lopera. Z 12_027_P K Lopez. G 21_057_P 21_058_P 21_059_P Kaćunić. A 11_018_P 13_032_P Kafarov. V 22_041_P 32_015_P López. J 11_016_P Kaim. A 44_002_O López-Fonseca. R 13_005_O 22_051_P 22_074_P Kano. J 32_019_P López. J 11_016_P Kaplan. R 22_017_P López-Fonseca. R 13_005_O 22_051_P 22_074_P Karadurmuş. E 21_070_P 41_021_P López-Grimau. L 22_039_P Karakoç. V 42_014_P López-Lilao. A 22_087_P

43 López-Pérez. M.F 22_078_P 41_017_P Medrano.M 21_063_P Lora García. J 22_078_P 41_017_P Meghani. B 12_024_P Lorenzo. D 13_004_O Mena. E 22_065_P 22_066_P Luna. D 41_018_P Menacho. J 12_002_O Luna. Y 21_023_P 21_028_P 22_020_P Méndez. J.A 12_019_P Lupo. B 31_015_P Merayo. N 33_005_P M Meriño. L 22_041_P 32_015_P Macanás. J 44_007_P Mete Kockar. A.O 32_011_P 41_010_P Machulek. J. A 22_056_P Meziani. D 22_018_P 44_005_P Machulek. J. A 22_057_P Miguel. N 22_077_P Madadi. H 44_004_O Millera. Á 13_008_P 13_010_P 13_011_P Madrid. Y 33_008_P 13_016_P Maestro. A 31_015_P 33_010_P 41_018_P Min. B.M 12_029_P 12_030_P 41_022_P 44_016_P 44_018_P Minghao. S 22_025_P Makhkhas. Y 22_079_P 44_017_P Miralles. N 22_053_P Mallol. G 22_087_P Miranda. R 33_008_P Mane. R. B 22_011_O Mirón-López. G 43_002_P Manero. M.H 33_007_P Mitsunaga. T 41_015_P Manickam. S 22_003_O Miyatake. K 11_008_P Mantell. C 12_015_P Mohammadi. M 44_004_O Marce. M 22_082_P Monfort. E 21_007_O 22_087_P Marcilla. A 11_009_P Montalbán. M.G 11_015_P 12_023_P Marco. P 22_024_P 22_028_P Montañés. M.T 22_032_P 44_010_P Margallo. M 21_035_P 21_036_P Monte. M.C 21_066_P 33_005_P Marie. C 41_004_P Monteagudo. J.M 22_059_P 33_006_P Marimon-Margarit. N 41_003_P Montenegro. Z 44_016_P Marín-Torres.A 22_032_P Montero. C 13_015_P 13_026_P Maroto-Valer. M 21_022_P Montes. A 12_015_P Marrero. P 33_009_P Montiel. V 21_010_O Marrero-Carballo. R 43_002_P Montserrat Trenchs. R 21_014_P Marrodán. L 13_010_P Moon. J.H 12_029_P 12_030_P 12_031_P Martí. M 22_062_P 21_081_P Martí. V 22_052_P Moral. A 21_066_P Martín del Valle. E.M 42_002_O 21_011_O Moraleja. I 33_008_P Martín. E 22_091_P Moreira. C.D 21_024_P 21_025_P Martín. L.E 11_011_P Morimoto. M 11_006_P Martín. M.J 12_003_O Morral. E 22_042_P Martinez de la Ossa. E.J 12_015_P Morsi. M.B 41_008_P Martínez. C 21_015_P Mosteo. R 22_007_O Martínez. M 22_052_P 22_053_P Mousavi. S.M 13_038_P 13_006_O Martínez. O 22_074_P Moutsatsou. A 41_002_O Martínez-Gallegos. J.F 11_014_P 42_013_P Moya. A 44_003_O Martínez-Lozano. S 21_005_O 22_030_P Munoz. M 22_044_P Martín-Lara. M.A 21_015_P Muñío. M 31_008_P Martins. R. C 22_010_O Muñoz. E 32_004_O Martín-Torre. M.C 21_004_O 21_032_P Muñoz. I 21_004_O 21_032_P Marzal. P 22_069_P Muñoz. J 11_001_O 11_010_P 21_006_O Maspoch. M.Ll 44_001_O 32_009_P 21_044_P Massa. P 22_071_P Muñoz. P 22_088_P Mata-Alvarez. J 22_085_P 22_083_P Murillo. M.B 22_037_P Mateo. S 21_003_O Musulin. E 32_005_P Matijašević. Lj 32_007_P Mutjé. P 21_054_P May-Masnou. A 41_022_P 44_018_P N Mazzer. H 21_076_P Naeem Al-Hazmi. R 32_026_P Medina. F 22_080_P 22_011_O Navarrete. B 21_022_P 21_029_P 33_001_P

44 Navarro. C 33_003_P Parthasarathy. S 22_003_O 22_019_P Navarro. S.L.B 31_005_P Pascual-González. J 21_068_P Navarro-Jordà. M 22_055_P Pawłowska. J 44_002_O Negro. C 22_075_P 33_005_P Pawłowski. J 44_002_O Nessark. B 41_013_P Pèlach. M.A 12_019_P 21_054_P Niaei. A 13_006_O 13_038_P Peláez Cid. A.A 22_008_O 22_043_P Nikolic. L.B 12_012_P Peleteiro. S 21_071_P 21_074_P 21_072_P Nikolic. V.D 12_012_P Peluffo. M 22_070_P Nioi. C 42_015_P Penín. L 21_071_P 21_072_P Nobandegani M.S 13_020_P Penya-Roja. J.M 22_081_P Nomen. R 12_002_O Perçin. I 42_014_P Nuez. I 11_016_P Pereyra. C 12_015_P O Pérez Bote. J.L 22_063_P 22_064_P Oar-Arteta. L 13_025_P Pérez Maqueda. L.A 44_001_O Octavio. M 22_088_P Pérez. A 22_001_O Okumura. R 12_010_P Pérez. C 22_030_P Olaya. M.M 11_009_P Pérez. E 12_026_P Olazar. M 11_005_P 13_032_P 21_057_P Pérez. N 11_017_P 21_058_P 21_059_P Pérez-Corona. M.T 33_008_P Oliet. M 33_008_P Pérez-Moya. M 22_055_P Oliveira. A. C 22_010_O Pérez-Rodríguez. N 21_024_P 21_025_P Oliveira. M.B 11_002_O Pérez-Uriarte. P 13_002_O 13_022_P Oliveira. S.C 22_056_P 22_057_P Peydro. M.A 41_017_P Omer Arioz. B 32_011_P 41_010_P Pico. M.P 21_055_P Ormad. M.P 22_007_O 22_031_P 22_046_P Pinedo. J 22_005_P 22_077_P Pintar. A 22_017_P Ortega. J 11_016_P 12_026_P 33_009_P Piñas. F.F 22_091_P Ortiz. I 22_086_P Piotrowski. P 44_002_O Ortori. C.A 22_019_P Pizzi. A 13_009_P Ould-dris. A 41_004_P Planas. A 42_004_P Oulego. P 22_089_P Png Gonzalez. I 41_017_P Ovejero. G 11_011_P 41_012_P Porras. M 41_022_P 44_018_P Ovelleiro. J.L 22_007_O 22_031_P 22_046_P Pou Ibar. J.O 21_014_P 21_033_P 22_077_P Pozo. C 32_002_O Ozgumus. S 44_012_P Prades. Ll 42_010_P 42_003_O Özkahraman. B 44_011_P 43_001_P Prado. G.N 13_030_P Prieto. D 22_075_P Özsoy-Güneş. Z 43_003_P Pueyo. N 22_031_P 22_077_P Ozturk. B 32_027_P Puig. J 12_019_P 21_054_P Ozturk. Z 32_027_P Puigjaner. L 32_004_O P Pulido. G 22_091_P Pacheco. R 31_009_P 31_010_P Pütün. E 21_047_P Palenzuela. M.V 22_026_P Pütün A.E 21_047_P 21_048_P 22_049_P Palomar. A 22_077_P Q Palomar. J 12_026_P Qiang. Z 22_012_P 22_092_P Palos. R 21_021_P Quinta-Ferreira. R. M 22_010_O Panahi. P.N 13_006_O 13_038_P Quintanilla. A 22_044_P Parajó. J.C 21_060_P 21_061_P 21_062_P Quiñones. D.H 22_066_P 21_064_P 21_074_P 21_075_P Quirante. N 32_001_O 32_022_P 32_023_P 31_006_P 21_071_P 21_072_P 32_024_P Pardo. F 22_070_P 22_013_P Quispe. V 22_037_P Park. J 21_081_P Qu. J 22_092_P Park. J.H 12_029_P 21_081_P Park. Y.C 12_029_P 12_030_P 12_031_P

45 R Ruiz-Hernández. A 21_051_P Rabia. C 13_014_P Ryu. H.J 21_081_P Radillo Ruíz. R 22_008_O 22_043_P S Rakotondramaro. H 13_001_O Saavedra. J 22_041_P 32_015_P Ramesh. K 32_016_P Sable. S.S 22_011_O 22_080_P Ramirez. A 12_027_P Sadkaoui. A 31_009_P 31_010_P Ramirez. P 11_001_O Sáez. A 21_010_O 41_020_P Ramis. X 31_002_O Sagristà. M.Ll 33_003_P Real. F.J 22_006_O 22_029_P Sahin. F 21_050_P Reina Hernández. J 21_017_P 21_018_P Şahin. S 12_025_P Remigy. J.C 12_001_O Salari. D 13_006_O 13_038_P Remiro. A 13_017_P Saldarriaga. J.F 22_022_P 22_023_P Rey. A 22_065_P 22_066_P Sales-Pardo. M 21_051_P Reyes-Labarta. J.A 32_024_P 11_009_P Salihi. E.C 12_028_P Reyes-Requena. A 11_014_P Salinas. P 13_011_P Ribao. P 22_086_P Salmi. T 13_001_O Ribó-Besolí. J 41_022_P Salomoni. A 21_007_O Riboul. D 42_015_P Sampedro. C 22_051_P Rigby. S 12_024_P Sancaktar. E 41_021_P Rincón-Romero. J.F 11_014_P Sánchez Ortiz. A 31_001_O Ríos. R 11_016_P 11_017_P 33_009_P Sánchez. M 11_017_P Riu. M 31_015_P Sánchez-Álvarez. J.M 21_011_O Rivas. F.J 22_063_P 22_064_P Sánchez-Jiménez. P.E 44_001_O Rivas. S 21_061_P 21_062_P Sanchez-Marcano. J 22_002_O Rivero. M.J 22_086_P Sánchez-Tovar. R 22_032_P 44_010_P Roca. A 33_003_P 22_021_P Sanfelix. V 22_087_P Rode. C.V 22_011_O Sanna. A 21_022_P Rodrigo. M.A 21_003_O Sans. C 22_012_P 22_084_P 22_092_P Rodrigues. C.E.C 31_005_P 12_016_P Sansores-Paredes. M.L 43_002_P Rodríguez. A 21_065_P 22_026_P 33_008_P Santamaría. E 31_014_P 33_010_P 44_016_P 41_012_P 41_018_P Rodríguez. E 22_006_O 21_021_P 22_024_P Santana. O.O 44_001_O 32_009_P 22_029_P Santos. A 13_004_O 21_055_P 22_013_P Rodriguez. J.J 22_044_P 22_070_P 22_009_O Rodríguez. L 33_003_P Santos. E 22_083_P 32_021_P Rodríguez. M 33_001_P Santos. J 21_006_O 21_044_P Rodríguez. N.A 21_045_P 21_046_P Santos. V 21_061_P 21_062_P Rodríguez. N.R 21_045_P 21_046_P Santos-Silva. A.C 31_012_P Rodríguez. R 22_038_P Saquete. M.D 12_017_P 12_018_P Rodriguez. S 22_009_O 21_055_P Sarsağ-Gümüş. M 43_003_P Rodríguez-Fernández. E 32_021_P Sato. T 11_006_P 11_007_P 11_008_P Rodriguez-Galán. M 22_020_P 21_028_P 21_029_P 41_011_P Roig. R 22_085_P Savic. I.M 12_012_P 12_012_P 22_036_P Roldán. G 22_006_O 22_029_P 22_036_P Romaní. A 21_074_P 21_071_P 21_072_P Sawada. M.M 31_005_P Romero. A 13_004_O 22_009_O 21_055_P Sayouty. E.H 22_079_P 44_017_P 22_013_P 22_070_P Scharlack. N. K 31_005_P Romero. V 22_024_P 22_025_P 22_028_P Segarra. C 44_013_P Ronda. A 22_001_O 21_015_P Segovia. F 31_002_O 12_004_P Rosal. A 22_026_P Sempere. J 12_002_O Rosas. J.M 22_013_P Serra. A. C 42_001_O Rouch. J.C 12_001_O Serra. E 12_002_O Roumila. Y 44_005_P 22_018_P Sert. H 32_008_P Royo. E 13_010_P Shahraki. F 13_020_P Ruiz-Femenia. R 32_023_P Shimosaka. A 41_015_P

46 Shin. J.S 21_081_P Urakawa. A 22_011_O Shirakawa. Y 41_015_P Uzun. B.B 21_047_P Shokry. A 32_003_O V Shun. D 21_081_P Valencia. S 12_020_P Sierra. A 22_041_P Valero. P 22_007_O Sierra. I 13_025_P 13_026_P Valle. B 13_017_P Siller. L 12_028_P Vargas. F 21_064_P 21_065_P Sim. J 12_029_P Vázquez Bautista. J 22_008_O 22_043_P Simões. P 42_001_O Vega. L.F 11_002_O 21_077_P Simón. E 13_004_O Vega. F 21_022_P 33_001_P Simón. F.X 22_030_P Ventura. S.P.M 21_013_O Simosaka. A 41_014_P Vermorel. N 22_081_P Solé. A 22_028_P Vicaria. J.M 42_013_P Solé. M 22_042_P Vicente. J 13_025_P 13_026_P Solís. R.R 22_063_P 22_064_P Vicente. M 33_004_P Solla-Gullón. J 21_010_O Viguri. J.R 21_004_O 21_032_P Sosa. R.C 12_023_P Vila. C 21_061_P 21_062_P Sotelo. J.L 41_012_P Vilaseca. M 22_038_P 22_039_P Soykan. C 32_008_P Vilches. L.F 21_028_P 21_029_P Stojiljkovic. S.T 22_036_P Villaescusa. I 22_053_P Stüber. F 22_033_P 22_061_P Villaseñor. J 21_003_O Sultan. G 41_021_P Víllora. G 11_015_P 12_023_P Sumikawa. M 11_007_P Villota. N 22_015_P 22_016_P Surribas. A 21_005_O 42_007_P Viteri. F 13_016_P Susarte. M 22_088_P Vizcaino. E 21_045_P 21_046_P Swinnen. N 22_075_P W T Wang. J 12_028_P Tabernero Oller. M 21_033_P Wärnå. J. 13_001_O Taktak. F 12_022_P 32_008_P 41_009_P Wright. A 12_024_P Tamahkar. E 44_014_P Weng Khim. T 32_016_P Tanaka. R 11_006_P X Taouk. B 13_001_O Xu. K 22_092_P Tavares. M 22_062_P Y Tenorio. G 22_001_O Yamamoto. H 11_006_P 11_007_P 12_008_P Terfi. S 21_020_P 12_009_P 12_010_P 41_011_P Tijero. A 33_005_P 21_066_P Yáñez. R 31_006_P Tiscar. J.M 44_013_P Yazumi. N 12_008_P Tobón. S 41_020_P Yenice. E 44_015_P Toledo. J.M 33_008_P Yıldız. M 32_008_P Topcu. Y 13_034_P 13_039_P Yilmaz. O 13_028_P Torrades. F 22_058_P Yurkadul. M 13_029_P Torrado Agrasar. A 21_024_P 21_025_P Yurtdas. S 13_029_P Torres. J 22_007_O Yustos. P 33_008_P Tosun. Ç.G 21_034_P Z Trigo. R 11_015_P 12_023_P Zarghami. R 32_005_P Trinidad. P 22_088_P Zerizer. A 13_009_P Trujillo. M.C 22_001_O Zheng. J 13_001_O Trujillo-Cayado. L.A 21_006_O 21_044_P Ziemann. C 21_007_O Türker. G 43_003_P Turon. X 42_004_P U Uçar. T Upegui. S 44_015_P 22_022_P 22_023_P

47 Going beyond linear dynamic viscoelasticity JA Carmona 1, P Ramirez 1, N Calero 1, MC Garcia 1 and J Muñoz 1. 1 Departamento de Ingenieria Quimica. Facultad de Química. Universidad de Sevilla c/p. Garcia González, Sevilla, Spain Tel.: ; address: Small amplitude oscillatory shear (SAOS) is a well-established technique to study the viscoelasticity of a wide range of materials. This technique requires that tests are conducted within the linear viscoelastic range (LVR), which guarantees the material microstructure is not irreversibly broken down by shear. Unfortunately, state of the art rheometers fail to apply strain or stress amplitudes low enough to guarantee the LVR when dealing with very soft materials, such as some hydrocolloid-based systems. This is especially dramatic within some composition and temperature ranges. Recently, large amplitude oscillatory shear (LAOS) has proven to be a sensitive technique in order to detect microstructural changes in complex fluids such as biopolymer networks, colloidal gels, etc 1,4. In addition, LAOS results may be useful to describe the mechanical behaviour of materials at large deformations, well beyond the linear viscoelastic region, which are closer to real processing conditions 2. We illustrate the applications of LAOS with xanthan gum aqueous dispersions at different NaCl concentrations, on account of the great technological interest of this bacterial polysaccharide. LAOS is shown to be much more sensitive than small amplitude oscillatory shear (SAOS) to the influence of NaCl concentration. This is illustrated by a complete rheological characterization of the system by means of both full-cycle (average elastic modulus and dynamic viscosity) and local methods (strain-hardening and shear-thickening ratios) 1. The different rheological behaviours observed were related to the microstructures of the xanthan gum molecules as a function of the NaCl content. Acknowledgments: The financial support received (Project CTQ ) from the Spanish MINECO and from the European Commission (FEDER Programme) is kindly acknowledged. References: 1 Ewoldt, R. H., Hosoi, A. E., McKinley, G. H. (2008). New measures for characterizing nonlinear viscoelasticity in large amplitude oscillatory shear. J. Rheol, 52(6), Steffe, J (1996). Rheological Methods in Food Process Engineering, second edition (second printing).freeman Press, East Lansing, MI, Melito, H.S., Daubert, C.R., Foegeding, E.A. (2012). Validation of a large amplitude oscillatory shear protocol. Journal of Food Engineering, 113(1), Carmona, J. A., Ramírez, P., Calero, N., Muñoz, J. (2014). Large amplitude oscillatory shear of xanthan gum solutions. Effect of sodium chloride (NaCl) concentration. Journal of Food Engineering. 126,

48 PHYSICOCHEMICAL CHARACTERIZATION OF THE BIODIESEL PRODUCTION PROCESS USING A MOLECULAR-BASED APPROACH. F. Llovell 1, M.B. Oliveira 2, J.A.P. Coutinho 2, L. F. Vega 1,3 1 MATGAS 2000 AIE, Campus de la UAB, 08193, Bellaterra, Barcelona, Spain 2 CICECO, Chemistry Department, University of Aveiro, Aveiro, Portugal 3 Carburos Metálicos/Air Products Group. C/Aragón, 300, Barcelona, Spain Phone: , Fax: Corresponding author: Scientific Topic: 1.1. Applied Thermodynamics, Fluid Dynamics, Heat Transfer New regulation environmental laws are promoting the use of bio-derived fuels face to classical fossil fuels. Among them, biodiesel has stayed at the forefront of fuels for engines as it is technically viable, economically competitive, socially responsible and environmentally friendly, and has become a promising route for a sustainable production. However, accurate design of unit processes requires detailed knowledge of the phase behavior and physicochemical characterization of the different compounds involved in the different steps. In this sense, theoretical models able to provide thermodynamic information in a wide range of conditions are needed. In this work, we apply a coarse-grained reliable theoretically-based sound model, the soft-saft equation of state (EoS), 1 as a tool for the development, design, scale-up, and optimization of biodiesels production and purification processes, through the description of fatty acid esters/biodiesels thermodynamic properties, as well as the phase equilibria of systems formed at the biodiesel production and purification industrial units. For this purpose, a series of molecular models for each molecule are proposed, according to the chemical structures and particularities of each compound. The Density Gradient Theory approach 2 coupled with soft-saft is used for the description of interfacial properties, while viscosities are calculated through the Free-Volume Theory, 3 in an integrated model, where all these properties are calculated in a consistent manner. The density, surface tension and viscosity data for fatty acid methyl and ethyl esters, ranging from C 8:0 to C 24:0, with up to three unsaturated bonds, are described in a range of pressures going from atmospheric conditions up to 150 MPa, and in the temperature range from to K. Once these compounds are characterized, the high pressure densities and viscosities for 8 biodiesels are predicted with the soft-saft EoS, without needing any further adjustment. 4 In a second step, the water solubility in fatty acid esters, and the vapor-liquid equilibria of fatty acid ester + short alcohols systems, formed at biodiesel production and purification industrial units, are studied through a new association scheme to explicitly take into account the solvation phenomenon between esters and water/alcohols. The selected model is able to describe the water solubility and the VLE of binary systems composed of fatty acid esters and methanol/ethanol, in wide ranges of temperature and pressure, using only one binary interaction parameter. 5 Finally, the solubility of supercritical carbon dioxide in fatty acid esters is also evaluated as a possible media during the production and purification steps. Acknowledgements: F. Llovell acknowledges a TALENT fellowship from the Generalitat de Catalunya. M.B. Oliveira acknowledges for her Post-Doctoral grant (SFRH/BPD/71200/2010). Additional support from Carburos Metálicos and the Catalan Government was also provided (2009SGR-666 and 2014SGR-1582). [1] F.J. Blas, L.F Vega, Mol. Phys. 92 (1997) [2] J. W. Cahn, J.E. Hilliard, 1958, J. Chem. Phys. 28 (1958) [3] A. Allal, C. Boned, A. Baylaucq, Phys. Rev. E, 64 (2001) [4] F. Llovell, R. M. Marcos, L. F. Vega, J. Phys. Chem. B 117 (2013) [5] F. Llovell; R. M. Marcos; L. F. Vega. J. Phys. Chem. B 117 (2013)

49 STUDY OF PARTICLE CYCLE TIMES IN DRAFT TUBE CONICAL SPOUTED BEDS I. Estiati, H. Altzibar and M. Olazar Department of Chemical Engineering, University of the Basque Country, P.O. Box 644, Bilbao, Spain; phone ; fax: ; Scientific topic: Applied Thermodynamics, Fluid Dynamics, Heat transfer The spouted bed is a fluid-particle contact technique that has been successfully applied to systems where fluidization has yielded unsatisfactory results. Different modifications of the original spouted bed (cylindrical with conical base) are proposed in the literature with the aim of improving its performance [1]. Conical spouted beds are highly versatile in the gas flow rate, allowing operating with particles of irregular texture, fine particles and those with a wide size distribution and sticky solids, whose treatment is difficult using other gas-solid contact regimes. These features of the conical spouted beds make them attractive for different applications. The ratio between the inlet diameter and particle diameter limits the scaling-up of spouted beds (the inlet diameter should be smaller than times the particle diameter). The insertion of a draft tube is the way of overcoming this limitation. Particle cycle time is defined as the time the particle takes to travel from the top of the annulus downward and back again to its starting point. Since the proportion of time spent by a particle in the spout is insignificant compared with that spent in the annulus, particle cycle times can be deduced from solid flow patterns in the annulus [1]. Knowledge of particle cycle time is very useful to ascertain the bases of the spouted bed technique. Furthermore, information on this parameter and particle trajectories is essential for spouted bed applications, given that the average cycle time regulates energy and mass transfer, and influences chemical reactions [2]. The main aim of this work is to gather information about particle cycle times in conical spouted beds provided with different internal devices and without devices. Runs have been carried out in conical spouted beds of different geometry according to a factorial design of experiments. The purpose of this design has been to study the effect on particle cycle times of the following: the insertion of a draft tube and the different factors of the contactor. The material used for operation is glass beads of m of particle diameter. The results show that when the height of the entrainment zone of the nonporous draft tube is higher the three average cycle times are lower. This is explained by a larger fraction of particles entering the spout when the height of the entrainment zone is higher, which gives way to higher solid circulation rate and lower cycle times [3]. Furthermore, the air flow rate required for stable spouting is also higher as the height of the entrainment zone is longer. Consequently, more air diverts from the spout into the annulus at the bottom of the bed, thereby contributing to a more vigorous solid circulation in the whole bed. Furthermore, the values of the maximum cycle time are 2-fold higher than the values of the minimum cycle time. The former correspond to the trajectory in the annulus following the wall of the contactor, whereas the latter corresponds to the trajectory along the external surface of the draft tube. In fact, several authors measured the maximum cycle times (particle velocity at the wall) and proved that the maximum cycle is severely affected by wall friction [4]. It should also be noted that, entrainment zone height have a greater impact on the maximum cycle time than on the minimum and average cycle times. Bibliography 1 Epstein, N., Grace., J. R., (Ed.), Cambridge University Press: New York (2011). 2 Makibar, J., Fernandez-Akarregi, A. R., Alava, I., Cueva, F., Lopez, G., Olazar, M., Chemical Engineering and Processing: Process Intensification, 50, (2011). 3 Makibar, J., Fernandez-Akarregi, A. R., Diaz, L., Lopez, G., Olazar, M., Powder Technology, 219, (2012). 4 He, Y. L., Qin, S. Z., Lim, C. J., Grace, J. R., Canadian Journal of Chemical Engineering, 72, (1994).

50 ESTIMATION OF HANSEN SOLUBILITY PARAMETER OF AROMATIC COMPOUNDS BY GROUP CONTRIBUTION METHOD T. Sato 1, S. Araki 1, M. Morimoto 2, R Tanaka 3 and H. Yamamoto 1 1. Kansai University, Yamate-cho, Suita, Osaka, , Japan 2. National Institute of Advanced Industrial Science and Technology, 3-9 Toranomon 4- tyome, Minato-Ku, Tokyo , Japan 3. Japan Petroleum Energy Center, 16-1 Onogawa, Tsukuba-Shi, Ibaragi , Japan Tel , Fax , 1.1 Applied Thermodynamics, Fluid Dynamics, Heat transfer Hansen solubility parameter(hsp) is paid much attention as the physical properties to predict the solubility of substance in the organic solubent. HSP is composed of the disperstion force factor ( d ), the dipole interaction force factor ( p ), and the hydrogen-bonding force factor( h ). The group contribusion methods were reported by E. Stefanis et al., D. Kreveren et al. and other reserchers. Recently, it is required to develop the group contribution method to estimate the HSP value of aromatic confounds such as asphaltene or phthalocyanine compounds. Brifely this accuracy improvement is an issue because these conventional group contribution methods deal with the widely compounds. In this study, our aim is to establish the group contribution method for aromatic compounds based on the method reported by D. Kreveren et al. The 44 group parameters for aromatic compounds was estimated by using the HSP values of 442 aromatic compounds reported by C. Hansen. The HSP values agree rather well with the values of this study and the HSP values reported by C. Hansen compared to other group contribution methods.

51 MEASUREMENT OF GASSOLUBILITY OF OXYGEN FOR PURE AND MIXED SOLVENTS AND CORRERATION BY HANSEN SOLUBILITY PARAMETER T. Sato, Y. Hamada, M. Sumikawa, S. Araki and H. Yamamoto Kansai University, Yamate-cho, Suita, Osaka, , Japan Tel , Fax , 1.1 Applied Thermodynamics, Fluid Dynamics, Heat Transfer The gas solubility data of oxygen in organic solvents are needed in many industries such as petroleum, food and semiconductor because deterioration of the product may be caused by dissolved oxygen in the solvents. In this study, gas solubility of oxygen in pure and mixed solvents was measured at K and kpa. In adddition, gas solubility of oxygen is correlated with the Hansen solubility parameter. The Hansen solubility parameter(hsp) have recently attracted attention as a physical property to predict solubility in various solvents. HSP is represented by δ d (MPa) 1/2, δ p (MPa) 1/2, and δ h (MPa) 1/2. δ d, δ p and δ h are the dispersion force factor, the dipole interaction force factor, and the hydrogen-bonding force factor, respectively. It was measured that solubility of oxygen in alcohols, alkanes, cyclohexane, benzene, toluene, acetone, dichloromethane and amides. HSP of oxygen was calculated by the measurement value of oxygen solubility in 21 pure organic solvents. First of all, the HSP distance between oxygen and solvents (R a ) was calculated by the arbitrary HSP values of oxygen. The linearity between the logarithm of oxygen solubility in pure organic solvents (log x) and R a was confirmed. The HSP value of oxygen is determined to minimize the correlation coefficient of this line. HSP of oxygen was estimated as δ d = 6.7 (MPa) 1/2, δ p = 0.0 (MPa) 1/2, δ h = 3.8 (MPa) 1/2, δ t = 7.7 (MPa) 1/2. The correlation coefficient between solubility of oxygen in organic solvents and R a showed high value The solubility of oxygen in mixed solvents calculated by HSP was larger solubility than the ideal solubility as well as the measured value. It is considered that this is due to the gap between the estimated HSP value of mixed solvent and ideal.

52 TEMPERATURE DEPENDENCE OF HANSEN SOLUBILITY PARAMETERS OF POLYETHYLENE GLYCOL Kana Miyatake, Takashi Sato, Sadao Araki, Yamamoto Hideki Kansai University, Yamate-cho, Suita, Osaka, , Japan Tel , Fax , 1.1 Applied Thermodynamics, Fluid Dynamics, Heat Transfer Hansen solubility parameter (HSP) is often used to predict the solubility and dispersibility. However, the dependence property of the HSP value of polymers on temperature is not clarified because the temperature dependence of the structure morphology is complex. Therefore, in this study, we discussed the effect of temperature on the HSP value of Polyethylene Glycol (20,000 molecular weight; PEG-450) that is one of the most famous polymers. We estimated the HSP value at each temperature by Hansen solubility sphere method. Saturated solutions of PEG-450 were prepared at different temperature from 288 K to 303 K and then the solubilities in several organic solvents were measured by thermogravimeters. From these results, we considered the temperature dependence of the HSP value of polymer. δ d of PEG-450 increased and δ p and δ h decreased with increasing temperature. L. Williams et al. reported that δ d, δ p and δ h of CO 2 decreased with the increase of temperature [1]. The behavior of δ d of PEG-450 is different with that of CO 2. It is considered that this is caused by the change of the structure morphology of PEG-450 with temperature. [1] L. L. Williams, J. B. Rubin, and H. W. Edwards, Ind. Eng. Chem. Res. 2004, 43,

53 MAPPING BINARY LIQUID-VAPOR OR LIQUID-LIQUID-VAPOR EQUILIBRIA REGIONS, INCLUDING THE DIFFERENT AZEOTROPIC BEHAVIOURS, AS A FUNCTION OF THE NRTL BINARY PARAMETERS J.A. Reyes-Labarta*, M.M. Olaya and A. Marcilla Dpto. Ingeniería Química, Universidad de Alicante, Apdo. 99, Alicante 03080, Spain. Telf. (34) Fax (34) Scientific topic: 1.1. Applied Thermodynamics, Fluid Dynamics, Heat Transfer. Thermodynamics and Transport Properties As it is very well know, the synthesis and design of separation processes requires the use of models to represent the phase equilibrium data, which involves the previous correlation of experimental data to obtain the values of the corresponding parameters [1-2]. In previous works, we have studied the capabilities and limitations of the classical G E models used in phase equilibrium data correlations, such as NRTL model, in representing the behaviour of different LV, LL and LLS equilibrium data [3-6]. In the preset work, the relations between the binary parameters A ij of the NRTL model and the existence of different equilibrium regions (i.e.: LV, LL or LLV), as well as the different possible azeotropic behaviours are analyzed for different component systems. The Gibbs free enthalpy curve and the corresponding y-x and T-x,y diagrams along a matrix of Aij parameters has been studied within a range including the typical values observed in DECHEMA Chemistry Data Series. Results obtained obviously depend on the vapour pressure of the pure components studied, the total pressure as well as on the nonrandom parameter in the NRTL model. In all the cases studied values of =0.2 and P=760 mmhg have been used. Figure 1 shows qualitatively as example, the results obtained for a system where the boiling temperatures of the pure components are around: 60 and 100 ºC. The different equilibrium regions can be observed clearly showing the transition between the different behaviours as a function of the values of the interaction parameters of the NRTL equation. Thus, depending on the Aij values different equilibrium behaviours can be obtained such as, LV without azeotropes, a homogeneous LV azeotrope (of minimum or maximum temperature), a heterogeneous azeotrope, 2 homogeneous azeotropes or even systems with two different LLE including 1 heterogeneous azeotrope, etc. The size and evolution of these regions depends on the boiling temperatures of the pure components studied, mainly the regions with no azeotrope that increase (decreasing the regions with homogeneous and heterogeneous azeotrope) with the difference of these temperatures. The knowledge of these types of behaviours would be of great interest in parameter optimization when correlating experimental data. Bibliography [1] Reyes-Labarta, J.A.; Serrano, M.D.; Velasco, R.; Olaya, M.M.; Marcilla, A. Approximate Calculation of Distillation Boundaries for Ternary Azeotropic Systems. Ind. Eng. Chem. Res. 2011, 50(12), [2] Reyes-Labarta, J.A.; Grossmann, I.E. Disjunctive Programming Models for the Optimal Design of Liquid-Liquid Multistage Extractors and Separation Sequences. AIChE J., 2001; 47-10, [3] Marcilla, A; Olaya, M.M.; Serrano M.D.; Reyes-Labarta, J.A. Aspects to be considered for the development of a correlation algorithm for condensed phase equilibrium data for ternary systems. Ind. Eng. Chem. Res. 2010, 49(20), [4] Marcilla, A.; Olaya, M.M.; Serrano, M.D.; Reyes-Labarta, J.A. Methods for Improving Models for Condensed Phase Equilibrium Calculations. Fluid Phase Equilib. 2010, 296(1), [5] Marcilla, A; Olaya, M.; Serrano M.D.; Velasco, R.; Reyes-Labarta, J.A. Gibbs Energy Based Procedure for the Correlation of Type 3 Ternary Systems Including a Three-Liquid Phase Region. Fluid Phase Equilibria. 2009, 281, [6] Reyes-Labarta, J.A; Olaya, M.; Velasco, R.; Serrano M.D.; Marcilla, A. Correlation of the Liquid-Liquid Equilibrium Data for Specific Ternary Systems with One or Two Partially Miscible Binary Subsystems. Fluid Phase Equilibria. 2009, 278, 9-14.

54 INFLUENCE OF CONCENTRATION ON THE RHEOLOGICAL BEHAVIOUR OF DIUTAN GUM SOLUTIONS M.C. García, M.C. Alfaro, and J. Muñoz. Departamento de Ingeniería Química. Universidad de Sevilla. C.P. García González, Facultad de Química, 41012, Sevilla, SPAIN. Tlfno: Scientific Topic 1.1: Applied Thermodynamics, Fluid Dynamics, Heat Transfer (Rheology). Diutan gum (DG) belongs to group of polysaccharides called sphingans since it is obtained by aerobic fermentation from Sphingomonas sp. ATCC (1). This is an anionic biopolymer with a high molecular weight, which ranges from 2.88 to 5.18 MDalton. The backbone structure of diutan gum consists of a repeated configuration of rhamnose, glucose, glucoronic acid and glucose units (2, 3). It is produced commercially for applications such as industrial, oilfield, civil engineering or personal care utilizations due to its ability to modify the rheological properties of aqueous solutions. It is able to thicken liquids, stabilize emulsions, suspend solids or form gels. Diutan gum can form aqueous solutions whose rheological properties are stable even at high temperature and exhibit high viscosities at low concentrations (1). This work studies the influence of diutan gum concentration, in the wt % range, on the rheology of 0.5% wt NaCl aqueous solutions at 25ºC. Hydration was achieved by homogenizing the solution at 700 rpm with an Ika-Visc MR-D1 homogenizer (Ika, Germany) equipped with a sawtooth-type impeller a) first, at room temperature for 5 hours and b) subsequently, at 50ºC for 1 hour. A controlled-stress AR-2000 rheometer (TA Instruments) was used to determine a) the linear viscoelastic properties by small amplitude oscillatory shear, b) the zero-shear viscosity by creep compliance tests and c) the onset of non-linear flow properties by conducting tests at constant shear stress. In addition, a Haake- MARS controlled-stress rheometer (Thermo) was used to determine step-wise flow curves. Frequency sweep assisted by oscillatory shear time tests were used to determine the mechanical spectra, which exhibited viscoelastic properties within the whole gum concentration range studied and showed a significant dependence of the angular frequency on the viscoelastic moduli. Although the storage modulus values (G ) were above the loss modulus (G ) throughout most of the frequency range studied, a crossover could be reached at low frequency. This point allowed calculating the longest or terminal relaxation time. The dynamic viscoelastic moduli increased with diutan concentration, whereas the characteristic crossover frequency steadily went down. Step-wise flow curves exhibited shear thinning behaviour in the diutan gum concentration range studied, with a trend to reach the zero shear Newtonian viscosity at very low shear rates. The concentration dependence of the zero shear viscosity calculated from linear creep compliance tests will be compared to that predicted by the extrapolated values calculated from flow curves. References: (1) W. Schmidt, H.J.H. Brouwers, H.C. Kühne, B. Meng, The Working Mechanism of Starch and Diutan Gum in Cementitious and Limestone Dispersions in Presence of Polycarboxylate Ether Superplasticizers, Applied Rheology 23 (5), (2013) (2) T. A. Chowdhury, B. Lindberg, U. Lindquist, J. Baird, Structural studies of an extracellular polysaccharide, S-657, elaborated by Xanthomonas ATCC Carbohydr Res 164 (1987) (3) S. Campana, J. Ganter, M. Milas, M. Rinaudo, On the solution properties of bacterial polysaccharides of the gellan family. Carbohydr Res 231(1992), Acknowledgments The financial support received from the Spanish Ministerio de Economía y Competitividad (MINECO) and from the European Commission (Feder Programme) is kindly acknowledged (project CTQ ).

55 THERMODYNAMIC STUDY OF PVAc METHANOL DILUTED SOLUTIONS J. Camacho #1, D. Blanco #1, L.E. Martín #1, E. Díez #1, G. Ovejero #1 #1 Grupo de Catálisis y Procesos de Separación (CyPS) Departamento de Ingeniería Química, Facultad de C. Químicas Universidad Complutense de Madrid, Avda. Complutense s/n, 28040, Madrid, Spain. Scientific Topic: 1: Chemical Engineering Fundamentals. 1.1: Applied Thermodynamics, Fluid Dynamics, Heat Transfer Abstract: The objective of this work is to develop a thermodynamic study of Poly-vinyl acetate (PVAc) - methanol mixtures by means of Intrinsic Viscosity technique, to obtain the Flory Huggins interaction parameter. The importance of this study is that methanol is the employed solvent in the PVAc industrial production process. According to Flory Huggins theory [1], the solvent activity coefficient (key parameter to model a purification process) can be obtained by means of Eq. 1. In this equation, a 1 is the activity coefficient of the solvent, ϕ 2 is the polymer volumetric fraction, and χ is the Flory-Huggins polymer-solvent interaction parameter. This parameter can be experimentally determined by means of Intrinsic Viscosity (IV) measurements as the IV of a polymersolvent mixture can be related to the Flory-Huggins parameter by plotting the Stockmayer-Fixman [2] 1/2 1/2 relationship ([η]/m w vs M w ) (Eq 2), where M w is the viscous-average polymer molecular weight, r is the ratio between the molar volume of the polymer and then molar volume of the solvent, ϕ 2 is the polymer volumetric fraction, [η] θ is the IV under theta conditions V 1 is the solvent molar volume, υ 2 is the polymer specific volume and ϕ 0 is the Flory universal constant (equal to 2.8E23 if the IV units are ml.g -1 ) and N A is the Avogadro number K0 0,51 B 0M w ln( a1) ln(1 2) 1 2 (1) M w (2) 2 r K 0 1 B 2 M VN In this work, the IV measurements of methanol PVAc systems have been carried out employing three different PVAc materials with different molecular weights all of them purchased from sigma Aldrich. Their viscousaverage molecular weight was determined by means of Mark Hawkings relationship (Eq. 3) with, for PVAcmethanol system at 53ºC, an a value of 0.59 and a value of K of 36.6 g.ml -1 [3]. The IV values have been determined (besides at 53ºC to determine M) at 40ºC, 50ºC and 60ºC, with the aim of calculating the Flory Huggins parameter, following a procedure already employed in literature [4]. K M (3) a w Table 1 shows the obtained values of the viscous-average molecular weight while Table 2 shows the obtained results for all PVAc-methanol systems at the four studied temperatures. As it can be seen, the higher is the value of M, the higher the IV. On the other hand, it can be noticed that Flory Huggins parameters are below 0,5, what indicates complete miscibility between the polymer and the solvent. Table 1 Table 2 Mw IV (dl.g -1 ) PVAc PVAc - 1 PVAc - 2 PVAc - 3 χ PVAc T = 40ºC 0,328 0,545 0,836 0,499 PVAc T = 50ºC 0,329 0,529 0,932 0,499 T = 53ºC 0,315 0,547 0,910 0,495 T = 60ºC 0,327 0,510 0,938 0,495 Literature cited: [1] P.J. Flory, J. Chem. Phys. 1942, 10, 51. [2] M. Kurata, Y: Tsunashima in J. Brandrup, E.H. Immergut, E.A. Grulke, Polymer Handbook 4 th ; Wiley: New York, 1999, chapter VII. [3] W.H. Stockmyer, M: Fixman, J. Polym. Sci. Part C 1963, 1, 137. [4] G. Ovejero, P. Pérez, M.D. Romero, E. Díez, I. Díaz, Euro. Polym. J. 2010, 46, w 1 A

56 APPLICATION OF THE DISPERSION MODEL AND COMPARISON WITH HYDRODYNAMIC PARAMETERS IN POROUS MEDIA COLUMN Boluda-Botella, N., García Cortés, A.N., Cenador Marín, I., Hernández Teruel, M.J. and Acevedo Sempere, M. Chemical Engineering Department, University of Alicante, Apdo. 99, E Alicante, Spain. irene Fluid Flow Modelling in Porous Media Reactive transport experiments carried out in columns filled with different porous media (aquifer sediment and soil-sea sand mixtures), with injection of seawater or calcium chloride showed differences between tracer breakthrough curves (BTC), used to calculate the column hydrodynamic parameters [1, 2]. Experiments in columns filled with glass beads (2 mm) have been carried out in this paper with the main goal to study the transport processes. The experimental set-up consisted of a cylindrical stainless steel column (22.4cm x 2.5cm), connected to HPLC pump that injects continuously a tracer (0.04 M CaCl 2 ), with an upward flow (0.5 ml/min), displacing resident freshwater. A conductivity detector recorded changes in outlet flow conductivity. The obtained BTC (dimensionless concentration, versus time), together with other experimental data such as flow, length and diameter column, were employed to determine column hydrodynamic characteristics with the program ACUAINTRUSION TRANSPORT, designed in the Chemical Engineering Department of the University of Alicante (http://hdl.handle.net/10045/2691). The software fits the experimental data using the analytical solution of the convection-dispersion equation [3], and minimizes the square of the mean deviation between the experimental and calculated compositions. Then the program provides calculated BTC, Darcy velocity (u), interstitial water velocity (v), mean residence time t m (L/v), column Péclet number (Pe=vL/D L ), effective porosity (, longitudinal dispersion coefficient (D L ), and dispersivity ( L/Pe). Table 1 includes the calculated parameters and Figure 1 the modelled BTC with experimental data. The study of the dispersion can be performed with different approximations, as is shown by Levenspiel [4] and presented in this paper. Dispersion model in the case of an ideal pulse with small dispersion (D/uL<0.01) produces a symmetric curve represented by the equation: π D exp ul 4 D 1 ul where C is the concentration and θ is dimensionless time (t/t m ). Dispersion module of the recipient determines the axial dispersion degree. Step BTC was calculated from the pulse concentration (ec 1) and the values of t m (5452 s) and (2.34x10-3 ) were optimized by minimized differences between experimental and calculated concentrations. The value obtained corresponds to parameters of Table 1, when includes interstitial water velocity. Figure 1 shows the experimental and calculated BTCs obtained. A very good agreement between them is observed. Table 1. The transport parameters obtained with ACUAINTRUSION TRANSPORT Figure 1. Experimental BTC and modelled with optimization of equation (1) and calculated with ACUAINTRUSION TRANSPORT (C C o )/(C F C o ) u v DL tm Pe= (cm/h) (h) vl/d (cm/h) (cm 2 /h) (mm) Experimental OPTIMIZATION ACUAINTRUSION Time (h) References [1] Boluda Botella, N., Gomis Yagües, V. and Ruiz Beviá, F Influence of the transport parameters and chemical properties of the sediment in experiments to measure reactive transport in seawater intrusion. J. Hydrol, 357, [2] Boluda-Botella, N.; León, V.M.; Cases, V.; Gomis, V.; Prats, D Fate of Linear Alkylbenzene Sulfonate in agricultural soil columns during inflow of surfactant pulses. J. Hydrol, 395, [3] Lapidus, L. and Amundson, N.R., Mathematics of adsorption in beds. VI. The effect of longitudinal diffusion in ion-exchange and chromatographic columns. J. Phys. Chem. 56, [4] Levenspiel, O Ingeniería de las reacciones químicas. 3 ª ed. Limusa Wiley, 670 pp.

57 RHEOLOGICAL BEHAVIOUR, PHASE DIAGRAM AND MICELLE GEOMETRY OF NON-IONIC SURFACTANT FATTY ALCOHOL ETHOXYLATES. A.I. García-López *, A. Reyes-Requena, J. F. Rincón-Romero and J.F. Martínez-Gallegos. Chemical Engineering Dept., Faculty of Sciences, University of Granada. Avda. Fuentenueva s/n, Granada, Spain. Phone: , fax: , Topic 1.1: Chemical Engineering Fundamentals. Applied Thermodynamics, Fluid Dynamics, Heat Transfer. Mixing, Rheology, Multiphase Flow and Fluid Flow Modelling Surfactants have a vast number of industrial applications due to their interfacial properties, forming part of numerous commercial products especially if they are formulated as emulsions or dispersions. Notwithstanding, their main application is in detergent formulations for domestic and technical use. The annual amount of these products dumped in sewage effluents is quite important, thus giving rise to several issues related with aquatic environment pollution. This situation can be amended by modifying the composition of these products. Thus, the inclusion of highly biodegradable surfactants such as fatty alcohol ethoxylates, obtained from renewable sources and with favourable performance properties [1-2], offers an improvement chance for these cleaning products. The rheological behaviour of aqueous surfactants solutions may be complex [3]. The surfactant micellar estructure developed at specific conditions can be related with the rheological behaviour, and so, the study of the rheological evolution of non-ionic surfactants in aqueous solutions allows to advance in the knowledge of their inner microstructure and micellar architecture [4], the surfactant micelle type being a key factor. Furthermore, the phase diagrams of the compounds studied provide understanding about their micellar configuration, thus, a study of their rheological evolution would give information about their phase diagrams, and as a consequence, rheological behaviour changes could show structural changes. In the present work we have studied the rheological behaviour and phase diagrams of two non-ionic surfactants fatty alcohol ethoxylates at different temperatures and concentrations: Findet 1214N/23 (average molecular formula C12.6E11, weight mass 629, water content 0.31 wt.%) and Findet 1214N16 (average molecular formula C12.6E4, weight mass 369, water content less than 0.33 wt.%) [5]. Rheological properties of surfactants solutions were determined by a rotational viscosimeter, with thermostatic jacket, VT 500 from Haake. The phase behaviour as a function of the temperature was determined in binary systems water:surfactant as described in a previous work [6]. Both Findet showed a Newtonian behaviour at low concentrations where micellar phase L 1 is present, followed by a pseudoplastic behaviour with increasing concentration, which denoted a phase change towards cubic I 1 or hexagonal H 1 structures that explains the high viscosity observed. At higher concentrations a decrease in viscosity was detected caused by the appearance of crystalline laminar phases which would allow the sliding between different layers when are subjected to shear stress. References [1] E. Jurado, M. Fernandez-Serrano, J. Nuñez-Olea and M. Lechuga. Primary biodegradation of commercial fatty-alcohol ethoxylate surfactants: characteristic parameters. J. Surfactants Detergent 10 (2007) [2] J.F. Martínez-Gallegos, V. Bravo-Rodríguez, E. Jurado-Alameda, A.I. García-López. Polyoxyethylene alkyl and nonyl phenol ethers complexation with potato starch. Food Hydrocolloids 25 (2011) [3] J. Schulte, S. Enders, K. Quitzsch. Rheological studies of aqueous alkylpolyglucoside surfactant solutions. Colloid. Polym. Sci., 277 (1999) [4] 6.H. Kahl, S. Enders, K. Quitzsch. Experimental and theoretical studies of the system n-decyl- -Dmaltopyranoside + water. Colloid. Surface. A, (2001) [5] V. Bravo, E. Jurado, A. Reyes, A.I. García, R. Bailón and M. Cuevas, Determination of average molecular weight of comercial surfactants: Alkylpolyglucosides and Fatty Alcohol Ethoxylates, J. Surfactants Detergent 8 (2005) [6] E. Jurado, V. Bravo, J.M. Vicaria, A. Fernández-Arteaga, A.I. García-López, Triolein solubilization using highly biodegradable non-ionic surfactants, Colloids and Surfaces A: Physicochemical Engineering Aspects 326 (2008)

58 DENSITIES, REFRACTIVE INDEX AND EXCESS MOLAR VOLUMES IN MIXTURES OF IMIDAZOLIUM BASED IONIC LIQUIS WITH WATER C. L. Bolívar, M. G. Montalbán, R. Trigo, G. Víllora * Chemical Engineering Department, University of Murcia, P.O. Box 4021, Campus of Espinardo, E-30100, Murcia, Spain, tel Scientific Topic: Applied Thermodynamics, Fluid Dynamics, Heat Transfer Ionic liquids (ILs), made up of organic salts and liquids at room temperature, have numerous advantages over organic solvents conventionally used in separation processes as liquid phase in supported liquid membranes due their negligible vapour pressure, the greater capillary force and the fact their solubility in surrounding phases can be controlled by selecting the most appropriate cation and anion. Perhaps their most salient feature is that their physicochemical properties can be finely adjusted via slight structural modifications of the cation or anion; making them potentially useful as designer solvents [1]. The determination of a product s physicochemical properties is essential in the design of various physical and chemical processes, especially in the case of a new class of substance such as an ionic liquid [2]. But, even if their interesting properties have been known and studied for some time, much work remains to be done to achieve an accurate physicochemical characterization of systems containing an ionic liquid [3]. In this work, the density and refractive index for a set of these systems were measured at atmospheric pressure throughout the composition range at various temperatures. The data obtained were then used to evaluate excess molar volumes, excess refractive indices and examine the relation between the density and the refractive index for binary mixtures of water and ILs. As an example, Figure 1 shows the strong correlation between density and refractive index for the binary mixture formed by 1-ethyl-3 methylimidazolium tetrafluoroborate [emim + ][BF 4- ] and water. These data were used to calculate excess volumes by using expressions firmly based on the physical significance of each quantity. The experimental results for all systems were fitted by a method of least squares with all points weighted equally to Redlich-Kister polynomial equation (Figure 2) 0,9 0,8 d (g/cm3) 1,4 1,3 1,2 1,1 1 0,9 0,8 1,32 1,34 1,36 1,38 1,40 1,42 Figure 1. Density and refractive index for mixtures [emim + ][BF 4- ]-water at K IR X = 0 X = 0,1 X = 0,2 X = 0,3 X = 0,4 X = 0,5 X = 0,6 X = 0,7 X = 0,8 X = 0,9 X = 1 Vm 0,7 0,6 0,5 0,4 0,3 0,2 0, ,2 0,4 0,6 0,8 1 X (Fracción) Figure 2. Plot of excess molar volume of mixtures [emim + ][BF 4- ] and water at different temperatures 20ºc 30ºc 40ºc 50ºc 60ºc 70ºc References [1]. A. A. Miran Beigi, M. Abdouss, M. Yousefi, S. M. Pourmortazavi, A. Vahid, J. Mol. Liq. 177 (2013) [2]. E. J. González, A. Dominguez, E. A. Mecedo. J. Chem. Eng. Data. 57 (2012) [3]. M. A. Iglesias-Otero, J. Troncoso, E. Carballo, L. Romaní. J. Chem. Thermodynamics 40 (2008) Acknowledgements This work was supported by the European Commission (FEDE /ERDF) and Spanish MINECO (CICYT) through the project CICYT CTQ and by SÉNECA foundation 1195/PI/09.

59 ADVANCED INSTRUMENTATION TO DETERMINATE BINARY MIXTURES PHYSICAL PROPERTIES J. López, J. Ortega, I. Nuez, R. Ríos Grupo de Ingeniería Térmica e Instrumentación (IUSIANI). Universidad de Las Palmas de Gran Canaria. Campus de Tafira, Las Palmas de Gran Canaria, Spain. 1.1 Applied Thermodynamics, Fluid Dynamics, Heat Transfer Designing chemical engineering processes requires the knowledge of physicochemical properties of both pure compounds and mixtures. The aim of this work is to develop an instrument that permits to obtain a certain physicochemical property based on another previously measured in the laboratory. With this technique it is possible to determine both pure compounds and mixture properties by knowing the non-linear relationship between the property to calculate and experimental properties. In order to do so, only binary systems at K have been studied in this work. There are numerous studies that consist in determining [1] and correlating [2] binary mixtures physicochemical properties, which are based on empirical relationships as proposed by Eykman [3], Gladstone- Dale [4] y Lorentz-Lorenz [5]. In this present work, as a first case, the relationship between the density and the refractive index will be determined, because these properties are essential in the characterization and identification of substances. Artificial neural networks (ANNs) have become a powerful tool for chemical applications due to their flexibility and ability to model non-linear systems without prior knowledge of an empirical model. ANN provides an advantage over traditional fitting methods for some chemical applications. For this reason it have been decided to use them to establish relationships between different properties (density and refractive index), and they will be the core or "brain" of the designed instrument. This prevents using nonlinear empirically derived relationships. Besides previously mentioned physicochemical properties (density and refractive index), properties of the subgroups that comprise the molecule have been added as input variables to the neural network: surface area (Q) and volume (R), according to Bondi s contribution method [6], that defines a compound as a combination of these groups. As a result, the large degree of prediction of the neural network allows to obtain all possible binary mixture properties, just from the physicochemical property determined experimentally, Q and R of at least one compound in the mixture. A general outline of the designed instrument shown in Figure 1. Based on input values, density or refractive index, it can be chosen a number of options allowing to calculate physicochemical functions or generate all mixtures that are suitable for the input value. In conclusion, the instrument offers a wide range of possibilities, allowing to obtain any the physicochemical property from another one determined experimentally and all possible combinations between the different groups of compounds that meet the condition to fit the measured value. Figura 1: Development of instrumentation [1] J.Ortega. J. Chem. Eng. Data, (1982) 27 (3), [2] J.Ortega, J.S. Matos. Materials Chemistry and Physics. (1986) 15. [3] J.F. Eykman, Rec. Trav. Chem., 14 (1895) 185. [4] D. Dale, F. Gladstone, Phil. Trans. Roy. Soc. London, 148 (1958) 887. [5] H. A. Lorentz, Wied. Ann., 9 (1880) 641; L. Lorenz, ibid.,11 (1880) 70. [6] Bondi, A. Physical Properties of Molecular Liquids, Cristals and Glasses; Wiley: New York, 1968

60 ACCURATE CALCULATION OF EXPANSION COEFFICIENTS AND THEIR IMPACT ON MULTI-PROCESS SIMULATION Sánchez, M.; Florido, X.; Pérez, N.; Fernández, L.; Ríos, R. Laboratorio de Termodinámica y Fisicoquímica de Fluidos (SIANI), Parque Científico- Tecnológico, Campus de Tafira. Las Palmas de Gran Canaria, 35017, Spain Applied Thermodynamics, Fluid Dynamics, Heat One of the substances characteristic parameters is the isobaric thermal expansion coefficient which, in the case of a solution, is expressed mathematically as: 1 v volumetric thermalexpansion coefficent v T x, p This parameter has a special significance, especially in science, because of its direct involvement in the molecular interactions interpretation of the compounds in solution. Obviously, this impact is also reflected in performance of systems and process design modeling carried out. In this work, thermal expansion coefficient is introduced into the modeling process through a polynomial model developed in our group for the Gibbs function referred to: g E (p,t,x i ) 2 i i, 1 i=0 g z z g p T z donde: g g T g T g p g p T (2) 2 2 i i0 i1 i2 i3... This equation is used to carry out a multi-property correlation (LVE, LLE, h E, v E E, c p, ) using a genetic algorithm as a tool with optimized adjustment of various quantities considered as targets in the procedure. It was analyzed the aforementioned representation goodness in the separation process design, with a practical application that is presented. Another interesting contribution of this paper is the reconsideration of expansiveness concept established for the solutions. A thermal coefficient for volume variation of the solution is defined as: 2 v g vt i 1 vt i (3) T px, p T Ti 1 Ti expression that also takes part in the multi-objective function that is considered in the correlation process. This procedure is applied to a set of binary solutions formed from saturated hydrocarbons and esters, for which literature shows a dense database on indicated properties. 1 id v T v id o o where z1 1 z2 2 (4) v v For the chosen solutions, this parameter results differ from those calculated by the usual method described in the literature [1]. Their integration in the multi-function correlative procedure resulted in a group of acceptable results. The presented poster exposes the impact of this parameter results in the overall context of the projected simulation. 1.-Wisniak, J.; Cortez, G.; Perala, R.D.; Infante, R.; Elizade, L.E.; Amaro, T. A.; Garcia, O.; Soto, H. J. Chem. Thermodyn, 2008, 40,

61 INFLUENCE OF IMPELLER SPEED ON BORAX CRYSTALLIZATION IN DUAL-IMPELLER BATCH COOLING CRYSTALLIZER Antonija Kaćunić, Marija Ćosić, Nenad Kuzmanić Faculty of Chemistry and Technology, Department of Chemical Engineering Teslina 10/V, Split, Croatia phone: , fax: Chemical Engineering Fundamentals - Applied Thermodynamics, Fluid Dynamics, Heat Transfer - Mixing, Rheology, Multiphase Flow and Fluid Flow Modelling This work gives an insight into the impact of impeller speed in a dual-impeller crystallizer on the process of batch cooling crystallization of disodium tetraborate decahydrate (borax). Experiments were conducted in a 15 L baffled batch cooling reactor with specific geometrical characteristics at linear cooling rate of 6 C/h. Mother liquor mixing was performed using the straight blade turbine (4-SBT) that created a radial flow pattern in the system. Mentioned specific geometrical characteristics primarily relate to the liquid level to vessel diameter ratio (H/d T ). Since that ratio was 1.3, an installation of a second impeller was required. The ratio of impeller diameter to vessel diameter, D/d T was 0.33 while the ratio of impeller off-bottom clearance and impeller spacing to the impeller diameter ratios, c/d and s/d respectively, equaled 1. In order to reveal the degree of influence that a dual-impeller system has on the process of crystallization of borax, the same had to be compared to the single-impeller system setup. Considering the fact that the observed system is a solidliquid suspension, initial experiments were carried out at the recommended impeller speed that ensured the state of a complete suspension (N JS ). Further runs included entering the intermedial suspension state since the impeller speed, N to N JS ratio was varied from 1 to 2. This kind of an experimental setup enabled a detailed analysis of the impact of different impeller speed on nucleation and crystal growth kinetic parameters, growth rate, crystal size distribution (CSD) and crystal shape as well. During the process, mother liquor concentration was monitored in-line by the use of a Na ion-selective electrode. Linear crystal growth was determined by the means of optical microscopy where the samples were analyzed using Motic Images Plus 2.0 software. At the end of the process, crystal product was dried and then subjected to sieving to determine the crystal size distribution. To calculate the power consumption at different impeller speeds, data acquisition software was used to monitor and analyze torque values. Results showed that an installation of a second impeller in a system with geometrical characteristics described earlier, leads to a decrease in N JS but with no significant change in power consumption. The effect that an increase in impeller speed in a dual-impeller system has on nucleation kinetic parameters, crystal growth kinetic parameters, growth rate and crystal size distribution is evident. This influence is especially pronounced when it comes to crystal shape of the final product at N/N JS =2 where more than 85% of the final crystal product is regularly shaped. An increase in impeller speed in a dual-impeller system shows an expected increase in power consumption but with no fluctuations in its value over time. Nevertheless, it should be emphasized that these experiments were carried out in laboratory scale and that formation of a new (solid) phase in the system would most likely have to have an impact on the change of power consumption if the same would be implemented in a much larger scale.

62 FIBER CHARACTERIZATION FOR CO 2 ABSORPTION L. Gomez-Coma 1, A. Garea 1, A. Irabien 1, J.C Rouch 2,3, J.F. Lahitte 2,3 and J.C. Remigy 2,3 1 Universidad de Cantabria, Chemical and Biomolecular Engineering Department, Avda Los Castros s/n Santander, Spain 2 Université de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 118 Route de Narbonne, F Toulouse, France 3 CNRS, Laboratoire de Genie Chimique, F Toulouse, France Separation Techniques Among the available membranes, dense polymer composite hollow-fiber membranes are promising for gas permeation applications coupled with the use of gas/liquid contactors [1]. Carbon dioxide is one of the major contributors to climate change. The CO 2 capture and sequestration (CCS) is a concern globally today to reduce the impact on the atmosphere and protect humans against the risks associated with CO 2 pollution. A wide range of technologies exist for CCS based on physical and chemical processes including absorption, adsorption, membranes and cryogenics [2]. Post-combustion process based on ionic liquids and a membrane contactor have emerged as new attractive alternative to traditionally systems because of their zero emission solvent features compared to amines and their controlled interfacial area and independent control of gas and liquid flow rates respectively [3-4]. The aim of this work is the comparison between fibers based on PVDF and different additives and these fibers including two different ionic liquids. On one hand, the 1-ethyl-3-methylimidazolium ethylsulfate [emim][etso 4 ] who presents low viscosity, low toxicity, low cost and only physical absorption [5] and on the other hand the 1- ethyl-3-methylimidazolium acetate [emim][ac] who has high solubility and chemical absorption [6]. In order to compare the fibers, the thickness of the composite fiber was examined by scanning electron microscopy (SEM). Fibers were first immersed in ethanol, cryofractured in liquid nitrogen, and then cut. Deposit thickness was measured from the SEM image of a cross section. The mechanical properties were analized too. Thanks to the Bluehill program was possible calculate the deformation to traction and the elasticity. The gas permeation of composite hollow fibers was measured using pure gas CO 2. Laboratory-made stainless steel modules were used for the tests. One to three fibers around 30 cm long were assembled in each module. The gas was fed into the shell side, and the gas permeation flux was measured at the outlet of the lumen side. The pressure was increased slowly in steps of 0.5 bar to 15 bar. Each measurement was recorded after 100 s of flux stabilization. The bubble point was measured. All the above tests were performed with the fibers in both wet and dry conditions. Upon characterization, fibers were introduced in a membrane contactor with a PVC shell side. Finally, a nondispersive absorption of CO 2 was carried with both ionic liquids. Acknowledgements This research has been funded by the Spanish Ministry Economy and Competitiveness (Project ENE ). References [1] E. Lasseuguette, J.C. Rouch, J.C. Remigy. Industrial and Engineering Chemistry Research, 2013; 52(36): [2] A.B. Rao, E.S. Rubin, Environmental Science and Technology. 2002; [3] P. Luis, T. Van Gerven, B. Van Der Bruggen. Progress in Energy and Combustion Science, 2012; 38: [4] J. Albo, A. Irabien. Journal of Chemical Technology and Biotechnology, 2012; 87(10): [5] A. Arce, H. Rodríguez, A. Soto. Green Chemistry, 2007; 9: [6] L. Gómez-Coma, A. Garea, A. Irabien. Separation and Purification Technology, 2014;

63 MATHEMATICAL MODELING AND SIMULATION OF CARBON DIOXIDE CAPTURE USING VACCUM PRESURE SWING ADSORPTION A. Gutiérrez, J. Menacho, E. Serra, R. Nomen and J. Sempere * IQS School of Engineering, Universitat Ramon Llull. Via Augusta, 390, Barcelona, Spain Scientific Topic: 1.2 Separation Techniques Capture of CO 2 by Vacuum Pressure Swing Adsorption (VPSA) from flue gases of power plants was considered recently in some works. Mathematical modeling and simulation of separation of CO 2 with suitable adsorbents is essential for the evaluation of CO 2 capture from power plants. In this study, we have simulated the breakthrough curves for the adsorption of carbon dioxide on VPSA processes using zeolite 5A for CO 2 capture from a mixture with 15% CO 2 85% N 2 (resembling post-combustion flue gases of a coal-fired power station) using the experimental characterization published in recent bibliography. A model based on the LDF approximation for the mass balance, including energy balance and momentum was proposed, which is able to satisfactorily reproduce all of the experimental data. The models are described by partial differential equations (PDEs) including conservation equations, models for equation of state, equilibrium, thermodynamic, and transport properties. The resulting models involve different unknown parameters to be estimated from the available experimental measurements. The breakthrough curves of these components are the basis of the design of the cycle of the VPSA process, where the regeneration is carried out by reducing the total pressure of the system under a pre-defined scheduling. The regeneration steps will define the final power consumption of the process. The selective adsorption of these components (termed as heavy components) is normally carried out at the highest pressure of the system and then desorption (regeneration) is accomplished at a lower pressure, involving use of vacuum. In this work, the results of the mathematical model have a trend similar to that of the experimental data. Therefore, this modelling strategy is particularly suitable to demonstrate how the entire unit works and to identify operating constraints that may be caused by the equipment that affect the unit productivity, as well as the evaluation of the size of the capture plant appointed to the amount of flue gas per unit volume. In addition, it could be developed a practical CO 2 capture costs sheet including both capital and operating costs, which account for all process equipment and fixed general maintenance costs and labor costs. However, the CO 2 capture cost of adsorption might be still higher than the cost of the amine-based solvant absorption process, typically monoethanolamine (MEA) because of the investment in the equipment. With further improvements in the capacity of the adsorbent, both the operating and capital costs can be reduced, and the VPSA process can be a promising and economical CO 2capture technology. The figure 1 shows the characteristic surface of adsorption curves obtained by mathematical simulation of a column. Figure 1: Surface of adsorption curves obtained by mathematical simulation of a column

64 BIOGAS UPGRADING: SILOXANE REMOVAL BY ADSORPTION AND REGENERATION BY AOPs. Alba Cabrera-Codony, Rafael Gonzalez-Olmos, Maria J. Martín LEQUIA, Institute of Environment. University of Girona, Campus Montilivi, Girona, Catalonia, Spain. Telephone: , Fax: , Topic: Chemical Engineering Fundamentals, Separation Techniques, Distillation, Adsorption, Extraction. Siloxanes are a class of organosilicon compounds widely used in several industrial and household applications. The use of these products has increased intensely over the past fifteen years and therefore the presence of siloxanes in both wastewater and landfill wastes has also risen accordingly. Therefore, biogases from both sources contain siloxanes, which combustion produces abrasive microcrystalline silica, that causes serious damage to gas engines, microturbines and fuel cells, hampering the recovery of energy from biogas. Thus, the removal of siloxanes is a challenge for the effective recovery of energy from this renewable resource. For the removal of gaseous siloxanes, various solid adsorption materials, both activated carbon and inorganic zeolites, were evaluated for their elimination efficiencies. The adsorption experiments were conducted at lab-scale with a nitrogen flow with a concentration of 1000 mg l - 1 of octamethylcyclo-tetrasiloxane (D4). The D4 concentrations in the outflow were continuously measured by gas chromatography. The adsorption capacity was found to be related with the textural development of the activated carbons, achieving an adsorption capacity up to 1700 mg D4 g -1. Both natural and synthetic zeolites have been tested, and the best performance was obtained by an iron-containing synthetic zeolite with a capacity of 410 mg D4 g -1. Inherent to the adsorption process, there is the problem of the regeneration of the spent materials in order to avoid them becoming a residue. In this sense, advanced oxidation processes (AOPs) are becoming important technologies for treating hardly biodegradable contaminants. These processes are based on the generation of reactive radicals, mainly hydroxyl radicals, which oxidize the target pollutant. In this work, ozone and hydrogen peroxide have been used to regenerate D4-exhausted activated carbons as well as zeolites and promising results have been obtained, achieving recoveries of 90% for both zeolites and activated carbons which have iron on its composition. Moreover, some zeolites could be reused for up to 5 adsorption/oxidation cycles as they are more resistant to the oxidation than activated carbons.

65 CONTINUOUS ULTRASOUND EXTRACTION OF BORAGE POLYPHENOLS: DETERMINATION OF TOTAL POLYPHENOLS AND EFFECTIVE DIFFUSIVITY F. Segovia #1, M.P. Almajano #1* Chemical Engineering Department, Technical University of Catalonia, Avda. Diagonal 647, Barcelona, Spain. Phone , Fax Separation Techniques Borage (Borago officinalis L.) is a typical Spanish plant. Borage leaves are a cheap raw material for the production of polyphenols, because it is a by-product of an industrial process, and in addition, the disposal of this material incurs a cost which can be minimized by its use, because during processing 60% of the plant is byproduct. The properties of polyphenols as antioxidants have been widely recognized. They are associated with reduced risk of cancer, cardiovascular diseases, diabetes and Alzheimer's disease. Furthermore, antioxidants from natural sources could be used to increase the stability of food such as the ability to prevent lipid peroxidation. The polyphenols of the borage has attributed many health effects such as: antispasmodic, antihypertensive, antipyretic, aphrodisiac, demulcent, and diuretic properties. It is also considered useful to treat asthma, bronchitis, cramps, diarrhea, palpitations and kidney ailments. Moreover, it was also shown the borage extract is effective in preventing oxidation in fermented dry sausages enriched with ω-3 polyunsaturated fatty acids (PUFA). For these reasons the borage extract is an economical and safe antioxidant. One of the polyphenols found in borage is rosmarinic acid, which is responsible for some of the antioxidant properties of rosemary extracts which is also widely used by the food industry. Rosmarinic acid has a high antioxidant capacity and it is present in the majority of Lamiaceae species. The main problem is to find the best methodology to extract these polyphenols. One of the more extended and efficient method is the use of extraction with ultrasound (US) assisted. The aim of this work is to determine the effective diffusivity of polyphenol from borage by-product in continuous US extraction. The ranges of the variables were: temperature (20 C and 40 C), methanol content (0% and 50% v/v) and time (0 120 min). US-assisted extraction was carried out at 40 KHz, 250W in a temperature controlled US bath. For both methanol content extractions (0% and 50% v/v), the effective diffusivity presented in two phases, a slow and a fast phase (see Figure). In addition, the amount of polyphenols increased with the application of US a 17% at 20ºC for aqueous extraction and 38% at 40ºC for alcoholic extraction. Effective diffusivity values in water extraction assays were between 4.45x10-9 m 2 /s and 5.67x10-9 m 2 /s. The effective diffusivity was lower, between 2.97x10-9 m 2 /s and 3.74x10-9 m 2 /s when ethanol was the solvent. In conclusion, effective diffusivity with US-assisted extraction has been calculated, for the first time, to borage leaves by-product. References: Naczk, M.; Shahidi, F. Phenolics in cereals, fruits and vegetables: occurrence, extraction and analysis. J. Pharm. Biomed. Anal. 2006, 41, Gironi, F.; Piemonte, V. Temperature and solvent effects on polyphenol extraction process from chestnut tree wood. Chem. Eng. Res. Des. 2011, 89, Ayala-Zavala, J. F. et al. Agro-industrial potential of exotic fruit byproducts as a source of food additives. Food Res. Int. 2011, 44,

66 Development and characterisation of a polymer inclusion cellulose acetate membrane containing calix[4]resorcinarenes as a carrier for metal ion transport N. BENOSMANE a,b, B. BOUTEMEUR b,*, M. HAMDI b a Département de Chimie, Faculté des Sciences, Université de Boumerdès, Boumerdès, Algérie. b Laboratoire de Chimie Organique Appliquée. Faculté de Chimie USTHB BP 32 El-Alia, Alger, Algérie. address: c Lead, copper and zinc are heavy metals of concern for their role in environmental pollution, as have toxic effects in humans. The presence of these metals in the human body may induce elevated blood pressure, anaemia, and gastrointestinal, cardiovascular, and nervous [1]. Currently, due to anthropogenic activities where lead is the raw material, its removal from wastewater is a problem of great significance [2]. Due to concern for the environment and the possibility of using a very low amount of the extractant, liquid membrane-based separation methods are considered viable alternatives to currently employed solvent extraction methods [3 5].This work is a continuation of a previous study [6,7], where the preparation and characterisation of unplasticised cellulose acetate membranes (CA) was studied. In order to use CA-calix[4]resorcinarene membranes for the removal of lead waste, a special process should be followed to protect man and the environment. In this study, the transport of Pb(II), Zn(II), and Cu(II) ions through a polymer inclusion membrane (PIM) containing cellulose acetate as the support, calix[4]resorcinarene as the carrier, NPOE, and NPOT was first used as plasticiser (with CA as the support) in acidic aqueous solution. The effects of HCl (in the feed and receiving phase solutions), PIM thickness, amount of plasticiser (in the membrane), carrier structure and concentration (in the membrane) on transport were investigated. The calix[4]resorcinarene concentration varied from 0.01 mg to 0.13 mg, and it was determined that the transport of metal ions increased with a carrier concentration up to 0.9 mg. It was also observed that the transport of metal ions through the PIM tended to increase with the HCl concentration. Facilitated transport of Pb(II) across the membrane against its concentration gradient was demonstrated with lead fluxes as high as μmol.m-2.s-1, and the experiments demonstrated that metal ion transport through the membrane occurred by a facilitated counter-transport mechanism. The PIM was characterised by SEM, FTIR, DRX, TGA and water content measurements. The stability of the PIM was also investigated. References [1] C. Sgarlata, G. Arena, E. Longo, D. Zhang, Y. Yang, R.A. Bartsch, Journal of Membrane Science. 323 (2008) [2] G. Salazar-Alvarez, A.N. Bautista-Flores, E.R. de San Miguel, M. Muhammed, J. Gyves, Journal of Membrane Science. 2005, 250, [3] L. Boyadzhiev, Z. Lazarova, in: R.D. Noble, S.A. Stern (Eds.). Elsevier Science B.V. 1995, [4] P.K. Mohapatra, V.K. Manchanda, Indian Journal Chemistry. 2003, 42A, [5] N.M. Kocherginsky, Q. Yang, L. Seelam, Separation and Purification Technology. 2007, 53, [6] N. Benosmane, S. M. Hamdi, M. Hamdi, B. Boutemeur, Separation and Purification Technology. 2009, 65, [7] N. Benosmane, B. Guedioura, S. M. Hamdi, M. Hamdi, B. Boutemeur, Mat. Sci. Eng C. 2010, 30,

67 SYNERGISTIC EFFECT OF MIXED SOLVENTS IN EXTRACTIVE DISTILLATION TO PRODUCE FUEL ALCOHOL L. García, G. Rodríguez, I. Gil Carrera Edificio 453, Oficina 318, Universidad Nacional de Colombia, Bogotá Colombia Scientific Topic: 1.2 Separation Techniques Anhydrous ethanol is widely used in the chemical industry as a raw material in chemical synthesis, and as solvent in production of paint, cosmetics, sprays, perfumery, medicine and food, among others. Furthermore, mixtures of anhydrous ethanol and gasoline may be used as fuels, reducing environmental contamination and improving gasoline s octane indexes, mainly due to the addition of ethanol. Figure 1. Liquid-Liquid equilibrium diagram for ethanol/water/gasoline system at 50 C. The ternary diagram for the ethanol/water/gasoline system (Fig. 1) shows an immiscibility zone, which restricts the water content in the ethanol-gasoline mixture, since the addition of small quantities of water cause phase separation and ethanol distribution in these phases. Studies have shown that the maximum quantities of water in an E10 mixture are ppm. This work was performed via the Aspen Plus process simulator, while calculations of activity coefficients for the mixture were performed via the NRTL thermodynamic model, which was validated with experimental data, using the Aspen Split simulator. Initially, the ethanol-water-glycol systems were analyzed separately, to further establish a quaternary-system relationship through the Residue Curve Map. The proper correlation of the NRTL model with experimental data supports the definition of the starting point for the thermodynamic modeling of the system, and further certifies the property of ethylene glycol and glycerol to modify the vapor-liquid equilibrium curve, eliminating the azeotrope and obtaining high-purity ethanol. The effect of different mixtures of ethylene glycol and glycerol were analyzed through simulations. The whole composition range was studied and the results showed that in those cases in which solvents were used as pure substances, glycerol proved to be more effective than ethylene glycol in achieving a high purity product while under the same operating conditions, but requiring higher energy consumption. The importance of analyzing the effect of input temperature for the azeotropic mixture on the extractive column relies on the various possibilities that this represents upstream. In certain occasions, azeotropic alcohol may come from rectification column in liquid or vapor phase; also, it is possible to establish heat recovery schemes within the process, in order to adjust the thermal condition of feed. Although preheating the mixture could increase the cost of the process, it is feasible to consider an integrated heat exchanger network in the system. The selected thermodynamic model accurately matches the experimental data on vapor-liquid equilibrium in ternary systems. This study allows for the definition of the operating conditions for an extractive distillation process that uses a mixture of glycols as separating agent. In the case of extractive distillation of ethanol, it is not positive to divide the separating agent stream into two different stages, since single-stage feed provides better results. Furthermore, it may be concluded that the optimal stage for separating agent feed is stage 4 and that as this stage approaches to the overhead, the energy consumption increases and the amount of ethanol present in the distillate decreases. Additionally, it was found that the mixing of ethylene glycol and glycerol is positive for the operation, since the high capacity to retain water by glycerol is leveraged, while at the same time, the operating temperatures for the column bottom are kept at moderate levels, due to the presence of ethylene glycol, a solvent that features a boiling point lower than that of glycerol. Composition of glycerol in the glycols mixture enables the indirect regulation of the distillate purity and the reboiler energy consumption.

68 OXYGEN PERMEATION AND TRANSPORT PROPERTIES TEANSPORT PROPERTIES OF Ca 0.2 Sr 0.8 Ti 1-x Fe x O 3- S. Araki 1, N. Yazumi 1, S. Hamakawa 2 and H. Yamamoto 1 1. Kansai University, Yamate-cho, Suita, Osaka, , Japan 2. Advanced Industrial Science and Technology (AIST), Umezono, Tsukuba, Ibaraki , Japan Tel , Fax , 1.2 Separation Techniques, Membrane Separation As materials having the potential for high oxygen permeability, ABO 3 perovskite-type oxide ionic and electronic mixed conductors have attracted much attention. Perovskite type mixed conductors such as CaTiO 3 -type oxide, LaGaO 3 -type oxide, SrFeO 3 -type oxide, and other types have been reported as oxygen-permeable mixed conducting oxides. In privious study, thin dense films of Ca 0.8 Sr 0.2 Ti 0.7 Fe 0.3 O 3 perovskite-type oxide were prepared on the same component porous substrate by using spin coating method to separate oxygen from air at high temperature. For use as both thin dense film materials and porous substrates, these CSTF materials were prepared using different procedures, respectively. CSTF used at the porous substrate was prepared using a solid state reaction (ssr-cstf). CSTF used for the film material was prepared by using the citrate method (cit-cstf). However, the improvement of oxygen permeability for CaTiO 3 -type perovskite type oxide membrane is required. In this study, we confirmed the effect of the Fe-doped amount to Ca 0.2 Sr 0.8 Ti 1-x Fe x O 3 (CSTF) on oxygen permeability. The oxygen permeability increased with the increase in the Fe-doped amount of up to 0.7. O 2 -TPD of CSTF samples was measured. O 2 desorption peak were observed at around 700 K. O 2 desorption increased with the increase of Fe-doped amount. In addition, the temperature of O 2 desorption decreased with Fe-doped amount. It is considered that this O 2 desorption is associated with oxygen permeability. Thus, the increase of Fedoped amount would improve the oxygen permeability within the range that the chemical stability can be maintained.

69 INFLUENCE OF REACTION TIME AND CONCENTRATION OF ACID CATALYST FOR SILICA SOL ON MEMBRANE PERFORMANCE OF HYDROPHOBIC SILICA MEMBRANES D.Gondoh, S.Araki and H.Yamamoto Kansai University, Yamate-cho, Suita, Osaka, , Japan Tel , Fax , 1.2 Separation Thechniques Recent years, many studies for the separation of organic compounds from organic/water mixtures by pervaporation (PV) have been reported. It is possible to separate azeotropic mixtures, thermally degradable mixtures, and organic aqueous solutions of low concentration by PV. In our precious study, the suitable pore for organic compounds such as ethyl acetate, ethyl methyl ketone and isopropyl alcohol in hydrophobic silica membranes was prepared by the molecular template method with using cetyltrimethylammoniumbromide (CTAB) on a porous alumina support with γ-alumina interlayer by a sol-gel method. Particularly, this membrane showed the high separation factor for the separation of ethyl acetate (EA) from EA/water mixtures by PV. In this study, we conformed that the effect of silica precursors, the reaction time of silica sol and the concentration of acid catalyst on the separation properties of hydrophobic silica membranes. Tetraethoxysilane (TEOS), tetramthoxysilane (TMOS) and phenyltrimethoxysilane (PhTMS) were used as the silica precursors because the hydrolysis and condensation velocity is different. PhTMS-TEOS and PhTMS- TMOS hydrophobic silica membranes were prepared at 1, 3, 9 and 24 h of reaction time by sol gel method. The PV experiment of ethyl acetate (EA) (5wt%) / water was carried out by using hydrophobic silica membranes prepared in each reaction time. The membrane separation factor of both membranes was increased by 9 h of the reaction time and almost same separation factor was obtained after 9 h. In addition, the hydrophobic silica membranes were characterized by field emission scanning electron microscopy (FE-SEM) and permporometry measurement. PhTMS-TEOS hydrophobic silica membranes were prepared at concentration of nitric acid 0.10, 0.51, 1.00 and 1.92 mol dm -3 to confirm the effect of acid concentration on the separation property. PV measurements of ethyl acetate (EA) (5wt %) / water were carried out by using PhTMS-TEOS hydrophobic silica membranes prepared at each concentration of nitric acid. The separation factor of membrane prepared at 0.10 mol dm -3 nitric acid was lowest and separation factor at 0.51 mol dm -3 was highest. The separation factor of membranes prepared above 0.51 mol dm -3 of nitric acid decreased with the increase of the concentration of nitric acid. It was conformed that the optimum nitric acid concentration was 0.51 mol dm -3.

70 ADSORPTION PROPERTIES OF GLUTARALDEHYDE-CROSSLINKED POLY(VINYL ALCOHOL)/SODIUM ALGINATE POLYMER GEL FOR HAZARDOUS ORGANICS REMOVAL FROM WATER R. Okumura, S. Araki and H. Yamamoto Kansai University, Yamate-cho, Suita, Osaka, , Japan Tel , Fax , 1.2 Separation Techniques Poly (vinyl alcohol) (PVA) polymer gels show the swelling-shrinking behavior with changing temperature. In addition, the hydrophobic-hydrophilic balance on surface of polymer gels is reversibly changing with volume change. These properties are effective to separate hazardous organics from water. Recently, phenols are widely used as raw materials for synthetic resin, medical product and others. Therefore, it is important to develop the adsorbents to separate phenols from the wastewater of industrial and medical facilities. In this study, PVA cross-linked with glutaraldehyde (GA) polymer gels were prepared. The effect of the ratio of GA to PVA on the pore structure, swelling-shrinking behavior and adsorption property of p-chlorophenol was confirmed. Pore structure of GA gel is observed by a scanning electron microscope (SEM). The number of pore increased with increasing the ratio of GA to PVA. Swelling-shrinking behavior was confirmed at the temperature range from 283 to 323 K. Swelling ratio based on the volume of GA at 283 K was measured. Swelling ratio decreased with the increase of temperature. Adsorption experiment of p-chlorophenol is carried at K. Adsorbed amount is measured by using UV-Vis spectrophotometer. Adsorbed amount of p-chlorophenol increased with increasing the ratio of GA.

71 PROCEDURE FOR AMYGDALIN ISOLATION FROM PLUM SEEDS Ivan M. Savic 1 *, Vesna D. Nikolic 1, Ivana M. Savic 1, Ljubisa B. Nikolic 1, Dragljub G. Gajic 2,3 1 Faculty of Technology, University of Nis, Bulevar oslobodjenja 124, Leskovac, Tel.: ; fax: , 2 Center of Excellence DEWS, University of L Aquila, Italy 3 Department of Signals and Systems, School of Electrical Engineering, University of Belgrade, Serbia 1.2 Separation Techniques Amygdalin {[6-O-(β-D-Glucopyranosyl)-β-D-glucopyranosyl]oxy}(phenyl)acetonitrile is a natural chemotherapeutic agent which belongs to the group of diglucoside [1]. It can be found at over 1,200 plants, such as the seeds of apricot, peach, almond, black cherry and apple [2, 3]. Amygdalin has proved effective in the treatment of tumors of the lung, breast, prostate, colon and lymphomas [4]. Thus, the aim of this study was to optimize the procedure for amygdalin extraction, i.e. isolation from the plum seeds using multilayer perceptron (MLP). The extraction time, the ethanol concentration, the solid to liquid ratio and the temperature were used as the inputs for training the neural nets and the yield of amygdalin was used as the output. About 70% of the total performed experiments (35 experimental runs) were used for training the neural nets, while per 15% for testing and validation. The values of process parameters were varied in order to investigate their effects on the yield of amygdalin. The architecture MLP (4-3-1) was presented as the optimal neural net for prediction of the amygdalin yield. The correlation coefficient of and the value of root mean square error of indicate the adequate proposed model. The following conditions: the extraction time of 120 min, 100 % (v/v) ethanol, the solid to liquid ratio of 1:25 (m/v) and the temperature of 34.4 C were obtained after optimization studies, i.e by using the simplex algorithm. The experimental value of the yield (25.30 g per 100 g of the extract) was in good agreement with the predicted value (25.42 g per 100 g of the extract). The extraction was performed under reflux and using the water bath in order to maintain the temperature of the system. After extraction, the solid phase was separated from liquid phase by vacuum filtration. Then, the extract was evaporated in the rotary evaporator at 50 C and dried in the desiccator. Thus obtained extract was treated with diethyl-ether (10 cm 3 ), which is suitable for dissolving the fatty compounds and precipitation of amygdalin due to the pure solubility. The purity of native amygdalin determined in relation to the available standard of amygdalin was >90%. After that, amygdalin was structurally characterized by using ESI-MS n, FTIR and UV methods. Acknowledgments. The support from the Marie Curie FP7-ITN "ENERGY-SMARTOPS", Contract No: PITN- GA , the Erasmus Mundus Action II EUROWEB Project and the Ministry of Education, Science and Technological Development of the Republic of Serbia under the project TR is gratefully acknowledged. References 1. I. M. Savic, V. D. Nikolic, I. M. Savic, Lj. B. Nikolic, M. Z. Stankovic, Research Journal of Chemistry and Environment, 16(4), 80 (2012). 2. I. F. Bolarinwa, C. Orfila, and M. R. Morgan, Food Chemistry, 152, 133, (2014). 3. J. Lee, G. Zhang, E. Wood, C. Rogel Castillo, A. E. Mitchell, Journal of Agricultural and Food Chemistry, 61(32), 7754 (2013). 4. S. Milazzo, S. Lejeune and E. Ernst, Support Care Cancer, 15(6), 583, (2007).

72 REUSE OF TEXTILE EFFLUENTS TREATED WITH PVDF ULTRAFILTRATION MEMBRANE V. Buscio, M. Crespi and C. Gutiérrez-Bouzán INTEXTER, Universitat Politècnica de Catalunya-BarcelonaTech, C/Colom 15 (08222, Terrassa-Spain), Tel , Fax Chemical Engineering Fundamentals: Separation Techniques Textile industry is characterized by high water consumption. Up to m 3 water are required to produce one tone of textile product [1]. Wastewater from textile industry contains different kind of dyes and chemical additives [2], which cannot be easily degraded. The most used wastewater treatments are based on biological or physical-chemical processes, although most of them show disadvantages in the removal of residual dyes. For this reason, the membrane technology is nowadays an attractive alternative to treat textile wastewater. In addition, it produces an uncoloured permeate able to be reused. To study the feasibility of PVDF ultrafiltration membranes to treat textile wastewater, two disperse dyes (CI Disperse Orange 30 and CI Disperse Rubine 73) were selected in this work for the membrane filtration study. Disperse dyes are used for polyesters fibres. The membrane provided a high quality permeate, able to be reused in new dyeings. The COD removal was about 90% and 96% colour removal was achieved (figure 1). In different published studies, the membrane fouling was a major problem to the further application of UF technology in wastewater Figure 1- Synthetic textile effluents before and after the membrane treatment treatment, because it produces a reduction in the permeability and consequently the maintenance cost of the membrane was increased and its life time was reduced. In this work, very low fouling was observed which demonstrate the feasibility of applying this type of membranes to treat textile wastewater. After the membrane treatment, the two permeates were reused in new dyeing process. The reuse of wastewater from polyester dyeing is an important challenge since the polyester fibre demand has been growing in the last decades. Nowadays this fibre represents about the 50% of the total world textile fibre consumption and it still has an increasing demand [3]. In new dyeings, 100% of the obtained permeate was reused. Finally fabrics dyed with the reused water were evaluated respect to references carried out with decalcified tap water. The colour differences obtained were lower than 1.5 (table 1), which is the maximum value accepted by the industry. Table 1- Colour differences obtained in the permeate reuse study Dye Colour differences CI Disperse Rubine CI Disperse Orange Due to the huge amounts of water consumed in the textile mills, the feasibility of permeate reuse is a promising result. Consequently, it is stated that the membrane treatment is advantageous from both the environmental and the economical point of view. Acknowledgments: The authors thank the financial support from the Spanish Ministry of Economy and Competitiveness (CTM ) and Valentina Buscio is granted by UPC. References [1] N. Tahri, G. Masmoudi, E. Ellouze, A. Jrad, P. Drogui, R. Ben Amar. J. Clean. Prod. 2012; 33: [2] Y. Zheng, S. Yu, S. Shuai, Q. Zhou, Q. Cheng, M. Liu, C Gao. Desalination 2013; 314: [3] S.M. Burkinshaw, G. Salihu. Dyes and Pigments 2013; 99:

73 NATURAL BIOACTIVE MICROPARTICLES FROM EUCALYPTUS LEAVES BY SUPERCRITICAL FLUID PROCESSES C. Chinnarasu 1 ; A. Montes 2 ; L. Casas 2 ; C. Mantell 2 ; C. Pereyra 2 *; E.J. Martinez de la Ossa 2 1 Department of Environmental Science, PSG College of Arts and Science, Bharathiar University, Coimbatore, India. 2 Department of Chemical Engineering and Food Technology, Faculty of Sciences, University of Cádiz, International Excellence Agrifood Campus (CeiA3), Puerto Real, Cádiz, Spain Phone: Fax: *E mail: 1.2 Separation Techniques Polyphenols are natural compounds of great interest as a high structural diversity, and their high spectrum of biological activity such as antioxidant 1. Eucalyptus leaves contain mainly hydrolysable tannins, terpenyl derivatives, ellagic acid derivatives, flavonols, hydroxybenzoic acids, and phloroglucinol 2. Supercritical fluid (SCF) technologies are interesting alternatives so present several advantages including the use of green solvents, faster and more selective process, and the low degradation of chemical compounds 3. Particularly, the supercritical fluid extraction (SFE) uses the high power of supercritical fluids to extract many natural compounds from the leaves and supercritical antisolvent (SAS) precipitation process uses the high power to dissolve the organic solvents to cause the precipitation of natural compounds once they are dissolved in the organic phase. In this work SFE and SAS process has been used to precipitate the bioactive compounds from eucalyptus leaves. The SFE experiment was carried out in a pilot plant developed by Thar Technologies (model SF1000). The set points of the operating conditions were pressure of 10 MPa, temperature of 55 ºC, CO 2 flow rate of 16 g/min and ethanol flow rate of 4 g/min. The SAS experiment was carried out in another pilot plant developed by Thar Technologies (model SAS200). The nozzle of 100 µm, pressure of 15 MPa and temperature of 50 ºC into the vessel, CO 2 flow rate of 20 g/min, sample flow rate of 2 g/min and the washing time of 30 minutes were used as set points. A rapid mutual diffusion between the supercritical CO 2 and the ethanol solvents causes supersaturating of the eucalyptus ethanol extract solution, leading to precipitation of the bioactive microparticles. The precipitated powder was analysed by scanning electron microscopy (SEM). As can be seen in Fig.1. the morphology was successfully improved from irregular prismatic shape of the eucalyptus leaves extract to spherical microparticles near nanometer ( nm) of the precipitated particles. Fig.1. SEM images of microparticles of eucaliptus bioactive compounds obtained by SFE and SAS process, respectively. References [1] Stephane Quideau, Denis Deffieux, Celine Douat-Casassus, Laurent Pouysegu. Plant Polyphenols: Chemical Properties, Biological Activities, and Synthesis. Angew.Chem. Int. Ed. 50, (2011), [2] Lila Boulekbache-Makhlouf, Emmanuelle Meudec, Jean-Paul Mazauric,Khodir Madani and Véronique Cheynier. Qualitative and Semi-quantitative Analysis of Phenolics in Eucalyptus globulus Leaves by Highperformance Liquid Chromatography Coupled with Diode Array Detection and Electrospray Ionisation Mass Spectrometry. Phytochem. Anal. 24, (2013), [3] M.R. Marostica, A.Leite, N.Romanelli, V.Dragano. Supercritical fluids extraction and stabilization of phenolic compounds from natural sources review (supercritical extraction and stabilization of phenolic compounds), Open Chem.Eng. J. 4, (2010) Acknowledgments We gratefully acknowledge the CeiA3 (2013/14 Co-Supervised Doctoral Theses For Foreign PhD students) for financial support.

74 BEHAVIOUR OF TERPENES, SESQUITERPENES AND OXYGENATED COMPOUNDS DURING THE ESSENTIAL OIL DETERPENATION PROCESS BY LIQUID-LIQUID EXTRACTION, AT K C. E. C. Rodrigues, C. C. Koshima, D. Gonçalves Separation Engineering Laboratory (LES), Department of Food Engineering (ZEA-FZEA). University of Sao Paulo (USP), P.O. Box 23, Zip Code , Pirassununga, SP, Brazil. Phone: Fax: Chemical Engineering Fundamentals - Separation Techniques. Citrus oils are widely used by flavor, food, cosmetic, pharmaceutical, and chemical industries. They are composed by terpenic hydrocarbons, which constitute the major group and oxygenated terpenes, which are generally considered preferable because of their pleasant odor. The industrial practice to remove terpenic hydrocarbons to concentrate the oil in oxygenated compounds is known as deterpenation and can be accomplished by liquid-liquid extraction using short chain alcohols as solvent [1]. Phase equilibrium data are important for the design of extraction process. This work presents experimental data for systems composed by components of essential oils (monoterpenes - limonene, -pinene, -terpinene; sesquiterpene - - caryophyllene; and oxygenated compounds - linalool, citronellal, carvone, citral, eugenol) and solvent (ethanol with different contents of water), at K. Aqueous solvents with water mass fractions varying from 0.06 to 0.40 were used in this study. They were prepared by diluting absolute ethanol (Merck, Germany), purity greater than 0.998, into deionised water (Millipore, USA). The liquid liquid equilibrium data were determined using polypropylene centrifuge tubes [2]. The components were weighed on an analytical balance. The tubes were vigorously stirred at 2800 rpm for at least 10 min at room temperature (close to 298 K), centrifuged for 20 min at 5000 g at T = (298.2 ± 1.5) K and then placed in a thermostatic bath at T = (298.2 ± 0.1 K) for 20 h. After this treatment, the two phases became clear, with a well-defined interface, and the composition of both phases was measured. The concentrations of essential oil components and ethanol were determined by chromatography using a FID detector [3]. The water concentration was determined by Karl Fischer titration, with a KF Titrino. In this work, all measurements were performed at least in triplicate. Figure 1a presents the solubility of the monoterpenes and sesquiterpene in the solvent-rich phase (w terp/sesq ) SP, and figure 1b shows the solubility of the solvent (ethanol+water) in the terpene-rich phase (w solvent ) TP as a function of the water mass fraction in the solvent (w S water ). It can be noted that the solubility between terpenic compounds and the solvent decreases as the water content increases. In fact, this trend is a result of the reduction in miscibility caused by the presence of the water in the system. It is also possible to observe that the solubility of systems containing the -caryophyllene is lower than the solubility of monoterpenes, independently of solvent hydration level. This behavior may be consequence of the molecular structural differences among the hydrocarbons considered in this study. In fact, sesquiterpene contains an additional isoprene unit which can confer its lower solubility. Concerning the distribution coefficients (k i ) for the oxygenated compounds, shown in figure 2a, these data verify that as the water content in the solvent phase increased, the values of the k i decreased, regardless of the type of compound studied. Considering the solvent with 0.23 mass fraction of water in the solvent and 0.05 of oxygenated compound in the overall composition, it is possible to note that the k value of eugenol is 4.5 major than k values of cetone and aldehydes, and it is 2.3 major than k value of linalool. In fact, the k values of the alcohols are larger than k of other components and they seem to be dependent on the composition of the terpene mixture. The oxygenated compounds always showed the highest distribution coefficients among the components of the essential oil (figure 2), making deterpenation a feasible process. References: [1] Cháfer, A. et al. Fluid Phase Equilib. 2005, 238, [2] Chiyoda, C. et al. J. Chem. Eng. Data 2011, 56, [3] Gonçalves, D. et al. J. Chem. Thermodyn. 2014, 69, Figure 1 Solubities at K. Figure 2 Distribution coefficients at K. The authors wish to acknowledge FAPESP, CAPES and CNPq for the financial support.

75 ETHANOL DEHYDRATION WITH HEAVY ALCOHOLS: LL EQUILIBRIA OF THE SYSTEM WATER+ETHANOL+UNDECANOL AT 15ºC V. Gomis, N. Boluda, A. Font, M.D. Saquete, J. García-Cano and J. Crichton University of Alicante. PO Box 99, E Alicante (Spain). Phone: , Fax: , Separation techniques Bioethanol is one of the possible alternatives to conventional fuels. It is produced by fermentation of biomass in an aqueous medium. To use it as a fuel it has to be separated from the water and other compounds present in the fermentation broth. Liquid-liquid extraction is one of several techniques that exist to do that. A heavy alcohol could be used as an extractant. In order to analyze the viability of their use it is necessary to know the phase equilibria of the water+ethanol+heavy alcohol system involved in the extraction. In two previous works the solid-liquid-liquid equilibrium (SLLE) data of the systems water+ethanol+1-decanol [1] and 1-dodecanol [2] were published. In the present work LLE data of the system with 1-undecanol at 15ºC have been determined experimentally and the results compared with the other systems. The experimental determination was carried out by preparing heterogeneous known mixtures of water, ethanol and 1-undecanol, stirring and settling in a thermostatic bath at 15ºC. Samples from both liquid phases were taken and analyzed with gas chromatography. Furthermore the water content in each phase was verified using the Karl Fisher technique. The solubility experimental results in weight fraction are presented in figure 1. In the same figure the LLE data for the system with 1-decanol are presented, showing that both diagrams are very similar. Both diagrams differ from the system with 1-dodecanol where there is a solid+liquid+liquid region. Figure 1. LLE diagrams for the ternary systems water+ethanol+heavy alcohol The obtained data can be used to simulate the extraction of ethanol with heavy alcohols. The three alcohols studied could be used in the dehydration of ethanol. Among those alcohols, the 1-dodecanol could be highlighted since the combination of melting and solidification in the temperature studied could improve the economic aspects of the extraction, and the solvent could be recovered via crystallization with an important saving in the cost of the process. Bibliography [1] N. Boluda V. Gomis, H. Bailador, A. Pequenin, Influence of the Temperature on the Liquid-Liquid-Solid Equilibria of the Ternary System Water + Ethanol + 1-Decanol, J. Chem. Eng. Data 56,2011,, [2] N. Boluda, V. Gomis, F. Ruiz, H. Bailador, The influence of temperature on the liquid liquid solid equilibria of the ternary system water + ethanol + 1-dodecanol, Fluid Phase Equilibria, 235, 2005,

76 LIQUID-LIQUID PHASE EQUILIBRIUM DATA FOR THE WATER + 2- PROPANOL + 1-UNDECANOL SYSTEM V. Gomis, N. Boluda, A. Font, M.D. Saquete, J. García-Cano and K. Davidson University of Alicante. PO Box 99, E Alicante (Spain). Phone: , Fax: , Separation techniques 2-Propanol has been widely used in industry as a solvent or chemical intermediate, as well as in consumer applications typically in everyday products such as cleaning products. During the manufacturing of 2-propanol via direct hydration it is formed in an aqueous solution that needs to be recovered. This is typically done by distillation, however this is limited due to the formation of an homogeneous azetrope. In many cases, liquidliquid extraction is used after distillation when further extraction is required. Particularly, Ahmet Alp Sayar (1991) analyzed the behaviour of different solvents at a constant temperature of K, mainly hydrocarbons and heavy alcohols, as entrainers for the 2-propanol dehydration process [1]. Liquid-liquid extraction requires reliable multicomponent phase equilibrium data to design and optimised the separation process. In this sense, the aim of the research was to determine the viability of using 1-undecanol as a solvent in the extraction of 2-propanol from water at two different temperatures: K and K. Samples of ternary mixtures within the heterogeneous region were prepared and were allowed to settle under isothermal conditions until the phases separated. After the phase equilibrium had been reached, an appropriate amount of each conjugate layer was withdrawn for quantitative analysis. After a known amount of ethanol as an internal substance had been added to the weighted sample, the 2-propanol and the 1-undecanol content was determined by gas chromatography using a flame ionization detector. The water content of each sample was determined by means of the Karl-Fischer method. The material balances and thus the reliability of the experimental results were checked. The experimental tie lines and the binodal curves at each investigated temperatures are plotted in Figure 1. (a) (b) Figure 1. LLE diagrams (mass fraction) for the ternary systems water + propanol + 1-undecanol at K (a) and K (b). In order to estimate the performance of the 1-undecanol as entrainer, the distribution coefficients and the separation factors were determined and compared with other heavy alcohols. Industrial purposes usually require a distribution coefficient values higher than 0.2 and separation factors higher than 10. Taking this into account, 1-undecanol may be a suitable entrainer for the isopropanol dehydration. However, the temperature can affect the process substantially since only the liquid-liquid equilibrium data obtained at K gives separation factor above 10. Stoicescu et al.[2] did a similar analysis for the dehydration of 1-propanol trying different heavy alcohols and found that 1-decanol and 1-dodecanol could serve as separating agents for 1-propanol at K. Bibliography [1]. Sayar, Ahmet Alp. Liquid-liquid equilibria of some water + 2-propanol + solvent ternaries. Journal of Chemical and Engineering Data 36 (1991): [2]. Stoicescu, Cristina; Iulian, Olga and Isopescu, Raluca. Liquid-Liquid Phase Equilibria of 1-Propanol + Water + n-alcohol Ternary Systems at K and Atmospheric Pressure, Journal of Chemical and Engineering Data 56 (2011):

77 FRACTIONATION OF RECYCLED PULP SUSPENSIONS IN A HYDROCYCLONE Llop, M.F., Puig, J., Méndez, J.A., Pèlach, M.A LEPAMAP Grup, Department of Chemical Engineering, Universitat de Girona. Avda M. Aurèlia Capmany, Girona Scientific Topic: Chemical Engineering Fundamentals Separation Techniques The paper properties are determined by the fibres morphology and can be controlled by adjusting the proportions of fine and coarse fractions. The classification of these fibres in different fractions is of great interest for the pulp containing both fractions, as for example recycled pulp. Hydrocyclones are the equipment with valuable efficiency for this purpose which is widely used in the paper mills. Although the patent of the first hydrocyclone has over a hundred years, its use to classify fibres pulp is something more recent (Pesch, 1963). The centrifugal fractionation process is based on the different slip velocity of the fibres in a flow subjected to a centrifugal field. As the fibres velocity is related to the fibres morphology can be fractionated in different sizes. Coarse and dense fibres, with low specific surface area have high centrifugal slip velocity and concentrate in the cleaner rejects. Fine fibres with high specific surface area have lower centrifugal slip velocity because of their smaller size, apparent density or the presence of surface fibrillated fibres. These particles are concentrated mostly in the clearer accepts. Due to the interaction of the fibres, a fraction of them tend to concentrate in the cleaner rejects, but much slower. The centrifugal separation of pulp components, and especially the separation of fibres according to their morphological properties, requires relatively free motion between the fibres and thus low concentration in order to minimise fibre interactions and avoid fibre flocculation. The objective of this contribution is to analyse the influence of several parameters and the operation conditions on the fractionation efficiency of the fibrous suspension from recovered kraft liner paper. The parameters which define fibres morphology: arithmetic length, length weighted in length, diameter and percentage of fines obtained by MorFi analyser from TEchpap, are analysed and discussed. To analyse the influence of the operational conditions, different flow rates and pressures have been operated. The results are obtained under centrifugal fractionation conditions using two stages of fractionation cleaners operating at low fibre consistency in order to achieve high fractionation efficiency. The effect of the work conditions modified during the cleaning process such as feed consistency, pressure drop and reject amount is analysed. The most important conclusions obtained include the real fractionation of the fibres in this two stage cleaning process. The reject flow contains higher percentages of long fibres compared with the accepted flow that contains shorter fibres in all cases. Long fibres that are coarser and denser have high centrifugal slip velocity and they are concentrated in the cleaner reject flow. Shorter fibres have lower centrifugal slip velocity because of their smaller size or because of their increased drag coefficient due to surface fibrillation. It is recommendable to work at percentages of reject flow not higher than 20%. At higher values, the fractionation process doesn t work. The suitability to work in diluted state has confirmed in this experimental study. Pulp consistencies of 0.5% in the feed flow give the best results of centrifugal fractionation. The results about fine distribution in the different flows of the centrifugal process are not conclusive, and the fibre diameter is not affected by the process. ACKNOWLEDGEMENTS Authors wish to acknowledge the financial support of the Ministry of Science and Innovation of Spain to the Project CTM C02-02 and also to Escola Politècnica Superior from Universitat de Girona. REFERENCES - Ämmälä, A., Jokinen, H., Niinimäki, J., Yli-Viitala, P. Hydrocyclone sand separation, Appita J., 60(4) Saint Amand, F.J. Principles & Technology of Cleaning /Fractionation, 10 th Advanced Training Course on Deinking Technology, Centre Technique du Papier, Grenoble (Fr) Technical Information Paper, TIP An introduction to centrifugal cleaners from Pesch, A.W., Process for preparation of fibers having different characteristics US Patent A April, 16 th 1963.

78 PURE SILICA ZEOLITE ITQ-29 / POLY(1-TRIMETHYLSILYL-1-PROPYNE MIXED MATRIX MEMBRANES FOR CO 2 /N 2 SEPARATION A. Fernández-Barquín* #1, C. Casado-Coterillo #1, S. Valencia #2 and A. Irabien #1 #1 Department of Chemical and Biomolecular Engineering, Universidad de Cantabria, Av. Los Castros s/n, Santander, Spain; *corresponding author: tel , #2 Institute of Chemical Technology (UPV-CSIC), Av. Los Naranjos s/n, Valencia, Spain Scientific Topic: 1. Chemical Engineering Fundamentals The atmospheric concentration of greenhouse gases (GHGs) has increased significantly over the last century. There are increasing concerns for global warming caused by the effects of GHGs, particularly CO 2. Membranes have received a great deal of attention as alternative energy-efficient process separating CO 2 from other light gases and therefore, reducing greenhouse gas emissions [1]. The permeability and selectivity values of membranes should be as high as possible for their efficient use in industrial gas separation applications. In particular, the impact of membrane material in CO 2 removal is as important as process conditions [2]. However, there is a well-known trade-off between permeability and selectivity of polymeric membranes [3]. Different strategies have been reported to overcome this limit. Mixedmatrix membranes (MMMs), hybrid membranes formed by selective inorganic materials dispersed into polymer continuous matrix were proposed as a feasible option to improve the performance [4]. Zeolites, crystalline alumina-silicates composed of AlO 4 and SiO 2 tetrahedra, which build up a network of channel and cavities, were the first molecular sieves used as fillers in MMMs. The addition of small-pore zeolites to the membrane casting solution can improve the selectivity of a gas pair separation [5], and enhancing thermal and mechanical stability and moisture resistance. Pure silica ITQ-29 is a hydrophobic small-pore zeolite with LTA framework and Si/Al =, which is very stable even after calcination at 900 ºC in the presence of atmospheric moisture [6] and it can sieve and process small molecules with high precision, even in the presence of water or other polar molecules.. In this work, mixed matrix membranes have been prepared from poly(1-trimethylsilyl-1-propyne) (PTMSP), the most permeable polymer known, having an extraordinarily high fractional free volume, and pure silica LTA-type zeolite ITQ-29 at different loadings. Their permeability, diffusivity and solubility performance in CO 2 / N 2 separation has been evaluated in the temperature range from 25 to 100ºC. Financial support from the Spanish Ministry of Economy and Competitiveness (MINECO) under projects ENE and CTQ , is gratefully acknowledged. C.C.C. also thanks the Ministry for the Ramón y Cajal grant (RYC ) at the Universidad de Cantabria. References [1] R.S. Haszeldine. Science, : [2] B.T. Low, L. Zhao, T.C. Merkel, M. Weber, D. Stolten. J. Membr. Sci., : [3] L. M. Robeson. J. Membr. Sci., : [4] J. Gascón, F. Kapteijn, B. Zornoza, V. Sebastián, C. Casado, J. Coronas. Chem. Mater., : [5] C. Casado-Coterillo, J. Soto, M. T. Jimaré, S.Valencia, A. Corma, C. Téllez, J. Coronas. Chem. Eng. Sci., : [6] A. Corma, F. Rey, J. Rius, M. J. Sabater, S. Valencia. Nature, :

79 REMOVAL PROCESS OF ARSENIC (V) IN AQUEOUS SOLUTION BY REVERSE OSMOSIS A. Abejón, A. Garea, A. Irabien Departamento de Ingenierías Química y Biomolecular, Universidad de Cantabria, Avda. de los Castros s/n, Santander, SPAIN Tel.: , Fax: , Separation Techniques Arsenic is a semi-metal situated in group 15 of the periodic table, directly below phosphorous. In the nature, it can appear in four different oxidation states (As -3, As 0, As +3, As +5 ), but the most common in ground water are arsenate (As +5 ) and arsenite (As +3 ). In the last years, it has been known that a long-term intake of arsenic causes serious chronic symptoms in many countries, especially in Bangladesh, China, Mongolia and Taiwan. For this reason, the World Health Organization (WHO) has established the maximum contaminant level (MCL) in 10 µg/l [1]. Currently, in order to comply with the maximum contaminant level, numerous techniques are been studied (ion exchange, coagulation and flocculation, precipitation, adsorption and membrane technologies). Among the available technologies applicable for water treatment, membrane filtration has been identified as a promising technology to remove arsenic from water [2]. The aim of this work is to demonstrate through experimentation and optimization the technical and economic viability of removal arsenic (V) using reverse osmosis. The experimental facility is a flat-sheet membrane unit for reverse-osmosis at laboratory scale (SEPA CF II, GE Osmonics). The membrane cell can accommodate any 19 x 14 cm flat sheet membranes, resulting 140 cm 2 of effective membrane area. Different commercial reverse osmosis membranes have been evaluated for arsenic removal. The best results were obtained with the BE membrane (manufactured by Woongjin Chemical), since the permeate flow and rejection values are higher when compared to the rest of preselected membranes. Different membrane transport models [3] were tested to represent the performance of the BE membrane. Estimation of all the parameters appearing in the models is performed by Aspen Custom Modeler software [4]. Optimization of design and operation conditions was also executed. GAMS software was selected as optimization tool to manage the posed nonlinear programming (NLP) model using CONOPT3 solver. The General Algebraic Modelling System (GAMS) is a high-level modelling system for mathematical programming and optimization. It consists of a language compiler and a stable of integrated high-performance solvers [5]. References [1] World Health Organization. Guidelines for Drinking Water Quality, 3 rd edition, Geneva, Switzerland, (2008). [2] Uddin, M.T., Mozumder, M.S.I., Islam, M.A., Deowan, S.A., Hoinkis, J., Nanofiltration Membrane Process for the Removal of Arsenic from Drinking Water, Chem. Eng, Technol. 30, 9 (2007) [3] Soltanieh, M.; Gill, W.N. Review of reverse osmosis membranes and transport models, Chem. Eng. Commun., 12 (1981) [4] Abejón, R., Garea, A., Irabien A., Ultrapurification of hydrogen peroxide solution from ionic metals impurities to semiconductor grade by reverse osmosis, Sep. Purif. Technol., 76 (2010), [5] Brooke, A., Kendrick, D., & Raman, R. GAMS: A user s guide, release Washington, DC. (1998). GAMS Development Corporation.

80 POLY [2-(DIMETHYLAMINO)ETHYL METHACRYLATE]/ PUMICE COMPOSITE HYDROGEL: PREPARATION, CHARACTERIZATION AND APPLICATION IN RAPID ADSORPTION OF HUMIC ACID F. Taktak *, Z. İlbay *,** * Uşak University, Engineering Faculty, Department of Chemical Engineering, 64200, Uşak, Turkey, phone: , fax: ** Istanbul University, Engineering Faculty, Department of Chemical Engineering, Avcılar, Istanbul, Turkey, , fax: , 1.2. Separation Techniques We report the synthesis of novel poly [2-(dimethylamino) ethyl methacrylate] / pumice (PDMA / Pumice) composite hydrogel and its adsorptive features for humic acid (HA) through batch tests. FTIR results showed that pumice was well incorporated with the PDMA matrix. Scanning electron microscopy (SEM) was used in order to determine the morphology of composite hydrogel. The adsorption capacity increased with increasing ionic strength and initial HA concentration, while decreased with increasing ph and adsorbent dosage. HA adsorption onto PDMA / Pumice could be expressed well by Freundlich isotherm model and pseudo second order kinetic model. The highest adsorption capacity of the PDMA / Pumice gel was found to be per gram of hydrogel. At the same time, it was showed that high reusability without any considerable decrease after four cycles. Results show that it is possible to express that the PDMA / Pumice composite gel exhibited suitable adsorbent characteristics for the rapid removal of HA in water treatment process. Keywords Hydrogel composite, Adsorption mechanism, Humic acid, Kinetics, Isotherms

81 LIQUID-LIQUID EQUILIBRIA FOR TERNARY MIXTURE OF [BMIM + ][MESO 4 - ]+ N-HEXANE + AN ORGANIC COMPOUND INVOLVED IN THE KINETIC RESOLUTION OF RAC-2-PENTANOL C.L. Bolívar, M.G. Montalbán, R.Trigo, R.C. Sosa and G.Víllora * Department of Chemical Engineering. Faculty of Chemistry, University of Murcia (UMU), Murcia SPAIN.*Corresponding author. Tel.: ; Scientific Topic: Separation Techniques Ionic liquids(ils) have been shown to be good solvents for use in many chemical and biochemical processes. Applications include the usage of ionic liquids as potential solvents to perform the extraction of a wide diversity of compounds, however, the extraction of the compounds from the IL medium need to be further studied. The key to an effective (liquid + liquid) extraction process is the discovery of a suitable solvent. Recently, the use of ionic liquids as entrainer for extractive distillation, salt distillation of azeotropes or close boiling mixtures are considered in the industry, because of their extremely low vapor pressures, thermal stabilities and a high solvating capacity for organic, inorganic and organometallic compounds 1. In our group, previous works about the application of ILs in the separation processes [2,3] showed the growing interest in the equilibria data in order to increase the amount of physico-chemical data available for ternary mixtures involving ionic liquids and therefore to create a database of knowledge relating to their applicability in separation processes. The aim of this work was to evaluate the liquid-liquid equilibrium of four ternary systems containing the room temperature ionic liquid 1-butyl-3-methylimidazolium ethyl methylsulfate, [bmim + ][MeSO 4- ] + n-hexane + an organic compound involved in the racemic resolution of rac-2-pentanol (rac-2-pentanol, vinyl butyrate, rac-2- pentyl butyrate and butyric acid) at K and atmospheric pressure. The binodal curves and the tie lines compositions of the conjugate solutions has been obtained by means of refractive index (ionic liquid rich phase) and by gas cromatography (hexane rich phase) to determine their potential for selectively extracting organic compounds from a hexane reaction mixture. The tie line data have been correlated through the use of the NRTL (non-random two-liquids) equation, which provides a good correlation of the experimental data. In Figure 1, an example of binodal curve and tie lines obtained for the [bmim + ][MeSO 4- ]+n-hexane+butyric acid system is shown. References 1. Hwang I. C.; Park S. J., In S. J., 2013, Journal of Industrial and Engineering Chemistry, Article in Press, DOI /j.jiec Hernández-Fernández F. J., De Los Ríos A. P., Gómez D., Rubio M., Tomás-Alonso F, Víllora G., 2008, Fluid Phase Equilibria, 263, De Los Ríos A. P., Hernández-Fernández F.J., Gómez D., Rubio M., Víllora G., 2012, Separation Science And Technology, 47, Acknowledgements This work was supported by the European Commission (FEDER /ERDF) and Spanish MINECO (CICYT) through the project CICYT CTQ and by SÉNECA foundation 1195/PI/ Butyric Acid n-hexane [bmim + ][MeSO - 4 ] Figure 1. Binodal curve and tie lines for ternary mixture of [bmim + ][MeSO 4- ] + Butyric Acid + n-hexane at K

82 EVALUATION OF MOVING-BED ADSORPTION PROCESSES FOR POST- COMBUSTION CO 2 CAPTURE Bishan Meghani 1, Andrew Wright, Trevor Drage, Sean Rigby 1 The Energy Technologies Building, Innovation Park, Triumph Road, University of Nottingham, NG7 2TU, UK, 0044(0) Separation Techniques Due to the high regeneration energy demands for amine absorption processes for post-combustion CO 2 capture, alternative technologies such as solid adsorption processes have been considered. Other practical issues such as corrosion of equipment and loss of solvent can be avoided with adsorption processes. However, heat integration and fast heating or cooling of the adsorbent is difficult to perform in commonly used fixed-bed adsorption processes, in which adsorption and regeneration is performed successively in a vessel packed with adsorbent. In this study, the feasibility of moving-bed adsorption processes involving fluidised-bed, co-current and countercurrent systems is investigated. Three types of adsorbents that have been considered are supported amine material, activated carbon and zeolite 13X. A mathematical model based on material, energy and momentum balances for these moving-bed processes has been constructed. Numerical simulations for various configurations of moving-bed systems with and without heat integration have been performed. It is shown that the amine supported adsorbent in a counter-current adsorber and regenerator offers the highest CO 2 recovery and the lowest regeneration energy. In addition, this adsorbent is favourable for flue gas conditions above 40 C and containing moisture. Heat integration is essential to significantly reduce the regeneration energy below that required by amine absorption technologies. After carrying out a sensitivity analysis of important parameters affecting CO 2 recovery and regeneration energy, it is found that the adsorbent temperature into the adsorber and the kinetic constant have the greatest influence.

83 OPTIMIZATION OF ULTRASOUND-ASSISTED EXTRACTION OF ACTIVE COMPONENTS FROM SATSUMA MANDARIN (CITRUS unshiu MARC.) LEAVES via RESPONSE SURFACE METHODOLOGY Ş. İ. Kırbaşlar, Z. İlbay and S. Şahin Istanbul University, Engineering Faculty, Department of Chemical Engineering, Avcılar, Istanbul, Turkey, Tel: , Fax: , E- Polyphenols and flavonoids are of great significant by virtue of their antioxidant, antibacterial and antitumor activities. In this study, dried Satsuma mandarin (Citrus unshiu Marc.) leaves were supplied by Batı Akdeniz Tarımsal Araştırma Enstitüsü, (BATEM) Antalya, Turkey. Before being used, leaves were sieved whose average diameter were between mm. Ultrasonic homogenizer (Sonics VCX 750, 20 khz) was used to extract leaves. Mettler Toledo SevenEasy ph Meter was used to control desired ph values of solvent. Hydrocloric acid, water and sodium hydroxide were used to adjust ph levels at 4.7 and mg of dried leaves and 40 ml of solvent were sealed in extractor and ultrasonic probe was immersed in extractor. After the extraction procedure, the supernatant was filtered through 0.45 µm syringe filter and stored at -20 C until analysis for biochemical measurements. Response Surface Methodology (RSM) was used in order to assess extraction factors on the ultrasound-assisted extraction (UAE) of total polyphenol content (TPC) and total flavonoid content (TFC) from Satsuma mandarin leaves. Experimental conditions on responses (TPC, TFC and consumed extraction energy) were selected such as ph (4-10), extraction time (15-75 min), amplitute (30-70 %). The extraction parameters were investigated by using face-central composite design (FCCD) combined with RSM. Total phenolic content (TPC) and total flavonoid content (TFC) were determined by the Folin-Ciocalteu assay, aluminium chloride; respectively. Optimal parameters were found as 63 min, amplitute (%), ph= Under these conditions, the TPC, the TFC and consumed extraction energy (Joule) were , and 40114; respectively, which are in agreement with that of second-order polynomial models. Keywords: Optimization, total phenol content, total flavonoid content, Satsuma mandarin

84 INFLUENCE OF MODELING IN A DISTILLATION PROCESS DESIGN WITH NEW EXPERIMENTAL METHOD. APPLICATION OF A MULTIPROPERTY MODEL WITH MULTIOBJECTIVE OPTIMIZATION Pérez, E.; Ortega, J.; Palomar, J.; Fernández, L. Florido, X. Laboratorio de Termodinámica, Parque Científico-Tecnológico, Campus de Tafira. Las Palmas de Gran Canaria, 35017, Spain , 1.1 Applied Thermodynamics, Fluid Dynamics, Heat Transfer. The importance of different separation operations in the chemical industry, which is attributed the 60-80% of total system consumption, is beyond doubt. Therefore, the correct optimization of equipment and facilities related to those operations generates, in many cases, the difference between success and failure of a design, which entails important economic losses at best. Currently, there are tools in chemical engineering that allow a preliminary evaluation of the so-called process engineering. A group of these tools consists in techniques, ranging from simulation (Aspen, CHEMCAD, etc.) to tests of the process under study, by using small- or medium-scale plants. Simulation allows estimating process results based on input data obtained from experimentation. This is one of the handicaps that commercial simulators present, because they solve engineer s needs based on inputs that may not be suitable, which influence negatively on the design. Another problem is the lack of thoroughness of some of the behavior models, which causes errors that increase progressively, especially when extrapolations are used in the model. In this regard, it is necessary to feed the model with new and better data. EXPERIMENTATION/ DATABASE INPUT MATHEMATICAL MODELLING OUTPUT THEORETICAL AND EXPERIMENTAL SIMULATION For this work case, with ELV modeling, the equations and methods used in activity coefficients calculation, whose purpose is to reproduce equilibrium curves by gamma-phi formulation, are particularly sensitive. Commercial simulators use different models that can be programmed according to the nature of the studied system. Here it is intended to illustrate the effects that different models produce in new systems (recent and rigorous experimentation) and also to analyze the impact on a distillation column simulation and design. For practical interest, zeotropics and azeotropics systems have been differentiated considering that separation potential in each case is different. Correlative and predictive models (UNIFAC 1 and COSMO-RS 2 ) from the literature present results which are evaluated in this work by comparing them with the application and utility of an own model 3, 4 which allows the representation of multiple properties with the same set of parameters, using a multiobjective optimization procedure. [1] Weidlicht, U.; Gmehling, J. Ind. & Eng. Chem. Res., 1987, 26, [2] Klamt, A.; Eckert, F. Fluid Phase Equilib. 2000, 172, [3] Ortega, J.; Espiau, F.; Wisniak, J. Ind. & Eng. Chem. Res., 2010, 49, [4] Fernández, L.; Pérez, E.; Ortega, J.; Canosa, J.; Wisniak, J. Fluid Phase Equilib, 2013, 341,

85 EXTRACTION OF CHLOROGENIC ACID SHELL COFFEE USING SUPER CRITICAL TECHNOLOGY AND EVALUATION OF ANTIOXIDANT ACTIVITY Yasmin Lopera 1*, Zaida Lopera 2, Andres Ramirez 3, Juan Carlos Jaramillo 3 1: M.Sc Ing Química, Centro Tecnológico del Mobiliario-SENA. Medellín, Colombia 2: AOXLAB S.A.S. Laboratory of antioxidants and oxidative stress 3: Sanadores Ambientales * Contact: Topic : Separation techniques Coffee shell constitutes an important percent of the fresh weight of the coffee. Developing alternative technologies for efficiently using this abundant agroindustrial by-product represents an important challenge in tropical regions as Colombia. Alike coffee beans, offee pulp has been recognized as a potential source of phenolic acids with promising applications, from which chlorogenic acid (5-cafeoyl quinic acid, 5-CGA) has been found to be a major constituent (31 42%) 5-CGA fromcoffee aqueous extracts has been widely associated to a broad range of bioactivities Biological and pharmacological properties of 5-CGA are primary attributed to its capacity to donatehydrogen atoms of the phenolic ring to free radicals, thus inhibiting oxidation processes. However, the antioxidant properties an technological applications of Colombian coffee shell are unknown. n this work the propose is obtain chlorogenic acid using supercritical fluids technology for the extraction of coffee antioxidants compounds using agroindustrial resources for the future development of medical applications. Samples obtained from the supercritical fluids with CO2, the extraction conditions were 45 C and 350 bar at diferent times 2, 3 y 4 h. The reaction mixture were dissolved in methanol and filtered through a 0.45_m syringe filter (Millipore). The analyseswere performed using a HPLC systemconsisting of a Hitachi L-6200A intelligent pump, a Hitachi L-7200 autosampler, and a Hitachi L-4500 diode array detector.the chromatographic separations of ester and chlorogenic acid were done by a reverse-phase C18 column (250mm 4.6mm, 5_m particle size, Hyperclone, Phenomenex). The temperature of the column was set at 35 C and the injection volume was 20_l. Gradient elution was employed with a mobile phase consisting of acetonitrile (A) and 1% glacial acetic acid in water (B). The flow rate was kept constant at 1.0ml/min for a total run of 55 min. The systemwas run with a gradient program as follow: 0 10% B in 15 min, 10 20% B in 10min, 20 40% B in 5 min, % B in 10min, maintaining 100% B for 5min, and returning to 0% B isocratic for 5 min as post-run for equilibration of the column. Some of the results obtained are shown in Table 1 and 2. Table 1. Antioxidant activity of coffee shell

86 Table 2. Chlorogenic content of samples of supercritical fluid extraction *CQA : 4 acidos-cafeoíl-quínico FQA: 3 acidos feruoíl-quínico dicqa: 6 acidos di-cafeoilquínico

87 REMOVAL OF NICKEL (II) FROM AQUEOUS SOLUTIONS BY MODIFIED GRAPHEN OXIDE Elif Caliskan Salihi 1,2,*, Jiabin Wang 1 and Lidija Siller 1 a Newcastle University, School of Chemical Engineering and Advanced Materials, Newcastle upon Tyne, NE1 7RU, United Kingdom b Marmara University, Faculty of Pharmacy, Department of Basic Pharmaceutical Sciences, 34668, Haydarpasa, Istanbul, Turkey , Separation techniques Heavy metal pollution in the aquatic environment is a serious environmental problem. In the recent years, several methods have been extensively studied and adsorption is now recognized as an effective and economic method for the treatment of waste waters contaminated with heavy metals. The adsorption process offers flexibility in design and operation as well as producing high-quality treated effluent in many cases (1). Nickel (Ni) is the 24th most abundant element in the Earth s crust and used in many industrial and commercial applications including electroplating, batteries manufacturing, forging, metal finishing and mining; which leads to environmental pollution by Ni. Exposure to highly Ni-polluted environments has the potential to produce various pathological effects in humans; such as contact dermatitis, lung fibrosis, cardiovascular and kidney diseases and cancer (2). In this context, the objective of this study is to investigate graphen oxide (GO) for the removal of Ni (II) from aqueous solutions as a function of time, solute concentration, ph and adsorbent concentration; and modification of graphen oxide surface using SDS (sodium dodecyl sulphate) for enhanced Ni (II) removal. The results found showed that: GO produced is an effective adsorbent for the removal of Ni (II) from aqueous solutions and has the potential to be used for the treatment of waste waters or drinking waters. The modification of GO with SDS (GO-SDS) dramatically increases the uptake of Ni (II), although it does not change the time to reach equilibrium. Removal of Ni (II) from aqueous solutions onto GO/GO-SDS is highly sensitive to ph changes. The driving force of the adsorption of Ni (II) is electrostatic attraction and Ni (II) adsorped on the GO surface chemically besides ion exchange. References (1) F. Fu, Q. Wang; Removal of heavy metal ions from wastewaters: A review; Journal of Environmental Management; 92 (2011) 407. (2) V. Coman, B. Robotin, P. Ilea; Nickel recovery/removal from industrial wastes: A review; Resources, Conservation and Recycling ; 73 (2013) 229.

88 EFFECT OF PORE STRUCTURE AND DESORPTION PRESSURE ON ADSORPTION BREAKTHROUGH BEHAVIORS OF CARBON DIOXIDE/NITROGEN MIXTURE IN VARIOUS KINDS OF ZEOLITE PELLETS J. -H. Moon #1, J. SIM #1, J. H. Park #1, Y. C. Park #1 and B. -M. Min #1 #1 Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon , Korea, Tel : , FAX : , Scientific Topic : 1.2 Separation Techniques The effect of pore structure and desorption pressure on CO 2 /N 2 breakthrough behaviors for 4 different adsorbents was studied at a fixed bed reactor. Commercial zeolite 3A, 4A, 5A, and 13X pellets were used as adsorbents. Cyclic operations were executed with varying desorption pressure from vacuum (0 bar) to 3 bar while other conditions such as adsorption step pressure (3 bar), temperature (293 K), composition (CO 2 /N 2 =10:90 vol%) and flow rate (400 sccm) were fixed at constant values. Each adsorption and desorption step was set as 80 min, which totaled up to 160 min per a cycle. 5 cycles with adsorption and desorption steps were run overall. After the experiment, breakthrough time, saturation time, and adsorption amount were measured and compared in order to find an optimum adsorbent and a proper operating condition for a post combustion CO 2 capture process. Fig. 1 Schematic diagram of fixed bed system

89 DEVELOPEMENT OF COUNTRY SPECIFIC GREENHOUSE GAS EMSSION FACTOR FOR ENERGY SECTOR IN SOUTH KOREA J.-H. Moon#1, J. -S. Lee #1, G. -H. Han, #1 Y. C. Park #1, and B. -M Min #1 #1 Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon , Korea, Tel : , FAX : , Scientific Topic : 1.2 Separation Techniques Greenhouse gas emission factor (EF) for the energy sector in Korea has been developed for understanding current status and preparing mandatory reduction. In order to ensure the objectivity, accuracy and reliability of the methodology, EF were developed in consideration of the international guide line, IPCC G/L (2006). Tier 3 leveled GHG emission factors were calculated on the basis of CH 4 and N 2 O contents from the selected boiler systems for the energy and the industrial processes. We executed i) comparison analysis with IPCC G/L, ii) uncertainty analysis and iii) expert validation. Then the EF and the its making procedure were reported (submitted) to the Korea government and EFDB (emission factor data base). In this conference, we will present the correct methodology for developing EF and the trend of GHG emission in Korea. Table GHG emission prospect in Korea 2005 (10 3 tco2 eq.) 2020 (10 3 tco2 eq.) 2020 (emission rate, %) Energy (fuel combustion) 467, , % Non-Energy 100, % - Industrial process 64, , % - Agriculture, Livestock 20,896 18, % - Waste 15,487 13, % Summation 568, , %

90 THE CATALYTIC CONVERSION OF PROPYLENE OXIDE TO PROPYLENE CARBONATE BY METAL-ORGANIC POROUS MATERIALS H. KIM #1, J. -H. Moon #1, D. H. Chun #1 and Y. C. Park #1 #1 Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon , Korea, Tel : , FAX : , Scientific Topic : 1.2 Separation Techniques Propylene carbonate is widely used as electrolytes in lithium-ion batteries, raw materials for polycarbonates and polar aprotic solvents. The considerable effort has been devoted to the synthesis of propylene carbonate by CO 2 fixation. During past decades, therefore, many CO 2 fixation catalysts have been synthesized and investigated. Metal-organic porous materials are porous frameworks with pores and channels self-assembled from metal ions and organic building units. Unsaturated metal centers of metal-organic porous materials play an important role as a Lewis acidic site for the synthesis of propylene carbonates from CO 2 and propylene. In this presentation, we will introduce the synthesis of metal-organic porous catalysts and their catalytic activity for CO 2 fixation. Details of the work will be presented. Fig. 1 Schematic diagram of CO 2 fixation

91 THERMAL SAFETY OF AN EXOTHERMIC LIQUID LIQUID REACTION SYSTEM H. Rakotondramaro #1, J. Zheng #1, J. Wärnå #3, L. Estel #1, B. Taouk #1, T. Salmi #3, C. Crua #2, S. Leveneur #1 1. LSPC-Laboratoire de Sécurité des Procédés Chimiques, INSA Rouen, BP08, Avenue de l Université, Saint-Etienne-du-Rouvray, France; fax: School of Engineering, Faculty of Science and Engineering, The University of Brighton, Brighton BN2 4GJ, UK 3. Laboratory of Industrial Chemistry and Reaction Engineering, Process Chemistry Centre, Åbo Akademi University, Biskopsgatan 8, FI Åbo/Turku, Finland. Chemical Engineering Fundamentals: Chemical Reaction Engineering: Chemical Reactors Assessment of thermal risk for chemical process is not an easy task. Indeed, one should know kinetics of synthesis reactions but also of secondary reactions, which occur at higher temperature and are more temperature sensitive. In this study, different accident scenarii based on cooling failure and agitator system failure were studied and modeled. Thermal assessment of vegetable oil epoxidation was studied. Epoxidized vegetable oils are key intermediate for the valorization of carbon dioxide into high added value products. One of the greenest way to produced such intermediate is the Prileschajew method. In this method, peroxycarboxylic acid (PCA) is produced from hydrogen peroxide and caraboxylic acid in the aqueous phase, then PCA transfers to the organic phase to epoxidize the unsaturation. During this liquid liquid reaction system, several exothermic reactions occur in both phases. Thus, mass and energy balance should be coupled. Epoxidation of oleic acid by peroxyformic acid was used in this study [1]. Experiments were performed at different initial temperatures, concentrations and formic acid feeding rate in a calorimetric reactor in semi-batch mode and under isoperibolic mode. Different temperature probes were installed in the reactor system. A deep investigation of thermal effects was performed under normal condition in order to propose a mathematical model in case of cooling or agitation failure. Figure 1 shows that in case of cooling failure and under normal condition. One can notice that under cooling failure, the energy released is more important. This project was financially supported by E3C3. The E3C3 project (n 4274) was selected by the European INTERREG IV A France (Channel) England Crossborder Cooperation Programme, co-financed by ERDF. 110 Normal condition Temperature [ C] Reactor temperature Cooling failure Jacquet temperature Reactor temperature Jacket temperature 60 Cooling failure Jacket temperature Time [min] Figure 1. Experiments carried out under normal condition and under cooling failure. References 1. Interaction of thermal and kinetic parameters for a liquid liquid reaction system: Application to vegetable oils epoxidation by peroxycarboxylic acid; S. Leveneur et al.; Journal of The Taiwan Institute Of Chemical Engineers

92 EFFECT OF BINDER IN THE PROCESS OF DME CONVERSION TO PROPYLENE USING A ZSM-5 ZEOLITE CATALYST P. Pérez-Uriarte, A. Ateka, E. Epelde, M. Gamero, J. Bilbao, A.T. Aguayo Department of Chemical Engineering, University of the Basque Country, P.O.Box 644, Bilbao, Spain, tel: , Topic: 1.3. Chemical Reaction Engineering INTRODUCTION DME can be regarded as one of the possible key agents in the conversion of nonpetroleum feedstock to motor fuels and valuable chemical products, such as olefins [1]. DME transformation into propylene (DTO process) is an alternative to the MTP (Methanol to Propylene) process. The interest lies in the prospects for DME synthesis from sources alternative to oil, with lower thermodynamic limitations in comparison to the synthesis of methanol and with a higher capability for co-feeding CO 2 with syngas [2, 3]. In this work the effect of binder in the process of transformation of DME to propylene (required to use the catalyst in a fluidized bed) has been studied with the aim of maximizing the selectivity of propylene and of other light olefins. EXPERIMENTAL For that purpose, a catalyst based on a HZSM-5 zeolite of SiO 2/Al 2O 3 = 280 ratio (Zeolyst Int.) with two different binders has been synthesized. The zeolite has been agglomerated with boehmite or with bentonite that confer a matrix with meso- and macropores to the catalyst particle which contribute to attenuating deactivation. The experiments were carried out in a fixed bed reactor at atmospheric pressure, at 350 ºC, a space time of 1.25 g zeolite h (mol C ) -1 and time on stream of 4h. The products were continuosly analyzed in a gas cromatograph (Micro- GC Agilent CP-490). It is noteworthy the thermal cracking of DME above 400 C, with formation of CH 4 and CO. RESULTS Figure 1a shows an increase of DME conversion and olefins yield at zero time with boehmite like a binder. On the other hand, Figure 1b shows that catalyst deactivation at 350 ºC is very slow for both boehmite and bentonite, which is an advantage over the SAPO-34 catalyst, that although it is more selective to propylene, it deactivates considerably faster [4, 5]. S i (%) C2H4 a) C3H6 60 C4H8 80 b) Paraffins C2-C4 BTX 50 C HZ-280 boehmite HZ-280 bentonite X DME (%) X DME (%) Figure 1. Effect of blinder on DME conversion and product yields at zero time (a) and the evolution with the time on stream of DME conversion at 350 ºC (b). The amount of coke deposited on the catalyst agglomerated with boehmite is lower than 1.6 wt %; in addition the catalyst is regenerated by combustion of coke with air at 550ºC. REFERENCES [1] Batova, T.I.; Khivrich, E.Kh.; Shirobokova, G.N.; Kolesnichenko, N.V.; Pavlyuk, Yu.V.; Bondarenko, G.N.; Petr Chem, 53, 383 (2013). [2] G.A. Olah, A. Goeppert, G.K.S. Prakash, J. Org. Chem., 74, 487 (2009). [3] A.T. Aguayo, J. Ereña, D. Mier, J.M. Arandes, M. Olazar, J. Bilbao, Ind. Ing. Chem. Res., 46, 5522 (2007). [4] S-G. Lee, H-S. Kim, Y-H. Kim, E-J. Kang, D-H. Lee, C-S. Park, J. of Ind. and Eng. Chemistry, 61 (2014). [5] Y. Cui, Q. Zhang, J. He, Y. Wang, F. Wei, Particuology, 468, 11 (2013) Time (min) HZ-280 boehmite HZ-280 bentonite

93 DEACTIVATION OF BIFUNCIONAL CATALYSTS FOR THE SYNTHESIS OF DIMETHYL ETHER IN A SINGLE STAGE M. Ibáñez, A. Ateka, J. Albo, A.T. Aguayo, J. Ereña, P. Castaño Department of Chemical Engineering, University of the Basque Country (UPV-EHU), PO Box 644, Bilbao, Spain Topic: 1.3. Chemical Reaction Engineering. 1. INTRODUCTION. The synthesis of dimethyl ether (DME) in a single stage integrates methanol synthesis and dehydration of that. The advantage of the single step is that the operation temperature could be raised avoiding the thermodynamic limitations of the methanol synthesis while enabling using CO 2 as feedstock. The catalysts consist in a metallic function and an acidic function with low acidity to prevent the formation of hydrocarbons [1]. In this work we have studied the deactivation origin and the influence of metallic function (Cu-Zn-X) with X= Al 2 O 3, ZrO 2, MnO on the deactivation of catalysts. 2. EXPERIMENTAL. The bifunctional catalysts prepared by physical mixture of metallic and acid functions, CuZnAl 2 O 3 /SAPO-18 (CZA); CuZnZrO 2 /SAPO-18 (CZZ); CuZnMnO/SAPO-18 (CZM), which have been used in the synthesis of DME (275 C, 30 bar, W/F 0 =10.18 g cat h(mol C ) -1, 5 h), feeding synthesis gas (H 2 /CO=3). The deactivated catalysts have been characterized using a set of different analytical techniques (TPO, FTIR, FTIR-TPO/MS ). 3. RESULTS. Catalysts with MnO and ZrO 2 are significantly more selective (DME selectivity is greater than 90 %) than the one with Al 2 O 3. The results of metal initial dispersion (D i ) for fresh and final dispersion (D f ) for deactivated catalysts are summarized in Table 1. It is noteworthy that the catalysts with MnO and ZrO 2 have a higher initial metal dispersion, lower coke content and attenuate the effect of blocking the metallic centers by coke. Table 1. Properties of fresh and deactivated catalysts. CZA CZZ CZM Di (%) Df (%) Cc (%) Figure 1 shows the FTIR spectra for the spent catalysts. The intensities of IR vibrational bands have been plotted, each one has been assigned to the vibration of molecular bonds in the coke as follows [2]: 1580 cm -1, coke or polyaromatics condensed (PAC); 1610 cm -1, olefins; 2930 cm -1, -CH and -CH 2 ; and 2960 cm -1, -CH 3. It is noteworthy that the bands of highest intensity are aliphatic groups. Three fractions of coke have been identified by TPO: i) over the metal centers (by degradation of methoxy ions), ii) in the interface of these and iii) in the SAPO- 18 channels and inside these crystals. Intensity (a.u.) PAC Dienes -CH 2 and -CH -CH 3 CZA CZZ CZM Figure 1. Intensities of several characteristic vibrational bands corresponding to cited catalysts. 4. REFERENCES. [1] Ereña, J., Sierra, I., Aguayo, A.T., Ateka, A., Olazar, M. Chem. Eng. J., 174, 660 (2011). [2] Ibáñez, M., Artetxe, M., Lopez, G., Elordi, G., Bilbao, J., Olazar, M., Castaño, P., Appl. Catal. B: Environ., , (2014). 5. ACKNOWLEDGMENT. The financial support of this work was undertaken by the Ministry of Science and Education of the Spanish Government (Projects CTQ ; CTQ ) and of the Basque Government (Projects IT748-13; BFI09-69; BFI ).

94 Self-condensation of Cyclohexanone using Amberlyst-15 as catalyst. D. Lorenzo, E. Simón, A. Santos, A. Romero Chemical Engineering Department. Universidad Complutense de Madrid, Av. Complutense s/n, Madrid, Spain TOPIC: 1.3 Chemical Reaction Engineering. 1. Introduction Cyclohexanone is an important intermediate of the chemical industry. It is mainly used to produce caprolactam and adipic acid, which are used as precursors of nylon fibers. Furthermore, cyclohexanone takes part in the 2-(1-cyclohexen-1-yl) cyclohexanone and 2- cyclohexylidencyclohexanone production, that are important intermediates in the synthesis of 2-phenylphenol (OPP). This compound can be used as biocide in different fields such as agriculture, fine chemistry or health care and household industries. On the other hand, OPP is employed to preserve fruits and vegetables, to control different pests as well as to disinfect surface materials. Additionally, it is a suitable preservative compound in cosmetic, plastic, textile and paper industries (Lorenzo et al 2013). The scope of this work is the development of a kinetic model capable of explaining the influence of temperature, catalyst concentration and presence of water in the reactor media. 2. Experimental Different experimental setups were used to analyze the influence of the variables. First of all, the stability of Amberlyst-15 was studied in a fixed bed reactor meanwhile the kinetic model was obtained with two kinds of batch reactors. The first one worked at vacuum pressure with continuous removing of formed water. In the second configuration, reactions were carried out at higher pressure conditions in order to study the water effect. Finally, the obtained kinetic model was validated in the fixed bed reactor. 3. Results Experiments carried out in the fix bed reactor reveal that the high stability of Amberlyst 15 allows to work under continuous operation conditions. so a kinetic model is very useful to design a reactor to produce 2-(1-cyclohexen-1-yl) cyclohexanone and 2- cyclohexylidencyclohexanone as intermediate of OPP. On the other hand, results obtained in batch reactors show that an increasement of the reaction temperature or catalyst concentration produces a higher dimer and by-product formation. If higher reaction conditions are applied a maximum of the dimer concentration is achieved; it is followed by an important decrease due to the trimer production. Moreover, it can also be observed that the self-condensation of cyclohexanone is highly affected by the presence of water in the media. It is due to the inhibitory effect of water over the system, which modifies the kinetic constants and products distribution. Furthermore, an equilibrium stage is observed and it is due to the reversibility of the cyclohexanone self-condensation (Lorenzo et al., 2013). All these effects can be explained with the kinetic model developed in this work. D. Lorenzo, A. Santos, E. Simon, A. Romero, Kinetic of Alkali Catalyzed Self-Condensation of Cyclohexanone, Ind. Eng. Chem. Res., 52 (2013) ACKNOWLEDGEMENTS The authors acknowledge financial support provided from FPU grant with reference AP from the Spanish Ministry of Education, Culture and Sports.

95 NANOESTRUCTURED Co 3 O 4 CATALYSTS DEVELOPMENT FOR CHLORINATED VOLATILE ORGANIC COMPOUND OXIDATION Jonatan González-Prior, Maitane Gabilondo, Beatriz de Rivas, Rubén López-Fonseca, Jose Ignacio Gutiérrez-Ortiz*. Department of Chemical Engineering. Faculty of Science and Technology. University of Basque Country (UPV/EHU). P.O. 644 E48080 Bilbao. Spain. Phone: Fax: Chemical Reaction Engineering: Catalysis In recent years the cobalt spinel, Co 3 O 4 has received great attention for removal of volatile organic compounds (VOCs). However, this material suffers from high temperature sintering with consequent loss of activity. Therefore, this work focuses on the study of the preparation of nanocrystalline cobalt oxides with diverse morphology to improve its catalytic properties and its subsequent application in the removal of 1,2- dichloroethane (DCE). Thus, we have developed three cobalt spinel catalysts, trying to grow crystals in different dimensions. Thus a catalyst was synthesized growing the crystal in one dimension, forming a rod (Co-R), another that grows in two dimensions forming a sheet (Co-S) and the latter in three directions, forming a cube (Co-C). It has also been prepared an oxide by direct calcination of the cobalt salt (Co-DC). The materials were characterized by N 2 adsorption-desorption, X-ray diffraction, scanning electron microscopy and temperature-programmed reduction with H 2. The oxidation reaction was carried out in a fixed bed reactor, with a GHSV = 30,000 h -1 (1,000 ppm of DCE in air) and the analysis of the exhaust gases was carried out with an online gas chromatograph (DCE, CO, CO 2 ), volumetry (Cl 2 ) and potentiometry (HCl). The textural and structural properties of oxides are shown in Table 1. As can be seen, the structuring of the samples significantly changes the phisical properties of the oxides. Thus, nanorods synthesis only slightly reduces the crystal size of the sample but does not improve the active area available for oxidation. However, the formation of sheets or cubes substantially improved the active surface of the oxides, reducing crystal size in both cases. Moreover, a gradual improvement of these properties is observed as obtained morphology develops in more dimensions, obtaining an increase of the surface as follows: Co-R < Co-S < Co-C. On the other hand, a partial reduction of the oxide is observed at low temperatures, especially for the samples Co-S and Co-C, suggesting active species with high mobility lattice oxygen. These two samples also have greater reduction properties, whereas the rod-shaped structure has the highest temperature reduction of cobalt species. Table 1. Textural and structural properties of the synthesized catalysts Catalyst Area, m 2 /g Pore diameter, Å Crystal size, nm Co-R 5, Co-S Co-C Co-DC 5, The catalytic oxidation of DCE is shown in Figure 1. Nanostructured oxides show higher activity than the Co 3 O 4 prepared by direct calcination. Additionally, the sample which presents the best activity is the sample Co-C. In fact, the activity is closely related to the physical properties of the oxides, as the order of activity is the same as the BET surface area. Furthermore, the activity in the samples Co-S and Co-C is also enhanced by their high mobility lattice oxygen. Therefore, a compromise between the active surface and reducibility of the samples is necessary since an improved reduction capability alone does not guarantee better activity during the oxidation reaction. The main reaction products are CO 2, HCl Figure 1. Activity of the Co 3 O 4 samples and Cl 2, where CO is not detected at any temperature, because of the oxidation power of the cobalt oxide. At 500 ºC no other chlorinated compounds are detected for the sample CO-C, although they appear for the other samples as their activity go down for the samples Co-S, Co-R and Co-DC. [1] L. Hu, Q. Peng, Y. Li, J. Am. Chem. Soc. 2008, 130, 16136

96 PROCESS OPTIMIZATION STUDIES OF NH 3 -SCR OF NOx OVER Ba-CeO2-MnOx MIXED OXIDE CATALYST BY RSM Aligholi Niaei 1 a, Seyed Mahdi Mousavi a,b, Dariush Salari a, Parvaneh Nakhostin Panahi c a Department of Chemical Engineering & Applied Chemistry, University of Tabriz, Tabriz, Iran. b Faculty of Chemistry, University of Kashan, Kashan, Iran. C Department of Chemistry, University of Zanjan, Zanjan, Iran. KEYWORDS: NOx; Cerium Mixed Oxide; Process parameters; Design of Experiments; Optimization. The studies of the NOx emission control are one of the most important issues in the environmental protection, because of various human and environment problems such as respiratory diseases, acid rain, photochemical smog [1, 2]. The selective catalytic reduction of NOx with ammonia (NH 3-SCR) is a well-known and effective technology for NOx emission control [3-5]. In recent years, ceria mixed oxide catalysts have been developed for NOx reduction, due to theirs good oxygen storage and release capabilities as well as redox properties [6-8]. The results of our primary studies revealed that the CeO 2 -MnO x mixed oxide has the best performance than other Ce-M (M=Fe, Co, Ni, Cu) mixed oxides and Ba loading enhanced its performance [9]. In the present research, design of experiments (DOE) is used to the studies of process parameters on performance of Ba-CeO 2 -MnO x mixed oxide in NH 3 -SCR. The CeO 2 -MnO x mixed oxide with Mn/(Ce+Mn) molar ratio of 0.25 was prepared by the sol-gel method. Barium was loaded on the CeO 2-MnO x mixed oxide by wetness impregnation method [9]. The loading amount of Ba was fixed to the molar ratio of Ba/(Ce+Mn) = The NH 3- SCR tests was performed in a fixed bed reactor with a feed gas mixture consisting NO, NH 3, O 2 and Ar as balance (total flow rate of 200 cm 3 min -1 ). Different GHSV were obtained by changing the volume of catalyst bed. A GC (SHIMADZU model 2010 plus) equipped with a Molecular sieve (HP- Molesieve) column was utilized to measure the concentration of N 2 and N 2 O. NO conversion and N 2 selectivity were calculated using the following equations: N 2 N 2O out NO Conversion % 100 (1) N 2 out Selectivity % NO N N O in N 100 (2) 2 A response surface methodology (RSM) combined a CCD with α = ±2 is utilized to model and optimize the effect of process parameters, including concentration of O 2 (vol. %), NH 3/NO ratio in the gas feed, gas hourly space velocity (GHSV) and reaction temperature ( C) on the NO conversion and N 2 selectivity as responses. The actual and coded values of independent variables are shown in table out 1 Corresponding author: Prof. of Chemical Engineering, Phone: , Fax: ,

97 Table 1. The levels of the independent operation variables in actual and coded value Independent variables Ranges and levels -2 (-α) (+α) Concentration of O 2 (vol. %) (X 1) NH 3 /NO ratio (X 2 ) GHSV (h -1 ) (X 3 ) Reaction temperature ( C) (X 4) A total of 31 experiments were designed by using CCD. A regression model for both responses (NO conversion (Y 1 ) and N 2 selectivity (Y 2 )) was obtained by using the method of least square (MLS) based on the experimental results. These regression models are used to describe the behavior of the responses relative to studied process parameters. The ANOVA of the generated regression models confirmed that the models were highly significant, as the F-values for Y 1 and Y 2 were found to be and 26.06, respectively. The R 2 values for both generated model were greater than 0.9, confirming the capability of RSM model in fitting the obtained experimental data. Figure 1: Pareto graphic analysis of: (a) NO conversion, (b) N 2 selectivity The Pareto analysis calculates the percentage effect of each factor on the response, using the generated regression model. The Pareto graphic analysis for both responses is shown in Fig. 1. According to the generated RSM models, GHSV had largest effect on the NO conversion, while it was an insignificant parameter on the N 2 selectivity in design space. Also NH 3/NO ratio was most effective parameter on the N 2 selectivity. The perturbation plot for Y 1 and Y 2 is shown in Fig. 2. It can be seen that GHSV has the linearly negative effect on the NO conversion and the relatively flat line of GHSV indicated that this variable has insignificant effect on the N 2 selectivity.the NO conversion was found to increase linearly in proportion to the reaction temperature. The O 2 concentration and NH 3 /NO ratio had curvature effects in the design space. The O 2 concentration has a quadratic effect, so that the NO conversion increased with increasing of O 2 concentration, but once it exceed to 5 vol. %, the NO conversion showed nearly no change. To determine the optimum values of process parameters in NH 3-SCR, optimization of multiple responses was performed by the maximization of the desirability function. The optimum values of process variables and related responses with 0.87 for the desirability are shown in table 2.

98 Figure 2: Perturbation plot for Y 1 and Y 2 response (A: %O 2, B: NH 3/NO, C: GHSV, D: temperature) Under the optimum conditions: 4.75 vol.% O 2, NH 3 /NO ratio of 0.9, GHSV of h -1 and C, the predicted values for NO conversion and N 2 selectivity over Ba-CeO 2 -MnO x were 96.47% and 93.96%, respectively. Verification experiment performed at the predicted conditions and experimental response was close to the predicted value, confirming the validity and adequacy of the quadratic models developed by CCD. Table 2. NH 3-SCR performance of Ba-CeO 2-MnO x catalyst at optimum values of process parameters Optimum condition NO conversion (%) N2 selectivity (%) O 2 (vol. %) NH 3/NO ratio GHSV (h -1 ) Reaction temperature ( C) Predicted Observed Predicted Observed References [1] S. Roy, M.S. Hegde and G. Madras, Catalysis for NOx abatement, Appl. Energ. 86 (2009) [2] A.A. Basfar, O.I. Fageeha, N. Kunnummal, Electron beam flue gas treatment (EBFGT) technology for simultaneous removal of SO2 and NOx from combustion of liquid fuels, Fuel 87 (2008) [3] M. Kang, E.D. Park, J.M. Kim and J.E. Yie, Manganese oxide catalysts for NOx reduction with NH3 at low temperatures, Appl. Catal., A 327 (2007) [4] P. Nakhostin Panahi, D. Salari, A. Niaei and S.M. Mousavi, NO reduction over nanostructure M-Cu/ZSM-5 (M: Cr, Mn, Co and Fe) bimetallic catalysts and optimization of catalyst preparation by RSM, J. Ind. Eng. Chem. 19 (2013) [5] S.M. Mousavi, A. Niaei, D. Salari, P.N. Panahi and M. Samandari, Modeling and Optimization of Mn/Activate Carbon Nanocatalysts for NO Reduction: Comparison of RSM and ANN Techniques, Environ. Technol. 34 (2013) [6] H. Xu, Q. Zhang, C. Qiu, T. Lin, M. Gong and Y. Chen, Tungsten modified MnOx CeO2/ZrO2 monolith catalysts for selective catalytic reduction of NOx with ammonia, Chem. Eng. Sci. 76 (2012) [7] J. Wang, M. Shen, J. Wang, M. Cui, J. Gao, J. Ma and S. Liu, Preparation of FexCe1-xOy solid solution and its application in Pd-only three-way catalysts, J. Environ. Sci. 24 (2012) [8] W.J. Hong, S. Iwamoto and M. Inoue, Direct NO decomposition over a Ce Mn mixed oxide modified with alkali and alkaline earth species and CO2-TPD behavior of the catalysts, Catal. Today 164 (2011) [9] S.M. Mousavi, A. Niaei, M. J. Illán Gómez D. Salari, P.N. Panahi, V.Abaladejo-Fuentes, Characterization and activity of alkaline earth metals loaded CeO 2 -MOx (M = Mn, Fe) mixed oxides in catalytic reduction of NO, Materials Chemistry and Physics, 143 (2014)

99 EFFECT OF THE THERMAL TREATMENT AND THE METAL LOADING ON THE PROPERTIES OF METAL-CONTAINING CATALYSTS MADE FROM HYDROTALCITE S. GARCÉS, S. KORILI, A. GIL * Department of Applied Chemistry, Public University of Navarra, Edificio Los Acebos, Campus Arrosadia, E Pamplona, Spain *Corresponding author, tel. (fax): , Topic: 1. Chemical Engineering Fundamentals Chemical Reaction Engineering. Catalyst. Metal mixed oxides prepared by calcination of hydrotalcite like precursors have gained increasing importance in many catalytic processes as in the synthesis of hydrocarbons, reforming of methanol and methane, oxidation of VOCs, elimination of NO x, and decomposition of N 2 O [1-3]. Interesting features of these materials are their basic properties, the dispersion of the active phases, the high specific surface areas, the thermal stability and the mixed oxides homogeneity. This study is focused on the effect that can have the thermal treatment of the support prior to the impregnation by the metals, and the nature and loading of the metal oxides, on the properties of the final catalysts. The catalysts were prepared from a commercial hydrotalcite, Mg 6 Al 2 CO 3 (OH) 16 4H 2 O (Aldrich). Supported metal catalysts were prepared by wet impregnation of the fresh and the calcined support with solutions of cobalt (Co(NO 3 ) 2 6H 2 O, Panreac), iron (Fe(NO 3 ) 3 9H 2 O, Riedel-deHaën) and nickel salts (Ni(NO 3 ) 2 6H 2 O, Panreac). The catalysts were dried at 100 ºC for 16 h before being calcined in air at 500 ºC for 4 h to obtain the final supported catalysts. The nominal metal oxide loading of the catalysts was between the 0 and 15 wt.%. Metal content was determined by inductively coupled plasma optical emission spectroscopy (ICP- OES) using a Varian Vista-MPX instrument. Nitrogen adsorption experiments were performed at -196 ºC on a static volumetric apparatus (Micromeritics ASAP 2010 adsorption analyser). The samples were previously degassed for 24 h at 200 ºC at a pressure lower than Pa. X-ray diffraction (XRD) patterns were obtained using a Siemens D-5000 diffractometer with Ni-filtered Cu Kα radiation. The intensities were measured over 2 theta range 4-90º. Temperature programmed reduction (TPR) experiments were carried out on a Micromeritics TPR/TPD 2900 instrument. The samples were pre-treated with N 2 at 200 ºC for 2 h, at a heating rate of 10 ºC/min, under a flow of 30 cm 3 /min. The TPR tests were carried out from room temperature up to 1000 ºC, at a heating rate of 10 ºC/min, under a total flow of 30 cm 3 /min (5% H 2 in Ar, Praxair). Pulse NH 3 chemisorption experiments for acidity measurements were performed on the same instrument as in TPR analysis. The samples were pretreated at a heating rate of 10 ºC/min under a N 2 flow of 30 cm 3 /min to 400 ºC for 4 h and cooled at 70 ºC in the same stream. Ammonia pulses (0.5 cm 3 ) were injected at 70 ºC until the area of consecutive eluted pulses was constant. The specific surface area of the support after thermal treatment was 220 m 2 /g. The metal catalysts, except those with high metal loading, had also high surface area, a fact that can be related to the mild method employed in the synthesis of the samples. The phases detected by XRD were Co 3 O 4, Fe 2 O 3, NiO, and mixed phases of MgO and spinel structures, results that were confirmed from the TPR measurements. The temperatures of reduction of these phases present in the samples were higher than the ones of the metal oxides used as references, indicating the existence of metal-support interactions. The acidity of the support was favoured by the heat treatment, while the acidity of the metal catalysts decreased with increasing metal loading. Acknowledgements. This work was supported by the Spanish Ministry of Economy and Competitiveness (MINECO) through the project PRI-PIBAR S. Garcés acknowledges financial support from Public University of Navarra through a PhD fellowship. References [1] G. Gennequin, S. Siffert, R. Cousin, A. Aboukaïs. Top. Catal., 52 (2009) 482. [2] G. Fornasari, M. Gazzano, D. Matteuzzi, F. Trifiro, A. Vaccari. Appl. Clay Sci., 10(1995) 69. [3]. Z. Jiang, J.Yu, J. Cheng, T. Xiao, M. O. Jones, Z. Hao, P. Edwards. Fuel Processing Technology, 91 (2010) 97.

100 2,5-DIMETHYLFURAN OXIDATION AND ITS INTERACTION WITH NO. Katiuska Alexandrino, Ángela Millera, Rafael Bilbao, María U. Alzueta. Aragón Institute of Engineering Research (I3A). Department of Chemical and Environmental Engineering. University of Zaragoza. C/ Mariano Esquillor, s/n Zaragoza. Spain Phone: , 1.3. Chemical Reaction Engineering. Kinetics. Abstract Oxygenated fuels have been proposed as alternative fuels or fuels additives to reduce exhaust emissions from gasoline and diesel engines. The development of detailed kinetic models and laboratory experiments to validate the models are of vital importance to understand the behavior of these fuels when are burned. In the same way, the experimental and modeling study of the interaction of these biofuels with some contaminants present in the combustion chamber, such as nitrogen oxide (NO), is of great importance. 2,5-dimethylfuran (C6H8O; 2,5-DMF) is a candidate to be used as an oxygenated fuel or additive. This biofuel has gained importance because it exhibits some better physical-chemical properties than other well-knows biofuels such as ethanol: higher boiling point ( 287 K), insolubility in water and higher energy density ( 40 %). Laboratory experiments and a modeling study of the 2,5-DMF conversion and its interaction with NO have been performed at atmospheric pressure in the K temperature range. The oxygen concentration has been varied to account for pyrolytic to very fuel-lean conditions (λ=0-30). The 2,5-DMF concentration used was 100 and 300 ppm and the NO concentration was 900 ppm. Figure 1 shows an example of the experimental and computational results obtained for the oxidation of 100 ppm of 2,5-DMF under fuel-rich conditions (λ=0.7) in both the absence and presence of NO. The presence of NO is seem to have influence on the 2,5-DMF oxidation regime. Also, the influence of the inlet C/N ratio in the NO conversion has been analyzed. As an example, the concentration profiles of NO for C/N=0.67 and 2 from pyrolytic to stoichiometric conditions are show in Figure 2. Acknowledgement The authors express their gratitude to the Aragón Government (GPT group) and to MINECO and FEDER (Project CTQ ), for financial support. Ms. K. Alexandrino acknowledges to MINECO for the predoctoral grant awarded (BES ). Figure 1. Oxidation of 100 ppm of 2,5-DMF for λ=0.7 without and with NO. Figure 2. Concentration profile of NO for C/N=0.67 and 2 and λ=0, 0.3, 0.7 and 1.

101 Activation of Melamine Urea Formaldehyde adhesives with of Hydrophilic/Hydrophobic Hyperbranched Poly(amidoamine)s and Their Application in Particleboards Fabrication S. Amirou 1, H.A. Essawy 2, A. Zerizer 1, A.Pizzi 3 1 URMPE, University of M Hamed Bougara Boumerdes, Algeria 2 Dept. of Polymers and Pigments, National Research Center, Dokki 12311, Cairo, Egypt 3 LERMAB, University of Lorraine, 27 rue Philippe Seguin, BP 1041, Epinal, France Abstract Hyperbranched polymers (HBPs) of poly(amidoamine)s (PAMAMs) exhibiting various levels of hydrophilicity were used as modifiers for melamine urea formaldehyde (MUF) adhesives via different routes: either together with, or at the expense of sodium hydroxide during the ph adjustment at the end stage of preparation, in different proportions in the former case while at a fixed concentration in the latter. Their co-condensability together was proved using forurier transform infrared (FTIR) spectroscopy and 13 C nuclear magnetic resonance (NMR) as well. The utilization of these structures as modifiers for MUF, which are used frequently in particleboards production, resulted in multiple advantages. First, the use of hyperbranched structures is more advantageous with respect to dendritic ones (used before in our previous studies, refs 1,2) at least from the economic point of view. Further, their use as final additives either prior to use or at the final stage of preparation, in finite amounts, yielded considerable upgrading of the mechanical properties of the produced particleboards as deduced from the measured dry internal bond (IB) strength. This extended also to the wet IB strength and thickness swelling, which are measures of the resistivity to hydrolytic degradation. These results were in parallel to a predictive investigation on the different resins using thermomechanical analysis (TMA). The results could be correlated with the relevant hydrophilicity and degree of branching of the hyperbranched PAMAMs as well as the resins reactivity, measured in the form of gel times. References 1- X. Zhou, H.A. Essawy, A. Pizzi, X. Li, H. Pasch, N. Pretorius, G. Du, J. Polym. Res., 20(10), Ar. No. 267 (2013). 2- X. Zhou, H.A. Essawy, A. Pizzi, J. Zhang, X. Li, G. Du, J. Polym. Res., 21(3), Ar. No. 379 (2014). 1

102 OXIDATION OF DIMETHOXYMETHANE UNDER HIGH-PRESSURE CONDITIONS Lorena Marrodán, Eduardo Royo, Ángela Millera, Rafael Bilbao, María U. Alzueta* Aragón Institute of Engineering Research (I3A). Department of Chemical and Environmental Engineering. University of Zaragoza. C/ Mariano Esquillor, s/n Zaragoza. Spain *Phone: //Fax: , Scientific Topic: 1.3 Chemical Reaction Engineering Diesel engines are widely used because of their excellent fuel efficiency, reliability and durability, but unfortunately, they produce important amounts of NO x and particulate matter (PM). Therefore, it would be desirable to reduce these emissions, but it is difficult to reduce both of them simultaneously. A promising method to solve this is to use oxygenated alternative fuels or to add the oxygenated compounds as additives to the diesel fuel without changes in the combustion systems [1]. In this context, dimethoxymethane (DMM), or methylal, is a diether and has some properties such as a high oxygen fraction, relatively high cetane number, high volatility and a good solubility in diesel that make it an appropriate additive for diesel fuels [2]. The DMM oxidation experiments have been carried out in an installation which consists of a feeding system, a reaction system (quartz tubular flow reactor) and a gas analysis system. It can operate under pressure conditions up to 60 bar. The influence of temperature ( K), stoichiometry (λ = 0.7, 1 and 20) and pressure (1, 20, 40 and 60 bar) on the DMM conversion has been investigated in order to determine the oxidation behavior of this compound in a wide range of conditions, as are possible to find in a combustion chamber. The main products obtained are CO, CO 2, methanol and methyl formate for all the stoichiometries studied and, for fuel-rich and stoichiometric conditions, also H 2 and CH 4. The results indicate that, when pressure is raised above atmospheric, the temperature for the onset of the DMM oxidation is shifted to lower temperatures; this change is larger for oxidizing conditions. In addition, the experimental results have been used to validate and extend the kinetic mechanism for describing DMM oxidation. The used kinetic mechanism is based on the C 1 -C 2 mechanism developed by Glarborg et al. [3], updated and extended later [4, 5]. Additional subsets for dimethyl ether [6] and methyl formate [7] had been added. The DMM reaction sub-mechanism suggested by Dias et al. [8] has been taken as starting point. Calculations have been performed using Senkin which runs in conjunction with Chemkin library. References [1] Z.H. Huang, Y. Ren, D.M. Jiang, L.X. Liu, K. Zeng, B. Liu, X.B. Wang, Energy Convers. Manage. 47 (2006) [2] R. Zhu, X. Wang, H. Miao, Z.H. Huang, J. Gao, D. Jiang, Energy Fuels 23 (2009) [3] P. Glarborg, M. U. Alzueta, K. Dam-Johansen, J.A. Miller, Combust. Flame 115 (1998) [4] P. Glarborg P., M.U. Alzueta, K. Kjærgaard, K. Dam-Johansen, Combust. Flame 132 (2003) [5] M.S. Skjoth-Rasmussen, P. Glarborg, M. Ostberg, J.T. Johannenssen, H. Livbjerg, A.D. Jensen, T.S. Christensen, Combust. Flame 136 (2004) [6] M.U. Alzueta, J. Muro, R. Bilbao, P. Glarborg, Isr. J. Chem. 39 (1999) [7] M.U. Alzueta, V. Aranda, F. Monge, A. Millera, R. Bilbao, Combust. Flame 160 (2013) [8] V. Dias, X. Lories, J. Vandooren, Combust. Sci. Technol. 182 (2010) Acknowledgments The authors express their gratitude to the Aragón Government (GPT group) and to MINECO and FEDER (Project CTQ ), for financial support.

103 THE OXIDATION PROCESS OF DIMETHYL CARBONATE AS FUEL ADDITIVE UNDER COMBUSTION CONDITONS María Abián, Pablo Salinas, Ángela Millera, Rafael Bilbao, María U. Alzueta* Aragón Institute of Engineering Research (I3A), University of Zaragoza, Spain. Campus Río Ebro, R&D Building, C/ Mariano Esquillor s/n, Zaragoza. Phone: , Fax: Scientific Topic: 1.3 Chemical Reaction Engineering Fuel reformulation through the use of oxygenated additives has been considered as an interesting option both, to reduce the harmful soot emissions and to overcome the dependence on fossil fuels, since many of them are bio-derived fuels. Dimethyl carbonate is of interest as oxygenated fuel additive since it presents relative high oxygen content as compared with other additives and suitable characteristics to be used in combustion systems. In this context, the present work analyses the oxidation process of dimethyl carbonate, at atmospheric pressure, in a quartz flow reactor, which has been already used in many previous works [i.e. 1]. Experiments have been carried out in the K temperature range and for different air excess ratios (λ). The stoichiometry values analysed have been varied from λ=0.3 (very fuel-rich conditions) to λ=35 (very fuel-lean conditions), aiming to cover a wide range of operating conditions. Besides to the experimental study, experimental results have been simulated and interpreted in terms of a literature detailed gas-phase kinetic mechanism, to identify the elementary steps involving dimethyl carbonate conversion and main gas products formation, as function of the different operating conditions. The base reaction mechanism is taken from the work of Glarborg et al. [2] to describe the combustion of small hydrocarbons, with minor modifications and updates [3], together with the ethanol reaction subset of Alzueta and Hernández [4]. In the present work, the DMC reaction subset proposed by Glaude et al [5] has been implemented in the mechanism used for the modelling study of the present work. Calculations have been performed using Senkin which runs in conjunction with Chemkin library. References [1] M. Abián, C. Esarte, A. Millera, R. Bilbao, M.U. Alzueta, Energy Fuels 22 (2008) [2] P. Glarborg, M.U. Alzueta, K. Dam-Johansen, K.J.A. Miller, Combust. Flame 115 (1998) [3] M. Abián, J. Giménez-López, R. Bilbao, M.U. Alzueta, Proc. Combust. Inst. 33 (2011) [4] M.U. Alzueta, J.M. Hernández. Energy Fuels 16 (2002) [5] P.A. Glaude, W.J. Pitz, M.J. Thomson, Proc. Combust. Inst. 30 (2005) Acknowledgements Authors acknowledge the Aragón Government, the European Social Fund (ESF) and MINECO (through project: CTQ ) for financial support. M. Abián acknowledges University of Zaragoza and Thermo-Chemical Processes Group (GPT) for the grant awarded.

104 KINETIC MODEL FOR CATALYTIC REFORMING OF NAPHTA Burcu Keçeciler, Nihan Uzunoğlu and Koray Kahraman TÜPRAŞ-Turkish Petroleum Refineries Corporation, R&D Center, No: Kocaeli TURKEY, phone , fax , Chemical Engineering Fundamentals, Chemical Reaction Engineering, Chemical Reactors Catalytic reforming of naphtha is one of the most important processes for high octane gasoline manufacture and aromatic hydrocarbons production. In this work a kinetic model for the naphtha catalytic reforming process is presented. We use a lumped kinetic network with 35 lump in the range of C1-C14. This network can represent dehydrogenation, dehydrocyclization, isomerization and hydrocracking reactions that occur with petroleum feedstock. In the developed model, the component lumping strategy is based on a paraffins, isoparaffins, olefins, naphthaleness and aromatics (PONA) analysis. The model numerically integrates the mass and energy balance equations for the combined feed and recycle gas in each reactor. The reaction patterns and reactors are modelled using a system of partial differential equations (PDE). The process model is used to predict temperature, reformate composition profiles and octane number in a commercial continuous catalytic regeneration unit (CCR) consisting of a series of four catalytic reactors. The commercial and predicted results compatibility is very satisfactory.

105 H 3 PW 12 O 40 ACID: A NOVEL AND RECYCLABLE HETEROPOLY ACID FOR THE MICROWAVE-ACCELERATED OF SYNTHESIS OF 3, 5-DIARYL-1H-PYRAZOLE Yamina ABDI 1, Chérifa RABIA 2, Maamar HAMDI 1, Baya BOUTEMEUR 1* 1. Laboratoire de Chimie Organique Appliquée, Faculté de Chimie. Université des Sciences et de la Technologie Houari Boumediène. BP 32, El-Alia , Bab- Ezzouar. Alger, Algérie Laboratoire de Chimie du Gaz Naturel, Faculté de Chimie. Université des Sciences et de la Technologie Houari Boumediène. BP 32, El-Alia , Bab-Ezzouar. Alger, Algérie. The pyrazole ring is one of the fundamental heterocycles. Its derivatives have certainly been shown to exhibit various pharmaceuticals and biological activities [1]. Including antimicrobial, anti-inflammatory, hypoglycemic, antihypertensive and analgesic[2-4] properties. In recent years, there have been enhanced interests in the synthesis of pyrazole derivatives due to their wide applications [5].In that way, we decided to study the reactivity of [3-(4-nitrophenyl) oxiran-2-yl phenyl) methanone with several binucleophilic amines in ethanol treating with PW 12 under microwave irradiation. The heterocyclic products were characterized by IR, 1 H and 13 C NMR, and mass spectra. O NO 2 O + NH 2 -XH NO 1 2 HPA M.W Scheme 1 2(a,b) N X a: X= NH b: X= Nph References: [1]. A. H. Wyllie; J. F. Kerr; A. R. Currie, Int. Rev. Cytol. 1980, 68, [2]. S.P. Singh, R. Naithani, R. Aggarwal, O. Prakesh, Indian J. Heterocycl. Chem. 2001, 11, [3]. L.V.G. Nargund, V. Hariprasad, G.R.N. Reddy, J. Pharm. Sci. 1992, 81, [4]. G. Menozzi, P.L. Schenone, Mosti, J. Heterocycl. Chem. 1993, 30, [5]. C.Thompson, Science 1995, 267,

106 COKE FORMATION AND GROWTH DURING ETHANOL STEAM REFORMING ON A Ni/La 2 O 3 -Al 2 O 3 CATALYST C. Montero, P. Castaño, B. Aramburu, J. Bilbao and A.G. Gayubo. Chemical Engineering Department. University of the Basque Country UPV/EHU. P.O.Box.644, Bilbao-Spain. Telephone Chemical Reaction Engineering: Catalyst Ethanol, obtained by biomass fermentation, is considered a promising feed for obtaining H 2 by steam reforming (SRE) because it is easy to store, handle and less toxic than other oxygenates. The SRE reaction has been performed over several catalytic systems based on metals deposited on oxide supports. Among these, Ni supported on La 2 O 3 -Al 2 O 3 is a suitable catalyst due to its high activity and low cost. Despite this catalyst is more stable than others, it suffers a severe carbon deposition [1]. In this work we have studied the evolution with time on stream (TOS) of the amount and nature of the coke deposited on a Ni/La 2 O 3 αal 2 O 3 catalysts during SRE, in order to determine the coke formation and growth. The Ni/La 2 O 3 -αal 2 O 3 catalyst (10%Ni-10%La 2 O 3 ) was prepared by incipient wetness impregnation method [2], followed by an equilibration treatment by SRE-coke combustion cycles. Prior to reforming reactions, it is reduced in-situ at 700 ºC (2 h). The experiments were carried out in a fluidized bed reactor under the following conditions: space-time (W/F 0 ) = 5.2 g catalyst min g EtOH -1, 500 ºC, steam/ethanol molar ratio (S/E) = 3, time on stream between h. The properties of the fresh and used catalysts were analyzed by N 2 adsorptiondesorption, H 2 chemisorption and X-ray diffraction (XRD). The nature and amount of coke deposited on the catalyst were analyzed by Temperature Programmed Oxidation (TPO), Scanning and Transmission Electron Microscopy (SEM-TEM), Raman Spectroscopy and X-Ray Photoelectron Spectroscopy (XPS). The results of product distribution, surface degradation, coke content, and coke characterization are summarized in Table 1. Table1: Ethanol conversion, products yield, coke content and catalyst characterization for different values of time on stream. Yields a Coke SBET Vpore XPS analysis TOS XEtOH H2 CO CH4 Acetaldehyde (wt%) (m 2 /g) (cm 3 /g) %C %O ª Yields referred to the maximum stoichiometric values. The ethanol conversion and H 2 yield drop drastically between 4-8 h of reaction, according to an accelerated coke growth and surface modification. The SEM and TEM images ratify the presence of coke nanofibers with diameters between nm, whose formation is incipient before 4 h but which grow rapidly for higher time on stream. The coke nanofibers have a limited impact on catalyst deactivation, but they are responsible for the increase in the superficial area and their growth is correlated with CO and CH 4 concentration. On the other hand, a high concentration of acetaldehyde promotes the formation of encapsulating coke, which is the main responsible for catalyst deactivation because it blocks the nickel active sites. Ni 0, NiO or La 2 O 3 species were not identified on the surface of the deactivated catalyst by XPS analysis. However, the deposition of oxygenated coke has been detected at low time on stream, which evolves towards more graphitic structures with time on stream. [1] C. Choong, Z. Zhong, L. Huang, Z. Wang, T. Ang, A. Borgna, J. Lin, L. Hong,, L. Chen. Appl Catal A: Gen. 2011, 407: [2]B. Valle, B. Aramburu, A. Remiro, J. Bilbao, A.G. Gayubo. Appl Catal B: Environ. 2014; 147:

107 POLYCYCLIC AROMATIC HYDROCARBON (PAH) AND SOOT FORMATION IN THE PYROLYSIS OF OXYGENATED COMPOUNDS USED AS DIESEL FUEL ADDITIVES Fausto Viteri, Ángela Millera, Rafael Bilbao, María U. Alzueta*. Aragón Institute of Engineering Research (I3A). Department of Chemical and Environmental Engineering. University of Zaragoza. C/ Mariano Esquillor s/n, Zaragoza, Spain. *Phone: Fax: Chemical Reaction Engineering - Chemical Reactors Environmental concern related to the emissions of combustion engines is important nowadays. Within the combustion chamber, conditions including high temperatures and low oxygen concentrations are present, and important pollutants can be formed, including soot and polycyclic aromatic hydrocarbons (PAH). PAH are important because of the toxic nature of some of them. For this reason, the USA Environmental Protection Agency (EPA) defined 16 priority PAH, which are regulated by USA government policies [1]. The present research is centered on the study of the 16 EPA-PAH and soot formed in the pyrolysis of different kinds of oxygenated compounds that have been proposed as fuel substitutes or fuel additives, because of their ability to minimize soot formation and their renewable character [2], but at our knowledge there are no studies focused on the PAH formation from these compounds. The additives analyzed in this work have different functional groups, including alcohols, esters and ethers, and include isomers, with the aim of comparing the results. All experiments are carried out in the Combustion Reaction Laboratory of the GPT (Thermo-chemical Processes Group) of the University of Zaragoza, in a quartz flow reactor setup, under well controlled laboratory conditions, in the K temperature range, by using different oxygenated compound inlet concentrations (in the range ppmv) and at atmospheric pressure. The present study uses the method developed by our research group, for the quantification of PAH found in gas and particle phases from pyrolytic processes using gas chromatography-mass spectrometry [3]. The procedure involves the trapping of PAH in two phases: the first is found on the soot surface and stuck at the reactor walls, and the other, which corresponds to the gas phase, is retained by XAD-2 resin which is packed in a thin-tube, placed after the filter used to collect soot. PAH formed on the reactor walls are also collected by washing the reactor with dicloromethane. PAH retained on the soot surface and the resin are subjected to Soxhlet extraction, using dicloromethane as well, and later they are concentrated by the rotary evaporator. Finally, all the samples are analyzed by gas chromatography-mass spectrometry (GC/MS) and the PAH are quantified. Acknowledgements The authors express their gratitude to MINECO and FEDER (Project CTQ ) and Aragón Government for financial support. Mr. F. Viteri acknowledges the University of Zaragoza and Ecuadorian Secretaría Nacional de Educación Superior, Ciencia, Tecnología e Innovación (SENESCYT), for the predoctoral grant awarded. References [1] K.-H. Kim, S. A. Jahan, E. Kabir, and R. J. Brown. Environ. Int. 60. (2013) [2] P. Pepiot-Desjardins, H. Pitsch, R. Malhotra, S. Kirby, and A. Boehman. Combust. Flame (2008) [3] N. Sánchez, J. Salafranca, A. Callejas, Á. Millera, R. Bilbao, and M. U. Alzueta. Fuel (2013)

108 EFFECT OF TEMPERATURE ON Ni/La 2 O 3 - Al 2 O 3 CATALYST DEACTIVATION BY COKE DURING CRUDE BIO-OIL STEAM REFORMING B. Aramburu, A. Remiro, B. Valle, J. Bilbao, A.G. Gayubo University of The Basque Country, Chem. Eng. Department, Bilbao, Spain tel , fax: Scientific topic: Chemical Reaction Engineering The steam reforming of bio-oil is considered an interesting route for hydrogen production with low CO 2 emission. The technology of bio-oil production by flash pyrolysis of lignocellulosic biomass is already mature [1], and the steam reforming avoids the costs of bio-oil pre-treatment required for other routes of bio-oil exploitation. Ni supported catalyst are commonly used in bio-oil reforming studies [2], and they suffer from a noticeable deactivation by coke, which depends on operating conditions This work studies the effect of reaction temperature (in the 550 to 700 ºC range) on the deactivation by coke deposition of Ni/La 2 O 3 - Al 2 O 3 catalyst (prepared by wet impregnation of α-al 2 O 3 support with nitrate solutions of 10 wt% Ni and 10 wt% La 2 O 3 ) in bio-oil steam reforming. The reaction equipment consists of two steps in series: 1) thermal treatment step at 500 C, for feed volatilization and controlled deposition of pyrolytic lignin [3], 2) catalytic reforming step in a fluidized bed reactor. The bio-oil (obtained from pine sawdust) is composed of 51 wt% organics (C 4.0 H 6.0 O 2.9 ) and 49 wt% water. The Ni/La 2 O 3 - Al 2 O 3 catalyst is reduced in situ for 2 h at 700 C before each reforming reaction. molco 2 /mg cat s T, ºC Cc wt % (a) Temperature, ºC Time on stream, min Fig. 1. Results of the TPO analysis of the coke deposited on Ni/La 2 O 3 - Al 2 O 3 catalyst (b) and evolution with time on stream of hydrogen yield (a) during bio-oil steam reforming at S/C 6, g catalyst h/g bio-oil and different values of reaction temperature. TPO curves (Figure 1b) show two coke domains, one at low temperature ( ºC) and other one at high temperature (above 500 ºC). For high reaction temperature (700 ºC) only high temperature coke exists, which is a filamentous coke formed from CH 4 (by decomposition reaction) and CO (by Boudouard reaction). At low reaction temperature the bio-oil conversion is lower and the concentration of oxygenated compounds of bio-oil (mainly ketones and aldehydes) in the reaction medium increases. Those oxygenates are the precursors of the low temperature coke, which encapsulates metallic active sites and provokes the rapid deactivation observed specifically in the case of 550 ºC. It is also observed that the increase in the reaction temperature affects to the burning temperature of each type of coke, which shifts towards higher temperatures. Y H T, ºC (b) [1] A. Oasmaa, Y. Solantausta, V. Arpiainen, E. Kuoppala, K. Sipilä, Energy Fuels 2010; 24; [2] B Valle, A Remiro, AT Aguayo, J Bilbao, AG Gayubo. Int. J. Hydrogen Energy 2013; 38; [3] AG Gayubo, B Valle, AT Aguayo, M Olazar, J Bilbao. J. Chem. Tech. Biotech. 2010; 85;

109 Steam Methane Reformer Modeling and Optimization Mojtaba Sinaei Nobandegani 1, Farhad Shahraki 2, Tayebeh Darbandi 3, Mohammadreza Sardashti Birjandi 2, Bizhan Honarvar 4 1 Department of Chemical Engineering, International Campus, University of Sistan & Baluchestan, Chabahar, Iran; Phone: , Fax: , 2 Department of Chemical Engineering, University of Sistan & Baluchestan, Zahedan, Iran 3 Department of Chemical Engineering, Shahrood Branch, Islamic Azad University, Marvdasht, Iran 4 Department of Chemical Engineering, University of Fars Science and Research, Islamic Azad University, Iran Scientific Topic: 1.3 Chemical Reaction Engineering Increasing the environmental pollution and shortcoming of fossil-fuels encourage researchers to look for an alternative environmental-friendly source of energy. Regarding to above-mentioned problems, hydrogen can be an alternative energy source. Hydrocarbon reforming is one of the most promising techniques for hydrogen production. The steam methane reforming is the most common procedure and also one of the traditional methods to convert the methane to hydrogen. In the present work, the steam methane reforming has mathematically been studied. One-dimensional mathematical model in axial direction in steady state conditions has been represented to describe this process, and it has been solved using the Matlab software. To validate the proposed model, results have been compared to those of experimentally provided by Bandar Abbas refinery. The absolute average deviation was about 3.7% that indicate the model is in a good agreement with experimental data. Furthermore, the effects of flow rate and temperature of the feed and tube wall temperature on the reformer performance were numerically simulated. Finally, the model has been optimized in a multiobjective optimization to minimize the methane slip and maximize the hydrogen production, simultaneously. The results illustrate that for the kmol/h feed, the minimum value of methane slip and maximum value of hydrogen production are and kmol/h, respectively. Key-words: Steam Methane Reforming, Optimization, Mathematical Modeling, Hydrogen Production

110 THE EFFECT OF TEMPERATURE ON SLURRY HYDROCRACKING REACTION OF NAPHTHALENE Solmaz Akmaz and Pegah Amiri Caglayan Department of Chemical Engineering, Istanbul University, Avcilar, Istanbul Telephone number: Fax number: Solmaz Akmaz: 1.3 Chemical Reaction Engineering Hydrocracking is one of the most efficient refining methods to convert heavy hydrocarbons into lighter ones due to demand of lighter and more quality products. Slurry phase hydrocracking method which has been applied in recent years is very effective on heteroatoms, olefinic and aromatic structures. Catalyst and reaction conditions play important role on the hydrocracking reactions. The most recent studies on the processing of heavy oils showed that the untreated iron-containing solid heterogeneous catalysts in the form of powder gave effective results. Heavy petroleum includes high amount of aromatic compounds. Feedstock which contains aromatic compounds, make hard refinery process. Naphthalene is one of the important aromatic compounds in heavy petroleum. Heavy petroleum generally has 10 % naphthalene by weight although this range sometimes changes typically. Petroleum contains thousands of complex molecules. Therefore it is impossible to explain the reactions during hydrocracking. So the information which is obtained from the hydrocracking reactions of model compounds is aimed to be a resource to explain the hydrocracking reactions of petroleum. In this study, ironic based catalyst with metal oxide and elementary sulfur was used as cheap and effective catalyst in the slurry hydrocracking reactions of naphthalene. In order to understand the hydrocracking reactions of naphthalene as aromatic model compound, the effect of the temperature and time were investigated during hydrocracking reactions. Reactions were carried out in 10 ml stainless steel bomb type reactor with 200 rpm speed for mixing under 100 bar of H 2 initial pressures. To investigate the effect of reaction temperature and time, hydrocracking reactions were carried out at different temperatures such as 400, 425 and 450 C for holding times from10 to 90 minutes. At the end of each reaction, reaction products were analyzed by gas chromatography and mass spectrometry. Catalysts were also analyzed by X Ray Diffraction before and after the reactions. Naphthalene yielded tetralin, 1-methylindane, indane, butylbenzene, ethylbenzene, toluene, benzene and remaining naphthalene after hydrocracking reactions at all temperatures. Hydrogenation, isomerization, ring opening and dealkylation reactions take place during hydrocracking of aromatic compounds. As temperature increased, the disappearance rate of naphthalene increased. Ethylbenzene, toluene and benzene exhibited increasing yields with increasing time and temperature.

111 MODIFIED HZSM-5 ZEOLITES FOR INTENSIFYING PROPYLENE PRODUCTION FROM ETHYLENE Eva Epelde, Paula Pérez-Uriarte, Andrés T. Aguayo, Javier Bilbao, Ana G. Gayubo Chemical Engineering Department, University of the Basque Country, P. O. Box 644, Bilbao, Spain, Tel.: , Fax: , Scientific Topic: Chemical Reaction Engineering-Catalysis The present demand of individual light olefins is undergoing significant changes conditioned by their interest as raw materials, with a current shortage in propylene production. Furthermore, steam cracking (the main olefin production unit, with ethylene being the major product) will be boosted by feeding ethane (obtained from shale gas extraction) [1]. Within this scenario, light olefin interconversion arouses great interest with a view to adjusting its production to market prices and requirements. This work aims to study the selective transformation of ethylene into propylene on HZSM-5 zeolites (SiO 2 /Al 2 O 3 =80, denoted HZ-80) modified by 1 wt% K (1K/HZ- 80) or P (1P/HZ-80) and by mild in situ steaming treatment at 400 ºC (HZ-80-ST). The parent and modified zeolites (25 wt%) were agglomerated by wet extrusion with bentonite as binder (30 wt%) and alumina as inert charge (45 wt%). Catalyst particles (sieved to mm size) were calcined at 570 ºC for 2 h. The surface area and porous structure was determined by N 2 adsorption-desorption. The total acidity and acid strength of the catalysts have been determined by DSC-TPD of tert-butylamine (t-ba) [2]. Figure 1 shows the t-ba-tpd profiles of the zeolites synthesized. The parent zeolite shows two main peaks: one at low temperature (190 ºC) related to strong acid sites and the second peak identified at higher temperature (270 ºC) corresponding to weak acid sites, that require higher temperature for cracking t-ba. The modifications of HZSM-5 zeolite are effective for decreasing acid site density and acid strength, especially when K is added into the zeolite. However, it should be noted that mild in situ steaming, slightly increases acid strength T (ºC) Figure 1. t-ba-tpd profiles for parent and modified HZ-80 zeolites. Experiments have been carried out under the following operating conditions: 500 ºC, space time 3.2 (g catalyst h) (mol CH2 ) -1 ; ethylene partial pressure 1.35 bar; time on stream, up to 15 h. Table 1 shows the results at zero time on stream (fresh catalysts) of ethylene conversion, light olefin (propylene and butenes) yield and the selectivity of the different lumps of products. 1K/HZ-80 shows the highest propylene selectivity at zero time on stream since the attenuation of total acidity and acid strength gives way to a decrease in secondary reactions of hydrogen transfer and condensation (with the corresponding decrease in ethylene conversion). However, this catalyst shows a very low stability (results not shown). P doping and mild in situ steaming are suitable treatments, as they also contribute to adjusting the acidity of HZSM-5 zeolite for attenuating coke deposition (Table 1), while ensuring a good balance between ethylene conversion-stability-propylene yield. Table 1. Effect of the HZSM-5 zeolite modifications on the catalytic performance at zero time on stream Catalyst X YC3H6 YC4H8 Selectivity (%) Cc (%) (%) (%) CH4 C3H6 C4H8 C2-C3 C4H10 C5+ BTX (wt%) HZ K/HZ P/HZ HZ-80-ST Among the catalysts studied the maximum propylene yield is obtained (37%) with HZ-80 zeolite (SiO 2 /Al 2 O 3 =80) modified by mild in situ steaming, for a time on stream of 11.3 h. This is an interesting result from the point of view of implementing a new process for ethylene transformation, in a fluidized bed reactor with catalyst circulation, with an average residence time of the catalyst around 11-12h. [1] E. Mazoyer, K.C. Szeto, J.M. Basset, C.P. Nicholas, M. Taoufik. Chem. Commun. 48 (2012), [2] E. Epelde, A.G. Gayubo, M. Olazar, J. Bilbao, A.T. Aguayo. Chem. Eng. J. (2014), TPD t-ba, mol t-ba (s g zeolite ) HZ HZ-80-ST 3-1P/HZ K/HZ-80 2

112 INFLUENCE OF WATER ON CATALYST STABILITY IN THE STEAM REFORMING OF DIMETHYL ETHER J. Vicente, J. Ereña, L. Oar-Arteta, I. Sierra, J. Bilbao, A. G. Gayubo Departamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, E Bilbao, Spain; tel , Chemical Reaction Engineering. Catalysis Hydrogen is considered a suitable fuel to meet ever-increasing energy demand because it may be produced from renewable sources. The dimethyl ether (DME) steam reforming (SRD) is a process of growing interest, given that DME is relatively inert, non-corrosive, non-carcinogenic and can be stored and handled as LPG, which means it is more readily used as a fuel and in fuel cells. The SRD process occurs in two steps in series: DME hydrolysis (on the acid function), (CH 3 ) 2 O + H 2 O 2CH 3 OH; and methanol steam reforming (on the metallic function), CH 3 OH + H 2 O 3H 2 + CO 2. In addition to increasing the reforming reaction rate, the presence of water in the reaction medium contributes to attenuating coke deposition. Nevertheless, excess steam in the SRD reaction medium may partially oxidize the metal active sites. This paper studies the influence of water on catalyst stability in SRD reaction, in order to delimit the conditions that minimize coke deposition without deteriorating the metallic function. The bifunctional catalyst is composed of a CuO-ZnO-Al 2 O 3 metallic function and a HZSM-5 zeolite treated with NaOH to moderate acidity. The experimentation has been carried out in a fluidized bed reactor (connected online to a MicroGC Agilent 3000 for product analysis), with steam/dme molar ratios between 3 (minimum according to stoichiometry) and 6, by carrying out runs using different values of water and inert gas (He) flow rate, with the following operating conditions: 325 ºC, W/F DME,0 = 0.13 g catalyst h/g DME, P DME = 0.16 bar. Figure 1 shows the evolution with time on stream of DME and methanol conversions for steam/dme ratio values of 3 and 6. The decrease in the conversions with time on stream is less pronounced for the steam/dme ratio of 6, which is consistent with the hypothesis that coke is formed through methoxy ions as intermediates and an increase in the amount of water in the reaction medium contributes to inhibiting the formation of these ions. The higher DME and MeOH conversions obtained as the steam/dme ratio is increased evidence that catalyst deactivation is attenuated, although this attenuation of deactivation has presumably different effect on each step (DME hydrolysis and methanol reforming) of the global SRD process. From the results of Figure 1 it is concluded that the effect the steam/dme ratio has on attenuating deactivation is more severe for methanol reforming than for DME hydrolysis. X DME X MeOH X DME X MeOH S/DME Time on stream, h Figure 1. Effect of steam/dme ratio on the evolution with time on stream of DME conversion and methanol effective conversion. Moreover, the coke content in the catalyst (determined by TPO) is higher for a steam/dme ratio of 3 (4.8 mg/g catalyst ) than for a ratio of 6 (1.8 mg/g catalyst ). A comparison of the TPO profiles corresponding to the catalysts deactivated in runs with different steam/dme ratios in the feed reveals that an increase in the content of water in the reaction medium attenuates the deposition of coke on the metallic sites to a greater extent, which is consistent with the more severe attenuation of the methanol reforming reaction than DME hydrolysis. Based on these results, it is concluded that an increase in the steam/dme ratio favours catalyst stability in the SRD reaction. In the light of the results obtained previously on the effect of the steam/dme molar ratio on the values at zero time on stream of H 2 yield and product concentration, a steam/dme ratio in the 4-5 range is established as suitable, given that above this value the energy cost is likely to be excessive. Acknowledgements This work has been carried out with the financial support of the Department of Education, Universities and Research of the Basque Government (Project IT748-13), the University of the Basque Country (UFI 11/39 UPV/EHU), and the Ministry of Science and Innovation of the Spanish Government (Projects CTQ and CTQ ).

113 EFFECT OF TEMPERATURE AND METAL TYPE ON THE PERFORMANCE OF Ni AND Co CATALYSTS FOR ETHANOL STEAM REFORMING J. Vicente, A. G. Gayubo, J. Ereña, C. Montero, I. Sierra, J. Bilbao Departamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, E Bilbao, Spain; tel , Chemical Reaction Engineering. Catalysis The growing interest in replacing fossil fuel raw materials with biomass for hydrogen production is explained by the need to decrease greenhouse gas emissions. Among biomass-derived compounds, bioethanol (i.e. aqueous ethanol produced by sugar fermentation) is the one with the best perspectives for large scale-valorisation in order to meet the increasing demand for H 2 for use as fuel and raw material in the petrochemical industry [1]. The steam reforming of ethanol (SRE) occurs according to the stoichiometry: CH 3 CH 2 OH + 3H 2 O 6H 2 + 2CO 2. In this paper a study has been conducted on the SRE reaction on different Ni and Co catalysts synthesized on several supports (SiO 2, and -Al 2 O 3 ) in a fluidized bed reactor (to ensure bed isothermicity). The results allow analysing the effect of both temperature and the type of metal and support on the reaction indices (ethanol conversion and yields and selectivities of H 2 and by-products: CO 2, CO, CH 4 and acetaldehyde (C 2 H 4 O)). In order to compare the kinetic performance of the catalysts, the results have been grouped into those corresponding to temperatures below 500 ºC and those above this temperature, given that the WGS reaction equilibrium shifts towards the left for the latter. Consequently, 500 ºC is the temperature for the lowest CO selectivity in the product stream, which is interesting for a subsequent H 2 purification step. Figure 1 shows that, below 500 ºC, H 2 selectivity is higher with 10Co/Si and 10Co/Al catalysts (10 wt% of Co nominal content supported on SiO 2 and - Al 2 O 3, respectively) than with Ni ones (10Ni/Si, 10Ni/Al), due to the lower CH 4 selectivity and despite CO and C 2 H 4 O selectivities are higher. These results evidence that Co catalysts have a good kinetic performance for SRE reaction at low temperature, due to their low activity for methanation. Furthermore, the difference in the H 2 selectivity between both groups of catalysts is lower than that corresponding to methanation activity due to the higher activity of Ni catalysts for WGS reaction below 500 ºC. As temperature is increased, C 2 H 4 O reforming and decomposition (to CO and CH 4 ) and CH 4 reforming are enhanced with all these catalysts, especially with Ni ones, for which CH 4 selectivity above 500 ºC decreases significantly. S H Ni/Si 10Ni/Al Co/Si 10Co/Al Temperature, ºC Figure 1. Effect of temperature on H 2 selectivity. Reaction conditions: steam/ethanol molar ratio, 6; space time, 0.14 g catalyst h (g ethanol ) -1 ; P EtOH, 0.11 bar. Therefore, CH 4 selectivity above 600 ºC is lower with Ni catalysts than with Co ones, which gives way to a higher H 2 yield with the former. Moreover, CH 4 selectivity at 700 ºC is almost null for Ni catalysts and it is very low for Co ones, which is interesting for H 2 purification by removing CH 4 in down-stream steps. The support affects the kinetic behaviour, although to a lesser extent than the factors mentioned above, i.e., type of metal and reaction temperature. The catalyst of Ni supported on SiO 2 has a higher activity for the WGS reaction than that supported on -Al 2 O 3, and therefore CO selectivity is lower and that of CO 2 is higher. Acknowledgements This work has been carried out with the financial support of the Department of Education, Universities and Research of the Basque Government (Project IT748-13), the University of the Basque Country (UFI 11/39 UPV/EHU), and the Ministry of Science and Innovation of the Spanish Government (Projects CTQ and CTQ ). Carolina Montero is grateful for the Ph.D. grant from the National Secretariat of Higher Education, Science, Technology and Innovation of Ecuador-SENESCYT (Contract ). References [1] Menon V, Rao M (2012) Progress Energy Comb Sci 38:

114 Fabrication of Highly Stable Low-Density Self-Assembled Monolayers by Click Thiol-yne Reaction Leila Safazadeh,Brad Berron Phone: , Address:177 F. Paul Anderson Tower, Lexington, KY Fax: Chemical Reaction Engineering Self-assembled monolayers have tremendous impact in interfacial science, due to the unique opportunity they offer to tailor surface properties. Low-density self-assembled monolayers are an emerging class of monolayers where the environment-interfacing portion of the adsorbate has a greater level of conformational freedom when compared to traditional monolayer chemistries. This greater range of motion and increased spacing between surface-bound molecules offers new opportunities in tailoring adsorption phenomena in sensing systems. In particular, we expect low density surfaces to offer a unique opportunity to intercalate surface bound ligands into the secondary structure of protiens and other macromolecules. Additionally, as many conventional sensing surfaces are built upon gold surfaces (SPR or QCM), these surfaces must be compatible with gold substrates. Here, we present the first stable method of generating low density self-assembled monolayer surfaces on gold for the analysis of their interactions with protein targets. Our approach is based on the 2:1 addition of thiol-yne chemistry to develop new classes of y-shaped adsorbates on gold, where the environment interfacing group is spaced laterally from neighboring chemical groups. This technique involves an initial deposition of a crystalline monolayer of 1,10 decanedithiol on the gold substrate, followed by grafting of a low-packed monolayer on through a photoinitiated thiol-yne reaction in presence of light. Orthogonality of the thiol-yne chemistry (commonly referred to as a click chemistry) allows for preparation of low-density monolayers with variety of functional groups. To date, carboxyl, amine, alcohol, and alkyl terminated monolayers have been prepared using this core technology. Results from surface characterization techniques such as FTIR, contact angle goniometry and electrochemical impedance spectroscopy confirm the proposed low chain-chain interactions of the environment interfacing groups. Reductive desorption measurements suggest a higher stability for the click-ldms compared to traditional SAMs, along with the equivalent packing density at the substrate interface, which confirms the proposed stability of the monolayer-gold interface. In addition, contact angle measurements change in the presence of an applied potential, supporting our description of a surface structure which allows the alkyl chains to freely orient themselves in response to different environments. We are studying the differences in protein adsorption phenomena between well packed and our loosely packed surfaces, and we expect this data will be ready to present at the GRC meeting.

115 Synthesis of SnO 2 /ZrO 2 catalyst for supercritical water gasification of glucose N. Ayas (1), S. Yurtdas (2), M. Yurdakul (1) (1) 1* Anadolu University, Faculty of Engineering, Department of Chemical Engineering, 2 Eylul Campus, 26470, Eskisehir, Turkey (2) Karamanoğlu Mehmetbey University, Department of Energy Systems Engineering, Karaman, Scientific Topic: Chemical Reaction Engineering-Catalysis 1. Introduction Supercritical water gasification (SCWG) of biomass is a promising technology for hydrogen energy. Tin oxide is an important material for various technological applications such as gas sensors and conductive coatings but has received little attention as carrier for supported catalysts. SnO 2 -based catalysts have been reported to be active for different reactions such as oxidative dehydrogenations, catalytic CO oxidation [1, 2]. On the other hand Sn may block the active sites for CO adsorption and/or dissociation, thus suppressing the undesired methanation reaction [3]. ZrO 2 is also preferred as a metal support for heterogeneous catalysts due to its good physical and chemical characteristics like thermal stability and toughness [1]. 2. Experimental 1.1. Preparation of catalyst In this study, SnO 2 /ZrO 2 catalysts with different Sn percentages (15, 30, 45 %(w/w)) were synthesized by co-precipitation method. Firstly SnCl 4.5H 2 O and ZrO(NO 3 ) 2.6H 2 O salts were dissolved in 100mL distilled water. Then the solution was heated up to 65 o C with stirring. The ph of the solution was increased from 8 to 9 by adding NH 4 OH dropwise. The next step on the process was aging of the solution for 2 hours at 65 C and stirring at 300 rpm. Then, the precipitate was washed with ethanol and filtered. Then the precipitate was dried for 24 hours in an oven at 110 C. Next, the grounded precipitate was calcined at different temperatures (500, 600, 700, 800, 900, 1000) C for an hour in dry air atmosphere Characterization of catalyst The obtained catalysts were characterized by XRD, XRF, TGA, SEM and BET analysis Gasification reactions Obtained catalysts were testes on SCWG reaction of glucose. Reactions were carried out at 400 C for 1 hour with 1:20 glucose-water ratio and 0.5 g catalyst using PARR reactor. Composition of the gas mixture was determined by μgc. 3. Results and Discussion XRD patterns of the obtained catalysts at different calcinations temperatures and XRD patterns of the catalysts with different Sn percentages were given in Figure 1a, b. (a) (b) Figure 1. XRD pattern of SnO 2 /ZrO 2 catalysts at different calcinations temperatures (a) XRD patterns of SnO 2 /ZrO 2 catalysts with different Sn ratios (b) Surface characteristics of the SnO 2 /ZrO 2 catalysts are given in Table 1.

116 Table 1. BET surface area of the SnO 2 /ZrO 2 catalysts Percentage(w/w) Surface area (m 2 /g) Pore Volume (cm 3 /g) Pore Size (nm) 15% SnO 2 /ZrO % SnO 2 /ZrO % SnO 2 /ZrO Composition of the obtained gas from the reaction is given in Table 2. Table 2. Composition of the gas mixture Percentage(w/w) Component (%) H 2 CH 4 CO CO 2 C 2 H 4 C 2 H 6 C 3 H 6 C 3 H 8 15% SnO 2 /ZrO % SnO 2 /ZrO % SnO 2 /ZrO Conclusions According to the results of the supercritical water gasification of glucose it was seen that H 2 percentage of the gas mixture decrease with SnO 2 percentage in catalyst. The highest content of the hydrogen was obtained using 15% SnO 2 /ZrO 2 catalyst. 5. References [1] Guo Y., Review of catalytic supercritical water gasification for hydrogen production from biomass, Renewable and sustainable Energy Reviews, Vol. 14, Issue 1 (2010), p [2] Hagemeyer A., Hogan Z., High surface area tin oxide, Applied Catalysis, 317 (2007) [3] Xie F., Characterization and catalytic properties of Sn-modified rapidly quenched skeletal Ni catalysts in aqueous-phase reforming of ethylene glycol, Journal of Catalysis, 241 (2006)

117 WATER-GAS SHIFT REACTION UNDER SUB-CRITICAL WATER CONDITION O. Yilmaz and N. Ayas Anadolu University, Faculty of Engineering, Department of Chemical Engineering, 26555, Eskisehir, Turkey Phone: /6508 Fax: Scientific Topic: Chemical Engineering Fundamentals-Chemical Reaction Engineering The water-gas shift reaction (WGSR), is an important industrial process for the production of hydrogen from synthesis gas (H 2 /CO) which is further used for ammonia production in the fertilizer industry, petroleum refineries for a variety of operations and recently as fuel for power generation and transportation [1, 2]. In recent years, there has been a renewed interest WGSR because of its potential use in conjunction with fuel-cell power generation [3]. WGSR is a moderately exothermic reversible reaction and hence the equilibrium constant of the reaction decreases with increasing temperature [1]. Also, lower temperatures are favorable from the point of view of steam economy. Therefore, the availability of catalysts which facilitate the reaction at low temperatures is a key question in water-gas shift chemistry [2, 4]. In this work, WGSR was performed in a high temperature, high pressure (500 o C, 5000 psi) reactor, supplied from the Parr Instruments Co. About 30 ml of deionized water and 1 g of NaOH was charged into the reactor, and argon served as an inert sweep gas in the reaction medium. Then the reactor was heated to reaction temperature (250 o C). High purity CO (99.5%) was fed into the reactor at 3 bar pressure by Dwyer flow meter. Gas mixture analysis was performed using micro gas chromatography (µgc). Experiments were performed in the range of min. Gas composition of the WGSR as a function of time in the presence of 1 g NaOH, at 250 o C and 1:0.03 H 2 O:CO molar ratio is given in Figure 1. Possible Reactions; Figure 1. Gas product composition of WGSR in the presence of NaOH According to Figure 1, CO is consumed until the reactor could reach the reaction temperature and main gas products were determined as H 2 and CH 4. After 30 reaction time 0.11 moles of C 2 H 4 were obtained with regard to Fischer-Tropsch synthesis synth gas and further reaction time it was consumed [5]. H 2 O and CO reacted to form H 2 and CO 2, according to WGSR (1). It is thought that equations (4) and (5) could not occur due to the fact that CO formation was not observed during the reaction. Although, the CO 2 amount was detected as 3.62% in the first 60 min, CO 2 was consumed with time according to the equations of (2), (6) and (7). It has been considered that CH 4 was particularly formed according to the equations of (8) and (9) and XRD analysis supported the presence of sodium acetate. NaOH promotes the WGSR and it is completed after 90 min. Equilibrium between H 2 and CH 4 was observed after 120 min. References [1] B. Smith R. J., M. Loganathany, M.S. Shantha, Int. J. Chem. Reactor Eng., 8, (2010) p [2] H. Schulz, A. Görling, W. Hieringer, Inorg. Chem., 52, (2013) p [3] Y. Li, Q.F.M. Flytzani-Stephanopoulos, Appl. Catal. B: Environ., 27, (2000) p [4] D. Mendes, A. Mendes, L.M. Madeira, A. Iulianelli, J.M. Sousa, A. Basile, Asia-Pac. J. Chem. Eng., 5, (2010) p

118 APPLICATION OF MODEL-FREE KINETICS TO THE STUDY OF SHALE DEVOLATILIZATION. J. Foltin, G.N. Prado and A. C. L. Lisbôa State University of Campinas, School of Chemical Engineering, Campinas - SP Brasil phone: (55) Chemical Reaction Engineering - Kinetics The study of pyrolysis kinetics of carbonaceous materials is necessary to design reactors as well as to better understand the mechanism of decomposition. This study aims to investigate the kinetics of shale decomposition by pyrolysis, by analyzing the mass loss under a specified temperature profile. Thermogravimetric Analysis (TGA) and the model-free kinetics approach are used to obtain the data and results for shale pyrolysis. The raw material was supplied by the oil shale plant of Petrobras located in São Mateus do Sul, Pr, Brazil. The samples were analyzed using heating rates of 5, 10, 20, 25 and 50 C/min, at temperatures ranging from 110 C to 540 C. The dependency of the activation energy to the degree of conversion was analyzed. Keywords: oil shale, model-free kinetics, pyrolysis.

119 PRODUCTION OF METHANOL FROM CARBON DIOXIDE OVER Cu 2 O/ZnO ELECTRODES J. Albo 1, L. Gomez 2, P. Castaño 1 and A. Irabien 2 1. Universidad del País Vasco, Departamento de Ingeniería Química, Apdo. 644, Bilbao, Spain 2. Universidad de Cantabria, Departamento de Ingenierías Química y Biomolecular, Avda. de los Castros s/n., Santander, Spain Scientific Topic: Chemical Reaction Engineering Abstract Over the past few years, the electrochemical valorisation of CO 2 has gained important attention. Conversion of CO 2 by means of electrochemical reduction becomes an excellent mechanism of storing intermittent renewable energy, mitigating at the same time CO 2 emissions into the atmosphere and dealing with the undesirable effects of global warming. Among the value added chemicals produced from CO 2 electro-reduction, methanol possesses stable storage properties with a relatively high energy density, and can be produced with a minimum overpotential (less energy losses) [1]. Because of the early stage of the development of CO 2 valorisation processes, the purpose of the proposed research is the development of electrocatalytic systems for the effective conversion of CO 2 into methanol. Researchers over the past three decades have identified several materials that are capable of reducing CO 2 electrochemically. Among the various metal electrodes employed for this purpose, Cu-based materials have been found to be the most promising catalysts for methanol manufacturing with both intermediate hydrogen overpotentials and carbon monoxide adsorption allowing further reduction to methanol [1]. For example, Chang et al. [2] deposited Cu 2 O particles onto a carbon cloth electrode for CO 2 reduction and carried out cyclic voltammetry measurements; the results showed that methanol was the predominant product. Furthermore, Ohya et al. [3] demonstrated that the faradaic efficiencies of methane and ethylene were much higher in Cu 2 O/Zn particle-press electrode than in a metallic Cu electrode. Probably, Zn does more than just provide a surface for the Cu, but also stabilizing Cu + atoms and removing impurities which can deactivate the catalyst for methanol production in the long run. In order to improve methanol yield, faradaic efficiencies and the stability of the electrode surface we evaluate in this study the CO 2 reduction at Cu 2 O/ZnO electrodes in a parallel plate type electrochemical cell, which allows the electrochemical reduction of CO 2 in continuous operation. The parallel-plate cell consists of two compartments divided by an ion exchange membrane. A Pt plate is selected as the anode, along with an Ag/AgCl as a reference electrode. An aqueous KHCO 3 is used as electrolyte. The results are compared to current state of the art for CO 2 electro-reduction to methanol. Acknowledgments Financial support from the Spanish Ministry of Economy and Competitiveness (MINECO) as Juan de la Cierva program (JCI ) at Basque Country University is gratefully acknowledged. Reference [1] Ganesh, I. Renew. Sust. Energ. Rev. 31 (2014) [2] Chang, T.Y., Liang, R.M., Wu, P.W., Chen, J.Y., Hsieh, Y.C. Mater. Lett. 63 (2009) [3] Ohya, S., Kaneco, S., Katsumata, H., Suzuki, T., Ohta, K. Catal. Today. 148 (2009)

120 KINETICS OF RICE HUSK CHAR GASIFICATION WITH CARBON DIOXIDE J. Alvarez, G. López, M. Amutio, M. Artetxe, I. Barbarias, A. Arregi, M. Olazar PO Box 644, E48080 Bilbao, Spain Chemical Reaction Engineering Rice husks are promising feedstock for pyrolysis because of their steady supply from rice plants and suitable physical properties for providing bio-oil. However, economic viability is only obtained when pyrolysis processes are not limited to primary products, but rather they include stages for obtaining higher value added products, such as high quality active carbons. Physical activation of lignocellulosic chars with carbon dioxide is a conventional manufacturing process of activated carbons. The kinetic information of this process is of special relevance for the design of a reactor for char activation process. The aim of this work is to study the reactivity of rice husk char with CO 2 to confirm the suitability of the model proposed for predicting the experimental data. In this study, kinetics parameters are calculated for the gasification of the char obtained from rice husk fast pyrolysis in a conical spouted bed reactor at 500 ºC. In order to improve the carbon content of the sample, a previous treatment with HCl (1M) and a dissolution of Na 2 CO 3 (15 wt. %) was carried out to extract the impurities and the silica present in the char, which accounted for up to 51 wt. %. The experiments were conducted using thermogravimetric equipment (TGA) with a char particle size in the mm range. The sample was heated in an inert atmosphere (nitrogen) flow until the carbonization temperature (800 C) was reached. Once that temperature was attained, nitrogen flow was maintained for 1 h until the carbonization of the sample was completed. After that, the furnace temperature was lowered to 600 ºC and the gasifying gas was introduced into the reactor with a flow rate of 50 ml min -1. Then, the sample was heated to 900 ºC at various heating rates (5, 10 and 20 ºC min -1 ) and using different CO 2 concentrations in the inlet gas (100, 75 and 50 vol. %, respectively). Finally the temperature was maintained at 900 ºC for 10 min in order to complete the gasification of the char. The kinetic parameters (activation energy, pre-exponential factor and reaction order) were determined based on a modified volume-reaction model. The fit between the calculated results and the experimental values of DTG was carried out by means of a program developed in MATLAB. The activation energy and the pre-exponential factor of best fit are KJ mol -1 and s -1 atm -0.85, respectively. The gasification reaction rate of rice husk char with CO 2 may be expressed as: dx/dt= ( ) exp(-343.5/rt)(p CO2 ) 0.85 (1-X) Fig 1 shows that the results calculated by using the modified volume-reaction model are consistent with the experimental results for rice husk char gasification. Conversion a Calculated Experimental Temperature Temperature (K) Time (min) Time (min) Figure 1. Experimental and calculated char conversion values for a heating rate of 10 K min -1 and CO 2 partial pressures of 1 atm (a) and 0.5 atm (b). Conversion b Calculated Experimental Temperature Temperature (K)

121 THERMOKINETIC ANALYSIS OF PYROLYSIS OF AQUATIC BIOMASS, LIGNITE COAL AND THEIR BLENDS Selim Ceylan 1, *, Yıldıray Topcu 1, Zeynep Ceylan 2 1 Ondokuz Mayıs University, Chemical Engineering Department, 55139, Kurupelit, Samsun 2 Ondokuz Mayıs University, Industrial Engineering Department, 55139, Kurupelit, Samsun Corresponding Author Phone : Scientific topic : 1.3 Chemical Reaction Engineering - Kinetics This study aims to investigate non-isothermal thermokinetics of the co-pyrolysis of aquatic biomass, Ulva lettuce and coal. Seven weight ratios of blends were pyrolyzed under dynamic conditions from temperature C at 20 C/min heating rate. The co-pyrolysis processes of samples were mainly composed of three stages. Ulva lettuce started to decompose within the temperature range of C. However, coal decomposition was occurred at about between 220 C and 600 C. The devolatilazition behavior of each fuels was obtained individually and compared with the behavior of the blends to quantify existence of synergetic interactions. Formation of higher than expected volatile matter indicated synergetic interactions. By using correlation coefficients of different reaction models describing the co-pyrolysis were determined and the best fit models for different stages of the co-pyrolysis were used to describe pyrolysis mechanism. Simulation of co-pyrolysis utilizing calculated kinetic parameters was carried out and results showed good agreement with experimental data. Non-isothermal region

122 EXPERIMENTAL INVESTIGATION OF FARADAIC AND ENERGETIC EFFICIENCIES IN AN ACTIVE DIRECT METHANOL FUEL CELL Z. İlbay *, M. Bayramoglu ** * Istanbul University, Engineering Faculty, Department of Chemical Engineering, Avcılar, Istanbul, Turkey, , fax: , ** Gebze Institute of Technology, Engineering Faculty, Department of Chemical Engineering, Gebze/Kocaeli, Turkey, , fax: Chemical Reaction Engineering This study deals with the experimental assessment of the faradaic as well as energetic efficiencies of active direct methanol fuel cell (DMFC). Initially, polarization studies were done to assess the effects of operating conditions namely, methanol concentration, fuel cell temperature and flow rates of air and methanol solution on the fuel cell performance. The test system was equipped with various sensors to collect on-line carbon dioxide and water vapor concentration and with sampling ports to collect liquid samples to measure off-line methanol, formaldehyde and formic acid concentrations by means of HPLC and UV spectroscopy. A factorial experimental plan with methanol concentration and fuel cell temperature as process variables was conducted to collect the process data during 3 hour runs. Stoichiometric and various efficiencies calculations were performed based on the mass balance model of the system and the process data. Keywords: DMFC; faradaic efficiency; energetic efficiency; methanol; formaldehyde; formic acid; methanol crossover.

123 FENTON-LIKE OXIDATION OF ORANGE II WITH NATURAL ARGENTINIAN DIATOMITES N. Inchaurrondo 1, J. Chirinos 2, J. Font 2, P. Haure 1 1 INTEMA- CONICET/UNMdP, Dpto. Ingeniería Química/ Div. Catalizadores y Superficies, Juan B. Justo 4302, 7600 Mar del Plata, Argentina; tel , 2 Departament d'enginyeria Química, Universitat Rovira i Virgili, Av. Països Catalans 26, Tarragona, Spain; Tel.: , Scientific Topic: Advanced Techniques for Effluent Treatment Diatomite is an abundant, low cost material, widely available from a sustainable source. Its composition includes mainly opal or hydrous silica (SiO 2 -H 2 O) but also alumina, iron, alkali metal oxides, and a minor amount of other impurities, such as P 2 O 5 and TiO 2. This natural material is commonly used as adsorbent and catalyst support, yet the presence of a relatively high percentage of iron would enable its use as heterogeneous Fentonlike catalyst without requiring major modifications. In this contribution, thermally treated Argentinean diatomite (0.4 wt% Fe) was used as Fenton-like catalyst for the degradation of the azo-compound Orange II (OII) in a laboratory batch reactor. The raw diatomite was sieved between 7 and 8 mesh ( mm). Then, calcination was carried out at three different final temperatures, 500, 700 and 1000 C, under air atmosphere in a programmable furnace. Fresh and calcined samples were thoroughly characterized. Calcination resulted in the removal of impurities, the skeletal structure of diatoms partially collapse at higher temperatures, but the original geometry was mostly preserved. Upon calcinations, the Fe percentage increased from 0.41 % (raw) to 0.45 % (700 C) and the shrink and hardening of individual particles was generated. This may have contributed to the gradual reduction of the surface area from 79 m 2 /g (raw) to 35 m 2 /g (700 C). Preliminary experiments discarded the effect of adsorption on OII removal in the ph range 3 to 4. Orange II Fenton-like tests were performed varying the diatomite calcination temperature, reaction temperature (50, 60, 70, 80 C); catalyst load (0.48, 0.96, 1.92 and 3.84 g), H 2 O 2 dose (10.96, 13.7, mmol/l) and ph (2-4). Table 1 summarizes most relevant results attained at 240 min. Table 1. OII, TOC and H 2 O 2 final conversions (240 min) under the whole operating conditions studied. Calcination Catalyst H2O2 OII T ( C) Initial ph T ( C) (g) (mmol/l) (mg/l) XOII XTOC XH2O ,72 13, ± ± ,84 13, ± ± ,84 13, ± ± ,84 13, ± 6 74 ± ,84 13, ± ± ,84 13, ± ± ,84 13, ± ± ,84 13,7 3, ± 2 65 ± ,84 13, Negligible 54 ± ,84 13,7 3, ± 1 33 ± ,48 13, ± ± ,96 13, ± 2 93 ± ,92 13, ± 3 94 ± ,96 10, ± ± ,96 20, ± 5 73 ± 5 Complete decoloration (100%) and TOC abatement (68 %) were achieved after 240 min at 70 C using a catalyst concentration of 0.96 g/l and the stoichiometric requirement of oxidant. The amount of Fe leached was less than 1 mg/l. The diatomite catalyst performance is comparable or even better to that reported in literature, using an OII concentration higher than the commonly evaluated.

124 PREPARATION OF M-Ag/ZSM-5 (M: Mn and Fe) BIMETAL NANOCATALYST FOR NH3-SCR of NO Aligholi Niaei a,1, Parvaneh Nakhostin Panahi a,b, Darush Salari a, Seyed Mahdi Mousavi c a Department of Chemical Engineering & Applied Chemistry, University of Tabriz, Tabriz, Iran. b Department of Chemistry, University of Zanjan, Zanjan, Iran. c Faculty of Chemistry, University of Kashan, Kashan, Iran. In this study, monometallic Ag/ZSM5 and bimetallic M-Ag/ZSM-5 (M: Mn and Fe) nanocatalysts were prepared by impregnation method and investigated for NO selective reduction by ammonia in excess oxygen. Ag/ZSM-5 nanocatalysts showed a good activity, but produced large amounts of N 2 O and selectivity to N 2 was low. The modification of Ag/ZSM-5 catalyst through the addition of Mn and Fe transition metals was carried out for improvement of N 2 selectivity. Transition metal oxides were active in the decomposition of N 2 O to N 2. The activity of H-ZSM-5, Ag/ZSM5 and M-Ag/ZSM-5 nanocatalysts in NH 3 -SCR reaction are presented in Figure 1. Fe-Ag/ZSM-5 bimetallic nanocatalyst showed the highest activity of 95% NO conversion and 73% selectivity to N 2 at 300 C. Figure 1: NO conversion (a) and selectivity to N2 (b) of Ag/ZSM-5 and M-Ag/ZSM-5 Several techniques, X-ray diffractometry (XRD), Transmission electron microscopy (TEM), Nitrogen adsorption-desorption (BET), Ammonia temperature-programmed desorption (NH 3 -TPD), and X-ray photoelectron spectroscopy (XPS), were employed to characterize of Ag/ZSM5 and bimetallic Ag-M/ZSM-5 nanocatalysts. TEM results revealed that the uniform distribution of metal particles exist in Fe-Ag/ZSM-5 catalyst. XPS results also showed that ferric species are enriched on the surface at Fe-Ag/ZSM-5 nanocatalyst and according to the results of NH 3 -TPD measurements; the Fe-Ag/ZSM-5 had more acidic strength than other catalysts which may be possible explanations for the highest activity of the Fe-Ag/ZSM-5 catalyst. References 1. S. E. Maisuls, K. Seshan, S. Feast, J. A. Lercher, Appl. Catal. B. 29, 69 (2001). 2. A. Jodaei, D. Salari, A. Niaei, M. Khatamian, S. A. Hosseini, J. Environ. Sci. Health, Part A. 46, 50 (2011). 1 Corresponding author: Prof. of Chemical Engineering, Phone: , Fax: ,

125 THERMAL BEHAVIOUR AND KINETICS OF MACROALGA BIOMASS DURING PYROLYSIS Zeynep Ceylan 1, *, Selim Ceylan 2, Yıldıray Topcu 2, 1 Ondokuz Mayıs University, Industrial Engineering Department, 55139, Kurupelit, Samsun 2 Ondokuz Mayıs University, Chemical Engineering Department, 55139, Kurupelit, Samsun Corresponding Author Phone : Scientific topic : 1.3 Chemical Reaction Engineering - Kinetics Biomass is an important alternative to fossil fuels because it is clean, renewable and fast growing. Macro algae have been proposed to have great potential as biomass. Macro algae primarily composed of polysaccharides can be converted into fuels such as bio-oil or bio-gas by pyrolysis. Thus, a comprehensive knowledge of pyrolysis process and kinetic analysis of different aquatic biomasses is required. In this study, the pyrolytic and kinetic characteristics of macroalga, Cystoseria barbata, from coast of Samsun, Turkey was evaluated at heating rates of 5, 10, 20 and 40 C min 1 under N2 atmosphere using a thermalgravimetry (TG). Kinetic parameters were determined using non-isothermal methods. Model-free methods are more reliable than model fitting methods in determination of activation energy because they can be used without knowledge on reaction model. In this study model free Friedman Method was used to calculate activation energy during pyrolysis. The obtained activation energy was applied in Coats Redfern method to calculate kinetic parameters including pre-exponential factor and reaction order. Simulation of macroalgae pyrolysis using data obtained from TGA analysis showed good agreement with experimental data ln(dx/dt) /T Fig.1. Plots for determination of activated energy at different conversion by Friedman Method

126 UTILISING CARBON DIOXIDE: INTEGRATING ENVIRONMENTAL SUSTAINABILITY CONSIDERATIONS INTO PROCESS DESIGN Rosa M. Cuéllar-Franca 1 and Adisa Azapagic 1 1 School of Chemical Engineering and Analytical Science, The Mill, Sackville Street, The University of Manchester, Manchester M13 9PL, UK Tel.: +44 (0) ; Fax: +44(0) Chemical Engineering for Sustainable Development 2.1 Natural Resources Sustainability: Life Cycle Assessment An increasing interest in carbon capture and utilisation has opened the door for exploring opportunities for using waste CO 2 as a feedstock for the production of high-value products such as fuels. The production of synthetic fuels from fossil resources such as coal or natural gas is a well-established practice, especially in countries with limited reserves of crude oil. However, while the possibility of converting waste CO 2 into synthetic fuels is attractive, the life cycle environmental implications of such fuels are uncertain, mainly because of the high thermodynamic stability of CO 2 and the demanding process conditions, i.e. high temperature and pressure. Thus, there is a risk of producing synthetic fuels from capture CO 2 with the overall CO 2 emissions higher than if the waste CO 2 was discharged directly into the environment. To explore this issue, the paper considers production of synthetic diesel in a Fischer-Tropsch (FT) process using waste CO 2 from anaerobic digestion of sludge from wastewater treatment. Using an Aspen model, the study shows how life cycle considerations can be integrated into process design and how environmental hot spots can be translated into key design targets to improve the environmental sustainability of the system from cradle to grave. Several process alternatives are considered, including different sources of hydrogen and recycling levels of monoethanolamine (MEA). The results indicate that the MEA is the main hot spot and with no recycling (regeneration), total global warming potential (GWP) of the FT diesel is nine times higher than for conventional (fossil) diesel. However, by setting design targets for MEA recycling, it is possible to produce FT diesel from CO 2 with the GWP comparable to that of conventional diesel. In the case of hydrogen sourced from natural gas reforming, the target of a minimum of 95% recycled MEA must be achieved; if using hydrogen from naphtha cracking or from water electrolysis, this target is 92% because the hydrogen from these sources has lower life cycle impacts. Increasing MEA recycling beyond the target levels will lead to lower impacts from synthetic than fossil diesel. These findings illustrate how consideration of life cycle environmental impact in early stages can enable engineers to optimise design by focusing on the life cycle stages that have the highest impacts, thus leading to more sustainable systems by design. Key words: Carbon capture and utilisation (CCU), Fischer Tropsch fuels, Life cycle assessment (LCA), global warming potential (GWP), chemical process design.

127 SUSTAINABLE WET FLUE GAS DESULFURIZATION: FROM LAB-SCALE BATCH REACTOR TO PILOT SCRUBBER R. del Valle-Zermeño 1,*, J. Aparicio 2, M. Guembe 2, J.Formosa 3, J.M. Chimenos 1 1 Departament de Ciència de Materials i Enginyeria Metal lúrgica, Universitat de Barcelona, Martí I Franquès, 1, E Barcelona, Spain 2 Magnesitas Navarras, S.A. Zubiri, Spain. 3 Departament de Construccions Arquitectòniques II. Universitat Politècnica de Catalunya, Barcelona, Spain. * Corresponding author: Tel.: ; Fax: address: Scientific Topic: Chemical Engineering for Sustainable Development The Industrial Emissions Directive (2010/75/EU) related to the Integrated Pollution Prevention and Control have demanded the Cement, Lime and Magnesium Oxide industries to reduce the SO 2 emissions to limits as low as 400 mg/nm 3 and in some cases to 50 mg/nm 3. Furthermore, the Best Available Techniques (BAT) document derived from the same directive have also fostered to do this achievement by means of sustainable methods that include the use of low-waste technologies and the recovery and recycling of the substances generated. The production of magnesium oxide from the calcination of natural magnesite entails the use of coal-fired kilns that release to the atmosphere the sulphur contained in coal. So far, the most widely applied Flue Gas Desulfurization (FGD) technology for the abatement of sulphur emissions has been the limestone wet FGD process, because of its simplicity, availability, low cost and relatively high removal efficiencies [1 4]. However, the increasingly regulatory limits have encouraged the use of sustainable and more efficient alternatives. For this purpose, the initial research focused on the potential reutilization of the by-products from the calcination process. These by-products are usually referred to as Low-Grade magnesium (hydr)oxide (LG-MgO/Mg(OH) 2 ) and had proven to be effective in several environmental applications such as the stabilization of electrical arc furnace (EAF) dust prior landfill, in the removal of ammonium and phosphates from industrial wastewaters, as ignifugant filler in polymers and for the formulation of Chemically Bonded Phosphate Ceramics [5 8]. These by-products are characterized for being a mixture of mainly magnesium (hydr)oxides and different proportions of calcium (hydr)oxides, dolomite, siliceous materials and other impurities such as Fe and S, altering their alkaline behavior and therefore their acid neutralization capacity [9]. Because of these reasons, it seemed that these by-products could be a sustainable and effective alternative for treating the exhaust gases at the outlet of the calcination kiln. Taking into account all the above mentioned, the authors carried out several lab-scale experiments using a discontinuous batch reactor. The desulfurization experiments were performed by placing different slurries (L) with different solid-to-water (S/W) ratios of the different by-products in a stirred glass reactor where a simulated gas (SO 2 concentration= ppmv = 26,176 mg m -3 ) was injected and bubbled from the bottom. The results allowed to define the optimum conditions and the most suitable by-product for 100% removal efficiency [10,11]. The results obtained were extrapolated to a pilot scale plant (packed column scrubber) using two transposition variables, the liquid-to-gas ratio (L/G) and the ph of the slurry. This transposition was made possible by taking into advantage the mass-transfer controlled nature of the process and the promising results obtained during the laboratory stage of the study. There are few studies concerning the transposition of variables, and most of them have focused in the same technology at different scale [12]. The aim of this study is to present the methodology employed during the transposition process and the results derived from the scaling, highlighting the most important results and the obstacles found during the process and the set-up of the pilot plant scrubber. The pilot plant is nowadays successfully under operation and the industrial plant is set to be constructed by the end of To the knowledge of the authors, this is the first study concerning the transposition process of two different technologies at two different scales for wet FGD.

128 References [1] R. Biswas, S. Devotta, T. Chakrabarti, R.A. Pandey, Flue Gas Desulfurization: Physicochemical and Biotechnological Approaches, Crit. Rev. Environ. Sci. Technol. 35 (2005) [2] B. Dou, W. Pan, Q. Jin, W. Wang, Y. Li, Prediction of SO2 removal efficiency for wet Flue Gas Desulfurization, Energy Convers. Manag. 50 (2009) [3] J.B.W. Frandsen, S. Kiil, J.E. Johnsson, Optimisation of a wet FGD pilot plant using fine limestone and organic acids, Chem. Eng. Sci. 56 (2001) [4] F.J. Gutiérrez Ortiz, F. Vidal, P. Ollero, L. Salvador, V. Cortés, A. Giménez, Pilot-plant technical assessment of wet flue gas desulfurization using limestone, Ind. Eng. Chem. Res. 45 (2006) [5] J.M. Chimenos, A.I. Fernández, G. Villalba, M. Segarra, A. Urruticoechea, B. Artaza, et al., Removal of ammonium and phosphates from wastewater resulting from the process of cochineal extraction using, Water Res. 37 (2003) [6] A.I. Fernández, J.M. Chimenos, N. Raventós, L. Miralles, F. Espiell, Stabilization of electrical arc furnace dust with low-grade MgO prior to landfill, J. Environ. Eng. 129 (2003) [7] J. Chimenos, A. Fernandez, A. Hernandez, Optimization of phosphate removal in anodizing aluminium wastewater, Water Res. 40 (2006) [8] J. Formosa, J.M. Chimenos, A.M. Lacasta, M. Niubó, Interaction between low-grade magnesium oxide and boric acid in chemically bonded phosphate ceramics formulation, Ceram. Int. 38 (2012) [9] J.M.C. R. del Valle-Zermeño, J. Giró-Paloma, J.Formosa, Low-Grade Magnesium Oxide by-products for environmental solutions: characterization and geochemical performance, Appl. Geochemistry. Submitted (2014). [10] del Valle-Zermeño, R., Formosa, J., Aparicio, J., Chimenos JM, Reutilization of Low-Grade Magnesium oxides for flue gas desulfurization during calcination of natural magnesite: a closed-loop process, Chem. Eng. J. (n.d.). [11] J.M.C. R. del Valle-Zermeño, M.Niubó, J. Formosa, Synergistic effect of the parameters affecting wet flue gas desulfurization using magnesium oxides by-products, (n.d.). [12] F. Theron, Z. Anxionnaz-Minvielle, N. Le Sauze, M. Cabassud, Transposition from a batch to a continuous process for microencapsulation by interfacial polycondensation, Chem. Eng. Process. Process Intensif. 54 (2012)

129 MICROBIAL FUEL CELLS FOR ENERGETIC VALORIZATON OF WASTE STREAMS S. Mateo, J. Lobato, P. Cañizares, J. Villaseñor, M.A. Rodrigo, F.J. Fernández* Chemical Engineering Department. University of Castilla La Mancha. Campus Universitario s/n Ciudad Real. Spain. Phone: (ext. 6350), Fax: , Scientific Topic (2. Chemical Engineering for Sustainable Development, 2.1 Natural Resources Sustainability, Renewable Raw Materials and Waste Valorization) A Microbial fuel cell (MFC) is a bioelectrochemical device which converts the chemical energy of a fuel into electrical energy with the aid of biocatalytic reactions carried out by microorganisms. These microorganisms can be present in the anodic chamber, where they oxidize substrates, generating electrons, protons and other metabolic products, and /or on the cathodic chamber where microorganisms reduce chemical specie. Electrons generated in the oxidizing reactions taking place in the anodic reactions pass through an external circuit, generating an electrical current, and when they reach the cathode, where the electrons are used in the reduction reactions. Usually these reactions involve the consumption of protons, which diffuse from the anodic compartment through a membrane, and oxygen to produce water. One of the main applications of MFC is the energy harvesting from wastes. In this work the fundamentals of this interesting technology as well as some applications are presented, moreover it has been analyzed the performance of several kinds of MFC for waste streams valorization. With this aim, the conventional MFC were analyzed and compared with those presenting modifications to enhance the performance. The modifications were focused on coupling the MFC with other well know natural technologies because of the low-cost and know-how of these processes, being the main objective in all the cases to harvest the energy contained waste streams. The modifications studied were based on the following: o Algae based biocathodes: in this configuration the cost of aeration is reduced by changing the mechanical aeration device to an algal oxygen supply, which can also reduce CO 2 emissions. Hence, a photosynthetic culture of algae at the cathode, with light radiation, utilizes CO 2 as the carbon source for photosynthesis and produces oxygen, which acts as an electron acceptor for electricity generation. Algae can also act as a biological electron acceptor while simultaneously reducing carbon dioxide to biomass. For example, it is possible to couple photosynthetic bioreactors using microalgae in the cathode with anaerobic oxidation of organic substrates in the anode produced by photosynthesis or contained in a wastewater flow. When sunlight is converted into electricity within the metabolic reaction scheme of a microbial fuel cell, this system is described as a Photo-synthetic Microbial Fuel Cell. o Constructed wetland MFC: this configuration is based on the combination of two principles: Plants biocathode: in this configuration the roots of a living plant supply oxygen to the cathode. Benthic MFC: in this configuration the sediment supplies organic substrate to the oxidation reaction taking place in the anodic chamber. In these systems, the cathode is usually located next to the overlying of the surface water. In these conditions, there is a natural redox potential difference between the two electrodes and no membranes are located between them. The organic matter in the sediment is the fuel or electron donor for the MFC, and it can be of natural origin (e.g. humic acids, decomposing biomass) but also can be organic pollution (e.g. oil hydrocarbons).

130 ph DEPENDENCE LEACHING TESTS: METAL RELEASE FROM CONTAMINATED SEDIMENT IN A POTENTIAL CARBON STORAGE AREA M. Camino Martín-Torre*, Iciar Muñoz, Alberto Coz, Berta Galán, Javier R. Viguri Department of Chemistry and Process & Resources Engineering, ETSIIT, University of Cantabria, Avda. de los Castros s/n, Santander, Cantabria, Spain * Presenting author: tel.: ; fax: ; Scientific topic: Natural resources sustainability; Green chemistry and engineering Sediment is the principal sink for trace metals in aquatic systems. Modifications in the media, like ph changes, might mobilise these pollutants, endangering the natural equilibria. Oceans and water-sediment systems are expected to modify their ph value as a consequence of the acidification produced by the increase of CO 2 emissions, by potential leakages from Carbon Capture and Storage (CCS) sites or by accidental chemical spills. In this work, two different leaching tests are used to assess the release of pollutants (As, Cd, Cr, Cu, Ni, Pb, Zn) and Dissolved Organic Carbon (DOC) from a contaminated sediment located in a potential CCS area in the North of Spain. For the most feasible ph changes, the influence of ph with initial acid/base addition (CEN/TS 14429) and with continuous ph control (CEN/TS 14997) is analysed. Both essays are carried out for 48 hours and using seawater as leaching solution to simulate real scenarios. The differences between both methodological procedures allow to evaluate two types of acidification: the initial addition of acid (CEN/TS 14429) represents a potential sporadic CO 2 leak whereas the maintenance of a ph value (CEN/TS 14997) mimics a constant acidification. Different quantities of acid are needed to achieve the same ph value, showing that both types of acidification have different influence on the buffer capacity of the sediment-seawater system. Although metal release depends on the ph dependence leaching test applied, the highest mobilisation of metals happens at the most acidic conditions in both essays. In order to have a tool for pre-incidental planning and risk assessment in the sea area, a geochemical model using Visual MINTEQ 3.0 is accomplished. The main components of the contaminated sediment and seawater, the adsorption to Fe- and Al-(hydr)oxides and the influence of organic matter were considered. Modelled results match well with the experimental ones. When it does not occur, modelled values are more conservative, warning the environment to be damaged. Hence, obtained results can be useful to predict environmental impact assessment of the acidification/alkalinisation of seawater in contact with contaminated sediment. Acknowledgements This work was supported by the Spanish Ministry of Economy and Competitiveness, Project CTM C02-01, ERDF included. M.C. Martín-Torre was funded by the Spanish Ministry of Economy and Competitiveness by means of an F.P.I. fellowship no. BES

131 ANAEROBIC CO-DIGESTION OF OLIVE OIL MILL WASTES AND PIG MANURE FOR THE MAXIMIZATION OF BIOGAS PRODUCTION E. Genescà 1. S. Martínez-Lozano, E. Borràs, J. García Montaño, A. Surribas 1 LEITAT Technological Center, R&D Environmental and Bio Technologies Department, C/ Innovació, 2, Terrassa (Barcelona), 2.1 Natural Resources Sustainability The olive oil industry produces high amount of solid wastes (Solid Olive Mill Wastes, SOMW) and wastewater (Olive Mill Wastewater, OMW). A total amount of 2.5M tones of OMW and olive washing wastewater, 4.1M of tones of two-phase SOMW and 0.4M of tones of three-phase SOMW are yearly produced in Spain 1,2,3. These residues are difficult to manage and treat because of their high organic load (including oils, fats and polyphenols) and they are disposed into vessels for natural drying and stabilisation. This strategy produces negative environmental impacts such as atmospheric pollution (odors), land use, insect plagues, overflowing and other problems in high pluviometry locations leading to stop-up industrial production and economic sanctions. This problem is increased in regions with water scarcity where most of olive industry is located 4. Anaerobic Digestion (AD) is a mature technology used at industrial scale for the treatment of organic residues aiming to produce biogas and stabilized wastes which can be used for fertilizer applications. The high organic content of SOMW and OMW, including AD inhibitors such as Polyphenolic compounds and long chain fatty acids (LCFAs) limits the use of AD as reliable technology for the efficient treatment of these wastes. This study is focused on valorisation of SOMW and OMW and the maximization of biogas production using AD technology at laboratory and semi-pilot scale using pig manure as a co-substrate. In a first stage of the research, a ratio of 1SOMW:1OMW was selected for AD experiments from other ratios according (1) the amount of wastes produced by the olive oil mill, (2) the theoretical C:N:P ratio of wastes mixtures, (3) the resulted COD and Polyphenol content from mixing wastes, and (4) Biochemical Methane Potential (BMP). An inoculum from and industrial AD of a wastewater treatment plant was selected for BMP. In a second stage, pig manure (P) was selected as a co-substrate in order to supply the nitrogen requirements for the success of AD. According to BMP tests, a 3 to 1 ratio of pig manure to olive waste (3P:1O) gave better biogas production yield (0.19L CH 4 /g COD removed) and was selected as optimal co-substrate ratio. Ratios with lower pig manure content (1O:1P, 3O:1P) showed inhibitory behavior. The optimal conditions (3P:1O, mesophilic) were scaled up to a 5L digester. The process was started in batch mode and the conditions were switched to continuous mode once the system was stabilized. Continuous mode was initiated feeding the 3P:1O mixture (0.635 kg organic volatile matter/m day or kg total organic dry matter/m 3 day) into the reactor and mantaining an hydraulic retention time (HRT) of 40 days. The system was stabilised producing around 2L biogas /day (0.44 m 3 biogas/m 3 reactor day). Methane content of biogas was 70%. After 40 days of operation in a continuous mode, the system was then fed with 3P:2O ratio maintaining the same HRT (2.029 kg organic volatile matter/m3 day or kg total organic dry matter/m 3 day). The system was stabilised producing 2.7L biogas/day (0.60 m 3 biogas/m 3 reactor day). Methane content of biogas was 65%. Finally, after 50 days of operation using 3P:2O ratio, the system was then fed with 1P:1O. The system has been in operation 80 days with the 1P:1O mixture (2.126 kg organic volatile matter/m 3 day or kg total organic dry matter/m 3 day) showing significant fluctuations in biogas production with an average production of 2.3L biogas/day (0.51 m 3 biogas/m 3 reactor day). Methane content of biogas has been 63%. At the moment the feed has been switched back to the 3P:2O ratio as it is the optimal feeding composition. With the aim of increasing the OLR a second strategy is now ongoing by which 3P:2O composition is kept as optimal inlet and the HRT is being reduced. This study was performed in the frame of Biogas2PEM-FC project (7FP Capacities, SME ) (GA: ). The project aims to develop and demonstrate a novel and integrated solution for the efficient valorisation of SOMW and OMW by integrating enhanced AD technology with further biogas reforming and proton exchange membrane fuel cells (PEM) technology at pilot scale. 1 M.J. Paredes, E. Moreno, A. Ramos-Cormenzana, J. Martinez, Characteristics of soil after pollution with wastewaters from olive oil extraction plants. Chemosph, 16(7) (1987), M. DellaGreca, P. Monaco, G. Pinto, A. Pollio, L. Previtera, F. Temussi, Phytotoxicity of low-molecular-weight phenols from OMW, Bull.Environ.Contam.Toxicol. 63(3) (2001) G. Rana, M. Rinaldi, M. Introna, Volatilisation of substances alter spreading olive oil wastewater on soil in a Mediterranean environment, Agric.Ecos.&Env., 96(1-3) (2003) C.J. McNamara, C.C. Anastasiou, V. O Flaherty, R. Mitchel. Bioremediation of olive mill wastewater. International Biodeterioration and Biodegradation, 61 (2008),

132 INFLUENCE OF THE EMULSIFIER CONCENTRATION ON THE PHYSICAL STABILITY AND RHEOLOGY OF ECO-FRIENDLY NANOEMULSIONS L.A. Trujillo-Cayado, J. Santos, M.C. Alfaro, N. Calero and J. Muñoz Departamento de Ingeniería Química. Facultad de Química. Universidad de Sevilla c/ P. García González, 1, E Scientific topic: Green Chemistry and Engineering Many industrial products, such as traditional agrochemical formulations use flammable and toxic solvents. These are being gradually replaced by less toxic and eco-friendly alternatives. In this study, we examined the influence of surfactant concentration on the preparation and physical stability of nanoemulsions. The formulation involves the use of a mixture of green solvents (N,N-dimethyldecane amide and -pinene) as dispersed phase and a non-ionic polyoxyethylene glycerol ester as emulsifier (Levenol C-201). Fatty acid dimethylamides (FAD) are among green solvents that can find applications in agrochemicals. -Pinene is also a renewable solvent, which may be obtained from pine resins or distillation. Polyoxyethylene glycerol esters derived from cocoa oil are non-ionic surfactants that fulfil the environmental and toxicological requirements to be used as emulsifiers in order to design eco-friendly products. Emulsions were prepared using a high-pressure homogenizer based on micro-channel technology (microfluidizer). Microfluidics is the methodology of choice if fluid-like emulsions with submicron mean diameters and narrow droplet size distributions (DSD) are the target, given that this technology allows reaching extremely high shear rates. Once emulsions are prepared, it is essential to detect the onset of any destabilization process at an early stage to shorten aging tests. In addition, determining the destabilization mechanisms provides outstanding feedback on formulation and processing variables. The cooperative information provided by multiple light scattering, laser diffraction and rheology offers a clear panoramic view of the stability of dispersions as a function of aging time. One of the critical parameters that must be carefully controlled in emulsion formulation is the emulsifier concentration. A minimum surfactant bulk concentration is required to fully cover the available interfacial area created during the emulsification process. However, an excess of surfactant in solution will lead to the formation of micelles in the continuous phase. It is well known that non-adsorbed surfactant micelles could induce the flocculation of emulsion droplets due to a depletion mechanism. Although flocculation is a reversible process, it could promote some irreversible destabilization mechanisms such as creaming and / or coalescence. The concentration of non-ionic polyoxyethylene glycerol fatty acid ester surfactant was found to significantly influence the oil droplet size distribution, rheological properties and physical stability of emulsions studied. Below 1 wt% surfactant, emulsions were mainly destabilized by creaming and coalescence. Increasing surfactant concentrations in the (2 3) wt% range yielded greater apparent viscosities and lower flow index values due to the fall of droplet diameters. These emulsions, prepared at intermediate surfactant concentrations, exhibited enhanced stability due to the fact that their high viscosity avoids creaming and the existence of a reduced number of flocs resulted in limited coalescence. Above 4 wt% surfactant, the mean droplet diameters of emulsions aged for 1 day levelled off indicating the lack of significant droplet coalescence and their flow curves were more shear thinning as demonstrated by their lower flow index values. As emulsions aged, the creaming index calculated from multiple light scattering increased due probably to a depletion flocculation phenomenon, which subsequently led to an increase of droplet sizes (coalescence). This work is a contribution to the development of sustainable product engineering by scouting the applications of green solvents in model agrochemical emulsions. These new findings can have applications concerning the rational design of eco-friendly emulsions with promising applications in agrochemical formulation. ACKOWLEDGMENTS The financial support received (Project CTQ ) from the Spanish Ministerio de Economía y Competitividad and from the European Commission (FEDER Programme) is kindly acknowledged. The authors are also grateful to BASF and KAO for providing materials for this research.

133 QUARTZ COATING TO REDUCE ITS TOXICITY IN CERAMIC COMPOSITIONS E. Monfort 1, A. Escrig 1, M.J. Ibáñez 1, G. Bonvicini 2, A. Salomoni 2, O. Creutzemberg 3, C. Ziemann 3 1 Instituto de Tecnología Cerámica AICE, Universitat Jaume I, Castellón (Spain). 2 Centro Ceramico di Bologna (CCB), Bologna (Italy). 3 Fraunhofer Institute for Toxicology and Experimental Medicine (ITEM), Hannover (Germany) Author presenting the communication: Eliseo Monfort T Topic: Green Chemistry and Engineering Abstract: Inhalation of respirable crystalline silica, for example as quartz, produces the well-known pathological reaction called silicosis. Ceramic industries use quartz-containing raw materials, such as clay, sand or quartz as such and can present considerable amounts of this pollutant in the work environment. The substitution of quartz in the ceramic compositions is not possible because it plays a key role in the manufacturing process. Numerous studies suggest that the toxicity of quartz is conditioned by the surface chemistry of the quartz particles and, in particular, by the density and abundance of silanol groups. Blocking these groups so that they do not interact with cellular membranes would theoretically be possible in order to reduce or even to nullify the toxic effect [1,2]. In this study, some feasible compounds have been identified that could be readily incorporated into the ceramic process. Subsequently, taking into account technical and economic criteria three compound were selected to coat the quartz contained in traditional ceramic compositions: propyltrimethoxysilane (PTMO), a commercial aminosilane and nano-alumina. Quartz coating treatment, in general, consisted of the following steps: a) Preliminary hydrolysis (necessary for PTMO and other organosilanes) in which their alkoxy groups dissociated, gave rise to silanol groups; b) Dispersion of the additive in water; c) Addition of the quartz and stirring of the resulting suspension during the requested reaction time; and d) Addition of the remaining components of the formula. The coating quality was studied by different instrumental techniques (TG, ζ potential, SEM and XPS) confirming that the reaction between quartz and the coating agents had occurred and showed thermal stability up to temperatures of 550ºC. Toxicity tests showed that coated quartz was significantly less toxic than untreated quartz. Pilot trials were run to check the behaviour of the treated compositions during the ceramic process; subsequently the ceramic final product properties were measured. The feasibility of coating implementation into different ceramic processes and the quality and stability of quartz coatings were demonstrated. Finally, the results of the industrial trials, carried out at the facilities of the industrial partners of the project consortium, denote that the proposed coating treatment of quartz in ceramic compositions reduces dramatically the quartz toxic activity at reasonable costs. Acknowledgements: This study is part of the activities of the SILICOAT project, funded under the Seventh Framework Programme of the European Union (FP7/ ), by Grant Agreement nº The authors also wish to thank the personnel at all the centres, organisations, and companies participating in the project: APICER (Portugal), ATOMIZADORA, PORVASAL y ASCER, (Spain), FLAMINIA (Italy), WALKÜRE, ZIEGEL y BVKI (Germany). References: 1. Fubini, B. Surface chemistry and quartz hazard. Ann. Occup. Hyg. 42(8), , Schins, R.P.F.; Duffin, R.; Höhr, D.; Knaapen, A.M.; SHI, T.; Weishaupt, C.; Stone, V.; Donaldson, K.; Borm, P.J.A. Surface modification of quartz inhibits toxicity, particle uptake, and oxidative DNA damage in human lung epithelial cells. Chem. Res. Tox., 15, , 2002.

134 SAFETY LIFE CYCLE ANALYSIS APPLIED TO THE ENGINEERING OF SAFETY VALVES IN PROCESS PLANTS Josep Basco, Lyondellbasell, Tarragona, Tf ; Joaquim Casal, UPC, Barcelona; Juan Antonio Vilchez, TIP,s, Barcelona. Life Cycle Assessment Pressure relieving systems, comprised of relief devices, are required to be installed on process equipment to prevent internal pressures from rising to levels, which could cause catastrophic equipment failure. They are intended to operate only during emergency situations, when a plant failure, accident or maloperation has caused an overpressure condition that the basic system design and its control systems cannot resolve. Pressure relief systems are the final and ultimate line of protection against catastrophic equipment failure and therefore are extremely critical safety elements. However this criticality is not always accounted for in existing plants. A literature survey shows that approximately 40% of installed pressure equipment has at least one pressure relief system deficiency (Berwanger, 2000); or that 17% of a total of 4000 safety valves analyzed have a deficiency: undersized valve, inlet pressure drop > 3%, total back pressure > 15% for non-bellows valves etc. (Westphal, 2003). In order to avoid this situation a new framework has been developed. It extends the concepts of safety life cycle of IEC (IEC 61511, 2003) as applied to the relief devices. The steps of the new conceptual framework comprise: a) Hazards and risk assessment, including a Process Hazard Analysis (Hazop, What-if etc.); b) Allocation of safety valves as layers of protection according to a LOPA analysis; c) Safety requirements specifications (relief load analysis, relief load calculation, inlet/outlet pressure drop, stability calculations to avoid chattering, forces and moments imposed to safety valve flanges, acoustic induced vibration, noise, body bowl chocking etc.); d) Installation, commissioning and validation (pre start-up safety review); e) Operation and maintenance according to a methodology to find the optimal inspection interval as API 581 Risk Based Inspection Technology; f) Management of change; g) Technical integrity audits and h) Dismantling. The new procedure was applied to existing polypropylene plants. Results are discussed and a list of recommended best practices is presented. Berwanger, P.C. et al (2000). Analysis identifies deficiencies in existing pressure relief systems. Process Safety Progress, 19 (3), Westphal, F.; Köper, O. (2003). Database-supported documentation and verification of pressure relief device design in chemical plants. Journal of Loss Prevention in the Process Industries, 16, IEC /3 (2003) Functional Safety - Safety Instrumented Systems for the process industry sector, IEC, Geneva, Switzerland.

135 ELECTROCHEMICAL VALORIZATION OF CO 2 : FORMATE PRODUCTION USING GAS DIFFUSION ELECTRODES A. Del Castillo 1, M. Alvarez-Guerra 1, J. Solla-Gullón 2, A. Sáez 2, V. Montiel 2, A. Irabien 1 1 Universidad de Cantabria, Dep. Chemical and Biomolecular Engineering, ETSIIT Avda. Los Castros s/n, Santander Spain. 2 Institute of Electrochemistry, University of Alicante Ap. 99, Alicante Spain 2. Chemical Engineering for Sustainable Development 2.1 Natural Resources Sustainability Green Chemistry and Engineering Reducing greenhouse gases emissions is necessary to mitigate climate change. In this sense, the development of new greener processes with a negative environmental impact is an interesting strategy to reduce the CO 2 emissions. Electrochemical valorization allows the conversion of CO 2 into added-value chemical products, such as raw materials for industries or liquid fuels. Particularly, electrochemical valorization has been suggested as an excellent way to store intermittent renewable energy like solar or wind energy, allowing the balance of electrical production. Among all the different electroreduction products, one of the most interesting is formate. Formate is used by several industries as raw material and it has been pointed out as a suitable fuel for fuel cells. Sn is an interesting electrocatalyst to convert CO 2 to formate as shown in our previous work [1]. Recently research efforts are focused on the use of gas diffusion electrodes (GDE) in electrochemical reduction of CO 2 [2]. These electrodes increase the available active surface of catalyst and allow operating the electrochemical cell at higher current densities. GDEs are formed by a catalyst that is deposited over porous layer. In this work different particle size and different loads of Sn were tested to analyse their influence on a process for continuous electroreduction of CO 2 to formate. The best GDEs were then used on an experimental system for continuous CO 2 electroreduction in a filter-press type cell at ambient temperature and pressure conditions to analyse the influence of operational variables.. Cyclic voltammetries were performed using particles of different size (150 µm, 10 µm and 150 nm) and using different charges (0.1, 0.75, 1.5, 5 mg Sn cm -2 ). According with the results obtained, cyclic voltammetries and cronoamperommetries were carried out using particles of 150 nm at different loads (0.1, 0.75, 1.5, 5 mg Sn cm -2 ) deposited over carbon paper as porous support. Physical characterization of these electrodes was performed using Scanning Electron Microscopy (SEM) micrographs. After electrochemical characterization, electrodes of 0.1 and 0.75 mg Sn cm -2 were tested on an experimental system for continuous CO 2 electrochemical reduction in a filter-press type cell. The faradaic efficiency and the rate of formate production were obtained to assess the performance.. Using these optimized electrodes was possible to obtain better results than previous work [3], GDEs with 150 nm particles allowed achieving rates of formate production over mol m -2 s -1 and faradaic efficiencies over 60%, working at current density of 120 ma cm -2. Acknowledgements: This work was conducted under the framework of the Spanish Ministry of Science and Innovation Project ENE References: [1] Alvarez-Guerra M., Del Castillo A., Irabien A., Continuous electrochemical reduction of carbon dioxide into formate using a tin cathode: Comparison with lead cathode. Chem. Eng. Res. Des. 2014; 92: [2] Prakash G.K.S., Viva F.A., Olah G.A., Electrochemical reduction of CO 2 over sn-nafion coated electrode for a fuel-cell-like devic.e J. Power Sources 2013; 223: [3] Del Castillo A., Alvarez-Guerra M., Irabien A., Continuous CO 2 electroreduction to formate using Sn cathodes: GDEs vs. plate electrodes 10thESEE 2014

136 OPTIMIZATION OF MICROALGAE CULTURE FOR BIODIESEL PRODUCTION A. González-Garcinuño, J.M. Sánchez-Álvarez, E.M. del Valle 1, M.A. Galán [1] Corresponding author: Eva M. Del Valle. Department of Chemical Engineering, University of Salamanca. P/Los Caidos s/n, Salamanca, Spain. Mail: Phone: Scientific topic: Green Chemistry and Engineering Human population will incredibly raise during next years, reaching ten billion people in It implies that energy needs will also exponentially increase to levels that can not be met with current sources. In addition, fossil fuel stocks are decreasing and their prices keep on rising to unaffordable amounts. For this reason, researching on alternative energies emerges as an essential field, so as to discover new sources which have appropriate characteristics for their use and do not cause adverse effects in environment. One possible alternative is microalgae culture in controlled conditions. Microalgae can accumulate lipids in high amounts, which could be transesterified with methanol in order to produce biodiesel. It has also been tested that biodiesel from microalgae obeys international quality criteria from ASTM. In our study, we have tried out different experiments with two microalgae strains: Scenedesmus abundans and Chlorella elliposoidea, which have not already been described in the literature. Optimizing microalgae culture medium is the main objective of this work, in which we have searched the best composition in order to increase lipid accumulation in our strains. Particularly, we have studied the effect of different nitrogen sources at different concentrations, in biomass yield and lipid production. These experiments have been done under heterotrophic and autotrophic conditions. On the one hand, heterotrophic cultures show nitrogen-substrate inhibition kinetics, which a high inhibition constant value in both strains. This substrate inhibition forces a reduction in nitrogen concentration, which is a desirable action, reducing the cost of bioreaction. Biomass yield exceeds three million cells per milliliter, and lipid accumulation reaches up to 25% w/w under the best conditions. On the other hand, autotrophic cultures do not show this inhibition and reveal good yields under particular conditions. Biomass yield is more than four million cells per milliliter in this case, showing a lipid balance similar to the heterotrophic one. However, fermentation time is longer in autotrophic culture remaining two more days in latent phase thus causing a reduction in lipid productivity value. After biomass disruption, lipids were extracted and evaluated using GC-MS, with the aim of identifying fatty acid profile. Relative amount of different fatty acids is really important for biodiesel production because it must respect criteria from ASTM, and this depends of original fatty acids profile. Plenty of our cultures provide a fatty acid profile which is adequate for specifications. Moreover, a new oleic acid isomer was found to be produced by both strains under heterotrophic conditions. This fatty acid has a double bond in its eleventh carbon and not in traditional number 9, and it has not been extensively studied, resulting in limited data about it. Further studies must be performed in order to determine the chemical characteristics of this special fatty acid which our cells produce in high percentage. In summary, Scenedesmus abundans and Chlorella elliposoidea are good strains for biodiesel production. Future experiments ought to optimize carbon and phosphorous sources, and fermentation conditions such as temperature, aeration or agitation. When all these parameters are defined, we will continue our research scaling-up the process.

137 MULTI-OBJECTIVE OPTIMIZATION APPLIED TO THE MINIMIZATION OF THE ENVIRONMENTAL IMPACT OF WATER CONSUMPTION IN AGRICULTURE: A CASE STUDY OF WHEAT PRODUCTION IN SPAIN Ángel Galán-Martín a *, Gonzalo Guillén-Gosálbez a,b, Assumpció Antón c, Laureano Jiménez a a Departament d Enginyeria Química, Universitat Rovira i Virgili, Av.Països Catalans 26, Tarragona (Spain). b School of Chemical Engineering and Analytical Science, University of Manchester, Mill, Sackville Street, Manchester M13 9PL (United Kingdom). c Institut de Recerca i Tecnología Agroalimentàries (IRTA), Ctra Cabrils, km 2, Cabrils (Barcelona-Spain). *Presenting author. Tel.: (+34) ; Fax: (+34) ; Scientific Topic: Chemical Engineering for Sustainable Development/Natural Resources Sustainability/Energy, Water and Materials/Life Cycle Assessment Water consumption in arid and semiarid countries is unsustainable and causes degradation of ecosystems. In Spain, almost 75 percent of all the freshwater consumption corresponds to the agricultural sector. In this backdrop, the reduction of freshwater use in agriculture is essential to ensure a sustainable development of future generations and to reduce the associated environmental impact. The aim of this study was to develop a systematic multi-objective optimization tool for the proper spatial allocation of rain-fed and irrigated agriculture that minimizes the environmental impact derived from water consumption and maximizes simultaneously the production rate of crops. To derive our approach, we developed a computer-based linear programming model that integrates water footprint data and life cycle assessment principles to support decision-making in water resource planning and management. The solution of the linear programming model allows obtaining the optimal distribution of the rain-fed and irrigated agriculture areas pursing several objectives such as minimal damage to ecosystem quality, minimal damage to resources or maximum production. The single-objective optimization provides a unique optimal solution, while the output of the multi-objective consists of a set of Pareto points representing the optimal trade-off between the conflicting objectives considered. The capabilities of our tool were illustrated through its application to a case of study of wheat production in Spain. The model identifies the optimal wheat rain-fed along with the irrigated areas in each watershed that improve water productivity and minimize the environmental damage to ecosystem quality and water resources. The single-objective optimization achieved significant improvements as compared with the current situation in each objective. However, worsening of the non-optimized objectives takes place, leading to unbalanced solutions that behave well in one criterion and poor in the others. Multi-objective optimization allowed obtaining a set of trade-off optimal solutions in which both bi-criteria objectives improved the current situation. From the set of Pareto points, decision-makers should select the best one according to their preferences and considering the views of the farmers and stakeholders. The developed systematic multi-objective optimization tool provides a useful framework for decision-makers, as it guarantees the adoption of optimal solutions and the implementation of more sustainable agricultural production patterns. The proper distribution of rain-fed and irrigated crops is essential to minimize the environmental impact associated to water consumption and to ensure water availability for a sustainable growth. The specific results generated for the Spanish agricultural systems show that significant reductions in impact can be attained by properly managing the land available.

138 IONIC LIQUID RECOVERY IN IONIC LIQUID-BASED THREE PHASE PARTITIONING (ILTPP) SYSTEMS E. Alvarez-Guerra, 1,* S.P.M. Ventura, 2 J.A.P. Coutinho 2 and A. Irabien 1 1 Departamento de Ingenierías Química y Química Biomolecular, Universidad de Cantabria, Avda. de los Castros s/n, Santander, Spain, Tel.: , Fax: Departamento de Química, CICECO, Universidade de Aveiro, Aveiro, Portugal, Tel.: , Fax: * 2. Chemical Engineering for Sustainable Development 2.1. Natural Resources Sustainability Green Chemistry and Engineering Ionic Liquid-based Three Phase Partitioning (ILTPP) [1] is a novel technique to recover proteins that combines the use of Ionic Liquid-based Aqueous Two Phase Systems (ILATPS) [2] with results that are characteristic of Three Phase Partitioning (TPP) [3]. ILTPP with ionic liquid/salt systems based on 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BmimTfO) and sodium dihydrogenophosphate (NaH 2 PO 4 ) has been successfully applied to the recovery of lactoferrin, a bovine whey protein that stands out due to its nutraceutical properties [4]. However, the development of the ILTPP technique highly depends on the recyclability of the ionic liquid due to the significant impact that this component has on the economic and environmental profile of the process. The aim of this work is the assessment of the ionic liquid recovery to reduce its consumption. For this purpose, the thermodynamic equilibrium is characterized so that the composition of the ionic liquid rich and salt rich phases are determined. In addition, two different additional steps in the process to enhance the ionic liquid recyclability are studied: the increase of the salt mass fraction, and the water removal from the salt-rich phase by means of vacuum evaporation. The models developed to describe each alternative process were experimentally verified. Results show that the ionic liquid that cannot be reused in the process varies between 0,8 and 5% [5]. In this way, the protein concentration in the feed stream is identified as the main variable that has influence in the ionic liquid recovery: the higher the protein concentration, the lower the ionic liquid losses. However, despite the apparently low value of these ionic liquid losses, additional recovery steps should be included in the process to reduce the associated economic and environmental impacts. This work demonstrates that the increase of the salt concentration has a very limited effect on the ionic liquid recovery at relatively high protein concentrations in the feed stream, although this approach is often proposed in literature [6]. In fact, this alternative may even increase the ionic liquid losses under certain experimental conditions, due to operational constraints and only small additions of salt can be profitable. In contrast, water removal from the salt-rich phase by means of evaporation achieves the complete recovery of both ionic liquid and salt agents, so ILTPP may not require a net consumption of reagents. These conclusions can also be applied to ILTAPS if solutes are successfully back-extracted, because both techniques use the same systems. Acknowledgements Enrique Alvarez-Guerra acknowledges the financial support of the Teaching staff Vice-chancellorship of Universidad de Cantabria to carry out the research stay at Universidade de Aveiro. References [1] E. Alvarez-Guerra, A. Irabien, Sep. Sci. Technol., 2014, in press (DOI: / ). [2] M.G. Freire, A.F.M. Cláudio, J.M.M. Araújo, J.A.P. Coutinho, I.M. Marrucho, J.N.C. Lopes, L.P.N. Rebelo, Chem. Soc. Rev., 2012, 41, [3] C. Dennison, R. Lovrien, Protein Expr. Purif., 1997, 11, 149. [4] E. Alvarez-Guerra, A. Irabien, J. Chem. Technol. Biotechnol., 2014, in press (DOI: /jctb.4401). [5] E. Alvarez-Guerra, S.P.M. Ventura, J.A.P. Coutinho, A. Irabien, Fluid Phase Equilibr., 2014, 371, 67. [6] C. Li, J. Han, Y. Wang, Y. Yan, J. Pan, X. Xu, Z. Zhang, J. Chem. Eng. Data, 2010, 55, 1087.

139 BIO-OIL PRODUCTION FROM HAZELNUT SHELLS VIA PYROLYSIS IN A FLUIDIZED BED REACTOR. Josep O. Pou Ibar (1), Carles Colominas Guàrdia (1), Rubén Montserrat Trenchs (1) (1) Industrial Engineering Department, IQS School of Engineering, Universitat Ramon Llull. Via Augusta, 390, 08017, Barcelona, Spain (ext. 290), 2. Chemical Engineering for Sustainable Development Natural resources sustainability. Renewable raw materials and waste valorization 1. Introduction The present energy framework has reached values unsustainable if the demand and consumption and the energy reserves currently available are compared. In addition the level of atmospheric CO 2 has increased at an alarming rate since the beginning of the industrial era. This increase is due mainly to the energy generation and is one of the main causes of global warming and climate change of the planet. One of the ways to cope both with the search of energy independence a CO 2 emissions reduction is via using biomass. Biomass has a wide variety of forms but all of them have the common denominator of being a mixture of lignin, cellulose and hemicellulose. One of the typical ways of using biomass is by burning it alone or mixed with coal establishing some synergies which are not completely understood [1]. Another energetic use of biomass includes the pyrolysis, which is a way to convert it into liquid products suitable to be used in an internal combustion engine. The energetic use of Biomass should be limited to agricultural wastes as for example nut crops wastes. Spain, with a yearly production of nearly tons, is the second main hazelnut producer in the UE. Thus, with a ratio of 40% of waste/whole fruit, there are nearly 7200 ton/year of biomass waste that is, in the best cases, burnt to make heat. There is a big energetic potential in the pyrolysis of hazelnut or other nut shells. Table 1. Analyses of hazelnut shells C (wt.%) H (wt.%) 5.06 N (wt.%) 0.83 O (wt.%) Moisture (wt.% as received) 17 Calorific value (kj kg -1 ) Experimental The hazelnut shell samples (Coryllus avellana, Tonda di Giffoni variety) have been taken from El Morell (Tarragona) located in the NE of Spain. The pyrolysis experiments were performed in N 2 atmosphere in a stainless steel tubular reactor ( 40 x 9 cm) heated by an electric furnace (45 x 40cm) with the temperature being controlled with two thermocouples in the furnace and one inside the reactor. 50g of air dried hazelnut shells in the range of 0.5 < D < 0.75mm particle size were placed inside the reactor and N 2 flow controlled by a flowmeter. The experiments were carried out with a temperature increment of 7K min -1 to the final temperature of 600ºC until no further significant release of gas was observed. The liquid products were collected in a recipient maintained at 0ºC. They comprised and aqueous phase and an organic phase they were finally analyzed via gas chromatography. The elemental analysis was carried out on the hazelnut shells (Table 1) 3. Results and Discussion At the end of the pyrolysis the liquid product yields obtained were 31% (in weight). This was a bigger conversion ratio of what was reported in literature [2] but after the chromatographic analysis, it was observed that the biggest amount of obtained products were furfural and phenolic alcohols, typical products of the first stages of the lignin pyrolysis. The analysis of the organic phase gave a considerable amount of oleic acid. 4. Conclusions The pyrolysis o hazelnut shells have been carried out giving good yields in liquid products conversion. However, the products obtained are far from the desired hydrocarbon mixture that can be used as querosene or gas-oil. The substances obtained are typical of the previous stages of lignin pyrolysis so more retention time inside the reaction and higher pressure is needed to reach the complete conversion. 5. References [1] J. O. Pou, Y. E. Alvarez, J. K. Watson, J. P. Mathews, S. Pisupati, Journal of Analytical and Applied Pyrolysis, 95, (2012) p [2] A.E. Pütün, A. Özcan, E. Pütün, Journal of Analytical and Applied Pyrolysis, 52, (1999) p. 33.

140 PHYSICO-CHEMICAL CHARACTERIZATION OF THE TWO-PHASE OLIVE MILL SOLID WASTE FOR ITS USE IN THERMAL DEGRADATION PROCESSES A. Ronda, M. Calero, F. Corpas-Iglesias, T. Cotes, F.J. Iglesias-Godino, M.A. Martín-Lara, C. Martínez Departamento de Ingeniería Química, Facultad de Ciencias, Universidad de Granada. Tel Fax Natural Resources Sustainability Over the last 10 years the manufacture of olive oil has undergone important evolutionary changes in the equipment used for the separation of olive oil from the remaining components. Therefore, the new two-phase olive oil mills produce three identifiable and separate waste streams. These are: 1) the wash waters from the initial cleansing of the fruit; 2) the wash waters from the secondary centrifuge and 3) the aqueous solid residues from the primary centrifugation. As well as offering process advantages they also reduce the water consumption of the mill. The introduction of this technology was carried out in 90% of Spanish olive oil factories. In addition, the solid residue (two-phase olive mill solid waste, TPOMSW) has a high organic matter concentration giving an elevated polluting load and it cannot be easily handled by traditional technology which deals with the conventional three-phase olive cake (Borja et al., 2006). The use of this solid residue is of great economic and social importance for the Mediterranean area, as it accumulates in large amounts during olive oil production. The exploitation of TPOMSW, from an environmental point of view, may be approached in a number of ways, such as composting, gasification, steam explosion treatment for obtaining hydroxytyrosol or the extraction of oils (Alburquerque et al., 2004; Giannoutsou et al., 2004; Ollero et al. 2003; Fernandez Bolaños et al., 2003). Specially, in recent years, thermal degradation of olive stone and other olive oil by-products was the subject of interest of a large amount of research, focusing mainly on the degradation mechanism, kinetics and emission of volatile substances. This work aims to report a complete physic-chemical characterization of the TPOMSW for its use in the processes of thermal degradation. Thus, this study may be helpful for evaluating the possibility of managing this waste in pyrolysis, gasification and combustion plants as methods of utilization of this waste. Results showed that TPOMSW presents a size distribution with about 66% of particles higher than 1.00 mm, while the percentage of fines (size<0.250mm) is only of 1.50%. These results allow its direct use as solid fuel in most of the available technologies without a prior step of milling. On the other hand, the moisture content is very high (around 70%), being one of the main characteristics of the solid that difficult its direct use as fuel. However, the low sulphur value presents in the sample (<0.1%) is very suitable from the environmental point of view, reducing SO 2 emissions over conventional fuels. The results of the proximate analysis of TPOMSW are within the range of most biomass waste: 76.12% of volatile matter, 12.31% of fixed carbon and 5.32% of ash. Likewise, the higher calorific value obtained was 4897 kcal/kg. This value is within the proper range of most of the waste with similar characteristics and indicates that the TPOMSW has energy content sufficient to propose its possible use as solid fuel. Finally, the study of the surface of the solid by FE-SEM analysis showed that the porosity of TPOMSW is superficial, of size below 10 microns, while the results of microanalysis indicate that the inorganic material is mainly composed of calcium and potassium carbonates and, to a lesser extent, magnesium carbonate, silica, alumina and copper and iron oxides. Alburquerque, J.A.; González, J.; García, D. y Cegarra, J.; Agrochemical characterization of alperujo, a solid by-product of the two-phase centrifugation method for olive oil extraction, Bioresource Technology, 91 (2), (2004). Borja R.; Raposo F.; Rincón B. Treatment technologies of liquid and solid wastes from two-phase olive oil mills. Grasas y Aceites, 57 (1), (2006). Fernández Bolaños J, Heredia A, Rodríguez Gutierrez G, Rodríguez R, Jiménez A, Guillén R. Method for obtaining purified hidroxitirosol from products and byproducts derived from olive tree. EU Patent N A1 ( ) Giannoutsou EP, Meintanis C, Karagouni AD Identification of yeast strains isolated from a two-phase decanter system olive oil waste and investigation of their ability for its fermentation. Bioresource Technology 93, Ollero P, Serrera A, Arjona R, Alcantarilla S The CO2 gasification kinetics of olive residue. Biomass and Bioenergy 24,

141 ILFD PROJECT LEACHATE TREATMENT FROM LANDFILL Author: Joaquín Reina Hernández c/cardaire 31 1º 4º Terrassa Barcelona. Spain. Telf Scientific Topic: Chemical Engineering for Sustainable Development 2.1 Natural Resources Sustainability Abstract One of the most vexing issues on management of municipal solid waste like the landfill or in waste water treatment facility is the leachate. This fluid comes mainly from the degradation of organic matter of MSW, to what other liquids as rainwater, irrigation water, are added. This water is highly polluting water, which should be treatment for its minimization or future manipulation. In the present article, a new technology for treating landfill leachate is proposed which is based on the contact between dispersed phases. That is liquid and reactive. Inerting is a physical-chemical process that allows you to modify the characteristics of leachability of a waste. This means that the components of material are transformed into insoluble, and in this way, is reduced their mobility and also removal dangerous components The ILFD technology facilitates contact between flows (leachate-reactive) involved in the process, this significantly improving transport processes of heat, mass and momentum, which favor the development of reactions that take place. This allows minimizing operational costs by reducing the amount of reagents used, compared with the inerting on mass, this last technology is current on the market, making it more attractive from the economic point of view this process. Fig 1.ILFD plants Fig 2. Result of the leachated treatment. References. 1. Giraldo., E. TRATAMIENTO DE LIXIVIADOS DE RELLENOS SANITARIOS: AVANCES RECIENTES. F a c u l t a d d e I n g e n i e r í a. UNIVERSIDAD DE LOS ANDES Reina,. J Spray drying for concentrated treatment. Proceeding. 9º Congreso Mediterráneo de Ingeniería Química. Barcelona. Spain, 3. Reina, J El secado por aspersión. Una alternativa para el tratamiento de los concentrados procedentes de planta de ósmosis inversa. Retema Reina. J Modelos tecnológicos en el tratamiento de lixiviados. XI CONFERENCIA ATEGRUS SOBRE VERTEDEROS CONTROLADOS. Municipalia. Feria de Lleida. 5. Science report Improved definition of leachate term from landfills, Environment Agency, Science Report P1-494/SR1.

142 FROM THE BIOGAS TO VEHICLE FUEL BIOLIMP-ENERGY PLANT FOR BIOMETHANE PRODUCTION Author: Joaquín Reina Hernández c/cardaire 31 1º 4º Terrassa Barcelona. Spain. Telf.: Scientific Topic: Chemical Engineering for Sustainable Development 2.1 Natural Resources Sustainability Abstract Biogas from different sources is a valuable material for the energy production, chemical products and bio-fuels. Because it is a renewable energy, it is inexhaustible, clean and can be used in a self-administered manner, which enables production to be planned and adapted to consumption needs. The use of biogas causes less pollution and constitutes a viable alternative, given the noticeable depletion of fossil fuels, the prices of which are now increasing. The biogas is upgraded/enrichment by removing carbon dioxide (CO 2 ) basically to raise the calorific value and create a gas with constant quality with similar proprieties likes natural gas. Currently there are many techniques for this purpose; one of the techniques more apply is chemical scrubber. The present work, focus on the development a plant for biomethane production from the landfill gas for is use as vehicle fuel. Inside of the work is explained the different stages of the plant. The plant is based on chemical reaction using an alkanoamina (MEA). The plant is located in Vacarisses landfill belonging to Hera Holdin group and with it is met the fuel necessity of the landfill This kind of technologies allows getting a high quality of biomethane and a CO 2 stream of the high level concentration, at the same time. This plant is the result of the research and development work made by Energy & Waste group in the biogas topic and it is the first plant of the Spanish government. Fig 1.. Biomethane production plant. Different parts Fig 2. General view of the Biolimp-Energy plant. References. 1. Persson, M. Evaluation of upgrading techniques for biogas Report Swedish Gas Center 142. November 2003, Schweden. 2. Jönsson, O. and Dahl, A.; Adding gas from biogas to the gas grid. Report Swedish Gas Center 118. July 2001, Schweden. 3. Persson, M. Jönsson, O and Wellinger, A. Biogas Upgrading to Vehicle Fuel Standards and Grid Injection. Swedish Gas Center (SGC). 2006, Schweden. 4. Reina Hernández, J.; From the biogas to vehicle fuel. Study of CO2 absorption in a pancked column.10º Congreso Mediterráneo de ingeniería Química. 2005, Barcelona- Spain. 5. Reina Hernández, J.; Biogás para la automoción o su inyección en la red de gas natural. Environment industry journal, Infoenviro, July/August 2007.

143 TECHNO-ECONOMIC ASSESSMENT OF THE PDO PRODUCTION FROM LIGNOCELULLOSIC MATERIALS H. A. Forero a, V. Hernández a, Carlos A. Cardona a * a Instituto de Biotecnología y Agroindustria, Departamento de Ingeniería Química. Universidad Nacional de Colombia sede Manizales. Cra. 27 No , Manizales, Colombia. * Presenting author Tel.: ext ; fax: ext (Carlos A. Cardona). Scientific Topic: Natural Resources Sustainability Currently the chances of achieving substantial increases in value-added raw materials and wastes by its processing represents one of the most important prospects for agribusiness development. Nowadays, 1,2- Propanediol (1,2-PDO) and 1,3-Propanediol (1,3-PDO) are chemical platforms produced from petrochemical route which are important intermediates used in the production of polymers, cosmetics, lubricants, medicines, and as promoters for many synthetic reactions. Due to their possibilities as chemicals building blocks for many uses in the industry, PDOs have received special attention in the industrial biotechnology field. According to this, in the present work a techno-economic analysis for the production of PDOs is performed using lignocellulose as raw material for its production and processing. Several scenarios are shown based on different conversion pathways as function of feedstock distributions and technologies for the joint production of PDOs from lignocellulose. These scenarios are compared with the current process operating in conventional ways. A simulation procedure was used in order to evaluate the proposed schemes for all the scenarios including technoeconomic and environmental assessments. This analysis serves as a reference line on the technological, economic and environmental feasibility to implement such type of processes in biotechnological industry.

144 CATALYTIC CRACKING OF SCRAP TYRE PYROLYSIS OIL (STPO) IN FLUID CATALYTIC CRACKING UNITS (FCCU) OPERATING CONDITIONS E. Rodríguez, A. Ibarra, I. Hita, R. Palos, J. Bilbao, J.M. Arandes Univ. Basque Country, Dep. Chemical Engineering, P.O. Box 644, 48080, Bilbao (Spain); tel , fax: , Topic: 2. Chemical Engineering for Sustainable Development Natural Resources Sustainability: Renewable Raw Materials and Waste Valorization. Conversion of wastes to energy is one of the recent trends in minimising not only the waste disposal but also could be used as an alternate fuel. In order to prevent rubber wastes and in particular discarded automobile tyres from damaging the environment, it is highly desirable to recycle this material in a useful manner. In reference to the composition of the obtained gasoline (Fig.2), the main compounds from gasoline are aromatics and olefins, whereas naphthenes and paraffins appear in a small quantity, comparatively. Further, all the product yields, but n-paraffins, tend to decline as both the processing temperature and the catalyst rate increase. In the present work, the STPO was fed to a batch CREC Riser Simulator laboratory reactor with the aim of studying the product yields derived from catalytic cracking. Experimental studies were conducted using an equilibrium commercial FCC catalyst, under similar operating conditions to the FCCU. Therefore, the temperature range was from 500 to 560 ºC, the catalyst to oil mass ratios (C/O) from 3 to 7 and the contact time of 3 seconds. Product identification was carried out by GC-MS and they were analyzed by GC. Coke yields were assessed by TGA. Product yields were grouped in lumps: dry gas (C 1 -C 2 ), LPG (C 3 -C 4 ), gasoline (C 5 - C 12 ), LCO (C 13 -C 18 ) and HCO ( > C 18 ). Dry Gas LPG Gasoline 70 LCO HCO Coke Feedstock 3 C/O 5 7 Figure 1. Product yields distribution at 430 ºC vs. C/O ratio. Yields wt.% As shown in Fig.1, the STPO catalytic cracking produces a dramatically increase in gasoline yields due to the conversion of the LCO and HCO lumps from STPO, specially at C/O ratio 3 and 500 ºC, while dry gas and LPG yields enhance with the C/O ratio and the temperature increases. Considering that cyclic olefins (64 %) and aromatics (34%) are the major compounds in the feed [1], the results can be attributed firstly to the cyclic olefins dehydrogenation, which favors the production of aromatics. Secondly to cracking reactions, which favor olefins formation and finally to the aromatic side-chain cracking, which leads to the formation of both compounds (aromatics and olefins). On the other hand, the decrease in almost all gasoline product yields, except n-paraffins, at increasing C/O ratio and temperature can be justified by the enhancement production of dry gas and LPG at these operating conditions and the hydrogen transfer reactions, which promote the paraffins formation. Yields, wt.% C/O:3 C/O:5 C/O:7 0 n-paraffins i-paraffins Olefins Naphthenes Aromatics Figure 2. Gasoline components yields at 530 ºC. Thus, it can be concluded that 3 and 500 ºC are the most appropriate C/O ratio and temperature for enhancing the gasoline production. Additionally, as a result of the high quantity of aromatics and olefins formation, the gasoline obtained has a high octane number (97.9). [1] M. Arabiourrutia, G. Lopez, G. Elordi, M. Olazar, J. Bilbao. Chem Eng Sci 62 (2007), Acknowledgements: MINECO by financial support to the Project CTQ

145 EVALUATION OF MEA DEGRADATION IN CO 2 CHEMICAL ABSORPTION PROCESS AT DIFFERENT CO 2 PARTIAL PRESSURES F. Vega 1, A. Sanna 2, B. Navarrete 1, M. Maroto-Valer 2, M. Cano 1 1 Chemical and Environmental Engineering Department, School of Engineering, University of Seville, C/ Camino de los Descubrimientos s/n Seville, Spain, phone: (+34) Centre for Innovation in Carbon Capture and Storage (CICCS), School of Engineering and Physical Sciences, Heriot-Watt University, EH14 4AS, Edinburgh, UK Scientific Topic: 2.1 Chemical Engineering for Sustainable Development (Energy, Water and Materials) Abstract Among the alternatives to mitigate CO2 emissions from fossil-fuel power plants, post-combustion capture using chemical absorption has been shown as a mature and available technology that can obtain high concentrated CO2 stream from typical flue gas operating conditions: low CO2 partial pressure, large amount of gas and the presence of pollutants such as SO2 and NOX [1]. Two main types of amine degradation have been identified: 1) thermal degradation in the stripper unit and, 2) oxidative degradation in the absorber due to the presence of O2 in the flue gas. On the other hand, high energy penalty related to solvent regeneration is considered a key issue hindering a large deployment of this technology [2]. Several authors proposed a hybrid technology between oxycombustion and post-combustion capture in order to optimize CO2 capture and minimize operating and investment costs. This technology is based on the use of oxygen-enriched air as an oxidizer with flue gas recirculation, providing a higher CO2 concentrated flue gas which can lead to further improvements on CO2 capture using chemical absorption as separation technology [3]. The aim of this work is to investigate the effects of the presence of higher CO2 concentration in the flue gas on oxidative degradation of the solvent by means of degradation rates and degradation product evaluation. In this case, MEA was selected as solvent to be tested under different CO2 partial pressure. The experimental tests were carried out for 30 days at typical temperature bulge at absorber column, 70 C, and 1bara, using synthetic flue gases with different composition: from 15 to 50 vol.% CO2 and from 3 to 6vol.% O2, balanced with nitrogen. Liquid Chromatography combined with Mass Spectrometry (LC-MS) was used to quantify amine concentration remained in the solution [REF] and to quantify main degradation products cited in the literature. Results have shown that the solubility and diffusion coefficient of O2 decrease, and consequently, the amine degradation rates decrease in presence of high CO2 concentration References [1] H. P. Mangalapally, H. Hasse. Chemical Engineering Science 2011; 66: [2] G. T. Rochelle. Current Opinion in Chemical Engineering 2012; 1: [3] E. Favre, R. Bounaceur, D. Roizard. Separation and Purification Technology 2009; 68:

146 HYDRAULIC ROAD BINDERS USING FLY ASH BASED GEOPOLYMERS Y. Luna, L. Fernández, C. Leiva, A. Cornejo, C. Fernández Pereira Departament of Chemical and Environmental Engineering. Escuela Técnica Superior de Ingenieros. University of Seville, Camino de los Descubrimientos s/n 41092, Sevilla, Spain. Phone: Scientific Topic: 2. Chemical Engineering for Sustainable Development Natural Resources Sustainabillity Soil stabilization is an important operation utilized in civil engineering to introduce infraestructures, mainly of transport, in zones where initially the land do not let it. Traditionally, these stabilizations have been carried out with cement or lime, but the economics and environmental operations make interesting other viable alternatives. Geopolymers is an alternative option with the mechanical advantages that make them suitable for this field. The geopolymers were based on fly ashes (FA) and pipeclay (PC) is used as material simulating the soil. Different compositions were prepared mixing fly ash and pipeclay following the same methodology than in other publications [1], varying the percentages of each one (fly ash/pipeclay: 87/13, 67/33 and 50/50) and using sodium silicate (with sodium hydroxide in order to increase the Na 2 O/SiO 2 ratio in mixture) or sodium hydroxide as activating solution. Different test were carried out in order to assess the use of geopolymers as hydraulic road binders: compressive strength, volumetric expansion, setting time, density and one leaching test, the NEN 7345-tank leaching test. The results of compressive strength showed values upper than 9 MPa at 28 days of curing at ambient temperature (Figure 1). The compressive strength and the setting time decrease when the amount of fly ash increases. The density keeps practically constant in all mixtures. Regarding the leaching analysis only must be appreciated an increment of Sb and Se in the leachates of all mixtures, increasing when the amount of fly ash increases. The results have been positive and it can be concluded that the soil stabilization can be a future application field for the geopolymers being the mixture 50/50 which show the best results for the tests carried out. 14 RC (MPa) days 28 days 60 days 0 87/13-NaSil 67/33-NaSil 50/50-NaSil 67/33-NaOH 50/50-NaOH Figure 1. Compressive strength of geopolymers. [1] C. Fernández Pereira, Y. Luna, X. Querol, D. Antenucci, J. Vale. Waste stabilization/solidification of an electric arc furnace dust using fly ash-based geopolymers. Fuel 88 (2009)

147 PRODUCTION OF FERULOYL ESTERASE FROM VINE TRIMMING SHOOT AND CORNCOB Pérez-Rodríguez, N., 1 Moreira, C.D., 1,2 Torrado Agrasar, A., 1 Belo, I., 2 y Domínguez, J.M. 1 1 Department of Chemical Engineering, Faculty of Sciences, University of Vigo (Campus Ourense), As Lagoas s/n, Ourense, SPAIN. Phone: , Fax: , 2 CEB-Centre of Biological Engineering, University of Minho, Campus de Gualtar, Braga, Portugal. 2.1 Natural Resources Sustainability Vine trimming shoot and corncob which are lignocellulosic wastes from vineyard and maize crops representing a global harvested area of 7x10 6 Ha and 1.8x10 8 Ha respectively (FAOSTAT, 2012). On the other hand, feruloyl esterases (EC ) are a class of enzymes responsible of ferulic acid and other cinnamic acids release from plant cell wall polysaccharides (Benoit et al., 2008). This enzyme can release phenolic compounds such as ferulic, p-coumaric, caffeic and sinapic acids with applications in the food, health, cosmetic, and pharmaceutical industries. Production of fuel ethanol from renewable lignocellulosic materials is another field where feruloyl esterase is used for its synergistic effects on cellulase and xylanase activities. Papermaking industry also employs feruloyl esterase to obtain high quality fibres and this esterase has been used to improve digestion of complex plant cell walls in animals (Benoit et al., 2008; Ou et al., 2011). Aspergillus terreus CECT 2808 was the selected fungus, after a previous microorganism screening, to produce feruloyl esterase from vine trimming shoot (VTS) and corncob as substrates by solid state fermentation (SSF). The fungus was adapted by growing in PDA supplemented with ethyl ferulate. Substrates were moistened (1:3.6 (w/w)) with an optimized solution (NaNO 3 10 g/l; KH 2 PO 4 9 g/l; (NH 4 ) 2 SO g/l; yeast extract 6 g/l). Ultraflo L (Novozymes, Denmark) was used as control. The enzymatic activity values obtained even exceeded those present in the commercial preparation, as it can be observed in the results achieved after seven days in 250 ml Erlenmeyer flasks, which are shown in the following table: Extract Feruloyl esterase (U/mL) Xylanase (U/mL) VTS Corncob Mixture (1:1 (w/w)) Ultraflo L Feruloyl esterase production was scaled up in an horizontal heat-sterilized double-jacketed glasscolumn reactor (26.3 cm length and 2.62 cm diameter) kept at 30 ºC under static conditions, under different aeration rates (0, 0.4, 0.7, 0.85 and 1 L/min). Preliminary results assayed with VTS improved the amount obtained in flask, achieving the highest value (0.034 U/mL) at a flow of 0.7 L/min. Consequently, VTS and corncob can be valorized to environmentally sustainable production of this enzyme with multiple industrial applications. Bibliography Benoit, I., Danchin, E.G.J., Bleichrodt, R.-J., De Vries, R.P. Biotechnological applications and potential of fungal feruloyl esterases based on prevalence, classification and biochemical diversity. Biotechnol Lett 2008; 30: Food and Agriculture Organization of the United Nations. FAOSTAT. Available in: Date of consultation 04 April (updated: 07 February 2014). Ou, S., Kwok, K.-C. Ferulic acid: Pharmaceutical functions, preparation and applications in foods. Journal of the Science of Food and Agriculture 2004; 84: Acknowledgments We are grateful to the Spanish Ministry of Science and Innovation (project CTQ ), which has partial financial support from the FEDER funds of the European Union, for the financial support of this work and to the Spanish Ministry of Education, Culture and Sports for the Pérez-Rodríguez s FPU fellowship.

148 ENZYMATIC RELEASE OF FERULIC ACID FROM VINE TRIMMING SHOOTS AND CORNCOB Pérez-Rodríguez, N., 1 Moreira, C.D., 2 Torrado Agrasar, A., 1 Belo, I., 2 y Domínguez, J.M. 1 1 Department of Chemical Engineering, Faculty of Sciences, University of Vigo (Campus Ourense), As Lagoas s/n, Ourense, SPAIN. Phone: , Fax: , 2 CEB Centre of Biological Engineering, University of Minho, Campus de Gualtar, Braga, Portugal. 2.1 Natural Resources Sustainability Ferulic acid is the most abundant hydroxycinnamic acid in cell wall polysaccharides (Benoit et al., 2008). This acid can perform several functions including antioxidant, antimicrobial or anti-inflammatory and it has reported to play an important role in prevention or treatment of some human diseases particularly atherosclerosis, cancer or diabetes (Srinivasan et al., 2007; Zhao & Moghadasian, 2008). Ferulic acid also has a range of applications in the cosmetic industry where it is used for its anti-aging effect and in the food industry is employed as an additive antioxidant or transformed into other valuable molecules such as flavour precursors of aromatic constituents used in some foods (Ou & Kwok, 2004 ). Feruloyl esterases (EC ), a class of enzymes that are involved in the hydrolysis of the ester linkages of ferulic and diferulic acids (Koseki et al., 2009), release ferulic acid and other cinnamic acids from plant cell wall polysaccharides (Benoit et al., 2008). Vine trimming shoot and corncob are residues from agroindustrial sector whose lignocellulosic nature made them liable to be valorized as a source of ferulic acid. Consequently, in the present work, these materials were the substrates for enzymatic hydrolysis to produce ferulic acid solutions able to be used as a food additives precursor media and made from an environmentally friendly process. More in detail, Aspergillus terreus CECT 2808 is a fungi strain which was selected in a previous research to obtain feruloyl esterases from vine trimming shoot, corncob or their mixture as carbon sources. The feruloyl esterase activity of enzymatic extracts generated from each material has been evaluated in the same substrate where this enzyme was produced and in the other two. Ultraflo L was employed as a control. As a result, maximum ferulic acid release by fungi extract were mg/l from corncob and mg/l from vine trimming shoot, so corncob was the material with the major quantity of this hydroxycinnamic acid release after 33 hours of hydrolysis. However, in terms of percentage of ferulic acid release from the total possible to release from the material, vine trimming shoot compared with corncob ( %) has been the best one with a remarkable yield of extraction of %. Bibliography Benoit, I., Danchin, E.G.J., Bleichrodt, R.-J., De Vries, R.P. Biotechnological applications and potential of fungal feruloyl esterases based on prevalence, classification and biochemical diversity. Biotechnol Lett 2008; 30: Koseki, T., Fushinobu, S., Ardiansyah, Shirakawa, H., Komai, M. Occurrence, properties, and applications of feruloyl esterases. Applied Microbiology and Biotechnology 2009; 84: Ou, S., Kwok, K.-C. Ferulic acid: Pharmaceutical functions, preparation and applications in foods. Journal of the Science of Food and Agriculture 2004; 84: Srinivasan, M., Sudheer, A.R., Menon, V.P. Ferulic acid: Therapeutic potential through its antioxidant property. Journal of Clinical Biochemistry and Nutrition 2007; 40: Zhao, Z., Moghadasian, M.H. Chemistry, natural sources, dietary intake and pharmacokinetic properties of ferulic acid: A review. Food Chemistry 2008; 109: Acknowledgments We are grateful to the Spanish Ministry of Science and Innovation (project CTQ ), which has partial financial support from the FEDER funds of the European Union, for the financial support of this work and to the Spanish Ministry of Education, Culture and Sports for the Pérez-Rodríguez s FPU fellowship.

149 SIMPLIFIED MODELS FOR IONIC LIQUID RECOVERY IN IONIC LIQUID- BASED THREE PHASE PARTITIONING (ILTPP) PROCESS E. Alvarez-Guerra, * P. Herrero and A. Irabien Departamento de Ingenierías Química y Química Biomolecular, Universidad de Cantabria, Avda. de los Castros s/n, Santander, Spain, Tel.: , Fax: * 2. Chemical Engineering for Sustainable Development 2.1. Natural Resources Sustainability Green Chemistry and Engineering Ionic Liquid-based Three Phase Partitioning (ILTPP) is a novel technique to recover proteins that promotes the protein accumulation at the liquid-liquid interface [1]. This technique uses ionic liquid/salt systems that form an ionic liquid-rich and a salt-rich phases in a similar way as Ionic Liquid-based Aqueous Two Phase Systems (ILATPS) [2]. Due to the importance of the net ionic liquid consumption in the economic and environmental profile of this process, our previous studies have analyzed the ionic liquid that can be reused [3]. For this purpose, the thermodynamic equilibrium to obtain the phase compositions and the mass balances of the process are required. The description of the thermodynamic equilibrium is similar to previous works [4, 5], with the exception that the binodal curve at very high salt concentration is replaced by a single exponential function. Therefore, the determination of the phase compositions implies the simultaneous solution of a non-linear system of 4 equations, which requires obtaining 7 adjusting parameters [3]. In addition, the calculation of the ionic liquid losses of the process involves some clearly non-linear equations. The aim of this work is the assessment of the model used to describe the ionic liquid recovery in the ILTPP process so that the number of parameters required and the complexity of calculations can be reduced, which is useful for further economic or environmental assessment of the process. In this way, a trade-off between complexity and accuracy in the model that describes the ionic liquid that is recovered (R) should be reached. The methodology used for achieving this objective is based on the model discrimination approach previously reported [6]. Regarding the thermodynamic equilibria, the compositions of the liquid phases involved in the ILTPP process are in the extremes of the binodal curve, so these two regions of the binodal curve are adjusted to exponential functions based on 2 parameters, linear equations or constant functions composed of a single parameter. Different models obtained from the combination of the previous functions to model the composition of the ionic liquid rich- and salt-rich phases are assessed. In all cases, the adjusting parameters involved are statistically significant (confidence level at 95%). However, any simplification of the binodal curve at high salt concentrations leads to unacceptable errors in the estimation of R. In contrast, the general equation of the binodal curve (an exponential function with 3 parameters) that describes the ionic liquid-rich phase can be replaced by an exponential function based on 2 parameters with a negligible error in R (mean average percentage error, MAPE < 10-3 ). Furthermore, this region could also be explained by a constant function so that only 5 parameters are used in the overall model, since even though MAPE increases one order of magnitude, it is also relatively low. With respect to the simplification of the mass balances, the impact of considering the salt contained in the ionic liquid-rich phase negligible is assessed; despite the relatively low errors obtained, this assumption does not imply any reduction in the number of parameters or in the non-linearity of equations. In conclusion, the simplification of the model for the ionic liquid recovery in the ILTPP process can be especially achieved replacing the equation that describes the binodal curve at high concentrations of ionic liquid. References [1] E. Alvarez-Guerra, A. Irabien, J. Chem. Technol. Biotechnol., 2014, in press (DOI: /jctb.4401). [2] Z. Li, Y. Pei, H. Wang, J. Fan, J. Wang, Trac-Trend Anal. Chem., 2010, 29, [3] E. Alvarez-Guerra, S.P.M. Ventura, J.A.P. Coutinho, A. Irabien, Fluid Phase Equilibr., 2014, 371, 67. [4] J.C. Merchuk, B.A. Andrews, J.A. Asenjo, J. Chromatogr. B, 1998, 711, 285. [5] C.M.S.S. Neves, M.G. Freire, J.A.P. Coutinho, RSC Adv., 2012, 2, [6] G.F. Froment, K.B. Bischoff, Chemical reactor analysis and design, 2 nd ed., John Wiley & Sons, Inc., 1990, USA.

150 DEVELOPMENT OF FIREPROOF MORTARS COMPOSED BY BAGASSE COMBUSTION ASHES C. Leiva, C. Arenas, M. Rodríguez-Galán, L.F. Vilches, A. Cornejo, Y.Luna, B. Alonso-Fariñas. Department of Chemical and Environmental Engineering. Escuela Técnica Superior de Ingenieros. University of Seville, Camino de los Descubrimientos s/n 41092, Sevilla, Spain. Phone: Scientific Topic: 2. Chemical Engineering for Sustainable Development Natural Resources Sustainability: Renewable Raw Materials and Waste Valorization. As a result of high growth in the use of biomass in energy production, there has been an increase in the volume of biomass ashes generated, and this requires an effort to achieve technological developments, using such ash in large quantities, reduce the fraction for the landfill and the environmental problems it causes. To achieve this goal, the most desirable alternative is the use of ash in products with a high added value. Therefore, we have studied the properties of mortars composed of bagasse ash (CB), gypsum and fibers, with a view to their use in the manufacture of fireproof products that can be used as building panels. Different proportions of ashes and gypsum were analyzed (40, 50 to 60%w of bagasse ashes), keeping constant the ratio of fiber (0.5% w) and the water/solid ratio (0.6). The samples were removed from the moulds two days after their preparation. The mortars were left to cure for 28 days at room temperature. After these 28 days: density, volumetric expansion, compressive and flexural strength, surface hardness and fire resistance [1] and leaching test according to EN have been determined. Density, compressive and flexural strength, surface hardness decreases with the increasing bagasse ashes. The fire resistance of the mortar to 40%w bagasse ashes is very similar to those of commercial products on the market are composed by commercial gypsums. Higher dosages of bagasse ashes have slightly lower heat resistance, as it shown in Figure 1. Bagasse ashes present no problem about leaching of heavy metals Temperature non exposed surface (ºC) % CB 60 % CB 40 % CB Time (min) Figure 1. Fire resistance of bagasse ashes mortars. [1] L. F. Vilches, C. Leiva, J. Vale, J. Olivares and C. Fernández-Pereira. Fire Resistance Characteristics of Plates Containing a High Biomass-Ash Proportion. Ind. Eng. Chem. Res. 2007, 46,

151 RECYCLING OF COAL COMBUSTION BOTTOM ASH AND FGD GYPSUM IN CEMENT PRODUCTION M. Rodríguez-Galán, C. Leiva, L. Caraballo, C. Arenas, L.F. Vilches, A. Cornejo, B. Alonso- Fariñas, B. Navarrete. Department of Chemical and Environmental Engineering. Escuela Técnica Superior de Ingeniería. University of Seville, Camino de los Descubrimientos s/n 41092, Sevilla, Spain. Phone: Scientific Topic: 2. Chemical Engineering for Sustainable Development Natural Resources Sustainability: Renewable Raw Materials and Waste Valorization. Material recycling provides a significant environmental benefit to the industry. Use of substitutes for cement has clear advantages: reducing the amount of clinker and energy needs and the greenhouse gases emissions, saving space in landfills and the reduction of raw materials produces a smaller impact on nature. Bottom ash and FGD gypsum are two of by-products formed in a combustion furnace of pulverized coal. The uses of bottom ash are diverse, from the manufacture of lighter concrete blocks to use as aggregate in pavements. However, its use as a feedstock for the production of clinker or filler cement is increasing [1]. The FGD gypsum is a synthetic product from the gas stream desulfurization in power plants which use fuels with a sulfur content. This FGD gypsum has similar characteristics to the natural gypsum, although their majority and minority traces compositions and the shape of the crystals are slightly different [2]. The main objective of this research is to study the potential of bottom ash and FGD gypsum as a partial replacement of portland cement to favor the recovery of these by-product and obtaining a lower density cement [3]. Different compositions and different size particles (16, 22.4, 48 m particle size) have been studied. Several properties such as compressive strength, setting time, volume stability and heat of hydration have been tested in order to analyze the substituting of these materials in cement according to European regulations. The compressive strength decreases with the addition of bottom ash and FGD gypsum, and is higher with smaller particle size ash. The setting time increases with the addition of bottom ash and decreases with particle size. The volume stability in all cases meets the requirements of EN The heat of hydration is increased with the addition of bottom ash and FGD gypsum. The heat of hydration is increased for smaller particle sizes. In conclusion, pastes with a 50 % of clinker, 50% of bottom ash and with average size 16 m satisfice all the specifications for CEM IV / B 32.5 R according to EN Figure 1. Compressive Strength of different compositions. [1] Vom Berg, W.; Feuerborn, J. Present situation and perspective of CCP management in Europe World of Coal Ash (WOCA), Lexington, Kentucky, (EEUU), [2] Pflughoeft-Hassett, D; Hassett, D.; Eylands, K. A comparison of properties of FGD & Natural Gypsum products. FGD Workshop, Atlanta (EEUU), [3] Coal Combustion By-Products (CBBs). Center for Applied Energy Research. University of Kentucky, 2014.

152 ELECTRODIALYSIS POWERED BY PHOTOVOLTAIC SOLAR ENERGY: A SUSTAINABILITY ASSESSMENT C. Fernandez-Gonzalez, * A. Dominguez-Ramos, R. Ibáñez and A. Irabien Departamento de Ingenierías Química y Química Biomolecular, Universidad de Cantabria, Avda. de los Castros s/n, Santander, Spain, Tel.: , Fax: * 2. Chemical Engineering for Sustainable Development 2.1. Natural Resources Sustainability Energy, Water and Materials Current production of fresh water from seawater (SW) and brackish water (BW) is well known to be an energy intensive process. The environmental sustainability of the selected process is therefore compromised by both the specific energy consumption (SEC) and the high salts concentration in the obtained brines. The approach to avoid the environmental consequences from the SEC is the integration of renewable energies with desalination, especially at isolated locations. Reverse Osmosis (RO) and Electrodialysis (ED) are currently two main options considered for the desalination of SW and BW due to their lower energy consumption compared to thermalbased technologies [1]. Both the pressure gradient in RO and the electrical field in ED can be directly supplied by renewable energies such as wind power and photovoltaic solar energy. Even if RO-PV is the preferred option between current available plants (31% of the worldwide capacity from renewable powered stations [2]), ED-PV presents some advantages worthy of consideration for a larger market implementation. From a technical point of view, ED does allow a simpler operation and maintenance as well as adaptation to intermittent energy inputs when compared to RO [3,4]. Therefore, RO-PV is considered as reference technology, thus the aim of this work is to describe the current sustainability of ED-PV as an alternative technology for fresh water production purposes. The main ED-PV technical and economic barriers are identified as well. Environmentally, ED demands an SEC ranged between kwh m -3 which still falls in the conventional figures for RO considering the same water source. Consequently, any improvement has a large impact because the total power of PV modules is reduced. On the other hand, from an economy perspective, in the case of ED- PV of BW, a time trend ( ) of the water cost obtained from an ED plant connected to the grid power (ED-Grid) or directly powered by photovoltaic modules (ED-PV) in a sunny area was developed. Considering the increase of the electricity cost, and the decrease of the ion exchange membranes and photovoltaic investment costs, under the most favorable conditions, ED-PV could be potentially cheaper against ED-Grid before Under the worst conditions in our study, 20 to 30 additional years would be necessary. The three main barriers for ED-PV are identified as: a) technical barriers, related to the matching of the intermittent output of the renewable energy with the water demand, b) techno-economic barriers associated with the efficiency and performance of membranes and solar modules, and c) economic barriers associated with the initial investment in ion exchange membranes and photovoltaic modules leading to a relatively high cost of the treated water. Social issues as well as economic figures of RO-PV will be also included. Acknowledgements Financial support from MICINN under project CTM is gratefully acknowledged. The author C. Fernandez-Gonzalez thanks the Ministry of Education for a FPI grant BES References [1] A. Al-Karaghouli, L.L. Kazmerski, Renew. Sus.t Energ. Rev., 2013, 24, 343. [2] M. Papapetrou, M. Wieghaus, C. Biercamp, Roadmap for the Development of Desalination Powered by Renewable Energy. Promotion of Renewable Energy for Water Production through Desalination [3] S.A. Kalogirou. Prog. Energ. Combust., 2005, 31, 242. [4] L. García-Rodríguez, Sol. Energy, 2003, 75, 381.

153 CONVERSION OF THE ORGANIC FRACTION OF THE MUNICIPAL SOLID WASTES INTO BIO-ETHANOL F.J. Fernández*, P. Cañizares Chemical Engineering Department. University of Castilla La Mancha. Campus Universitario s/n Ciudad Real. Spain. Phone: (ext. 6350), Fax: , Scientific Topic (2. Chemical Engineering for Sustainable Development, 2.1 Natural Resources Sustainability, Renewable Raw Materials and Waste Valorization) Energy consumption has increased during the last century due to the world population development and growth. One of the potential options to solve the environmental and energetic problems is by means of the wastes valorization, because it is a renewable fuel, which avoids the negative environmental impacts generated by petroleum-based fuels. The main bio-fuels are bio-ethanol and bio-diesel. The bio-ethanol can be produced by using different technologies. One of the most important technologies is the fermentation. Fermentation processes produce bio-ethanol by means of biological transformation of sugars, being the most adequate option the use of natural resources such as: energy-rich crops, mainly sugarcane and corn, (first-generation biofuels) and lignocellulosic biomass (second-generation biofuels). Because of that, current production of bio-ethanol relies on ethanol from starch and sugars but there has been considerable debate about its sustainability and ethics implications. Because of that, other organic substrates should be used to produce the bio-ethanol. In this context, bio-ethanol produced from the Organic Fraction of Municipal Solid Wastes (OFMSW) seem to be a very interesting option. At the same time, the European Landfill Directive, 1999 strongly advice to minimize the use of landfills in European countries. Being the objective to reduce the amount of biodegradable municipal solid wastes (MSW) discarded into landfills to 75% of 1995 levels by 16 July 2006, to 50% by 16 July 2009 and to 35% by 16 July The major components of the MSW are organics (37,4%) and paper (32,3%), accounting for more than 60% of the total mass weight. Because of that, the substrates contained in the OFMSW seem to be a very interesting option for bio-ethanol production because green energy can be extracted from the waste at the same time that no landfill disposal neither subsequent waste stabilization is required. The biological conversion of OFMSW into bio-ethanol presents several technical obstacles. Being the most important the efficient utilization of the raw material to obtain high ethanol yields and productivity. In this sense, the hydrolysis of the OFMSW to fermentable monosaccharides is still technically problematic because of the complexity of the organic substrates contained. These structural characteristics, made the pre-treatment a key stage in the bio-ethanol production from OFMSW. The aim of the pre-treatment is to break down the complex substrates and made them more accessible in the subsequent stages. In this context, the aim of this work was to study the effect of the acid pre-treatments on the bio-ethanol production from the OFMSW. In order to evaluate the effect of the pre-treatment on the bio-ethanol production from OFMSW not only stoichimetric but also kinetic determinations were carried out. Kinetic parameters are of paramount importance in the design of the fermentation stages and are also very important to control these systems. When applying the acid pre-treatment, based on sulphuric acid digestion, the bio-ethanol production was significantly increased and the lag phase observed at the beginning of the fermentation stage was significantly decreased.

154 CO 2 LEAKAGES FROM CCS IN SUB-SEABED GEOLOGICAL FORMATIONS: HEAVY METAL RELEASE FROM MARINE SEDIMENT M. Camino Martín-Torre*, Iciar Muñoz, Berta Galán, Javier R. Viguri Department of Chemistry and Process & Resources Engineering, ETSIIT, University of Cantabria, Avda. de los Castros s/n, Santander, Cantabria, Spain * Presenting author: tel.: ; fax: ; Scientific topic: Natural resources sustainability; Green chemistry and engineering Environmental conditions are changing because of large-scale perturbations provoked by human activities, especially the emission of greenhouse gases. Among the options to reduce them and stabilise their concentrations in the atmosphere at levels that avoid dangerous interference with the climate system, the CO 2 capture and storage (CCS) is one of the most promising alternatives. The possibility of CO 2 release from the geological storage site could produce an acidification in the aquifer which mobilise the pollutants present in sediment, marshes and caprock formations in contact with the CO 2 leakage location or in the area immediately surrounding. There are no specific standards to evaluate this indirect effect so a ph dependence leaching test with continuous ph control thought for the characterisation of wastes is modified to mimic these scenarios. CO 2 leakages could produce a diminution in the ph reaching values as low as 4 thus the ph dependence leaching test is carried out in the ph range: 4-7. Some modifications, like the particle size, the time of essay and the use of seawater as leaching agent, were done to adapt the standard test to this application. The release of As, Cd, Cr, Cu, Ni, Pb and Zn is assessed during the 96 hours of experiment, when the equilibrium is verified. Dissolved Organic Carbon (DOC) is also evaluated in order to analyse its potential influence on the release of some elements, especially Cu. In relation to the contaminant release behaviour with ph, As, Cd, Ni, Pb, Zn and DOC concentrations increase at higher levels of acidification; the release of Cd at the most neutral ph values and of Cr in almost the whole ph range studied are below the detection limits. Cu is the only element under study without a clear pattern, being its release value at any time very close to the detection limit. As is the only element whose release achieves a maximum after 24 hours of contact, decreasing at longer times. This behaviour can be attributed to the readsorption of As oxyanions such as arsenate and arsenite on the positive charged sediment surface. The release of the studied heavy metals reachs a plateau of concentration suggesting equilibrium conditions. The obtained results from ph dependence leaching test with continuous set point titration offer useful information on the long-term influence of seawater acidification on As and metal mobility; in addition, allows the determination of the acid neutralization capacity and the kinetics of metal release upon acidification assuming a worst-case scenario. Acknowledgements This work was supported by the Spanish Ministry of Economy and Competitiveness, Project CTM C02-01, ERDF included. M.C. Martín-Torre was funded by the Spanish Ministry of Economy and Competitiveness by means of an F.P.I. fellowship no. BES

155 REDUCTION OF CO 2 TO CO IN VOLTAIC ARC TUBULAR REACTOR. Carles Colominas Guàrdia (1), Josep O. Pou Ibar (1), Miguel Tabernero Oller (1) (1) Industrial Engineering Department, IQS School of Engineering, Universitat Ramon Llull. Via Augusta, 390, 08017, Barcelona, Spain (ext. 290), 2. Chemical Engineering for Sustainable Development Natural resources sustainability. Renewable raw materials and waste valorization 1. Introduction The concept of energy independence and the need of cleaner energy and therefore of development of renewable energy sources are well known. For decades the sector is receiving aid and investment from both the Spanish Government and the European Commission. The reduction of atmospheric CO 2 is a necessity that is receiving attention from the last few years. There is currently a market for emissions of CO 2 and a desire to reduce emissions of this gas, but the decreasing number of investments in nuclear power stations planned for the future points to a return to coal as a source of reliable and cheap energy and a significant increase in the emissions of CO 2. Possible strategies developed to cope with the atmospheric CO 2 can be grouped into: capture of CO 2, reduction of emissions or reduction of CO 2 that is already in the atmosphere. Reduction of CO 2 to other useful compounds such as CO and methanol have been studied elsewhere [1, 2] and can be achieved with satisfactory conversion rates using photoreduction or voltaic discharge. Table 1. Studied variables for CO 2 reduction 2. Experimental CO 2 have been reduced to CO in Ar atmosphere inside a tubular quartz reactor with a conical Variable CO 2 molar fraction (in Ar) Voltage (V) Range electrode. Several variables have been studied. The variables and its range can be seen in Table 1. The reaction products have been analyzed using mass spectroscopy. 3. Results and Discussion The reduction of CO 2 is almost Intensity (ma) instantaneous showing conversion grades of CO 2 into CO of between 2.71% and 15.41% depending on the reaction Frequency (khz) conditions. These results are, in some cases, considerably larger than those reported in literature [3]. Best conversion ratios are achieved at high voltages and low concentration of CO 2 in Ar. 4. Conclusions The reduction of the molecule of CO 2 have been carried out in a voltaic arc reactor giving good yields in CO 2 to CO conversion. However, the energetic and economic balance is not economically acceptable yet. 5. References [1] J. O. M. Bockris, International Journal of Hydrogen Energy, vol. 35, pp , Jun [2] T. Weimer, K. Schaber, M. Specht, and A. Bandi, Energy Conversion and Management, vol. 37, pp , Jun-Aug [3] H. Matsumoto, S. Tanabe, K. Okitsu, Y. Hayashi and S. L. Suib, Bulletin of Chemical Society of Japan, vol. 72, pp , May 1999.

156 Synthesis, Characterization and Fuel Cell Performance of Phosphoric Acid doped Polybenzimidazole Membrane Çağla Gül TOSUN, Levent AKYALÇIN and Hasan Ferdi GERÇEL Anadolu University, Engineering Faculty, Chemical Engineering Department, Iki Eylul Campus Eskişehir/Turkey, Phone: /6343, Fax: , Natural Resources Sustainability (Energy, Water and Materials) World s energy consumption is increasing rapidly due to population growth, industrialization and technological developments. Despite of increasing energy demand, fossil fuel resources are expected to be depleted more rapidly. Furthermore the greenhouse gases which arise from burning of fossil fuels increased the average temperature of the world to the highest values of the last thousand years. At this point of view, researches are majored on alternative energy resources since fossil fuels cannot be a fuel type for the future. Recently one of the most important alternatives to be a solution to the energy production is hydrogen which is an energy carrier and only yields water when it is burned. One of the devices which are utilized to use hydrogen in production of electrical energy efficiently is fuel cell. Fuel cells are devices which are converting chemical energy of hydrogen into electrical energy directly, efficient, environmentally-friendly, noiseless and are being evaluated in the category of advanced technologies. Fuel cells find acceptance as clean and highly efficient electrical energy solution of the future. There are several types of fuel cells, which are classified with respect to working temperatures and electrolytes. Polymer electrolyte membrane fuel cells (PEMFC) are considered under the low temperature fuel cells having a polymer electrolyte. PEMFCs are preferred especially in vehicles and portable devices due to their high power density and energy conversion efficiency and low working temperature. Perflorosulphonic acid based polymer membranes such as Nafion are frequently used in PEMFC due to their mechanical properties and high proton conductivity. On the other hand, Nafion like membranes are depend on water for proton conduction and they do not work at elevated temperatures greater then 100. Over the last decade, researchers focused on developing high temperature fuel cell membranes to overcome that problem. Among the all alternative polymer electrolyte membrane candidates, phosphoric acid doped polybenzimidazole membrane outweighs because of its high fuel cell performance at temperatures above 100. In this study, polybenzimidazole were synthesized by solution polymerization using diaminobenzidine and isophtalic acid as monomers and polyphosphoric acid as a reaction solvent. The reaction was carried out through 18 hours at 195 C under the nitrogen atmosphere. The synthesized polymer was characterized by FTIR, NMR, and TGA. The membrane was prepared by the solution casting method. The membrane was doped with 13.5 M phosphoric acid for 11 days to improve its proton conductivity. Finally, the membrane was tested in a polymer electrolyte fuel cell. The membrane was showed a high thermal stability and proton conductivity. The maximum power density achieved from the cell was 139 mw/cm 2 at 110 C and atmospheric pressure.

157 Sustainability evaluation of Municipal Solid Waste Incineration using a Life Cycle Assessment approach Maria Margallo, Ana Hernández, Rubén Aldaco, Angel Irabien Departamento de Ingenieras Química y Biomolecular, Universidad de Cantabria Avda. de los Castros s/n 39005, Santander Tel , fax: Topic: 2.1 Natural Resources Sustainability (Life cycle assessment) Abstract An increasing number of publications related to the Life Cycle Assessment (LCA) of waste were observed in recent years. The trend is likely to reflect the importance of LCA as an increasingly accepted approach to analyse the environmental performance of waste management. Most of these LCA studies were conducted in Europe, in particular in Italy [1], Spain [2] and Denmark [3] reflecting the existence in these countries of active LCA communities, a public interest in LCA results for decision support and a specific and lasting political focus on environmental optimisation of the management of solid waste [4]. Most of these LCA studies applied conventional impact assessment methods such as CML 2001 [5] or EDIP 97 [6]. This study proposes a technical way to carry out the Environmental Sustainability Assessment (ESA) of Municipal Solid Waste Incineration (MSWI) using two main objectives: Natural Resources Sustainability (NRS) and Environmental Burdens Sustainability (EBS) [7]. However, both functions are rarely normalized thus remained as functions rather than variables. The methodology suggest the normalization of EBS based on the threshold values proposed in the European Pollutant Release and Transfer Register E-PRTR [7], and a similar procedure based on the average consumption of natural resources of the Spanish MSWI plants for the normalization of NRS. Therefore, NRS and EBS can be normalized and the comparison between NR and EB can be accomplished. This methodology will help the decision maker at choosing the best option within Environmental Sustainability Assessment, reducing complexity as the two main functions can be converted into comparable variables that can be further used in multiobjective optimization. As case study several MSWI plants or Waste to Energy (WTE) plants located in Spain were selected in order to assess and compare the environmental performance of the plants. References [1] De Feo G and Malvano C (2009) The use of LCA in selecting the best MSW management system. Waste Manage 29 (6), [2] Aranda Usón A, Ferreira G, Zambrana Vásquez D, Zabalza Bribián I, Llera Satresa E (2013) Environmentalbenefit analysis of two urban waste collection systems. Sci Total Environ , [3] Kirkeby J, Birgisdottir H, Hansen TL, Christensen TH, Bhander GS, Hauschild M (2006) Evaluation of environmental impacts from municipal solid waste management in the municipality of Aarhus, Denmark (EASEWASTE). Waste Manage Res 24 (1), [4] Laurent A, Baka I, Bernstad A, Niero M, Gentil E, Hauschild MZ, Christensen TH (2014) Review of LCA studies of solid waste management studies-part I: Lesson learned and perspectives. Waste Manage 64, [5] Guinèe JB, Gorrée M, Heijungs R, Huppes G, Kleijn R, de Koning A, van Oers L, Wegener Sleeswijk A, Suh S, Udo de Haes HA, de Bruijn H, van Duin R, Huijbregts MAJ, Lindeijer E, Roorda A A H, Weidema BP, (2001) Life cycle assessment; An operational guide to the ISO standards; Characterisation and Normalisation Factors. Centre of Environmental Sciences, Leiden University. [6] Wenzel H, Hasuschild M, Alting L (1997) Environmental assessment of products, Vol1: Methodology, tools and case studies in product development. Klumer Academic Publisher, Hingham, MA; USA. [7] Margallo M, Aldaco R, Irabien A (2014) Environmental management of bottom ash from municipal solid waste incineration based on a life cycle assessment approach. Clean Technologies and Environmental Policy. DOI /s [8] E-PRTR, European Pollutant and Release Transference Register (2010). Accessed 22 October Acknowledgements The authors gratefully acknowledge the financial support of the project ENE given the Spanish Ministry of Science and Innovation and the project LIFE08 ENV/E/000135: FENIX-Giving packaging a New Life project.

158 EUROPEAN REGULATORY FRAMEWORK OF MSWI FLY AND BOTTOM ASH VALORIZATION Ana Hernández, María Margallo, Rubén Aldaco, Ángel Irabien Chemical and Biomolecular Engineering Department, Universidad de Cantabria Avda. de los Castros s/n 39005, Santander Tel , Topic: 2.1 Natural Resources Sustainability (Renewable Raw Materials and Waste Valorization) Abstract The aim of integrated waste management is to deal with society s waste in an environmentally and economically sustainable way. Within the framework of integrated waste management, municipal solid waste incineration (MSWI) represents a suitable alternative for reducing the amount of waste to be landfilled, recovering its energy and, at the same time, allowing for waste hygienization. However, the increasingly more stringent limits imposed in recent years on atmospheric emissions from waste energy recovery plants have produced a considerable shift from the gaseous emissions to the solid residues of the process. MSWI produces two main types of solid residues which are bottom ashes (BA) and fly ashes (FA), identified as non hazardous and hazardous waste by the European Waste List respectively. BA composition is mainly non-combustible materials and unburned organic matter. However, due to the combustion process and the air control systems, FA have an important content of heavy metals, soluble salts and toxic organic pollutants. In Europe, utilization of MSWI BA is either practiced or considered more and more as a viable option. BA are commonly recycled as construction materials in road base or concrete applications [1]. In Denmark, France, Germany and in Netherlands national legislation has been implemented to regulate utilization of MSWI BA. Denmark and the Netherlands have set governmental targets for utilization of MSWI BA, the target being 85% in Denmark and close to 100 % in Netherlands, whereas the actual utilization is 98% and 67% respectively. Though France and Germany have no governmental targets, high utilization rates are obtained, 72% and 65 % respectively. The legislation in all these countries is based on leaching criteria, but leaching limit values vary up to three orders of magnitude. Also there are great differences in test methods. Thus there are significant differences in the approaches used by regulatory bodies to develop criteria for utilization and also differences in the approach of the question of utilization or disposal itself [2]. In contrast FA utilization is not common and are mainly landfilled, previously treated, since its valorization is still under a research phase in most countries. Possible applications of FA are partial replacement of raw materials to produce cement and concrete, glass and ceramics, road pavement, fertilizers, adsorbent, zeolites, etc [3, 4]. Since valorization of solid residues from MSWI plants avoids landfilling and the use of natural resources, improving the energy balance of MSWI, it is desirable to create common regulations throughout Europe in order to maximize their recovery. It is also important to devise standard test methods, to ensure that the environmental assessments are made on the same basis. Since management of solid residues from thermal treatments is a significant environmental concern [3], this paper aims to review the European regulatory framework of BA and FA valorization. References [1] Margallo M, Aldaco R, Irabien A. Life cycle assessment of bottom ash management from a municipal solid waste incinerator (MSWI). Chemical Engineering Transactions. 2013;35: [2] ISWA-WG Thermal Treatment. Subgroup bottom ash from WTE-Plants Management of bottom ash from WTE plants. An overview of management options and treatment methods [3] Sabbas T, Polettini A, Pomi R, Astrup T, Hjelmar O, Mostbauer P, et al. Management of municipal solid waste incineration residues. Waste Manage. 2003;23(1): [4] Zacco A, Borgese L, Gianoncelli A, Struis RPWJ, Depero LE, Bontempi E. Review of fly ash inertisation treatments and recycling. Environmental Chemistry Letters. 2014;12(1):

159 BIOREFINERY DESIGN BASED ON MACAMBO (Theobroma bicolor) FRUIT A. A. González, J. A. Dávila, C. A. Cardona Universidad Nacional de Colombia. Departamento de Ingeniería Química Cra. 27 No , Manizales, Colombia. Instituto de Biotecnologia y Agroindustria. Tel.: Ext: 50417; fax: Ext: s: Specific Topic: 2. Chemical Engineering for Sustainable Development 2.1 Natural Resources Sustainability Amazonas is the largest Colombia Department in extension and is regarded as part of region with most biological biodiversity in the world; with a great potential to develop new value added products by biotechnological routes. However, these great potential it is not used in a correct way to take advantage over its big biodiversity therefore, it is necessary to increase efforts in the production of value added products from this region. On the other hand, natural products demand is increase in the market. This fact gives the opportunity to use biological compounds extracted from plants, fruits and other biodiversity from Amazonas region. However, many of these compounds, such as antioxidants, are found in small amounts within the vegetable matrix, which requires combining strategies in order to make it economically competitive. Biorefinery concept is analogous to that of oil refinery. It is about getting multiple products from biomass, taking advantage of the various constituents of the raw material and intermediate products, maximizing the quantities produced according to market needs. In this sense, this work paper presents techno-economic evaluation for obtaining antioxidants from macambo (Theobroma bicolor), under biorefinery concept. A simulation procedure was used in order to evaluate biorefinery scenario using the commercial software Aspen Plus v8.0 (Aspen Technology, Inc, USA). The total production cost was evaluated as well as the energy consumption of the processes. The chemical composition of makambo fruit was determined experimentally. Techno-economic assessment was made in the Amazon context. This result served as the basis to draw recommendations on technological and economic feasibility as well as social aspects for the implementation of this kind of projects in the Amazonas Department.

160 REDUCING SUGAR PRODUCTION FROM SEVEN AGROINDUSTRIAL COLOMBIAN WASTES J. A. Dávila, L. V. Daza, A. A. González, C. A. Cardona Universidad Nacional de Colombia. Departamento de Ingeniería Química Cra. 27 No , Manizales, Colombia. Instituto de Biotecnologia y Agroindustria. Tel.: Ext: 50417; fax: Ext: s: Specific Topic: 2. Chemical Engineering for Sustainable Development 2.1 Natural Resources Sustainability Colombia has an important agroindustrial wastes as a result of the fruits, vegetables and other crops processing. One characteristic of some Colombian agroindustrial wastes is that some of them are potential raw materials to be used as feedstock for reducing sugar production due to its content in cellulose and hemicellulose. Reducing sugars can be used as a platform to produce other important products by fermentative ways. In this sense, this works presents a study of the potential reducing sugar production from seven agroindustrial wastes, which are lulo (Solanum quitoense), peel avocado (Persea americana), seed avocado, peel pineapple (Ananas comosus), blackberry (Rubus fruticosus), peel mandarin (Citrus nobilis) and peel orange (Citrus cinensis). Acid hydrolysis tests were developed for all agroindustrial wastes considered and DNS (3,5-Dinitrosalisilic acid) method was used to evaluate reducing sugar concentration after acid hydrolysis process. According to this, for the best yield was developed a techno-economic assessment using Aspen Plus V8.0 evaluating an enzymatic hydrolysis after acid hydrolysis. Techno-economic assessment was made in the Colombian context and the total production cost was calculated taking into account raw material, depreciation expense, utilities, general and administrative cost as well as operating cost. Two scenarios were considered with and without heat integration to evaluate the reducing on utilities into the process. Finally, this work also demonstrates that computer-aided process engineering tool are a promising tool to carry out the evaluation of reducing sugar production.

161 ASSESSING THE LIFE CYCLE ENVIRONMENTAL IMPACTS OF ELECTRICITY GENERATION IN TURKEY Burcin Atilgan 1 and Adisa Azapagic 2 School of Chemical Engineering and Analytical Science, The Mill, Room C16, Sackville Street, The University of Manchester, Manchester M13 9PL, UK contact: Turkey is a developing country with a rapidly growing economy and population. Like many other countries, it has difficulties in meeting energy demand as the endogenous fossil energy resources are not sufficient. On the other hand, Turkey has several advantages in terms of variety and its potential of renewable energy resources compared to fossil fuels. The electricity demand in Turkey has been growing rapidly, reaching 211,208 GWh in 2010, almost seven-fold higher than in the mid 80s. In 2010, the coal and gas power plants generated 153,190 kwh, contributing 73.6% to the total generation. The most important renewable energy source to generate electricity is hydropower (24.5%). The high share of fossil fuels in Turkey s electricity mix together with the increasing demand has led to a steady increase in GHG emissions from the sector, growing by 115% between 1990 and It is, therefore, important that Turkey identifies and implements sustainable energy technologies suitable for the country, if climate change and other environmental impacts are to be curbed. This paper sets out to estimate for the first time the life cycle environmental impacts of the electricity mix in Turkey, using 2010 as the base year. Two functional units are considered: i) generation of 1 kwh of electricity; and ii) annual generation of electricity (211,208 GWh in 2010). The scope of the study is from cradle to grave, comprising extraction, processing, and transportation of the fuels, their use to generated electricity in power plants, and plant construction and decommissioning at the end of its useful lifetime. There are 13 lignite, 5 hard coal, imported coal and asphaltite, 34 gas, 55 reservoir hydropower, 205 run-of-river hydropower, 39 wind and 6 geothermal power plants in Turkey all of which are considered in this study. GaBi v6 software has been used to estimate eleven environmental impacts using the CML Baseline method. Example results include the global warming potential (GWP) estimated at 1,092 g CO 2 -eq./kwh from coal and 477 g CO 2 -eq./kwh from gas power plants. By contrast the GWP of hydropower plants is 6.7 g CO 2 - eq./kwh; corresponding figures for wind turbines and geothermal plants are 7.2 g and 63 g CO 2 -eq./kwh, respectively. In 2010, 113 Mt CO 2 eq. life cycle emissions were generated from 211 TWh of generated electricity in Turkey. The results highlight the importance of reducing the share of fossil fuels in the electricity mix which would lead to significant reductions in environmental impacts from the electricity sector, including GHG emissions.

162 CONTINUOUS PROCESS FOR THE ELECTROCHEMICAL REDUCTION OF INDIGO DYE X. Coma, V. Buscio, M. Crespi and C. Gutiérrez-Bouzán INTEXTER, Universitat Politècnica de Catalunya-BarcelonaTech, C/Colom 15, Terrassa, Spain, Tel , Fax Chemical Engineering for Sustainable Development: Natural Resources Sustainability Indigo is one of the most popular textile dyes. It represents 7% of the total dyes consumption for cellulosic fibres dyeing [1]. Indigo (C 16 H 10 N 2 O 2 ) is a natural dye with molecular weight g/mol. This dye is insoluble in aqueous solutions, but soluble in polar organic solvents. Previously to the dyeing process, the indigo must be submitted to a reduction stage to obtain its leuco form (soluble in aqueous solutions) (figure 1). This stage is carried out under alkaline conditions using a strong reducing agent such as sodium dithionite (Na 2 S 2 O 4 ) [2]. The fibres are passed through a bath which contains the reduced indigo. A considerable excess of reducing agent is necessary to avoid the oxidation of the dye baths, which causes environmental problems due to the generation of sulphites, sulphates and sulphur. For this reason, it is important to find new possibilities to reduce the indigo dye to minimize the dithionite consumption. Figure 1- Chemical structure of indigo dye and its leuco form (reduced state) In this work, the indigo dye was firstly reduced by the traditional method and then the feasibility to maintain the dye reduced by an electrochemical process, without the continuous addition of any reducing agent, was studied. The study was carried out in a cell (2 L) with two compartments separated by Nafion-324 membrane. The anode was made of Ti/Pt and the cathode was made of Ni. Firstly, the influence of the electrochemical process on the dye bath stability was determined. It was found that the electrochemical process was able to extend the stability of the leuco form, that is, to maintain the dye longer in the reduced state. The influence of active surface of the cathode, type of material and current density were evaluated. Six different current intensities were selected ranging from 0.1 to 6 A. It was observed that 0.5 A was the optimum value. At higher intensities, a large amount of hydrogen was generated, which caused the movement of the dye bath. This movement produced the contact of the dye with air, increasing its oxidation. At lower intensities, the potential difference between the electrodes was not enough to maintain the dye in the reduced form. The results obtained in this work show that the electrochemical reduction of indigo dye is an interesting challenge from the environmental and the economical point of view, since it allows to decrease the consumption of Na 2 S 2 O 4 during the dyeing process with indigo dye. Acknowledgements: The authors thank the financial support from the Spanish Ministry of Economy and Competitiveness (CTM ) and Valentina Buscio is granted by UPC. References [1] M.A.Sanromán, M. Pazos, M.T Ricart, C. Cameselle. Engineering Geology 2005; 77: [2] A. Roessler, X. Jin. Dyes and Pigments 2003; 59:

163 TECHNO-ECONOMIC EVALUATION OF THE PHB PRODUCTION FROM MILK WHEY AS FEEDSTOCK Catalina Alvarez C.; Juan Carlos Higuita V. Universidad Nacional de Colombia sede Manizales, Street 27 # 64-60, Manizales, Caldas- Colombia, (57+6) ext , Scientific Topic: Natural Resources Sustainability One of the most important applications of oil is as petrochemically-derived polymers, which due to their nonbiodegradability cause a major environmental problem. Hence, natural polymers or those originated from microorganisms, such as polyhydroxyalkanoates have increased their industrial value. One of the main problems associated to the industrial production of biopolymers like Polyhydroxybutyrate (PHB), is the high cost of raw materials and the energy consumed in its production. One alternative to solve these problems is the use of different agroindustrial wastes as substrate (such as whey derived from the cheese processing). To test the feasibility of PHB production at laboratory scale using Bacillus megaterium as the producing microorganism, an initial pretreatment step to remove nitrogen from the whey medium was implemented. The B. megaterium growth curves were carried out using whey as substrate and a PHB accumulation of 1.5 g/l was observed after 26h. The techno-ecomomic evaluation was performed using Aspen Plus 8.0, for the production and purification of PHB and demonstrated that the production costs are around 4.0 U.S./kg PHB, being high for whey due to the need of the pretreatment processes.

164 ANALYSIS OF OPTIMAL CONDITIONS FOR THE GROWTH OF Chlorella vulgaris USING VINASSE AS SUBSTRATE Juan D. Garcia M; Catalina Álvarez C; Juan C. Higuita V. Universidad Nacional de Colombia Street 27 # Manizales, Caldas Colombia, ext 55309, Scientific Topic: Natural Resources Sustainability The microalgae studies have been increasing in recent years due to its potential to be transformed in value added products such as fatty acids and carbohydrates for biofuels production. The study of the different metabolic pathways has allowed the use of agro-industrial wastes as carbon source for microalgae growth in heterotrophic conditions. The waste resulting from the alcohol production process from sugar cane known as vinasse has become an environmental problem, because of its high production and poor final disposal. This residue has a great potential to be used as carbon source for the culture of some microalgae species considering its residual amount of reducing sugars, nitrates and phosphates, which are essential macronutrients in the heterotrophic metabolic pathway of the microalgae growth. The culture of C. vulgaris in vinasse can be used as a bioremediation method considering its low costs and high production rates. In this work, the growth of the microalgae Chlorella vulgaris under heterotrophic conditions using different vinasse concentrations (0%-95%) as a carbon source was studied. Initially, the microalgae was adapted to the new culture conditions, such as ph, aeration and some micronutrients were additionally added to the culture media. As a result, the use of different vinasse concentrations shows the increase in cell concentration, reaching the maximum after 200 hours of fermentation. Furthermore, the best culture conditions were using 80% of vinasse in the medium, where the highest biomass concentration was presented, as shown in figure 1. The possibility of growing microalgae in vinasse was demonstrated as an alternative for the bioremediation and final disposal of this agroindustrial waste. A. B. Figure 1. Profile of Biomass and sugar consumption of Chorella vulgaris grown in different vinasse concentrations. A. Dry weight; B. Reducing sugars consumption.

165 EMULSOR-SCREEN PROCESSING OF SUBMICRON ECO-FRIENDLY EMULSIONS J. Santos, L.A. Trujillo-Cayado, N. Calero, M.C. Alfaro and J. Muñoz Departamento de Ingeniería Química. Facultad de Química. Universidad de Sevilla c/ P. García González, 1, E Scientific topic: Green Chemistry and Engineering Submicron emulsions with a narrow droplet size distribution and suitable physical stability are raising growing interest since they are finding enhanced applications in several industrial fields, such as those dealing with personal care and cosmetics, health care, food systems, pharmaceuticals, and agrochemicals (Sonneville, 2004). There is a need to replace the traditional organic solvents by more environmentally favourable solvents in process engineering, washing and cleaning applications and in formulated products, where they are used as encapsulation agents, carriers or emission-free coalescents (Gani et al, 2006). Consequently, the renewed interest in search of appropriate greener and alternative solvents for use in emulsions has grown markedly. Fatty acid dimethylamides (FAD) are among green solvents that can find applications in agrochemical emulsifiable concentrates. N,N-dimethyldecanamide is a great solvent for agrochemical uses due to the fact it is readily and rapidly biodegradable. The main targets of this work was the study of the rheological properties, droplet size distribution, and the physical stability of slightly concentrated O/W emulsions formulated with a mixture of 40 wt % green solvents (N,N-dimethyldecanamide Agnique AMD-10 from BASF and D-Limonene used with a 75/25 mass ratio). This ratio of solvents was previously demonstrated to provide the optimum physical stability (Santos, 2014). 4% wt of a fully biodegradable commercial polyoxyethylene glycerol ester, Levenol C-201 (KAO) of HLB number 13 was used as emulsifier. The preparation of emulsions was carried out using a rotor-stator homogenizer, equipped with an emulsor mesh screen which promotes extensional flow in addition to extensive shear flow. The homogenization rate ranged from 4000 rpm to 8000 rpm and the emulsions were prepared at room temperature. The laser diffraction technique demonstrated that the emulsions prepared exhibited a monomodal size distribution at the lowest homogenization rate (4000 rpm), which shifted to bimodal size distributions at higher homogenization rates. It must be emphasized that above 4000 rpm, submicron Sauter s mean diameters as low as 340 nm could be obtained. It is noteworthy that we did not need to use high-energy input devices, such as a micro-channel homogenizer to get such a low mean droplet diameter. All emulsions exhibited shear thinning behaviour, which fitted the Cross model with a range of zero shear viscosity values from 1.2 and 2800 Pa s. In addition, emulsions processed above 5000 rpm exhibited weak-gel like viscoelastic properties when studied under small amplitude oscillatory shear. Flow curves showed an increase in viscosity with aging time for emulsions processed at the lower homogenization rates, which was consistent with the occurrence of incipient creaming, as also supported by multiple light scattering. In contrast, drops in zero shear viscosity and also in the storage and loss moduli with aging time were detected for emulsions processed above 5000 rpm. This was a clear indication of the occurrence of some coalescence, which was also confirmed by the rise of droplet sizes measured by laser diffraction. Multiple light scattering supported the results obtained by the above techniques. We demonstrate that the optimum homogenization rate was 4000 rpm on account of the lack of coalescence and of a low creaming rate. ACKOWLEDGMENTS The financial support received (Project CTQ ) from the Spanish Ministerio de Economía y Competitividad and from the European Commission (FEDER Programme) is kindly acknowledged. The authors are also grateful to BASF and KAO for providing materials for this research. REFERENCES Gani, R, Jiménez-González, C., ten Kate, A., Crafts, P.A., Jones, M., Powell, L, Atherton, J., Cordiner, J. (2006) Chemical Engineering, 113, Santos J, Trujillo-Cayado LA, Calero N, Muñoz J. (2014) AIChE Journal. DOI: /aic Sonneville-Aubrun O, Simonnet J, L`Alloret F. (2004) Adv Colloid Interface Sci :

166 BIOCONVERSION OF HYDROLYZED BAGASSE SUGARCANE IN ETHANOL BY Spataspora arborariae UFMG-HM19.1A *Guadalupe Bustos V., Erika Vizcaino G., Nadia A. Rodríguez D., Alfredo Del Angel, Nubia R. Rodríguez D. (1) Unidad Académica Multidisciplinaria Mante. Universidad Autónoma de Tamaulipas Blvd. E.C. González 1201, Col. Jardín CP * Tel- Fax: (52) ext Cd. Mante Tamaulipas, México. Scientific Topic: 2. Chemical Engineering for Sustainable Development. 2.1 Natural Resources Sustainability: Renewable Raw Materials and Waste Valorization Abstract There are several potential crops for bioenergy, those considered eligible by SAGARPA (2008), are sugarcane, sweet sorghum and sugar beet for ethanol production and jatropha, castor and palm oil for biodiesel production. In this investigation the biotech use of sugarcane bagasse for ethanol production was studied by determining the appropriate fermentation conditions that enable high performance, using the yeast- HM19.1A Spataspora arborariae UFMG. Ethanol is an alcohol fuel with many likely to be widely used as automobile fuel, because it is less hygroscopic, has a heat of more combustion and lower heat of vaporization and most importantly is much less toxic (Sánchez et al. 2007). Gasoline oxygenate several advantages, such as higher oxygen content, high octane, reduce more emissions of carbon monoxide and pollutes water sources. The effect of the stirring and temperature in the process of bioconversion of hydrolyzed bagasse sugarcane in ethanol was evaluated according to a full 2 2 factorial planning with three replications at the center point, taking in response parameters (Yx / s), (Yp / s) and (Qp), the trials were performed in 125 ml Erlenmeyer flasks with a total volume of 50 ml, evaluating agitations 200, 250 and 300 rpm and temperatures of 30, 33 and 36 C. The fermentation medium was hemicellulosic hydrolyzate from sugarcane bagasse detoxified and concentrated, containing about 50 g/l of total sugar supplemented with 3 g/l yeast extract, inoculated with yeast Spataspora arborariae UFMG HM19.1A at shakers. The results showed that after experimenting with 5 treatments, the 1 and 5 obtained the best conditions for the production of ethanol by yeast Spataspora arborariae UFMG - HM19.1A. Achieving product conversions (Y p/s) of and g/g cell conversion (Yx/s) of and g/g (yield and productivity (Qp ) of and g/lh respectively). In the first trial planning was observed slow nutrient consumption (around 60 %), unlike the others, but with a high production of ethanol (1.7 g/l at 72h). Moreover, the five test showed increased production of ethanol with yeast Spataspora arborariae UFMG-HM19.1A, with a higher efficiency in the consumption of nutrients close to 91% and therefore a yield of 3.6 g/l of ethanol to 24h, demonstrating the importance of temperature and oxygenation status of the culture media on the production of ethanol. Despite the low values obtained Yp/s and Yx/s yeast Spataspora arborariae UFMG-HM19.1A, test 5 showed a good Qp (0.153 g / Lh), higher than those found by Dilon, 2010, in the which obtained g/lh in hydrolyzate made with sugarcane bagasse with 75 g/l of sugars supplemented with 5 g/l yeast extract and presented by Nigam 2001 trials, which obtained 0.10 g/lh with hydrolyzed hemicellulosic of wood, supplemented with 3 g / L yeast extract, 5 g/l of peptone, 2 g/l of KH 2 PO 4, 1 g/l of (NH 4 )2PO 4 and 0.5 g/l of MgSO 4 7H 2O and inoculated with the yeast Pichia stipitis Y-7124 and higher rates of consumption of fermentable sugars 91%. References SAGARPA;Programa de Producción Sustentable de Insumos para Bioenergéticos y de Desarrollo Científico y Tecnológico. Pág (2008). Sánchez T, Ó; Cardona A.C.A.; Producción de alcohol carburante. Una alternativa para el desarrollo agroindustrial. Manizles, Caldas, Colombia. Pag (2007). Dilón F. A.; Utilição da Levadura Pichia stipitis UFMG-IMH 43.2 para obtenção de etanol em hidrolisado hemicelulosico de bagaço de cana de açúcar. Dissertação Maestrado em Biotecnologia Industrial- Escola de Engenharia de Lorena, Universidade de São Paulo, Lorena, Brasil. (2010).

167 KINETIC STUDY OF ETHANOL PRODUCTION BY Spataspora arborariae UFMG- HM19.1A IN MEDIA HYDROLYZATE SUGARCANE BAGASSE DETOXIFIED *Guadalupe Bustos V., Erika Vizcaino G., Nadia A. Rodríguez D., Alfredo Del Angel, Nubia R. Rodríguez D. Unidad Académica Multidisciplinaria Mante. Universidad Autónoma de Tamaulipas Blvd. E.C. González 1201, Col. Jardín CP * Tel- Fax: (52) ext Cd. Mante Tamaulipas, México. Scientific Topic: 2. Chemical Engineering for Sustainable Development. 2.1 Natural Resources Sustainability: Renewable Raw Materials and Waste Abstract The sugarcane bagasse is a lignocelulosic natural resource that presents very interesting features, such as its renewability, low economic value and abundance. Therefore it has a growing potential as a feedstock for the chemical and biotechnology industries. Bagasse sugarcane as residue of the sugar industry has been used for the production of electricity as paper pulp, for obtaining structural products. Ethanol is an alcohol fuel with a good chance of being widely used as automobile fuel, for it must be anhydrous alcohol at least 99.6 % degrees Gay Lussac (Ocrospoma L., et al., 2008). The use of ethanol as oxygenate in gasolines represents several advantages, such as increased oxygen content, high octane, reduce more emissions of carbon monoxide and pollutes water sources. Compared with the methanol, ethanol is less hygroscopic, has a higher heat of combustion and a lower heat of vaporization and most importantly is much less toxic (Sanchez et al., 2007). The performance of the fermentation process for ethanol production is greatly affected by the type of yeast used. Pure cultures are isolated and obtained through breeding (Almeida et al., 2001). The effect of the stirring and temperature in the process of bioconversion of hydrolyzed bagasse sugarcane in ethanol was evaluated according to a full 22 factorial planning with three replications at the center point, taking in response parameters (Yx / s), (Yp / s) and (Qp), the trials were performed in 125 ml Erlenmeyer flasks with a total volume of 50 ml, evaluating agitations 200, 250 and 300 rpm and temperatures of 30, 33 and 36 C. The fermentation medium was hemicellulosic hydrolyzate from sugarcane bagasse detoxified and concentrated, containing about 50 g/l of total sugar supplemented with 3 g/l yeast extract, inoculated with yeast Spataspora arborariae UFMG HM19.1A at shakers. The results showed that after experimenting with 5 treatments, the 1 and 5 obtained the best conditions for the production of ethanol by yeast Spataspora arborariae UFMG - HM19.1A. Achieving product conversions (Y p/s) of and g/g cell conversion (Yx/s) of and g/g (yield and productivity (Qp ) of and g/lh respectively). In the first trial planning was observed slow nutrient consumption (around 60 %), unlike the others, but with a high production of ethanol (1.7 g/l at 72h). Moreover, the five test showed increased production of ethanol with yeast Spataspora arborariae UFMG-HM19.1A, with a higher efficiency in the consumption of nutrients close to 91% and therefore a yield of 3.6 g/l of ethanol to 24h, demonstrating the importance of temperature and oxygenation status of the culture media on the production of ethanol.despite the low values obtained Yp/s and Yx/s yeast Spataspora arborariae UFMG-HM19.1A, test 5 showed a good Qp (0.153 g / Lh), higher than those found by Dilon, 2010, in the which obtained g/lh in hydrolyzate made with sugarcane bagasse with 75 g/l of sugars supplemented with 5 g/l yeast extract and presented by Nigam 2001 trials, which obtained 0.10 g/lh with hydrolyzed hemicellulosic of wood, supplemented with 3 g / L yeast extract, 5 g/l of peptone, 2 g/l of KH 2 PO 4, 1 g/l of (NH 4 )2PO 4 and 0.5 g/l of MgSO 4 7H 2 O and inoculated with the yeast Pichia stipitis Y-7124 and higher rates of consumption of fermentable sugars 91%. References Alves, J. (2007). Estudo da produção de etanol por Pichia stipitis empregando hidrolisado de palha de arroz. Dissertação Maestrado em Biotecnologia Industrial- Escola de Engenharia de Lorena, Universidade de São Paulo, Lorena Ocrospoma L., y col., (2008). Situación y perspectiva de los biocombustibles en el Perú. Recursos energeticos - Biocarburantes. Lima, Perú. Instituto Interamericano de Cooperación para la Agricultura(IICA).Pág.37_38 Sánchez T, Ó; Cardona A.C.A (2007) Producción de alcohol carburante. Una alternativa para el desarrollo agroindustrial. Manizles, Caldas, Colombia. Pag

168 EVOLVED GAS ANALYSIS (TG/FT-IR/MS) AND REACTION KINETICS OF DIFFERENT OIL SEEDS DURING PYROLYSIS Gamzenur Özsin, Murat Kılıç, Ayşe E. Pütün * Anadolu University, Department of Chemical Engineering, Eskişehir, Turkey * phone: ; fax: Scientific Topic: 2. Chemical Engineering for Sustainable Development 2.1 Natural Resources Sustainability Pyrolysis characteristics and reaction kinetics of three different oil seeds (sunflower, Camelina sativa and soy bean seeds) were determined by thermogravimetric analysis (TGA) coupled with Fourier transform infrared spectroscopy (FT-IR) and mass spectroscopy (MS). In order to enlighten slow pyrolysis behaviours, seeds were pyrolysed from room temperature to 1000 C using 10 C/min heating rate under nitrogen atmosphere. Mass loss stages were identified by TG and dtg curves and pyrolysis processes were found to compose of successive thermal degradation stages at different temperature intervals. By determining onset and final reaction temperatures a kinetic analysis was performed by Coats and Redfern method and orders of reactions, frequency factors and activation energies were calculated. To understand the type and amount of major evolved gasses, series of FT-IR and MS spectrum were collected online during the decomposition of lignocellulosic structures. By the help of functional group analysis and m/z signals, profiles of evolved species were obtained in the entire temperature range.

169 DECOMPOSITION CHARACTERISTICS OF BIOMASS-COAL-POLYMER MIXTURES VIA PYROLYSIS Gamzenur Özsin 1, Murat Kılıç 1, Esin Apaydın-Varol 1, Başak B. Uzun 1, Ayşe E. Pütün 1, Ersan Pütün 2,* 1 Anadolu University, Department of Chemical Engineering, Eskişehir, Turkey 2 Anadolu University, Department of Materials Science and Engineering, Eskişehir, Turkey * phone: ; fax: Scientific Topic: 2. Chemical Engineering for Sustainable Development 2.1 Natural Resources Sustainability In this study, co-pyrolysis characteristics of biomass-coal-polymer mixtures were investigated. Corn stalk, polyethylene terephthalate (PET) and lignite were selected as biomass, polymer and coal samples and their mixtures were prepared by mixing them in a definite ratio of 1:1 (w/w). Pyrolysis experiments were performed at 550 C using 10 C/min heating rate under nitrogen atmosphere in a fixed bed reactor and yields of solid, liquid and gas products were determined. Subsequently, the obtained solid and liquid products were analysed by using different characterization techniques. The structural properties of the produced chars were investigated with SEM-EDX, BET and elemental analysis. On the other hand, tar characterization was performed by GC/MS, and FT-IR, 1 H-NMR and elemental analysis. Based on the analyses results, biomass interactions with polymer and coal were determined. In this manner, effects of using a polymer material and a low-ranked coal as an additive to the biomass pyrolysis were discussed. Acknowledgments. The authors would like to thank Anadolu University Scientific Research Council for the financial support of this work through the projects 1001F068.

170 CONVERSION OF FRUIT PULP INTO ENERGY RICH GAS PRODUCTS BY SUPERCRITICAL WATER GASIFICATION E. Demirel and N. Ayas Anadolu University, Faculty of Engineering, Department of Chemical Engineering, 26555, Eskisehir, Turkey Phone: /6508 Fax: Scientific Topic:Chemical Engineering for Sustainable Development-Natural Resources Sustainability In the recent years, biomass utilization for energy considerations is increasing due to the diminishing of primary energy sources and growing environmental concern [1]. SCWG (supercritical water gasification) is an innovative technology for converting biomass into valuable combustible gas, possibly with a large content of hydrogen and other gases which are CO 2, CH 4 and small amounts of CO and C 2 -C 3 hydrocarbons. Depending on the reaction conditions several intermediate compounds are formed during the reaction such as alcohols, acids, aldehydes, diols, ketones, phenols, furfurals and other compounds. Additionally, some of these compounds are converted to char/coke after undergoing a polymerization reaction [2]. Today H 2 production is of interest above all for the use of fuel cells in electricity production [3]. In the present study, the main objective is to utilize fruit pulp as a raw material by producing combustible gases using SCWG technique in the presence of an alkali catalyst. The effect of reaction parameters such as temperature, time and biomass ratio on the yields of liquid, gaseous and solid products as well as their compositions was investigated. Variables which maximize the production of H 2 gas were determined. Physical (elemental analysis, moisture, ash, protein, oil content) and chemical properties (cellulose, hemicellulose, lignin, inorganic constituents and heating value) of the fruit pulp, which is a side product of a fruit juice factory, were determined according to the standard procedures. Supercritical water gasification of the pulp was conducted in a batch reactor using K 2 CO 3 as catalyst. Effect of temperature ( C), reaction time ( min.) and biomass ratio ( %, w/w) on the gasification efficiency and composition of the gas products were investigated. The online analysis of gaseous products was performed using a Micro Gas Chromatography (μgc). Table I shows the compositions of the main gas products as a function of reaction temperature for constant reaction time (120 min.), catalyst ratio (30%, wt.) and biomass ratio (2.5%, wt.). Table I. Gas compositions Temperature Relative ratio (%, mol/mol) ( C) H 2 CO 2 CH 4 C 2 H 6 C 2 H 4 C 3 H 6 C 3 H It can be seen from the table that the amount of H 2 increases with temperature while that of CO 2 decreases. Amounts of CH 4 and C 2 H 6 increase up to 500 C and tend to decrease for further increase in temperature. The highest H 2 content in the gas product was achieved at 600 C with the value of 46.2% by mole. It was found from the experimental results that the amount of gas product increases while those of liquid and solid products decrease with an increase in temperature. An increment in dry matter ratio of the feed was found to lead to higher tar content and decreased gas yield. Therefore, maximum H 2 yield (22.7 mol/kg biomass) was obtained using a biomass ratio of 2.5%. References [1] M. Detournay, M. Hemati, R. Andreux, Biomass steam gasification in fluidized bed of inert or catalytic particles: comparison between experimental results and thermodynamic equilibrium predictions, Powder Technol., 208(2), (2011) p [2] A.G. Chakinala, S. Kumara, A. Kruse, S.R.A. Kerstena, W.P.M. van Swaaija, D.W.F. Brilmana, Supercritical water gasification of organic acids and alcohols: the effect of chain length, J. of Supercritical Fluids, 74, (2013) p. 8. [3] A. Kruse, A. Henningsen, A. Sınağ, J. Pfeiffer, Biomass gasification in supercritical water: influence of the dry matter content and the formation of phenols, Ind. Eng. Chem. Res., 42(16), (2003) p

171 ZSM-5 Catalysis in Pyrolysis Reactions Sahin F. Chemical Engineering Faculty, Hitit University, TURKEY ABSTRACT Demand for energy and its resources increase day by day due to the rapid out growth of population and urbanization. Major conventional energy resources like coal, petroleum and natural gas are at the verge of getting extinct, so biomass can be considered as the promising environment friendly renewable energy obtains. One of the thermo-chemical conversion processes is pyrolysis that has been used to convert the biomass into various energy products. In this study, five kinds biomass species (pine, furfural, alkaline lignin, plastic waste and glucse) process are discussed in detail. It was observed that different types of biomass sources and pyrolysis conditions; change the chemical composition and properties of pyrolsis products. Pyrolysis is thermal decomposition occurring in the absence of oxygen. In particular, the concentration of oxygenates can be reduced by using acidic zeolite catalysts (ZSM-5). Since, the active sites and pore dimension of ZSM-5 catalysis significantly influence the product distribution, all researches determined acid side of the zeolite. As aresult, they observe that the yield of product and the selectivity to desired products can be controlled by tuning of the acidity and pore size of the catalyst. From the literature, it can be concluded that lower process temperatures favour the production of charcoal. High temperatures and longer residence times increase biomass conversion to gas, and moderate temperatures and short vapour residence time are optimum for producing liquids. Three products are always produced, but the proportions can be varied over a wide range by adjustment of the process parameters. In all study, the main problem that scientists dial with is how to efficiently remove the abundant oxygen content from biomass-derived products and convert it into a hydrophobic molecule. They are still work on this problem, so there is no appropriate method to solve this problem has found yet. The residue formed, ash remained after pyrolysis in addition to coke/char. Coke is undesired product of the pyrolysis process. In order avoid from coke formation, it should be increase catalyst loadings, so more active species were converted into liquid products, thus preventing them reacting to coke, resulting in decrease of solid and increase of liquid amount. Although pyrolysis is still under developing stage, but during current energy scenario, pyrolysis has received special attention is it can convert biomass directly solid, liguid and gaseous products by thermal decomposition of biomass in the absence of oxygen. Keywords: Biomass, ZSM-5 catalyst, pyrolysis 1

172 MULTI-OBJECTIVE OPTIMIZATION METHOD BASED ON INPUT-OUTPUT MODELS TO MINIMIZE THE LIFE CYCLE GREENHOUSE GAS EMISSIONS OF THE EUROPEAN ECONOMY Daniel Cortés-Borda a, Antonio Ruiz-Hernández a, Gonzalo Guillén-Gosálbez a,c *, Maria Llop b, Roger Guimerà a, Marta Sales-Pardo a a Departament d Enginyeria Química, Universitat Rovira i Virgili, Av.Països Catalans 26, Tarragona (Spain), (+34) ; b Centre de Recerca en Economia Industrial i Economia Pública (CREIP), Universitat Rovira i Virgili, Av. Universitat 1, Reus (Spain). c School of Chemical Engineering and Analytical Science, University of Manchester, Mill, Sackville Street, Manchester M13 9PL, United Kingdom Scientific Topic: Chemical Engineering for Sustainable Development/Natural Resources Sustainability/Energy, Water and Materials/Life Cycle Assessment The high greenhouse gases atmospheric concentration has led to severe dangers for Earth s climates and ecosystems. Worldwide governments have placed greenhouse gas emissions mitigation as a priority, and have started to implement stringent measures based on the reorganization of the way in which society develops (work, transport, leisure, city planning, housing, electricity production, etc.). A large body of literature has studied different technological alternatives to mitigate global warming by adopting an engineering approach, mainly through carbon sequestration, the use of renewable energy sources, and the improvement of energy efficiency in processes and buildings. However, less work has been devoted to the analysis of global warming mitigation at a wider scale, that is, to the study of how to reduce greenhouse gas emissions from a macroeconomic viewpoint. In macroeconomics, the input output models provide an exhaustive description of the economic transactions between final consumers and productive sectors in complex international trade networks. The input-output models are often extended to environmental issues by considering the pollution intensity vectors of the production technologies in the conventional input output model. This allows translating the economic output of each sector into tangible environmental loads (e.g. greenhouse gas energy related emissions). The environmentally extended input output (EEIO) models have demonstrated so far to be flexible, transparent and accurate, which makes them quite appropriate for conducting life cycle assessment studies in numerous fields. Existing studies using EEIO models provide quantitative information on the environmental loads related to the economic activities, but they are not providing specific guidelines on how to mitigate them. Some other authors have gone one step further and implemented EEIO models to identify aprioristic strategies leading to significant impact reduction. Unfortunately, the latter are based on a "what if" analysis. That is, they explore the consequences of a set of scenarios previously defined, restricting the analysis to a reduced number of alternatives that may eventually result in suboptimal solutions. A possible manner to overcome such limitation consists on integrating systematic optimization techniques with EEIO models. The present work proposes systematic multi-objective optimization method for simultaneously minimizing the global warming potential (assessed through a life cycle assessment methodology) and maximizing the total output of the European Union. The calculations are performed using the Comprehensive Environmental Data Archive EU25 database, which considers 487 sectors (including household activities) for the EU-25 economy in The highly disaggregated EEIO identifies specific economic activities that are ultimately responsible for the impact. The present method identifies sectors with low direct greenhouse gas emissions but large indirect ones. Results are given as a Pareto front, in which each intermediate solution reduces the global warming potential with respect to the previous solution at the expense of restricting progressively the total output of the economy. Results showed that with the existing technology the global warming potential could be lowered in greater proportion than the economic output by restricting adequately the demand of specific sectors.

173 Electrosynthesis of dimethyl carbonate from CO2 and methanol in the presence of [bmim][br]: the influence of the electrochemical cell configuration I. Garcia-Herrero, A. del Castillo*, M. Alvarez-Guerra, A. Irabien Department of Chemical and Biomolecular Engineering, ETSIIT, Universidad de Cantabria, Avenida de los Castros s/n, Santander, Spain; Tel: ; Natural Resources Sustainability/ Green Chemistry and Engineering Different strategies for reducing carbon dioxide emissions and mitigating climate change are being developed. Among them, CO 2 electrovalorization has attracted much attention because it allows the captured CO 2 to be converted into valuable products and can serve as a future excellent way of storing the intermittent and difficult to predict energy produced from renewable sources such as solar or wind energy [1]. Dimethyl carbonate (DMC) is an environmentally friendly valuable chemical of great interest, used as alkylating agent, alternative to conventional solvents, building block in the production of higher carbonates and potential gasoline additive due to its high oxygen content. DMC traditional routes implied the use of hazardous phosgene and CO. Hence, new greener paths are being developed. Among them, the direct synthesis of DMC from CO 2 and methanol is considered the most promising route due to the replacement of toxic raw materials by CO 2 and the substitution of multistep processes by a direct synthesis route [2]. The purpose of this work is to study the valorization of CO 2 by the electrosynthesis of DMC from methanol in the presence of the ionic liquid [bmim][br] and CH 3 OK with different cell configurations. The experimental system included two tanks, two peristaltic pumps (Watson Marlow 323 S/D), a potentiostat/galvanostat AutoLab PGSTAT 302 N (Metrohm, Inc.) and a filter-press electrochemical cell (Micro Flow Cell ) supplied by ElectroCell. Pt/Nb plates (99.5% Pt) with a surface area of 10 cm 2 were used as electrodes. The filter press cell enables the operation using two different configurations: (i) divided cell in anodic and cathodic compartments by an ion-exchange membrane and (ii) undivided cell. The performance of the process using a cation exchange membrane, Nafion 117 [3], and an anion exchange membrane, fumasep FAB-PK-130 was compared with the absence of membrane. The proposed approach avoids the conventional addition of toxic compounds such as carcinogenic CH 3 I and provides experimental evidences that contribute to increase the available knowledge about this process. The performance of the process was studied for up to 48 h under atmospheric pressure and 303 K. The liquid and gas phases were analyzed by gas chromatography-mass spectrometry. Methyl formate, dimethyl ether and bromomethane were detected in the gas phase. Regarding the liquid phase, no by-products were detected when the FAB-PK-130 membrane and no membrane were used compared to the Nafion 117 study. A kinetic analysis based on DMC evolution is performed. Moreover, a reaction scheme based on the byproducts detected is proposed. A six fold increase is achieved in undivided configuration compared to the divided configuration, which involves a 85 mmol L -1 final concentration of DMC. References [1] Alvarez-Guerra, M., Del Castillo, A., & Irabien, A. Chem. Eng. Res. Des. 2014, 92(4), [2] Cao, Y., Cheng, H., Ma, L., Liu, F., & Liu, Z. Catal. Surv. Asia, 2012, 16 (3), [3] Garcia-Herrero, I., Alvarez-Guerra, M. & Irabien. A. J. Chem. Technol. Biot. Accepted. DOI: /jctb.4445 Acknowledgements Financial support to project ENE is gratefully acknowledged. I. Garcia-Herrero also thanks the FPI postgraduate research grant (BES ).

174 ALLOCATION OF GHG EMISSIONS IN COMBINED HEAT AND POWER SYSTEMS IN PAPER INDUSTRY Aldrich, R., Llauró, F.X., Puig, J., Mutjé P., Pèlach, M.A LEPAMAP Grup, Department of Chemical Engineering, Universitat de Girona. Avda M. Aurèlia Capmany, Girona Scientific Topic: Chemical Engineering for Sustainable Development 2.1 Nature Resources Sustainability The paper industry is responsible for a considerable amount of greenhouse gas (GHG) emissions mainly due to its intensive energy requirements. In Spain, this industrial sector had installed in 2009 nearly 60 CHP plants transforming it from a large electricity consumer into an integrated energy business operation producing electricity efficiently. The production of heat and power streams in a cogeneration system, i.e., a combined heat and power (CHP) plant, releases considerable amounts of GHG emissions into the atmosphere. Such emissions are already subjected to legislation globally. The amount of GHG emissions is usually calculated from the product of the total amount of energy activity multiplied by an emission factor. However, each energy output stream should get a share of emissions responsibility. This fact could assist in assigning weights to the emissions generated for power and thermal purposes in a combined heat and power plant. However, developing a suitable method of allocating emissions in a cogeneration system is still a concern and a subject research for scientists, companies and policy makers. This work exposes and evaluates different published allocation methods and applies them to a real case of a combined heat and power plant integrated in a paper mill and proposes a new allocation method and does the comparison with published ones. A typical CHP plant configuration is used to compare the different allocation methods. This system is composed of a primary energy mover (a gas-fired turbine) with its corresponding generator. The exhaust gases go to a heat recovery steam generator (HRSG) and to a back pressure steam turbine with an intermediate steam extraction. The HRSG produces a high pressure (HP) steam and a steam turbine produces electricity and low pressure steam (LP). The steam production is provided to a paper mill process. The published efficiency methods are based on the efficiency of facilities. CHP plants produce energy using a variety of generators driven by a range of different motive forces. The efficiency method bases its emissions allocation according to the amount of fuel used to produce each energy output. Thus, the method accounts for the efficiency of generating each heat or power output related to a different type of energy. The publisehd methods based on thermodynamic analysis consider that all the energy contained in electrical power is useful and is therefore used for calculations and the energy involved output streams is the key to allocating emissions. On the other hand, these methods can differ in the evaluation of the thermal energy (steam energy basis and steam exergy basis). Both the steam energy and exergy methods take into account that electrical energy can be totally converted into work, but not all the thermal energy can achieve the same purpose. The existing methods have in common an allocation base of emissions into the utilisable output streams of the CHP plant. Nevertheless, authors consider that inefficiencies concerning both those intrinsic to the system and the operational ones should be weighted with an allocation method. For this reason, an alternative method of CHP emissions allocation based on the aforementioned considerations has been composed and developed. The proposed methodology is formulated according to efficiency indicators considering the BATs of different CHP components. ACKNOWLEDGEMENTS Authors wish to acknowledge the financial support of the Ministry of Science and Innovation of Spain to the Project CTM C REFERENCES - Ämmälä, A., Jokinen, H., Niinimäki, J., Yli-Viitala, P. Hydrocyclone sand separation, Appita J., 60(4) Saint Amand, F.J. Principles & Technology of Cleaning /Fractionation, 10 th Advanced Training Course on Deinking Technology, Centre Technique du Papier, Grenoble (Fr) Technical Information Paper, TIP An introduction to centrifugal cleaners from Pesch, A.W., Process for preparation of fibers having different characteristics US Patent A April, 16 th 1963.

175 ETHERIFICATION OF CRUDE GLYCEROL BY BENZYL ALCOHOL M. P. Pico*, S. Rodríguez, A. Santos, A. Romero Dpto Ingenieria Quimica, Facultad de Ciencias Químicas, Universidad Complutense Madrid. Ciudad Universitaria S/N Madrid, Spain. *: phone: fax: Scientific Topic: Chemical Reaction Engineering Introduction The use of renewable energies is gaining attention all over the world and one of the employed energy sources is biodiesel. The main by-product of this process is glycerol, whose production is approximately 10 wt. % of the total biodiesel obtained [1]. Therefore valorization of glycerol obtained from biodiesel as initial raw material would be desirable from an economical point of view. One of the ways of glycerol revalorization is the preparation of alkyl ethers of glycerol by etherification. This strategy allows the valorization of a by-product and the improvement of biodiesel performance as biofuel, since these tert-butyl ethers from glycerol offer an alternative to oxygenated compounds which are currently added to fuels [2]. These reactions can be performed with different olefins and alcohols, e. g. benzyl alcohol [3-5]. The scope of this work is the study of crude glycerol (G) etherification with benzyl alcohol (BZ) over a strong acid ion-exchange commercial resin (Amberlyst 15) and a molar ratio of 1:1 BZ:G. Reactions were carried out at vacuum pressure with continuous removing of formed water. Results and discussion This etherification process has been studied at a reaction temperature of 90 ºC and different catalyst concentrations referred to the starting amount of reactants (4.6, 9.2, 13.8 and 23 wt%). Samples withdrawn after each reaction were analyzed off-line by a gas chromatograph. These experiments have been carried out with nonpurified glycerol has been obtained from biodiesel production with soya oil and potassium methoxide as catalyst; The content of volatile components is high as well as the amount of alkali metals present in the media (K and Na). In Figure 1a, a comparison between results obtained with pure and non-purified glycerol can be observed. Glycerol conversion decreases drastically. In order to reduce this negative influence, OH groups and metallic cations have been neutralized. After this pre-treatment, a reaction is carried out with a catalyst concentration of 4.6 wt%. The results derived from this experiment are shown in Figure 1b and as it can be observed, the values obtained are very similar to those achieved with pure glycerol. Consequently, non-purified glycerol with metallic cations and remaindered OH compounds can behave as pure glycerol if they are previously neutralized ,6 wt% 9,2 wt% 13,8 wt% 23 wt% 4,6 wt%--pure 9,2 wt%--pure ,6 wt% 4,6 wt%--pure 4,6 wt%--neutralized X G 0.4 X G t (min) t (min) Figure 1. Comparison between pure glycerol and a) non-purified glycerol, b) non-purified glycerol and neutralized glycerol (T=90 ºC, initial molar ratio Bz:G 1:1) Acknowledgements Authors acknowledge financial support for this research from the Spanish Ministry of Science and Innovation under projects PRI-PIBAR and AGI Santander-ECL References [1] Rahmat N, Abdullah AZ, Mohamed AR. Renewable and Sustainable Energy Reviews 14, (2010). [2] Klepáčová K, Mravec D, Hájeková E, Bajus M. Petroleum and Coal 45 (1-2), (2003). [3] Pico MP; Rodríguez S; Santos A; Romero A. Industrial and Engineering Chemistry Research 52, (2013) [4] Pico MP; Rodríguez S; Rosas JM; Santos A; Romero A. Journal of Chemical Technology and Biotechnology 88, (2013) [5] Pico MP; Romero A; Rodríguez S; Santos A. Industrial and Engineering Chemistry Research 51, (2012)

176 HYDROTHERMAL CARBONIZATION OF TWO PHASE OLIVE MILL WASTE: CHARACTERIZATION OF THE HTC-CHAR AND DETERMINATION OF THE KINETICS FROM THE SOLID MASS YIELD V. Benavente *, J. Gordon, E. Calabuig, A. Fullana Department of Chemical Engineering, University of Alicante, Ap. 99, Alicante, Spain *Presenting author: Tlf: ext Fax: Scientific Topic: 2.1. Renewable Raw Materials and Waste Valorization Spain currently produces a large quantity of olive oil and 2.4 million hectares of land is dedicated to its production. The newest production method uses 2-phase centrifugation process, which produces olive oil and a highly polluting two-phase olive mill waste (TPOMW). Approximately 4 million tonnes of TPOMW is produced per year and this waste has high moisture content, making it difficult to handle, store and transport [1]. In this work, TPOMW was converted via hydrothermal carbonization (HTC) to a carbon rich solid with improved combustion properties (HTC-char), more suitable for energy generation. TPOMW was treated in a sealed lab scale batch reactor at C for residence times of 0, 1, 2, 4, 8 and 24 hours. During the process, water was evaporated producing autogenous pressure, preventing the evaporation of all moisture present, improving the energetic feasibility of the process. Then, the samples were filtered and subsequently dried in an oven. Solid mass losses during the HTC process were recorded and the HTC-char samples were analysed through heating value measurements, elemental analysis, ash content analysis and moisture content analysis. These techniques were selected to determine how the HTC process affected the physical and chemical properties of the HTC-char. Simplifying the multitude of reactions that occur during HTC process, the global kinetics of the reaction was estimated assuming a first order reaction and a 100% conversion for the 24 h experiment by using the mass yield values at each reaction time (Y t ) to determine the conversion as X=(Y t - 100)/(Y 24h - 100). It was found that as the residence time of the HTC reaction was increased, the moisture content of the HTC-char was reduced through filtration from 55% for the 0-hour experiment to less than 30% for the 24-hour experiment. Visually, for longer residence times there was a distinct phase separation between the HTC-char produced and the wastewater. The increase in dewatering for longer residence times is caused by a reduction in the viscosity of the water under the HTC conditions and a reduction of the hydrophilic nature of HTC-char due to the elimination of hydroxyl groups and the degradation of cellulose during the HTC process. The carbon content of the HTC-char increased from 64% to 73% and the low heating value (LHV) increased from 25 MJ/kg to 31 MJ/kg as the residence time was increased, reaching values similar to that of bituminous/subbituminous coal. The oxygen/carbon and hydrogen/carbon ratios were reduced as the residence time increased. The oxygen/carbon ratio was reduced at a faster rate than the hydrogen/carbon ratio. This suggests that the ratio of the decarboxylation reaction rates to the dehydration ones is higher in HTC than dry pyrolysis. The mass yield of HTC-char decreased from 70% in the 0-hour experiment to 50% in the 24-hour experiment. Although there is a reduction in yield, the properties of the HTC-char fuel are improved. Regarding to the kinetics, results are plotted in Figure 1. It was found a good fitting for a first order global reaction, being k = h -1. ln(1-x) time (h) ln(1-x) = t R² = Figure 1. First order reaction kinetics fitting. The process transforms the TPOMW from a brown lignocellulosic waste to a black coal like material with improved energy density (MJ/kg) and increased hydrophobicity. Accordingly, HTC process appears to be a possible method for the treatment of TPOMW and production of HTC-char. References: [1] Roig, A., Cayuela, M.L., Sánchez-Monedero, M.A., An overview on olive mill wastes and their valorization methods. Waste Manage. 26,

177 PRODUCTION OF HYDROGEN FROM PLASTIC WASTE BY PYROLYSIS AND CATALYTIC STEAM REFORMING I. Barbarias, M. Artetxe, M. Amutio, G. Lopez, J. Alvarez, A. Arregi, M. Olazar Univ. of the Basque Country, Dpt. Chem. Engineering PO Box 644, Bilbao, tel , Fax: Scientific Topic: 2.1 Natural Resources Sustainability Hydrogen production using steam reforming of methane is the most economical method among the current commercial processes. Approximately 96 % of the hydrogen is produced from fossil fuels conversion [1]. Processes using wastes and raw materials are also attractive because of their promising economic and environmental benefits. The use of different types of plastics has greatly increased in recent years, and the disposal of plastic waste has become a major environmental issue. These waste plastics could be used to generate six million tons of hydrogen per year [2]. The challenge is to efficiently convert these polymers into hydrogen at a cost similar to that for the existing natural-gas-based technologies. The production of hydrogen throughout a thermal-catalytic two-step process has been studied. High density polyethylene (HDPE) steam reforming has been carried out in a two-step unit for hydrogen production. Continuous pyrolysis of HDPE has been conducted in a conical spouted bed reactor at 500 ºC, and the volatiles formed (mainly waxes) have been reformed in a fluidized bed catalytic reactor. The influence of the temperature in the ºC range, space time in the g cat min g HDPE -1 range and steam/plastic ratio in the 3-5 range has been studied. Nickel commercial catalyst has been used as it is particularly good catalyst for hydrogen production from steam catalyst. Gas composition (vol. %) ºC 650 ºC 700 ºC This figure shows the composition of the gas formed at different reforming temperature. As observed, an increase in the temperature enhances slightly hydrogen formation due to the endothermic nature of the reaction involved. At the same time, the CO concentration increased and CO 2 concentration decreased, as a result of the prohibition of WGS reaction at higher reforming temperature, which may be related to his endothermic nature. The content of CH 4 and C 2 -C 3 is negligible compared to H 2, CO and CO 2 concentration. An increase in the space time from 8.3 g cat min g HDPE -1 to 20.8 improve the transformation of waxes, enhancing the yield of hydrogen (from 70 wt.% to 86 wt.%). The yield of CO 2 decrease as space time increased whereas the yield of CO increases. Regarding to the steam/plastic ratio, an increase in the S/P and, consequently, in the concentration of steam in the reaction environment favours the water gas shift reaction and so methane and other hydrocarbon steam reforming. Hence, an increase in the S/P ratio promotes H 2 and CO 2 formation, but hinders CO and hydrocarbon formation [1] Balat, M., Internationak Journak of Hydrogen Energy, 33, 4013 (2008) [2] Czernik, S., French, R.J., Energy Fuels, 20, 754 (2006).

178 HYDROGEN PRODUCTION BY STEAM REFORMING OF PYROLYSIS VOLATILE PRODUCTS OF PINE SAWDUST A. Arregi, M. Amutio, G. Lopez, M. Artetxe, J. Alvarez, I. Barbarias, M. Olazar Univ. of the Basque Country, Dpt. Chem. Engineering PO Box 644, Bilbao, tel , Fax: Natural Resources Sustainability Nowadays hydrogen is mainly produced by steam reforming of natural gas, light hydrocarbons or naphthas, generating CO 2 and contributing negatively to the greenhouse effect [1]. Biomass can be a clean substitute to fossil fuels because of its low cost and environmental advantages. Therefore, pyrolysis-catalytic steam reforming of biomass has been studied, considering this process a promising and environmentally friendly route to produce hydrogen. The steam reforming of oxygenated compounds is an endothermic reaction which is favoured at high temperatures and it can be described as the following reaction (considering the WGS reaction) [2]: m CnH mok (2n k)h2o nco2 2n k H 2 (1) 2 The influence that temperature (in the ºC range), space-time (between g catalyst h g biomass -1 ) and S/B ratio (between 2-5) have on the steam reforming of pyrolysis volatile products has been studied. This process has been carried out in a pilot plant provided with two reactors in-line. The pyrolysis of pine sawdust takes place in a spouted bed reactor at 500 ºC and the volatiles are reformed in a subsequent fluidized bed reactor. A commercial Ni reforming catalyst has been used in the second step which is a highly active catalyst for the reforming of oxygenated compounds. High initial conversion of pyrolysis products is achieved above 600 ºC with 0.28 g catalyst h g biomass -1 and S/B=4 (> 99.7 %), while at 550 ºC the initial conversion is very low (58.3 %). Above 600 ºC, the effect of temperature on initial carbon conversion, catalyst deactivation and hydrogen yield is of little significance. However, when temperature is increased, higher CO and lower CO 2 yields have been obtained, because the WGS reaction is less favoured at high temperatures. CH 4 and other hydrocarbons initial yields (ethylene, ethane, propylene and propane) are very low in temperature range studied. The effect of space-time has been studied at 600 ºC and S/B= 4. Volatile products of the first step are not fully converted to gas with 0.14 g catalyst h g biomass -1 (91.6 %). Above this value, the initial conversion obtained has been higher than 98.5 %, obtaining a maximum value with 0.28 g catalyst h g biomass -1 (99.7 %). Higher H 2 and CO 2 yields and lower CO, CH 4 and hydrocarbons yields have been obtained when space-time is increased. Moreover, carbon conversion decreases with time on stream due to catalyst deactivation, although it is less pronounced at high space-time values. Regarding to S/B ratio, up to 99.5 % of initial conversion is achieved in the whole range of S/B studied (between 2-5) at 600 ºC and with space-time of 0.28 g catalyst h g biomass -1. When S/B ratio is increased higher H 2 and CO 2 yields have been obtained, as a consequence of favouring the reforming and WGS reactions. Instead, CO and CH 4 yields decrease with increasing the S/B ratio. REFERENCES [1] J. Remón, F. Broust, J. Valette, Y. Chhiti, I. Alava, A.R. Fernandez-Akarregi, J. Arauzo, L. Garcia, Int. J. Hydrogen Energy, 39, (2014). [2] A.C. Basagiannis, X.E. Verykios, Catalysis Today, 127, (2007).

179 BIOMASS AND HDPE COGASIFICATION IN A CONICAL SPOUTED BED REACTOR A. Erkiaga, J. Alvarez, G. Lopez, M. Artetxe, I. Barbarias, A. Arregi, M. Olazar University of the Basque Country, Department of Chemical Engineering, P.O. Box E48080 (Bilbao) Spain Natural Resources Sustainability One of the main advantages of tertiary thermal treatments and especially of gasification is the possibility to treat jointly different residues. Thus, the separation cost is reduced and feedstock availability is considerably improved, avoiding seasonal problems and increasing the runtime of gasification units [1]. Moreover, the cogasification of different wastes is a combined strategy boosting the construction of big plants, with lower unit operating costs, higher efficiency and better control of emissions [2]. Furthermore, the reactor design plays a critical role in gasification. Thus, the hydrodynamic features of the reactor should be suitable for handling residues of different density and granulometry, minimizing the segregation problems in the bed. The excellent performance of the conical spouted bed reactor has been proven for the steam gasification of biomass [3] and HDPE [4]. This work deals with the effect the mass ratio of HDPE/pine wood sawdust in the feed has on the steam gasification process. The experiments were carried out using olivine as catalyst, which is an inexpensive magnesium iron silicate with tar cracking properties. Cogasification has been carried out in a conical spouted bed reactor in continuous regime at 900 ºC using a steam/feed ratio of 1. The bed of the conical spouted bed reactor contains 70 g of olivine (particle diameter in the mm range). Water flow rate is 1.5 ml min -1 in all the studied conditions, corresponding to a steam flow rate of 1.86 L min -1, which is approximately 1.5 times that corresponding to the minimum spouting velocity. The runs have been carried in continuous regime by feeding 1.5 g min -1 of biomass/hdpe mixtures (50% of each material and a mixture made up of 75 % of biomass and 25 % of HDPE). The results have been compared with those obtained in the gasification of single materials and the synergies regarding gas yield and composition and tar content in the gaseous stream have been analyzed. Significant differences are observed for the biomass and HDPE gasification. The gas yield obtained in the steam gasification of HDPE (178.7 g/100 g of HDPE) is more than 2.5 times higher than that obtained in the gasification of biomass. Moreover, the tar content in the gaseous stream is ten times higher in the gasification of biomass (58.2 g Nm -3 on a dry basis) than in the gasification of pure HDPE (5.1 g Nm -3 on a dry basis). Furthermore, the char yield reaches a value of 4.3 wt % in the gasification of biomass and is almost negligible in the gasification of HDPE (0.3 % wt). A positive synergetic effect in the biomass gasification has been shown by cofeeding HDPE. A 25 % HDPE in the feed causes a reduction in tar content in the gaseous stream of around 50 %, which evidences the synergetic effect of HDPE in the gasification of biomass. The tar concentration obtained in the biomass gasification process is 58.2 g Nm -3, with this value being reduced to 9.7 g Nm -3 when 50 % of HDPE is in the feed. However, the advantage of increasing HDPE content above 50 % is limited, given that the tar content in the gasification of pure HDPE is 5.1 g Nm -3. Similarly, the char yield also decreases more than the average corresponding to the HDPE content in the feed, which evidences a synergetic effect of the mixture. Cofeeding biomass and HDPE has also a significant effect on the gas composition obtained. The effect of cofeeding both materials is especially noteworthy in the experiment carried out with 50 % of biomass and 50 % of HDPE, in which the hydrogen concentration is similar to that obtained with pure HDPE, 57 % and 58 % respectively. However, when 25 % of HDPE is fed into the reactor, hydrogen yield is only slightly improved compared to the gasification of pure biomass. Moreover, methane concentration is considerably reduced by cofeeding plastics, but those of CO and CO 2 are only slightly modified. References [1] Ruoppolo G, Ammendola P, Chirone R and Miccio F, Waste Manage, 32 (2012) [2] Kern SJ, Pfeifer C and Hofbauer H, Ind Eng Chem Res, 52 (2013) [4] Erkiaga A, Lopez G, Amutio M, Bilbao J and Olazar M, Chem Eng J, 237 (2014) [5] Erkiaga A, Lopez G, Amutio M, Bilbao J and Olazar M, Fuel, 109 (2013)

180 OBTENTION OF HIGH BIOETHANOL CONCENTRATIONS FROM CORN RESIDUES Iria Ana Ares-Peón, Belén Gómez *, Gil Garrote, Juan Carlos Parajó 1 Chemical Engineering Department, Science Faculty, University of Vigo, Ourense, Spain and CITI (Centro de Investigación, Transferencia e Innovación) University of Vigo, Tecnopole, San Cibrao das Viñas, Ourense, Spain Phone: , Fax: , Scientific topic: 2.1 Renewable Raw Materials and Waste Valorization. Introduction The process for producing ethanol from cellulosic materials is more complicated than its production from sugar or starch, but they are developing technologies to allow the profitable conversion of cellulosic biomass into fuels and other chemicals. These technologies can be introduced under biorefinery concept, since includes the inedible fractionof lignocellulosic biomass to produce biofuels, cellulose, hemicellulose, lignin and products. The development and implementation of biorefinery processes is critical to fulfill the vision towards a sustainable economy based on biological resources. Corn cobs is an economically viable and very promising raw material for bioethanol production by the enzymatic hydrolysis of cellulose and the sugar fermentation by Saccharomyces cerevisiae sequentially or simultaneously. Many different types of processes for ethanol fermentation have been proposed, including batch fermentation, continuous fermentation, continuous fermentation with cell recycling, fed-batch cultures and repeated-batch cultures. As for fed-batch fermentation, the intermittent addition of glucose, without the removal of the fermentation broth, into the fed-batch culture is one of the most common methods for the production of ethanol in the industry. Fed-batch culture implies low levels of substrate concentration during the course of fermentation, while ethanol is accumulating in the medium. This type of cultivation regime, along with the cell recycling, is the most employed technology for bioethanol production due to the possibility of achieving higher volumetric productivities. Materials and methods In this work, CC spent solid obtained by treatment at 202ºC with a liquid to solid ratio (LSR) of 8 was used. This solid was subjected to different conditions of fermentation with Saccharomyces cerevisiae: Simultaneous Saccharification and Fermentation (SSF), Separated hydrolysis and fermentation (SHF) and fed-batch (FB). The first stage fermentation is carried out under conditions made RLS of 5 andenzyme to substrate ratio (ESR)of 9, the second stage of fermentation is carried out at 2.5 of RLS and RES of 5. Like a strategy to improve process performance. Enzymatic prehydrolysis to SHF was carry out at 48.5ºC, ph 4.5 and 150 r.p.m during 72 hours. Results: The results obtained to conditions used in the first stage were: to SSF assay maximum ethanol concentration of 56 g/l, corresponding to 95% of potential ethanol. Trying to improve this production method, FBand SHF was used, obtaining 59 g/l and 56 g/l of ethanol respectively,which corresponds to 100% and 95% of potential ethanol. The same conditions as the SSF assay were used but adding solid at different stages (0, 24 and 48 hours to FB and 0,24,48 and 72 hours to SHF ) and dividing the total amount of enzymes between loads or not. On the other hand, we carried out a SSF and a fed-batch fermentation decreasing the LSR to 2.5. In the fed-batch processing, the solid was added into three (0, 24 and 48 hours) or four phases (0, 24, 48 and 72 hours). The nutrients and enzymes were added at the different stages or only at the beginning. Under these conditions, the SSF is not cost effective, however the study of the fed-batch led to very good results, from an 27.83% in the SSF assay to 52.21% of potential ethanol in the fed-batch assay. Based on these data it could be concluded that fed-batch favors the ethanol production at low LSR.

181 A Biorefinery Process Based on Autohydrolysis Valorization of hardwood 1,2,* Sandra Rivas, 1,2 Carlos Vila, 1,2 Valentin Santos, 1,2 Juan Carlos Parajó 1 Chemical Engineering Department, Polytechnical Building (Campus Ourense), University of Vigo , Ourense, Spain. 2 CITI-University of Vigo. Tecnopole, San Cibrao das Viñas, Ourense, Spain. * Phone: ; Fax: Scientific Topics 2.1 Renewable Raw Materials and Valorization. Abstract Due to the limited availability of raw materials and the tightening of environmental regulations, the use of alternative raw materials and the development of integrated technologies capable of maximizing the added value of products is a priority. Lignocellulosic materials are a renewable source of raw materials from which a wide range of products can be obtained. Birch (Betula alba) is a species appropriated for reforestation of degraded soils, that covers about hectares in northwest Spain. In Galicia, the covered surface (about ha) can provide about m 3 of wood (Gorgoso et al., 2007). The processing of lignocellulosic materials in biorefineries is based on the selectieve separation of their main components, in a way that the resulting fractions are suitable for further processing into products with commercial value. The Agenda 2020 Technology Alliance has emphasized on the interest of extracting hemicelluloses prior to pulping of wood, an objective that can be achieved by performing an autohydrolysis stage before pulping (Yañez et al., 2009). Autohydrolysis is an environmentally friendly technology enabling the separation of the hemicellulosic fraction as soluble products using hot water as a separation agent, operating in pressurized reactors. Operating under appropriated conditions, the soluble products from hemicelluloses correspond mainly to poly- or oligooligosaccharides (POS), which can be employed for specific applications, for example as ingredients for functional foods owing to their antioxidant and/or prebiotic properties. In this work, the operational conditions for autohydrolysis of Betula alba were optimized to obtain maximum concentrations of POS with low concentrations of monosaccharides. Liquors obtained from autohydrolysis, containing mainly xylose units in oligomeric and polymeric saccharides (XylPOS), were purified by membrane processing and ion exchange. POS were assayed for composition and DP distribution by HPLC, HPAEC-PAD and HPSEC. This type of information is of basic importance to understand their biological properties (Moure et al., 2006). References Gorgoso, J. J.;Álvarez González, J. G.; Rojo, A.; Grandas-Arias, J. A. (2007). Modelling diameter distributions of Betula alba L. stands in northwest Spain with the two-parameter Weibull function. Investigación Agraria: Sistemas y Recursos Forestales 16(2), Yañez, R.; Romaní, A.; Garrote, G.; Alonso, J.L.; Parajó, J.C. (2009). Processing of Acacia dealbata in aqueous media: A first step of wood biorefinery. Industrial and Engineering Chemical Research, 48, Moure, A, Gullón P., Domínguez, H., Parajó, J. C. (2006). Advances in the manufacture, purification and applications of xylo-oligosaccharides as food additives and nutraceuticals. Process Biochemistry, 41(9):

182 Delignification of autohydrolyzed wood by organosolv methods 1,2 Carlos Vila, 1,2,* Sandra Rivas, 1,2 Valentin Santos, 1,2 Juan Carlos Parajó 1 Chemical Engineering Department, Polytechnical Building (Campus Ourense), University of Vigo , Ourense, Spain. 2 CITI-University of Vigo. Tecnopole, San Cibrao das Viñas, Ourense, Spain. * Phone: ; Fax: Scientific Topics 2.1 Renewable Raw Materials and Valorization. Abstract The decline in oil reserves and the environmental concerns drive to a transition towards the bioproduction of energy, chemicals and materials. Biorefineries, designed to the accomplish the transformation of lignocellulosic materials into products and energy, is expected to play a crucial role in the future bioeconomy (Olsson et Saddler, 2013). In a near future, biorefineries are expected to expand the production of chemicals and biofuels from renewable feedstocks, and to diversify the products obtained from the different lignocellulose-derived fractions using new technologies. Several strategies aiming at the integrated use of lignocellulosic materials have been studied, including preextraction of hemicelluloses and further delignification of the resulting solids. In this field, consecutive autohydrolysis and organosolv delignification steps have been used for the separate recovery of hemicellulose, lignin, and cellulose (Amendola et al., 2012; Vila et al., 2014). Autohydrolysis, which yields hemicellulose-free solids, has been studied as a preliminary stage for commercial pulping processes starting from a variety of substrates (Helmerios et al., 2010). Organosolv, sulfur-free processes cause a limited environmental impact, and are an interesting alternative to commercial pulping technologies. Birch (Betula alba) is the most common broad-leaved specie in northern Europe, and the fourth most abundant forest species in the northwest Spain. Birch presents an important contribution for biodiversity and is appropriated as a pioneer tree for reforestation of degraded soils. This work provides an experimental assessment on the processing of birch wood by consecutive stages of autohydrolysis and organosolv pulping. Under selected operational conditions, autohydrolysis of birch leads to a liquid phase composed mainly by xylooligosacharides, with small concentrations of monosaccharides and furfural. Four different organosolv delignification processes (Acetocell, Acetosolv, Alcell and Milox) were assayed under selected operational conditions. Based on the obtained results, the Acetocell method was selected for further optimization using the Response Surface Methodology based on a Box-Behnken experimental design. References Olsson, L., Saddler, J., (2013). Biorefineries, using lignocellulosic feedstocks, will have a key role in the future bioeconomy. Biofuels, Bioproducts and Biorefining, 7 (5), Helmerios, J., Vinblad von Walter, J., Rova, U., Berglund, K.A., Hodge, D.B., (2010). Impact of hemicellulose pre-extraction for bioconversion on birch Kraft pulp properties. Bioresource Technology, 101, Vila, C., Santos, V., Parajó, J.C. (2014). Manufacture of microcrystalline cellulose from Eucalyptus globulus wood using an environmentally friendly biorefinery method. Journal of Wood Chemistry and Technology, 34 (1), Amendola, D., De Faveri, D.M., Egües, I., Serrano, L., Labidi, J., Spigno, G., (2012). Autohydrolysis and organosolv process for recovery of hemicelluloses, phenolic compounds and lignin from grape stalks. Bioresource Technology, 107,

183 MULTI-OBJECTIVE OPTIMIZATION APPLIED TO MINIMIZE THE ECONOMIC COST AND THE ENVIRONMENTAL IMPACT OF BUILDING INSULATION Joan Carreras 1*, Abdallah el Badry 1, Dieter Boer 1*, Gonzalo Guillén-Gosálbez 2, Laureano Jiménez 2, Luisa F. Cabeza 3, Marc Medrano 4 1 Departament d Enginyeria Mecanica, University Rovira i Virgili, Av. Paisos Catalans 26, Tarragona, Spain, 2 Departament d Enginyeria Química, University Rovira i Virgili, Av. Països Catalans 26, Tarragona, Spain 3 GREA Innovació Concurrent, Edifici CREA, Universitat de Lleida, Pere de Cabrera s/n, Lleida, Spain 4 CESDA (European University College of Aviation), University Rovira i Virgili, Carretera del Aeropuerto s/n, Apartado de Correos 481, 43206, Reus, Spain *Presenting author. Tel.: (+34) ; Fax: (+34) ; Scientific Topic: Chemical Engineering for Sustainable Development/Natural Resources Sustainability/Energy, Water and Materials/Life Cycle Assessment The energy consumption of the building sector has been estimated to be around 40% of the total energy expenditure in Europe. Buildings are considered to be responsible for up to 50% of the total CO 2 emissions worldwide, taking into account both direct and indirect impacts. For those reasons, this is a sector with large potential for environmental improvements and a demand for adequate measures for mitigating global warming. Many energy efficiency strategies can improve the energetic performance of a building, improving also the environmental impact without compromising comfort. Among them, building insulation appears as a promising option. In the experimental installations of the GREA (research group at the University of Lleida) house-like cubicles are being tested with different construction systems, materials and passive strategies in order to evaluate their performance in terms of energy demand. The cubicles are located in Puigverd de Lleida (northeast Spain) with internal size of 2.4 x 2.4 x 2.4 m. The continental Mediterranean climate of that location is characterized by cold winters and dry hot summers. The tested materials include different types of bricks and insulation materials. The present work addresses the thermal modelling of these cubicles considering the use of different materials. Climate data from Lleida was used. We propose a systematic method to analyse both, economic and environmental aspects, simultaneously and find optimal solutions representing the best possible trade-off between them. The cost and environmental impact are quantified taking into account both the construction and operation phase, thereby assessing the consumed energy over the operational phase and the materials used in the construction and in the disposal phases. The thermal loads of the modelled cubicles were calculated using EnergyPlus, a widely used building energy simulation program. The environmental impact was quantified following life cycle assessment principles. To assist designers in the retrofit of the building, we formulate a multi-objective model that considers the simultaneous minimization of the cost and environmental impact of the cubicles. The effect of different construction and insulation materials was evaluated. A set of Pareto solutions was generated and carefully analysed in order to get insight into the problem. The results of this paper indicate that, for our case studies, our systematic approach identifies solutions entailing improvements of around 40% in both objectives (compared to the base case that follows standard common practices). This systematic methodology is aimed to guide decision-makers towards retrofit alternatives with better economic and environmental performance, thereby improving the overall construction processes.

184 FAST GROWING BIOMASS VALORIZATION BY ENVIRONMENTALLY FRIENDLY PROCESSES Elena Domínguez 1*, Fátima Vargas 2, Gil Garrote 1, Juan Carlos Parajó 1 1 Chemical Engineering Department, Science Faculty, University of Vigo, Ourense, Spain and CITI (Centro de Investigación, Transferencia e Innovación) University of Vigo, Tecnopole, San Cibrao das Viñas, Ourense, Spain 2 Chemical Eng. Dept. Faculty of Science. University of Cordoba. Universitary Campus of Rabanales. Marie-Curie building (C-3). N-IV road, km. 396, Cordoba, Spain. Phone: , Fax: , Scientific topic: 2.1 Renewable Raw Materials and Waste Valorization. Introduction Paulownia is a fast growing lignocellulosic material, suitable for second generation bioethanol production. The production of biomass from Paulownia varied in the range dry ton/ha/year, higher values that can be obtained with other hardwoods. This high biomass production reduces the surface required for biomass and also the transportation costs. Lignocellulosic materials can be fractionated applying environmentally friendly processes, as autohydrolysis, that separate valuable hemicellulose derived compounds (mainly xylooligosaccharides, and sugars and furans in minor amounts) in liquid phase, obtaining a solid phase enriched in cellulose and lignin, more susceptible to further treatments, as the enzymatic hydrolysis needed for obtaining sugars for fermentative bioethanol production. This work deals with the fractionation of Paulownia by means of non isothermal autohydrolysis, following by enzymatic hydrolysis of resulting solid phases, in order to select the most suitable conditions for recovering xylooligosaccharides and sugars in liquid phase and a solid phase with improved enzymatic susceptibility. Materials and methods Paulownia and water were placed in a 3.75 L pressurized reactor. The media were stirred at 150 rpm using a liquid to solid ratio (LSR) of 8 g liquid/g oven-dry raw material. Autohydrolysis was carried out under non-isothermal operation up to reach maximum temperatures in the range C. The solid phase from the hydrothermal pretreatment was washed with distilled water and employed for solid yield determination. Samples of solids were air-dried, subjected to quantitative acid hydrolysis, and analyzed for glucan, xylan, arabinan, acetyl groups, and Klason lignin. Enzymatic hydrolysis (EH) was carried out in 100 ml Erlenmeyer flasks, placed in an incubator with orbital agitation (150 rpm) at 48.5 C for 96 h. The ph of media was set at Commercial enzymes ( Celluclast 1.5 L cellulases and Novozym β-glucosidase) were employed. EH assays were carried under the following conditions: LSR = 20 g liquid/g oven-dry substrate, enzyme to substrate ratio (ESR) = 20 FPU/g oven-dry substrate, and β-glucosidase to cellulase ratio = 5 IU/FPU. These conditions were selected to assess the possible limitations in cellulose conversion caused by the solid loading as well as to provide a deeper insight on the influence of pretreatment conditions on the enzymatic susceptibility. Results Enzymatic hydrolysis of solid phases obtained under selected conditions yielded glucose concentrations up to g/l (corresponding to cellulose to glucose conversions to 92.3%) for the hydrothermal pretreatment of 218ºC. Under this condition the composition of solid phase was 53.8 g glucan per 100 g raw material, 1.9 g xylan per 100g raw material and 38.1 Klason lignin g per 100g raw material. 6.6 g oligomers per 100 g raw material were present in liquors from the hydrothermal processing. It was shown that autohydrolysis is an effective method for improving the enzymatic susceptibility of Paulownia wood.

185 RENEWABLE BIOFUELS PRODUCTION FROM AGRICULTURAL RESIDUES Fátima Vargas 1, Elena Domínguez 2 *, Alejandro Rodríguez 1, Gil Garrote 2 1 Chemical Eng. Dept. Faculty of Science. University of Cordoba. Universitary Campus of Rabanales. Marie-Curie building (C-3). N-IV road, km. 396, Cordoba, Spain. 2 Chemical Engineering Department, Science Faculty, University of Vigo, Ourense, Spain and CITI (Centro de Investigación, Transferencia e Innovación) University of Vigo, Tecnopole, San Cibrao das Viñas, Ourense, Spain Phone: , Fax: , Scientific topic: 2.1 Renewable Raw Materials and Waste Valorization. Introduction Cereal straws are an important source of raw material for several industries. Considering that one kilogram of cereals generates approximately one kilogram of residue (straw), this agricultural activity creates a large quantity of residue each year. Because of its abundance and chemical composition, barley straw can be considered as a good option for the 2 nd generation bioethanol production. The aims of this work are: a) To study the Enzymatic Hydrolysis (EH) after applying different temperatures of autohydrolysis in order to find out the highest glucose concentrations and cellulose to glucose conversions, b) To carry out Simultaneous Saccharification and Fermentation (SSF) under the selected conditions and optimal temperature of autohydrolysis found out in the previous stage a). Methodology Barley straw was milled through a 2 mm screen and air-dried. Chemical characterization was carried out according to TAPPI standards for the analysis of moisture, ashes, extractives and Klason Lignin. The content of sugars was determined by using an HPLC with a Refractive Index Detector. In order to determine the optimal autohydrolysis temperature for barley straw, 7 essays at different temperatures (between ⁰C) were carried out in a presurized reactor of 600 ml of total volume, with a liquid to solid ratio (LSR) of 8 g liquid/g dry material. Essays to carry out enzymatic hydrolysis with the pretreated solids in 250 ml Erlenmeyer flasks placed in orbital shakers at 150 rpm and 48.5ºC. Commercial enzymes were used, Celluclast cellulases and Novozym β-glucosidases. Aliquots were withdrawn at given times to quantify the conversion to glucose. Pretreated solids in the optimal conditions of autohydrolysis were used to carry out a SSF in fed-batch mode. Experiments were performed in 250 ml Erlenmeyer flasks and placed in orbital shakers at 120 rpm and a set temperature of 35ºC. In SSF in fed-batch mode, substrate, enzymes and nutrients were fed in three or four separated additions depending on the experiment: at the beginning of the fermentation, after 24h, 48h and 72 hours in those experiments in which a fourth load was done. Fed-batch SSF lasted up to 121 hours. The microorganism used in the experiments was Saccharomyces cerevisiae Samples were taken at given times and analysed by HPLC. Results Compositional analysis indicates the following: 34.09% glucan, 16.82% xylan, 2.26% Arabinan, 1.52% Acetyl, 19.70% Klason Lignin, 6.75%, extractives and 7.61% ashes. After carrying out the autohydrolysis pretreatment, the contents of glucan were 43.19%, 44.38% 46.59%, 50.35% 51.91% 53.63% and 55.64% for temperatures of 200, 205, 210, 215, 220, 225 and 230ºC, respectively. The maximum conversion in enzymatic hydrolysis of cellulose into glucose was 83%, reached when the solid was pretreated at 230ºC. For temperatures of autohydrolysis above 215ºC the conversion to glucose was higher than 70%. From SSF fed-batch results, it can be concluded that the highest conversion to ethanol, 51.0 g ethanol/l (74% of the theoretical value), was obtained when the substrate and nutrients were fed in three different additions but the enzymes were all added at the beginning of the essay. When the total amount of enzymes was put in three different times, the conversion to ethanol decreased to 63%, 43.5 g ethanol/l. On the contrary, when the substrate and nutrients were added in four different loads, it did not make a difference if the enzymes were added 100% at the beginning of the fermentations or in four different additions because the conversions to ethanol obtained were the same, 45.5 g/l, 66% of the theoretical value. In those experiments in which just 1/3 or 1/4 of the total of enzymes were added, the conversion to ethanol dramatically dropped to 37% and 33%, respectively.

186 MULTI-OBJECTIVE OPTIMIZATION OF INTERNATIONAL ECONOMIES VIA MULTI-REGIONAL INPUT-OUTPUT ANALYSIS: APPLICATION TO THE US ECONOMY J. Pascual-González 1, G. Guillén-Gosálbez 1* and L. Jiménez 1 1 Departament d Enginyeria Química, Universitat Rovira i Virgili, Av. Països Catalans 26, Tarragona Abstract 43007, Spain In recent years, new environmental policies have been developed to reduce the environmental impact of human activities. Designing these policies in an effective manner is challenging because it requires a detailed knowledge of the whole economic and environmental system and the way in which they interact with each other. In terms of economics, input-output analysis (IO) is widely used to predict changes in an entire economy according to changes in the demand of a single (or several) sectors. This method studies the effects that different sectors have on the economy as a whole. Purely economic IO tables can be modified so as to include environmental aspects, giving rise to environmentally extended input-output tables (EEIO). These tables contain information on the environmental assessment of the economic transactions taking place in a region, but provide no guidelines on how to reduce such an impact. We present in this work a systematic approach to reduce the environmental impact of a whole economy. Our strategy combines multi-objective optimization and multiregional input-output models within a single unified framework that allows identifying the activities whose control and regulation can lead to larger reductions of impact at a minimum decrease in gross domestic product (GDP). We have applied our tool to the economy of the United States in order to identify the best policies to be implemented in practice for optimizing simultaneously the economic and environmental performance. We have employed in the calculations the World Input-Output Database (WIOD), which was originally developed to analyze the effects of globalization on trade patterns, environmental pressures, and socio-economic development across a wide set of countries. WIOD describes the economic inputs and outputs in monetary terms of 35 manufacturing sectors covering 27 EU countries and 13 other major countries in the world for the period 1995 to Our approach provides valuable insight into how to reduce the impact globally. By adopting this birds eye view of a whole economy, it is possible to determine how the final demand (and the total production) of every sector in an economy should be modified so as to improve simultaneously the economic and environmental performance of an economy. * Corresponding author: tel

187 PROPERTIES OF UREA FORMALDEHYDE POLYMER COMPOSITE FILLED WITH THE STERILIZED MEDICAL WASTE F. Boran #1, S. Bayrak #2 and E. Karadurmuş #1 #1 Hitit University, Faculty of Engineering, Department of Chemical Engineering, Çorum, 19030, Turkey, and , Renewable Raw Materials and Waste Valorization The evaluation of medical waste instead of releasing into the nature is possible. So the waste is evaluated economically and will contribute to the national economy. In our country, medical waste is rendered sterile by steam and dry heat sterilization that are environmentally friendly and do not release toxic emissions. This amount of waste due to population growth and other requirements will be increased day by day. We consider that the disposal of these wastes by environmentally friendly Technologies is quite important to be evaluated again. The waste which are traded in Dry heat sterilization, can be evaluated for various uses because of sterile, dry, granular structure and therefore these wastes were used for this study. The aim of this study is to obtain an environmentally friendly building materials for use in various fields of the sterilized medical waste. As binders for this purpose due to inexpensive and easily processed using ureaformaldehyde (UF) resins, the sterilized medical waste - polymer composites were prepared in laboratory conditions. After sterilized medical wastes and additives were blended thoroughly, the mixtures are pressed by laboratory scale, in an electrically heated hydraulic press 20x20 cm in size at certain pressure and temperature. Five different polymer composite are manufactured by Containing different amounts of UF resins that are % 10, 15, 30, 40, 60 of the sterilized medical waste. Thickness swelling, (TS) and water absorption (WA) of the composites were carried out. The addition of UF resins have increased water resistance of these composites. However, the composites with 60% and 40 % of UF resins showed significantly better results for WA and TS. In the Flame retardant test, flammability is found to increase with increasing the amount of the additive. Density and water retention for the best flame retardant composite were measured as 0,56 g/cm 3 and % 7 respectively. Also, mechanical strength tests which applied to composite samples and FTIR analysis were performed.

188 FURAN MANUFACTURE FROM LIGNOCELLULOSIC MATERIALS BY REACTION IN CATALYZED IONIC LIQUIDS Susana Peleteiro * ; Lucía Penín; Aloia Romaní; Gil Garrote and Juan Carlos Parajó Chemical Engineering Department, Science Faculty, University of Vigo, Ourense, Spain and CITI (Centro de Investigación, Transferencia e Innovación) University of Vigo, Tecnopole, San Cibrao das Viñas, Ourense, Spain Phone: , Fax: , 2 Biological Engineering Center (CEB), Campus Gualtar, University of Minho, Portugal. Scientific topic: 2. Chemical Engineering for Sustainable Development Natural Resources Sustainability INTRODUCTION Biomass derived furans (5-hydroxymethylfurfural and furfural) have emerged as an important platform chemical for the production of value added chemicals and liquid fuels that are currently obtained from petroleum. Lignocellulosic materials (LCM) are considered a widespread, renewable resource with an enormous potential for the manufacture of products enabling the development of a biobased economy. According to the biorefinery philosophy, LCM are expected to contribute to the development of a competitive bioeconomy as well as to play a key role in the industrial progress and economic growth in the XXI century. Ionic liquids (ILs) are considered green chemicals owing to their physical, chemical, and technological properties. The utilization of ILs in lignocellulose biorefineries is an attractive and versatile possibility, as they can be employed for multiple purposes, for example as a reaction media for furan production, a field where there is a significant room for improvement. MATERIALS AND METHODS IL was molten, dried, heated to the target temperature (in the range C) and mixed with a catalyst (chromium (III) chloride, aluminium (III) chloride, tangstophosphoric acid and/or combination of various catalysts). Once the catalyst was dissolved, the considered MLC was added to the medium (in the range g MLC/ 100 g BmimCl) under stirring. Zero time corresponded to substrate addition. At preset reaction times (in the range 1-60 min), samples from the reaction media were withdrawn, diluted immediatly with distilled water (at a mass ratio of 20 g water/g sample), homogenized, and assayed for composition by HPLC-RI and HPLC- DAD. RESULTS AND DISCUSSION The optimal conditions of temperature, time, sustrate/il ration and catalyst for furan production from MLCs were identified. The maximun HMF conversions achieved were 40.3, 41.2 and 39.4% to corn stover, Eucalytus globulus and Pinus pinaster, respectively. In case of furfural, the values obtained were 28.1, 18.5 and 39.8%. These experimental data confirmed the potential of the environmentally friendly method to produce furans from corn stover, Eucalyptus globulus and Pinus pinaster, as well as for enabling an integral benefit of the feedstock according to the biorefinery philosophy.

189 POLYOLS PRODUCTION BY LIQUEFACTION OF PAULOWNIA WOOD Lucía Penín; Susana Peleteiro * ; Gil Garrote and Juan Carlos Parajó Chemical Engineering Department, Science Faculty, University of Vigo, Ourense, Spain and CITI (Centro de Investigación, Transferencia e Innovación) University of Vigo, Tecnopole, San Cibrao das Viñas, Ourense, Spain Phone: , Fax: , Scientific topic: 2. Chemical Engineering for Sustainable Development Natural Resources Sustainability. Green Chemistry and Engineering INTRODUCTION Lignocellulosic materials (LCM) are an abundant and renewable source of raw materials useful for a variety of industries. LCM are mainly composed by polysaccharides (cellulose and hemicelluloses) and lignin, with a high content in hydroxyl groups. Their conversion in low value bio-based polyols with high reactivity and their use as feedstock for polymer synthesis is interesting option. This conversion can be carried out by applying a liquefaction process using acid catalyzed polyethylenglycol, as PEG 400. Glycerol, a compound with three hydroxyl groups, is an abundant byproduct of several industries, as biodiesel production, and with low price, and can be used with the PEG 400 in liquefaction processes. The main purpose of this work was to study the production of polyols by liquefaction of Paulownia wood, using sulfuric acid catalyzed PEG 400:glycerol mixtures and determining the optimal operational conditions and the properties of polyols. MATERIALS AND METHODS Raw material: Paulowia wood was analyzed following NREL standard methods for determination of glucan, xylan, arabinan, acetyl groups, uronic acids, acid soluble lignin, Klason lignin, proteins, extractives and ashes. Liquefaction was carried out at ºC in media containing polyethylenglycol 400, glycerol and sulfuric acid (as catalyst) during 1 to 2 h. When the liquid reaches the desired temperature, Paulownia wood was added to obtain a liquid:solid ratio of 10 g liquid/g wood, on oven basis. At the end of reaction, the media was cooled and dioxane:water 4:1 w/w was added and filtered to separate liquid and solid phases. Solid phase was washed first with dioxane and then with water and used for yield determination and assayed for composition. Liquid phase was used for hydroxyl number determination and used for gas chromatography-mass spectrometry determination of liquefaction products. RESULTS AND DISCUSSION Operational conditions for wood liquefaction in sulfuric acid catalyzed polyethylenglycol 400/glycerol media (as temperature, time, glycerol:peg 400 ratio, sulfuric acid concentration) were explored. At ºC during 2 h, the liquefaction yield varied in the range %. At 140 ºC with a ratio PEG 400:glycerol = 4, and 3% of sulfuric acid, the hydroxyl number was mg KOH/g. Using a temperature of 160 ºC, a ratio PEG 400:glycerol = 4, and 2.5% of sulfuric acid the hydroxyl number increase up to g KOH/g. In GC-MSD analysis of selected samples several compounds was identified: 1,1-diethoxypropane, 2- ethyl-1,3-dioxolane-4-methanol, 1-(2-hydroxy-5-methylphenyl)-ethanone, acid 4-oxo-pentanoic or erythritol, 4- Methylmannitol. These data demonstrates the suitability of the production of polyols by PEG 400: glycerol : sulfuric acid liquefaction.

190 BIOFUEL PRODUCTION FROM STEAM EXPLOSION PREPREATED BIOMASS Romaní, Aloia 1 ; Peleteiro Susana 2 ; Garrote, Gil 2* ; Ballesteros, Ignacio 3, Ballesteros, Mercedes 3 and Parajó, Juan Carlos 2 1 Biological Engineering Center (CEB), Campus Gualtar, University of Minho, Portugal. 2 Chemical Engineering Department, Science Faculty, Campus Ourense, University of Vigo, Spain 3 Renewable Energies Department, CIEMAT, Research Centre for Energy, Environment and Technology, Madrid, Spain Phone: , Fax: , Scientific topic: 2. Chemical Engineering for Sustainable Development Natural Resources Sustainability INTRODUCTION The prices of fossil fuels have increased in the last decade so that the interest for search of renewable energy sources has grown notably. The bioethanol from lignocellulosic materials (LCMs) can be an interesting alternative to fossil fuels. The Eucalyptus globulus wood (EGW) is a LCM suitable for the ethanol production from cellulosic fraction. The second generation bioethanol is obtained by three main steps: i) pretreatment; ii) saccharification and iii) fermentation. MATERIALS AND METHODS The EGW was submitted to steam explosion treatment in order to alter the structure of LCM and improve the enzymatic accessibility. The pre-treatment was carried out in a steam explosion prototype at T = 210ºC during 10 min. The solid treated was employed as substrate in a simultaneous saccharification and fermentation assays using an orbital shaker (100 rpm) at 35ºC and ph = 5. A factorial design of 3 factors and 2 levels (3 2 ) was carried out to study the influence of Liquid Solid Ratio (4-16 g/g) and Enzyme Substrate Ratio (4-16 FPU/g). The used enzymes were Celluclast 1.5 and Novozymes 188N, provided kindly for Novozymes. The yeast Saccharomyces cerevisiae (CECT- 1170) was used to fermentation the released glucose. RESULTS The treated solid was composed of 68% of cellulose, 2.8% of xylan and 30% of lignin. The cellulose recovery was of 97% (g cellulose/100g cellulose of raw material) and solubilisation of xylan was of 90%, mainly composed of xylose and xylooligosacarides (9.7 and 12.5 g/l, respectively). The variable more influential was Liquid Solid Ratio. The maximum ethanol concentration was 69 g/l (corresponding to ethanol yield of 83%) under conditions Liquid Solid Ratio 4g/g and Enzyme Substrate Ratio 16 FPU/g.

191 PAULOWNIA BIOREFINERY USING SEQUENTIAL NON ISOTHERMAL AUTOHYDROLYSIS STEPS Yolanda Álvarez, Elena Domínguez, Gil Garrote *, Juan Carlos Parajó Chemical Engineering Department, Science Faculty, University of Vigo, Ourense, Spain and CITI (Centro de Investigación, Transferencia e Innovación) University of Vigo, Tecnopole, San Cibrao das Viñas, Ourense, Spain Phone: , Fax: , Scientific topic: 2.1 Renewable Raw Materials and Waste Valorization. Introduction Lignocellulosic materials are an abundant, cheap and renewable source of raw materials for the production of second generation bioethanol, an alternative to fossil fuels with growing interest. This production can be integrated in a biorefinery scheme, in which the material is fractionated in its main fractions (cellulose, hemicelluloses, lignin) for their individual valorization and the production of fuels, chemicals and/or energy. Bioethanol production needs several steps:i) pretreatment with alteration of structure and/or partial solubilization, ii) sugars production by hydrolysis, and iii) sugars fermentation to ethanol. Autohydrolysis is an interesting and environmentally friendly pretreatment, consisting in the heating of material in aqueous suspension, solubilizing hemicelluloses, mainly as xylooligosaccharides (useful for a variety of industries), and improving the enzymatic susceptibility of resulting solid phase (enriched in cellulose and lignin). This work deals with the study of fractionation of Paulownia, a fast growing biomass, by non isothermal autohydrolysis, applying two sequential autohydrolysis treatments: first in conditions leading to maximum xylooligosaccharides recovery in liquid phase, and a second treatment (applied to solid phase of first treatment) in order to improve its enzymatic susceptibility. Materials and methods Raw material analysis: Paulownia was milled through 2 mm screen, air dried and analyzed by standard methods to determine ashes, extractives, glucan, xylan, arabinan and Klason lignin content (by quantitative acid hydrolysis). Non isothermal autohydrolysis: Paulownia and water were mixed to obtain a liquid to solid ratio of 8 g liquid/g raw material, and placed in a pressurized reactor, autohydrolysis was carried out under non-isothermal operation up to reach maximum temperatures (in the range C for first stage, and in the range ºC in the second stage) and then the suspension was cooled and liquid and solid phases were separated by filtration. Analysis of resulting phases: solid phases were washed with distilled water, employed for solid yield determination, and subjected to quantitative acid hydrolysis, in order to determine its composition (with the same methods that raw material). Liquid phases were analyzed by HPLC for their contents in sugars, organic acids and furans, and subjected to posthydrolysis (with H 2 SO 4 4% w/w, 40 min, 121 ºC) to determine the content in oligosaccharides. Enzymatic hydrolysis: was carried out in 100 ml Erlenmeyer flasks, in an incubator at orbital agitation of 150 rpm, at 48.5 C, with ph = 4.85, using commercial enzymes kindly supplied by Novozymes (Celluclast 1.5 L and Novozym), under the following conditions: liquid to solid ratio of 20 g liquid/g substrate, enzyme to substrate ratio of 20 FPU/g substrate. Results In the liquid phase of first non isothermal autohydrolysis carried out at 204 and 210 ºC, high xylooligosaccharides concentrations were obtained, corresponding to close to 70% initial xylan, confirming the suitability of this stage as part of biorefinery scheme. Glucan content of solid phases increase from 34% in raw material up to 52.1% in autohydrolysis carried out at 210 ºC. In the second autohydrolysis stage, xylooligosaccharide concentration was lower (due to high hemicelluloses solubilization in first stage) and glucan content increase up to 58.7 % (first stage carried out at 199ºC and second stage at 210ºC). In the enzymatic hydrolysis of solid phases obtained with only the first autohydrolysis stage, glucan-toglucose conversions lower than 60% of maximum theoretical value (total conversion of glucan to glucose without degradation) were obtained with relatively long times of 72 h. The use of the 2 nd autohydrolysis stage improves conversions up to close to 100% (and higher than 85% in all experiments) and requires lower times, with higher concentrations at h.

192 TEXTILE DYEING APPLYING PROTIC IONIC LIQUIDS M. Iglesias 1, R.S. Andrade 1, H. Mazzer 2, L. Cardozo 2 1 Universidade Federal da Bahia, Dpto. Engenharia Química, Salvador, Brasil; tel , 2 Universidade Estadual de Maringá, Dpto. Engenharia Química, Maringá, Brasil. Chemical Engineering for Sustainable Development - Natural Resources Sustainability - Green Chemistry and Engineering Dyeing processes are extremely important for marketing and differentiation of textile products. The dyeing occurs through the fixation of the dye molecules into the fibers, usually using water as the main solvent in the process [1]. The temperature and time controlling are two key factors and, of course, the dyeing solvent. Currently, there is great interest in finding environmentally friendly substances for this process, with a double objective, reduce the huge water consumption into textile processes and improve dyeng quality. Ionic liquids are versatile new media for many chemical synthesis, enzymatic catalysis and green engineering processes as it should be observed into open literature [2]. They can be of hydrophobic or hydrophilic nature depending on the structures of ions. However, unlike conventional molten salts, these materials often melt at low temperature. This is achieved due to the incorporation of the bulky functional structures as anion and/or cation and the structure avoids the ions packing easily into an ordered electrostatic net structure and, then, solid phase at ambient conditions. Ionic liquids can be used as robust solvents due to their wide liquid window when compared with other conventional organic solvents. The so-called protic ionic liquids show additional advantages due to their simple synthesis, low cost and biodegradability [3]. As a continuation of previous works on protic salts, in this work we propose an alternative procedure to dye cotton fibers using new protic ionic liquids (PIL s) as solvent substitute for water. With the aim of analysing the quality of the studied PIL s as dyeing solvents for cotton textile industry at different operation conditions, in this work a wide study of the properties (tensile strength, abrasion resistance and absorption color) of the dyed fibers was made. These measurements determine their efficiency as dyeing vectors and then, their dispersive power for textile processes. Fig 1. Different protic ionic liquids used in the dyeing process References [1] J. Koh, Textile Dyeing. Ed. Peter J. Hauser. [2] N.V. Plechkova and K. R. Seddon, 2007.Chemical Society Reviews, [3] T. L. Greaves and C. J. Drummond, Chemical Reviews, 108,

193 INJECTION OF CO 2 IN WATER: THERMOPHYSICAL AND FLUID FLOW MODELLING USING AN ADVANCED EQUATION OF STATE AND CFD F. Llovell 1, J. Hermann 2, W. Chang 2, S. Guri 2, L. F. Vega 1,2 1 MATGAS 2000 AIE, Campus de la UAB, 08193, Bellaterra, Barcelona, Spain 2 Carburos Metálicos/Air Products Group. C/Aragón, 300, Barcelona, Spain Phone: , Fax: Corresponding author: Scientific Topic: 2.1. Natural Resources Sustainability Water is probably the most fundamental building block of life on Earth. However, increasing human needs are posing a problem, as evidence of a lack of potable water is affecting an important sector of the population. A drastic intensification of the process efficiency in desalinization and water treatments is urgently required. In those processes, the ph is the most important chemical parameter, as it affects all the equilibrium compounds, preventing the formation of other substances. Classical ph reductors are the chlorhidric and the sulphuric acid. However, the corrosive and toxic nature of these substances is a major drawback. In the search for environmentally friendly alternatives, carbon dioxide (CO 2 ) is an excellent alternative, because of its very low reactive nature at ambient conditions, and its low toxicity and corrosiveness. Hence, the substitution of chloride compounds and other volatile organic compounds by CO 2 represent a positive net environmental balance in water treatment. Therefore, injection of CO 2 in water must be optimized in order to find the appropriate ratios and operating conditions, which will mainly depend on the ph of the medium and the thermodynamic and fluid flow characteristics. In this contribution, we present a complete study of the phenomena involved during the CO 2 injection in water. From one side, a refined equation of state, named soft-saft [1], is used to study the thermodynamics of the CO 2 -water system. Soft-SAFT specifically includes the hydrogen-bonding effects in water molecules, and is able to accurately describe water and aqueous mixtures. Based on statistical mechanics, a molecular model is proposed to determine the vapour-liquid and liquid-liquid equilibria of water-co 2 in a wide range of conditions in good agreement with the experimental data. In a similar manner, the viscosity of these mixtures is calculated using the Free-Volume-Theory (FVT), which is integrated into soft-saft in a common framework. Once the thermophysical properties of the system are determined, the fluid flow behaviour is studied using Computational Fluid Dynamics, in order to evaluate the diffusivity of the gas in water, as well as the ph evolution depending on different injection conditions. The study is completed with some additional experimental work evaluating the consumption and efficiency of carbon dioxide as a ph neutralization substance, by presenting the results got after a series of experiments developed in a pilot plant designed for this purpose, using five different dissolution systems and various water qualities. Acknowledgements: F. Llovell acknowledges a TALENT fellowship from the Generalitat de Catalunya. Additional support from Carburos Metálicos and the Catalan Government was also provided (2009SGR-666 and 2014SGR-1582). [1] F.J. Blas, L.F Vega, Mol. Phys. 92 (1997)

194 UPGRADING OF LOW RANK COAL WITH HIGH-MOISTURE BY USING CARBON DIOXIDE/STEAM MIXTURE GAS J. H. Park #1, C. -H. Lee #1, D. Shun #2, D. -H. Bae #2, H. -J. Ryu #2, J. -H. Moon #2, J. -S. Shin #2, G. Y. Kim #3, and J. Park #2 #1Department of Chemical and Biomolecular Engineering, Yonsei University, Seoul, Korea, Tel : , Fax : , #2 GHG Research Laboratory, Korea Institute of Energy Research, Daejeon, Korea #3Graduate School of Energy Science and Technology, Chung Nam National University, Daejeon, Korea Scientific Topic : 2.1 Natural Resources Sustainability In general, coals are classified as high and low rank coals depending on their properties such as moisture content, heating value, impurities etc. Here, brown coal and some sub-bituminous coal are considered as low rank coals (LRCs). These LRCs are difficult to operate in power plants since the high moisture content in coal possibly reduces the power plant s efficiency and increases flue gas emissions. The other disadvantages of high-moisture, low-rank coal are its low calorific value, costly transportation, spontaneous combustion, and bed operability. However, if these fuels are upgraded, those can replace relatively expensive bituminous coal. The CCS (Carbon Capture and Storage) technology can reduce the amount of carbon dioxide emitted from the power plants, and iron & steel companies, etc. Therefore, many plants plan to build a CCS process in order to solve the problems of climate change all over the world. The CCS technology can be divided into the post-combustion technology, the pre-combustion technology and the oxygen combustion technology. Especially, among many CCS technologies, one of the advanced concepts for capturing CO 2 is an absorption process with re-generable sorbents. This CO 2 capture process discharges CO 2 /steam mixture gas around o C of temperature behind the regeneration reactor. The CO 2 /steam mixture gas can be used as heat sources for drying coal. In this study, the purpose of our work is to integrate a CCS and a fluidized bed coal dryer. The operation was performed using CO 2 as a fluidization gas in a dryer and CO 2 /steam mixture gas as heat source for drying LRC through the heat exchanger. The experiment was performed with respect to temperature, flow rate and mixing ratio of CO 2 /Steam mixture gas in order to determine the optimum operating conditions.

195 MULTIPLE BISORPTION-DESORPTION CYCLES IN A FIXE-BED COLUMN TO REMOVE Pb(II) BY TREATED OLIVE TREE PRUNNING A. Ronda, G. Blázquez, G. Tenorio, A. Pérez, M.C. Trujillo, M. Calero Departamento de Ingeniería Química, Facultad de Ciencias, Universidad de Granada. Tel: , Fax: , Environmental Technology and Risk Analysis The high capacities of metal sorption by biosorbents, the possibility of a full regeneration of the biosorbent with a minimum amount of residual heavy metal and the reuse of biomass are important for cost-effective implementation of a biosorption process (Aldor et al., 1995). However, the interest of regeneration will depend to aspects like the cost and availability of the biosorbent, the value of metal recovery, the cost of regeneration process, etc. The heavy metal elution from biosorbents can be achieved by using various eluting agents (basics or acids) utilizing the different desorption mechanisms to release the adsorbed heavy metal ions into the solution (Yu and Kaewsarn, 2001; Lodeiro et al., 2006; Singh et al., 2008; Fagundes-Klen et al., 2010; Duarte et al., 2011 and Singha and Das, 2011). In this work it has been studied the utilization of olive tree pruning chemically activated with NaOH 1M as biosorbent to remove lead, focusing in the study of regeneration of this solid and in its utilization in successive cycles of biosorption-desorption. First, desorption experiments were performed to choose the best desorbent agent. So, several agents (basic and acid) were tested to determine their desorption capacity at a concentration of 1M. Results showed that the agent with highest desorption capacity was hydrochloridric acid. Later, several concentrations of this agent were tested to choose the best concentration of regeneration. The tested concentrations were from 0.05 to 0.7 M. A concentration of 0.3 M was chosen for the desorption experiments. Therefore, five cycles of biosorption-desorption of lead were carried out in a packed-bed column at the following operational conditions: inlet lead concentration = 150 mg/l, flow rate = 6 ml/min, solution ph = 5, biosorbent mass = 5 g (bed height = 4.4 cm), temperature = 25 ºC, operation time = 1440 min, desorption time = 120 min, desorption agent concentration = 0.3 M. These conditions were chosen according to previous studies (Castro et al., 2009; Martín-Lara et al., 2012). Biosorption results showed a marked decrease in biosorption capacity between the first cycle and the second one (from mg/g to mg/g); however, after the second cycle, the decrease with cycles was slight. This behavior can be related with the retention of Na + ions by the biosorbent during chemical treatment (Na + cations can be exchange with Pb 2+ during the first biosorption cycle and increase the biosorption capacity of this cycle). Also, a life factor of 20 cycles was determined for this biosorbent. The life factor represents successive number of cycles until a total exhaustion of the bed. Finally, from desorption curves it was obtained that desorption capacities were very similar in all cases, while the peak concentration between the first cycle and the other ones, was slowly decreasing from the second cycle. However, the time of this peak concentration was remained in a small range, between 6 and 10 min. So, the efficiency of the process was kept practically constant in a value around to 40%. Aldor, I.; Fourest, E.; Volesky, B. Desorption of cadmium from algal biosorbent, Can, J. Chem. Eng. 516 (73) (1995) 516. Castro, F.; Blázquez, G.; Calero, M.; Martín-Lara, M.A.; Díaz, J., Afinidad 66 (543) (2009) Duarte Zaragoza, V.M.; Carrillo, R.; Gutierrez Castorena, C.M. Environ. Technol. 32 (2001) 353. Fagundes-Klen, M.R.; Veit, M.T.; Borba, C.E.; Bergamasco, R.; De Lima Vaz, L.G.; Da Silva, E.A. Water Air Soil Pollut. 213 (2010) 15. Lodeiro, P.; Herrero, R.; Sastre de Vicente, M.E. J. Hazard. Mater. 137 (2006) Martín-Lara, M.A.; Blázquez, G.; Ronda, A.; Rodríguez, I.L.; Calero, M. Multiple biosorption desorption cycles in a fixed-bed column for Pb(II) removal by acid-treated olive stone. Journal of Industrial and Engineering Chemistry 18 (2012) Yu, Q.; Kaewsarn, P. Sep. Sci. Technol. 36 (2001) Singh, A.; Kumar, D.; Gaur, J.P. J. Hazard. Mater. 152 (2008) Singha, B.; Das, S.K. Colloids Surf. B 84 (2011) 221.

196 ENZYMATIC MEMBRANE REACTORS FOR ANTIBIOTICS DEGRADATION IN WASTEWATERS: TETRACYCLINE AS CASE STUDY R. Abejón, M. de Cazes, M.P. Belleville and J. Sanchez-Marcano Institut Européen des Membranes (IEM), ENSCM, UM2, CNRS. Université de Montpellier II2, CC 047, Place Eugène Bataillon, Montpellier, France. 2.2 Environmental Technology and Risk Analysis: Advanced Techniques for Effluent Treatment Antibiotics are not completely depleted by classical wastewater treatments, so conventional and MBR integrating wastewater treatment plants must incorporate specific advanced treatments for the elimination of this type of refractory micropollutants. Neither membrane technologies such as nanofiltration and reverse osmosis, nor adsorption on activated carbon (both options have been deeply taken into consideration for antibiotics removal) are able to transform these pharmaceuticals into less hazardous chemicals. By contrast, advanced oxidation processes under certain conditions can degrade antibiotics to biologically inactive compounds, hence they should be recommended as more effective treatment options. Oxidative enzymes have to be taken into account within the framework of advanced oxidation processes and they can be very useful for wastewater treatments and might be more interesting compared to other chemical or physical oxidative processes regarding toxicity of TPs generated after degradation of biologically active molecules, such as antibiotics. Enzymatic membrane reactors are based on a semipermeable membrane which promotes the separation of the enzyme from the reaction mixture including substrates and/or products. Several enzymatic membrane reactor configurations have been tested, but more investigation is still required to advance in the design of this type of reactors and their direct application to real wastewater treatment processes for antibiotics degradation and other industrial processes (Ben Ameur et al., 2014). The present work is related to the development of mathematical models in order to simulate the performance of enzymatic membrane reactors. They were applied to investigate the potentiality of laccase immobilized over ceramic membranes for the degradation of tetracycline, a very common antibiotic appearing as micropollutant in aquatic bodies, including wastewaters, even effluents from wastewater treatment plants (de Cazes et al., 2014). The technical viability of the proposed designs based on these simulated enzymatic membranes reactors connected in series has been demonstrated for the treatment of the different types of effluents (municipal, hospital and industrial pretreated wastewaters). For all the investigated cases, enzymatic membrane reactors appeared as realistic alternatives to other suggested treatments and they could be coupled to existing plants without suffering from severe space limitations due to disproportionate equipment dimensions (Abejón et al., 2014). References - Abejón, R.; de Cazes, M.; Belleville, M.P.: Sanchez-Marcano, J. (2014). Large-scale enzymatic membrane reactors for tetracycline degradation in WWTP effluents, Water Research (under review). - Ben Ameur, S.; Gijiu, C.L.; Belleville, M.P.; Sanchez, J.; Paolucci-Jeanjean, D. (2014). Development of a multichannel monolith large-scale enzymatic membrane and application in an immobilized enzymatic membrane reactor. Journal of Membrane Science 455: de Cazes, M.; Belleville, M.P.; Petit, E.; Llorca, M.; Rodríguez-Mozaz, S.; de Gunzburg, J.; Barceló, D.; Sanchez-Marcano, J. (2014). Design and optimization of an enzymatic membrane reactor for tetracycline degradation. Catalysis Today (in press).

197 Sonocatalytic Degradation of Rhodamine-B using Pilot-scale Triple Frequency Ultrasound Cavitation Reactor (TF-USCR) S.Parthasarathy, S.Manickam, X.Y. Liew, Y.V. Lim, K.W. Choo, D.R. Bibi, R.L.Gomes Manufacturing and Process Technology Research Division, University of Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom, Telephone number: ; (S.Parthasarathy). Scientific Topic: Chemical Engineering for Sustainable Development Environmental Technology and Risk Analysis Advanced Techniques for Effluent Treatment Rhodamine B (RhB) is a widely used dyeing component in textile industries for silk, cotton and leather. The dye containing wastewater is a serious environmental issue due to the large volume produced (70000 tons/annum) as well as its carcinogenic and teratogenic effects on living organisms [1]. Several approaches have been used over the years for RhB removal such as chemical and biological treatments and advanced oxidation processes, which include Fenton s reagent, photocatalytic oxidation and ozone in combination with hydrogen peroxide [2]. However, most of the processes have met with limited success and have not been economically feasible at large scale treatment [1]. Owing to this, identifying a suitable technology for RhB removal is necessary. Cavitation is defined as the phenomena of the formation, growth and subsequent collapse of microbubbles or cavities in milliseconds, which release large magnitudes of energy over a very small location [1]. To date, research on RhB is limited to lab-scale and the lack of pilot-scale studies could be a contributing factor for the failure of industrial plant trials [2]. Hence the present work focuses on the degradation of RhB using a pilotscale triple frequency ultrasound cavitation reactor (TF-USCR) with the capacity of 15 L. In this work, different operating parameters including initial ph, initial dye concentration, ultrasound frequency, power density, sonication time, hydrogen peroxide (H 2 O 2 ) concentration and titanium dioxide (TiO 2 ) loading on the degradation of RhB was evaluated in order to identify the optimum condition that would achieve the highest RhB degradation in water. The optimisation studies were conducted over a ph range of 5 to 9, with an initial dye concentration (1, 2 and 5 mg/l), ultrasound frequency (28, 40 and 70 khz), power density (20, 60 and 75 W/L), sonication time (5-45 min), H 2 O 2 concentration (2660, 3984 and 5305 mg/l) and TiO 2 loading ( mg/l). The maximum RhB degradation was observed at a starting ph of 5.5, indicating that the oxidation potential of OH * was higher in an acidic medium when compared to basic conditions. Meanwhile, the degradation rate of RhB was observed to increase with a corresponding decrease in the initial RhB concentration. The RhB degradation was observed to be higher at 40 khz frequency, with an initial dye concentration of 1 mg/l. Lower frequency was favoured due to the fact that larger number of bubbles generated at higher frequency resulted in coalescence of bubbles which might act as a barrier for further transfer of acoustic energy. Results also gave sufficient evidence that the extent of RhB degradation increases as the power density decreases. It was found that by applying a single frequency (40 khz) with a power density (20 W/L) resulted in the maximum RhB degradation. Further, it was observed that the RhB degradation efficiency improves with additives: 25.87% using 2660 mg/l of H 2 O 2 and 33.98% by 1334 mg/l of TiO 2 loading. It was noted also that the degradation rate decreased with the combined addition of both H 2 O 2 and TiO 2 which was mainly due to that the excess hydroxyl radicals generated tend to recombine and led to the formation of H 2 O 2 which acted as hydroxyl radical scavengers itself. This led to a decrease in the amount of hydroxyl radicals responsible for the degradation of RhB. Based on the observed results, it could be concluded that the sonocatalytic degradation utilising the 15 L pilot-scale TF-USCR appeared to be an appropriate green processing technology for the removal of RhB and scale-up is commercially feasible in the near future. Keywords: Ultrasound cavitation, Rhodamine-B, Hydrogen peroxide, Wastewater treatment References 1. M. Sivakumar, A. B. Pandit, Ultrasound enhanced degradation of Rhodamine B: optimization with power density. Ultrason. Sonochem..8 (2001) S. Manickam, N.B. Zainal Abidin, S. Parthasarathy, I. Alzorqi, E.H. Ng, T.J. Tiong, R.L. Gomes, A. Ali, Role of H 2 O 2 in the fluctuating patterns of COD (chemical oxygen demand) during the treatment of palm oil mill effluent (POME) using pilot scale triple frequency ultrasound cavitation reactor. Ultrason. Sonochem. 21 (2014)

198 REMEDIATION METALLURGIC INDUSTRY WASTEWATER USING IRON NANOPARTICLES B. Calderon and A. Fullana Chemical Engineering Department, University of Alicante, San Vicente Street, s/n, San Vicente, Alicante, Spain, phone: X.1116, fax: Environmental Technology and Risk Analysis Advanced Techniques for Effluent Treatment. Wastewater coming from metal finishing process contains high amounts of heavy metal, as zinc, chromium, cadmium and cupper. These compounds are highly toxic and some of them are carcinogenic. Common treatments applied to these kinds of wastewater are precipitation, adsorption or ion exchange. Nevertheles, these treatments present high operational costs and generate sludge. Zero valent iron nanoparticles (nzvi) have been recently shown to be effective for environmental remediation of a wide variety of environmental contaminants, such as chlorinated organic solvents, organochlorine pesticides, metals and PCBs (1). Moreover, they have the advantage of being non toxic and cheap. Regarding to heavy metal, nzvi have been proved to present high rate and capacities due to their large surface area and high number of actives sites. Nanoparticles present a core-shell structure. Core is composed of metallic iron and acts as an electron donor source. Shell layer composition is similar to iron oxides and it facilitates the sorption, surface complexation and transports the electrons from the core. So, nzvi can produce both reduction and adsorption mechanisms to remove the contaminants (2). The aim of this work will be to prove the effectiveness and promising applications of iron nanoparticles in the treatment of a real wastewater coming from the metal finishing industry, which contained chromium and zinc. nzvi particles have been synthesized in the lab by the borohydride reduction method: Fe H 3 2O 6 3BH 4 3H2O Fe 3B OH 3 10,5H2 (1) To perform the experiments, nzvi are added to a batch reactor containing the wastewater under continuous mixing. At certain times, samples are taken from the reactor, are separated using a magnet and a syringe filter and then are analyzed by inductively coupled plasma mass spectrometry (ICP-MS) to determine the concentration of the heavy metal in the water. nzvi are characterized at the beginning and end of the reaction with transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Studies showed that nzvi had very high removal capacity for both metals, showing a reductant mechanism to eliminate chromium and an adsorption process to eliminate zinc. Removal efficiency of 99% of the contaminants was achieved and removal capacity for nzvi was determined to be between 25 to 50 mg/g for chromium and from 50 to 70 mg/g for zinc. Moreover, addition of stabilizers to avoid nanoparticles agglomeration was studied and showed best results for chromium elimination but worst for zinc adsorption. 1. Yan, W.; Lien, H. -.; Koel, B. E.; Zhang, W. -. Iron nanoparticles for environmental clean-up: Recent developments and future outlook. Environ. Sci. Process. Impacts 2013, 15, Li, X. -.; Zhang, W. -. Sequestration of metal cations with zerovalent iron nanoparticles - A study with high resolution x-ray photoelectron spectroscopy (HR-XPS). J. Phys. Chem. C 2007, 111,

199 EVOLUTION OF CONCENTRATION AND HUMAN RISK OVER TIME DUE TO PETROLEUM HYDROCARBONS IN SOIL J. Pinedo*, R. Ibáñez, Á. Irabien Department of Chemical and Biomolecular Engineering, University of Cantabria, Avda. los Castros s/n, Santander, Spain. Phone: Fax: ABSTRACT Waste management Accidental oil spills from human activities is a common cause of environmental contamination, posing numerous risks and threats to the human health and the environment [1]. Petroleum hydrocarbons are commonly grouped in the parameter Total Petroleum Hydrocarbons (TPH). However, this parameter shows restrictions when deriving the risk associated to a certain TPH concentration. Thus, TPHs should be divided into different groups with similar physico-chemical properties, as recommended by the European Soil Framework Directive [2]. Fractions are usually divided according to the Equivalent Carbon Number (EC). Unacceptable risks should be assessed, determining the remediation urgency. The risks associated to a certain concentration usually decreases over time due to weathering processes. Therefore, when assessing a soil it is not only important to determine the current risk, but also the future risk, to determine the remediation urgency. The study follows up the TPH fraction concentration and the associated risks of a real soil spiked with petroleum hydrocarbons for two years. A clean soil was taken in a high-populated area of a medium size city (Santander- Spain, inhabitants). The previously dried soil matrix was spiked with a mixture of diesel and heavy oil (8:2, w/w) at 5000 mg/kg of TPH concentration. The followed protocol aims to produce a homogenous contamination, in which petroleum substances were absorbed in the soil, simulating the real conditions and ensuring a consistent soil matrix spiking. The diesel-heavy oil mixture was added to the entire soil matrix, using n-hexane as dispersant. To evaporate the n-hexane, the spiked matrix was allowed to evaporate during three days. As some spiked hydrocarbon are also evaporated the total 5000 mg/kg initially introduced is not reached. Spiked soils are analyzed in terms of TPH fractions, divided into four aliphatic (EC9-12, EC12-16, EC16-21, EC21-40) and four aromatic (EC10-12, EC12-16, EC16-21, EC21-36) fractions. Initial TPH fraction concentrations were measured at time zero, as well as 12, 18 and 24 months later. A risk-based tiered approach was carried out applying the software RBCA Tool Kit for Chemical Releases; that enables quantitative evaluation of site-specific risk [4]. Two potential scenarios of interest were proposed (scenario 1: residential with children, scenario 2: industrial with adult-workers) taking into account the different pathways (scenario 1: soil and outdoor air, scenario 2: indoor air). The results indicate that the aliphatic compounds are present in higher concentrations than the aromatic ones over the time. Additionally, there is a predominance of the heavier fractions over the lighter ones. Regarding the weathering processes, all fractions present a decreasing in their concentrations, being more pronounced in the lighter fractions. The risk assessment evidenced the relative importance of each fraction for the human risk, showing a gradual decrease over the time. Results show that although lighter fractions are present in lower concentrations, their associated risks are predominant over the heavier fractions. The aliphatic EC12-16 fraction have the highest risks; nonetheless, the obtained results do not evidence risks for neither scenario. These results will help in the future decision-making for the soil management. ACKNOWLEDGEMENTS The authors are grateful for the financial support provided under projects CTM and CTM REFERENCES [1] Park I.S., Park J.W. Determination of a risk management primer at petroleum-contaminated sites: Developing new human health risk assessment strategy. Journal of Hazardous Materials 185 (2011) [2] Commission of the European Communities, Thematic Strategy for Soil Protection, [SEC(2006)620] and [SEC(2006)1165], COM(2006)231 final. Brussels. [3] NJDEP (New Jersey Department of Environmental Protection) Analysis of Extractable Petroleum Hydrocarbon Compounds (EPH) in Aqueous and Soil/Sediment/Sludge Matrices, Version 3.0. Office of Data Quality, Trenton, NJ, USA [4] Connor, J.A., R.L. Bowers, T.E. McHugh and AM.H. Spexet. User s manual RBCA Tool Kit for Chemical Releases, GSI Environmental Inc., 2009.

200 OZONATION OF THE SELECTED EMERGING CONTAMINANTS DEET AND NORPTRIPTYLINE: KINETICS AND IDENTIFICATION OF BY-PRODUCTS E. Rodríguez*, F.J. Benítez, J.L. Acero, F.J. Real, G. Roldán. Dpto. de Ingeniería Química, Universidad de Extremadura, Avda De Elvas s/n Badajoz, tfno: ; Environmental Technology and Risk Analysis Nowadays, the consumer society has led to an increase in the use of different substances (such as pharmaceutical compounds, disinfectants, contrast media, laundry detergents, surfactants, pesticides, dyes, paints, preservatives, food additives, and personal care products) which constitute a new kind of aquatic pollutants that have been increasingly detected in ground and surface waters (Stuart et al. 2012). These substances are called emerging contaminants (ECs), and have been recently discovered in very low concentrations in the environment. Their presence can potentially cause deleterious effects to aquatic organisms and human health, even at those low concentrations. Recent research studies are focused on the degradation of ECs, mainly by Advanced Oxidation Processes. This study is based on the ozonation process, which constitute a promising technology for the removal of these products. Two representative compounds were selected to be subjected to ozonation processes: N,Ndiethyl-m-toluamide (DEET, a repellent insect) and nortriptyline hydrochloride (antidepressant drug). The kinetic study performed provided ozonation apparent rate constants, which remained almost unaffected for DEET in the ph range 2-9, with an average value of 0.123±0.003 L mol -1 s -1. O, ozonation rate constants for nortriptyline varied from 2.40 x10 3 to 472 x10 3 L mol -1 s -1 in the ph range Due to the ionic nature of this substance, with a pk a of 10.2, the specific rate constants of the protonated and neutral species were determined, being the values obtained 2.13 x10 3 and 2.01 x10 5 L mol -1 s -1, respectively. The theoretically calculated k app rate constants were plotted in Figure 1 (lines) vs. ph, together with the experimental values (symbols): as can be observed, there is a quite good agreement between calculated and experimental results, which confirms the goodness of the proposed model. By means of liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS) analysis, the main by-products formed in the ozonation reactions were identified (14 for DEET and 27 for nortriptyline). According to these compounds tentative reaction mechanisms for the ozonation of both emerging contaminants are proposed and discussed. Figure 1. Apparent rate constants (k NH ) for nortriptyline ozonation reaction at different phs. Comparison of theoretical and experimental values. Acknowledgements. This research was supported by Gobierno de Extremadura through Project RNM021. E. Rodriguez thanks to the Gobierno de Extremadura for her FPI Ph.D. Grant. References M. Stuart, D. Lapworth, E. Crane, A, Hart, Sci. Total Envir. 416 (2012) 1-2.

201 EVALUATION OF THE BACTERIAL INACTIVATION CAPACITY IN WATER OF A NEW COMMERCIAL NANO-TIO 2 SUSPENSION P. Valero, J. Torres, M.P. Ormad, R. Mosteo, J.L. Ovelleiro. Department of Chemical Engineering and Environmental Technologies, Architecture and Engineering School, University of Zaragoza, María de Luna 3, 50018, Zaragoza, Spain. Phone number: Advanced Techniques for Effluent Treatment TiO 2 photocatalysis is a promising disinfection technique capable of using the solar light to generate reactive oxygen species which are able to inactivate bacterial cells [1, 2]. The main objective of this research work is to evaluate the disinfection capacity of a new commercial nano-tio 2 suspension (Levenger) in comparison to the standard TiO 2 Degusssa P25. Several factors are studied: type of TiO 2, concentration of TiO 2, type of matrix and time of treatment. The microorganism Enterococcus sp. is used as bacterial indicator. Two types of samples were used in this research work to assess the influence of the matrix: distilled water 0.9% NaCl inoculated with Enterococcus sp. pure cultures and wastewater treatment plant (WWTP) effluent coming from an activated-sludge plant at laboratory-scale which simulates the characteristics of real treated urban wastewater [3]. The samples were placed in quartz reactors with agitation inside a solar chamber (Atlas Suntest CPS+/XLS+) and then irradiated at nm with an intensity of 500 W/m 2 for different times, being the maximum temperature reached inside the solar chamber 35 o C. Two different types of commercial TiO 2 were used: TiO 2 Levenger in suspension and TiO 2 powder Degussa P25. TiO 2 concentrations between 0.25 and 2 g/l were applied [4]. Enterococcus sp. were immediately analyzed after the treatments. The bacterial inactivation was determined as Log 10 (N t /N 0 ), where N 0 and N t are the Enterococcus sp. concentrations before and after disinfection. Sedimentation experiments, measuring turbidity as control parameter, were carried out to determine the feasibility of TiO 2 separation. a) b) Figure 1. a) Inactivation of Enterococcus sp. in distilled water with 1 g/l TiO 2. N CFU/100 ml. b) Inactivation of Enterococcus sp. in WWTP effluent with 1 g/l TiO 2. N CFU/100 ml In general, it was observed that the presence of TiO 2 led to an increase in the inactivation of the studied bacteria in both water matrixes, in comparison to the UVA-visible irradiation treatment without catalyst (see Figure 1). In the WWTP effluent sample, both catalysts had similar disinfection efficiency. However, in distilled water the TiO 2 Degussa P25 produced more Enterococcus sp. inactivation than the TiO 2 Levenger. The concentration of TiO 2 only had influence in the experiment with distilled water sample using TiO 2 Levenger, in which an increase of the catalyst dose (up to 1 g TiO 2 /L) produced higher disinfection. In addition, it was observed that the bacterial inactivation increased with higher times of treatment, especially in the presence of both TiO 2. About TiO 2 separation experiments, both catalysts had similar tendency of sedimentation in the WWTP effluent, being the clarification of the water much more noticeable during the first minutes of decantation. References [1] Malato S., Fernández P., Maldonado M.I., Blanco J., Gernjak W Catalysis Today 147, [2] McGuigan K.G., Conroy R.M., Mosler H.J., Preez M., Ubomba E., Fernández P. J. Haz Mat , [3] Rodríguez-Chueca J., Mosteo R., Ormad M.P., Ovelleiro J.L Solar Energy 86, [4] Rincón A.G., Pulgarín C Applied Catalysis B: Environmental 44,

202 ENVIRONMENTAL APPLICATION OF WEBER BLUE AGAVE FIBERS IN TEXTILE DYESTUFFS REMOVAL A.A. Peláez Cid 1, A.R. Cárcamo Gómez 1, J. Vázquez Bautista 1, R. Radillo Ruíz 2, A.M. Herrera González 3 1 Facultad de Ingeniería de la Benemérita Universidad Autónoma de Puebla, Edificio 108A, Ciudad Universitaria, Colonia San Manuel, Puebla, Pue. México, CP 72570, Tel ext. 7632, 2 Grupo Carolina S.A., Naucalpan de Juárez, México. 3 Instituto de Ciencias Básicas e Ingeniería, Universidad Autónoma del Estado de Hidalgo, Pachuca, Hidalgo, México Scientific topic of the work: Environmental Technology and Risk Analysis (Advanced Techniques for Effluent Treatment) ABSTRACT Mexico is often recognized worldwide for its Tequila production which reached a volume of 2.27x10 5 m 3 in The extraction of Tequila from the heart of Weber Blue Agave (Agave Tequilana) generates a large amount of waste, mainly leaves, because 3.6 kg of agave are required to produce a single liter of tequila. Although diverse applications have been found for these fibrous residues, the amount generated is so high that it would be possible to take advantage of these to prepare adsorbents with environmental applications to remove textile dyestuffs present in industrial wastewater. This work proposes the preparation of cellulosic and carbonaceous adsorbents from the fibrous residue of blue agave. Both fibers extracted from agave leaves were either washed only (AgaNat) or chemically treated with an aqueous solution containing sodium hydroxide (AgaNaOH), and both proved highly effective for the removal of textile dyestuffs. The physically activated with water vapor fibrous carbon (CarAgaF) and the chemically activated with phosphoric acid granular carbon (CarAgaQ) also showed a high adsorption capacity for textile dyestuffs present in aqueous solution as well as wastewater. The specific surface area of the prepared adsorbents was calculated by means of the solution adsorption method at 303 K using Methylene Blue. The specific surface areas obtained were: 513, 212, and 201 m 2 /g for CarAgaQ, FAgaNat, and FAgaNaOH respectively. Aqueous solutions containing cationic (methylene blue, crystal violet, and aztrazon blue) and anionic (indigo carmine and direct blue 80) dyestuffs with a concentration of 500 mg/l were treated, and removal percentages ranging between 56 and 99% were obtained for cationic dyestuffs and between 14 and 95% for anionic dyestuff. Textile wastewaters containing vat and reactive dyestuffs were treated, and removal rates ranging between 37 and 89% were obtained for vat effluents on CarAgaQ. The improvement in the quality of the treated wastewater was obtained comparing the following parameters: Color, ph, electrical conductivity, total solid content, and COD before and after the treatment with the adsorbents prepared from the fibrous wastes from Weber Blue Agave. The surface morphology of the adsorbents was observed using SEM, and the functional groups were determined by FTIR with an ATR device, and correlated with adsorptive properties of the four adsorbents prepared.

203 OXIDATION OF PRIORITY AND EMERGING POLLUTANTS BY PERSULFATE ACTIVATED WITH ZERO-VALENT IRON Sergio Rodriguez *, Aurora Santos and Arturo Romero. (*) Dpt. Ingenieria Quimica. Facultad de Ciencias Quimicas. Universidad Complutense de Madrid. Scientific Topic: 2.2 Environmental Technology and Risk Analysis (Advanced Techniques for Effluent Treatment) Abstract The removal of diuron, (selected as an example of priority pollutant), Orange G (an azo dye widely used in the textile industry), caffeine and ibuprofen, (chosen as examples of emerging contaminants in common use) by using persulfate (PS) was studied in this work. Oxidant activation was conducted with zero valent iron (ZVI), generating sulfate radicals (SO 4 - ) capable of oxidizing most of the organic compounds in water due to its high redox potential. The reactions were carried out in a 0.5 L batch reactor at 20ºC, using different ZVI particle sizes. To determine the efficiency of the process, pollutant conversion obtained using ZVI as activator was compared with that obtained using the same amount of Fe 2+. An example of obtained results can be seen in Figure 1, where caffeine was employed as target pollutant. In these runs it was observed that a slow, continuous release of Fe 2+, as that provided by reaction of ZVI with PS, greatly improved system efficiency. An explanation to that phenomenon may be that reaction of PS with ZVI is a fluid-solid reaction, carried out on the external surface. Particle size used may allow moderate release rate of Fe 2+ in the medium so unproductive sulfate radical consumption produced by an excess of Fe 2+ (Equation 3) is minimized, thus optimizing the economy of the process. 2 (1) Fe S O Fe SO SO (2) (3) Furthermore, a kinetic model capable of accurately predict the experimental results was proposed and validated, considering the corrosion reaction of ZVI that takes place on the surface of the particles and the subsequent generation of persulfate radicals and oxidation of contaminants in the aqueous phase a) b) C C (mg/l) C C (mg/l)) t (min) t (min) Figure 1. Oxidation of Caffeine with PS activated by a) Fe (II). b) ZVI (Rp = 0.33mm). [C] 0 = 25 mg / L, [PS] 0 = 7.47mM, [ZVI] 0 = mm, [Fe (II)] 0 = 0.25 mm. Acknowledgements The authors acknowledge financial support provided from the Spanish Ministry of Economy and Competitiveness (project CTM ).

204 Screening of heterogeneous catalysts for dark and photo-fenton's oxidation of actual pharmaceutical industry wastewaters R. C. Martins 1*, A. C. Oliveira 2 and R. M. Quinta-Ferreira 1 1 Chemical Processes and Forest Products Research Centre (CIEPQPF), Department of Chemical Engineering, Faculty of Sciences and Technology, University of Coimbra, Coimbra, Portugal 2 Faculty of Pharmacy, University of Coimbra, Pólo das Ciências da Saúde, Azinhaga de Santa Comba Coimbra *Presenting author: Tel: ; Fax: ; Scientific Topic: Advanced Techniques for Effluent Treatment Pharmaceutical industries produce highly complex liquid effluents, which are potentially dangerous to the ecosystems. Generally speaking, the presence of biorefractory substances and the high seasonality leading to strong variations on the wastewater composition do not allow a correct treatment using the traditional biological systems. The use of advanced oxidation processes such as Fenton s peroxidation arises as suitable alternatives. In order to minimize the production of iron sludge that constitutes the main drawback of this technology, the hydrogen peroxide oxidant power may be enhanced by the presence of UV-visible light. Moreover, the application of solid materials can avoid the use of dissolved iron. In this context, the goal of the present research is to select a heterogeneous catalyst to be used in dark and photo-fenton s process on the treatment of effluents coming from pharmaceutical industry. Actual wastewater was collected from an industry that produces active principles of drugs. It presented a dark colour and a significant organic load (COD = 9520 ± 10 mgo 2 /L and TOC = 5134 ± 10 mgc/l). Due to the high amount of suspended solids, a coagulation step was applied and optimized before the oxidation experiments leading to a stream comprising 4270 ± 10 mgo 2 /L and 2855 ± 10 mgc/l of COD and TOC, respectively. It was verified that this pre-treatment was crucial for the efficiency of the posterior oxidation processes. In what regards dark and photo-fenton s, in four catalysts were screened both commercial and laboratory prepared, namely, N-150 (Fe 2 O 3 -MnOx), Fe-Ce-O 70/30, Red Volcanic Rock, and iron shavings (wastes from iron processing industry). From the results obtained, it was concluded that Fe-Ce-O 70/30 is the material that offers best experimental results in dark-fenton, reaching 59% and 66% of COD and TOC removal, respectively. The ph influence was also studied and it came to notice that this parameter affects the organic matter degradation efficiency, being ph 3 selected as optimal. Experiments regarding Photo-Fenton were also conducted, being concluded that the Red Volcanic Rock catalyst had the best degradation efficiency, 80% and 40% concerning COD and TOC, respectively. Moreover, there was a significant reduction in the active metal leaching with the use of radiation. Tests of biodegradability were still carried out showing the suitability of this catalytic system in getting an effluent able to be subjected to a posterior purification in a biological process. This work suggests that the catalysts Fe-Ce-O 70/30 and the natural Red Volcanic Rock are promising in the catalytic oxidation of real wastewater coming from a pharmaceutical industry through heterogeneous Fenton and Photo-Fenton. Acknowledgements: R. C. Martins gratefully acknowledge FCT Fundação para a Ciência e Tecnologia, Portugal, by the financial support under the grant (SFRH/BPD/72200/2010).

205 DEGRADATION AND MINERALIZATION OF PHARMACEUTICAL POLLUTANTS BY CATALYTIC OZONATION: IN SITU ATR-FTIR STUDIES S.S. Sable 1, P. P. Ghute 1, F. Medina 1, R. B. Mane 2, C.V. Rode 2, D. Fahrnasova 3, A. Urakawa 3, S. Contreras 1 1 Department d Enginyeria Quimica, Universitat Rovira i Virgili, Av. Països Catalans, 26, Tarragona , Spain. Tel: (+34) , Fax: (+34) Chemical Engineering and Process Development Division, CSIR-National Chemical Laboratory, Pune , India. Tel: (+91) , Fax: (+91) Institute of Chemical Research of Catalonia (ICIQ), Av. Paisos Catalans Tarragona, Spain. Tel: (+34) , Fax: (+34) Scientific Topic: 2.2 Environmental technology and Risk analysis Pharmaceutical compounds, like lipid regulators are appearing worldwide in the aquatic environment. They are among the group of emerging pollutant as their toxic effect even at very low concentration has raised a big concern. The efficient removal of emerging hazardous and toxic organic pollutants belonging to the class of pharmaceuticals, pesticides, aromatic hydrocarbons etc. from water is going to be a challenging endeavor. Clofibric acid (CFA) is the main pharmacologically active metabolite of the lipid lowering drug, clofibrate. Numerous studies have demonstrated the occurrence of CFA in surface, groundwater and even drinking water (1). Advanced Oxidation Processes (AOPs) could be an interesting and effective technology for removal of recalcitrant contaminants. Among the various AOPs, catalytic ozonation is proved as an effective technology for the removal of organics from wastewater (2). This work investigated the catalytic ozonation of CFA in the presence of Cu-based catalysts. In situ attenuated total reflection FTIR (ATR-FTIR) spectroscopy was used to investigate the possible catalytic mechanism. Nanostructured Cu 1 :Al 1 and Cu/ZrO 2 catalysts were synthesized by co-precipitation method and their catalytic activity in the degradation of clofibric acid (CFA) was investigated by catalytic ozonation under ambient conditions. Catalysts were characterized by techniques like XRD, XPS, HR-TEM, TPR, N 2 physisorption and ICP. (CFA,100 O3 (CFA,100mg/L) (CFA,100 Catalysts %TOC Removal 2h 6h Cu (mg/l) Leaching O Cu 1 Al Cu/ZrO Cu 2+ (3.5 mg/l) Table 1. Degree of mineralization of CFA (100mg/L) after 2 and 6h of single and catalytic ozonation (CFA,100 (CFA,100 mg/l) (CFA,100 (CFA,50 (CFA,25 mg/l); (CFA,100mg/L) (CFA,100 mg/l) ph7; (CFA,10 (CFA,50 (CFA,25 mg/l); ph10; 60; mg/l); 120; ph10; ph7; ph7; (CFA,10 (CFA,50 (CFA,25 mg/l); ph10; 60; 60; 30; mg/l); (CFA,50mg/L) ; O3 30; mg/l); O3 mg/l); ; O3 O O3 (CFA,25mg/L) ; (CFA,100 (CFA,25 30; (CFA,100 (CFA, (CFA,100 (CFA,25 (CFA,25mg/L) mg/l); (CFA,100 O3 mg/l); mg/l); (CFA,10mg/L) (CFA,10 120; (CFA,100 (CFA,50 (CFA,25 mg/l) 30; ; mg/l); 0; (CFA,100mg/L) ph7 mg/l); ph10; ph7; 0; 0; 0.00 (CFA,100mg/L) ph10 T ime (min) Fig.2. Degree of mineralization in 2h of O 3 with diff. concentration of CFA and ph with Cu 1 Al 1 catalyst Nanostructured Cu 1 Al 1 oxide catalyst showed the highest efficiency for the degradation and mineralization of CFA, achieving 82% and 96% mineralization in 2 and 6h, respectively, without any leaching of Cu. The efficiency of this catalyst has also been demonstrated at low concentrations of CFA. Cu/ZrO 2 catalysts also showed good activity, achieving 70% and 86 % mineralization in 2 and 6h, respectively. Selected catalysts were reused in consecutive runs to assess their stability. Point zero charge of the ph of catalyst and radical scavenger effect was also studied with Cu 1 Al 1 nanostructure catalyst. ATR-FTIR studies confirmed that the reactive oxygen species are generated on the catalyst surface by the interaction of ozone in aqueous solution, which promotes. OH radicals. Further studies will be focused on screening of these catalysts for the degradation of Ibuprofen (IBP) and N, N- Diethyl-meta-toluamide (DEET). References 1. Cruz-Morato C.; Jelic A.; Perez S.; Petrovic M.; Barcelo D.; Marco-Urrea E.; Sarra M.; Vicent T. Bio. Eng. J. 2013, 75, Guo Y, Yang L.; Cheng X.; Wang X. J. Env. Anal. Toxicol. 2012, 2.7. %TOC Removal

206 ASSESSMENT OF FE FOULING ON LP UV LAMP SLEEVES A.Cruz 1,*, M. Li 2, C.Sans 1, S.Esplugas 1, Z. Qiang 2,* 1 Department of Chemical Engineering, University of Barcelona. C/Martí i Franquès 1, 08028, Barcelona, Spain. Phone: (+34) Fax: (+34) Key Laboratory of Aquatic Science and Technology, Research Center for Eco- Environmental Sciences, Chinese Academy of Sciences, 18 Shuang-qing Road, Beijing , China *Corresponding author s: 2.2 Environmental Technology and Risk Analysis The use of UV lamps for disinfection and advanced oxidation (e.g. UV/H 2 O 2 ) is increasing as the UV technologies are being developed and improved. One of the main problems while using these technologies is the reduction of UV lamps efficiency due to the formation of fouling on the surface of quartz sleeves that protect the lamps from direct contact with water. Many foulants are well known, such as calcium carbonate, calcium sulfate and other substances that precipitate on sleeve surfaces due to a local increase of water temperature, but the most important ones are those with iron components [1]. Iron has a very high absorbance of UV light of 254 nm, which makes that a low amount of this foulant can produce a high reduction of the process efficiency. In this work, different amounts of iron were spiked into the tap water supplied by Beijing water distribution system. The amended tap water was then used as feed water for a UV reactor coupled with two micro fluorescent silica detector (MFSD) which could measure online the fluence produced by the UV lamp and allow monitoring its efficiency by calculating the fluence decay and the fouling factor. A constant recirculating flow of 60 L h -1 from a 50 L tank was used. Feed water was maintained at constant temperature by recirculating it through a cooling system. Feed water was also analyzed and spiked periodically in order to maintain a constant chemical composition. Figure 1. Installation used for the experimental procedure After arriving to a previously established fouling factor, the system was stopped and the foulants on the lamp sleeve surface were removed and analyzed to evaluate the amount of iron and other studied components by using inductively coupled plasma atomic emission spectroscopy (ICP-AES). This study contributes to a better understanding of the influence of Fe on the composition and time of iron fouling of the lamp sleeves. Acknowledgements Authors are grateful to the European Project IRSES-WATECH (318926) for funds received to carry out this work. Bibliography [1] L.-S. Lin, C. T. Johnston, and E. R. Blatchley, Inorganic fouling at quartz:water interfaces in ultraviolet photoreactors I. Chemical characterization, Water Res., vol. 33, no. 15, pp , Oct

207 DEGRADATION AND MINERALIZATION OF PHARMACEUTICAL POLLUTANTS BY CATALYTIC OZONATION: IN SITU ATR-FTIR STUDIES S.S. Sable 1, P. P. Ghute 1, F. Medina 1, R. B. Mane 2, C.V. Rode 2, D. Fahrnasova 3, A. Urakawa 3, S. Contreras 1 1 Department d Enginyeria Quimica, Universitat Rovira i Virgili, Av. Països Catalans, 26, Tarragona , Spain. Tel: (+34) , Fax: (+34) Chemical Engineering and Process Development Division, CSIR-National Chemical Laboratory, Pune , India. Tel: (+91) , Fax: (+91) Institute of Chemical Research of Catalonia (ICIQ), Av. Paisos Catalans Tarragona, Spain. Tel: (+34) , Fax: (+34) Scientific Topic: 2.2 Environmental technology and Risk analysis Pharmaceutical compounds, like lipid regulators are appearing worldwide in the aquatic environment. They are among the group of emerging pollutant as their toxic effect even at very low concentration has raised a big concern. The efficient removal of emerging hazardous and toxic organic pollutants belonging to the class of pharmaceuticals, pesticides, aromatic hydrocarbons etc. from water is going to be a challenging endeavor. Clofibric acid (CFA) is the main pharmacologically active metabolite of the lipid lowering drug, clofibrate. Numerous studies have demonstrated the occurrence of CFA in surface, groundwater and even drinking water (1). Advanced Oxidation Processes (AOPs) could be an interesting and effective technology for removal of recalcitrant contaminants. Among the various AOPs, catalytic ozonation is proved as an effective technology for the removal of organics from wastewater (2). This work investigated the catalytic ozonation of CFA in the presence of Cu-based catalysts. In situ attenuated total reflection FTIR (ATR-FTIR) spectroscopy was used to investigate the possible catalytic mechanism. Nanostructured Cu 1:Al 1 and Cu/ZrO 2 catalysts were synthesized by co-precipitation method and their catalytic activity in the degradation of clofibric acid (CFA) was investigated by catalytic ozonation under ambient conditions. Catalysts were characterized by techniques like XRD, XPS, HR-TEM, TPR, N 2 physisorption and ICP. (CFA,100 O3 (CFA,100mg/L) (CFA,100 Catalysts %TOC Removal 2h 6h Cu (mg/l) Leaching O Cu 1Al Cu/ZrO Cu 2+ (3.5 mg/l) Table 1. Degree of mineralization of CFA (100mg/L) after 2 and 6h of single and catalytic ozonation (CFA,100 (CFA,100 mg/l) (CFA,100 (CFA,50 (CFA,25 mg/l), (CFA,100mg/L) (CFA,100 mg/l) ph7, (CFA,10 (CFA,50 (CFA,25 mg/l), ph10, 60, mg/l), 120, ph10, ph7, ph7, (CFA,10 (CFA,50 (CFA,25 mg/l), ph10, 60, 60, 30, mg/l), (CFA,50mg/L) , O3 30, mg/l), O3 mg/l), , O3 O O3 (CFA,25mg/L) , (CFA,100 (CFA,25 30, (CFA,100 (CFA, (CFA,100 (CFA,25 (CFA,25mg/L) mg/l), (CFA,100 O3 mg/l), mg/l), (CFA,10mg/L) (CFA,10 120, (CFA,100 (CFA,50 (CFA,25 mg/l) 30, , mg/l), 0, (CFA,100mg/L) ph7 mg/l), ph10, ph7, 0, 0, 0.00 (CFA,100mg/L) ph10 T ime (min) Fig.2. Degree of mineralization in 2h of O 3 with diff. concentration of CFA and ph with Cu 1 Al 1 catalyst Nanostructured Cu 1Al 1 oxide catalyst showed the highest efficiency for the degradation and mineralization of CFA, achieving 82% and 96% mineralization in 2 and 6h, respectively, without any leaching of Cu. The efficiency of this catalyst has also been demonstrated at low concentrations of CFA. Cu/ZrO 2 catalysts also showed good activity, achieving 70% and 86 % mineralization in 2 and 6h, respectively. Selected catalysts were reused in consecutive runs to assess their stability. Point zero charge of the ph of catalyst and radical scavenger effect was also studied with Cu 1 Al 1 nanostructure catalyst. ATR-FTIR studies confirmed that the reactive oxygen species are generated on the catalyst surface by the interaction of ozone in aqueous solution, which promotes. OH radicals. Further studies will be focused on screening of these catalysts for the degradation of Ibuprofen (IBP) and N, N- Diethyl-meta-toluamide (DEET). References 1. Cruz-Morato C.; Jelic A.; Perez S.; Petrovic M.; Barcelo D.; Marco-Urrea E.; Sarra M.; Vicent T. Bio. Eng. J. 2013, 75, Guo Y, Yang L.; Cheng X.; Wang X. J. Env. Anal. Toxicol. 2012, 2.7. %TOC Removal

208 REMOVAL OF BISPHENOL-A FROM WASTEWATERS USING SLUDGE CARBON/TIO2 NANO COMPOSITES S. Athalathil a, B. Erjavec b, R. Kaplan b, A. Fortuny c, A. Pintar b and A. Fabregat a* a Departament d Enginyeria Quimica, ETSEQ, Universitat Rovira i Virgili, Av. Paisos Catalans 26, Tarragona, Catalunya, Spain b Laboratory for Environmental Sciences and Engineering, National Institute of Chemistry, Hajdrihova 19, SI-1001 Ljubljana, Slovenia c Departament d Enginyeria Quimica, EPSEVG, Universitat Politecnica de Catalunya, Av. Victor Balaguer s/n, Vilanova i la Geltru, Catalunya, Spain Tel: + (34) ; Fax: + (34) ; 2. Chemical Engineering for Sustainable Development: Advanced Techniques for Effluent Treatment Over the past years, titanium dioxide (TiO 2) nano materials have gained great importance due to their high stability, non toxicity, useful photochemical activities and potential application for photoreaction, semi conductors, solar cells, and electro chemicals, but still suffer due to the low efficiency, high cost and short irradiation range. Due to the economic benefits, many researchers have been gearing up on the development of cost-effective and low toxicity catalysts or materials from waste biomass. To date, the amount of harmful sludge residues has raised day by day due to the urbanization and industrialization, and these wastes solid are available even at no cost. If these sludge materials are converted into useful catalysts or supporting materials that could be utilized for the treatment of hazardous compounds found in the environment. In the present work, sludge carbon/tio 2 nano composites were fabricated by different methods (Figure. 1a), and their catalytic activity was successfully evaluated in various advanced oxidation process (AOPs). BET surface area of nano composites gained up to 309 m 2 /g, and high Bisphenol-A (BPA) removal was achieved for the catalytic wet air oxidation (42 h), photo-catalytic (Figure 1(b), 60 min) and catalytic ozonation (5 min) were 96, 36 and 75 %, respectively DARK TIME C/Co DS800 DSHD DSCTW DSSGS DSCTAW Time (min) (a) (b) Figure 1. (a) Schematic diagram of the methodology adopted for the synthesis of nano composites and (b) photo catalytic removal of BPA solution. The surface modifications process gave desired catalytic activity, higher surface area and good surface chemistry of the nano composites. Both CT and HD produced nano composites with good crystalline and photo activity. The nano composites produced from harmful sludge materials can be used as cost - effective catalysts for the removal of hazardous pollutants from the water and wastewaters. References [1] T. Kasuga, M. Hiramatsu, A. Hoson, T. Sekino, K. Niihara. Adv. Mater. (1999), [2] T. Jitianu, A. Cacciaguerra, R. Benoit, S. Delpeux, F. Beguin, S. Bonnamy.Carbon. (2004),

209 ORGANIC POLLUTANT DEGRADATION USING SYNTHETIC AND NATURAL METAL PHOSPHATE MATERIALS: A COMPARATIVE STUDY Y. Roumila, R. Bagtache, D. Meziani and K. Abdmeziem* USTHB, Faculté de Chimie, Laboratoire d Electrochimie-Corrosion, Métallurgie et Chimie Minérale, BP 32 El Alia, Bab-Ezzouar, Alger, Algérie Tel/Fax : Scientific topic: 2.2 Environmental technology and risk analysis Among the many techniques available for wastewater treatments, adsorption and heterogeneous photocatalysis are well known and widely used. They require the presence of solid materials as adsorbents and/ or catalysts. Therefore, many efforts have been devoted for developing new compounds. Among them, metal phosphate materials are receiving continuing attention due to their potential applications in this field. As a contribution in this scientific topic, we aimed to synthesize metal phosphate materials to be used in the treatment of dye-containing wastewaters. Due to the resistance of these toxic pollutants to biodegradability, the problems caused by the contaminated effluents are of significant environmental and technical importance. In the present work, we report first on the synthesis of metal phosphate compounds, with varying the metal cation. The materials were further used successively as adsorbents and photocatalysts. They were prepared by the hydrothermal route and then characterized by means of several physico-chemical techniques, among them: powder X-Ray diffraction, chemical and thermal analyses, scanning electron microscopy, UV-Vis diffuse reflectance measurements and Fourier transform infrared spectroscopy. The as-synthesized materials were subsequently subjected to methyl violet adsorption and photocatalytic degradation, from aqueous solutions. Methyl violet is a cationic triaryl methane dye, frequently used as a colouring agent. The photocatalytic activity of the samples was evaluated by monitoring the degradation of the dye under visible light irradiation. The same adsorption and photocatalytic experiments were conducted with natural phosphate rock samples that had previously undergone some physical treatments. The whole study was carried on with varying some experimental factors such as contact time, catalyst dose, initial dye concentration, temperature and ph of the solution. Indeed, adsorption and photocatalytic processes are greatly dependent on these parameters. All results were compared to each other and conclusions were issued concerning the more efficient and rather cheapest material/ method system to such application. Keywords: Photocatalysis, Adsorption, Hydrothermal synthesis, Metal phosphate, Natural phosphate rock, Dye.

210 Sustainable Water Resource Engineering through the development and application of Novel Bioanalytical Tools S.Parthasarathy, C.A.Ortori, D.A. Barrett, R.L.Gomes. Manufacturing and Process Technology Research Division, University of Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom, Telephone number: ; (S.Parthasarathy). Scientific Topic: Chemical Engineering for Sustainable Development Environmental Technology and Risk Analysis Advanced Techniques for Effluent Treatment Identifying bioactive chemicals in environmental waters to date has utilised a targeted approach, whereby the analyte one wishes to detect is already known. To date, determination of conjugates of bioactive chemicals has been confined to steroids and no attempt has been made to analyse pharmaceutical conjugates in environmental waters. This paper will introduce the novel bioanalytical measurement techniques developed for the life sciences into the field of environmental engineering and utilise these adapted bioanalytical measurement techniques towards evaluating the design and optimisation of technologies relating to wastewater treatment. Bioactive chemicals such as pharmaceuticals and steroids are an emerging environmental and human health issue in water. Their presence in wastewater and aquatic environments is of global concern due to observations of severe reproductive abnormalities such as intersexuality in aquatic wildlife [1]. In England and Wales, Water Companies are responsible for wastewater treatment plants (WWTPs) and must adhere to regulatory drivers that ensure wastewater effluent does not impact the quality of the receiving rivers and the wildlife within [2]. Identifying bioactive chemicals of concern in wastewater has to date been a trial and error approach with the issue compounded by the fact that bioactive chemicals are predominantly excreted from the body in the conjugated form and may also metabolise through the WWTP. Research has primarily focused on the unconjugated (free parent) bioactive form and with little consideration of metabolites. These metabolites and the ease with which they deconjugate/degrade, will influence the transport and fate of the free bioactive chemical through the WWTP, and hence the resultant removal efficiency for the bioactive chemical [1, 2]. A step change is needed in determining bioactive chemicals in environmental water matrices, which will inform on the process efficiency of current and novel treatment technologies in the WWTP. The objectives for this work were: Method development and validation by LC-MS/MS using a novel three-pronged methodological approach (targeted, exact mass, neutral loss). Application of the methodologies to wastewater treatment plant to identify new bioactive chemicals, in particular pharmaceutical conjugates that have no available methodology and yet to be identified. A list of 38 bioactive chemicals were identified as priority emerging contaminants from the literature and utilised for the targeted method. Method development utilised solid phase extraction (Waters, UK) for sample preparation, with samples including spiked water and wastewater from a WWTP with a population equivalent of ~450,000. Analysis was undertaken using LC-MS/MS with either 4000 QTRAP hybrid triple-quadrupole linear ion trap mass spectrometers (Applied Biosystem, USA) and QQQ triple quadruple mass spectrometer (Thermo Scientific, USA) used in both positive and negative ion electrospray mode. Methodological approaches included targeted analysis (whereby the analytes of interest are known), neutral loss (for selective identification of those conjugates related to bioactive chemicals in a mixture) and exact mass (for the detection of selected bioactive chemicals, conjugates by summing the masses of the individual isotopes of the molecule). Application of the novel bioanalytical measurement techniques towards environmental water samples identified conjugated bioactive chemicals which have previously not been reported in the literature. Keywords: Environmental analysis; Bio-active chemical; SPE/LC MS/MS; Wastewater References 1. R. L. Gomes, W. Meredith, C. E. Snape, M. A. Sephton, Conjugated steroids: analytical approaches and applications. Anal. Bioanal. Chem. 393 (2009) S. Mompelat, B. Le Bot, O. Thomas, Occurrence and fate of pharmaceutical products and by-products, from resource to drinking water. Environ. Int. 35 (2009)

211 STABILIZATION/SOLIDIFICATION OF A METALURGICAL WASTE USING COAL FLY ASH AND COAL SLAG BASED GEOPOLYMER. INFLUENCE OF SLAG PARTICLE SIZE Y. Luna, A. Cornejo, C. Leiva, C. Arenas, M. Rodriguez-Galán Departament of Chemical and Environmental Engineering. Escuela Técnica Superior de Ingenieros. University of Seville, Camino de los Descubrimientos s/n 41092, Sevilla, Spain. Phone: Scientific Topic: 2. Chemical Engineering for Sustainable Development Environmental Technology and Risk Analysis-Waste Minimization and Treatment The stabilization/solidification (S/S) of electric arc furnace (EAFD) dust containing hazardous metals such as Pb, Cd, Cr or Zn by means of geopolymerization technology is described in this document following the same methodology than in other publications [1]. Geopolymers were prepared a class F coal fly ash (FA) and coal slag (ESC). Sodium silicate is used as activating solution. The influence of the particle size of coal slag is studied in order to find the relation between the mechanical and leaching properties with this parameter. So, geopolymeric S/S solids were prepared using the course slag (C-ESC) and a finer fraction of slag (F-ESC) (less than 2,5 µm), both substituting to the fly ash in the same proportion (since 16 % to 64 % in the mixture with a 20 % in weight of EAFD). S/S solids are submitted to different physical and chemical tests to evaluate the results obtained and to ascertain the efficiency of the process. Additions of slags get worsen the mechanical properties of the S/S solid decreasing the compressive strength (Figure 1). The use of the finest slags improves the mechanical properties of mixtures studied. Regarding the leaching results, the concentration of metals in UNE EN leachates are similar using course slag or finer slag, although elements as Mo, As, V, Se and Sb show the highest concentration in S/S solids prepared with the finest slag. Beside, there are no difference in the leaching of solids when the amount of slag increase, unless a slightly improvement of leaching of Pb, As, V y Cr. Compressive strength (MPa) Time (days) FA/C-ESC: 1/4 FA/C-ESC: 2/3 FA/C-ESC: 3/2 FA/C-ESC: 4/1 FA/F-ESC: 1/4 FA/F-ESC: 2/3 FA/F-ESC: 3/2 FA/F-ESC: 4/1 Figure 1. Compressive strength of S/S solids after 7, 14 and 28 days. [1] C. Fernández Pereira, Y. Luna, X. Querol, D. Antenucci, J. Vale. Waste stabilization/solidification of an electric arc furnace dust using fly ash-based geopolymers. Fuel 88 (2009)

212 TRATAMIENTO DE LOS POLVOS DE HORNO ELÉCTRICO DE ARCO PROCEDENTES DE LA FABICACION DE ACERO ESTRUCTURAL. PROCESO DE OBTENCIÓN DE ZINC Roca, A; Cruells, M; Cordova, K. Departament CMEM, Facultat de Química, UB, Martí i Franquès 1, Barcelona Environmental technology and risk analysis La investigación presenta un proceso hidrometalúrgico de recuperación de zinc que utiliza como fuente los polvos residuales obtenidos de la fabricación de acero estructural procedente de un horno eléctrico de arco que tiene como materia prima chatarra de hierro. El proceso ideal será el que tenga el menor número de etapas, el menor coste energético y que trabaje a temperatura ambiente, presión atmosférica, con reactivos de bajo coste, y generando residuos que sean reutilizables, recuperables o inertes. Para determinar el mejor proceso es necesaria una completa caracterización del residuo utilizando las técnicas siguientes: a) composición química elemental mediante fluorescencia de rayos X (FRX), y espectroscopía de emisión por plasma (ICP), b) especies presentes por difracción de rayos X (DRX), c) estados de agregación de las mismas y especies minoritarias por microscopía óptica de reflexión (MOR), microscopía electrónica de barrido y microanálisis (SEM-EDS). Los resultados obtenidos se presentan en la Tabla 1 y en la Tabla 2 Tabla 1 Composición química de los polvos residuales procedente de la fabricación de acero estructural Composición elemental (% en peso) Zn Fe Ca Pb Cl Mn Mg S K Na Si ,7 5,1 3,4 2,1 1,4 1,0 2,0 1,50 1,51 Elementos minoritarios (<1% en peso): Cu, Al, Cr, Cd, P, F Tabla 2 Especies presentes en los polvos residuales procedentes de la fabricación de acero estructural Especies mayoritarias ZnO, ZnFe 2 O 4, Fe 3 O 4, PbOHCl, Especies minoritarias MnCr 2 O 4, NaCl, Mn 3 O 4 Objetivo Se ha diseñado el proceso y ensayado etapa por etapa con el doble objetivo de: a) recuperación del zinc b) minimización de residuos Proceso: 1. Lavado con agua, 2. Lixiviación con H 2 SO 4 3. Recirculación del residuo al horno de fabricación de acero 4. Purificación del líquido de lixiviación 5. Electrólisis de la disolución de ZnSO 4 6. Recirculación del electrolito agotado o o o Bibliografia Roca, A.; Cruells, M.; Guerra, J.F.; Núñez, C., Reciclado de metales en polvos voladores de horno eléctrico de la fabricación de aceros. Actas del primer congreso de la Internacional de Química de la Anque.1990, Vol. 3. Reyad, A.; Shawabkeh, Hydrometallurgical extracción of zinc from Jordanian electric arc furnace dust, Hydrometallurgical, 2010, Vol Oustadakis, P.; Tsakiridis, P.E.; Katsiapi, A., Hidrometallurgical process for zinc recovery from electric arc furnace dust (EAFD). Parte I: Characterization and leaching by diluted sulphuric acid, Journal of Hazardous Material, 2010, Vol.179.

213 DETERMINATION OF KINETICS PARAMETERS FOR COMPOSTING PROCESS OF THE ORGANIC FRACTION OF MUNICIPAL SOLID WASTE WITH SOURCE SEPARATION J. F. Saldarriaga *, S. Upegui University of Medellín, Carrera 87 # 30-75, Medellín, Colombia, * Waste Minimization and Treatment To find out biodegradation behavior of wastes is important for an optimized design regarding composting process parameters such as processing time, pile area and the product quality. A high degradation rate usually indicates lower capital and operational costs for composting plants. In composting, there are different process management options, but, for the majority, maximizing the decomposition rate is one of the main objectives (Baptista et al., 2010). Kinetic model can be used as model to study composting process on an industrial scale for the optimization of the process. The degradation rate of waste can be predicted using kinetic models of the process indicators (temperature, organic matter content, moisture content, oxygen concentration, ph, C/N ratio, particle size, etc.). Kinetics of the process is used to determine waste biodegradability and generate a useful measure for the loss of organic matter during composting (Petric et al. 2012) kg of organic wastes from Altavista neighborhood, Medellín, were processed by composting. Previously MSW were mixed with 39 kg of biomass (pruning wastes) to reduce humidity content. Compost facility consists of 15 beds (1.50 m x 1.50 m) filled 1 m high. Wastes were winnowed twice a week to ensure aeration. Once a week and always before winnowing bed weight and height were measured, and samples of 500 g were taken in nine different points, preserved in zip bags and delivered to the lab for analysis according to usual procedures. Selected process variables (according to literature) were: humidity, temperature, electric conductivity, ph, total organic carbon (TOC) and oxygen (O2). Experimental data were adjusted to seven empirical correlations based on those published by Petric et al. (2012) but with a new set of the corresponding coefficients. The best-fit coefficients were obtained by optimization of an objective function defined as the difference between the experimental results and those calculated by the model tested. For this we have designed an algorithm in Scilab. Table 1 shows the coefficients for the best fit equation, and Figure 1 shows the results of the best fit. Figure 1. Fist of the all equations Figure 2. Best fit (Petric et al. 2012) References I. Petric et al. Evolution of process parameters and determination of kinetics for co composting of organic fraction of municipal solid waste with poultry. Bioresource Technology, 117 (2012), M. Baptista et al. Composting kinetics in full-scale mechanical biological treatment plants. Waste Manage, 30 (2010),

214 Evaluation of the Microbiota of Immature Compost and Moravia Soil for the Bioremediation of Soils Contaminated with Chlorpyrifos, Malathion and Methyl Parathion S. Upegui, J. F. Saldarriaga*, University of Medellín, Carrera 87 # 30-75, Medellín, Colombia, * Hazardous Wastes and Soil Remediation Organophosphate pesticides are widely used for pest control in agriculture and public health programs. However, they generate toxic wastes that contaminate cultivated soils and their surrounding environments search for alternatives to mitigate the impact of pollution by pesticides is a priority. Bioremediation is a strategy that presents important advantages for the treatment of contaminated soils due to its low cost and easy in situ application (Mosquera & Penuela, 2009; Upegui, et al., 2011). Compost has been proposed as an alternative for the treatment of soils contaminated by xenobiotics. This is because its nutrient contribution, increases microbial populations and augments the release of extracellular enzymes which depolymerize a wide variety of organic compounds. Moreover, highly contaminated soils have also been used for the selection of microbial populations capable of metabolizing different pollutants by using enzymes (Zhang, et al., 2006). Three organophosphorus pesticides (chlorpyrifos, malathion and methyl parathion) were selected in order to evaluate the bioremediation capacity of the microorganisms present in two complex matrices: immature compost (prepared from urban solid wastes) and an urban contaminated soil sample from a garbage-dumping site (Moravia Soil). Microcosm assays of 10 g of each matrix were contaminated with a mix of the three pesticides (130, 30 and 20 mg Kg-1 of chlorpyrifos, methyl parathion and malathion respectively), and they were kept for 30 days under controlled conditions in terms of light, temperature and humidity. Mineralization assays were used to evaluate the microbial activity in the matrices. It was found that the Moravia soil microorganisms were more suitable for bioremediation studies since they degraded all pesticides faster than the immature compost, which failed to degrade chlorpyrifos. The compost mineralization was four times greater than the soil mineralization. Microbial mineralization in the soil was not decreased by the application of the pesticides. However, microbial activity in the compost increased. Figure 1. pesticides degradation by Moravia soil microorganisms References Figure 2. Pesticides degradation by compost microorganisms Mosquera, R., & Penuela, G Biodegradación del malatión usando microorganismos nativos de suelos agrícolas. Revista Colombiana De Ciencias Pecuarias, vol. 22, Upegui, S. A., Peñuela, G. A., & Botero, L. R Efecto del enriquecimiento con nutrientes en la degradación de clorpirifos, malatión y metil paratión. Revista Ingenierías Universidad de Medellín, 10(18),

215 Zhang, X. X., Cheng, S. P., Zhu, C. J., & Sunm, S. L Microbial PAH-degradation in soil: degradation pathways and contributing factors. Pedosphere, 16(5),

216 EFFECT OF INITIAL ph IN THE DEGRADATION OF THE EMERGING CONTAMINANT METOPROLOL BY MEANS OF UVC/H 2 O 2 V. Romero *, E. Rodríguez, P. Marco, J. Giménez, S. Esplugas. Department of Chemical Engineering. University of Barcelona. C/ Martí i Franquès, Barcelona. Spain. Tel FAX *Corresponding author: Scientific topic: Advanced Techniques for Effluent Treatment Some pharmaceutical products and their metabolites are not removed from water during conventional biological treatment and enter the water supply via mainly urban wastewater treatment plants (WWTPs). These compounds can be biologically active, even at environmental concentrations (µg L 1 to ng L 1 ). In addition, they can be persistent and/or toxic and could, hence, be harmful to aquatic species. Their biodegradation varies from persistence to complete degradation. Among them it can be found the emerging contaminant Metoprolol (MET) that is a selective beta blocker. It is a highly prescribed pharmaceutical to treat hypertension, tachycardia, and heart failure [1, 2]. Owing to its widespread occurrence, Metoprolol (MET) has been degraded and mineralized by the assessment of UVC/H 2 O 2 treatment using a thermostated Pyrex-jacketed 2 L vessel, equipped with three fluorescent low pressure mercury lamps (Phillips TUV 8W, G8T5), whose nominal power was 8W each and emitted monochromatic radiation between nm, with a maximum of 254 nm. The intensity of the incident light inside the photoreactor was equal to 1.70(μEinsteins -1 ) at 254 nm. The solution was fully mixed with a magnetic stirrer to ensure sufficient mixing. The reaction temperature was kept constant at 25 ºC during all processes by thermostatic bath. The main goal to be achieved when applying this process is the removal of the MET present in water and assess the overall effect of the initial ph (ph 3, free and 9) using different H 2 O 2 concentrations (25, 50, 75, 100, 125 and 150 mg/l). Moreover, the evolution of parameters such as Total Organic Carbon (TOC), Specific UV Absorbance (SUVA), and hydrogen peroxide consumption was followed along the reaction time. The results obtained showed that there is not any remarkable influence on MET and TOC elimination when the initial ph is changed. Regarding to the optimum H 2 O 2 initial concentration used, the best result was obtained with 125 mg/l H 2 O 2. Almost a complete MET elimination was achieved within 7.5 minutes and 71% of mineralization at 230 minutes and free ph. Figure 1 shows degradation and mineralization trends of MET, it can be observed in Fig 1. a) that at the beginning of the process MET is degraded faster and then its degradation goes slower. The mineralization Fig 1. b) shows a constant decreasing trend during the reaction time for all series. a) b) MET/MET TOC/TOC Time (min) 125 mg/l H2O2, ph mg/l H2O2, free ph 125 mg/l H2O2, ph Time (min) 125 mg/l H2O2, ph mg/l H2O2, free ph 125 mg/l H2O2, ph 9 Figure1. (a)met and (b) TOC removal at different ph (3, 6.5 and 9), and 125 mg/l H 2 O 2. [1] H. Yang, T. An, G. Li, W. Song, W.J. Cooper, H. Luo, X. Guo, Photocatalytic degradation kinetics and mechanism of environmental pharmaceuticals in aqueous suspension of TiO 2 : A case of ß-blockers, J. Hazard. Mater. 179 (2010) [2] F.J. Benitez, F.J. Real, J.L. Acero, G. Roldan, Removal of selected pharmaceuticals in waters by photochemical processes, J. Chem. Technol. Biotechnol. 84 (2009)

217 METOPROLOL REMOVAL BY CATALYST -BICARBONATE-ACTIVATED HYDROGEN PEROXIDE IN DRINKING WATER V. Romero 1*, O. González 1, S. Minghao 2, S. Esplugas 1. 1 Department of Chemical Engineering. University of Barcelona.C/ Martí i Franquès, Barcelona. Spain. 2 College of Environmental Science and Engineering, Tongji University, Sipping Rd 1239, Shanghai, *Corresponding author: Scientific topic: Advanced Techniques for Effluent Treatment The occurrence of pharmaceutical drugs in surface, ground, and drinking waters is a growing environmental concern. This pollution is caused by emission from direct disposal of surplus drugs in households, excretion after drug administration to humans and animals, wastewater from fish and other animal farms, and industry. Some of these drugs, as - blockers, have been detected in the order of ng L 1 to gl 1 in waters. As an example, Metoprolol (MET), which is usually prescribed as antihypertensive or antiarrhythmic, has been quantified up to 2 gl 1 in sewage treatment plant effluents and to 1540 ng L 1 in rivers [1].The achievement of effective technologies for elimination of pharmaceuticals from their original sources is an emerging research area in environmental engineering. Catalyst -bicarbonate-activated hydrogen peroxide systems have been investigated to degrade 36.5 μm of MET. Bicarbonate (HCO 3 ), one of the most abundant anions in natural water, is relatively non-toxic and readily available at low cost. It is also an efficient activator for H 2 O 2 to generate active oxygen species such as peroxymonocarbonate (HCO 4 ) [2].In addition, HCO 3 is an important complexing ligand for some metal ions, leading to significant changes in their redox potentials. The complex between HCO 3 - and Co (II)/Fe (II) may form and serve as the catalyst to active H 2 O 2 to HO radicals in the system. In this study, we have investigated the role of different parameters such as catalyst, bicarbonate and H 2 O 2 concentration, ph, as well as, the manner of dosing bicarbonate and Iron (II).Bicarbonate was actually not able to degrade MET with H 2 O 2 in the absence of Co (II)/Fe (II) in drinking water, However, nearly 50% of MET was removed by Cobalt- Bicarbonate Hydrogen peroxide using 7.14 mm of NaHCO 3, 17 μm of Co (II) and mm of H 2 O 2 at free ph (6.5) in 120 minutes. The efficiency of the catalytic process improved when using Fe (II) as catalyst. A complete MET elimination was achieved when the total iron (II) concentration was divided in equal parts (5) and added at constant periods of time (12 minutes) during 1 hour (by steps), using 0.6 mm of NaHCO 3, 180 μm of Fe (II)(five additions of 36 μm Fe (II)) and0.73 mm H 2 O 2 at ph 3 in 40 minutes (Figure 1). 100 MET conversion (%) Time (min) 0.6 mm HCO3, 180 μm Fe (II), 0.73 mm H2O2 (by steps), ph mm HCO3, 17 μm Co (II), mm H2O2, ph 6.5 Figure1. MET degradation by Co 2+ /HCO 3- /H 2 O 2 and Fe 2+ /HCO 3- /H 2 O 2 systems. [MET] 0 =36.5 μm [1] A. Piram, A. Salvador, C. Verne, B. Herbreteau, R. Faure, Photolysis of -blockers in environmental waters Chemosphere, 73, (2008) [2] Aihua Xu, Xiaoxia Li, Shuang Ye, Guochuan Yin, Qingfu Zeng, Catalyzed oxidative degradation of methylene blue by in situ generated cobalt (II)-bicarbonate complexes with hydrogen peroxide, Applied Catalysis B: Environmental 102 (2011)

218 EXPLOITATION OF LIGNOCELLULOSIC RESIDUES GENERATED BY PAPER AND CITRUS INDUSTRIES BY COMPOSTING Jaime, P. 1 ; Domínguez, J. 1 ; Espinosa, E. 2 ; Palenzuela, M.V. 1 ; Rodríguez, A. 2 ; Rosal, A. 1 1 Department of Molecular Biology and Biochemical Engineering, Pablo de Olavide`s University, Seville, Spain. Corresponding author /Fax Department of Inorganic Chemistry and Chemical Engineering, University of Córdoba, Spain. Scientific topic of the work: 2. Chemical Engineering for Sustainable Development. 2.2 Environmental Technology and Risk Analysis (Waste Minimization and Treatment) The present work studies the feasibility of exploiting the resources contained in the huge amount of organic waste generated by the paper and the citrus processing industries by composting. These wastes lead to suppose a significant environmental impact, and also the management and the ex situ treatment of them represent a high economic cost for the companies. The lignocellulosic residues from the pre-treatment of the wheat straw, used in the company ECOPAPEL S.L. (Écija, Seville), are approximately 140 tonnes per annum and the black liquors, generated in the pulping process, are about m 3. Furthermore, the process used to obtain orange juice in the company Andévalo (Huelva) produces about tonnes per annum of orange peel. An experimental pile using these types of residues was performed in a pilot-scale plant and the process was monitored on-site for temperature. The pile was made adding 70 Kg of black liquors (67.3 litres and ph = 11.5) to a mixture of 140 Kg on a dry basis (1:1, w/w) composed of the residues from the wheat straw (11.5% moisture and ph = 6.2) and the residues of the oranges (72.0% moisture and ph = 3.4). Composting was performed during 60 days and the experimental pile was turned (with a manual spade) and irrigated up to 50% moisture once a week. In the process were reached temperatures above 50ºC during fifteen days, as well as the ph increased from 7.5 to 9.8 ph units and the percentage of organic matter (OM) decreased from 74% to 35% (Figure 1). Compost has met the limits set by RD 506/2013 (Spanish regulations) for the following parameters: moisture, organic matter and total nitrogen. The Normalized Concentration of each metal increased during composting process (Figure 2). However, according to the legislation (Table 1), the final product can be classified as high quality compost (Class A). This type of residues could be potentially useful as raw substrates in composting process. Oxidable Organic Carbon Normalized Concentration Time (days) Fig. 1: Evolution of the percentage of Oxidable Organic Carbon during composting. (%OM= %C 1.72) Time (days) Fig. 2: Evolution of the Normalized Concentration for each metal during composting Cu Cd Cr Ni Pb Zn Compost 56 ND Class A Class B Class C Table 1: Total concentration of heavy metals in the compost (the values are averages of three experimental measures, in ppm) and the limits which have been established by RD (Spanish regulations) for the Class A, B y C of compost. ND, non-detectable.

219 INTEGRATED WASTE MANAGEMENT CENTRE IN PETROCHEMICAL COMPLEX C.Mollet TECHNIP France, 6-8 Allée de l Arche Courbevoie, Tel : , 2. Chemical Engineering for Sustainable Development / 2.2 Environmental Technology and risk Analysis / Waste Minimization & Treatment Waste collection and management are a key issue for industrial sites anywhere in the world. Inappropriate waste management design can limit access to International Financing. During operation, inappropriate waste treatment and final disposal may cause pollution, may expose local population to sanitary diseases, etc., with a potential impact on the international reputation of the Operating Company. However, defining waste reminds a complex exercise. Wastes are generated by multiple sources: individual, school, industry manufacturing and wastes are various (substances, volume, properties ). Confronted to this complexity, authorities have generally replied in equally complex legislations linked with their national background. And, at the present time, there is no international definitive list defining which shall be considered as waste. From an industrial point of view the approach is simple : there are only two types of wastes. First category : waste with no or negative exchange value Second category : waste with positive exchange value (ie which can be recovered, recycled or reused as energy or raw materials). In light of the above, TECHNIP Environmental specialists have developed a rational approach to analyze industrial site waste generation, to propose a waste management centre adapted to the Complex specific needs and to promote as much as possible waste conversion from first to second category : from waste to resource. Such approach requires the knowledge of waste national/local legislation, of industrial site waste profile and also of regional waste economy in order to integrate the waste management facilities in the best manner for the local population. TECHNIP proposes an integrated waste management center designed according to infrastructures needs : conditioning facilities, secondary/primary storages, incinerator, landfill Nevertheless, the work cornerstone reminds the waste conditioning center focused mainly on waste valorization principle and in which innovative technologies as well as current practices can be proposed and operated together. Implemented on two major projects (design and construction of a large mine in Africa and design of a major integrated Petrochemical Complex in Asia), the resulting waste management units have a rapid return on investment with minor capital demand and ensure a sustainable development for the communities living in the plant vicinity. 3D views and animation will be used to help the audience understand the methodology and the extend of TECHNIP s approach.

220 ELIMINATION OF THE EMERGING CONTAMINANT METOPROLOL BY PHOTO-FENTON PROCESS WITH SUCCESSIVE AND CONTINUOUS IRON (II) ADDITIONS P. Marco*, V. Romero, A. Solé, J. Giménez, S. Esplugas. Department of Chemical Engineering. University of Barcelona. C/ Martí i Franquès, Barcelona. Spain. Tel FAX *Corresponding author: Scientific topic: Environmental Technology and Risk Analysis Tons of different classes of pharmaceuticals find their way to the environment at variable degrees, after their use and excretion through wastewater and sewage treatment systems [1]. Advanced Oxidation Processes (AOPs) are efficient technics for water treatment that allow the total or partial elimination of recalcitrant organic pollutants resistant to conventional treatments, reduction of toxicity or destruction of pathogen microorganisms. Among these AOPs, Photo-Fenton process (Fe (II)/H 2 O 2 /light) can be found. Fe (III) can catalyze the formation of hydroxyl radicals when irradiated with light of suitable wavelength ( nm), that is, ultraviolet and some visible light, [2].Thus, this process is characterized by photo-reduction of ferric to ferrous ions that is promoted concomitantly with the generation of additional HO. Photo-Fenton process stars with the classical Fenton s reagent. When the system is irradiated with UV or visible light, the photoassisted Fenton s process produces ferric ions as a by-product of the reaction between Fe (II) and H 2 O 2 and then is photochemically transformed back into ferrous ions. The reactions iron becomes cycled between the (+II) and (+III) oxidation states. The betablocker Metoprolol (MET) has been chosen as target compound and degraded by photo-fenton process. The device consists on a 2 L Pyrex-jacketed thermostatic vessel, equipped with three 8W BLB lamps placed in its centre. Lamps emitted radiation between 350 and 400 nm, with a maximum at 365 nm. The total iron (II) concentration was divided in equal parts (5) and added at constant periods of time (12 minutes) during 1 hour (by steps). The iron (II) concentrations used were 2.5 and 10 mg/l and H 2 O 2 concentrations were 25 and 150 mg/l. The results obtained are described in figure 1. The best MET degradation was reached within 10 minutes using 10 mg Fe (II)/L and 150 mg H 2 O 2 /L. Regarding to mineralization, 61.5% was achieved after 60 minutes. When initial H 2 O 2 concentration remains constant, it can be observed, in all the series, the higher concentration of Fe (II) leads to a higher degradation and mineralization rate. a) 1 b) 1 MET/MET TOC/TOC Time (min) Time (min) 2.5 mg/l Fe (II), 25 mg/l H2O2 10 mg/l Fe (II), 25 mg/l H2O2 2.5 mg/l Fe (II), 150 mg/l H2O2 10 mg/l Fe (II), 150 mg/l H2O2 Figure1. (a)met and (b) TOC elimination 2.5 mg/l Fe (II), 25 mg/l H2O2 10 mg/l Fe (II), 25 mg/l H2O2 2.5 mg/l Fe (II), 150 mg/l H2O2 10 mg/l Fe (II), 150 mg/l H2O2 [1] M. Gros, M. Petrovic, D. Barceló, Development of a multi-residue analytical methodology based on liquid chromatography tandem mass spectrometry (LC MS/MS) for screening and trace level determination of pharmaceuticals in surface and wastewaters, Talanta 70 (2006) [2] S. Parsons, IWA Publishing, Advanced Oxid. Processes for water and wastewater treatment. London, 2004.

221 REMOVAL OF SELECTED EMERGING CONTAMINANTS FROM DIFFERENT WATER MATRICES BY UF AND NF MEMBRANES E. Rodríguez*, J.L. Acero, F.J. Benítez, F.J. Real, G. Roldán. Dpto. de Ingeniería Química, Universidad de Extremadura, Avda de Elvas s/n Badajoz, Tfno: ; Environmental Technology and Risk Analysis Emerging contaminants many of which may be acutely or chronically toxic to aquatic organisms and may pose a health risk to man and animals alike- have been identified in natural waters and secondary effluents of municipal wastewater treatment plants. Optional tertiary treatment improves the quality of secondary wastewater and produces an effluent that can be used as a substitute for freshwater sources for household and industrial needs. Membrane technologies, such as microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) have been used in the removal from waters of emerging contaminants (ECs) for the production of drinking water [1] as well as for wastewater reuse [2]. In the present study, the removal of five selected emerging contaminants (chlorophene, methylindole, nortriptyline chlorhidrate, DEET and benzotriazole) by some UF and NF membranes was investigated, and the effects of the natural water matrix on the retention of ECs and on the permeate flux have been established. The three UF membranes had MWCO of 2,000, 5,000 and 20,000 Da (GK, PT and PW membranes respectively), and the three NF membranes (DK, HL and CK membranes) had similar MWCO, in the range Da. A laboratory membrane equipment was used, and the experiments were conducted in batch concentration mode. In a first stage, ECs were dissolved in pure water and filtration experiments were performed with the selected membranes at different ph. In the second stage, ECs were dissolved in different water matrices. The experimental results obtained revealed that J v decreased with the initial increase of the volume retention factor (VRF), and remained almost constant for higher VRF values. The almost constant values of permeate fluxes were reached for VRF values in the range Then, the steady-state permeate flux values J vss were calculated for all the experiments conducted, with results that varied from 10.1 to L h -1 m -2 in the UF process; and from 40.1 to L h -1 m -2 in the NF process, depending on the operating variables. The influence of ph on the values of J vss was slightly negative. At the same time, J vss values obtained for UP were higher than those obtained for natural water and secondary effluents due to membrane fouling. The retention coefficients obtained for the selected ECs in the experiments performed with the UF membranes followed the sequence CF > ML > NHCl > DT > BZ. According to these results, adsorption should be the main mechanism responsible for rejection of ECs by UF membranes. However, the retentions obtained with NF membranes followed the trend: CF > NHCl > ML > DT > BZ. Therefore, other mechanisms such as size exclusion and electrostatic repulsion must also contribute to the retention of ECs by NF membranes. Acknowledgements. This research was supported by Gobierno de Extremadura through Project RNM021. E. Rodriguez thanks to the Gobierno de Extremadura for her FPI Ph.D. Grant. References [1] H.E. Wray, R.C. Andrews, P.R. Berube, Sep. Purif. Technol. 122 (2014) [2] J.L. Acero, F.J. Benitez, F. Teva, A.I. Leal, Chem. Eng. J. 163 (2010)

222 REMEMBRANE Recovery of Reverse Osmosis Membrane at its End of Life C. Pérez, F.X. Simón, J. García-Montaño, S. Martínez-Lozano LEITAT Technological Center, c/ de la Innovació, Terrassa (Barcelona) Tel. (+34) Fax (+34) Scientific Topic: 2.2 Environmental Technology and Risk Analysis Reverse osmosis membranes are used in seawater, brackish water, and wastewater for desalination and treatment. Fouling of membranes (Fig. 1) unavoidably occurs during the filtration process decreasing both permeate production and quality. To recover the performance, it is necessary to clean the membranes. Membrane life usually lasts 5-10 years mainly due to aging and the irreversible fouling consequences. The main objective of REMEMBRANE project is to develop an innovative membrane recovery strategy to expand its life for the same or other applications avoiding landfill disposal and lengthening membrane s life cycle. Fig. 1. Fouled Membrane Different types of membranes (i.e. worn out, out of use) from different environments are considered. Autopsies and filtration brackish tests are done at lab scale. These tests aim to increase the knowledge on reagent selection and application time to achieve the desired recovery depending on the main fouling agent. Lab tests are very valuable to apply the best cleaning protocol in a subsequent pilot plant. At pilot scale, a mobile demonstration plant capable to recover RO commercial membranes on site at its end of life is constructed. The unit can diagnose membrane status, perform membrane cleanings and finally test recovered membranes in real conditions without interfering in day by day plant management. Before membrane cleaning processes, a membrane brackish test is performed (analogous to lab scale tests). Filtration performances are evaluated in terms of flow and permeate quality. These results allow diagnosing the status of the membrane. The membrane cleaning cycle is carried out after discharging the brine water according to previous lab tests. Thus, wash tanks are filled with selected reagent/s and (i.e. acid, basic, and oxidant). Following this, another brackish test is done in order to evaluate the effectiveness of the cleaning. In worse cases, membrane silting is too high to be improved by normal cleaning protocols and more intensive cleaning is needed. Thence, membrane is blocked from one side and a negative suction pump is connected to the other side (Fig. 2). Once the recovery cycle process is completed, membrane stability is operated for a long time in a membrane tube in order to assure that no degradation on the Fig.2. Membrane s pre-treatment recovery prototype recovered membranes is produced. REMEMBRANE goals are not only the construction of a demo plant. REMEMBRANE aims to extend membrane lifetime and thus convert a costly residue into a profitable product. Besides, the exhausted membranes currently sent to landfill will be reduced and therefore the disposals costs too. The REMEMBRANE project enhances and stimulates the regeneration of water by lowering the costs of investment and operation in water treatment plants. Last but not least, REMEMBRANE aims to implement and disseminate this technology around the world, particularly in scarce water regions. The authors are grateful to the partners of the REMEMBRANE project and the co-funding from the European Community under the LIFE+ financial instrument with the grant agreement LIFE11 ENV/ES/626.

223 STUDY OF THE INFLUENCE OF THE PRESENCE OF DISSOLVED SOLID IN THE REMOVAL OF CYANIDE IN WASTEWATER TREATMENT BY OZONE Pueyo N., Ormad M.P., Ovelleiro J.L. Grupo de Investigación de Calidad y Tratamiento de Aguas Universidad de Zaragoza c/ María de Luna, Zaragoza Tfno Advanced techniques for effluent treatment According to Royal Decree 60/2011 laying down Environmental Quality Standards in the field of water policy, the cyanide is considered a preferred substance and their presence in inland surface water must not exceed the concentration established by the Environmental Quality Standard. Therefore, the monitoring and measurement of cyanide in natural and wastewaters are considered essential requirement for proper environmental control. Currently, there are a variety of treatments cyanides in wastewater although advanced oxidation processes, which generate highly oxidizing species called hydroxyl radicals by oxidizing agents such as ozone, are the only treatment able to remove cyanide and generate less toxic compounds compared to conventional processes [2-4]. The purpose of this study is to analyze the influence of the presence of dissolved solids in the oxidizing effect of ozone on the removal of cyanides in wastewater. According to the objetive, the industrial wastewater with an initial cyanide concentration of 4 milligram per liter is treated by oxidation with ozone (at ph 9,6). Total dissolved solids, composed mainly of calcium carbonate and bicarbonate, are removed by a water softening process using sodium carbonate and calcium hydroxide. Calcium carbonate and bicarbonate are chemically precipitated as calcium carbonate by using of these reagents. The cyanide oxidation efficiency by ozone in wastewater depends on the ozone dose. The maximum efficiency obtained is 95 percent for an ozone dose of 265 milligram per liter. However, the ozone consumption is reduced to a concentration of 121 milligram per liter for the same cyanide oxidation efficiency 95 percent if the wastewater is pre-treated by the lime-soda ash softening process. This is due to the reduction of carbonate and bicarbonate ions in wastewater through the addition of optimal doses of lime and sodium carbonate 2,4 gram per liter and 2,0 gram per liter, respectively. According to the predicted [5-7], carbonate and bicarbonate ions in wastewater have free radical scavenging-effect. These free radicals are generated during the oxidation process so that the consumption of oxidizing agent is increased by the presence free radical scavengers. References [1] Real Decreto 60/2011 BOE 19, (2011) [2] Kim YJ, Qureshi I, Min KS (2003). Environ. Technol. 24, [3] Knorre H, Griffiths A (1985). Geotech. Eng. Prog [4] Sarla M, Pandit M, Tyagi DK, Kapoor JC (2004). Hazard. Mater. 116, [5] Gottschalk C, Libra JA, Saupe A (2000). Ozonation of water and wastewater: a practical guide to understanding ozone and its application [6] Hoigne J, Bader H (1976). Water Res [7] American Water Work Association Research Foundation, Compagnie Générale des Eaux (1991). Ozone in water treatment: application and engineering

224 OPTIMIZATION ON THE STABILIZATION/SOLIDIFICATION TECHNIQUE OF ELECTROPLATING SLUDGE BY STATISTICAL ANALYSIS M.T. Montañés*, R. Sánchez-Tovar and A. Marín-Torres Grupo Ingeniería Electroquímica y Corrosión. Departamento Ingeniería Química y Nuclear. Universitat Politècnica de València. C/ Camino de Vera s/n, Valencia (Spain) Tel: , Fax: , Environmental Technology and Risk Analysis: Waste Minimization and Treatment. Sludges from electroplating operations are potentially hazardous wastes due to the high mobility of the metals, such as chromium, nickel and copper, present in these wastes. Stabilization/solidification (S/S) technologies use binders and additives to reduce the mobility and toxicity of the pollutants contained in wastes. These processes are generally relatively inexpensive and easy to use; however, S/S could result in a significant volume increase and so, the final products could require additional landfill space. The S/S technology has been studied in previous works with electroplating wastes in terms of leach resistance. However, none of them has analyzed the toxicity of the final solid products or has taken into account the increase in volume that could take place. The aim of this research is to optimize the application of a S/S process using cement to electroplating sludge by means of the response surface methodology (RSM) in order to find a safer way of landfilling this waste, while minimizing the operational and landfilling costs. Concretely, this work studies the effect of the following processing parameters: the relative amount of water (30-50 wt.%), cement (10-50 wt.% in the solid components) and electroplating sludge (bal.) added to the mixtures. Commercial cement based on Portland cement (CEM II/A-L 42.5 R) was used. The effectiveness of the process is analysed in terms of leachate toxicity and chromium, copper and nickel retention. Moreover, the increase in weight and volume is also evaluated. Results show that all the mixtures could be disposed at a landfill, most of them at a non-hazardous waste one. Statistical analysis reveals that the studied parameters do not significantly influence the effectiveness of the process. The nickel retention percentage is practically equal to 100% regardless of the relative amount of cement and water. However, chromium and copper retention slightly diminish as the relative amount of cement increases, probably due to additional chromium and copper provided by cement. Moreover, toxicity slightly increases as the cement percentage increases. On the other hand, weight and volume increases are greater as the relative amount of cement and water increases; and statistical analysis reveals that the effect of both parameters on the weight and volume increases is significant. In order to find the optimum operating conditions which simultaneously minimized weight increase, volume increase, metals leached and toxicity, a multiple response optimization was performed. Figure 1 shows the obtained results. According to them, the optimum operating conditions correspond to the lowest cement percentage (10%) and to the lowest water percentage (30%). The final solid product could be disposed at a non-hazardous waste landfill and show low weight and volume increases (in fact, important decreases are observed). Optimized factors Cement (wt. %): 10.0 Water (wt. %): 30.0 Overall desirability: 0.73 Predicted response variables Weight increase (%): Volume increase (%): Leached Cr (mg/kg mixt.): 6.8 Leached Ni (mg/kg mixt.): 0.0 Leached Cu (mg/kg mixt.): 11.1 Toxicity EC 50 (TU): 0.0 Desirability Water Cement Desirability Figure 1. Operating conditions that minimized the overall desirability function and corresponding response variable values predicted using the response surface methodology.

225 Chlorophenols degradation by biologically activated carbon J. Chirinos 1, A. Fabregat 1, A. Fortuny 2, C. Bengoa 1, F. Stüber 1, J. Font 1 1 Departament d'enginyeria Química, Universitat Rovira i Virgili, Av. Països Catalans 26, Tarragona, Spain 2 Departament d'enginyeria Química, Universitat Politécnica de Catalunya, Av. Víctor Balaguer S/N, Vilanova i la Geltrú, Spain Tel.: , Scientific Topic: Advanced Techniques for Effluent Treatment In recent years, the massive mobilization of natural resources and the industrial synthesis of chemicals have produced significant ecotoxicological problems with serious consequences for all living organisms. This is particularly true for xenobiotic compounds, which exhibit structural elements or substituents that are rarely found in natural products. The chemical properties of xenobiotic compounds determine their toxicity, their persistence in the environment and the route in which they are degraded by microorganisms. Furthermore, the conventional technologies of waste water treatment have often failed to deal with many contaminated aqueous effluents, mainly due to the refractoriness of these xenobiotic compounds. The Environmental European Agency (EEA) has established a list of over 2000 chemical products, which are either toxic or environmentally hazardous [1]. In turn, chloroaromatic compounds are today among the most used industrial chemicals for the synthesis of a wide range of products, then occurring in the derived process waste water. Among this kind of pollutants, the EEA considered chlorophenols as the major group of chlorinated hydrocarbons, pesticides and biocides which account for a very high percentage of the nonagricultural pesticide use. Chlorophenols act as biocides by inhibiting the respiration and energy-conversion processes of the microorganisms. Also, they are toxic to man above 40 parts per million, to fish above 1 ppm, whilst concentrations as low as one part per thousand million can taint water. Therefore, due to their intrinsic toxicity, it is necessary to develop or improve feasible methods for their degradation, hence lowering the impact of such waste water effluents on aquatic environment. Several methods have been developed to reduce the impact of this kind of contaminated waste water effluents. Among them, the anaerobic treatment process is the only viable option for dechlorination of highly chlorinated compounds, considering that these compounds are barely attacked by oxidative routes [2]. The main purpose of this work is to establish a new approach based on the use of biologically activated carbon for treating effluents containing low concentration of chlorophenols. The studied system consists of an upflow stirred packed-bed reactor (USPBR) previously developed in the research group [3], where it is expected that the activated carbon performs both as an electron mediator promoting the reductive dehalogenation of chlorophenols and as a support for the anaerobic biofilm. The biological systems were prepared using anaerobic sludge from a municipal waste water treatment plant and were previously acclimated to each xenobiotic compound studied. The performance of the anaerobic system is being investigated for 2-chlorophenol, 2,4,6- trichlorophenol and pentachlorophenol under different operational conditions, i.e., the inlet concentrations were ranged from 25 mg/l to 100 mg/l and the space time was varied from 0.5 to 11 min. The results reveal high efficiencies for the degradation of these compounds. Complete conversion of pentachlorophenol and nearly complete conversion (around 95%) of 2,4,6-trichlorophenol were observed. The lower conversion values were obtained for 2-chlorophenol, reaching up to 70%. This method appears to be a new efficient alternative for the treatment of waste waters containing low concentration of highly chlorinated compounds. [1] EEA, European Environmental Agency and United Nations Environmental Program, Chemicals in the European Environment: Low doses, high stakes? [2] Savant, D.V.; Abdul-Rahman, R.; Ranade, D.R Bioresource Technol [3] Mezohegyi, G.; Bengoa, C.; Stüber, F.; Font, J.; Fabregat, A.; Fortuny, A Chem. Eng. J

226 USE OF IRON ORGANOMETALLIC COMPOUNDS IN THE DEPOLLUTION OF CONTAMINED SOILS BY METRIBUZIN A. Boucif, Z. Hank and S. Boutamine Université des Sciences et de la Technologie Houari Boumediene (USTHB), Faculté de Chimie, Laboratoire d Electrochimie, Corrosion, Métallurgie et Chimie Minérale, BP 32, El Alia, Bab-Ezzouar,16111, Algiers Algeria. Fax number : , e_mail : Environmental Technology and Risk Analysis Particular chemicals like pesticides which use, in agriculture, became inescapable are engendering an environmental pollution and more particularly that of the waters as well of surfaces as ground-water sheets. It is urgent, for preservation of public health, to reduce at most our exposure to these substances and to operate everything to reduce and control these pollutants. So, the presence of pesticides in drinkable waters is severely regulated and the producing companies of water, to conform to the established standards, are obliged to include in their networks of water treatment, processes to eliminate them. The adsorption on the synthetized metal organic complexes may be a technique to disinfect waters polluted by pesticides and other chemicals. In this context, some coordination compouds of iron were tested in the adsorption of mitrobuzin present in contaminated water. The retained organic molecules are natural products (flavonoids and purines) The preliminary results seems encouraging and we report them here. They are compared to those obtained with a conventional adsorbing agent, namely powdered activated carbon F400.

227 OPTIMIZATION OF PROCEDURE FOR REMOVAL OF COPPER(II) IONS FROM WATER Ivana M. Savic 1 *, Ivan M. Savic 1, Stanisa T. Stojiljkovic 1, Dragoljub G. Gajic 2 1 Faculty of Technology, University of Nis, Bulevar oslobodjenja 124, Leskovac, Tel.: ; fax: , 2 Center of Excellence DEWS, University of L Aquila, Italy 3 Department of Signals and Systems, School of Electrical Engineering, University of Belgrade, Serbia 2.2 Environmental Technology and Risk Analysis The presence of heavy metal ions in the water is one of the main problems today. Copper belongs in this group of heavy metals with the expressed bacteriostatic effect [1]. If copper exceeds the limited concentration range, it can be hazardous to human health. For this reason, and in order to preserve the environment, the special attention has directed on the removal of copper ions from water using different adsorbents [2-5]. Thus, the aim of this paper was to remove copper(ii) ions from water by adsorption. In order to model and optimize this adsorption process, the central composite design was used as a suitable mathematical technique. The adsorption time, x 1 (5 75 min), ph value of the solution, x 2 (1 7 mg dm -3 ) and the adsorbent dose, x 3 ( mg dm -3 ) were used as the independent variables, while the amount of removed copper(ii) ions was used as the dependent variable. The initial concentration of copper ions was 150 mg dm -3. Bentonite clay was used as an adsorbent for removal of heavy metal ions. After adsorption, the amount of adsorbed copper ions was determined using the indirect UV-VIS method that based on the formation of the dark blue tetraamminecopper(ii) ions [Cu(NH 3 ) 4 ] 2+ after addition of ammonia. A second order polynomial equation was applied for fitting the obtained data. After ANOVA testing, the statistical significant terms of the equation were noticed. In order to improve the performance of the proposed model, the insignificant terms were excluded from polynomial equation. The Lack of Fit F-value of 4.87 implies that the Lack of Fit is not statistical significant compared with the value of pure error. There is a 5.17% chance that a Lack of Fit F-value could occur due to noise. The obtained reduced model can be presented in terms of the coded variables in the following way: Y x1 2.03x x2 3.47x2 8.25x3 2.52x3 2.44x1x x2x3 The adsorption conditions: the adsorption time of 52.4 min, ph value of 5.63 and the adsorbent dose of mg dm -3 were obtained after optimization studies, i.e. using the numerical optimization method. Under these conditions, the experimental value (58.01%) and the predicted value (58.43%) of adsorbed amount of copper ions are in good agreement indicating the adequacy of the proposed model. Acknowledgments. The support from the Marie Curie FP7-ITN "ENERGY-SMARTOPS", Contract No: PITN-GA , the Erasmus Mundus Action II EUROWEB Project and the Ministry of Education, Science and Technological Development of the Republic of Serbia under the project TR is gratefully acknowledged. References [1] J. P. Ruparelia, A. K. Chatterjee, S. P. Duttagupta, S. Mukherji, Acta Biomaterialia, 4(3), 707 (2008). [2] I. M. Savic, S. T. Stojiljkovic, S. B. Stojanovic, K. Moder, Chemical Engineering and Technology, 35(11), 2007 (2012). [3] P. Senthil Kumar, S. Ramalingam, V. Sathyaselvabala, S. D. Kirupha, S. Sivanesan, Desalination, 266(1), 63 (2011). [4] C. C. Huang,Y. J. Su, Journal of hazardous materials, 175(1), 477 (2010). [5] M. S. Mansour, M. E. Ossman, H. A. Farag, Desalination, 272(1), 301 (2011).

228 PYROLYSIS OF ANAEROBIC DIGESTED PIG MANURE IN A FLUIDIZED BED Violeta Quispe*, Javier Ábrego, María Benita Murillo, Gloria Gea and María Atienza-Martínez. Thermo-chemical Processes Group, Aragon Institute of Engineering Research (I3A), Universidad de Zaragoza, C/Mariano Esquillor s/n, Zaragoza, Spain. * Phone: Scientific topic: 2.2. Waste Minimization and Treatment As the second largest pig producing country in the European Union, Spain s annual production of manure varies between 35 and 50 million tonnes [1]. Daily, between 94 and 188 million litres of pig slurry are generated, corresponding to an average production between 4 and 8 litres / day / animal that needs to be adequately managed. European legislation (Nitrates Directive, 91/676/EEC) has limited the amount of wastes which can be spread on land, increasing the cost of manure disposal [2]. The pig manure (PM) is a highly polluting waste whose chemical composition is variable, depending on many factors such as type of farm of origin, food, and storage of excreta. It causes degradation of soil and water resources, when the PM is not used properly or in areas with high concentrations of farms, which produce surpluses. Besides, it is a source of atmospheric CO 2 (the livestock sector generates 18% of CO 2 equivalent emissions). Currently, there is much interest in anaerobic digestion (AD) as a method of generating renewable energy from manures. However; AD does not reduce the nutrient content of PM which still needs to be recycled. One alternative to the problem of landspreading these digested manures may be to use thermochemical processes to produce renewable energy and biochar. Pyrolysis is a process whereby a biomass feedstock, such as woodchips, crop residues or manure, is heated to high temperatures in an oxygen-free atmosphere to produce a solid (biochar), a liquid and a gaseous fraction. The proportion of biochar, liquid and gas produced is dependent on the raw material, the heating rate, the reactor temperature and the residence time of the solid. The solid fraction can be an agricultural soil amendment rich in nutrients, whereas value-added products could be extracted from the liquid fraction. Alternatively, this liquid fraction together with the gaseous products can be combusted for energy purposes. This process could have some environmental and operational advantages over other thermochemical treatments [3]. Our group has done extensive research in the last 15 years on residue valorization via thermochemical treatments, especially on sewage sludge pyrolysis [4]. However, the works on pyrolysis digested PM are still scarce and further research is needed. The aim of the present work was to study the yields and properties of the products obtained from the pyrolysis of anaerobically digested and thermally dried pig manure (ADPM). The pyrolysis experiments were performed in a laboratory-scale fluidized bed plant at two different temperatures, 450 ºC and 525 ºC, with a solid feed rate of 3 g min -1 and a nitrogen flow of 3.5 LN min -1. The elemental and chromatographic composition of the product fractions (liquid, solid and gas), as well as their heating value, were determined. The main results obtained from the experimental work are: a. The liquid yield varies between 32% to 41% by weight, and the biochar yield within a range of 40% to 46%. Increasing temperature increases the liquid yield. b. Liquid from ADPM pyrolysis has two phases (organic and aqueous phase). Water is the main constituent in both phases (44% water in the organic phase and 75% in the aqueous phase). c. The heating value of the obtained biochar is similar to the one of dry and digested PM. d. Results seem encouraging in order to continue studying pyrolysis as a sustainable alternative for ADPM treatment. References: [1] Ro, K.S., et al., High-Temperature Pyrolysis of Blended Animal Manures for Producing Renewable Energy and Value-Added Biochar. Industrial & Engineering Chemistry Research, (20): p [2] Troy, S.M., et al., Effect of sawdust addition and composting of feedstock on renewable energy and biochar production from pyrolysis of anaerobically digested pig manure. Biomass and Bioenergy, (0): p [3] Cantrell, K.B., et al., Livestock waste to bioenergy generation opportunities. Bioresource Technology, (17): p

229 [4] Fonts, I., Gea, G., Azuara, M., Ábrego, J. and Arauzo, J., Sewage sludge pyrolysis for liquid production: A review. Renewable and Sustainable Energy Reviews, (5):p ACKNOWLEDGEMENTS. The authors want to express their gratitude to the University of Zaragoza for providing frame support for this work. Violeta Quispe wishes to thank Banco de Santander for her PhD grant.

230 CONTROL OF HAZARDOUS CHEMICAL SUBSTANCES IN TEXTILE MATERIALS R. Rodríguez, M.Vilaseca, M. Crespi and C. Gutiérrez-Bouzán INTEXTER, Universitat Politècnica de Catalunya-BarcelonaTech, C/Colom 15 (08222-Terrassa, Spain), Tel , Fax Chemical Engineering for Sustainable Development: Natural Resources Sustainability The textile articles are generated with a diverse range of techniques and often intensive chemical processes. Many of the man-made chemicals used to manufacture textiles are known to have intrinsic hazardous properties. For this reason, their release to the environment and effect on public health is a particular concern. In terms of legislation, the most toxic substances in textiles are: aryl amines, formaldehyde, carcinogenic dyes, phthalates, chlorinated phenols, nonylphenols, organotins, flame retardants and heavy metals. Due to their hazardous properties, all these compounds are regulated and controlled. The absence of these substances in textiles can be avoided by ensuring that the auxiliaries used throughout the textile process are to comply with the most demanding legislations. In addition, all of them are detectable with the available methods of extraction and analysis. The general regulatory is the EU General Product Safety Directive (2001/95/EC) which has as main objective to ensure the safety of products in the market. The tool used in the implementation of this directive is the RAPEX (Rapid Alert System for Non-Food Products), an early warning system which allows to restrict the marketing or use of products that are a risk to health and safety of consumers. The chemical regulation is the REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals), Regulation (1907/2006/EC). This regulation affects all sectors. In the textile industry, certain limits of toxic substances are established: azo dyes, nickel, cadmium, chlorophenols, phthalates, flame retardants, nonylphenols, dimethylfumarate and organotins. The eco-labels and manufacture brands also establish their own chemical substances limits. The most important ones are indicated in table 1. Table 1. Limit values for some of the most important toxic substances in textile materials. TOXIC LEGISLATION LIMIT VALUES SUBSTANCES or ECO-LABEL Aryl amines 30 ppm Reach Formaldehyde Babies(<3 years) < 20 ppm Direct skin contact < 30 ppm UE-Ecolabel No direct skin contact < 75 ppm Dimethylfumarate 0.1 ppm REACH Acknowledgments The authors thank the financial support from the Spanish Ministry of Economy and Competitiveness (CTM ). References [1] Reglamento (CE) nº 1907/2006 relativo al registro, la evaluación, la autorización y la restricción de las sustancias y preparados químicos. [2] DIRECTIVA 2001/95 CE DEL PARLAMENTO EUROPEO Y DEL CONSEJO de 3 de diciembre de 2001 relativa a la seguridad general de los productos.

231 RESPIROMETRIC BIODEGRADABILITY ASSESSMENT OF DYE-CONTAINING EFFLUENTS AFTER ELECTROCHEMICAL TREATMENT M. Vilaseca, V. López-Grimau, C. Gutiérrez-Bouzán and M. Crespi INTEXTER, Universitat Politècnica de Catalunya-BarcelonaTech, C/Colom 15, Terrassa, Spain, Tel , Fax Scientific Topic: Environmental Technology and Risk Analysis Textile dyes, mainly reactive dyes, are not properly eliminated in conventional biological treatments, being necessary the application of specific treatments for color removal before the discharge of dyeing effluents in the wastewater treatment plant. In this study, synthetic dyeing and washing baths are collected from cotton fabrics dyeing process with a trichromie of reactive azo/chlorotriazine dyes. These effluents are treated in an electrochemical reactor constituted by Ti/PtOx electrodes at current density of 6mA/cm 2. The characterization of untreated and treated samples is shown in Table 1. The electrochemical treatment achieves 98% color removal. Table 1. Characterization of untreated effluents and effluents electrochemically treated Dyeing Color Acceptable TOC Conductivity Cl ph Conc. effluent (Pt-Co) Color value* (mg/l) (ms/cm) (g/l) Untreated 12,000 No Treated 200 Yes *Color not visible at dilution 1/20 (Spanish legislation RD 849/1986). The presence of high Cl - concentration, common in the reactive dyeing process, promotes the indirect oxidation of the dye by generation of Cl 2. In order to evaluate if the Cl 2 -containing effluents can cause operational problems when they are discharged to the biological treatment plants, a respirometric biodegradability assessment is performed with an electrolytic respirometer BI The biodegradability and toxicity of the treated effluents with and without Cl 2 (Figure 1) is determined. 30 Consumption (mg O2/L) reference initial final without Cl2 final with Cl Time (h) Figure 1. Respirometric biodegradability assessments before and after the electrochemical treatment. The electrochemical decolorization treatment generates more biodegradable effluents than untreated effluents (higher O 2 consumption), mainly when Cl 2 is removed previously to the biological treatment. Discolored samples which contain Cl 2 require a longer period of adaptation. In addition, it can be stated that the electrochemical treatment does not generate toxic products, as inhibitory phenomenon are not observed In summary, decolorized reactive dyeing effluents can be discharged to the wastewater treatment plant. Acknowledgements: The authors thank the Spanish Ministry of Economy and Competitiveness (MINECO) for its financial support (Project CTM ).

232 DENITRIFICATION IN AN UP-FLOW STIRRED PACKED-BED REACTOR (USPBR) USING BIOLOGICAL ACTIVATED CARBON Y. García-Martínez, A. Fortunyand A. Fabregat Departament d'enginyeria Química, Universitat Rovira i Virgili, Av. Païssos Catalans 26, Tarragona, Spain, Tel.: and fax: , Departament d'enginyeria Química, Universitat Politécnica de Catalunya, Av. Víctor Balaguer S/N, Vilanova i la Geltrú, Spain. Scientific Topic: Advanced Techniques for Effluent Treatment Nitrate concentration in water aquifers has steadily been increasing over the years mainly due to the extensive use of nitrate containing compounds in different industries and their subsequent discharge in industrial, domestic or animal wastes. Conventional physical chemical methods for nitrate removal as ion exchange, reverse osmosis and electro-dialysis are expensive and require further treatment or disposal [1]. Biological removal of nitrogen has been recognized as the principal method in terms of cost, removal efficiencies and implementation [2]. Anaerobic digestion is widely used to remove organic matter from high strength wastewaters because of its relatively low sludge production and energy needs, compared to aerobic treatments [3]. The biological denitrification as an alternative treatment process converts nitrates to harmless nitrogen gas and enables the purification of water contaminated with nitrate due to the high specificity of denitrifying bacteria [1]. For denitrification to take place, there must be a source of organic carbon, wich is the electron donor to be oxidize by nitrite or nitrate [4]. Our research group has been working in the removal of azo dyes using an up-flow stirred packed-bed reactor (USPBR) filled with biological activated carbon (BAC) and using sodium acetate as electron donor. This study reported that the USPBR with BAC, is an effective and promising system for anaerobic azo dye degradation. The objective of the present work is to evaluate the existing system with nitrate as a new pollutant, using two different carbon sources, sodium acetate and methanol; additionally the amount of activated carbon (AC) in the packed-bed will be varied. It is expected that the anaerobic denitrification takes place in the existing USPBR with BAC obtaining high conversion rates at short space times as in the anaerobic azo dye degradation regardless the carbon sources used in the reduction of nitrate. Bibliography [1] Foglar, L., Gašparac, D. Desa. andwat. Treat. 2013; 51: [2] Shi, Z., Zhang, Y., Zhou, J. et al. Bioresour. Technol. 2013; 148: [3] Bernet, N., Delgenès, N., Delgenès, J.P., Moletta, R. Water Sci. Technol. 2001; 43(3): [4] Akunna, J.C., Bizeau, C., Moletta, R. Environ. Technol.1992; 13(9):

233 METHODOLOGY FOR ECO-EFFICIENT AND SAFE COMBUSTION OF GAS REFINERY J. Saavedra, V. Kafarov, L. Meriño, A. Sierra, M Gómez Universidad Industrial de Santander, Carrera 27 calle 9 Bucaramanga- Colombia, phone (57) , Scientific Topic: 2. Chemical Engineering for Sustainable Development. 2.2 Environmental Technology and Risk Analisys. (Process Safety Management) Primary fuel for combustion equipments can be natural gas or gas mixtures from the different processes occurring in the chemical, petrochemical and oil refining; the composition of these mixtures of fuel varies according to the characteristics of the fuels used, so that the combustion equipment presents operating parameters and conditions are continuously affected by the change in the fuel composition, it represent a risk for the stability of the process, generating environmental problems and structural damage due to corrosion in the equipment, breakage and deformation. To address the problems caused by the variability of the composition of fuels, we propose the design of a methodology based on the criteria of eco-efficiency, which integrates energy efficiency, environmental and the combustion equipment integrity. It presents the analysis of the combustion process in a furnace representing the petroleum refining industry. The starting point is the study of the physicochemical properties of the fuels, the phenomenological study of the combustion gases, evaluation of pollutant emissions and analysis of the parameters affecting the structure of the furnace. It presents analysis of combustion process in a furnace using at petroleum refining industry. First, operating conditions and composition of the gases used as fuel in furnaces were established; then, the mixtures were identified and representative cases involving operation of furnaces using Hysys and Premix program were simulated. The simulation results were compared with gas monitoring data taken at a refinery and compared with data obtained in the laboratory. According to information obtained by a review of historical data, computer simulation and experimental data, mathematical models were fitted to identify indicators for the integrated management of the combustion process. Thus, the proposed methodology includes management of combustion processes according to ISO 50001, with an index of eco-efficiency that allows decision making to the appropriation and adaptation of eco-efficient technologies for combustion having as energy efficiency constraints, to ensure the necessary energy requirements the process, environmental regulations regarding CO 2 emissions and damage in the furnaces when exposed to combustible mixtures of varying composition. Procedures defined for management energy system allowed evaluating fuel characteristics and products of combustion for establishing optimal mixtures with minimum environmental impact and favorable operational conditions. Optimum mixtures for ensuring compliance of the conditions of safe process and minimal environmental emissions presents Low Heating Value (LHV) around kcal/m 3. Composition of these mixtures can be described as combinations of methane between 40 and 60%, hydrogen 10 to 20% ethane and propane and between 2 and 10%.

234 MICRORESPIROMETRY AS AN EFFECTIVE TECHNIQUE FOR MONITORING BIOMASS GROWTH AND ACTIVITY IN CHALCOPYRITE BIOLEACHING PROCESSES E. Benzal, E. Morral, X. Guimerà, X. Gamisans, M. Solé and A. D. Dorado Department of Mining Engineering and Natural Resources, Universitat Politècnica de Catalunya, Bases de Manresa 61-73, Manresa, Spain * Phone: , Fax: Environmental Technology and Risk Analysis: Waste Minimization and Treatment Bioleaching is a technology that uses specific bacteria to extract valuable metals from minerals. The advantages of this technique over traditional methods (chemical leaching) include low cost, high efficiency and environment friendliness. Bioleaching allows to recovers metals from low grade ores at conditions where traditional techniques are not efficient and then, mining waste can be valorized and the impact on the environment is reduced. Chalcopyrite (CuFeS 2 ) is the most abundant of the copper sulfides but at the same time, it is the most refractory too. The main microorganisms involved in the bioleaching of sulfide minerals are iron- and sulfur-oxidizing bacteria (Rawlings 2002). In the bioleaching process the ion Fe 3+ plays an important role since it assists the process oxidizing the ore (Dorado et al. 2012). As a result, ferric iron is reduced to ferrous iron and then, the bacteria catalyze the cyclic regeneration of ferrous to ferric to promote continuous leaching of the sulfide mineral. However, Fe 3+ ions have a low solubility and they can lead to the precipitation of iron (III) hydroxides and other ferric complexes such as jarosite, depending on the impurities of the mineral and the mineral medium used to keep the biological activity. The precipitation affects negatively the mass transfer process and it causes the decrease in the extraction yield of the metal (Zhang et al. 2008). Moreover, the presence of precipitates makes the optical methods of monitoring not suitable for controlling the process. In this case, the use of microrespirometry allows the monitoring of biomass growth by means of low sampling volume (<1mL) and high precision. Additionally, negative effects over the activity of microorganisms can be detected immediately and corrected. In this work, the microrespirometry was used to evaluate the effect of the mineral medium composition in the bioleaching of copper from a chalcopyrite ore. The microbial consortium was obtained from a biotrickling filter treating high loads of H 2 S and the copper extraction efficiency was monitored by atomic absorption. As an example, Figure 1 shows the evolution of the respirometric rates at different moments along the experiment. DO(ppm) Day 1 5 Day 4 Day t(s) Figure 1: Respirometric tests during the bioleaching process. References: Dorado A.D., Solé M., Lao C., Alfonso P., Gamisans X., (2012) Effect of ph and Fe(III) ions on chalcopyrite bioleaching by an adapted consortium from biogas sweetening. Minerals Engineering 39: Rawlings, D. E, (2002). Heavy Metal Mining Using Microbes. Annual review of microbiology 56: Zhang Y.-S., Quin W.-Q., Wang J., Zhen S.-J, Yang C.-R, Zhang J.-W, Nai S.-S, Qiu G.-Z, (2008) Bioleaching of Chalcopyrite by Pure and Mixed Culture. Transactions of Nonferrous Metals Society of China 18(6):

235 ADSORBENTS PREPARATION FROM TEXTILE WASTE MATERIAL AND THEIR APPLICATION IN DYESTUFFS REMOVAL A.A. Peláez Cid 1, B.M. Espíndola Durán 1, J. Vázquez Bautista 1, R. Radillo Ruíz 2 1 Facultad de Ingeniería de la Benemérita Universidad Autónoma de Puebla, Edificio 108A, Ciudad Universitaria, Colonia San Manuel, Puebla, Pue., México, CP 72570, Tel ext. 7632, 2 Grupo Carolina S.A., Naucalpan de Juárez, México. Scientific topic of the work: Environmental Technology and Risk Analysis (Advanced Techniques for Effluent Treatment) ABSTRACT One of the main problems that textile-dying facilities face during their operations is environmental pollution caused by colored effluents. Among the solid residues that the textile industry produces, fabrics classified as waste material or those disposed of after their use are found. Considering these last two situations, using fabrics made from cotton as precursors to prepare effective adsorbents represents an ecological proposal to treat colored effluents. The preparation of three adsorbents obtained from cotton fabric wastes and their application in the removal of textile dyestuffs present in aqueous solutions and wastewater are presented in this work. A cellulosic adsorbent (TelaNaOH) was prepared treating the fabric with an aqueous Sodium Hydroxide solution. Two carbonaceous adsorbents were also prepared: One was physically activated at 673 K with water vapor (CarTelaF) and another was chemically activated at 673 K with a Phosphoric Acid solution (CarTelaQ). Micrographs show that both TelaNaOH and CarTelaF are fibrous materials while CarTelaQ is granular. Adsorption isotherms for Methylene Blue were constructed at 303 K. Only the carbonaceous adsorbents fitted Langmuir's Model which allows determination of their specific surface area: 879 and 336 m 2 /g for CarTelaQ and CarTelaF respectively. For CarTelaQ, the specific surface area was also obtained by means of Nitrogen adsorption at 77 K, and it was 1517 m 2 /g. Aqueous solutions containing 500 mg/l of basic (Basic Blue 9 and Basic Violet 3) and acid (Natural Red 4 and Acid Blue 74) type dyestuffs were treated and high removal percentages (up to 98 for basic and 80% for acid dyestuffs) were obtained using CarTelaQ. Different textile wastewaters containing vat (indanthrenes) and reactive dyestuffs were also treated. CarTelaQ proved the most effective, followed by CarTelaF, and TelaNaOH last. The improvement in quality of the wastewater treated was evaluated. The following parameters were quantified and compared: Color, ph, total solid content, electrical conductivity, and COD before and after the adsorption treatment.

236 ALUMINA-BASED CATALYSTS FOR PP-CWAO OF AQUEOUS PHENOL SOLUTIONS C. García-Figueruelo, M. Munoz, Z. M. de Pedro, A. Quintanilla, J.A. Casas, J.J. Rodriguez Sección de Ingeniería Química, Facultad de Ciencias, Universidad Autómona de Madrid, Cantoblanco Crta. Colmenar km15, Madrid, Spain. 2. Chemical Engineering for Sustainable Development Environmental Technology and Risk Analysis. Waste Minimization and Treatment. Wet air oxidation (WAO) is a well-established technology for the removal of pollutants from industrial process water and wastewater. The use of H2O2 as a radical promoter (PP-WAO) allows the achievement of higher degrees of oxidation and mineralization. Additionally, a catalyst (PP-CWAO process) can be added in order to employ milder operating conditions and reduce hydrogen peroxide consumption. Typically, homogeneous catalysts have been employed such as Fe, Cu or Mn salts. The heterogeneous catalysts have been mainly limited to the use of activated carbons as the support for Fe and Cu, or as catalysts themselves. Herein, the use of alumina-based catalysts is explored in order to increase the degrees of oxidation and mineralization in the treatment of phenolic wastewater using the PP-CWAO process. Different catalysts have been tested: 4%wt.Feox/ Al2O3, 4%wt.Femag/ Al2O3, prepared by the impregnation method followed by calcination and, in the case of the latter, also by reduction, in order to obtain a ferromagnetic catalyst [1]. In addition, Fe2SO4 and Al2O3 were catalytically tested to elucidate the effects of the metallic phase and of the support. The oxidation runs were conducted in a pressurized batch reactor (75mL) under the following operating conditions: T=127ºC, P=8atm, QO2=50mL/min, ph=3, C0,Phenol=1 g/l, C0,H2O2=2.5 g/l, Ccat=5.3g/L. Phenol conversion was slightly enhanced in presence of the four tested catalysts, achieving from 95 to 100% phenol conversion after 1 h of reaction. On the contrary, significant differences were found in the case of TOC removal, as seen in Figure 1. In the absence of catalyst, TOC achieved an asymptotic value of 40% conversion. This value was doubled with the presence of a solid catalyst, reducing the refractory TOC fraction up to almost 20%. These results are explained by the adsorption of the oxidation aromatic intermediates on the X TOC alumina surface (as shown by TGA analysis), occurrence that significantly contributes to the TOC reduction rate. The presence of Fe does not improve the alumina activity. To conclude, bare Al2O3 is a feasible catalyst for PP-CWAO and further research is under way to evaluate its stability and adequate performance. [1] Munoz, M. de Pedro, Z.M., Menendez, N., Casas, J.A., Rodriguez, J.J. A ferromagnetic gamma-aluminasupported iron catalyst for CWPO. Application to chlorophenols. Applied Catalysis B-Environmental, vol 136, pp , without catalyst Al 2 O 3 Fe ox. /Al 2 O 3 Fe mag./al 2 O 3 Fe 2+ (10 ppm) t (min) Figure 1. TOC removal profiles with different catalysts

237 DECOLORIZATION OF BAKER S YEAST EFFLUENT BY ULTRASOUND Didem Ildırar 1, Serap Fındık 1,* 1 Hitit University, Engineering Faculty, Chemical Engineering Department, 19100, Çorum, Turkey, phone : , fax: * Scientific Topic: Sustainable Chemical Engineering Baker s yeast effluents contain various pollutants that cannot easily be degradated by biological processes. Thus, it is necessary to use more effective processes, such as ozonation, fenton oxidation, coagulation/flocculation and ultrasound. Ultrasound is increasingly being seen as having a potential for the use in the treatment of wastewater. Sonochemical oxidation employs the use of ultrasound resulting in the cavitation phenomena which is defined as the phenomena of the formation, growth and subsequent collapse of microbubbles. Ultrasound irradiation destructs the contaminants in water because of localized high concentrations of oxidizing species, high localized temperatures and pressures. Baker s yeast industry uses molasses as a raw material. Molasses is end product of sugar industry. Wastewater from molasses processing presents large amount of coloured substances that give dark color and high organic load to the effluents. Dark colour prevents sunlight penetration and reduces photosynthetic activity and dissolved oxygen level of surface waters. In this study, ultrasound was employed for removal of color and chemical oxygen demand (COD) from baker s yeast effluent. Baker s yeast effluent was supplied from a factory which is located in the north of Anatolia. An ultrasonic homogenizator used for this study. Its operating frequency is 20kHz. The effect of operational parameters such as power, cycle, volume of wastewater, dilution ratio on decolorization and COD removal was investigated. Decolorization of baker s yeast effluent increased with increases of ultrasonic power and wastewater volume. 26.7% decolorization obtained at a power of 110W. There was no significant COD removal during the ultrasonic treatment. Keywords: Ultrasound, baker s yeast effluent, decolorization, chemical oxygen demand Acknowledgements The authors thank to Hitit University for their financial support of this project under contract of MUH

238 Evaluation of a commercial nano-tio 2 suspension photocatalytic activity in the 2,4 dichlorophenol oxidation. S. Escuadra, M.P. Ormad, A.M. Laseras, J. Gomez and J.L. Ovelleiro. Grupo Calidad y Tratamiento de Aguas, dpto. Ingeniería Química y Tecnología del Medio Ambiente. Torres Quevedo, EINA. C/ Maria de Luna 3, 50018, Zaragoza , Advanced Techniques for Effluent Treatment Phenol and its chlorinated derivatives are toxic compounds which contribute to water pollution. Chlorophenols are extensively used and generated in industrial processes as herbicide, fungicide, pesticide, solvent, paint and wood preservative and pulp industries [1] and [2]. Chlorophenols are listed among top priority pollutants due to their toxicity and water pollution contribution [3]. Heterogeneous photocatalysis is an Advance Oxidation Process (AOP) which is able to degrade organic micropollutants. Titanium dioxide is the most indicated semiconductor to use in photocatalytic water treatment due to its low toxicity, resistance to photocorrosion, availability, catalytic efficiency and relatively low cost. This treatment can be carried out by immobilized or fixed TiO 2 or with a TiO 2 suspension [3], [4], [5], [6] y [7]. The main objective of this research work is to analyse the 2,4 dichlorophenol (2,4-DCP) degradation. The used samples are distilled water with an initial concentration of 100 mg/l 2,4-DCP. The treatment consists of an heterogeneous photocatalytic treatment (solar chamber, nm wavelength, irradiation intensity of 500 W/m 2 and treatment time intervals from 30 to 240 minutes) using two different types of commercial TiO2 in a range concentration between 0.1 to 4 g/l at ph 7. The TiO 2 Levenger (marketed in a nano-tio 2 suspension) is compared with Evonik P25 TiO 2 (formerly known as Degussa P25, marketed in powder, worldwide reference reactive). The sedimentation capacity of both TiO 2 is also evaluated for being removed of the treated water with or without chemical precipitation by coagulation-flocculation (jar-test; 200 rpm 4 minutes and 40 rpm 20 minutes) with FeCl 3 (0-150 mg/l of Fe 3+ ), Ca(OH) 2 (ph between 7 to 10) and/or polyacrylamide (1mg/l). The results showed a 2,4-DCP degradation of % using both TiO 2 with an 1-4 hours treatment. It was checked that Degussa TiO 2 sedimentation depends more on the ph than Levenger TiO 2 sedimentation. Chemical precipitation increased the sedimentation rate. In general, Levenger TiO 2 showed a higher sedimentation rate in all carried out experiments, possibly due to it contains some additives which were detected by XR diffraction and XR fluorescence. References [1] S. Lathasree, A.N. Rao, B. Siva Sankar, V. Sadasivam, K. Rengaraj. Heterogeneous photocatalytic mineralisation of phenols in aqueous solutions. J. Mol. Catal. A: Chem., 223 (2004), p. 101 [2] M. Kilic, Z. Cinar. Hydroxyl radical reactions with 4-chlorophenol as a model for heterogeneous photocatalysis. J. Mol. Struct. THEOCHEM, 851 (2008), p. 263 [3] M. Pera-Titus, V. Garcia-Molina, M.A. Banos, J. Gimenez, S. Esplugas Degradation of chlorophenols by means of advanced oxidation processes: a general review. Appl. Catal. B: Environ., 47 (2004), pp [4] K. Nishida, S. Ohgaki. Photolysis of aromatic chemical compounds in aqueous TiO2 suspension. Water Sci. Technol., 30 (9) (1994), pp [5] C. Turchi, D.F. Ollis. Photocatalytic degradation of organic water contaminants: mechanisms involving hydroxyl radical attack. J. Catal., 122 (1990), pp [6] B. Bayarri, J. Gimĕnez, D. Curcó, S. Esplugas. Photocatalytic degradation of 2,4-dichlorophenol by TiO2/UV: kinetics, actinometries and models. Catal. Today, 101 (2005), pp [7] M. Umar, H.A. Aziz. Photocatalytic Degradation of Organic Pollutants in Water. Organic Pollutants - Monitoring, Risk and Treatment", book edited by M. Nageeb Rashed (2013), pp ISBN

239 PYROLYSIS OF TEXTILE WASTES: INTEGRATED KINETIC STUDY AND EVOLVED GAS ANALYSIS Gamzenur Özsin and Ayşe E. Pütün * Anadolu University, Department of Chemical Engineering, Eskişehir, Turkey * phone: ; fax: Scientific Topic: 2. Chemical Engineering for Sustainable Development 2.2 Environmental Technology and Risk Analysis In this study, pyrolysis of textile wastes were carried out in a thermogravimetric analyser (TGA) coupled with mass spectrometer (MS) and Fourier transform infrared spectrometer (FT-IR). Different heating rates (5, 10, 20 and 40 C/min) were used to summarize the pyrolysis characteristics through analysing the change of mass loss by heating textile waste from room temperature to 1000 C under nitrogen atmosphere. According to obtained TG and dtg thermograms, rate of mass loss changed with increasing heating rate and maximum dtg peak shifted to higher temperature regions. Temperature regimes were selected for studying the non-isothermal kinetics and dependences of the activation energy on the degree of conversion. For this purpose, different iso-conversional methods (Friedmann, Flynn-Wall-Ozawa, and Kissinger-Akahira-Sunose) were applied to non-isothermal thermogravimetric data and results were compared among themselves. All the three methods were found to be beneficial to predict pyrolytic behaviour of textile wastes, although there were small variations in the quantitative value of activation energy. Moreover, released gases determined by MS and FT-IR spectra during pyrolysis and temperature-dependent profiles of main volatile products were obtained. Acknowledgments. The authors would like to thank Anadolu University Scientific Research Council for the financial support of this work through the projects 1306F253.

240 BIOSORPTIVE REMOVAL OF HEAVY METAL IONS ONTO GRASS WASTE Murat Kılıç, Gamzenur Özsin, Ayşe E. Pütün * Anadolu University, Department of Chemical Engineering, Eskişehir, Turkey * phone: ; fax: Scientific Topic: 2. Chemical Engineering for Sustainable Development 2.2 Environmental Technology and Risk Analysis Biosorption is an innovative technology that employs inactive and dead biomass for the recovery of heavy metals from aqueous solutions. Generally harvest and industrial waste and non-edible biomass species are desired materials for evaluating as biosorbent material rather than edible ones. In this study, grass waste was evaluated as a low-cost biosorbent material for the removal of from aqueous solutions. The influences of ph, biosorbent dosage, initial metal ion concentration, contact time and solution temperature were studied in batch mode. Isotherm models were used to model the experimental equilibrium data. Experimental data were also used for determining the biosorption kinetics. Thermodynamic parameters were calculated to predict the nature of biosorption. The study showed that, grass waste seems to be an effective, low cost, and environmentally friendly biosorbent material for the removal of heavy metals from aqueous solutions.

241 SLOW PYROLYSIS KINETICS AND THERMOGRAVIMETRIC CHARACTERISTICS OF CRUDE OIL SLUDGE Murat Kılıç 1, Gamzenur Özsin 1, Esin Apaydın-Varol 1, Ersan Pütün 2, Ayşe E. Pütün 1,* 1 Anadolu University, Department of Chemical Engineering, Eskişehir, Turkey 2 Anadolu University, Department of Materials Science and Engineering, Eskişehir, Turkey * phone: ; fax: Scientific Topic: 2. Chemical Engineering for Sustainable Development 2.2 Environmental Technology and Risk Analysis Crude oil sludge generated from petroleum industry during crude oil transportation, storage and refinery process contains various hazardous hydrocarbons and pyrolysis process offers an important advantage for both disposal and conversion of such wastes. This study aims to investigate pyrolysis kinetics of petroleum sludge obtained from of a local petroleum refinery (Turkish Petroleum Refineries Co.-TÜPRAŞ) from the bottom of crude oil storage tank. Pyrolysis experiments were performed by a thermogravimetric analyser (TGA) under inert atmosphere. A non-isothermal method developed by Coats and Redfern have been utilized to calculate the kinetic parameters using the obtained thermogravimetric data. TG and dtg curves indicate the stages occurred during decomposition and different reaction orders were assumed to find out best fitting of experimental data with the model equations. The results of kinetic analysis showed that pyrolysis of petroleum sludge cannot be considered as a single reaction, due to the complex organic and inorganic content of the sludge. Pyrolysis reactions of petroleum sludge were based on successive steps under different sub temperature intervals. A further prediction of reaction orders according to regression analysis were performed and kinetic triplet was calculated. Acknowledgments. The authors would like to thank Anadolu University Scientific Research Council for the financial support of this work through the project 1202F030.

242 Assessment of iron chelates efficiency for photo-fenton at neutral ph Antonella De Luca 1, Renato F. Dantas 2, Santiago Esplugas 1 Dpt. of Chemical Engineering 1 Universidad de Barcelona, C/Martí i Franqués, 6th floor, 08028, Barcelona, Spain, Office: (+34) , Fax: (+34) , 2 Faculty of Technology, University of Campinas, Paschoal Marmo 1888, , Limeira, Brazil Scientific Topic: 2.2. Environmental Technology and Risk Analysis Over the last decades, increasing attention has been focused on several types of compound identified as contaminant of emerging concern (CECs). Due to their recalcitrant behavior, the presence of CECs in the environment can be essentially attributed to the degradation gaps of conventional Wastewater Treatments Plants (WWTPs). The harmfulness of CECs, even at small concentrations as well as, property of bioaccumulation and persistence, make them extremely dangerous for the human health. Thus, it s of fundamental importance provides WWTPs of specific treatments able to eliminate these recalcitrant compounds. The scientific community is constantly researching about novel treatments able to fill this degradation gaps. Advanced Oxidation Processes (AOPs), which are treatments technology based on the production of HO radicals able to oxidize or even mineralize almost all the organic molecules, are considered one of the most useful treatments to achieve CECs degradation. Among the AOPs, Fenton and photo-fenton processes are particularly powerful to achieve CECs removal. Nevertheless, some setting requirements of Fenton processes have limited the application at industrial scale. One of the most limits of Fenton process is the necessity to operate a tight control of the ph in order to avoid iron precipitation, which narrow optimum range of work is essentially far from the normal values of the WWTP effluents. Scientific community is working on the improvement of the operating conditions of Fenton processes in order to improve the applicability in wastewater treatments (Fenton and photo Fenton like processes). In this study photo-fenton like at neutral ph was applied for sulfamethoxazole (SMX) removal. In order to avoid iron precipitation, chelating agents were used to keep soluble the iron at circumneutral ph. Fe(III) was used to encourage the chelate stability and four chelating agents were tested (EDTA, NTA, oxalic acid and tartaric acid). Firstly, the correct molar ratio Ligant:Fe(III) was investigated in order to find out the correct proportion able to ensure the chelation of the total iron content. Afterwards, iron chelates were used as catalyst of photo Fenton process and SMX efficiency was checked to compare the catalytic activity of the chelates. Iron loss was also monitored to investigate the stability of the chelate under HO radical attack. Finally, a cost-benefit analysis was carried out to take into account not only the achievable efficiency but also, the TOC increase related with the use of chelating agent as well as the different costs that have to be supported employing the different compound tested. Among the chelating agents tested, the two aminopolycarboxylicacids (EDTA and NTA) were those who allowed achieving the higher efficiency in terms of SMX degradation (77.3%, 82.2%, 66.6%, 14.3% respectively with chelates od EDTA, NTA, oxalic acid and tartaric acid) with minimum loss if iron. Moreover, due to the high strength of chelation, higher efficiency can be obtained with minimal TOC increase. Finally, the better biodegradability of NTA respect EDTA, as well as, the best cost-benefit ratio of NTA chelates among all those tested, make it a useful option to perform photo Fenton like at neutral ph. Acknowledgements The authors thank the Ministry of Science and Innovation of Spain (project CTQ and Consolider- Ingenio 2010 CSD ) for their financial support.

243 ADVANCED Co/Ce/H-ZSM-5 CATALYSTS FOR THE DEEP OXIDATION OF CHLORINATED ORGANIC COMPOUNDS B. de Rivas, C. Sampedro, J. González-Prior, R. López-Fonseca and J.I. Gutiérrez-Ortiz Chemical Engineering Department, Faculty of Science and Technology Universidad del País Vasco UPV/EHU, P.O. Box 644, E-48080, Bilbao Phone: ; Fax: ; Scientific Topic 2.2: Environmental Technology and Risk Analysis Chlorinated volatile organic compounds (Cl-VOCs) are common industrial solvents and by-products from the manufacture of chlorinated chemicals such as plastics. These environmentally hazardous compounds are often carcinogens and mutagens and may deplete stratospheric ozone. However, since for a variety of applications, chlorinated hydrocarbons are still indispensable, techniques to avoid or reduce emissions of these compounds have to be developed. When the recovery of these compounds is not desired or economically feasible catalytic abatement for Cl-VOC-containing waste gases is one of the most important air pollution control techniques. The use of a catalyst opens up a different reaction pathway and allows oxidation to proceed at lower temperatures, which results in three technical advantages: lower energy requirements, diminished formation of NO x, and lower capital costs (due to the more compact design and lower insulation needs). The technical problem of depollution by chemical catalyzed reaction basically consists of three different aspects: activity, selectivity, and durability. One of the main goals when designing a catalyst apart from finding a composition that lowers the temperature required for the conversion is to lead to complete oxidation products, i.e. CO 2, H 2 O and HCl/Cl 2. This is the main objective of this work: design an efficient catalyst for the deep oxidation of 1,2-dichloroethane (DCE), compound chosen as model chlorinated compound. Our previous works concluded that ceria resulted an adequate catalyst for this specific environmental application. However, in spite of oxidising the DCE at relatively low temperature, it generated chlorinated byproducts whose decomposition required high temperatures (500 ºC). In addition, significant quantities of CO were also found at high temperatures. Therefore, in order to overcome these disadvantages, the ceria (12 wt.%) was deposited over a high surface support such as a H-ZSM-5 zeolite, via ethanolic impregnation (CeO 2 /Z-IME) [1]. As a result the temperature required for DCE decomposition was substantially diminished. In particular a reduction of 125 and 150 ºC was found in the values of T 50 and T 90, respectively, taking as reference the bulk ceria sample. This important shift in the oxidation temperature towards lower values was associated with a good synergy between the redox properties of ceria and the high surface and Brønsted acid sites of the zeolite. However, significant amounts of CO were still obtained. Next the viability of improving the activity of the CeO 2 /zeolite sample by adding cobalt oxide to its formulation was examined [2]. Hence, the introduction of cobalt oxide considerably inhibited the by-products formation and led the total oxidation of DCE towards CO 2 at much lower temperatures (Figure 1). Therefore, an optimum formulation of catalyst was found for chlorinated compounds oxidation (Co 3 O 4 (14)/CeO 2 /Z-IME). Finally, another point of interest was to evaluate the durability of this improved catalyst. Its performance was evaluated by analysing the evolution of conversion with time on stream for 72 h at the temperature needed for 70% of conversion. The incorporation of cobalt oxide to the catalyst noticeably enhanced the stability of the resultant material. Although at the beginning of the reaction (first 5 h) a slight decrease of activity was found mainly owing to the cobalt chlorination, the activity was then maintained with time on line Figure 1. Profiles of CO 2 production in DCE oxidation with the different catalysts ACKNOWLEDGEMENTS The authors wish to thank the Universidad del País Vasco UPV/EHU for the financial support of this work. [1] B. de Rivas, R. López-Fonseca, C. Jiménez-González, J.I. Gutiérrez-Ortiz, J. Catal 281 (2011) [2] B. de Rivas, C. Sampedro, E.V. Ramos-Fernández, R. López-Fonseca, J. Gascon, M. Makkee, J.I. Gutiérrez-Ortiz, Appl. Catal. A 456 (2013) Concentration CO 2, ppm Co 3 O 4 (14)/CeO 2 /Z-IME Temperature, ºC CeO 2 /Z-IME H-ZSM-5

244 SORPTION OF PHOSPATE AND ZINC ONTO HEMATITE AND MAGNETITE AS A MECHANISM OF ATTENUATION OF CONTAMINATION IN AGRICULTURAL SOILS Maria Martínez 1, Vicens Martí and Javier. Giménez Department d Enginyeria Quimica, ETSEIB, Universitat Politècnica de Catalunya (Barcelona Tech (UPC)), Av. Diagonal, 647, Barcelona (Spain), tel rosario.martinezpc.edu 2. Chemical Engineering for Sustainable Development 2.2. Environmental Technology and Risk Analysis Excess of natural and synthetic fertilizers applied to agricultural soils is a well-known source of contamination of nitrates and potential source of contamination of metals (copper and zinc) and phosphates (Alloway 2010). Mineral phases such as iron oxides, are present in agricultural soils and they might play a main role in the retardation of the transport of different contaminants (Giménez et al. 2007). The present communication shows the experimental study of sorption of phosphate and zinc onto magnetite (Fe 3 O 4 ) and hematite (Fe 2 O 3 ) in order to investigate the role of these oxides as potential attenuating phases to incorporate contaminants when fertilizers are used. Batch experiments were performed by mixing 0,2 grams of mineral and 15 ml of aqueous solution (phosphate or zinc) at different conditions (contact time, ph and concentration of phosphates and zinc). Kinetic results of phosphate sorption were satisfactory adjusted considering a pseudo second-order reaction model, with rate constants 4, and 3, m 2 mol -1 h -1 for magnetite and hematite, respectively. Equilibrium studies were performed after 72 h of contact time. The initial ph of the solutions ranged from 4 to 9, but the equilibrium ph was always around 7. This value is very close to the point of zero charge (ph zpc ) of the solids, determined to be 6,4 and 6,2 for magnetite and hematite, respectively. The total phosphate concentration ranged from 10-5 M (1 mg L -1 to 5, M (55 mg L -1 ). Langmuir isotherms were satisfactory fitted in both iron oxides and fitting parameters are shown in the following table: Mineral Qmax b R 2 ( mol m -2 ) (L mol -1 ) Magnetite 5, , ,998 Hematite 2, , ,994 The main objective of this work was to determine if zinc sorption was favoured in magnetite and hematite already saturated with phosphate, because the formation of phosphate complexes on the surface of the solids could change the net charge of the solids facilitating the sorption of positively charged species such as zinc. In this sense, the sorption of different concentrations of zinc ( mol L -1 ) was tested in solids saturated with phosphate. The results obtained showed a slight increase of zinc adsorbed onto minerals saturated with phosphate. This indicated that the presence of phosphate facilitated the sorption of zinc on the iron oxides. The main conclusion of this work is that magnetite and hematite in agricultural soils adsorb phosphate from fertilizers and that this sorption slightly attenuates the impact of zinc on groundwater. The present research work has been performed under the project ATTENUATION (CGL C04-0) funded by Spanish Ministry of Science and Innovation. References ALLOWAY, B. J. Heavy Metals in Soils. Editorial Springer London, 2010.

245 GIMÉNEZ J., MARTÍNEZ, M., DE PABLO, J., ROVIRA, M., DURO, L. Arsenic sorption onto natural hematite, magnetite and goethite. Journal of Hazardous Materials 141 (2007)

246 NICKEL REMOVAL FROM EXHAUSTED ELECTROPLATTING BATHS BY USING VEGETABLE WASTES María Martínez 1, Isabel Villaescusa 2, Nuria Fiol 2, Nuria Miralles 1 and Antonio Florido 1 1 Departament d'enginyeria Química, ETSEIB, Universitat Politècnica de Catalunya BarcelonaTech (UPC), Av. Diagonal, 647, Barcelona, Spain, tel , 2 Dept. Eng. Química. Escola Politècnica Superior. Universitat de Girona. c/ Mª Aurèlia Capmany, 61, Girona, Spain 2. Chemical Engineering for Sustainable Development 2.2. Environmental Technology and Risk Analysis During the last years our research group has been studying the use of industrial vegetable wastes as grape stalks and exhausted coffee to remove metals ions such as Ni(II), Cu(II), Pb(II), Zn(II), Cd(II) or Cr(VI) and Cr(III) in aqueous solution from the point of view to use these wastes as biosorbents in a low cost alternative to activated carbon for wastewater treatment. The optimal experimental conditions for the removal of each of these metal ions in synthetic solutions by using both biosorbents were determined in previous studies [Villaescusa et al. 2004; Martínez et al. 2006; Valderrama et al ]. In this work, the performance of grape stalks and exhausted coffee for the removal of nickel ions from an exhausted electroplating bath of a metal finishing industry from Barcelona (Spain) has been investigated. Batch and column experiments were carried out at room temperature by using grape stalk wastes (particle size mm), meanwhile in the case of exhausted coffee, two different particle size ranges were used, mm and mm for batch and column experiments, respectively. Kinetics and equilibrium studies were carried out in batch mode to determine the equilibrium contact time and to obtain the sorption capacity of sorbents. The data in both studies have been treated by using different models. Column experiments were designed to establish the optimal condition for the treatment of the industrial wastewater. The experiments were performed in packed bed up flow columns of different internal diameter and bed depth in order to predict the transport and sorption parameters. In all column experiments the flow rate was around 11 ml h -1. From perspective of process modelling, the dynamic behavior was described in terms of breakthrough curves. The bed depth service time (BDST), Thomas and Yoon Nelson models [Zhe et al. 2013] were used to analyze the experimental data and to determine model parameters. Batch results show that about 1hour was the time needed to reach equilibrium when using grape stalks and around 15 h when using exhausted coffee. In the case of exhausted coffee, the ph solution decreased during the sorption process from initial ph 5,5 to lower ph than the corresponding ph pzc (point zero charge). To avoid this, ph solution was controlled to a constant ph 5,5 and the equilibrium were achieved in 1h. Kinetic data of both sorption processes fit pseudo-second order model, indicating that chemisorption could be rate limiting in the sorption step. Experimental data of nickel sorption kinetic by using exhausted coffee and the model curve calculated from the pseudo-second order model are presented in Figure 1.

247 Qt (mg/g) ,07 mg/l Ni EC Pseudo t (s) Figure 1. Sorption kinetic of Ni(II) onto exhausted coffee (EC). Initial niquel concentration 19,07 mg/l, Solid/liquid ratio (g/ml) 1:15; controlled ph= 5,5. Equilibrium data of nickel sorption onto grape stalks and exhausted coffee fit adequately Langmuir model, indicating monolayer coverage. Results showed that maximum sorption capacity of grape stalks (4, mmol/g; 2,84 mg/g) is slightly higher than exhausted coffee (2, mmol/g; 1,70 mg/g). The maximum nickel sorption capacity of both sorbents was reduced to 50% compared to maximum sorption capacity determined using synthetic Ni(II) solutions. Thus, grape stalks and exhausted coffee performance for the removal of Ni(II) from the studied industrial wastewater are negatively affected by the presence of other compounds in the industrial wastewater. In the Figure 2 it can be seen the experimental data and theoretical model for Ni(II) sorption onto exhausted coffee. 3.50E E 02 qe (mmol/g) 2.50E E E E 02 Exhausted coffe Ni Langmuir 5.00E E Ce (mmol/l) Figure 2. Fitting of Langmuir isotherm equation for Ni(II) sorption to the data gathered from the equilibrium sorption experiments (symbols) onto exhausted coffee. Solid/liquid ratio (g/ml/) 1:15; controlled ph= 5,5

248 In column experiments, the best results were obtained by using 2.8 cm internal diameter columns and bed depth 6 cm and 8 cm for grape stalks and exhausted coffee, respectively. Breakthrough curves were successfully modelled by the proposed columns models. The results obtained demonstrated that grape stalks sorption capacity was higher than exhausted coffee but this one presented a higher sorption rate. In Figure 3, experimental breakthrough curves and modelled data by using the Thomas model for the Ni(II) sorption onto grape stalks at different initial Ni(II) concentrations are presented. 1.2 C/Co t (min) 108 ppm 142 ppm 540 ppm 108 ppm modelo 142 ppm modelo 540 ppm modelo Figure 3.Breakthrough curves for nickel sorption onto grape stalks at different initial concentrations. Flow rate=11 ml/h, 5 g of grape stalks, column: 2,6 cm internal diameter and 4,5 cm bed depth. Acknowledgements: Thanks are due to Samia Chater, Alex Luque, Laura Soler and Marc Sagrera for their help in part of the experimental work. This work was supported by MINECO (Spanish Ministry of Economy and Competitiveness), projects CTM C02-01/02. References: Martinez, M.; Miralles, N.; Hidalgo, S.; Fiol, N.; Villaescusa,I.; Poch, J.(2006) Removal of lead(ii) and cadmium(ii) from aqueous solution by using grape stalks wastes. Journal of Hazardous Materials 133: Valderrama, C., Arévalo, J.A., Casas, I., Martínez, M., Miralles, N., Florido A. (2010) Modelling of the Ni(II) removal from aqueous solutions onto grape stalk wastes in fixed-bed column.journal of Hazardous Materials 174: Villaescusa, I., Fiol, N., Martínez, N., Miralles, N., Poch, J., Serarols, J., (2004) Removal of copper and nickel ions from aqueous solutions by grape stalks wastes, Water Research, 38: Zhe XU; Jian-guo CAI; Bing-cai PAN,(2013) Mathematically modeling fixed-bed adsorption in aqueous systems. Journal of Zhejiang University-SCIENCE A (Applied Physics & Engineering) 14(3):

249 INVESTIGATION OF ADSORPTIVE/CATALYTIC EFFECT ON THE REMOVAL OF MANGANESE FROM WATER Nihan KAYA Chemical Engineering Department, Faculty of Engineering, Hitit University, 19030, Çorum, TURKEY Scientific Topic: Chemical Engineering for Sustainable Development Manganese occurs naturally in water, especially groundwater. It may causes adverse health effects, especially may affect neurological and muscle function in humans. And also water containing excessive amounts of manganese can stain clothes and sometimes add a "rusty" taste to water so it can affect the flavour and colour of water. The US Environmental Protection Agency has established a secondary (aesthetic) standard Maximum Contaminant Level (MCL) for manganese in drinking and/or using water of 0.05 ppm. Therefore the water containing high concentration of manganese is unsuitable for use as drinking and/or using water without appropriate treatment. The two most common treatment methods are removal by oxidation/filtration and adsorbing onto ion exchange resins. Oxidation involves the introduction of an oxidizing agent which chemically reacts with the manganese to form an insoluble particle which can then be physically filtered out through a media bed. Oxidation of manganese can be carried out the aeration (blowing/spraying air through the water) method. The process of oxidation followed by filtration is fairly easy and is often the treatment of choice. The use of ion exchange resins for the removal of manganese has limited application due to the requirement that the contaminants be in dissolved form and at very low levels. This is due to the tendency of oxygen to react with the manganese and therefore, increase the potential for plugging and buildup on the resin surface. In this study, the air oxidation of manganese in synthetic waters was studied. A series of batch experiments were performed at various concentration and ph values. Air was bubbled through the solution at about 50 ml/s to achieve the oxidation. The reaction temperature was maintained at 20 o C. In order to increase the contact between gas and liquid phases, glass beads with a diameter of 10 mm were added to the solution. The oxidation was tried on manganese dioxide, sepiolite and clinoptilolite supports. The amount of non removed manganese in water was determined by considering the standard of TS 6289 ISO 6333 Formaldoxime Spectrofotometric Methods. Oxidation efficiencies (%) were calculated for different conditions. Results of these studies indicated that the air oxidation of soluble manganese in water can be effectively performed in alkaline media and oxidation yield increased with an increasing ph and concentration values. Highest yield (99.2 %) has been obtained when 0.5 g MnO 2 was added to the alkaline solution (ph=11) as support. This result may be explained by the fact that manganese oxides catalyze manganese oxidation as efficiently as a chemical catalyst. And also oxidation required shorter time as compared to the other cases. High yields have also been achieved by adsorption-oxidation reactions when sepiolite or clinoptilolite were used instead of MnO 2. It was obtained that approximately same efficiency for adsorption of aqueous manganese on sepiolite and clinoptilolite. As a result of presence of supports (manganese dioxide, sepiolite or clinoptilolite) in solution, the oxidation was almost completed. Keywords: Adsorption, Aeration, Manganese, Oxidation, Water Pollution

250 DEGRADATION AND MINERALIZATION OF BISPHENOL A BY THE PHOTO FENTON PROCESS M. Navarro-Jordà, M. Graells, M. Pérez-Moya Escola Universitaria d Enginyeria Tècnica Industrial de Barcelona, Universitat Politècnica de Catalunya, BARCELONATECH tel , EUETIB, C/Comte d Urgell 187, Barcelona, Spain. Environmental Technology and Risk Analysis: Advanced Techniques for Effluent Treatment Bisphenol A (BPA; 2,2-bis (4-hydroxyphenyl) propane) is an industrial organic chemical basically used in the plastics industry as a monomer for producing epoxy resins and polycarbonates [1,2]. It is also a well-known endocrine disruptor agent that contaminates surface waters even at low concentration [3]. Unfortunately, BPA cannot be entirely removed from water solutions by conventional treatments. Additionally, in some cases, such treatments can lead to a series of by-products with higher endocrine disrupting effect [4]. Advanced Oxidation Processes (AOPs), among them the Fenton and photo-fenton processes, are efficient methods for BPA photodegradation [1]. However, they are energy-intensive processes and their cost is ought to be improved by reducing the reaction time as well as the consumption of reagents. In this work, the Fenton and the photo-fenton degradation of BPA (0,5 L, 30 mg L 1 ) was addressed. The process efficiency was evaluated under different H 2 O 2 and Fe(II) initial concentrations (2,37-6,41 mm H 2 O 2 and 1, , mm iron salt), while other variables were fixed (ph=3, 25ºC, UV light source). The treatment performance was assessed for a series of assays from a factorial design and was quantified in terms of the decay rate of total organic carbon (TOC) and the total conversion attained, according to a pseudo first order kinetics [5-6]. Given the initial conditions, the analytical expression for the TOC evolution is: o kt TOC TOC TOC TOC e (eq. 1) which can be expressed in terms of conversion (ξ) by the following equation: o max TOC TOC 1 e kt max being (eq. 2) TOC o Hence, the performance of the mineralization may be characterized by determining the two parameters of the model, ξ max (or [TOC] ) and k, which can be obtained by fitting the model to the experimental data under the least squares criterion. The results were plot k in front to identify different clusters and the conditions which produces higher mineralization rates References: [1] H. Katsumata, S. Kawabe, S. Kaneca, T. Suzuki, K. Oht. Degradation of bisphenol A in water by the photo- Fenton reaction. Journal of Photochemistry and Photobiology A: Chemistry 162 (2004) [2] M.J. Zhan, X. Yang, Q.M. Xian, L.R. Kong, Environmental Contamination and Toxicology, 76 (2006) [3] G. Levy, I. Lutz, A. Krüger, W. Kloas, Environmental Research, 94 (2004) [4] P.E. Stackelberg, E.T. Furlong, M.T. Meyer, S.D. Zaugg, A.K. Henderson, D.B. Reissman, Science of the Total Environment, 329 (2004) [5] M. Pérez-Moya, H. D.Mansilla, M. Graells, Journal of Chemical Technology and Biotechnology, 86 (2011) 826. [6] J.A. de Lima Perini, M. Pérez-Moya, R. F. Pupo Nogueira, Journal of Photochemistry and Photobiology A: Chemistry, 259 (2013) Acknowledgements: Financial support from the Spanish "Ministerio de Economía y Competitividad" and the European Regional Development Fund (both funding the research Projects EHMAN, DPI and SIGERA, DPI C02-01) is fully appreciated.

251 PHOTOCATALYTIC DEGRADATION OF METOPROLOL BY B-DOPED TIO 2 : IDENTIFICATION OF INTERMEDIATES R.P. Cavalcante 1, R.F. Dantas 2, B. Bayarri 3*, O. González 3, S.C. Oliveira 1, J. Giménez 3, S. Esplugas 3, Jr.A. Machulek 1. (1) Institute of Chemistry, Federal University of Mato Grosso do Sul, Av. Senador Filinto Muller, 1555, CP 549, CEP Campo Grande, MS, Brazil. (2) Faculty of Technology, University of Campinas, Paschoal Marmo 1888, Limeira, SP, , Brazil.. (3) Department of Chemical Engineering, University of Barcelona, C/ Martí i Franquès 1, Barcelona, Spain, * Corresponding author Scientific topic: 2.2. Environmental Technology and Risk Analysis Titanium dioxide (TiO 2 ) is one of the most efficient semiconductors for extensive environmental applications of photocatalysis. However, TiO 2 catalysts require activation by UV light because of its large bandgap (3.2 ev) [1]. Doping of TiO 2 with non-metals, such as boron, allows to extend its absorption range to the visible region. In the present work, TiO 2 doped with 5% (w/w) of boron was applied to degrade metoprolol tartrate salt (MET) under simulated sunlight. Additional objective in the study was to identify the main intermediates formed during the photocatalytic degradation of MET. The sol gel method was used to synthesize TiO 2 doped with 5% (w/w) B. The results of characterization showed that the catalyst presented excellent conditions for photocatalysis. The microscopy analysis scanning and transmission electron microscopy (SEM and TEM) revealed that the particles are uniform in size and nearly spherical shape. Characteristic peaks of anatase phase (25.4º, 37.9º, 48.1º, 54.2º, 55.2º, 62.8 and 75.4 ) and rutile phase (27.5º) were observed by X-ray diffraction (XRD). The bandgap (Eg) was 3.05 ev, determined by diffuse reflectance spectroscopy, and surface area was m 2 g -1, determined by BET. It was also possible to confirm the presence of boron, getting an actual value of 5.8% of boron determined by X-ray photoelectron spectroscopy (XPS). Photocatalytic degradation of MET in aqueous solution was performed using a Duran tubular photoreactor (0.078 L) located at the bottom of a solar simulator (Solarbox Co.fo.me.gra, 220V, 50 Hz), xenon lamp (Xe-OP, Phillips 1 kw) with a photon flux of Einstein s 1, determined by o-nitrobenzaldehyde actinometry. The photocatalytic activities of the obtained B-doped TiO 2 were investigated following the MET degradation during 180 min. 50 mg L -1 of MET and 0.4 g L -1 of catalyst were the concentrations chosen to run the experiments. MET degradation was monitored by HPLC and 70% of MET removal was obtained. For the identification of byproducts, the final sample mixture, at 180 minutes, was analyzed by electrospray ionization/mass spectrometry in positive electrospray model using a PerSeptive, TOF Mariner JascooAS-2050 plus IS mass spectrometer into the m/z range of The masses of the different products were determined from the peaks corresponding to the protonated molecule, [M + H] +. A total of 17 peaks of MET degradation intermediates were detected. The MET (C 15 H 25 NO 3 ) has a molecular weight [M + H] + = 268. Hydroxylated intermediates corresponding to the binding of OH radicals in the aromatic ring were detected: monohydroxylated derivative of MET and different fragments of the monohydroxylated were detected with m/z = 284, 270 and 256, dihydroxylated intermediates with m/z = 300 and trihydroxylated intermediates and fragments with m/z = 316 and 318. The attack of OH on the C atom next to the ether oxygen and the oxidation of the hydroxyl group yields the keto-tautomer with m/z = 282, and the OH attack on the C atoms of the aromatic ring of keto-tautomer yielded hydroxy intermediate with m/z = 298. After the breaking of a C C bond in the aliphatic part of the MET molecule, and amino-diol was identified as one of the dominant intermediates with m/z = 134. Different fragments of the ethanolamine side were also identified (m/z = 116, 120), probably due to the loss of the hydroxyl group and the loss of isopropyl moiety. The remaining peaks (m/z = 238, 240, 252 and 254) share the common fragmentation pattern and the formation of polar moieties (alcohols and aldehydes) probably by reactions which involve attack on the ether side chain followed by oxidation or elimination. Oxidative attack on the dimethylamine moiety results in intermediate m/z = 226 and in intermediate m/z = 150. Intermediates of similar molecular formula were identified by Romero et al., [2] and Abramović et al., [3] when metoprolol was photacatalytically degraded with TiO 2 Degussa P25 and TiO 2 Wackherr. [1] L. Liang, Y. Yulin, L. Xinrong, F, Ruiqing, S. Yan, L. Shuo, Z. Lingyun, F. Xiao, T. Pengxiao, X. Rui, Z. Wenzhi, W. Yazhen, M. Liqun. Applied Surface Science 265 (2013) [2] V. Romero, P. Marco, J. Giménez, S. Esplugas. International Journal of Photoenergy (2013) [3] B. Abramović, S. Kler, D. Sojić, M. Laušević, T. Radović, D. Vione, Journal of Hazardous Materials 198 (2011)

252 COMPARATIVE PHOTOCATALYTIC DEGRADATION OF METOPROLOL PHARMACEUTICAL IN AQUEOUS SOLUTIONS BY USING TWO TYPES OF TIO 2 PHOTOCATALYSTS: SCAVENGER STUDY R.P. Cavalcante 1, R.F. Dantas 2, B. Bayarri 3*, O. González 3, S.C. Oliveira 1, J. Giménez 3, S. Esplugas 3, Jr.A. Machulek 1. (1) Institute of Chemistry, Federal University of Mato Grosso do Sul, Av. Senador Filinto Muller, 1555, CP 549, CEP Campo Grande, MS, Brazil. (2) Faculty of Technology, University of Campinas, Paschoal Marmo 1888, Limeira, SP, , Brazil. (3) Department of Chemical Engineering, University of Barcelona, C/ Martí i Franquès 1, Barcelona, Spain, *Corresponding author: Scientific topic: 2.2. Environmental Technology and Risk Analysis Pharmaceuticals are considered as an emerging environmental problem, due to their possible adverse effects on human beings and natural organisms. Its continuous input and persistence to the aqueous system, even at low concentrations, may result in a potential risk for aquatic and terrestrial organisms [1]. Amongst the pharmaceuticals detected in receiving effluents, metoprolol tartrate salt (MET) is characterized by an increasing use in recent years, and, as a consequence, an increasing presence in aqueous effluents [2]. Heterogeneous photocatalysis with TiO 2 and UV light is considered one of the most promising AOPs for destruction of watersoluble organic pollutants. When TiO 2 is irradiated with UV light, photocatalytic reactions occur on the semiconductor surface generating reactive species such as, h VB+, e CB, OH, O 2, HOO, H 2 O 2, etc [3]. These species can lead to complete destruction of organic pollutants. In this context the main objective of the present work is focused on the photodegradation mechanism with different titania materials: Degussa P25 (80% anatase and 20% rutile, crystallites mean size 30 nm and surface area ~ 50 m² /g ) and CristalACTiV PC500 (anatase > 99%, crystallites mean size 8 nm and surface area ~ 350 m² /g). The mechanisms can be determined by examination of active species through the use of scavengers for hydroxyl radicals (tert-butanol, t-buoh), holes (formic acid, AcF), electron (Oxygen - saturation with air) and superoxide radicals (benzoquinone, BQ). Photocatalytic degradation of MET in aqueous solution was performed using a Duran tubular photoreactor (0.078 L), located at the bottom of a solar simulator (Solarbox Co.fo.me.gra, 220V, 50 Hz), xenon lamp (Xe-OP, Phillips 1 kw) with a photon flux Einstein s 1 ( nm), determined by o-nitrobenzaldehyde actinometry. The study was conducted using 50 mg L -1 MET, 0.4 g L -1 TiO 2 Degussa P25 and/or PC 500 with a suitable amount of each sequestering compound ( g L -1 BQ; 1.0 g L -1 AcF; or 60 ml L -1 t-buoh). MET degradation was monitored by HPLC. The results show that P25 catalyst is more efficient than PC 500, obtaining 80 and 60% of MET removal, respectively. Generally, anatase is considered to be the photoactive form, while rutile is considered to have low photocatalytic activity. However, for reasons that are not yet understood, mixtures of anatase and rutile (P25, 80% of anatase and 20% of rutile) have a better photo-activity than either phase by itself. A possible explanation resides in the fact that Degussa P25 disperses in water much more easily than PC500, probably due to different particle sizes. Nevertheless, other factors, such as crystal size, existence of structural defects into the crystalline framework, compositional impurities and chemical properties of the titania surface (polarity and hydroxylation grade), play an important role on the recombination rate of the redox pairs (e /h + ) [4]. Experiments involving scavengers showed very similar trends. For both catalysts, there is a large effect of the adding of AcF and tbuoh, which are responsible for capturing the reactive species h + and OH. This fact indicates that the main pathway for MET degradation is the OH attack, with some contribution of holes (h + ), as well related to the production of OH radicals. For the experiments with P25, the reactive oxygen species like superoxide radicals have a small part in the photocatalytic degradation pathway of MET, 10%, measured by the addition of BQ, which traps superoxide anions by a simple electron transfer mechanism. For experiments with the PC 500 the oxygen has a small contribution to the formation of hydroxyl radicals (12% increase in the degradation of MET). Oxygen is an electron scavenger used to inhibit recombination of the e /h + pair, promoting oxidative processes such as the formation of OH radicals. [1] D. Fatta-Kassinos, M.I. Vasquez, K. Kümmerer, Chemosphere 85 (2011) [2] V. Romero, N. De la Cruz, R.F. Dantas, P. Marco, J. Gimenez, S. Esplugas, Catalysis Today 161 (2011) [3] N. De la Cruz, V. Romero, R. F. Dantas, P.Marco, B. Bayarri, J. Giménez, S. Esplugas. Catalysis Today 209 (2013) [4] P. Pizarro, C. Guillard, N. Perol, J.-M. Herrmann. Catalysis Today 101 (2005)

253 USING EXPERIMENTAL DESIGN TO OPTIMIZE BARLEY STRAW EFFLUENT DEGRADATION BY FENTON REAGENT Francesc Torrades 1, José Antonio García-Hortal 2, Omar Folqués Martín 2 1 Departament d Enginyeria Química. ETSEIA de Terrassa, Universitat Politècnica de Catalunya (UPC), C/Colom, 11, E-08222, Terrassa (Barcelona) Spain. Tel: ; Fax: Departament d Enginyeria Tèxtil i Paperera. ETSEIA de Terrassa, Universitat Politècnica de Catalunya (UPC), C/Colom, 11, E-08222, Terrassa (Barcelona) Spain. Topic: 2.2. Environmental Technology and Risk Analysis The rapid increase in population around the world and the increased demand for industrial establishments, in particular, small and medium-scale pulp and paper industries, have created problems such as high levels of pollution that affect the fertility of soils and bodies of water as well as natural flora and fauna. The analysis of the current status of paper and pulp industry, tell us that to be in full accordance with the principles of sustainable development is a need to use as raw material items that are low cost, low social and environmental impact. In this sense the use of non-wood raw materials, like barley straw, could be a good alternative [1,2]. In this work, we use Fenton reagent, in a lab-scale experiment, for the treatment of a barley straw effluent, obtained from the pulping of barley straw, in a laboratory reactor under optimized conditions for the preparation of the pulp. Once filtered, diluted and ph adjusted to 3 units, the main characteristic of the barley straw effluent were: COD = 749 mg L -1 O 2, UV 254 = absorbance units and UV 280 = absorbance units. Response surface methodology and a 2 3 factorial design [3] were used to evaluate the effects of the three independent variables considered for the optimization of the oxidative process: temperature, Fe (II) and H 2 O 2 concentrations. The response functions were the decrease in COD, aromatic content (UV 254 ) and lignin content (UV 280 ). The methodology lets us identify and statistically evaluate the effects and interactions of the study variables and their roles in the efficiency of the treatment process. From obtained results, the use of Fenton s reactions has been proven to be highly effective for the treatment of such type of wastewaters; and accordingly, the high levels of chemical oxygen demand (COD), aromatic content (UV 254 ) and lignin content (UV 280 ) removal. These results suggest that it may be possible to develop a treatment process that combines an initial treatment using Fenton oxidation with a subsequent biological treatment. REFERENCES [1] A. Leponiemi, Non-wood pulping possibilities a challenge for the chemical pulping industry, Appita J. 61 (3) (2008), [2] F. Vargas, Z. González, R. Sánchez, L. Jiménez, A. Rodríguez, Cellulosic pulps of cereal straws as raw material for the manufacture of ecological packaging, Bioresources 7 (3) (2012), [3] S.L.C. Ferreira, R. E. Bruns, H.S. Ferreira, G.D. Matos, et al., Anal. Chim. Acta (597) (2007)

254 TREATMENT OF SYNTHETIC MUNICIPAL WASTEWATER CONTAINING ANTIPYRINE BY SONOPHOTOCATALYSIS J.M. Monteagudo*, A. Durán, A. Fernández, A. Carnicer, M.A. Alonso, J.M. Frades Department of Chemical Engineering, Grupo IMAES, Escuela Técnica Superior de Ingenieros Industriales, Universidad de Castilla-La Mancha, Avda. Camilo José Cela 3, Ciudad Real (Spain). Fax: Phone: , ext: Scientific Topic (2.2 Advanced Techniques for Effluent Treatment) The aim of this work was to study the mineralization of antipyrine (emerging contaminant) present in synthetic municipal wastewater effluent (ASMWE) using an innovative homogeneous sono-photocatalytic oxidation process (H 2 O 2 /UV/Fe/Ultrasound). The photocatalytic degradation efficiency was determined by the decrease in Total Organic Carbon (TOC) content. The mineralization process was found to follow pseudo-first order kinetics. Experimental kinetic constants were fitted using neural networks (NNs). The influences of the initial concentrations of H 2 O 2 and Fe(II) and Amplitude and Cycles (Length Pulse) on the mineralization reaction were studied. Under the optimal conditions ([H 2 O 2 ] o = 500 mg L -1, [Fe(II)] o = 27 mg L -1, Amplitude (%)= 20 and Cycles= 1) TOC removal increased up to 79 % in 50 min. The ASMWE-mineralization process in the sono-photo-fenton system can be described by a mechanism involving mineralization by direct photolysis, ultrasonically generated oxidative species, direct oxidation reaction with H 2 O 2, radical reaction (mainly HO ) and thermal pyrolysis inside the bubble. The radical reaction in the bulk solution was found to be the main mineralization pathway. The contribution of different mechanisms to overall mineralization was the following: radical reaction (94.85%), photolysis (3.65%), direct reaction with H 2 O 2 (0.86%), and reaction by ultrasonically generated oxidative species (0.64%). The role of the Fe catalyst on the radical reaction was studied. The toxicity profile of sono-photo-fenton process was also evaluated. Results demonstrated that sono-photo-fenton system is a potential alternative to control water pollution caused by emerging contaminants such as antipyrine. Pyrolysis 0.00% Photo reaction 3.65% Ultrasonically generated oxidative species 0.64% Direct reaction 0.86% Radical reaction 94.85% Figure 1. Experimental set-up Figure 2: Contribution of different mechanisms to overall mineralization

255 Novel compact anaerobic/aerobic reactors for the removal of azo dyes in wastewater A.Giménez 1, J.Chirinos 1, Y.García 1, A. Fabregat 1, A. Fortuny 2, C. Bengoa 1, F. Stüber 1, J. Font 1 1 Departament d'enginyeria Química, Universitat Rovira i Virgili, Av. Països Catalans 26, Tarragona, Spain; Tel.: , 2 Departament d'enginyeria Química, Universitat Politécnica de Catalunya, Av. Víctor Balaguer S/N, Vilanova i la Geltrú, Spain Scientific Topic: Advanced Techniques for Effluent Treatment Azo compounds constitute the largest group of synthetic dyes used in many industrial sectors such as textile, food, cosmetics and paper, which generate huge amounts of waste water. The principal purpose of this study is to develop a new alternative for treating industrial waste water containing low concentration of azo dyes, recalcitrant towards the typical sewage sludge treatment in the WWTPs due to their xenobiotic nature, thus occurring in their effluents. [1],[2],[3] The technology developed is based on the coupling, through selective biomembranes, of the anaerobic biological activated carbon (BAC) treatment for reductive breaking of the azo bond and a subsequent finishing biological or oxidation treatment. Both treatments allow high reaction rates at not demanding conditions. With this goal, defect-free carbon-based molecular sieve ceramic-supported membranes were prepared to process waste water containing low concentration of Orange 7. The carbon layer performs as an electron mediator favouring the reductive treatment of this type of pollutants. In addition to other known configurations as fixed bed, this system behaves as a physical barrier avoiding microorganism loss in the exit effluent. Likewise, efficient cleaning techniques can be easily applied to overcome problems associated to the overproduction of biomass over the membrane. [4][5] The biodegradation process has been optimized modifying several operation conditions such as biomass contact time, nutrients or the concentration ratio between Orange 7 and the external carbon source. Moreover, different membrane preparation procedures were applied in order to study the influence of the carbon layer properties on the degradation performance. Starting from sample solutions containing 0.14 mm of AO7, high biodegradation of AO7 was achieved (>90%). In addition, sulfanilic acid, an aromatic amine derived product seems to be also degraded under anaerobic conditions (>90%). Overall, COD removal of nearly 50% was obtained, too. References [1] F.P. van der Zee, G. Lettinga, J.A. Field (2001) Azo dye decolourisation by anaerobic granular sludge, Chemosphere [2] F.P. van der Zee, S. Villaverde (2005) Combined anaerobic aerobic treatment of azo dyes A short review of bioreactor studies, Water Res [3] F.I. Hai, K. Yamamoto, F. Nakajima, K. Fukushi, L.D. Nghiem, W.E. Price, et al., Degradation of azo dye acid orange 7 in a membrane bioreactor by pellets and attached growth of Coriolus versicolour, Bioresour. Technol. (n.d.). [4] G. Mezohegyi, F.P. van der Zee, J. Font, A. Fortuny, A. Fabregat, (2012) Towards advanced aqueous dye removal processes: A short review on the versatile role of activated carbon, J. Environ. Manage [5] G. Mezohegyi, C. Bengoa, F. Stuber, J. Font, A. Fabregat, A. Fortuny, (2008) Novel bioreactor design for decolourisation of azo dye effluents, Chem. Eng. J

256 WOOL DRY SCOURING J. Iglesias 1, Ll. Alerm 1, M. Tavares 2, S. Balsells 3, M. Jorba 3, L. Coderch 4, M. Martí 4 1 RMT SA, P.I. Can Magre, Narcís Monturiol 20-22, Santa Eulàlia de Ronçana, Spain 2 Têxtil Manuel Rodrigues Tavares SA, Av. Dr. Afonso Costa, s/n, Guarda, Portugal 3 LEITAT, Innovació 2, Terrassa, Spain 4 IQAC-CSIC, Jordi Girona 18-26, Barcelona, Spain phone fax Scientific Topic: 2.1. Environmental Technology and Risk Analysis Raw wool known as grease wool, prior to its textile use requires removing all not fibre content by a process known as wool scouring. Not fibre material contains several fractions such as a water soluble fraction (Suint), a solvent soluble (Wool grease-lanoline), dust and vegetal fibre (Dirty). Traditionally, grease wool scouring is made in complex counter current aqueous washing trains. Aqueous scouring generates a highly polluted waste liquid effluent of difficult and expensive treatment containing greasy wool not fibre components. Wool Dry Scouring project (WDS) is a R&D+I project granted by the European Commission (LIFE project) dealing with the generation of a new breakthrough technology. The WDS point of view is focused on maximising the value and yield of different components involved: wool, wool grease, suint and dirt for obtaining final by-products with a market value instead of waste effluents, which require a very complex and expensive treatment as well as an expensive disposal without economic and social value. The design of this process is focused on obtaining valuable wool of enhanced quality and valuable by-products without any waste stream that has to be disposed. Envisaged WDS process will be based on a grease wool counter current solvent extraction for removing solvent soluble by-products and while isolating the rest of wool contaminants directly as a dry matter. This process will try to generate enhanced whiter wool of improved combing yield due to a diminution of fibre entanglement. The expected wool grease fraction recovery will go from the current 40% on state of the art scourers to close to 99%. With this process, the problems of old solvent wool scouring process such as de Smet and Wooltech will be overcome. Experimentally, this process will be developed at industrial-pilot scale as a continuous, closed-loop system with the target of reducing substantially the current wool scouring net cost while minimising environmental impact of scouring activity. In this LIFE+Environmental Policy and Governance project two textile industries, one technological centre and one research centre will participate for the next three years. Acknowledgement: The authors wish to thank the LIFE+Environmental Policy and Governance LIFE11 ENV/ES/588 for the financial support.

257 PHOTOCATALYTIC OZONATION OF TRICLOPYR, AN HERBICIDE REFRACTORY TO OZONE R. R. Solís 1*, F.J. Rivas 1, J.L. Pérez Bote 2 1 Dpto. de Ingeniería Química y Química Física ( 2 Dpto. Anatomía, Biología Celular y Zoología), Universidad de Extremadura. Avda. Elvas s/n Badajoz, Spain. * Phone: , Fax: , Environmental Technology and Risk Analysis: Advanced Techniques for Effluent Treatment Triclopyr (3,5,6-trichloro-2-pyridinyloxyacetic acid, TRI) is a selective herbicide commonly used in control of broadleaf weeds in rice crops and defoliation of wooded areas. It is commercialized in the form of the more soluble amine or ester salts which are frequently formulated with many other compounds. After been used, TRI tends to spread and penetrate in the soil and water, becoming a problem for the environment. Photocatalytic ozonation is an oxidation process to treat highly refractory organic compounds such as triclopyr, leading important reductions in total organic carbon. In this work, photocatalytic ozonation, photocatalytic oxidation with oxygen, single ozonation and photolysis have been studied in order to assess the oxidation advantages of the first one compare to the others. Commercial titania P-25 has been used as catalyst. Black light has also been used as the radiation source. The experimental setup was a glass reactor placed in the middle of a cylinder with its internal wall covered by aluminium foil. Four black light lamps (15W emitting the range nm, maximum at 365 nm) were evenly distributed attached to the cylinder. Oxygen or an oxygen-ozone mixture (30 L h -1 ) was continuously bubbled into the water bulk by means of a diffuser. TRI was analysed by an Agilent 1100 HPLC, and TOC by a Shimazdu TOC 5000A analyser. The rate constants between TRI and O 3 or HO radicals were previously calculated. The direct rate constant between ozone and TRI at neutral ph was 20 M -1 s -1. The rate constants with HO at neutral ph were also determined by means of the system H 2 O 2 /UVC, leading to a value of M -1 s-1. From the Figure 1 it is observed that TRI is completely degraded in 5 minutes by UVA/TiO 2 /O 3 system while UVA/TiO 2 /O 2 needs 180 min. Single ozonation just led to a partial oxidation of 50% in 180 min. This behaviour is due to the low rate constant between O 3 and TRI; and even, 50% of this partial oxidation took place due to the HO indirect path reaction. UVA/TiO 2 /O 3 system is more efficient t (min) because of a higher HO concentration generated This can be explained by the highly efficiency of O 3 in trapping electrons in the conduction band of the semiconductor, leading to the production of more HO than the process in the presence of oxygen Similar results were obtained when TOC conversion was assessed. The best conversion percentage is shown by the photocatalytic process with O 3, leading to 70% of TOC conversion after 180 min of treatment. Single ozonation achieved almost 40% while UVA/TiO 2 /O 2 slightly improved the former results. In conclusion, this work shows an example where the use of photocatalytic ozonacion is presented as a promising process to treat highly refractory t (min) contaminants. C TRI /C TRI 0 1-TOC/TOC 0 Figure 1. TRI removal (5 ppm) and TOC conversion by different systems. Experimental conditions: C O3 =10 ppm, C TiO2 =0.5 g L -1., UVA;, O 3 ;, UVA/TiO 2 /O 2 ;, UVA/TiO 2 /O 3. Blank symbols correspond to TRI removal and solid ones to TOC conversion. Acknowledgements

258 The authors thank the economic support received from Junta de Extremadura and CICYT of Spain through Projects GRU10012 and CTQ C02-01, respectively. Mr. Rafael Rodríguez Solís thanks the Gobierno de Extremadura, Consejería de Empleo, Empresa e Innovación and FEDER Funds for his PhD grant.

259 PHOTOCATALYTIC OZONATION BY NITROGEN DOPED TITANIA OF HERBICIDES CLOPYRALID, PICLORAM AND TRICLOPYR R. R. Solís 1*, F.J. Rivas 1, J.L. Pérez Bote 2 1 Dpto. de Ingeniería Química y Química Física ( 2 Dpto. Anatomía, Biología Celular y Zoología), Universidad de Extremadura. Avda. Elvas s/n Badajoz, Spain. * Phone: , Fax: , Environmental Technology and Risk Analysis: Advanced Techniques for Effluent Treatment Clopyralid, (3,6-dichloro-2-pyridinecarboxylic acid, CLO), picloram (4-amino-3,5,6-trichloro-2- pyridinecarboxylic acid, PIC) and triclopyr (3,5,6-trichloro-2-pyridinyloxyacetic acid, TRI) are three chlorinated herbicides commonly used. After being used, they frequently pollute aqueous effluents which constitute a danger to the environment. As a possible way to remove these compounds from water, photocatalytic ozonation was studied. The radiation source applied was black light (emitting in the range nm, maximum at 365 nm). Bare or N-doped titania were the studied catalysts. The N doped TiO 2 catalyst was prepared by sol-gel process, using titanium isopropoxide and triethylamine as titanium and nitrogen sources. After the hydrolysis process, the resultant solution was autoclaved at 80ºC for 12h. The suspension was centrifuged and the residue was dried at 100 ºC. Thereafter, the gel was calcined under air atmosphere at 500ºC for 4h. Bare TiO 2 was synthetized following the same steps without adding a nitrogen source. Characterization of N-doped TiO 2 was carried out by XRD, XPS, TEM and SEM techniques. Anatase was found as the crystalline phase, and roughly 1% of dopant the agent was found. TEM reported the normal bipyramidal shape and SEM images reported surface rugosity. A glass reactor was placed in the middle of a cylinder with its internal wall covered by aluminium foil. Four black light lamps were evenly distributed and attached to the cylinder. An oxygen-ozone mixture (30 L h -1 ) was continuously bubbled into the water bulk by means of a diffuser. Herbicides were analysed by an Agilent 1100 HPLC, and TOC by a Shimazdu TOC 5000A analyser. Under the operating conditions used, the reactivity order found was PIC > TRI > CLO. Clopyralid, the most recalcitrant substance, was completely degraded in 60 min when the less reactive system was applied. The Figure 1 shows that N-doped titania slightly improves the results obtained by bare titania. However, when TOC is analysed, doped titania does significantly improve the results. Hence, bare titania achieves 70% t (min) of TOC removal in 180 min while N-doped titania overtakes it until 95% at the same time. The doped catalyst settles down by gravity after roughly 12 h. In order to assess a possible loss of activity, this catalyst was reused in four consecutive stability tests. The results, not shown, did not manifest any loss of activity either in herbicide removals or final TOC conversion percentages. From this work, it can be concluded that N- doping improves the photoactivity of bare titania, in terms of the organic compound and TOC conversion, even after being reused four times C herb /C herb 0 t (min) Figure 1. CLO, PIC, TRI removal (5 ppm each one) and TOC conversion by different systems. Experimental conditions: C O3 =10 ppm, C cat =0.5 g L -1. Series:, CLO bare TiO 2 ;, CLO N-doped TiO 2 ;, TRI bare TiO 2 ;, TRI, N-doped TiO 2 ;, PIC bare TiO 2 ;, PIC N-doped TiO 2 ;, TOC bare TiO 2 ;, TOC, N- doped TiO 2. Acknowledgements The authors thank the economic support received from Junta de Extremadura and CICYT of Spain through Projects GRU10012 and CTQ C02-01, respectively. Mr. Rafael Rodríguez Solís thanks the Gobierno de Extremadura, Consejería de Empleo, Empresa e Innovación and FEDER Funds for his PhD grant. 1-TOC/TOC 0

260 WO 3 MICROSPHERES FOR PHOTOCATALYTIC OZONATION OF DEET E. Mena, A. Rey, F.J. Beltrán, B. Acedo Departamento de Ingeniería Química y Química Física. Universidad de Extremadura. Avda. Elvas, s/n Badajoz, Spain. Phone: Fax: Environmental Technology and Risks Analysis: Advanced Techniques for Effluent Treatment In recent years, contamination of aquatic environment by anthropogenic organic compounds such as pharmaceuticals and personal care products (PPCPs) residues has become a subject of growing interest worldwide. N,N-Diethyl-m-toluamide (DEET), one of the most common and effective insect repellents, is widely used and has therefore been detected as a contaminant in groundwater, rivers, seawater, wastewater treatment plants effluents and even in drinking water treated by conventional systems, thus indicating its persistence and degree of recalcitrance to conventional treatments [1]. Photocatalytic ozonation, i.e. the combination of ozone and heterogeneous photocatalysis with an irradiated semiconductor, has proved to efficiently remove a great variety of organic pollutants increasing the production of oxidizing species compared to the single processes [2]. This work is focused on the use of WO 3 photocatalysts, which are visible-lightresponsive semiconductors, for the removal of the emerging contaminant DEET through photocatalytic ozonation using visible light as radiation source. WO 3 catalysts (WO 3 flocky microspheres) were prepared by hydrothermal synthesis following a modified procedure described elsewhere [3]. The solvent used was ethanol/water (40/60 v.%) and hydrothermal conditions 120 C for 48 h. The precipitates obtained were separated, washed, dried and then calcined at 500, 600 and 700ºC for 2 h. A fraction of each catalyst was also washed in the reacting system at the operating conditions of the photocatalytic runs. Characterization of the catalysts was carried out by XRD, SEM, N 2 adsorptiondesorption isotherms, XPS and DR-UV-Vis spectroscopy. Photoactivity was evaluated using a solar simulator equipped with a 1500 W Xe lamp (λ>390 nm, irradiation intensity 550 W m 2 ). A 500 ml capacity 3-neck round-bottom flask was used as reactor. An ozone generator was used to feed a mixture O 3 /O 2 at a flow rate of 15 L h -1 with 10 mg L -1 ozone. Unbuffered ultrapure water was doped with 5 mg L -1 of the target compound DEET and subjected to treatment during 2 h irradiation after a previous 30 min period of adsorption in the dark. DEET concentration, dissolved O 3, H 2 O 2 and total organic carbon (TOC) concentrations were analysed to follow the reaction evolution. Photocatalytic ozonation with WO 3 catalysts under visible light radiation was demonstrated to be an efficient process to remove DEET, reaching more than 99% removal in less than 20 min. The comparison of the activity and efficiency of the catalysts was carried out in terms of the degree of mineralization achieved after 2 h of the treatment. The catalyst synthetized by hydrothermal treatment was crystalized as hexagonal WO 3 structure and the calcination produced the transformation into monoclinic WO 3. Monoclinic structure of WO 3 seems to favor the catalytic activity, with TOC removal up to 50% in 2 h. In addition, Na phases were detected in these catalysts indicating an unsatisfactory washing procedure. In this way, a pretreatment of the catalysts in the same reaction conditions led to a decrease in the surface sodium content according to XPS results. These pre-activated catalysts were tested again during photocatalytic ozonation and gave place to better results of mineralization. A complete removal of DEET was achieved in 15 min using the best catalyst (calcined at 600ºC for 2 h and pre-activated), reaching around 70% mineralization at the end of the treatment. Acknowledgements This work has been supported by the Spanish Ministerio de Ciencia e Innovación (MICINN) and European Feder Funds through the project CTQ C02-01/PPQ. E. Mena thanks the Consejería de Empleo, Empresa e Innovación (Gobierno de Extremadura) and European Social Fund for providing her a predoctoral FPI grant (Ref. PD12059). References [1] W.A. Adams, C.A. Impellitteri, Journal of Photochemistry and Photobiology A: Chemistry, 202 (2009) 28. [2] E. Mena, A. Rey, B. Acedo, F.J. Beltrán, S. Malato, Chemical Engineering Journal, (2013) 314. [3] Y. Shen, D. Ding, Y. Deng, Powder Technology, 211 (2011) 114.

261 BORON DOPED TiO 2 PHOTOCATALYSTS FOR SOLAR PHOTOCATALYTIC TREATMENTS OF SELECTED PESTICIDES D.H. Quiñones, A. Rey, P.M. Álvarez, E. Mena, F.J. Beltrán, G. Li Puma 1 Departamento de Ingeniería Química y Química Física. Universidad de Extremadura. Avda. Elvas, s/n Badajoz, Spain. Phone: Fax: Department of Chemical Engineering, Loughborough University, LE11 3TU, Loughborough, United Kingdom. Phone: +44 (0) Fax: +44 (0) Environmental Technology and Risk Analysis: Advanced Techniques for Effluent Treatment Agricultural industry is considered as one of the productive sectors with the most negative effects on aquatic environments, since it consumes large volumes of water and generates water residues with high content of agrochemicals as pesticides and fertilizers. Most of them have been found to be persistent against conventional physicochemical treatments applied in wastewater treatment plants. Solar-driven photocatalytic processes have been highlighted as effective alternatives to completely eliminate this kind of pollutants [1]. Particularly, photocatalytic oxidation with boron doped TiO 2 (B-TiO 2 ) has demonstrated to increase the efficiency of TiO 2 in the use of solar radiation [2]. On the other hand, photocatalytic ozonation (i.e. the combination of an irradiated semiconductor with O 3 ) has demonstrated to efficiently remove a great variety of organic pollutants increasing the production of oxidizing species compared to the single ozonation and photocatalytic oxidation treatments [3]. In this work, the degradation of four pesticides: Diuron (DIU), o-phenylphenol (OPP), 2-methyl-4- chlorophenoxyacetic acid (MCPA) and terbuthylazine (TBA), which are commonly found in water ecosystems, is studied. The degradation methods used were photocatalytic oxidation, ozonation, photolytic ozonation, and photocatalytic ozonation with different B-TiO 2 catalysts studying the effect of B loading on the catalytic activity. TiO 2 and several B-TiO 2 catalysts with nominal boron content between 0-12 wt.% were prepared by a sol-gel procedure using boric acid and tert-butyl titanate as precursors. The suspended solid obtained after sol-gel synthesis was centrifuged, washed, and the resulting precipitate was calcined at 500ºC. Characterization of the catalysts was carried out by XRD, SEM, N 2 adsorption-desorption isotherms, XPS and DR-UV-Vis spectroscopy. Photoactivity was evaluated using a solar simulator equipped with a Xe lamp (λ>300 nm, 550 W m 2 ) feeding 10 L h -1 of an O 2 /O 3 mixture (5 mg L -1 ozone) in a ph free ultrapure water matrix containing 5 mg L -1 of each target compound. Experiments were carried out with a 30 min period of adsorption in the dark followed by a 2 h period of irradiation. Pesticides, dissolved O 3, H 2 O 2 and total organic carbon (TOC) concentrations were analysed to follow the reaction evolution. Bare and B-doped TiO 2 catalysts synthetized were active in the photocatalytic oxidation and photocatalytic ozonation of the pesticides DIU, OPP, MCPA and TBA. In general, all the O 3 treatments led to a faster depletion of the four pesticides regardless of the presence/absence of radiation and catalyst. Main differences were observed in terms of TOC removal being always higher when photocatalytic ozonation was applied. A nominal B loading near 6 wt.% seems to be optimal for solar-driven photocatalytic treatments regarding mineralization rate under the conditions studied here. Photocatalytic ozonation with this catalyst gave place to conversions higher than 99% in less than 30 min for DIU, OPP and MCPA whereas TBA was more refractory reaching 98% in 120 min, mineralization being around 80% at the end of the treatment. Acknowledgements Authors thank MINECO and ERDF Funds for the support through the Project CTQ C D.H. Quiñones thanks the MINECO for a predoctoral FPI grant and an aid to do a research stay. E. Mena thanks the Consejería de Empleo, Empresa e Innovación (Gobierno de Extremadura) and European Social Fund for a predoctoral FPI grant (Ref. PD12059). References [1] S. Malato, P. Fernández-Ibáñez, M. I. Maldonado, J. Blanco, W. Gernjak, Catal. Tod. 147 (2009) 1. [2] M.V. Dozzi, E. Selli. J. Photochem. Photobiol. C. 14 (2013) 13. [3] E. Mena, A. Rey, B. Acedo, F.J. Beltrán, S. Malato. Chem. Eng. J (2012) 131.

262 METHANE RECOVERY FROM ANAEROBIC BIOREACTOR EFFLUENTS BY DEGASSING MEMBRANE TECHNOLOGY M. Henares, M. Izquierdo, C. Gabaldón and V. Martínez-Soria Departament d Enginyeria Química, Escola Tècnica Superior d Enginyeria, Universitat de València, Avgda. Universitat s/n, Burjassot (Spain), Phone: , Fax: , Scientific topic: 2.2 Environmental Technology and Risk Analysis Introduction. Biogas generated in the anaerobic treatment of wastewater is mainly recovered in the gas phase leaving the reactor. However, a significant quantity of dissolved methane (D-CH 4 ) can be found in the water effluent, and this represents a loss of potential energy resource. This loss increases in the anaerobic treatments at psychrophilic conditions since CH 4 solubility increases with the decrease of the temperature (Bandara et al., 2012). Likewise, the presence of D-CH 4 can difficult the reuse of water in a close loop due to the possible oversaturation of CH 4. Moreover, the Global Warning Potential (GWP) of CH 4 for a hundred years horizon is 28 times higher than CO 2 (Myhre et al., 2013); thus, fugitive emission of CH 4 to the atmosphere by this route can seriously affect the overall GHG emissions of the anaerobic bioreactors. In this context, the aim of this study was to investigate the degassing membrane technology to recover the D-CH 4 from the recirculating stream of a laboratory scale Expanded Granular Sludge Bed (EGSB) anaerobic reactor, which treated a synthetic wastewater polluted with ethanol at 25 ºC. Material and methods. The membrane module PDMSXA-250 (PermSelect, MedArray Inc., USA) equipped with a dense hollow fiber membrane type of polydimethylsiloxane (PDMS) was used for degassing. The number of fibers was of 320 with an inner and outer diameter of 190 and 300 µm, respectively, resulting in a membrane area of 250 cm 2 based on outer diameter. According with the manufacturer, the filtered (40 µm) anaerobic effluent flowed through the lumen side using a peristaltic pump, resulting in liquid velocities between 0.46 and 0.71 m/min. A vacuum pump model N026.3.AT.18 (KNF Neuberger, Germany) was used for vacuum extraction of CH 4 from the shell side, getting transmembrane pressures (TMP) of 140 and 314 mbar. The performance of the degassing module was evaluated by measuring the D-CH 4 concentration in liquid samples taken from the inlet and outlet of the module. D-CH 4 concentration was evaluated using a headspace method in He atmosphere: 50 ml of water sample in 125 ml glass bottles were shaken at 25 ºC for 3 hours. CH 4 concentration in the headspace was analyzed with an Agilent 6850 Serie II Gas Chromatograph equipped with an Agilent HP- PLOT/Q column. Henry s law constant for CH 4 was of M/atm (Sander, R., 1999). Results. Operation time to reach a constant D-CH 4 concentration in the effluent was of around 45 min. The average inlet D-CH 4 concentration was of 32.9 ± 2.1 mg CH 4 /L. The D-CH 4 was effectively recovered with recovery efficiency higher than 70% of the inlet D-CH 4. Results indicated that for the range of liquid velocities tested, the influence of pressure variation was almost negligible, and outlet D-CH 4 concentration was found in an average value of 5.5 ± 2.1 mg CH 4 /L. Similar results were obtained in the experiments with a TMP of 341 mbar and liquid velocities of 0.62 and 0.71 m/min. This study shows the degassing membrane unit as a promising technology to recover the D-CH 4 from anaerobic effluents. Acknowledgements The research leading to these results has received funding from the People Programme (Marie Curie Actions) of the European Union's Seventh Framework Programme FP7/ / under REA grant agreement n Funding from Generalitat Valenciana through the Prometeo project 2013/53 is acknowledged. M. Henares acknowledges Generalitat Valenciana for financing support of her PhD. References Bandara, W.M.K.R.T.W., Kindaichi, T., Satoh, H., Sasakawa, M., Nakahara, Y., Takahashi, M., Okabe, S., Anaerobic treatment of municipal wastewater at ambient temperature: analysis of archaeal community structure and recovery of dissolved methane. Water Research 46, Myhre, G., D. Shindell, F.-M. Bréon, W. Collins, J. Fuglestvedt, J. Huang, D. Koch, J.-F. Lamarque, D. Lee, B. Mendoza, T. Nakajima, A. Robock, G. Stephens, T. Takemura and H. Zhang, Anthropogenic and Natural Radiative Forcing. In: Climate Change 2013: The Physical Science Basis. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change [Stocker, T.F., D. Qin, G.-K. Plattner, M. Tignor, S.K. Allen J. Boschung, A. Nauels, Y. Xia, V. Bex and P.M. Midgley (eds.)]. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA. Sander, R., Compilation of Henry s law constants for inorganic and organic species of potential importance in Environmental Chemistry. In: Acceded: February 2014.

263 SINERGETIC EFFECT OF COUPLING DIELECTRIC BARRIER DISCHARGE AND PHOTOCATALYSIS IN THE VOC REMOVAL M. Henares a*, J. Palau a, A.A. Assadi b, A. Bouzaza b, D. Wolbert b, M. Izquierdo a, J.M. Peña- Roja a, V. Martínez-Soria a a Departament d Enginyeria Química, Escola Tècnica Superior d Enginyeria, Universitat de València, Avgda. Universitat s/n, Burjassot (Spain) b Laboratoire Sciences Chimiques de Rennes - Équipe Chimie et Ingénierie des Procédés, UMR CNRS, ENSCR, Avenue du Général Leclerc, Rennes, France *Phone: , Fax: , Scientific topic: 2.2 Environmental Technology and Risk Analysis Photocatalytic and dielectric barrier discharge (DBD) treatments for VOC removal emissions are innovative techniques that have advantages (such as a reduced environmental impact) over conventional techniques; however, more studies are necessary to develop/implement their viable applications, especially in a potential coupling system. The main objective of this work was the degradation of a target VOC (isovaleraldehyde) using photocatalysis and DBD combinations to determine the potential synergy between systems, the effects on the reactor performance as well as the sequence for applying these techniques. The laboratory reactor consisted of a rectangular polymethyl metracrylate (PMMA) chamber containing two parallel PMMA sheets. In the centre of the reactor, four UV-A lamps were placed. The catalyst was a commercial fiberglass tissue supporting TiO 2 at its surface located on the internal face of the two PMMA sheets. Two adjustable sheets of glass installed parallel to each other supported the electrodes of dielectric barrier. As in the photocatalytic reactor, the distance between sheets (GAP) was adjustable. Non-thermal plasma was obtained by applying a sinusoidal high voltage between 0 and 60 kv. In order evaluate the effects of treatment sequence on the removal efficiency of isovaleraldehyde, experiments were designed where the reactor was internally divided into halves. DBD was implemented in one half while the other half was operated as a combined DBD and photocatalytic reactor. The synergistic effect of the combined reactor can be observed in Figure 1 by comparison with the performance of the DBD and photocatalytic individual reactors. In the coupled system the elimination capacity was even higher ( 15%) than the sum obtained for individually reactors and independent of the applied voltage studied. This indicated that coupling of the photocatalytic and DBD reactors significantly improved elimination. Elimination Capacity (mg C m -3 s -1 ) DBD Photo. Combined 17 kv GAP: 30 mm 4 1 m3 h -1 6 m2 3 h m 3 h -1 Figure 1. Elimination capacity values for isovaleraldehyde removal by DBD, photocatalysis and a combination of both at different air flow rates. Inlet concentration = 40 mg C m -3, Voltage = 17 kv and GAP = 30 mm. The sequence of VOC treatments, dielectric barrier discharge and photocatalysis coupled with dielectric barrier discharge, was studied. Experiments were performed using DBD treatment first, then combined and the sequence reversed. Results were also compared to the full reactor operating with both technologies. It was observed that the sequence of VOC treatments was important to removal efficiency. The use of dielectric barrier discharge in the first half and in the second half of coupled reactor system, showed higher removal efficiencies. Acknowledgements. The research leading to these results has received funding from the People Programme (Marie Curie Actions) of the European Union's Seventh Framework Programme FP7/ / under REA grant agreement n Ministerio de Educación (Spain, Project CTM /TECNO) is

264 acknowledged. M. Henares acknowledges Generalitat Valenciana for financing support of her PhD (Project: Prometeo/2013/053).

265 CU(II) REMOVAL FROM WATER BY AZOLLA SPECIES AS BIOSORBENTS M. Izquierdo a,*, P. Brouwer b and P. Marzal a a Departament d Enginyeria Química, Escola Tècnica Superior d Enginyeria, Universitat de València, Avgda. Universitat s/n, Burjassot (Spain), Phone: , Fax: , b Molecular Plant Physiology Department, Utrecht University, Padualaan 8, 3584CH Utrecht (the Netherlands), Phone: Scientific topic: 2.2 Environmental Technology and Risk Analysis Introduction. Wastewaters containing heavy metals represent a serious threat to local ecosystems. Conventional technologies for heavy metal removal are inadequate to treat large volumes of effluents containing relatively low metal concentration (1 100 mg L -1 ), showing an inability to reduce metal concentrations or high operational costs (Volesky and Naja, 2005; Nuygen et al., 2013). Biosorption are a suitable alternative for removing low concentrations of metals from wastewater and do not require high energy or chemical input. The aim of this study was to investigate the performance of Azolla filiculoides and Azolla pinnata as Cu(II) biosorbents, both in batch and in fixed-bed column systems. The effect of the pretreatment with water was studied in batch mode. Batch equilibrium isotherms at ph 5.5 were obtained for both pretreated biosorbents. In fixed-bed operation, the performance of pretreated biosorbents in sequential sorption-desorption cycles was evaluated. Materials and methods. Biosorbents were prepared as follows. Two batches of A. filiculoides (A.fil.) and of A. pinnata (A.pin.) were grown at a growth facility at Wageningen University at CO 2 concentrations of 800 ppm. Material was harvested and dried at 30 C for 3 days. Then, both materials were ground and sieved to mm. Materials were further pretreated by surface washing and subsequent stirring in distilled water for 24 hours at 100 rpm, to remove impurities from the cultivation (A.fil.-pretreated; A-pin.-pretreated). Batch equilibrium experiments were carried out in flasks with increasing amounts of biosorbent and 50 ml of a solution of 50 mg Cu(II) L -1 and 0.01 mol NaCl L -1 (background electrolyte) (ph=5.5, 100 rpm, 23ºC). Fixed-bed experiments were carried out in columns of 1.0 cm inner diameter with bed lengths of 10 cm, with the pretreated biosorbents. A Cu(II) solution of 10 mg L -1 (C 0 ) with 0.01 mol NaCl L -1 at ph 5.5 was fed into the columns in the biosorption cycles at 40 ml h -1. Around 0.5 g of biosorbent was packed into each column, with a porosity of approximately 0.9. When Cu(II) saturation was achieved (C/C 0 >0.97), Cu(II) was desorbed with 0.05 mol HCl L -1 as regeneration fluid fed at 80 ml h -1. Column effluent samples were collected regularly and Cu(II) concentration was analyzed by Atomic Absorption Spectrometry. Results and discussion. Batch Cu(II) isotherm of A.fil. showed a limitation in the Cu(II) uptake when high amounts of biosorbent was present, causing a curved-shape isotherm, which might be due to the presence of soluble polyphenols from the biosorbent that formed metal complexes that were not retained by the biosorbents. This observation was supported by the fact that in the Cu(II) isotherm with A.fil.-pretreated this limitation was not observed, probably due to the removal of polyphenols during the water pretreatment. Thus, pretreated materials were used for the rest of the study. Batch isotherms of pretreated A.fil. and A.pin. were described by Langmuir model (R 2 >0.98), with maximum sorption capacity (q max ) of 40.5 and 50.6 mg g -1, respectively. Comparable values are found in the literature for garden grass or other agricultural wastes such as citrus peels (Nguyen et al., 2013) In fixed-bed operation at 10 mg Cu(II) L -1 inlet concentration, the total Cu(II) uptake in the first sorption cycle was of 18.1 and 16.6 mg g -1 for pretreated A.fil. and A.pin., respectively. Such biosorption capacity differs from that on batch experiments, which was of 28 and 39 mg g -1 for the same Cu(II) concentration. Metal recovery in the desorption steps was higher than 94%. In a second biosorption cycle, the total metal uptake did not decrease, indicating that the acid regeneration did not affect the metal sorption capacity. Nevertheless, the slope of the breakthrough curves decreased, resulting in a reduction of the operation time until the breakthrough point (C/C 0 =0.05) of around 35%. Acknowledgements. Financial support was obtained from Generalitat Valenciana with the research project Prometeo 2013/053, and from Climate KIC-Pioneers into Practice program. References Nguyen T.A.H., Ngo H.H., Guo W.S., Zhang J., Liang S., Yue Q.Y., Li Q., Nguyen T.V., Applicability of agricultural waste and by-products for adsorptive removal of heavy metals from wastewater. Bioresour Technol, 148: Volesky B., Naja G. (2005). Biosorption: Application Strategies. In Proceedings of the 16 th Internat. Biotechnol. Symp., Harrison S.T.L., Rawlings D.E. and Petersen J., eds. IBS Compress Co., Cape Town, South Africa, pp

266 REMEDIATION OF A PAH-CONTAMINATED SOIL BY OXIDATION WITH FENTON REAGENT AND SIMOULTANEOUS SOLUBILIZATION WITH SURFACTANTS M. Peluffo, F. Pardo, A. Santos, A. Romero Chemical Engineering Department. Universidad Complutense de Madrid, Av. Complutense s/n, Madrid, Spain TOPIC: 2.2 Environmental Technology and Risk Analysis. Hazardous Wastes and Soil Remediation With the purpose of increase the effectiveness of In Situ Chemical Oxidation techniques, the combination of them, concurrently or sequentially with surfactants, has been of growing interest in the field of soil and groundwater remediation. By using ISCO techniques, a wide range of organic contaminants can be oxidized, but taking into account that reactions take place in the aqueous phase, the low solubility of pollutants limit the extent of the remediation techniques. The presence of surfactants result in a decrease of surface tension and increase the availability of the contaminant in the aqueous phase (Dugan et al., 2010), permitting them to be more easily degraded. A sandy loam soil was spiked artificially with 100 mg kg -1 each of 4 PAH, Anthracene (3 rings), Phenanthrene (3 rings), Pyrene (4 rings) and Benzo(a)Pyrene (5 rings), which are included in the list of 16 PAHs priority pollutants. Fenton and Fenton reagent coupled with surfactant (Sodium dodecyl sulfate) were used, with ferrous sulfate as the catalyst specie ([H 2 O 2 ] = 880 mmol L -1, [Fe] = 1 mmol L -1, [SDS] = 7.64 mmol L -1 ). Reactions were conducetd without ph adjustement, using PTFE 50 ml centrifuge tubes as reactors, stirred isothermally at 20 ºC in an orbital shaker. Ratio selected for aqueous phase to soil was 2 ml g -1. It has been studied the removal efficiency of every pollutant (Anthracene, Phenanthrene, Pyrene and Benzo(a) pyrene) with conventional Fenton reagent and surfactant enhanced Fenton reagent. Besides, the evolution of the different species (oxidant, surfactant, total iron in solution and contaminant) as well as ph, was followed during the reaction time and the identification of oxidation products and intermediates was carried out. It was found that natural ph of the slurries was slightly acidic at the experimental conditions, (around ph = 5). Regarding to contaminat removal, it was observed a faster consumption of Anthracene and Benzo(a)pyrene than Phenanthrene and Pyrene. Surfactant was oxidized progressively with reaction time, but in spite of this fact, removal efficiencies at the final reaction time were higher when reactions where conducted in the presence of surfactant. Dugan, P. J., Siegrist, R. L. & Crimi, M. L.: 2010, 'Coupling surfactants/cosolvents with oxidants for enhanced DNAPL removal: A review', Remediation 20, ACKNOWLEDGEMENTS The authors acknowledge financial support provided from the Comunidad Autónoma de Madrid throughout project CARESOIL (S2009AMB-1648) and from Spanish Ministry of Economy and Competitiveness, project CTM

267 NOVEL Fe(III)-Al 2 O 3 NANOCOMPOSITE AS FENTON-LIKE CATALYST FOR THE CWHPO OF PHENOLIC WASTEWATERS C. di Luca *, F. Ivorra, P. Massa and R. Fenoglio * Div. Catalizadores y Superficies, INTEMA- Facultad de Ingeniería, CONICET/UNMdP, Juan B. Justo 4302 (7600) Mar del Plata, Argentina, (242), 2.2 Environmental Technology and Risk Analysis: Advanced Techniques for Effluent Treatment Advanced Oxidation Processes (AOP s) are aqueous phase oxidation methods based on the intermediacy of hydroxyl radicals, leading to the abatement of organic pollutants at mild reaction conditions. Among different AOP s technologies, one interesting alternative is the Catalytic Wet Hydrogen Peroxide Oxidation (CWHPO). The so-called heterogeneous Fenton-like systems use a solid catalyst in the presence of hydrogen peroxide as oxidizing agent. These solid catalysts consist in transition metal species (primarily iron, but not exclusively) immobilized over different supports. One of the most relevant drawbacks for the practical implementation of these systems is the catalyst deactivation due to active species lixiviation into the acidic reaction medium. Among non-conventional methods of catalysts preparation, direct incorporation of active components during the synthesis of a porous matrix could provide a useful strategy to improve both active sites dispersion and metalsupport interactions. In recent studies, it was demonstrated that direct inclusion of iron during the synthesis of SBA-15 by co-condensation route resulted in an enhancement of catalyst stability when compared with samples prepared by conventional impregnation [1]. The goal of the present work is to study the addition of ferric species during the synthesis of alumina through a sol gel process by evaporation-induced self-assembly (EISA) and to investigate these catalytic materials in the CWHPO of phenol as model pollutant. The catalysts were synthesized from an adaptation of the experimental procedure reported by Morris et al. [2]. Aluminum isopropoxide and Fe(NO 3 ) 3.9H 2 O or FeCl 3 6H 2 O were used as metallic precursors ([Fe +3 ]:[Al +3 ]=0.064) in a ethanolic solution of a triblock copolymer (Pluronic P123) using an acid catalyst (HNO 3 or HCl, depending of the iron source nature). The molar ratios [Al +3 ]:[P123]:[EtOH]:[H + ] in the final solution were fixed at 1:0.017: 34.4:2.5. The homogeneous sol was aging for three days at 40 ºC and then calcined at 400 ºC (1 ºC/min, 4 h). Post-calcinations at 700 ºC and 900 ºC were performed in a stepwise manner. After the thermal treatment at 400ºC, all organic residues from previous preparation steps were removed from samples (as confirmed by TGA). At this temperature, no crystalline phases were detected by XRD; however, the presence of γ-al 2 O 3 phase was registered for the samples calcined at 700 ºC and 900 ºC. The physisorption measurements revealed a high BET surface area (~ 300 m 2 /g) and TEM analysis showed the presence of a partially ordered structure with the formation of narrow channels in the nanometric range (~ 4 nm). XPS and Mössbauer measurements exposed the presence of Fe +3 ions inserted into the Al 2 O 3 matrix, which is consistent with the methodology of preparation adopted. CWHPO of phenolic solutions (1 g/l) were performed in a batch reactor at 70 ºC for 6 h, using 1 g/l of catalyst and stoichiometric dosage of H 2 O 2. The experimental set-up used was the same as reported elsewhere [3]. Preliminary reaction runs were carried out with powdered samples synthetized from ferric nitrate or ferric chloride, and calcined at different temperatures (400, 700 and 900 ºC). All Fe(III)-Al 2 O 3 materials showed different time-evolution in the Phenol, Total Organic Carbon (TOC) and H 2 O 2 conversion levels and ph. After 3 h, all the catalysts allowed the total abatement of phenol and at final time, the TOC 6h resulted c.a. 80%, with a leached iron concentration below 6 ppm; except for the sample prepared from Fe(III)-nitrate and calcined at 900ºC (TOC 6h = 57%; Fe lix = 12 ppm). The amount of leached iron in the final supernatant was directly related with the acidity of the reaction medium due to the accumulation of acids intermediates from phenol incomplete mineralization. The optimal catalytic properties were achieved with the catalyst prepared from ferric chloride and calcined at 700 ºC; the TOC 3h resulted of 80% and the final leached iron was 1.9 ppm (~ 4% of the total initial Fe load), maintaining a constant ph ~ 3 during the last five hours of the reaction run. From these results, we concluded that Fe(III)-Al 2 O 3 nanocomposites prepared by EISA methodology showed good structural properties and a promising catalytic performance (activity and stability) for the mineralization of organic wastewaters. References [1] JA Botas, JA Melero, F Martínez, MI Pariente; Catal Today, 149 (2010) 334. [2] SM Morris, PF Fulvio, M Jaroniek; J Am Chem Soc, 130 (2008) [3] C di Luca, F Ivorra, P Massa, R Fenoglio; Ind Eng Chem Res, 51 (2012) 8979.

268 PRELIMINARY STUDY OF THE RECYCLING OF POLYURETHANE BY SPLIT-PHASE GLYCOLYSIS TO RECOVER OF POLYOLS I. Duque-Ingunza 1*, R. López-Fonseca 1, O. Martínez 1, I. Acillona 2, S. Arnaiz 2 and J.I. Gutiérrez-Ortiz 1 1 Department of Chemical Engineering, Faculty of Science and Technology, Universidad del País Vasco/EHU, E Bilbao, Spain 2 GAIKER-IK4, Technological Centre, 202, E Zamudio, Spain Tel.: ; Fax: ; Topic 2.2: Environmental Technology and Risk Analysis. Waste Minimization and Treatment Polyurethanes (PU) comprise a major engineering plastic material family with an annual production capacity world wide of nearly 12 million tonne (2007). Despite their spreading in different applications their recycling rate is low. Polyurethanes constitute a group of polymers with versatile properties and a wide range of commercial products. Polyurethane foams, are used for many engineering applications, such as thermal insulation in construction, cushions, acoustic and comfort applications in automotive and so on. The general purpose of the polyurethane feedstock recycling is to recover constituent polyol, a valuable raw material. One of the alternatives for the recycling of polyurethane foams includes their chemical treatment by glycolysis to convert the PU back to polyols. In this study, the split-phase glycolysis of flexible polyurethanes, from cushions and comfort applications was investigated to define the suitable treatment for this flexible PU waste. Glycolysis of flexible PU waste granules was carried out using diethyleneglycol in the presence of different simple chemicals acting as catalysts. The effect of various operation parameters on the catalysed depolymerisation was investigated in order to efficiently recover the polyol. The glycolysis reactions were carried out under atmospheric pressure in a glass stirred tank reactor. When the temperature of flexible PU foam reached the specified value, the hot DEG/catalyst mixture was fed. At given intervals, aliquots were sampled and cooled to room temperature. Samples were analysed by GPC. At the end of the reaction time obtained reaction product was separated by decantation and centrifugation, the upper phase contained the recovered polyol. In an attempt to find a highly active catalyst for the process but with a considerable environmental impact, several eco-friendly simple salts were examined namely, diethanolamine (mostly used in bibliography), sodium acetate, potassium acetate, sodium hydroxide, potassium hydroxide. From the comparison of the efficiencies it was found that sodium hydroxide could depolymerise PU to recover the initial polyol. After selecting the optimum catalyst the effect of the most important parameters affecting the reaction were analyse. The quantity of recovered polyol increased with an increase in DEG:PET molar ratio, temperature, amount of catalyst and reaction time. In order to check the purity of the recovered polyol after PU waste glycolysis, this was analysed by means of a number of analytical techniques, and the results were compared with those corresponding to a commercial highly pure polyol sample. Density of the recovered polyol ( kg/m 3 ) was quiet similar to the commercial (1021 kg/m 3 ), however the viscosity measured for the recovered polyol ( mpa s) was lower than the viscosity of the commercial polyol (3574 mpa s). Water content was determined by the Karl-Fisher method obtaining lower values in the case of the glicolised product ( % vs 5.72% for the commercial polyol). FTIR spectra of the starting polyol used in the synthesis of the polyurethane foams and the one recovered from the upper phase show that the chemical structure was quite similar. Finally, foaming assays were made to study the application of the upper layer obtained in the glycolysis of flexible PU foam. The foaming formulations were modified replacing original polyol by the recovered product but other products like foaming agents and catalyst were not added in this study. It was a noticeable difference between the PU foam obtained with the commercial polyol, the foam with the 33% of replacement and the foam with 50%. Foam obtained with the commercial polyol shows better foaming characteristics, however, foaming assay has to be completed with the optimization of the process by adding foaming agents, surfactants and catalyst and a further characterization of the obtained foams, as PU obtaining replacing 33% of the polyol showed encouraging results. ACKNOWLEDGEMENTS The financial support for this work provided by the Spanish Ministerio de Ciencia e Innovación (CTQ C02-01 and CTQ C02-02) and the PhD grant afforded by Fundación de Centros Tecnológicos Iñaki Goenaga to I. Acillona are gratefully acknowledged.

269 ASSESSING THE PVC EFFLUENT TREATMENT USING A MEMBRANE BIOREACTOR PILOT L. Blanco 1, D. Hermosilla 1, A. Blanco 1, N. Swinnen 2, D. Prieto 3 and C. Negro 1* 1* Department of Chemical Engineering, Faculty of Chemistry, Complutense University of Madrid, Avenida Complutense s/n, Madrid, Spain. Phone: , Fax: , 2 Solvay, Research and Innovation, Advanced Environmental Solutions, Belgium 3 Solvin Spain SL, Martorell, Spain Environmental Technology and Risk Analysis Different dispersing agents, as polyvinyl alcohol (PVA), are commonly used during PVC production for morphology control. Consequently, PVA can be found in the final effluent of these industries after a clarification step. PVA limits water reuse and the implementation of zero liquid discharge technologies as ultrafiltration (UF) and reverse osmosis, due to the impact of this compound on the membranes in terms of fouling (Balyan y Sarkar, 2013). Chemical and physical treatments have been found unsuitable for the removal of this polymer due to their higher cost and poor final effluent quality (Chou et al., 2010). Biological treatments have not been very applied due to the low PVA biodegradability as a result of its polymeric structure. However, PVA has been found to be biologically degradable under certain conditions and after a certain acclimatization period. Low COD and PVA loads, constant influx and ratios, and temperatures over 18ºC should be reached to insure a good biological degradation during these treatments (Schonberger et al., 1997). In this research a membrane bioreactor (MBR) pilot was implemented to treat the effluent from a PVC plant. Design and initial operational values were selected according to previous lab-scale and semi-pilot scale results (Blanco et al., 2013). Therefore, temperature was decreased from 45-60ºC to 20-35ºC prior to biological treatment in terms of bacteria stabilization and membrane specification. Anoxic and aerobic tanks were used for testing nitrification/denitrification treatments. A phosphorous source was continuously dosed for providing enough nutrients in the biological system. Moreover, antifoam and caustic soda were dosed for foam and ph control. Biosludge from an existing Waste Water Treatment Plant (WWTP) was used for seeding the MBR. Bacteria acclimatization was achieved after one month of treatment. 100% degradation of PVA could be obtained at continuous operation. For the filtration step submerged hollow fibre membranes were used for ultrafiltration (UF). Different UF/BP (backpulse) cycles were assessed during the piloting. During the piloting COD and TOC removals were higher than 90 and 85%, respectively. Moreover, a BOD removal higher than 95% was achieved. Ammonia and total nitrogen removals were dependent on ph, feed characteristics and nutrients dosage. Membrane performance was good in terms of fouling and solids retention. Flux was gradually increased without significant fouling effect. Cleaning in place (CIP) cleanings were daily done combining acid and alkaline compounds. Fouling was seen to significantly increase when CIP cleanings were not periodically done. Continuous feeding led to solids increase despite the low COD values in the influent and the high ratios PVA/COD. However, intermittent feeding and foam production led to significant solids losses, especially when PVA was not completely removed from the wastewater. Biosludge degradation and significant solid losses were found when higher aluminium concentrations were present in the influent. References Balyan, U. and Sarkar, B. Desalination and Water Treatment, DOI: / , Chou, W.-L. et al. Desalination 251, 12 19, Schonberger, H. et al. American Dyestuff Reporter, Blanco, L. et al. Treatment of effluents containing PVA by MBR+RO for re-using in a PVC process. ChemH 2 O2013 Congress. Madrid (Spain), Acknowledgements: This research was developed in the framework of the project E4WATER (280756) funded by the European Union.

270 NEW CERAMICS USING RECYCLED INDUSTRIAL SECONDARY RESOURCES TOWARDS SUSTAINABLE DEVELOPMENT V. Karayannis Department of Environmental Engineering, Technological Education Institute of Western Macedonia, Kila, 50100, Kozani, GREECE, Tel ; Congress Scientific Topic: 2. Chemical Engineering for Sustainable Development In the present work, the recycling and valorization of steel industry by-products in the development of new ceramic products is investigated, towards sustainable use of resources. Actually, the valorization of low price and largely available industrial secondary resources in the development of value-added construction materials can contribute to both production cost alleviations and environmental protection, with conservation of natural resources (clayey minerals), turning waste from one industry into useful feedstock for another one towards industrial symbiosis and ample coordination, which is strongly endorsed by current European Union policies. Since industrial solid residues, such as massive quantities of dust recovered from gas treatment upon steel making, contain several oxides, they can be considered as useful secondary resources substituting for traditional clayey raw materials in ceramics manufacturing. Particularly in steel-making dust (EAFD), predominant oxides are found to be iron and zinc oxides (over 50 wt. % of the dust). The recycling of steel dust is very important, as it is one of the major steel industry by-products, produced worldwide in large quantities, and generated from the volatilization of heavy metals when steel scrap is melted in the electric arc furnace. Volatilized metals are oxidized and subsequently solidified and detained in the form of fine powder in specially designed filters, which are placed in the furnace gas stream cleaning system. The use of EAF technology in steel making has been increasing considerably over the last decades resulting in the production of significant quantities of solid residues. Steel dust is currently considered as an additive in asphalt cement mixtures for road construction. So far, limited studies are reported on the utilization of this industrial residue in the manufacturing of construction materials including ceramics, vitreous and glass-ceramic products. For that purpose, standard ceramic clays were selected as the base materials and characterized. Then, various clay/dust mixtures were kneaded with water to form a plastic mass for extrusion of brick-shaped specimens by employing a laboratory pilot-plant simulation of industrial brick fabrication processes. The mixture workability, extrusion procedure and drying behavior of specimens were optimized in order to obtain integral specimens possessing sufficient green strength for firing at typical temperatures, up to 850, 950 and 1050 o C, in a controlled furnace. The effect of the by-product percentage and the firing temperature on bulk density, water absorption capability, open porosity, thermal conductivity and mechanical performance upon bend testing of ceramic brick specimens was determined. Especially, the modulus of rupture was analyzed using Weibull statistics to estimate both the distribution and reliability of fracture data for a broader assessment of brick quality. According to the results, the addition of steel dust up to 15 wt.% into clay mixtures is tolerable for an effective extrusion of ceramics, without significant variations in both mechanical performance and thermal conductivity of the fired materials. Sintering the steel dust-loaded clays either at 850 or 950 o C leads to production of ceramics with similar both thermal insulation and bending strength and reliability, and therefore the firing temperature can be maintained at lower levels to attain energy savings, thus contributing to lower greenhouse gas emissions. On the other hand, porosity reductions are obtained at 1050 o C, resulting in water absorptivity decrease, which could be of importance in terms of weathering and frost-resistance behavior. The beneficial utilization of industrial powders in value-added ceramic materials engineering can contribute to both production cost alleviations and environmental protection. Acknowledgement: This research has been co-financed by the European Union (European Social Fund - ESF) and Greek national funds through the Operational Program "Education and Lifelong Learning" of the National Strategic Reference Framework (NSRF) Research Funding Program: ARCHIMEDES III. Investing in knowledge society through the European Social Fund. Figure 1. Formation of plastic mass and extrusion of ceramic specimens for subsequent firing-sintering.

271 Bulk density (g/cm 3 ) 2 1,8 1,6 1,4 1, C 950 C 1050 C EAFD (%w/w) M.O.R (MPa) C 950 C 1050 C EAFD (% w/w) Figure 2. The effect of the % steelmaking-dust (EAFD) addition and also of the firing temperature on the open porosity, water absorption capacity, bulk density & modulus of rupture (MOR) upon bend testing of sintered ceramic specimens.

272 CYANIDE REMOVAL FROM WATER BY ADVANCED OXIDATION PROCESSES BASED ON OZONE AND HYDROGEN PEROXIDE N. Miguel, N. Pueyo, A.Palomar, M.P. Ormad, J.L. Ovelleiro Department of Chemical Engineering and Environmental Technologies. University of Zaragoza. María de Luna 3, Zaragoza (Spain) Tel.: Scientific Topic: 2.2. Environmental Technology and Risk Analysis. Advanced Techniques for Effluent Treatment Cyanide ion (CN -) is a chemical substance with known toxic nature, reason why it is preferred substance and its maximum permissible concentration in natural water is regulated by current legislation (Royal Decree 60/2011). For this cause, it is necessary to know the presence of this substance in wastewaters and, if necessary, reduce its concentration in the same prior to discharge. Due to this, the study of removing cyanides arises through advanced oxidation processes (AOPs), based on the generation of radicals that are capable of removing cyanides and consequently generates less toxic compounds that generated in other processes. AOPs can be carried out by using various reagents such as metallic catalysts, ozone, UV radiation, hydrogen peroxide, etc.. Specifically, the aim of this work is to study the effectiveness of AOPs based on ozone and hydrogen peroxide to remove cyanide from water. Samples are prepared in distilled water with a concentration of CN - about 5 mg L -1. These samples were subjected to different treatments: O 3, H 2 O 2 and O 3 +H 2 O 2. For each treatment the cyanide concentration is measured before and after treatment through the standard method 4500-CN - C and D based on a distillation of the sample and subsequent tritation. After that, the removal rates of cyanide in water are calculated for each treatment applied. Ozonation treatment is carried out with a ozonator FISCHER 500 previously calibrated. Ozone dose between 12 and 147 mg L-1 is applied. The ozonator is connected to a closed glass reactor where the sample is located. Ozone gas is transferred to the sample by the top of the reactor through a porous divider (O 3 introduced). Not all of the ozone produced reaches consumed in the reaction as part remains in the gas phase in the upper region of the reactor. The ozone should be destroyed (not consumed O 3 ) so two bubblers are placed in series to the reactor containing a solution of 2% potassium iodide. Ozone reacts with potassium iodide and oxygen reduced to leak into the atmosphere. The amount of unconsumed O 3 is calculated by a volumetric method with sodium thiosulfate. Also the residual dissolved ozone in water is measured by a colorimetric test (Merck), and may calculate the ozone consumed by the sample as: O3 consumed = O 3 introduced - O 3 not consumed - O 3 residual Treatment with hydrogen peroxide (Panreac, 30% w / v) is applied adding the reagent directly to the sample with stirring at 60 rpm for 5 minutes. H2O 2 applied doses vary between 25 and 150 mg L -1. Finally, the treatment O 3 +H 2 O 2 is applied. The procedure is the same as for the O 3 treatment, adding H 2 O 2 to the sample at the starting time of ozonation. In this case H 2 O 2 /O 3 molar ratios between 0.25 and 5 are applied. The results achieved at this moment are the next: - O 3 treatment is very effective in removing cyanides from the water, achieving almost complete removal with a dose about 50 mg L -1 O 3. - H2O 2 treatment is not effective in removing water cyanides. The higher percentage removal is less than 15% and is obtained at a hydrogen peroxide dose of 100 mg L Treatment with O3+H 2 O 2 is very effective in removing water cyanides, although a priori, the addition of H 2 O 2 is not a great improvement over the O 3 treatment.

273 P-6 P-7 P-1 P-9 P-3 P-8 I-2 P-10 APPLICATION OF FORWARD OSMOSIS TO CHEMICAL WASHING EFFLUENTS FROM BEVERAGE INDUSTRY E. Gonga Roselló, M. F. López-Pérez, J. Lora García, A. Abad Sempere Universitat Politècnica de València. Instituto de Seguridad Industrial Radiofísica y Medioambiental. Plaza Ferrandiz y Carbonell s/n, Alcoy E-03801, Spain corresponding Author: Scientific topic: 2.2 Advanced Techniques for Effluent Treatment In recent years, the soft drinks industry has needed special attention for sustainable water management. The reuse strategies cover a wide range of applications in order to water reclamation from wastewater treatment plant. Furthermore, according to the legislation such facilities require a more effective and frequent chemical cleaning, to prevent malfunctions or contamination that would alter the safety or quality of the products. This way of cleaning is known as CIP (Cleaning-in-place) and is working on the interior surfaces of pipes, vessels, and process equipment without disassembly, by hot water by injection, caustic and acid solutions with detergents and disinfection by chemical such as sodium hypochlorite. CIP generates a series of highly polluted effluents to be managed independently from the rest of the wastewater. Since the volumes of these wastes are low, the usual form of management is evaporation, which is an energyintensive and high cost. Forward osmosis (FO) has been studied as an alternative membrane technology to the treatment of CIP wastewater. FO has some advantages such as needs less pressure and lower energy than other technologies. FO is defined as the net movement of water across a selectively permeable membrane driven by a difference in osmotic pressure across the membrane [1]. The batch FO experiment setup for wastewater treatment is shown in figure 1. Flow-meter Pump Draw solution Scale Membrane module Scale E-8 E-9 Flow-meter Pump Wastewater The three major components of this setup are the cross-flow membrane cell, the draw solution flow loop, and the wastewater flow loop. The draw solution flowed on the active layer of the membrane and the feed on the permeate side. Concurrent flow wa used to minimize the shear force on the membrane. A flat-sheet cellulose triacetate (CTA) FO membrane from HTI OsMem with 34 cm 2 of effective area was used in all experiments. Draw solutio (DS) was prepared by dissolving NaCl in deionized water (DI) to achieve 38±1 g/l. The synthetic beverage industry wastewater ha soluble COD of mg/l, TKN of 54 mg/l, total P of 2,5 mg/l, TSS of 250 mg/l and ph of 5,4 [2]. Figure 1. Pilot plant scheme The water flux evolution showed similar values in all experiments, at the beginning of the experiment the water flux was around 5±0,1 L/m 2 h, however a decrease in water flux was observed until 3-4 L/m 2 h. This flux reduction can be attributed to different issues such as an osmotic pressure decrease, membrane fouling and concentration polarization at both sides of the membrane. Forward osmosis can be an appropriate technology in order to treat the CIP wastewater from beverage industries in order to reduce costs and environmental impact. [1] S.Oktay, G.Iskender, F.Germirli, G.Kutluay, D.Orhon, (2007) Desalination, 211, [2] B. D. Codaya, P. Xub, E.G. Beaudry et al. (2014) Desalination

274 CHEMICAL DURABILITY AND STRUCTURAL PROPERTIES OF PHOSPHATE GLASSES Y. Makhkhas *, S. Krimi ** and E.H. Sayouty * * Université Hassan II, Casablanca, Faculté des Sciences Ain Chock, Departement de Physique. (corresponding Author) ** Universit Hassan II, Casablanca, Faculté des Sciences, Departement de Chimie. Chemical Engineering for Sustainable Developments Environmental Technology and Risk Analysis The paper reports a study on phosphate glasses, containing chromium, iron and Sodium oxides. This kind of phosphate glasses provide high chemical stability against water and enhance the glass capacity to embed different chemical compounds. The sodium-chromium-iron phosphate glasses (26-y)Fe 2 O 3 -ycr 2 O 3-19Na 2 O 3-55P 2 O 5 (mol %), with (0 4) were prepared by direct fusion of the mixture of the reactants followed by quenching in the air. The Sample was annealed at 650 C for 48h. The glasses have been characterized by X-Ray diffraction, and the IR spectroscopy. Their dissolution rate at 90 C in distilled water showed a good chemical durability unlike borosilicate and window glasses. The chemical durability was then evaluated by weight losses of glass samples after immersion in hot distilled water for 30 days. Therefore it has been suggested that the chemical durability of these kinds of glasses is attributed to the replacement of P O P bonds by P O Cr and P O Fe bonds. The presence of P O Fe bands in higher concentrations makes the glass more hydration resistant. The P O Cr bands seem to play the same role than P O Fe bands. Keywords: Chemical durability, IR spectroscopy, Structure, glass formation, Sodium-chromium-iron-phosphate glasses, X Ray Diffraction, quaternary system.

275 REMOVAL OF PHARMACEUTICAL COMPOUNDS, IBUPROFEN AND CLOFIBRIC ACID BY HETEROGENOUS PHOTO FENTON- LIKE PROCESS WITH IN-SITU H 2 O 2 Pallavi P. Ghute*, Shailesh S Sable, Francesc Medina, Sandra Contreras Department d'enginyeria Química, Universitat Rovira i Virgili, Campus Sescelades, Avda. Països Catalans, 26, Tarragona-43007, Spain.Tel: (+34) , Fax: (+34) Scientific Topic: 2.2 Environmental technology and Risk analysis In recent years, concern regarding the presence of environmental xenobiotics such as pharmaceuticals and personal care products in surface and groundwater has been growing due to their adverse effects on aquatic life and potential impact on human health. Although the detected concentration of PhACs is often low, potential risk to human health and ecological environment still remains high as they are highly persistent and are resisting to water and waste water treatment. Studies have shown that complete removal of these compounds is difficult to accomplish by conventional wastewater techniques (1-2). Ibuprofen (IBP), a Non-Steroidal Anti-Inflammatory Drug (NSAID), is present in effluents of waste water treatment and in spite of its significant biodegradation rate, by-products generated during its biological oxidation appears to be toxic in nature. Another class of PhACs, clofibric acid (CFA), a primary metabolite of lipid regulator drug clofibrate, occurs in surface and groundwater due to its polar character.(3) Advanced Oxidation Processes (AOPs) could be an interesting and effective technology for removal of recalcitrant contaminants. Among the various AOPs, heterogenous Fenton like process in combination with UV light is highly efficient in waste water treatment. High mineralization degree of organic compounds was achieved by in situ generated H 2 O 2 from formic acid and oxygen by a novel Pd Fe catalytic system (4). The present work investigates the efficiency of the combined approach, heterogeneous Fenton reaction with in-situ hydrogen peroxide generation from formic acid and oxygen using Pd-magnetite nanoparticles (NPs) in presence of UVA light for oxidative degradation of ibuprofen and clofibric acid. Magnetite-Pd nanoparticles were synthesized using polyvinylpyrolidone as stabilizer and hydrazine hydrate as reducing agent. Ammonium hydroxide was used for co-precipitation of magnetite Nps. Further, synthesized NPs were impregnated on alumina and commercial TiO 2 (P25). Catalyst was characterized by XRD, ESEM and TEM. Decomposition of IBP (30ppm) and CFA (10ppm) was carried out in presence of black light lamps with power of 4 and 60W using Fe 3 O 4 -Pd supported alumina and TiO 2 catalyst (0.250g/L). Formic acid concentration used for in-situ H 2O 2 generation was 1mM with oxygen flow of 20ml/min. All reactions were performed for 6h. Photolysis and photocatalytic oxidation was also carried out using commercial TiO 2 and NPs supported catalyst. Fig1: CFA removal using different catalyst Fig 2: IBP removal and mineralization using 5wt%Fe 3 O 4 -Pd/TiO 2 Complete removal with ca. 50% mineralization of CFA was obtained in 6 h with 5wt%Fe 3 O 4 -Pd/TiO 2 catalyst with 4W lamp, whereas with power of 60W lamps, CFA was removed within 2h. As shown in above Figure 2, IBP is also almost completely decomposed with 40% mineralization in presence of UVA light with 60W power in 6h. References 1. Choina J.; Kosslicka H.; Fischer Ch.; Flechsig G.-U.; Frunza L.; Schulz A. Applied Catalysis B: Environmental, 2013, 129, Choi J; Lee H; ChoicY; Kim S; Lee S; Lee S;Choic W; Lee J. Applied Catalysis B: Environmental, 2014, 147, 8 3. Méndez-Arriaga F.; Esplugas S.; Gimenez J. Water Research, 2010, 44, Yalfani, M.S.; Contreras, S.; Medina, F. and Suieras, J., Phys.Chem.Chem.Phys, 2010, 12,

276 INFLUENCE OF VARIOUS INDUSTRIAL SOLVENTS ON THE ANAEROBIC BIODEGRADABILITY OF ETHANOL N. Vermorel, M. Izquierdo, C. Gabaldón, J.M. Penya-Roja Department of Chemical Engineering, Escola Tècnica Superior d Enginyeria, University of Valencia, Av. Universidad s/n, Burjassot (Spain), Phone: , Fax: , Scientific topic: 2.2 Environmental Technology and Risk Analysis Introduction. Solvents contamination in water creates some risk for human health and for the environment. Consequently, industrial emissions of solvents should be controlled and are regulated by laws, such as the European Industrial Emissions Directive (2010/75/EU). Complex mixtures of solvents can be found in industrial wastewaters and can be treated anaerobically. It is essential for the success of anaerobic digestion to determine the effect of each solvent on this process and detect eventual inhibitory or toxic effects. (Chen, Cheng, & Creamer, 2008). However, some industrial solvents found in wastewaters have not been studied yet. The aim of this study was to investigate the influence of industrial solvents, namely ethoxypropanol and methoxypropanol, on anaerobic digestion of ethanol in laboratory scale batch reactors. For this purpose, an industrial wastewater containing ethanol (the main compound) and ethylacetate, methoxypropanol and ethoxypropanol as the other major compounds was taken as a reference. Material and methods. AMPTSII by BioProcess Control was used to determine the biochemical methane potential (BMP) of the substrates in 500 ml batch reactors. The BMP assays were done according to the (EPA, 2008) guidelines. The inoculum was obtained from a wastewater treatment system treating the above-mentioned mixture of solvents for one year. The substrate initial total concentration in each reactor was kept at 2.0 gcod/l, according to the average substrate concentration in the industrial wastewater studied. Based on preliminary results, the inoculum to substrate ratio was kept at 3 on a COD basis. Every reactor was supplemented with appropriate nutrients, alkalinity and yeast extract, taking into account typical requirements reported in the literature (Singh, Kumar, & Ojha, 1999) and previous laboratory results. The tests were performed at 25 C. At first, the methane production with 100% ethanol was tested and used as a reference for the following experiments. Then trials with a mixture of ethanol/ethoxypropanol were performed with increasing ethoxypropanol percentages of 20, 40, 60, 80 and 100%. Likewise, trials were performed with a mixture of ethanol/methoxypropanol and methoxypropanol s percentages of 10, 30 and 80% (on a COD basis). Results and discussion. The methane s cumulative production for the experiment with a substrate consisting of 100% of ethanol was 231.7±5.9 NmL CH 4. This represents 82.7±2.1% of the expected (theoretical) methane production (280 NmL). The ethanol was degraded within 35.8 hours. Thus, the overall Specific Methonogenic Activity was 94.4±3.4 ml CH 4 g -1 VSS d -1. For the mixtures of solvents, the methane production was observed in 2 distinct periods of time, separated by t: the first production was probably associated to the ethanol biodegradation and the second to biodegradation of the other solvent. The first methane production was recorded within 35.8 hours, and the second one after t 300 hours. These first methane productions for the ethanol/ethoxypropanol mixtures, expressed as a percentage of the total methane production for the 100%- ethanol trial, were found to be: 80.6±1.9, 60.7±0.2, 42.6±1.1 and 20.7±1.8% for trials with 80, 60, 40 and 20% of ethanol respectively. For the ethanol/methoxypropanol mixtures, these percentages were: 18.9±0.13, 72.3±0.6 and 91.1±3.5% for substrates mixtures with 20, 70 and 90% of ethanol respectively. These results demonstrate that there is no influence of ethoxypropanol or methoxypropanol on the total methane production in anaerobic biodegradation of ethanol in these conditions. Future perspectives on this topic include the study of the other solvents influence on the degradation of ethanol and extending the concentrations levels studied to others typically found in other industries effluents. Optimization of the anaerobic degradation of the less biodegradable solvents should also be investigated (specific sludge acclimatation, nutrients supplementation optimization, etc.). Acknowledgements. The research leading to these results has received funding from the People Programme (Marie Curie Actions-ITN) of the European Union's Seventh Framework Programme FP7/ / under REA grant agreement n (TrainonSEC). Funding from Generalitat Valenciana (Prometeo/2013/053) is acknowledged. References Chen, Y., Cheng, J. J., & Creamer, K. S. (2008). Inhibition of anaerobic digestion process: A review. Bioresource Technology, 99(10), EPA (2008.). Fate, Transport and Transformation Test Guidelines OPPTS Anaerobic Biodegradability of Organic Compounds in Digested Sludge: By Measurement of Gas Production.

277 Singh, R. P., Kumar, S., & Ojha, C. S. P. (1999). Nutrient requirement for UASB process: a review. Biochemical Engineering Journal, 3(1),

278 A SIMPLE MODEL OF A GAS LIQUID REACTOR FOR SEMIBATCH OZONATION OF WASTEWATERS M. Marce (1), S. Esplugas (1), S. Baig (2). (1) Chemical Engineering Department, University of Barcelona, Martí i Franqués, 1 (08028) Barcelona, Spain. (2) Degremont SA, 183, avenue du 18 juin 1940, Rueil-Malmaison cedex France. ( *Corresponding author: Scientific topic: Advanced Techniques for Effluent Treatment When ozonizing in semibatch mode (continuous flow of ozonized gas through a stirred tank with water effluent, Figure 1) changes in ozone concentration in aqueous and gas phases with time takes place. At initial times, the reaction in the liquid phase do not let the ozone to accumulate in the water and lately, the aqueous ozone concentration increases from zero to a maximum and stable value. An interesting parameter named immediate ozone demand (IOD) is defined as the amount of ozone injected to water by unit volume until its aqueous concentration increases from cero. IOD corresponds to the step of fast removal of degradable compounds. Assuming negiglibe hold up of the gas phase, first order kinetics for dissolved ozone reaction and perfect mixing in liquid phase, the balance ozone aqueous concentration ([O3] L ) leads to the following equation: d[ O3] V dt V L * ] L L L d L 0 K a([ O3] [ O3] ) dv k [ O3 V (eq 1) Where V is the volume of the reactor, K L a the mass transfer coefficient, [O3] L * the ozone concentration in the aqueous phase at equilibrium with ozone in the gas phase and k d the first order decay constant of dissolved ozone. The value [O3] L * may be easy estimate through a modified Henry s law * [ O3] gas H mod [ O3] L (eq 2) Where H mod is a modified Henry constant and [O3] gas the concentration of ozone in the gas phase ranging from [O3] gas in to [O3] gas out. Assuming steady state and plug flow for the gas the ozone balance in gas phase leads to the following equation relating [O3] gas out and [O3] L : K LaVT K LaVT [ O3] gas out [ O3] gas in exp H mod[ O3] L 1 exp (eq 3) QgasH mod QgasH mod In the case of K L a and k d constants, equation 1 may be solved giving a complex analytical solution. According to figures 2 and 3, the experimental results using effluents coming from microfiltration treatment of urban wastewater (Domenjoud et al, Ozonation and GAC filtration for the control of organic micropollutants in urban wastewaters. IOA IUVA world congress 2011 Paris, France) fit quite well to this simple mathematical model. Acknowledgement This work was financially supported by the European Union within the framework of ACQUEAU (Project TRIUMPH).

279 Operación de un Bioreactor de Membranas Anaeróbico (BRM- An) para el tratamiento de agua residual vitivinícola N. Basset; E. Santos; J. Dosta; A. Guastalli; J. Mata-Álvarez Departamento de Ingeniería Química, Universidad de Barcelona, Martí i Franquès, Barcelona, Spain Resumen El creciente interés en el desarrollo de nuevas tecnologías compactas para tratamientos intensivos es debido a las estrictas regulaciones en materia de eliminación de residuos y el objetivo de reducir las necesidades energéticas y de espacio. El principal objetivo de este estudio es operar un bioreactor de membrana anaeróbico (BRM-An) con agua residual vitivinícola, con especial énfasis en las fluctuaciones típicas de este tipo de aguas. El primer periodo de operación del BRM-An se llevó a cabo con agua residual sintética con una concentración de demanda química de oxígeno (DQO) desde 1,0 a 9,6 g DQO L -1, que corresponden a una carga orgánica de 0,16 y 5,5 kg DQO m -3 d -1, respectivamente. Seguidamente, en el segundo periodo de operación, se alimentó el BRM-An con agua residual vitivinícola generada durante la época de vendimia, observando concentraciones de DQO entre 1,2 y 12 g DQO L -1, y una carga orgánica entre 0,34 y 3,6 kg DQO m -3 d -1. Se observaron bajas concentraciones de DQO en el efluente durante casi todo el periodo de experimentación sin presencia de ácidos grasos volátiles (VFA), obteniendo una eficiencia media de eliminación de materia orgánica del 92%. La producción de biogás se incrementó progresivamente acorde a la carga orgánica aplicada en cada periodo, consiguiendo un máximo de 1,26 m 3 CH4 m -3 digestor d -1 cuando el influente contenía 12 g DQO L -1. Abstract The anaerobic membrane bioreactor (AnMBR) is an interesting technology when intensive and compact treatments are needed to reduce space requirement. Its application to winery wastewater is worth considering due to its high organic load and low nutrient content. Moreover, as sludge and hydraulic retention times are independent parameters, the AnMBR could cope with influent fluctuations. A mesophilic AnMBR was operated with synthetic winery wastewater at lab scale progressively increasing the influent COD concentration from 1.0 to 9.6 g COD L -1, which corresponded to a maximum organic loading rate of 5.5 kg COD m -3 d -1. Then in the second period, real winery wastewater was fed to the AnMBR. COD concentration varied from 1.2 to 12 g COD L -1, achieving over 92% of organic matter removal and a biogas production up to 1.26 m 3 CH4 mdigester -3 d -1. Effluent COD concentration was below 100 g COD L -1 during all the experimental period, with low VFA content. Palabras clave Agua residual vitivinícola; Bioreactor de membranas anaeróbico; Eliminación de materia orgánica INTRODUCCIÓN En los últimos años, la tecnología del biorreactor de membrana (BRM) ha experimentado un gran crecimiento debido a sus numerosas ventajas en comparación con los tratamientos convencionales. La razón principal de tal éxito es su capacidad de obtener un efluente de alta calidad, libre de sólidos suspendidos, cumpliendo los requisitos legales en un espacio reducido. Sin embargo, la principal limitación de la tecnología BRM es el ensuciamiento de la membrana, que es el factor más importante a tener en cuenta debido a su estrecha relación con el consumo de energía (Judd, 2011). Esta es la razón por la cual la competitividad de la tecnología BRM se ve amenazada por el bajo coste de operación de los tratamientos convencionales. Es bien sabido que los procesos de digestión anaeróbica logran altas eficiencias de remoción de materia orgánica sin necesidad de oxígeno, baja producción de biomasa y, además, se obtiene energía a partir del biogás producido (Metcalf and Eddy, 2003). La tecnología BRM-An permite ampliar la gama de posibilidades de la digestión

280 anaeróbica, de modo que, gracias a la inmovilización de la biomasa, se convierte en un tratamiento válido para aguas tanto con alta como con baja carga orgánica. En la década de los 80 se empezó a aplicar esta tecnología para el tratamiento de residuos orgánicos y aguas residuales industriales con alto contenido orgánico de las destilerías, fosas sépticas, industrias de alimentos y papel, etc. (Liao et al., 2006). Debido a la retención de biomasa, que permite el desacoplamiento del tiempo de retención hidráulico (TRH) con el tiempo de retención de sólidos (TRS) se consigue tratar hasta 25 kg Demanda Química de Oxígeno (DQO) m -3 d -1 (Skouteris et al., 2012). El BRM-An se presenta como una tecnología que, además de eliminar los contaminantes del agua, es capaz de recuperar energía en forma de metano. El BRM- An puede convertir hasta el 98% de la DQO del influente en biogás (Van Zyl et al., 2008). Asimismo, el biogás producido en un BRM-An puede contener hasta un 80%- 90% de metano (Skouteris et al., 2012). El BRM-An es una tecnología interesante para el caso específico de las aguas residuales vitivinícolas, que se caracterizan por una alta carga orgánica, bajo contenido en nutrientes y alta variabilidad estacional. Este estudio pretende evaluar la viabilidad de un tratamiento BRM-An para este tipo de aguas industriales. MATERIALES Y MÉTODOS El BRM-An se instaló como un digestor tanque agitado de 4 L acoplado a un módulo de membrana externa de placa plana de microfiltración (Orelis, Rayflow Module) de 100 cm 2 de área. El agua residual a alimentar se colocó en un tanque refrigerado para evitar su degradación. Durante el primer periodo, el digestor se alimentó con agua residual sintética hecha con vino blanco diluido añadiendo NH 4 Cl y K 2 HPO 4 con una relación DQO:N:P de 800:5:1, así como NaHCO 3 para proporcionar cierta alcalinidad, aproximadamente 800 mg CaCO 3 L -1. En el segundo periodo, se recogió agua residual de una industria vitivinícola durante la época de vendimia, en la Tabla 1 se presentan los promedios de los parámetros principales con la correspondiente desviación estándar, destacando la importante variabilidad en la concentración de DQO. Debido a la escasez de nutrientes, los mismos reactivos se tuvieron que añadir para favorecer el crecimiento de la biomasa. Tabla 1. Características principales del agua residual vitivinícola en época de vendimia DQO (mg L -1 ) N-NH4 + (mg L -1 ) SST (mg L -1 ) SSV (mg L -1 ) ph Alcalinidad (mg L -1 ) 5126,8 (2627,6) 31,4 (10,1) 913,3 (115,4) 763,3 (120,7) 5,5 (0,7) 345,0 (50,4) RESULTADOS Y DISCUSIÓN En el primer periodo, la operación del BRM-An se llevó a cabo con agua residual sintética con una concentración de DQO desde 1,0 hasta 9,6 g DQO L -1, que corresponde a una carga orgánica de 0,16 and 5,5 kg COD m -3 d -1, respectivamente. Posteriormente, a partir del día 172, se alimentó el BRM-An con agua residual vitivinícola con una concentración de DQO entre 1,2 y 12 g DQO L -1, lo que implica una carga orgánica entre 0,34 y 3,6 kg COD m -3 d -1. Las fluctuaciones en la concentración de DQO del influente se presentan en la Figura 1. Se puede observar que las concentraciones de salida de DQO son muy bajas, por debajo de 100 mg DQO L -1, y no se detectaron ácidos grasos volátiles (AGV), consiguiendo eficiencias de remoción de materia orgánica por encima del 92%. Sin embargo, se debe destacar que, puntualmente los días 150 y 190, se detectaron valores de AGV de hasta 840 and 876 mg L -1 debido a fluctuaciones demasiado bruscas.

281 14 DQO influente DQO efluente 7 DQO inluente (g L 1 ) Tiempo (d) DQO efluente (g L 1 ) Figura 1. Evolución de la DQO a lo largo de la operación del BRM-An En la Figura 2 se puede observar la producción de metano a lo largo del periodo experimental, que incrementa a medida que la carga orgánica es mayor. Sin embargo, debido a las fluctuaciones en las características del influente, la producción de biogás también oscila, alcanzando un máximo de 1,26 m 3 CH 4 m -3 digester d -1 cuando la DQO de entrada era de 12 g COD L -1. A pesar de la variabilidad obtenida en la producción de biogás, el porcentaje de metano se mantuvo constante al 85%. Producción de metano (m 3 m 3 d 1 ) Tiempo (d) Figura 2. Producción de metano a lo largo de la operación del BRM-An OPERACIÓN DEL MÓDULO DE MEMBRANA El módulo de membrana acoplado al digestor fue caracterizado previamente siguiendo el procedimiento de Bae and Tak (2005), quienes midieron la resistencia total a la filtración como un conjunto de tres resistencias: a la membrana, a la torta y al ensuciamiento. Se determinó que la principal resistencia es debida a la torta que se deposita en la superficie de la membrana durante la filtración de lodo. De modo que la velocidad de flujo cruzado juega un papel importante, ya que a mayor velocidad se consigue una mayor fuerza de cizalla y un mayor desprendimiento de partículas. Por otro lado, según el procedimiento de Le Clech et al. (2003) se determinó el flujo crítico de 24 LMH, por debajo del cual se recomienda trabajar para evitar ensuciamiento severo.

282 Durante la operación del sistema conjunto BRM-An, se registró diariamente el flujo de la membrana, observando que disminuyó progresivamente. El módulo trabajaba con una velocidad de flujo cruzado constante de 0,64 m s -1 y a una presión de 0,2 bar. En la Figura 3 se observa que, en los primeros días, el flujo se mantuvo entre 20 y 25 LMH, aunque rápidamente decreció hasta alrededor de 15 LMH. Al cabo de 150 días el flujo disminuyó por debajo de 5 LMH, momento en el que la concentración de sólidos suspendidos volátiles (SSV) en el digestor eran de 7,6 g L -1, motivo por el cual se procedió a una limpieza química, siguiendo el protocolo del proveedor. El flujo se recuperó aunque se mantuvo alrededor de los 10 LMH durante el resto del periodo experimental. 30 Flujo (LMH) SSV Flujo (LMH) SSV (g L 1) Tiempo (d) Figura 3. Evolución del flujo y SSV durante la operación del BRM-An Puntualmente, a lo largo de la operación se determinó la permeabilidad de la membrana al agua destilada, relacionándola con el ensuciamiento a largo plazo. Inicialmente, se obtuvo una permeabilidad de 540 L m -2 h -1 bar -1. Al cabo de 30 días de operación, se observó un importante declive hasta los 163 L m -2 h -1 bar -1. Sin embargo, después de 150 días de operación la permeabilidad se mantenía en los 163 L m -2 h -1 bar -1, trabajando a una presión de 0,2 bar. CONCLUSIONES El BRM-An ha resultado ser una tecnología eficaz para el tratamiento de agua residual vitivinícola, eliminando altas concentraciones de materia orgánica con un requerimiento de nutrientes reducido. Para su aplicación a gran escala se debería considerar los aspectos energéticos, puesto que la digestión anaerobia es ventajosa en época de vendimia, pero cuando la carga orgánica es baja se debe evaluar su rentabilidad, sobretodo por el impacto energético que tiene la unidad de fitlración. AGRADECIMIENTOS Los autores agradecen el soporte financiero al proyecto CTM del Ministerio de Ciencia e Innovación de España, así como al Ministerio de Educación por la beca pre-doctoral FPU. Bae, T.-H., Tak, T.-M., Interpretation of fouling characteristics of ultrafiltration membranes during the filtration of membrane bioreactor mixed liquor. J. Memb. Sci. 264, Judd, S., The MBR Book - Principles and Applications of Membrane Bioreactors in Water and Wastewater Treatment, Second. ed. Butterworth-Heinemann, Oxford (UK). Le Clech, P., Jefferson, B., Chang, I.S., Judd, S.J., Critical flux determination by the flux-step method in a submerged membrane bioreactor. J. Memb. Sci. 227, Liao, B.-Q., Kraemer, J.T., Bagley, D.M., Anaerobic Membrane Bioreactors: Applications and Research Directions, Critical Reviews in Environmental Science and Technology. Metcalf, Eddy, Wastewater Engineering: Treatment and Reuse. McGraw-Hill Inc., New York. Skouteris, G., Hermosilla, D., López, P., Negro, C., Blanco, Á., Anaerobic membrane bioreactors for wastewater treatment: A review. Chem. Eng. J , Van Zyl, P.J., Wentzel, M.C., Ekama, G. a, Riedel, K.J., Design and start-up of a high rate anaerobic membrane bioreactor for the treatment of a low ph, high strength, dissolved organic waste water. Water Sci. Technol. 57,

283 COMBINATION OF ADVANCED OXIDATION PROCESSES AND BIOFILTRATION FOR RECLAMATION REVERSE OSMOSIS BRINE A. Justo*, O. González, C. Sans Department of Chemical Engineering, University of Barcelona C/Martí i Franquès 1, Barcelona (Spain) Phone: (+34) Fax: (+34) Environmental Technology and Risk Analysis The micropollutants and organic matter present in the concentrate streams generated from reverse osmosis (RO) based municipal wastewater reclamation processes poses environmental and health risks on its disposal to the receiving environment. The suitability of a biological activated carbon (BAC) process combined with pre-oxidation using the advanced oxidation process (AOPs) UV/H 2 O 2 or ozone for treating municipal wastewater RO concentrate was evaluated at lab scale during 320 days of operation. The combined UV/H 2 O 2 and ozone pre-treatment with the BAC filter reduced considerably the overall quality water parameters DOC, COD and UV 254 between 50-66%, 48-66% and 73-87%, respectively, compared with the BAC alone (28%, 19% and 37%, respectively). Moreover, although some pharmaceutical were partially removed by the BAC filter, integrated ozone or UV/H 2 O 2 pretreatment were necessary to total micropollutants removal achievements.

284 ANAEROBIC CO-DIGESTION OF FARM WASTES: ULTRA-SOUNDS PRE- TREATMENT ON LIGNOCELLULOSIC WASTES. X. Fonoll, R. Roig, N. Basset, J. Dosta and J. Mata-Alvarez Department of Chemical Engineering, University of Barcelona, C/ Martí i Franquès, no. 1, 6th floor, 08028, Barcelona, Spain. Agriculture is a field in constant growth which originates great amounts of wastes that need to be treated. Within this framework, the anaerobic digestion process arises as a satisfactory alternative, as it gives biogas and a stabilized digestate as products. In the present study, the co-digestion of two agricultural substrates is carried out: pig manure is used as main substrate, whereas crops waste serves as co-substrate. Given the lignocellulosic structure of the latter, which is very recalcitrant, the application of a pre-treatment poses as essential. With a great variety of studied pretreatments in literature, the effect of ultra-sounds (US) on crops waste has not been tested yet and thus, this research is an attempt to solve this situation. With the aim of increasing the biodegradability of crops waste and hence the biogas yield, an experimental study in which two anaerobic reactors are operated was performed. The first one (R1) serves as a reference, whilst the second (R2) is the one in which the ultra-sounds pre-treatment is implemented. Both reactors were operated with a hydraulic retention time set to 30 days and an organic loading rate of 2.3 kg VS/ (m 3 day). After a period of 70 days, the volatile solids loss was very similar either with or without applying US (52.3 % in front of 51.3 %, respectively). The methane specific production was 0.39±0.11 L CH 4 / (g VS day) with US and 0.46±0.06 L CH 4 / (g VS day) without. The remaining parameters remained constant and similar between both cases. Neither biogas production nor the stability of the process were affected by the application of an US pre-treatment.

285 INFLUENCE OF THE INOCULUM IN THE RESPIROMETRIC BIODEGRADABILITY OF OXIDIZED WATERS P.Ribao 1, S.Dominguez 1, M.J. Rivero 1, I. Ortiz 1 1 Department of Chemical and Biomolecular Engineering, University of Cantabria, Av. Los Castros s/n, Santander, Spain; Tel , Fax: Presenting author Scientific Topic: 2. Chemical Engineering for Sustainable Development. Landfill leachate is an effluent that cannot be directly discharged mainly because of high organic load and ammonium nitrogen. Moreover, in most of the cases it is not fully biodegradable; therefore, enhancement of its biodegradability applying Advanced Oxidation Processes (AOPs) will increase the yield of biological treatment [1]. Biodegradability is determined by OECD tests [2]; among them respirometric assay predicts in an easy and rapid way the behavior of a target compound or an effluent in a biological reactor. This test is based on the direct relationship between the specific oxygen uptake rate and the biomass activity. The bioassay simulates the typical operation conditions of an activated sludge unit, using high biomass to COD ratio, which allows a significant reduction of the testing time [3]. In this work two sequential batch reactors (SBR) have been tested with different origins for the inoculum, i) inoculum from a landfill leachate treatment plant (LLTP) and ii) inoculum from municipal wastewater treatment plant (MWWTP). In both cases, the activated sludge was maintained in a 50 liter sequential batch reactor (SBR). It is equipped with diffusers and mechanical stirring and a feed and discharge system by peristaltic pumps. The entire system is automatically controlled. The reactor performs two daily cycles with the following steps: filling, feeding, sedimentation and discharge. The feed consists of av mg/l of COD per cycle with a weight ratio COD/N/P, 100/5/1. The evolution of dissolved oxygen (DO), biomass concentration (VSS), and the parameter Y in the SBR (Figure 1) for two different types of sludge was examined. The parameter Y represents the fraction of the carbon source used for biomass growth. Both types of sludge kept acceptable values of dissolved oxygen. It was observed that the life time of biomass from LLTP was lower than from the MWWTP because of the low values of Y and suspended solids that are achieved after 30 days of operation. The value of Y has to be close to 0.68 and suspended solids around 3500 mg/l, values that are kept for 4 months in the SBR with sludge from MWWTP. Therefore, it is concluded that the sludge from a municipal wastewater treatment plant has better adaptability to respirometric assays than the sludge from landfill leachate biological treatment. Figure 1. Change in DO and VSS values (a) and y parameter value (b) with time in a WWTPs and LLTP. Financial support from the Spanish Ministry of Economy and Competitiveness and from FEDER funds (projects CTM and CTQ ) are gratefully acknowledged. Sara Dominguez also thanks the FPI postgraduate research grant (BES ). References [1] C. Comninellis, A. Kapalka, S. Malato, S.A. Parsons, I. Poulios, D. Mantzavinos, J. Chem. Technol. Biotechnol. 83 (2008) [2] Vázquez, G., Beltrán, R. Interciencia (2004), 29 (10), [3] Sanchis, S., Polo, A.M., Tobajas, M., Rodriguez, J.J., Mohedano, A.F. Chemosphere (2013) 93,

286 Influence of certain parameters of Chine clay on its dustiness A. LÓPEZ-LILAO 1, M. BRUZI 2, V. SANFELIX,3, A. GOZALBO 1,3, G. MALLOL 1,3, E. MONFORT 1,3 1 Department of Chemical Engineering. Universitat Jaume I. Castellón. Spain. 2 Ecole Nationale Supériere de Céramique Industrielle. Limoges. France. 3 Instituto de Tecnología Cerámica AICE. Universitat Jaume I. Castellón. Spain. Handling of particulate materials may pose a health risk to both workers inside the facilities (occupational health) and general population outside atmosphere (air pollution). To study the tendency of China clay (kaolin) to produce dust when it is handled, i.e., its dustiness, samples with different mean particle size were prepared and tested using the continuous drop method, one of the reference test methods according to standard EN 15051:2006 Workplace atmospheres Measurement of the dustiness of bulk materials Requirements and reference test methods. In this work, with a view to relating the dustiness of the materials to their properties, particle size distribution, specific surface area and Hausner ratio of these samples were determined. The results, in the range of sizes (3-10μm) included in this study, might be interpreted on the bases of the mechanisms involved in the particles emission process, concluding that surface forces dominate over volume forces. This information is deemed essential for establishing the most efficient preventive and/or corrective measures to reduce the generation of fugitive emissions of particulate matter during China clay processing, which may be extrapolated to particulate materials with similar properties. Keywords: particulate matter (PM); dustiness; fugitive emissions; occupational health; China clay. Type of communication: poster Corresponding author:

287 WaterReuse: el reto de la reutilización de agua de proceso en la industria. Autores: PEDRO TRINIDAD, PEDRO MUÑOZ, JOSÉ AGUIRRE, MANUEL SUSARTE Y MIGUEL OCTAVIO. DESTILERÍAS MUÑOZ GÁLVEZ, S.A MUGASA Es necesario avanzar hacia una mejor conexión entre mayor productividad y menor consumo y vertido de efluentes. La eficacia en la reducción de la carga orgánica con el sistema WaterReuse ya ha sido validada a escala de laboratorio con efluentes reales. El sistema ofrece claras ventajas frente al tratamiento aerobio y tiene amplias posibilidades de transferencia al sector de la industria alimentaria Los pronósticos de crecimiento en la UE para 2030 muestran que, considerando el consumo de agua en la agricultura, la industria y el ámbito doméstico, existirá una brecha entre la demanda y la oferta entorno al 40%. Dicha brecha tendrá que ser resuelta a través de estrategias como la reutilización. El proyecto WaterReuse, cofinanciado por el Programa Europeo LIFE+, propone un innovador sistema de mejorar la gestión eficiente del agua en el sector industrial aumentando la reutilización del agua y reduciendo la huella de Carbono de los tratamientos necesarios para eliminar la DQO. Será desarrollado por Destilerías Muñoz Gálvez, S.A., una PYME del sector químico, y validado en industrias alimentarias, en colaboración con el Centro Tecnológico Nacional de la Conserva y Alimentación. El proyecto tiene como objetivo testar y difundir un sistema que permitirá la reutilización de hasta un 95% del agua de proceso en la industria, considerando las diferentes reglamentaciones relativas a la calidad del agua y las especificaciones para su reutilización. Además de buscar la mayor eficacia, se pretende realizarlo con la máxima eficiencia. El tratamiento se ensayará en aquellos casos especialmente difíciles de caudales y composiciones variables con sustancias refractarias a biológico o tóxicas, que en general están desaconsejados para tratamientos clásicos, como los biológicos. Para ello partiendo del conocimiento y experiencia ganados en proyectos de laboratorio anteriores se ha diseñado y construido una planta piloto de demostración que aplica una combinación optimizada de tres tecnologías de reducción de carga orgánica, las tres consideradas MTB (Mejores Técnicas Disponibles): Filtración con membranas, Fotoquímica y Electro oxidación. Se utilizan paneles fotoeléctricos para generar una cantidad significativa del consumo energético de la planta. Además de diversos parámetros clásicos de proceso (Presiones Temperatura, Caudales.. monitorizan en continuo los parámetros electroquímicos de los reactores, calidad eléctrica de la red y TOC (Carbono Orgánico Total). Todos los datos de proceso son registrados por un PLC que ejerce las funciones de controlador automático de proceso, y que efectuará cálculos de optimización, decidiendo hasta que punto es aplicable cada una de las tecnologías, cuando se debe pasar a la siguiente o terminar el proceso, y buscar máximos de eficacia versus uso de recursos en función de condiciones iniciales tales coste de energía de la red, irradiación o producción eléctrica solar propia, máxima reducción de la Huella de carbono y de agua.

288 UNDERSTANDING THE EFFECT OF LEACHATE COMPOSITION ON ITS OXIDATION P. Oulego, S. Collado, A. Laca and M. Díaz Department of Chemical and Environmental Technology, University of Oviedo. E-33071, Oviedo, Spain. Tel.: Fax: Environmental Technology and Risk Analysis: Advanced Techniques for Effluent Treatment. Landfill leachates are defined as the aqueous effluent generated as a consequence of rainwater percolation through wastes, biochemical processes in the landfills waste's cells and the inherent water content of wastes themselves. They usually have high concentrations of organic contaminants, ammonia, heavy metals, and inorganic salts. Of the, The refractory humic substances, mainly humic acids and fulvic acids, are the main pollutants present in the leachates. Humic substances contribute to odor, color, taste as well as acidity problems in water supplies, and they have been identified as some of the major precursors for trihalomethane formation during water disinfection (chlorination) processes. Therefore and taking into account that landfilling is nowadays the main way of disposal for the enormous charge of municipal solid wastes generated all around the world, the development of affordable technologies for the treatment of such contaminant streams has become mandatory in the last few year with the aim to address the potential environmental threats of landfills [1]. To achieve a satisfactory removal of these pollutants from landfill leachate, several types of treatments have been adopted. Due to its cost-effectiveness, biological process is the most commonly employed method to remove the bulk of organic pollutants from landfill leachate. Nevertheless, although biological processes are quite effective when applied to relatively young leachates, they are less efficient for the treatment of older ones, due to their higher content in refractory compounds and ammonium. Advanced oxidation technologies are considered as one of the most promising options for leachate treatment due to its ability to enhance the biodegradability of the recalcitrant compounds in the leachate. Among them, wet oxidation appears to be an attractive method for the treatment of leachates. This technique is usually applied to contaminated waste streams which are too dilute to be incinerated (COD < 100 g/l) and/or with too low a level of biodegradability to be biologically treated (COD/DBO > 10) and frequently is applied prior to a biological treatment with the aim of obtain a significant decrease of overall leachate treatment cost [2]. Works on the suitable methods of leachates are mainly focused on the treatment of the leachate obtained from a specific landfill or on the removal of a pure compound that is selected as model pollutant due to its toxicity and/or abundance in the leachates (usually, humic or fulvic acids). Nevertheless, the composition of landfill leachates varies greatly depending on a lot of factors, such as landfill age, precipitation, seasonal weather variation, waste type and composition, landfill design and operational practice Consequently, a detailed study about the effects of the composition of the leachate on the performance and design of advanced oxidation process would be very useful in order to compare works carried out with different leachates and to achieve more general conclusions. In view of these considerations, the aim of this work has been to obtain a deeper knowledge of the effect of the main compounds usually found in leachates on the final effluent quality after oxidation, and in particular wet oxidation processes. For this purpose, the wet oxidations of a real leachate, its humic and fulvic fractions (separated by acid precipitation) and a commercial humic acid were carried out and compared with one another. These experimental results are used to determine the interactions between fractions and the weight of each one on the degree of mineralization, biodegradability, toxicity and color. References: 1.Renou, S., et al., Landfill leachate treatment: Review and opportunity. Journal of Hazardous Materials, (3): p Collado, S., A. Laca, and M. Diaz, Decision criteria for the selection of wet oxidation and conventional biological treatment. Journal of Environmental Management, (0): p

289 USE OF CO-CULTURES FOR THE SIMULTANEOUS BIODEGRADATION OF CYANIDE AND PHENOLIC COMPOUNS R. G. Combarros, S. Collado, A. Laca and M. Diaz Department of Chemical and Environmental Technology, University of Oviedo. E-33071, Oviedo, Spain. Tel.: Fax: Environmental Technology and Risk Analysis: Hazardous Wastes and Soil Remediation There is no doubt that activated sludge plants are the most widespread solution for the treatment of both municipal and industrial wastewater. Nevertheless, the cyanide and/ or phenolic compounds, which are frequently found in wastewaters from industrial plants such as petrochemical industries, coke-processing plants, metal finishing units, pharmaceutical factories, present an important problem in wastewater treatment plants, due to their toxic properties and the high amounts spilled out. These problems are being even more important during the last years, where the general trends are to build centralized industrial wastewater treatment plants, which receive the effluents from various industrial parks. Efficient removal of the cyanide and phenolic compounds requires new developments, which may be based on the study of alternative treatment techniques or the improvement of the existing biological treatments. In the first case, advanced oxidation processes (AOP) are considered as promising options due to their ability to enhance the biodegradability of the wastewater. These processes involve the generation of the hydroxyl free radical, which has a very high oxidation potential, by means of the use of strong oxidants (H 2 O 2, O 3 ), radiation (ultraviolet, ultrasound, electric beam) and/or catalysts (transition metal salts, photocatalyst). However, common drawbacks of AOP is the high demand of reagents or electrical energy for devices such as ozonizers, UV lamps, ultrasounds due to the high COD of the industrial wastewaters, which results in rather high treatment costs [1]. The improvement of the biological treatments using pure cultures of microorganisms specially adapted to metabolizing the contaminant appears to be an alternative to conventional or advanced processes. The pure cultures that are most active in biodegrading hazardous substances can be isolated by conventional microbiological methods, quickly identified by molecular-biological methods, and tested for pathogenicity and biodegradation properties. Applications of defined pure starter cultures have theoretical advantages: greater control over desirable processes; lower risk of release of pathogenic or opportunistic microorganisms during biotechnological treatment, and lower risk of accumulation of harmful microorganisms in the final biotreatment product. In the literature, the individual biodegradations of cyanide or phenolic compounds by Paracoccus thiocyanatus or Pseudomonas putida, respectively, are very well documented [2, 3]. However, as far as we know, there are no studies dealing with the simultaneous biodegradation of both compounds using a co-culture. This information could be employed as a reference during the comparison with those from other work using mixed cultures, in order to determine synergetic effects between species or the length of time required for acclimation. It is also a necessary previous step for investigating the potential benefits that may be obtained by the addition of a carefully selected pure cultures to a mixed culture for the degradation of these xenobiotics (bioaugmentation) Taking into account these considerations, the aim of the present work has been to evaluate the simultaneous biodegradation of thiocyanate (as model of cyanide pollutant) and salicylic acid (as model of phenolic pollutant) by a co-culture of P. thiocyanatus and P. putida. For this purpose, the individual and simultaneous biodegradations of thiocyanate and salicylic acid by a co-culture of both bacteria have been monitored in shake flask experiments under different initial concentrations Results have allow to determine the synergy/ inhibitory phenomena between species and to define the kinetic model and. Additionally, a flow cytometry procedure by using a double staining procedure (cfda/pi) has been developed and tested with the aim of determining the physiological status of the co-culture bacteria during the biodegradation process. References: 1. Andreozzi, R., et al., Advanced oxidation processes (AOP) for water purification and recovery. Catalysis Today, (1): p Combarros, R.G., et al., Influence of Biofilm on Activated Carbon on the Adsorption and Biodegradation of Salicylic Acid in Wastewater. Water, Air, & Soil Pollution, (2): p Katayama, Y., A. Hiraishi, and H. Kuraishi, Paracoccus thiocyanatus sp. nov., a new species of thiocyanate-utilizing facultative chemolithotroph, and transfer of Thiobacillus versutus to the genus Paracoccus as Paracoccus versutus comb. nov. with emendation of the genus. Microbiology, (6): p

290 ESTUDIO QUÍMICO FÍSICO DE NANO PARTÍCULAS DE Ce 3+ /Ce 4+ MEDIANTE DERIVADOS NAFTALIMÍDICOS *E. Martín a, G. Pulido b, F. Leganés b y F. F. Piñas b a Departamento de Química Física Aplicada, Facultad de Ciencias, UAM,28049 MADRID. Tfno, , Fax, b Departamento de Biología, Facultad de Ciencias, UAM, MADRID, SPAIN. 2.2 Environmental Technology and Risk Analysis Las nanopartículas en suspensión coloidal de las formas oxidadas del Ce, han sido ampliamente utilizadas en los últimos años, mostrando su utilidad en Biomedicina, actuando como antioxidantes en desórdenes cardiológicos y neurológicos, así como agente protector frente a radiación en células nocancerígenas (1). En la superficie de las nanopartículas destaca la presencia simultánea de las formas oxidadas Ce 3+ /Ce 4+, cuya estabilidad depende entre otros factores del rango de ph, siendo estables en entornos ácidos y precipitando como hidróxidos a ph básico.. En el medio acuoso a ph neutro según estudios previos, la forma predominante es la de Ce 4+ (2). Además, su configuración electrónica específica, ha permitido incorporarlas como impurezas, en pequeña proporción, sobre cristales dopados con óxidos de tierras raras ( Pr 3+, Lu 3+, Eu 3+ ), para la utilización en materiales electrónicos y en el desarrollo de futuros hardware destinados a la computación cuántica. Esta abundante utilización ha generado un interés por conocer con qué niveles de concentración pueden aparecer en aguas residuales, que posibles daños puedan generar en la materia viva presente en estas aguas y como puede influir su potencial peligrosidad en la cadena trófica. Hemos iniciado el estudio con una sonda fotolumiscente, la 3 Amino, N etil pirrolidin, 1,8 Naftalimida, ya estudiada en medios polares como acetonitrilo (3) y agua, para detectar concentración, interacciones, potencial redox e influencia de los factores ambientales en la estabilidad de ambos cationes presentes. La medidas por espectroscopía de absorción y fluorescencia realizadas para los dos tipos de partículas con diferente estructura geométrica elegidas: CNP5 (36% Ce 3+ ) y CNP6 (26% Ce 3+ ) en disolución acuosa, en presencia de la sonda en concentración M, muestran decrecimientos de intensidades, en especial en emisión, respecto a la absorción y emisión de la sonda aislada. Son mayores para la CNP6. El perfil del espectro no queda modificado, por lo que asociamos los decrecimientos a un posible agregado sonda nanopartícula sin propiedades de emisión radiativa. Se utilizarán otras sondas con diferente potencial de reducción, con el fin de clarificar el tipo de interacción establecida. BIEBLIOGRAFÍA (1) E. Hckert, A. Karakoti, S. Seal and W. T. Self, Biomaterials, 29(18) (2008), (2) A. S. Karakoti, S. V. N. T. Kuchibhatla, K. Suresh Babu and S. Seal, J. Phys. Chem. 111, (2007), (3) E. Martín and R. Weigand, Chem. Phys. Lett.,288(1) (1998)207. AGRADECIMIENTOS Esta investigación se desarrolla con el apoyo de los proyectos CTM C2 1 R y CTM C2 2 R del MINECO.

291

292 OXIDATION OF LEVOFLOXACIN BY PERMANGANATE IN WATER TREATMENT: KINETICS, MECHANISMS, AND ANTIBACTERIAL ACTIVITY VARIATION Ke Xu 1, Jiuhui Qu 1, Carme Sans 2, Santiago Esplugas 2, Zhimin Qiang 1, * 1. Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, 18 Shuang-qing Road, Beijing , China, Phone: (+86) , Fax: (+86) Department of Chemical Engineering, University of Barcelona, C/Martí i Franquès 1, Barcelona 08028, Spain, Phone: (+34) , Fax: (+34) Advanced Techniques for Effluent Treatment This study investigated the kinetics, mechanisms and antibacterial activity variation of levofloxacin (LF) during permanganate (PM) oxidation in water treatment. The reaction followed the second-order kinetics and its rate constant (k) decreased with an increasing ph from 6.5 to 8.5. This could be ascribed to the nucleophilicity of the O and N atoms in LF and the stronger oxidation potential of HMnO 4 than MnO 4. When using thiosulfate as a quencher for residual oxidant, the k value determined from the LF decay was similar to that determined from the PM decay. However, when using ascorbic acid as a quencher, a much higher k value was obtained due to the formation of superoxide radicals (O 2 ), which could further oxidize the LF. The generation of O 2 was confirmed with electron spin resonance analysis. Under typical water treatment conditions ([PM] o :[LF] o = 100:1), potential reaction pathways were established from the byproducts identified with ultra-performance liquid chromatography/hybrid quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS) and the inferred electron transfer and steric hindrance. The electron-rich C C and CH 3 moieties of LF could be oxidized by PM to C=C, CH 2 OH and COOH because of conjugation with the lone-pair electrons of the N and O atoms, and the oxidation potential showed an ascending order as follows: ( CH 3 CH 2 OH) > (C C C=C) > ( CH 2 OH COOH). The oxidation of CH 3 on the quinolone and piperazinyl moieties of LF mainly contributed to the 93% elimination of antibacterial activity at a reaction time of 5 min ([LF] o = 72 μg L -1 ). The decline of [LF] o to 54 μg L -1 revealed a hormesis effect to E. coli in comparison. This study clarified that PM could effectively eliminate both LF and its antibacterial activity in water treatment.

293 HOW HIGH POWER ULTRASOUND TREATMENT ON OLIVE PASTE AFFECTS THE VIRGIN OLIVE OIL PROCESS YIELD. Authors: Mohamed Aymen Bejaoui 1, Abraham Gila 1,2, Araceli Sánchez Ortiz 1, María Paz Aguilera Herrera 2, Gabriel Beltrán Maza 1, Antonio Jiménez Márquez 1 1 IFAPA Centro Venta del Llano. Junta de Andalucía. P.O. Box 50, Mengíbar, Jaén, Spain. 2 Fundación Citoliva, Centro Tecnológico del Olivar y del aceite Mengibar, Jaén, Spain. Phone: (+34) Fax number: (+34) Scientific Topic: Applied Chemical Engineering: Food Engineering Ultrasound, depending on the frequency, is used in various processes in the food industry and where a reproducible food processes can be performed with high reproducibility. The use of this technic is recently investigated for the pretreatment of olive paste step, which has an important impact on the virgin olive oil process yield. As reported by Jimenez et al. (2006; 2007), the use High Power Ultrasound (HPU) during olive paste malaxing has two major effects which are a rapid heating of olive paste and better extractability. Previous experiment at laboratory scale showed that the continuous application of HPU gave a higher process efficiency and lower cost, especially on the olive paste heating. A pilot scale device for continuous HPU application was performed for its use at experimental plant level. The device was composed of a rectangular pipeline where the ultrasound piezoelectric transducers were placed on the four surfaces of the pipeline, and applied three frequencies 20, 40 and 80 khz supplied by a generator of 900 watt. The experiments were carried out using olive paste, obtained after olive fruit crushing without kneading and then treated through the HPU device with an olive paste flow rate of 200 kg/h. Four treatment were assayed the reference without sonication and the remaining applying the three frequencies. After HPU treatment the olive paste was collected and the oil was extracted at `ABENCOR laboratory scale virgin olive oil extraction system. Two extraction conditions were compared, malaxation at 28ºC for 30 minutes and centrifugation against direct paste centrifugation. The liquid phases were recovered in a laboratory test-tube and after settling the volume of the oily phase was taken in order to determine the virgin olive oil process yield and extractability. The experiment was performed using olive fruits from `Picual cultivar collected at two different harvesting date, their moisture and oil content were analyzed. The principal effect of the HPU application on the olive paste was the instantaneous heating when it flow through the device for all the frequencies used when compared with the untreated paste. Regarding to the process efficiency, in general the application of HPU improve the process yield with respect to the untreated paste. Therefore, the single use of the HPU treatment was similar to that olive paste kneading at 30ºC. HPU treatment at 40 khz frequency followed by kneading produced higher olive oil extractability. These results may lead to think about the viability of this technique as a system of improvement of kneading or even as an alternative process. Jiménez A., Beltrán G., Uceda M., Aguilera M.P. (2006). Empleo de ultrasonidos de potencia en el proceso de elaboración del aceite de oliva virgen. Resultados a nivel de planta de laboratorio. Grasas y Aceites, 57(3), Jiménez A., Beltrán G., Uceda M. (2007). High-power ultrasound in olive paste treatment. Effect on process yield and virgin olive oil characteristics. Ultrasonics Sonochemistry, 14(6):

294 OXIDATIVE STABILITY NATURAL MILK MAYONNAISE EVALUATION WITH DIFFERENTIAL SCANNING CALORIMETER (DSC) F. Segovia #1, X. Ramis #2, A. García #1, M.P. Almajano #1* Chemical Engineering Department, Technical University of Catalonia, Avda. Diagonal 647, Barcelona, Spain. Phone , Fax Food Engineering Mayonnaises carry a high fat content, which makes them easily oxidized. Normally synthetic antioxidants, permitted by law, to protect them from oxidation, are added. However, each time more, consumers prefer to remove the antioxidants that are not naturally occurring. Therefore, the aim of this work is to make mayonnaise with high stability in the absence of synthetic antioxidants and to measure by differential scanning calorimeter (DSC). To protect them from oxidation, extracts from natural sources which are usually food processing waste, such as bone avocado and borage leaves have been used. Borage leaves are a cheap raw material, because it is a by-product of an industrial process, and in addition, the disposal of this material incurs a cost which can be minimized by its use. In the avocado industry the pulp is used, while the skin and the seeds are discarded as waste. These residues are rich in polyphenols with antioxidant and antimicrobial power. Both, avocado extract (AE) and borage extract (BE) have a high level of polyphenols. The properties of polyphenols as antioxidants have been widely recognized. They are associated with reduced risk of cancer, cardiovascular diseases, diabetes and Alzheimer's disease. Furthermore, antioxidants from natural sources could be used to increase the stability of food such as the ability to prevent lipid peroxidation. They are really useful to promote the oxidative stability of milk mayonnaise. The milk mayonnaise was made with 70% of sunflower oil (without their natural antioxidants) and skimmed milk, with a little amount of xanthan gum, starch (to stabilize it) and salt. A different proportion of AE, BE and butilhydroxyanisole (BHA) was added. And they were subjected to forced oxidation in two ways: 1) it was stored in an oven at 40 C and follow the oxidation by peroxide value (PV) 2) oxidative induction time measured by DSC The PV shows little differences between samples; however with a study of DSC isothermal this study provides interesting differences and it is possible to decide the best extract to be used as antioxidant. The addition of antioxidant extracts increased the maximum heat flow, depending on their type and concentration. Considering extracts individually, AE at 0.2% and 0.5% were the most effective at preventing oxidation because it resulted in the highest increase in heat flow, whereas BE at 0.3% provided the worst protection (see Figure). AE extract is as good as BHA at % and BHA-AE has similar values. Commercial mayonnaise has heat flow values lower than control sample. Peroxide values at 30 days storage was hydroperoxide/kg emulsion for the control sample while values lower than 4 meq hydroperoxide/kg emulsion were observed in the other samples which did not have significant differences. In conclusion, a new methodology has been described to measure the mayonnaise oxidative stability, very simple and fast. References Aguedo, M. et al. Composition of by-products from cooked fruit processing and potential use in food products. J. Food Compos. Anal. 2012, 27, Poyato, C. et al. Oxidative stability of O/W and W/O/W emulsions : Effect of lipid composition and antioxidant polarity. Food Res. Int. 2013, 51, Wardhani, D. H. et al. Inhibition kinetics of lipid oxidation of model foods by using antioxidant extract of fermented soybeans. Food Chem. 2013, 139,

295 EFFECTS OF FLAX SHIVE COATING WITH PARAFFIN WAX ON THE PROPERTIES OF LIGHTWEIGHT FLAX SHIVES-CEMENT COMPOSITE A Al-Mohamadawi, K. Benhabib, A. Goullieux Laboratoire des Technologies Innovantes (EA 3899), Université de Picardie Jules Verne, IUT de l'aisne - 48 rue d'ostende Saint-Quentin France, tel: +33(0) , Abstract France is the world s major flax producer. The flax culture produces the flax shives as a by-product that represents 50% of biomass weight. This lignocellulosic by-product has received a particular attention in the recent years where it has been used for manufacturing lightweight concretes due to its low cost, lightweight and thermal insulation properties. Without treatment lignocellulosic aggregates are not fully compatible with cement matrix leading to setting delay, significant dimensional variations and low mechanical strengths. To increase the compatibility between shive aggregates and cement, a coating treatment can be used. The coating purpose is to isolate flax shive aggregates from cement matrix preventing water absorption and migration of water-soluble molecules. This summary describes the use of paraffin wax for coating flax shives prior to their incorporation in a cement matrix. The choice of this coating substance is based on its physical and chemical properties: the paraffin wax is mostly found as white, light, odorless, non-degradable and hydrophobic; moreover it is also unaffected by most common chemical reagents. Consequently paraffin wax coating is able to protect shives from water, inhibiting their swelling and release of non-desirable components into the matrix. The aim of this work is to describe the development of wax coating process, to point out the impact of coating process operating parameters on coated shive properties (water absorption, bulk density) and to study the effects of this aggregate coating on physico-chemical, mechanical, thermal and hygral properties of lightweight flax shives-cement composite. During the coating process the flax shives are immersed into molten wax for a limited time then the excess wax is removed using a special hot-air technique. Coated shive properties are measured according to the operating parameters of the coating process. A water absorption less than 31,5% is obtained compared to over 210% for untreated shives. Moreover the apparent and real densities of wax treated shives do not change significantly compared to those of untreated shives. The effects of the aggregate coating on flax shives-cement composite properties are evaluated. Compared to composite elaborated with raw shives, the mechanical, thermal and hygral properties are improved and the bulk density increases.

296 VEGETABLE OILS EXTRACTION PROCESS USING RENEWABLE SOLVENTS AS SUBSTITUTES TO THE HEXANE C. E. C. Rodrigues, M. C. Capellini, K. K. Aracava, S. L. B. Navarro, M. M. Sawada, N. K. Scharlack Separation Engineering Laboratory (LES), Department of Food Engineering (ZEA-FZEA). University of Sao Paulo (USP), P.O. Box 23, Zip Code , Pirassununga, SP, Brazil. Phone: Fax: Applied Chemical Engineering - Food Engineering. Vegetable oils can be extracted from oleaginous materials using short chain alcohols, ethanol or isopropanol for instance as solvents. From the environmental standpoint, the use of short chain alcohols presents some very attractive advantages, once these may be produced by biotechnology, do not generate toxic residues, have a lower degree of flammability, and they are considered safe to human health [1]. The economic advantages are also evident, once ethanol is produced in large scale in Brazil, and may always be recovered to be reused in the process. In this work the performance of ethanol and isopropanol (absolute grade) and azeotropic ethanol in the extraction processes of different oleaginous materials obtained from different industries in Brazil (soybean collets Granol; rice bran pellets Irgovel; corn pellets and sunflower seed cake Caramuru; sesame seed cake Pazze; baru nut cake Flora do Cerrado) were evaluated by monitoring the oil yields at 50 to 90 C. Batch extractions were performed in an isothermal cylindrical reactor of 500 ml built in stainless steel, sealed to avoid solvent losses and equipped with a manometer, mechanical agitator and temperature controller [2]. The pre-set quantities of oleaginous material and solvent (solvent to solid mass ratio of 3, with exception to baru nut cake in which a mass ratio of 4 was used) were transferred to the extractor which has been submitted to the agitation (175 rpm) until the temperature reaches the desired value and kept under constant agitation for at least three hours. After extraction, the compositions of extract and raffinate phases were measured. The total solvent concentration in the phases was determined by evaporation at 60ºC. The water concentration was determined by Karl Fischer titration with a KF Titrino. The oil yield was calculated based on the initial oil content and residual oil in the raffinate phase, values determined according to method Am 5-04 [3]. In this work, all measurements were performed at least in triplicate. In Figure 1 it can be observed that the oil yield increased with increasing temperature for all kinds of solvents studied. For absolute ethanol (Figure 1a), the oil yields at 70 to 90 C to soybean were not statistically different; the same behavior can be noted to baru and sunflower seed cake when isopropanol is used as solvent in the temperature range of 80 to 90 ºC (Figure 1c). It can be inferred that temperature increases the miscibility of the oil in the solvent, thereby facilitating mass transfer between the phases. In relation to effect of water in the ethanolic solvent (Figures 1a and 1b), it can be seen that increasing the water content of the solvent suppresses the extraction of lipid components, possibly because of decreased oil solubility. For soybean collets is noted that the oil yield values for absolute and azeotropic ethanol, at 90 ºC, are statistically equal. It can be inferred that the use of ethanol or isopropanol in the vegetable oil extraction process is technically feasible, since it was obtained high oil yield values considering one equilibrium stage. However, the choice of the conditions of kind of solvent, solvent hydration and temperature must also take into account the characteristics of the protein fraction of the defatted meal, besides other design variables such as the retention index that has an important effect on the number of stages required to perform the extraction (volume of the extractor) and also in the recovery stage of the solvent adhered to the material (desolventization of meal). References: [1] Russin, T. A. et al. Food and Bioprocess Technology, 2011, 4, [2] Oliveira, R. et al. Food and Bioproducts Processing, 2012, 90, [3] AOCS (1998). Official methods and recommended practices of the AOCS (5th ed.). Champaign: American Oil Chemists' Society Figure 1 Yield of extraction. (a) absolute ethanol. (b) azeotropic ethanol. (c) absolute isopropanol. The authors wish to acknowledge FAPESP, CAPES and CNPq for the financial support.

297 COMPARATIVE EVALUATION OF NEW PREBIOTIC INGREDIENTS FROM ORANGE PEEL WASTES Belén Gómez 1*, Iria Ana Ares-Peón 1, Beatriz Gullón 2, Remedios Yáñez 1, Juan Carlos Parajó 1, José Luis Alonso 1 1 Chemical Eng. Dept. Faculty of Science. University of Vigo (Campus Ourense). As Lagoas Ourense. Spain. 1 CITI-Tecnopole, San Ciprián de Viñas, Ourense, Spain. phone: Center for Biotechnology and Fine Chemistry (CBQF), Portuguese Catholic University, Rua Dr. António Bernardino de Almeida, Porto, Portugal. 3.1 Food Technologies. Innovations in Food Processing. Introduction Pectin has been traditionally extracted from citrus peels or apple pomace and used as gelling, stabilizing and/or thickening ingredient in the food industry. However, pectin is also employed in the pharmaceutical field as an ingredient to treat gastrointestinal disorders and diabetes or to reduce high blood pressure or blood cholesterol levels. Recently, pectic-oligosaccharides (POS) has been proposed as a new class of prebiotics and several articles have been reported on the production and evaluation of their prebiotic potential (Gullón et al., 2013). The aims of this work were: a) to assess the refining process of POS mixtures obtained by hydrothermal processing of orange peel wastes (OPW), b) to evaluate their prebiotic potential by fermentation assays using human fecal inocula, and c) to compare its prebiotic potential with the ones of orange pectin and commercial FOS. Methodology OPW samples were subjected to water extraction to remove and recovery their free sugars (mainly fructose and glucose) and then reacted in aqueous media (autohydrolysis) using a 3.75 L stainless steel Parr reactor under reported conditions (Martinez et al., 2010). The resulting POS-containing liquors were then treated by membrane filtration (diafiltration and concentration) using a regenerated cellulose prep/scale spiral wound module with a 1 kda molecular weight cuttoff membrane and the final concentrate was freeze dried obtaining a final refined product enriched in POS. On the other hand, samples of OPW were subjected to an acid extraction of pectin followed by ethanol precipitation according to Hwang et al., (1998). Finally, in order to evaluate the prebiotic potential, in vitro fermentability assays were performed using fecal inocula from healthy volunteers. Commercial FOS were also used as substrate for comparisons. Short chain fatty acid (SCFA) production was determined by HPLC and changes in human bacterial populations were quantified by fluorescence in situ hybridization (FISH). Results The impurities content of the liquors was reduced substantially by membrane processing achieving a refined solid product containing 90% of POS. As it was expected, higher molecular weight was observed by HPSEC in pectin extracted from the acid method in comparison with the POS mixtures obtained by autohydrolysis. Higher contents of neutral sugars, especially arabinose followed by galactose, were observed in POS sample in contrast with a slightly higher amount of galacturonic acid present in orange pectin. As a result of the metabolic activity of the fecal bacteria, ph of the media decreased significantly. Similar final ph values were observed for POS and FOS whereas a lower ph decrease was observed when pectin was used as carbon source. The SCFA profiles were different for FOS and POS and the lowest value of total SCFA was found when orange pectin was used as substrate. All the bacterial groups studied in this work increased significantly with FOS, POS and pectin, but the best results were obtained for POS and FOS. References Gulloń, B., Gómez, B., Martínez-Sabajanes, M., Yáñez, R., Parajó, J.C. and Alonso, J.L. Pectic oligosaccharides: manufacture and functional properties. Trends Food Sci Technol, 2013, 30, Hwang, J.K., Kim, C.J. and Kim, C.T. Extrusion of apple pomace facilitates pectin extraction, J Food Sci, 1998, 63, Martínez, M., Yáñez, R., Alonso, J.L. and Parajó, J.C. Chemical production of pectic oligosaccharides from orange peel wastes. Ind Eng Chem Res, 2010, 49,

298 PRODUCTION OF FISH PROTEIN HYDROLYSATES ENRICHED IN ANGIOTENSIN CONVERTING ENZYME INHIBITORS BY MEMBRANE REACTOR F.J. Espejo-Carpio, P.J. García-Moreno, M. Marín-Suárez, M.C. Almécija, A. Guadix and E.M. Guadix Department of Chemical Engineering, University of Granada, Granada, Spain. Tel: ; Fax: ; Scientific Topic: 3.1. Food Engineering Discarding consists in returning to the sea a portion of the catch because of economic and political reasons. Fishes are usually discarded due to: their low commercial value, they are below the minimum landing size or they are specimens not allowed to land as a result of quota restrictions. Particulary, the Alboran Sea, which is the portion of the West Mediterranean Sea lying between the Spanish southern coast and the north of Morocco, is responsible for 42 % of catches in the region of Andalusia, a region which attaches great importance within the Spanish fishing fleet [1]. The main discards are non-commercial species such as bogue (Boops boops) and smallspotted catshark (Scyliorhinus canicula), but also commercial species such as sardine (Sardina pilchardus), horse mackerel (Trachurus mediterraneus) and axillary seabream (Pagellus acarne) which are discarded due to quota restrictions or minimal landing-size requirements. The practice of discarding has diverse adverse effects over the marine ecosystem. It reduces the number of juveniles but also produces produce an environmental problem due to alterations on marine trophic chains [2]. Therefore, apart from the political measures for reducing the discards, the implementation of upgrading processes for these resources is highly desirable. One of these processes could be the enzymatic hydrolysis of fish protein. It has been found that peptides with angiotensin converting enzyme (ACE) are released from fish proteins during the hydrolysis process [3]. ACE plays an important role in the blood pressure regulation and its inhibition would guide to a reduction in blood pressure. Consequently, the consumption of these active peptides might have a beneficial effect over people with hypertension. To this end, the peptides should remain active after gastrointestinal digestion and intestinal absorption to show an in vivo effect. Another issue to deal with is the complexity of the enzymatic hydrolysates which are composed by a mixture of peptides including some without any ACE inhibitory activity. Thus, the purification of the active peptides produced during the enzymatic hydrolysis would be highly desirable. To this end, filtration with ceramic membrane could be useful. This type of membrane presents better chemical resistance, wider ph and T limits and longer operating lifetimes than organic membranes. In a previous work, the hydrolysis of the discarded species from Alboran Sea was studied employing subtilisin and trypsin as enzymes. The most potent hydrolysate was obtained from the Scyliorhinus canicula muscle by a combination of subtilisin and trypsin. The size exclusion chromatography of this hydrolysate showed that peptides with molecular size below 1200 Da had the highest inhibitory activity. According to these previous results, the Scyliorhinus canicula hydrolysate was produced using the selected conditions. Subsequently it was filtered through ceramic membranes, 8 and 15 kda, in order to purify the product in the most potent fractions. The filtration was carried out in concentration mode and the flux was monitored during the process in order to not exceed 70% of flux decline. The concentration of protein as well as the ACE-inhibitory activity of the fractions (filtrate and retentate) was measured to determine the grade of purification. After the filtration, the membrane was subjected to a cleaning protocol which recovered the permeability of the membranes almost completely. In addition, the bioavailability of the active peptides was evaluated by simulating the gastrointestinal digestion. The ACE-inhibitory activity of the hydrolysate was measured before and after the digestion process to determine the susceptibility of the active peptides to digestion. REFERENCES [1] CAP-Consejería de Agricultura y Pesca. (2009). Análisis anual de la producción pesquera andaluza [2] A. Bozzano and F. Sardà (2002). Fishery discards consumption rate and scavenging activity in the northwestern Mediterranean Sea. ICES Journal of Marine Science 59: [3] I. Wijesekara and S-K Kim (2010). Angiotensin-I-Converting Enzyme (ACE) Inhibitors from Marine Resources: Prospects in the Pharmaceutical Industry. Marine Drugs, 8:

299 INFLUENCE OF TEMPERATURE AND TIME ON POLYUNSATURATED FATTY ACIDS CONCENTRATION BY LOW TEMPERATURE CRYSTALLIZATION G. De León-González, R. Morales, F.J. Espejo-Carpio, F. Camacho, A. Guadix, E.M. Guadix and M. Muñío Department of Chemical Engineering, University of Granada, Granada, Spain. Tel: ; Fax: ; Scientific Topic: 3.1. Food Engineering Many substances are well known to have functional effects: omega-3 fatty acids, oleic acid, phytosterols and others. Eicosapentaenoic and docosahexaenoic acids (EPA and DHA) are the most important omega-3 polyunsaturated fatty acids (PUFAs), both from marine sources. Some of the effects of PUFAs on human health are for example, improvements in infants development, preventive or mitigating effects on cardiovascular diseases, mitigating effects on inflammatory processes and preventive effects on some kind of cancer [1,2]. Marine oils are the main source of polyunsaturated fatty acids that can be concentrated either by enzymatic methods [3] or by low temperature crystallization as a winterization process [4]. Winterization process lies in the chilling of the oil to obtain two different phases, a crystallised or solid one and a liquid one, that can be separated by filtration. Saturated fatty acids are crystallised and mainly concentrated in the solid phase whereas PUFAs are concentrated in the liquid phase. Usually, oils in the form of free fatty acids are dissolved previously in a proper solvent to develop winterization [4]. In this work, the effect of two factors on PUFAs concentration by winterization was studied: temperature and time used in the process. Sardine oil was previously chemically hydrolysed [5] to obtain free fatty acids as substrates of the later winterization. Free fatty acids were mixed with hexane as solvent to get around 100 ml of a final mixture of 5% (v/v) of free fatty acids. Mixtures were placed in topaz coloured flasks. In the winterization process, temperatures tested were -55, -65, -75 and -85 ºC and time used were 1, 2, 3, 4, 6, 8 and 24 hours for each temperature. Crystallizations were carried out in duplicate with no significant differences and samples were vacuum-filtered to separate both phases. Identification of the fatty acids profile of the samples was developed by gas chromatography using nonadecanoic acid as internal standard. Analysis of the samples was carried out in triplicate with no significant differences. When comparing the different temperatures used, it can be observed that the concentration of PUFAs is higher when temperature is lower. At 24 hours, it can be found a 43% of PUFAs in the liquid phase at -55 ºC and almost 60% of PUFAs at -85 ºC. That means that lower temperatures improves the formation of saturated fatty acids crystals allowing the concentration of PUFAs in the liquid phase. It can be observed also that PUFAs concentrations increase with the time at all temperatures tested but in greater extent when working at -85 ºC. In this case the amount of PUFAs in the liquid phase increases around 80% from the initial one, whereas the increase where about 47%, 35% and 34% at -75, -65 and -55 ºC, respectively. [1] Pignier, C., Revenaz, C., Rauly-Lestienne, I., Cussac, D., Delhon, A., Gardette, J. and Le Grand, B. (2007). Direct protective effects of poly-unsaturated fatty acids, DHA and EPA, against activation of cardiac late sodium current. A mechanism for ischemia selectivity. Basic Res. Cardiol. Vol. 102: [2] Kuriki, K., Hirose, K., Wakai, K., Matsuo, K., Ito, H., Suzuki, T., Hiraki, A., Saito, T., Iwata, H., Tatematsu, M. et al. (2007). Breast cancer risk and erythrocyte compositions of n-3 highly unsaturated fatty acids in Japanese. Int. J. Cancer. Vol. 121: [3] Wang, W., Li, T., Ning, Z., Wang, Y., Yang, B., Ma, Y. and Yang, X. (2012). A process for the synthesis of PUFA-enriched triglycerides from high-acid crude fish oil. Journal of Food Engineering. Vol. 109: [4] López-Martínez, J.C., Camprea-Madrid, P. and Guil-Guerrero, J.L. (2001). γ-linolenic Acid Enrichment from Borago officinalis and Echium fastuosum Seed Oils and Fatty Acids by Low Temperature Crystallization. Journal of Bioscience and Bioengineering. Vol. 97 (5): [5] Wanasundara, U.N. (1997). Marine oils stabilization structural characterization and omega3 fatty acid concentration, PhD Thesis, Memorial University of Newfoundland, St. John s, NL, Canada.

300 EFFECT OF MICRONIZED NATURAL TALC ADDITION ON THE DISSOLUTION OF PROTEINS AND PECTIC CELL WALL POLYSACCHARIDES DURING INDUSTRIAL PROCESSING OF HOJIBLANCA OLIVE OIL Abir Sadkaoui 1,2*, Antonio Jiménez 1, Rafael Pacheco 2, Gabriel Beltrán1 ** 1 IFAPA Centro Venta del Llano. Junta de Andalucía. P.O. Box 50, Mengíbar, Jaén E , Spain. Tel.: ; fax: Departamento de Ingeniería Química, Ambiental y de los materiales. Universidad de Jaén, Spain. Tel.: * ** Scientific topic of the work: Food Technologies. Innovations in Food Processing In the present research, we intended to study in more detail the effect of oil extraction process using MNT on the changes in cell wall polysaccharide composition of: Hojiblanca olive cultivar. Industrial scale experiments were performed in the IFAPA pilot plant. Different doses of MNT were assessed: 0, 0.25%, 0.5% and 1% in order to evaluate their effect on protein and pectic cell wall dissolution. The cell wall material was isolated as an alcohol insoluble solid (AIS) and then, three distinct pectic fractions were extracted from it: water soluble pectin (WSP), chelator soluble pectin (CSP) and non-soluble pectin (NSP). In general, for the three pectic fractions, it was observed a decrease throughout the kneading step and then, a rise in olive pomace. The same trend was observed for total protein content and total pectin content. Conversely, the opposite trend was observed for the yield of AIS which significantly decreased in the pomace respect to the crushed olive paste. This decline may be explained by the degradation of AIS to alcohol soluble polymers. MNT addition strongly decreased both the yield of AIS, protein content as well as the different pectic fractions up to a dose of 0.5%. This finding confirms the existence of an electrostatic interaction between pectins, proteins and MNT (used at doses 0.5%), contributing to their complexation and their elimination within pomace, which obviously explains the increase of their content in this remnant solid after oil extraction. Greater MNT dose (1%) led to a substantial increase in all the studied parameters. Accordingly, we can infer that the excess of MNT couldn t adsorb both protein and pectic polysaccharides, thereby preventing their aggregation and leading to the increase of free-binding pectin and protein in the olive paste which indeed promote to formation of oil-in-water emulsions during kneading process.

301 EFFECT OF MICRONIZED NATURAL TALC PHYSICO-CHEMICAL CHARACTERISTICS AND DOSAGE ON THE BREAK-DOWN OF OIL-IN-WATER EMULSIONS Abir Sadkaoui 1,2*, Antonio Jiménez 1, Rafael Pacheco 2, Gabriel Beltrán 1**. 1 IFAPA Centro Venta del Llano. Junta de Andalucía. P.O. Box 50, Mengíbar, Jaén E , Spain. Tel.: ; fax: Departamento de Ingeniería Química, Ambiental y de los materiales. Universidad de Jaén, Spain. Tel.: * ** Scientific topic of the work: Food Technologies. Innovations in Food Processing The use of micronized natural talc (MNT) has proven to be very useful to break down emulsions formed during olive oil kneading process and improve the extraction rate. This study was aimed to obtain more insights in the mechanisms of MNT to break-down oil-in-water emulsions. For this purpose, laboratory scale experiments were performed in order to evaluate the effect of different pectin concentrations (0.5%, 1%, 1.5% and 2%), used as emulsifier agent, on the behavior of oil-in-water interface. Afterward, to evaluate the effect of MNT dosage as well as its physicochemical characteristics on breaking o reducing emulsions, four MNTs differing in their particle size (D50) and carbonate rate were assayed at doses ranging from 0% to 1%. Increasing pectin concentration gave a rise in the emulsifying activity (EA). The emulsifier effect of pectins was weakened by the addition of increasing MNT dose. MNT physicochemical characteristics markedly affected the rupture of oil-in-water emulsions. Nonetheless, their effect depends on the dose of MNT applied to the emulsion. The highest decrease in EA was observed for that MNT with the lowest D50 (2.4 µm) and the highest carbonate rate (4%) at 0.5 %.In general, MNT containing lower D50 and high rate of carbonate showed better capacity in breaking oil-in-water emulsion.

302 INFLUENCE OF TEMPERATURE ON PHYSICAL PROPERTIES OF CANADIAN MAPLE SYRUP M. Iglesias 1, R.S. Andrade 1, A.C. Santos-Silva 1 1 Universidade Federal da Bahia, Dpto. Engenharia Química, Salvador, Brasil; tel , Applied Chemical Engineering Food Engineering Food Technologies, Innovations in Food Processing Canada produces more than 85 per cent of the world s maple syrup. The vast majority of this product comes from the province of Quebec, which is the world's largest producer. Maple syrup is a syrup usually made from the xylem sap of sugar maple, red maple or black maple trees, although it can also be made from other maple species. Maple syrup is made by boiling between 20 and 50 litres of sap (depending on its concentration) over an open fire until 1 litre of syrup is obtained, usually at a temperature 4.1 C over the boiling point of water. Boiling the syrup is a tightly controlled process, which ensures appropriate sugar content. After processing, it consists primarily of sucrose and water, with small amounts of the monosaccharides glucose and fructose from the invert sugar created in the boiling process. Organic acids, the most notable one being malic acid, make the syrup slightly acidic. Maple syrup has a relatively low mineral content, consisting largely of potassium and calcium, but also contains nutritionally significant amounts of zinc and manganese. The optimisation of industrial operations, require knowledge of the thermodynamics of the compounds related to process, which can be determined either experimentally or by prediction based on an appropriate model, and a set of data. Although maple syrup is almost an unprocessed natural product, its industrial manufacture applies usual chemical and mechanical fluid operations, then the optimisation and appropriate equipment design are conditioned by a sufficient knowledge of mixing thermodynamics. Operations as pumping, evaporation or filtration are required for the sap treatment, a quality control during the process being applied, which is based on the evolution of physical properties of the sap throughout the process. In fact, refractive techniques are usual applied to determine the mature point of evaporation and the quality of the maple syrup, although no bibliographic data have been found in open literature. The importance of an adequate identification of the maple syrup finish point during evaporation has been pointed out in the open literature [1]. Despite its economical, cultural and nutritional importance of this natural product, only a few studies in the last years, have been developed related to its physicho-chemical properties. Due to this fact, the availability of accurate polynomials which show the temperature dependence of different thermophysical properties would be of prior interest in order to install automatized control devices to test the maturation point of maple syrup during elaboration. In this paper, we analyze the temperature effect on the maple syrup and aqueous dilution of this product, in terms of different physicho-chemical properties, assuming that in the last steps of maple syrup concentration no significative chemical changes take place and only water is removed. We have attempted to explain the physicochemical behaviour of the mixtures indicated above, to explore the strength and nature of the interactions between the components. To this end, we have developed an experimental work related to the study of density and ultrasonic velocity measurement, as a function of composition and temperature at the range K and atmospheric pressure. Our purpose is to discuss the dependence of these properties on mixing and other acoustic parameters on the composition and temperature, in order to provide a better understanding concerning the factors which contribute to the special behaviour in enclosing such macromolecules into mixtures, where the solvent is of shorter chain and different molecular nature. Due to the importance of theoretical on industrial design, different prediction models were applied for the studied magnitudes, and attending to the deviation computed data, we arrive at the conclusion that the application of the modified Rackett equation of state and CFT (Collision Factor Theory) [2, 3], show close agreement with the experimental data reported in this study. References [1] G. Graham, P. C. Goebel, R. B. Heiligmann and M. S. Bumgardner, Journal of Forestry, 104(2) [2] C. F. Spencerand and R. P. Danner, Journal of Chemical Engineering Data, 17(2) [3] W. Schaaffs, Acustica, 33(4),

303 OPTIMIZE OF HORIZONTAL CENTRIGUGE DECANTER PERFORMANCE TO AVOID OF FAT LOSS IN OLIVE POMACE USING ARTIFICIAL NEURAL NETWORKS. Estrella Funes, Yosra Allouche, Gabriel Beltrán, Antonio Jiménez. Instituto de Investigación y Formación Agraria y Pesquera (IFAPA) Venta del Llano Ctra. Bailen- Motril, km 18, Mengíbar (Jaén). España. Phone: , Fax: Scientific Topic: 3.1 Food Engineering. Food Technologies. Innovations in Food Processing This work presents the application of models based artificial neural networks (ANNs) to an olive oil mill. The work presents a solution to the integrated control of the mill, where the ANN-predictions can be used to optimize oil yield keeping quality standards. Two ANNs were created for real-time prediction of the fat content and moisture of olive residue (the olive pomace) produced from two-phases olive oil processing. In the creation of ANNs, different technological variables were considered as inputs as show Table1 together with oil spectrums from entrance horizontal centrifuge decanter (HCD) collected by NIR and pretreated with wavelet system. The dates considered correspond to four years. The artificial neural networks created were based on the algorithm feed-forward back-propagation with a supervised learning of descending gradients. The results indicate that the predict values of fat content pomace and moisture pomace were very well correlated with real laboratory values of r = and r = and the errors prediction (RMSE) and respectively. Predictive models can optimize of HCD performance to avoid of fat loss in olive pomace, besides the energy saving. Table 1 Qualitative, technological and mechanical variables with theirs values range used in ANN creation. Variables Parameters Range values Qualitative Fat content olive pomace(%) Moisture olive pomace(%) Technological Olive fruits temperature (ºC) MTN addition (%) 0-1 Water addition (l/h) Paste flow (kg/h) Paste temperature (ºC) Malaxation time (minutes) Mechanical Diameter grid of hammer crusher 4-7 Hammer rotation speed (rpm) Oil overflow point (mm)

304 STABILIZATION OF A NUT POWDER DISPERSIONS BY THICKENERS AND EMULSIFIERS Fábregas.A, Faulón.D, Santamaría. E, González.C and Gutiérrez, J.M * Chemical Engineering Department,Faculty of Chemistry, University of Barcelona, Barcelona 08028, Martí i Franqués 1-11, Spain * Nowadays, animal milk is the most common in the dairy field, although alternative milks have been increasing its presence due to intolerance to animal milk. One of the alternatives is vegetables milk and derivatives, but they do not contain vegetables themselves, since they are removed from the product once milk is extracted from the vegetable. Thus, the vegetable properties are wasted. For example, nuts contain omega-3 fatty acids, complex B vitamins, E vitamins and minerals such as magnesium, potassium and phosphor. Regarding this new society demand, it could be interesting to find an innovative and healthy substitute for animal milk and, furthermore, make the most of vegetables properties: a nuts smoothie. The main problem is that a smoothie is an aqueous dispersion of solid and fat particles that tends to present sedimentation of solid particles and creaming of fat globules. For this reason, the aim of this project is to stabilize an aqueous dispersion of nuts powder. To achieve it, a study of different food additives is carried out in order to determine their stabilizing effect. The different functional stabilizers that are studied are listed as follows: Lecithin as emulsifier that enables the stabilization of insoluble substances. Agar-agar, gellan gum and kappa-carrageenan as gelling agents, whose addition provides a jelly texture to the product. And finally, xanthan gum as thickener, so as give consistency to the product. These stabilizers, except lecithin, were dissolved in water, and in a different range of concentrations, were submitted to rheological tests to determine their behaviour in water. All the rheological characterization was made in a Rheometer Haake-Mars, at 25ºC and using plate and plate sensor. The rheological behaviour studied of the stabilizers in water was the gelling point, the yield shear stress, the viscosity at different shear rates and the frequency test. Later on and based on the results, stability tests were performed. Stability was measured by light backscattering profiles of all the dispersions in different periods of time. The apparatus used was TurbiScan. The profiles evolution reveals whether destabilization exists and, if so, by which mechanism is triggered according to its form. The dispersions were made with 10% of nuts and stabilizer; the concentration of which is modified according to the obtained results in order to find a suitable composition for the product. Dispersions were mixed following the same procedure to avoid the preparation influence in the results. The dispersion was homogenised by Ultra Turrax. Dispersions with best results were chosen to complete a further assay, which allowed the samples validation; they were manually re-dispersed and their stability was determined. This procedure is relevant so as to achieve social acceptance to product since smoothies should remain stable and maintain a good appearance as long as possible after the consumer has shaken them. Gellan and xanthan gum separately were the most promising additives to stabilize nuts powder dispersion. Mixed together they do not show synergy. Stability was improved by adding lecithin to gellan and xanthan gum respectively. The most optimum composition to stabilize a dispersion containing 10% w/w of hazelnuts is 0.01% w/w of xanthan gum and 0.02% w/w of lecithin. Financial support from CYCYT CTQ C03-02 is gratefully acknowledged

305 ALGINATE BEADS CONTAINING COCOA EXTRACT TO ENRICH A GELATIN DESSERT 1 Lupo, B; 2 Riu, M; 1 Maestro. A; 1 Gutiérrez, J.M and 1 González. C*. 1 Chemical Engineering Department, Faculty of Chemistry, University of Barcelona, Martí i Franqués 1-11Barcelona 08028, Spain 2 Nutrition and Food Science Department.Faculty of Pharmacy, University of Barcelona, Barcelona AV.JOAN XXIII, S/N * Food Engineering. Encapsulation of active components in alginate gel beads allows the control release of these components as well as protects them from external aggression or masks flavors. The objective of this work was to characterize alginate beads with encapsulated cocoa extract prepared by external and internal gelation and performed by extrusion method in order to evaluate the most proper bead to be incorporated into food for making it functional and even the acceptance of the gelatin dessert enriched with the cocoa beads by sensory analysis. Gel beads were prepared with different cocoa and calcium concentration for both gelation techniques. Morphology, texture and size analysis showed a clearly different structure of the beads. The ones prepared by internal gelation were more homogeneous. The mechanical properties of beads resulted in harder gel behavior for those obtained by external gelation respect to those beads formed by internal gelation. Cohesiveness and Gumminess were also compared between alginate/cocoa beads. When a higher calcium concentration was employed the hardness increased and the diameter of beads decreased. The release profile of polyphenols showed a retardation of the polyphenols when the higher calcium concentration for both gelation mechanisms studied. This aspect was slightly more noticeable for beads prepared by internal gelation. Alginate beads with the highest amount of cocoa extract and calcium concentration prepared by internal gelation were selected as bioactive capsules due their softer texture and the retardation of the polyphenols release in order to be incorporated into a gelatin dessert. The sensory analysis by the discrimination test of the enriched gelatin dessert showed that the astringent and bitter taste of cocoa extract was not perceived by the panelists from the organoleptic point of view for a confidence level of 95%. Thus the taste of the encapsulated compound was satisfactorily masked. Photograph of enriched gelatins dessert for the discrimination testing

306 OPTIMIZATION USING SURROGATE MODELS BASED ON A KRIGING INTERPOLATION: APPLICATION TO THE RIGOROUS DESIGN OF DISTILLATION COLUMNS N. Quirante, J. Javaloyes and J.A. Caballero. Institute of Chemical Processes Engineering. University of Alicante, PO 99, E Alicante, Spain. Telephone Fax Scientific topic: Process and Product Engineering. In this work, a new algorithm is presented for the rigorous optimization of nonlinear programming problems in which the objective function and/or some constraints are represented by noisy implicit black box functions. The noisy implicit black box functions are substituted by metamodels based on kriging interpolation. This kind of interpolation assumes that the errors are not independent, but a function of the independent variables. Kriging metamodel uses non-euclidean measures of the distance to avoid sensitivity to the units of measure. Its estimates are calculated from a weighted linear combination of available surrounding data points. Kriging metamodel includes adjustable parameters that weigh the importance of each variable for obtaining a good model representation. The quality of the kriging metamodel depends on the number of variables and on how much the bounds of the independent variables can be tightened. Surrogate models can be used at different levels: substitute the complete model (i.e. complete flowsheet), substitute some of the components (i.e. unit operations) trying to minimize the degrees of freedom and increase accuracy at the expense of increasing the number of surrogate models or simply develop a local approach of the complete model (or some of its components) followed by any trust region algorithm. We can use an algorithm based on fitting response surfaces -using a kriging metamodel- for the optimization of constrained-noise black box models that we are dealing with mixed systems in which a part can be represented by a metamodel (distillation columns and reactors) and the rest with and accurate model. If the algorithm is used to substitute deterministic models (without noise), the convergence of the model is guaranteed to a local stationary point, because it is possible to ensure that both the original model and their gradient information are matched by the metamodel within a given tolerance. The algorithm presented has proved to be robust, reliable and also allows a fast interpolation of values. We performed several examples to verify the effectiveness of the method. In this paper one of the applications is presented, the rigorous design of a conventional distillation column. The column is simulated with Aspen HYSYS v.7.3. First, the bounds for each independent variable are established. Sampling points, distributed around the search area, are generated inside the bounds. Next, the column is simulated in each sampling point. The values of dependent variables for each simulation are used to calibrate kriging parameters. We can replace the column by the surrogate model and use state-of-the-art optimizers (CONOPT, SNOPT) available in TOMLAB-MATLAB. In this way, a fast optimization is obtained. The surrogate model can be used either as an implicit model in which the surrogate model is treated in each iteration as an external equation -i.e. taking advantage of the robust matrix manipulation in MATLAB- or as a set of explicit equations directly included in the MINLP optimizer. In the first approach the model viewed by the solver is smaller and robust, but due to the non-convexities only a local minimum can be guaranteed. In the second approach the model viewed by the solver is large, and therefore, it is constrained to a reduced number of surrogate models, but it is possible to get global optimality. Assume we want to determine the minimum cost of a distillation column for separating a mixture of benzene, toluene and xylene (molar fractions: 0.35, 0.35 and 0.30, respectively). We want to recover at least 98.5% of the benzene fed with at least in molar fraction. The column has two degrees of freedom. We choose two independent variables that converge for most specifications: number of trays in the rectifying section and number of trays in the stripping section. As is shown in Table 1, satisfactory results were obtained. Table 1. Summary of optimal solution obtained with different methods (conventional column). Number of Trays Rectifying Section Number of Trays Stripping Section Condenser Heat Flow (kw) Reboiler Heat Flow (kw) Diameter (m) TAC 10-5 ($/year) KRIGING HYSYS The authors gratefully acknowledge the financial support by the Ministry of Economy and Competitiveness from Spain, under the project CTQ C02-02.

307 Enhanced epsilon-constraint method through the integration of objective reduction and sampling techniques Pedro J. Copado Méndez a, Carlos Pozo a, Gonzalo Guillén Gosálbez a,b and Laureano Jiménez Esteller a a. Departament d Enginyeria Química, Universitat Rovira i Virgili, Av. Països Catalans 26, Tarragona, Spain b. School of Chemical Engineering and Analytical Science, University of Manchester, Mill, Sackville Street, Manchester M13 9PL, United Kingdom Reduction in computational burdens whereas the quality of Pareto solutions is keeping Multi-objective optimization has recently gained wider interest in process system engineering (PSE), and in particular in green engineering problems in which environmental concerns must be accounted for in the optimization. The epsilon-constraint method is a widely used algorithm to for solving multi-objective optimization (MOO) problems. Its main drawback is that it is quite sensitive to the number of objectives, as its complexity grows exponentially in size with the number of criteria, and can get out of hand very easily for problems with several objectives. We propose in this paper an enhanced epsilon-constraint algorithm that reduces the computational burden of the standard version. This enhanced version of the original algorithm is based on two main improvements: (i) the use of rigorous objective reduction techniques that eliminate redundant criteria from the MOO model; and (ii) the application of pseudo/quasi-random sequences for generating the epsilon parameter values. We illustrate the capabilities of our approach through its application to two supply chain design problems in which we optimize the economic performance/total cost along with a set of environmental metrics quantified following LCA principles. Numerical results show that our method outperforms the standalone epsilon constraint algorithm in terms of number of unique Pareto points identified and CPU time spent in the calculations.

308 ADAPTIVE EVOLUTIONARY OPTIMIZATION OF COMPLEX PROCESSES USING A KRIGING BASED GENETIC ALGORITHM Ahmed Shokry, Kefah Hjaila, and Antonio Espuña Department of Chemical Engineering, Universitat Politecnica de Catalunya, Av. Diagonal, , Barcelona, Spain. Tele: , Scientific Topic (3.2 Process and Product Engineering) This work presents a methodology for the optimization of chemical processes using genetic algorithm and kriging metamodels. The methodology is appropriate when the use of computationally expensive and complex processes first principle models is required (e.g. modular process simulators as ASPEN). Such models face many obstacles when used in optimization using Derivative Based Optimizers (DBO), because of the inaccurate estimation of the derivatives; moreover DBO could be easily trapped in local optima [1]. Genetic Algorithms (GAs) are stochastic search procedures that mimic the biological evolution process. They do not require the derivatives estimation and so avoid the associated difficulties [2]. However, GAs require a huge number of evaluations of the fitness function so, their use to solve the complex real size problems which usually appear in industry would lead to unaffordable computational time and cost [1],[2]. Many works have proposed the use of accurate computationally inexpensive surrogate models instead of complex original models to reduce the computational cost of evaluating the fitness function and constraints [2]. Kriging surrogate models present outperforming characteristics, as high prediction accuracy and an ability to estimate a prediction variance (prediction uncertainty), which extends the kriging capabilities when compared with other metamodel types, and enables the use and development of new powerful optimization tools [1]. In this work, the use of GAs to continuously improve the metamodels accuracy during the optimization step allows to better exploit the potentials of the kriging estimated variance, taking into account the metamodels uncertainties as well as the predictions. In the first stage of the proposed algorithm, a set or a matrix ([X] n k ) of n input combinations of the k optimization/design variables X are evaluated (simulated) using the complex original process model, in order to obtain the output responses [Y] n (the objective and constraints); then, these data matrices ([X] n k ; [Y] n ) are used to fit the kriging metamodels (one kriging metamodel for each of the objective and the constraints). The second stage corresponds to the optimization itself: in each iteration, the GA explores the metamodels through a specified number of generations (Ng), and evaluates the metamodels predictions (fitness and constraints values) and variances which represent the uncertainty about the predictions. Once the specified number of generations has been reached, two individuals are selected from the last generation: the individual with best fitness value, and the individual with highest prediction variance. The original complex process model is evaluated at these two points to obtain accurate response values; then, these two new data are added to the original set of training points, and the metamodels are refitted to enhance the metamodels accuracy. Ng takes small values at the early iterations, as the uncertainty in the metamodels are expected to be relatively high, so the GA is just used to explore the whole search domain to identify the areas with high uncertainty in order to add points at these areas to enhance the metamodels. As the algorithm proceeds, Ng gradually increases, since the confidence in the metamodel results also increases; consequently, the GA is allowed to deeply explore the metamodels with less uncertainty. Results of the application of this procedure to different mathematical examples and to chemical process operation optimization case study show the benefits, both in terms of computational effort and, even more important, results reliability obtained through the proposed methodology. Acknowledgements: Financial support received from the Spanish "Ministerio de Economía y Competitividad" and the European Regional Development Fund, both funding the research Projects EHMAN (DPI ) and SIGERA (DPI C02-01) and the Agència de Gestió d'ajuts Universitaris i de Recerca AGAUR is thankfully acknowledged. [1] Caballero, J. A., & Grossmann, I. E. (2008). An Algorithm for the Use of Surrogate Models in Modular Flowsheet Optimization. AIChE Journal, 54, [2] Pehlivanoglu, Y. V., & Yagiz, B. (2012). Aerodynamic design prediction using surrogate-based modeling in genetic algorithm architecture. Aerospace Science and Technology, 23,

309 Mathematical knowledge management to support decision making in process systems engineering Edrisi Muñoz a, Elisabet Capón-García b, Jose M. Laínez c, Antonio Espuña d, Luis Puigjaner d a Centro de Investigación en Matemáticas A.C., Jalisco S/N, Mineral y Valenciana 36240, Guanajuato, México b Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland c Department of Industrial and Systems Engineering, University at Buffalo, Amherst, NY d Department of Chemical Engineering, Universitat Politècnica de Catalunya, Av. Diagonal, 647, E08028 Barcelona, Spain Scientific topic: Process and Product Engineering Abstract Nowadays, the application of analytical systems for decision-making has gained increased attention as a manner of gaining a competitive advantage to face globalization of markets and fierce competition. Recent trends in process industries are shifting the focus on the coordination of the decision making and the optimization of different decision levels. In fact, the border lines between the decision-making levels of the enterprise structure are often diffuse, and there are strong overlaps between planning in production, distribution or supply chain management and strategic planning. Semantic technologies seem to offer an appealing way to capture knowledge and integrate information, for supporting a smooth integration of information and mathematical modeling in a single framework. This work proposes an ontological framework which includes the integration of knowledge models both for mathematical and enterprise domains. On the one hand, the Mathematical Knowledge Management model aims at translating the elements (i.e., decisions, parameters, constraints, performance indicators) of enterprise mathematical models to a semantic representation. On the other hand, the Enterprise Process Ontology Project represents the process tasks and supply chain domain and is based on the work of Munoz, et al (2012). The Ontological Math Representation approach focuses in the semantic representation of the mathematical content of functions and equations. The mathematical expressions are represented as mathematical sets that are related among them by ontological properties. Thus, it handles the expression of functions, the quantification and the operators with qualifiers. The resulting relationships translate the mathematical expressions into the process explicit reality of the enterprise which is easier to understand by humans and machines. As a result, an integrated mathematical model is obtained and can be solved by exchanging xml files. Even more, in the classical hierarchical approach, this framework allows tracking the use of the elements of the different models and sharing the information obtained from their respective optimization, which may be performed separately. The integration of mathematical models from different hierarchical levels (SC models and scheduling models) has been successfully done. This provides an additional degree of freedom for the enterprise modeling. So far the enterprise ontology relied on rigid analytical models which cannot be easily modified according to the new reality circumstances (constraints, variables). The new feature developed in this work opens the ability of modifying the analytical models from the ontological framework, providing a higher flexibility. References E Muñoz, E Capón, J M Laínez, M Moreno-Benito, A Espuña, L Puigjaner, Operational, Tactical and Strategic Integration for Enterprise Decision-Making. Computer Aided Chemical Engineering,

310 EARLY FOAMING DETECTION IN A SWEETENING UNIT USING PCA Mahdieh Askrian a,d, Estanislao Musulin b, Raúl Benítez c, Moisès Graells d, Reza Zarghami a (a) School of Chemical Engineering, UT, Tehran, Iran, (b) CIFASIS - CONICET - UNR - AMU, S2000BTP, Rosario, Argentina. (c) Automation Control Department, (d) Chemical Engineering Department. (c,d) EUETIB, UPC, Comte d Urgell 187, Barcelona, Spain. Molecular and Process Modelling, Simulation and Optimization, CAPE The removal of sour gas components from the gas streams using chemical solvents, such as MDEA, is a requirement in most hydrocarbon processing plants. The acid gas constituents (H 2S and CO 2) react with an aqueous solution in a high-pressure absorber. Subsequently, the solvent is stripped from the acid gas in the regenerator at elevated temperature to reuse it. Figure 1 illustrates a typical gas treating plant employing an alkanolamine D scatter plot Normal Disturbance Fault Figure 1. Gas sweetening process Figure 2. 2D scatter plot in the reduced space. One of the most frequent faults in gas sweetening is amine foaming, which results in the loss of proper vapor-liquid contact, solution hold up and poor solution distribution. Some root causes of foaming includes accumulation of heavy hydrocarbon and solid particle in amine and antifoam trouble. The consequence is off-spec product, downtime and loss of amine and energy. Whenever operators distinguish foaming based process measurement trends, a shortterm measure is manual injecting of antifoam agent. However, disadvantage of this approach is misdetection due to existence of numerous variables, low experience and unconscious operators. Also, there are some other process disturbances in the system originated in downstream or upstream that can mislead the operator to detect foaming. On the other hand, overdose injection of antifoam has adverse effects on the filtration system. This work proposes a decision support software based on principal component analysis for detection of foaming in a sweetening plant. From the many process variables, operators tend to make decisions based on only one or two of them. Consequently, important information included in other variables, or in their relations, is discarded. This work proposes the use of PCA [1] to reduce the monitoring space without discarding relevant process variance. Due to the importance of process disturbances, PCA cannot be applied using their standard statistics (T 2 and SPE), due to the high number of false alarms they produce. However, a 2D scatter plot in the reduced space (Fig. 2) allows performing an early and reliable identification of foaming, thereby supporting operator decisions and reducing operating costs. Results show fast and efficient data analysis for practical fault detection and qualitative decisionmaking support. Further work is underway regarding quantitative assessment of confidence levels. Acknowledgements: Financial support from Spanish MINECO, the EU-ERDF (both funding the Project SIGERA, DPI C02-01) and Iranian South Pars Gas Complex is fully appreciated. Financial support from CONICET, ANPCyT and FCEIA-UNR is also acknowledged. References: [1] Kourti, T.; Lee, J.; MacGregor, J. Comput. Chem. Eng. 1996, 20, S745 - S750.

311 ENERGY IMPROVEMENTS OF THE AMMONIA REFRIGERATION SYSTEM OF AMMONIA PRODUCTION Lj. Matijašević, I. Dejanović, E. Kristan, K. Huljev Faculty of Chemical Engineering and Technology, University of Zagreb Marulićev trg 19, Zagreb, Croatia, Chemical Engineering for Sustainable Development: Energy, Water and Materials Many older industrial processes today require reconstruction in order to increase energy efficiency, production capacity and reduce pollution. Often, improving the operation of a single unit operation in the process influences detrimentally other units in the plant that need adjustment to the new situation. This work addresses cooling system of the synthesis section of the ammonia plant, designed by Pullman Kellog LTD. The process of ammonia production can be divided into two parts: preparing the gasses needed for the ammonia reaction and ammonia synthesis with refrigeration loops. Simplified process flow diagram of refrigeration loop is shown in Fig.1. The existing plant was reconstructed with application of new technologies, and after reconstruction energy efficiency and production capacity was increased and environmental emissions reduced. With all the improvements, there is the possibility for additional savings because the cooling system remained unchanged. Cooling system was analyzed using techniques for heat integration, in order to further reduce energy expended per unit of final product. Fig.1. The simplified flow diagram of cooling system Fig. 2. Grand composite curve of the system Simulation of the cooling system was carried out using ChemCad process simulator and heat analysis using the pinch technology algebraic method by Pinch Analysis Spreadsheet. The results showed that the reconstruction of plant can have substantial influence on energy efficiency. System has two pinch points, 140,5 0 C and -13,5 0 C (Fig.2), four exchangers do not work well and only with change in heat flow capacity savings can be achieved. Results are show in Table 1. Table 1. Results of heat analysis Pinch point C Exchanger H, existing kw H, reduced kw Saved water m3/h 140,5 E , E , ,5 E , E ,7 10 3

312 NOVEL TRIPLE-RESPONSIVE HYDROGELS BASED ON 2- (DIMETHYLAMINO) ETHYL METHACRYLATE by COPOLYMERIZATION with 2-(N-MORPHOLINO) ETHYL METHACRYLATE Fulya Taktak #1, Murat Yıldız #2, Cengiz Soykan #3 and Hakan Sert #1 #1,4 Department of Chemical Engineering, Faculty of Engineering, Uşak University, Uşak, Turkey #2 Department of Laboratory and Veterinary Health, Esme Vocational School, Uşak University, Uşak, Turkey #3 Department of Material Scince and Nanotechnology Engineering, Faculty of Engineering, Uşak University, Uşak, Turkey Product Design and Development In this investigation, novel copolymer hydrogels of triple responsive poly(n,n-dimethylaminoethylmethacrylateco-2-n-morpholinoethylmethacrylate) with different monomer ratios were prepared thorough free radical polymerization in the presence of N,N'-methylene bisacrylamide (MBAAm) as a crosslinking agent. The characteristics of the multi-responsive materials were determined by infrared spectroscopy (ATR-IR) and scanning electron microscopy (SEM). The swelling studies showed that all of the copolymer hydrogels exhibited ph-, temperature-, and salt- sensitive profile. The high temperature and existing of divalent salt effect causes a decrease with increasing the amount of PMEMA in the sample, gradually. It means that the swelling ratio can be tuned with introducing PMEMA comonomer. Fig. 1. FT-IR spectra of the hydrogels PDMAEMA, PMEMA and poly (DMAEMA 50 -co-mema 50 )

313 APPLICATION OF RECOVERY STRESS ANALYSIS ON POLY(LACTIC ACID) MODIFIED BY REACTIVE EXTRUSION J. Cailloux 1, A. García 1, F. Carrasco 2, O.O. Santana 1, M.Ll. Maspoch 1 1 Centre Català del Plàstic (CCP) - Universitat Politècnica de Catalunya (Spain) 2 Department of Chemical Engineering, Universitat de Girona (Spain) Applied Chemical Engineering. Process and Product Engineering. The main goal of this work is to assess the variation of the shape recovery ability due to the insertion of long chain branches in poly(lactic acid) (PLA) induced by a one-step reactive extrusion-calendering process [1]. All the samples were extracted from the central part of the extruded sheets which were previously "de-aged" and uniaxially stretched to nominal draw ratios (DR) of 1.5 and 2. Upon the latter treatment, the samples were subjected to a physical aging process at room temperature during 1, 3 and 4 weeks in order to reproduce industrial storage conditions. After these storage times, the shape recovery was evaluated by thermal limited shrinkage tests (iso-strain tests with controlled heating ramp) [2,3]. Tests were performed using a DMA device in tensile mode. The heating rate was set to 2 C/min from 30 C to 100 C. Upon heating, the reaction stress applied on the mobile grip was recorded and may be associated to the recovery stress of the sample. Figure 1 shows typical traces of the tests. When the sample is heated, the stress decreases due to thermal dilatation, and reaches a minimum at a temperature depending on the aging time (t a ). When the glass transition is reached, a significant increase in the stress recovery is observed which may be attributed to the thermal shrinkage of the sample. With increasing temperature a maximum is reached followed by a decrease until a stabilization plateau, which might be related to the stabilization of the mesomorphic crystalline phase generated during the previous stretching process. As t a increases, a decrease in the thermal shrinkage could be observed. At low t a, differences between unmodified (PLA) and long chain branched (PLA-REX) samples cannot be observed. However, as the aging time is increased, PLA-REX samples seem to show higher stress recovery, due to its lower rate of physical aging [4]. These results have been correlated with the molecular weight between entanglements (Me). Figure 1. Typical recovery stress vs temperature curves for samples stretched at DR = 2. Acknowledgement: The Ministry of Science and Innovation (grant number MAT C02-01) of the Spanish Government financially supported this work. [1] J. Cailloux, O.O. Santana, E. Franco-Urquiza, J.J. Bou, F. Carrasco, J. Gámez-Pérez, M.L. Maspoch. express Polymer Letters, 7(3), (2013). [2] Y.S. Wong, S.S. Venkatraman. Acta Materialia, 58, (2010). [3] C. Vechambre, A. Buleon, L. Chaunier, C. Gauthier, D. Lourdin. Macromolecules, 44, (2011). [4] J. Cailloux, O.O. Santana, E. Franco-Urquiza, J.J. Bou, F. Carrasco, M.Ll. Maspoch. Journal of Materials Science, 49(11), (2014).

314 CEMENT-PLASTICIZING CHEMICAL ADMIXTURE COMPATIBILITY IN CONCRETE PRODUCTION A.Evren Arioz#1, B. Omer Arioz#2, A. O.Mete Kockar#3 A.Anadolu University, Faculty of Engineering, Department of Chemical Engineering, 26555, Eskisehir, Turkey Tel: , Fax: B. Cimbeton, Cementir Holding, Isik Street, No:4B, Izmir, Turkey Applied Chemical Engineering, Process and Product Engineering Concrete is one of the most important materials in construction industry. As the population increases especially in countries like China and India, the costruction industry will grow fastly. In China, 40 billion square meters of combined residential and commercial floor space will be needed over the next 20 years (Torgal and Jalali, 2011). Concrete is produced by mixing together cement, aggregate, water and if required chemical admixtures. Use of plasticizing admixtures in concrete production is continuously increasing. Concrete is affected by factors such as polymer type, polymer-cement ratio, water-cement ratio, air content and curing conditions (Ohama, 1998). The important factor that affects the strength of concrete is the ratio of water to cement (w/c). The low water/cement ratios are preferred in concrete production. To enhance the workability and obtain the sufficient rheological properties, plasticizers which are the most common chemical admixtures in concrete production are used. (Anagnostopoulos, 2014). The important improvement in concrete industry was polycarboxylate based plasticizers. The structure of polycarboxylate polymers consists of a backbone and side branches. The properties of concrete such as workability, retention, cohesion and strength development can be changed by changing the length of a backbone and side branches (Scivener, 2009.) In this experimental study the mortars were produced by mixing cement, water and sand with different plasticizing admixtures by different ratios. Three different admixtures were utilized and the amounts of cement, water and sand were constant while superplasticizer ratios varied as % by weight of cement. The pastes poured into steel moulds and demoulded after 24 hours. The specimens cured at water bath for 3 and 28 days, and one group was aged for 28 days at atmospheric conditions in the laboratory. After aging, mechanical tests were performed on all the specimens.the specimens aged 28 days in water bath were used to investigate the microstructural analysis. The effects of plasticizer ratio on the mechanical properties of concrete were determined by flow properties and then compressive strength tests. To investigate the interaction between cement and superplasticiser, X-ray Diffraction Spectroscopy and Fourier Transform Infrared Spectroscopy were used. The compressive strengths of specimens cured at water bath were higher than the ones cured at atmospheric conditions. The highest strength obtained as MPa for the pastes cured at water bath for 7 days. The results revealed that the compressive strength of the concrete samples were decreased with increasing superplasticizer ratio. The fludity and workability increased as superplasticizer ratio was increased. References Anagnostopoulos A.C., Effect of different superplasticisers on the physical and mechanical properties of cement grouts, Construction and Building Materials, 50, , 2014.

315 Ohama Y., Polymer-based Admixtures, Cement and Concrete Composites, 20, , Scivener K.L., Nanotechnology and Cementitious Materials, (Ed.: Bittnar Z., Bartos P.J.M., Němecěk J., Šmilauer V., Zeman J.), Nanotechnology in Construction 3, Proceeding of the NICOM 3, Prague, Czech Republic, May 31-June 2, Torgal F.P., Jalali S., Eco-efficient Construction and Building Materials, Springer, London, England, 2011.

316 KINETIC AND THERMODYNAMIC STUDY OF NATURAL PHOSPHATE DISSOLUTION BY CALORIMETRY B. Belgacem #1,S. Leveneur #2, M. Chlendi #1, L. Estel #2, M. Bagane #1 1. Chemical Engineering Department, National Engineering School of Gabes (ENIG) University of Gabes, Tunisia 2. LSPC-Laboratoire de Sécurité des Procédés Chimiques, INSA Rouen, BP08, Avenue de l Université, Saint-Etienne-du-Rouvray, France; fax: Applied Chemical Engineering: Process and Product Engineering: Polymer and Solid Processing Phosphoric acid is an important chemical, essentially used as fertilizer. The world production of phosphoric acid is around 38 million tons per year. The basic process of phosphoric acid production is the attack of phosphate rock by phosphoric and/or sulphuric acid. The goal of this work is to determine the optimal operating conditions, i.e., temperature and mineral acid concentrations, for the dissolution of phosphate from a new phosphate deposit located in Tunisia. Two different calorimetric methods will be used: Calvet calorimeter C80 Setaram and a reaction calorimeter RC1 Mettler Toledo. The purpose of Calvet calorimeter is to estimate the enthalpy of dissolution at different temperatures, particule size distribution and mass of phosphate. The methodology developed by Jemal et al. [1-2] will be used. Figure 1 shows the heat profile of phosphate dissolution at 25 C. This process is exothermic. The second part of this study id to use reaction calorimeter such as RC1 Metler Toledo to follow the evolution of phosphoric acid concentration and be able to establish a kinetic model including thermal parameters Heat flow [mw] 10 5 Q =7,6 J Time [s] Figure 1. Heat profile for the dissolution of phosphate rock at 25 C. References 1. Kinetics and thermodynamics of the attack of a phosphate ore by acid solutions at different temperatures; K. Antar, M. Jemal; Thermochimica Acta 474 (2008) Etude cinétique et thermodynamique de la dissolution de la fluorapatite dans l acide phosphorique; K. Brahim, I. Khattech, J.P. Dubès, M. Jemal; Thermochimica Acta 436 (2005)

317 EFFECT OF FUEL COMPOSITION ON GAS EMISSIONS FROM FURNACE OIL REFINING INDUSTRY J. Saavedra, V. Kafarov, L. Meriño, A. carreño Universidad Industrial de Santander, Carrera 27 calle 9 Bucaramanga- Colombia, phone (57) , Scientific Topic: 3. Applied Chemical Engineering. 3.2 Process and Product Engineering. (Process Intensification) Companies that require gaseous fuel that burns in their processes, show concern for the reduction of emissions of greenhouse gases, at present, 69% of the greenhouse gases are produced by the burning of the refining processes and petrochemicals, which also generated a significant environmental impact. In Colombia, Ecopetrol it shows a good performance as the world leader in the field of sustainability, as measured by the Dow Jones sustainability index, which evaluates companies in economic, environmental and social. But, parameters and operating conditions for the ovens are affected by the composition of fuel gas, which may be a mixture of natural gas and process gas containing methane, ethane, propane and hydrogen. The process instability due to changes in gas composition represents a risk to industrial safety, environmental issues and structural damage due to high temperatures. In order to study this problem, the baseline emission of CO 2 generated was collected in furnaces; CO 2 historical data of the process were analysed and relationship with heating value was established which depended on the composition of the gas. Through statistical analysis of the results and the simulation of the combustion process, has determined that CO 2 values have a tendency to increase when using fuels of high calorific value, which should be regulate the use of mixtures containing compounds such as ethane and ethylene. Furnaces work with typical values of 1.5 to 2.5% excess oxygen, so that in the event of contributions from refinery gas streams to the fuel gas system, cause increased calorific value, it has the required minimum oxygen stoichiometrically for combustion. Evidenced an increase in CO 2 emissions caused by the change in the composition of fuel gas in furnaces, in this sense we propose the use of fuel gas streams having low calorific value and similar composition to natural gas. Higher adiabatic flame temperature are obtained for mixtures where methane, propane and hydrogen represent 65% of the mixture and also containing H 2 S, which can pose risks to the structure of the equipment for high temperature damage.

318 DYNAMIC MODELING AND SIMULATION OF CRUDE DISTILLATION UNIT T. Weng Khim, A.Hisyam and K. Ramesh* Process Systems Engineering Group (PSEG), Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang, Gambang, Kuantan, Malaysia. *Corresponding author: Tel: , Fax: Process and Product Engineering There is rapid growth in the usage and demand of crude oil in various industrial fields. The crude distillation unit (CDU) is the first major unit in the refinery. The purpose of this unit is to separate the crude oil into various blends by distilling the crude into fractions according to boiling point, so that each of the downstream processing units will have feedstocks that meet their particular specifications. CDU has 3 columns namely preflash unit, Atmospheric Distillation Unit (ADU) and Vacuum Distillation Unit (VDU). First, by fractionating the total crude through a preflash unit to remove butanes and lighter; second, by feeding the stabilized crude to a fractionator that operates at atmospheric pressure; and finally, by feeding the topped crude (high boiling fraction) from the ADU to a fractionator operated at a high vacuum. The vacuum tower is used to separate the heavier portion of crude oil into various boiling fractions to avoid the high temperatures necessary to vaporize the topped crude at atmospheric pressure. This prevents thermal cracking of the oil from occurring which would result in losses to dry gas, discoloration of the product, and equipment fouling due to coke formation. Based on the literature, most of the models available for Crude Distillation Unit (CDU) are steady-state models. But dynamic model is necessary in order to study the dynamics and improve the performance of CDU using proper control strategy. In this paper, both steady-state and dynamic model of CDU was developed using Aspen Plus. The mathematical model for the theoretical stage of the column was developed first and then based on the partial equations obtained, the relationship between input variable and output variable was studied. The flow sheet of CDU developed in Aspen plus is shown in Figure 1. Figure 1: Flow sheet of CDU Crude from three different sources were used in this study. First, Aspen Plus simulation of CDU was run in steady state mode and the results obtained were studied. The steady state results shown that increase in crude flow rate has resulted in drastic increase of residue flow rate in the product. Then dynamic simulation of CDU in Aspen Plus Dynamic was run and the dynamic behavior of CDU model was studied based on the results obtained.

319 SISTEMAS NEURO-FUZZY PARA LA TOMA DE DECISIONES Y OPTIMIZACIÓN DEL PROCESO DE ELABORACIÓN DEL ACEITE DE OLIVA VIRGEN. A. Jiménez Márquez 1 ;G. Beltrán Maza 1 ;MP Aguilera Herrera 2. 1 Centro IFAPA Venta del Llano. Junta de Andalucía. Ctra. Bailen-Motril Km. 18, Mengíbar, Jaén. (Spain). 2 Fundación CITOLIVA Parque Cientifico Tenológico GEOLIT. C/Sierra Morena- Manzana11, Edif.CTSA, Módulo 1, Mengíbar. Jaén. (Spain). 1 Telefono: Scientific topic: Process and Product Engineering. En el proceso de elaboración del aceite de oliva la naturaleza cambiante del fruto con el que se trabaja hace necesario un ajuste continuado de las Variables de Proceso, a fin de conseguir objetivos de productividad y de calidad, siendo las características de la materia prima, las condiciones de batido y los parámetros de regulación del decantador centrifugo horizontal, los principales condicionantes, con la dificultad añadida de su regulación de forma independiente debido la relación multifactorial que existe entre ellas y la dinámica no lineal del propio proceso, que hace que a menudo se trabaje en un entorno de gran incertidumbre, cumpliéndose con las premisas básicas para el desarrollo de controladores basados en los conceptos de la Inteligencia Artificial (IA). Redes Neuronales Artificiales (RNA) y Lógica Borrosa (LB), son algunas de las técnicas que pueden dar respuesta a ésta situación, cumpliendo con uno de los aspectos básicos del Control Inteligente como es el entrenamiento y aprendizaje, en imitación al ser humano, a partir de los datos recogidos en el propio proceso y de las acciones que realiza el operario, como experto, para ejecutar el control, y aprendiendo de cada acción para conseguir los objetivos con la mayor eficiencia. La simbiosis entre estas técnicas de inteligencia artificial puede constituir una solución muy efectiva ya que los neurocontroladores predictivos suelen originar numerosos procesos iterativos hasta encontrar el conjunto adecuado de valores de proceso que satisfagan el objetivo, mientras que mediante la implementación de sistemas FUZZY se podría reducir ese número de iteraciones yendo directamente al conjunto de valores más apropiado o más cercano, de acuerdo a las leyes o reglas establecidas a partir del conocimiento experto del proceso, con lo que el neurocontrolador ganaría en rapidez y efectividad. Consignas de control como: Si la humedad de la aceituna es inferior a la de consigna, abrir válvula de adición de agua; si los orujos están altos, reducir el caudal de masa al decanter; si los aceites salen sucios, reducir la adición de agua o reducir radio de descarga del aceite en el decanter; o si los aceites salen muy amargos, reducir temperatura de batido o disminuir tiempo de batido o añadir algo de agua al decanter; son habituales en el manejo de éste proceso y constituyen todo un conjunto de reglas del tipo SI condiciones ENTONCES acciones, propias de los sistemas FUZZY, que pueden ser parametrizadas y conformar una amplia base de datos experta constituyendo, así, un motor de inferencia de un sistema basado en la lógica difusa, que proporcione a un modelo neuronal de la planta el conjunto de valores de parámetros de proceso más adecuados a los objetivos establecidos. A lo largo de varios años se ha recolectado en planta real todo un amplio conjunto de datos sobre características de la materia prima, variables de proceso, características de los subproductos y características de los aceites elaborados. Estos datos han permitido diseñar un modelo neuronal de la planta y un sistema de decisión, basado en la lógica Fuzzy, cuyas reglas han sido definidas a partir del conocimiento que se tiene del proceso y análisis de datos mediante técnicas de Minería de Datos, tras la construcción de las tablas de decisión propias de estos sistemas obtenidad a partir de la aplicación de algoritmos de clasificación, del tipo J48, que han permitido extraer etiquetas y reglas de comportamiento. De acuerdo a las características de la materia prima y a las variables que gobiernan el proceso, el modelo neuronal de planta predice su comportamiento en cuanto a extractabilidad y características del aceite a la salida. Al establecerse unos objetivos, un sistema Fuzzy, en base a estas características y a las variables de proceso actuales, propone nuevas variables de proceso que permitan alcanzar esos objetivos, es decir, minimizar el error, en un proceso típico de control retroalimentado. (Proyecto Excelencia JJAA-MCI: AGR 6429_2010)

320 ARTIFICIAL NEURONAL NETWORK FOR HORIZONTAL SOLID BOWL DECANTER CENTRIFUGE SIMULATOR TO THE VIRGIN OLIVE OIL ELABORATION PROCESS A. Jiménez Márquez 1 ;E. Belén Funes 1 ;MP Aguilera Herrera 2 ;G. Beltrán Maza 1 1 Centro IFAPA Venta del Llano. Junta de Andalucía. Ctra. Bailen-Motril Km. 18, Mengíbar, Jaén. (Spain). 2 Fundación CITOLIVA Parque Cientifico Tenológico GEOLIT. C/Sierra Morena- Manzana11, Edif.CTSA, Módulo 1, Mengíbar. Jaén. (Spain). 1 Telefono: Scientific topic: Process and Product Engineering. Virgin Olive Oil is obtained only by mechanical procedures in oil mill. After crushing olives in hammer mill and kneading the olive paste in thermomalaxer, a solid-liquid separation is carried out in a horizontal solid bowl centrifuge (HSBC). Two phases, Olive pomace as byproduct and olive oil, as premier product, are obtained from HSBC. Their characteristics are influenced by variables related to centrifugal separation process that have to be optimized according to the olives characteristics. During four consecutive crop years, procesing data, analytical data and olive paste Near Infrared spectra were collected each day. These data have been used for Decanter modeling aimed to production and quality by using the Black Box technology and Artificial Neural Networks. Five neural network has been built that have been applied to design a simulator GUI Matlab based program. The parameters selected as neural network outputs were olive pomace moisture and fat for productivity and moisture, organic matter and total polyphenols content for olive oil quality. The crushing variables such as hammer rotation speed and sieve diameter, the kneading conditions (time and temperature), the Decanter variables as paste flow and water addition and oil overflow point, were some of the main factors considered as inputs to the Net together with the on-line Near Infrared spectra of the olive paste at the thermomalaxer. Simulator can predict the fat loss in olive pomace and certain quality characteristics of virgin olive oil by modification of the process variables values. This simulator can be used for real olive oil mill optimization in manual mode by predicting the best values for the variables considered, or in a feedback control system for automation of olive process. Theoretical formation of technicians may be another application to get training about how to act on process variables and how to get the best optimization strategies.

321 ADEM SIMULATION FOR PARTICLE BREAKAGE BEHAVIOR Junya KANO 1 and Shingo ISHIHARA 2, 1 IMRAM, Tohoku Univ., Katahira 2-1-1, Aobaku, Sendai, Japan, Phone: , Fax: , 2 GSES, Tohoku Univ., Katahira 2-1-1, Aobaku, Sendai, Japan Polymer and Solid Processing Grinding of solid materials is one of the most effective processing to produce fine particles, and the significance of grinding grows with each passing year due to the development of nanotechnology. Grinding has been used in many fields, for example, foods, cosmetics, medicines, mining and so on. However, in general, the efficiency of grinding is quite low because the mechanism of grinding have not been elucidated so far. Therefore, it is necessary to clarify the grinding mechanism and also to control the grinding process precisely. In this work, it has been attempted to analyse the grinding phenomena using computer simulation. A new simulation model ADEM (Advanced Distinct Element Method) has been developed. First of all, it has been applied to represent both non-spherical particles motion and particle breakage behaviour. In ADEM, cluster particle is represented by agglomerate of primary particles, and primary particles are connected by joint-spring. A cluster particle breakage was analysed by ADEM, the methods and results is shown as follows. We have performed the impact test and compression test of the cluster particle by ADEM. Simulation of impact test of the cluster particle has done at different velocities from 0.1 to 0.5 m/s. The size of fragments becomes smaller with increasing in the impact velocity (Figure 1). These results agree well with the empirical knowledge. The compression test was performed for three different kinds of spherical particles (quartz, feldspar and borosilicate glass) by ADEM using fitting parameter. The maximum strain and structure of primary particle are found to be two important parameters to represent the shapes of fragments after breakage. It can be seen good agreement with experimental results when adjusting these parameters. These results suggest that ADEM would be a useful tool to analyse the particle breakage behaviour and grinding process of solid materials. (a) 0.1 m/s (b) 0.3 m/s (c) 0.5 m/s Figure 1 Snapshots of fragments at each impact velocity.

322 STUDY OF A TWO STAGE MEMBRANE SYSTEM FOR CO 2 CAPTURE E. Rodríguez-Fernández, A. Fernández-Barquín, E. Santos, C. Casado-Coterillo* and A. Irabien Department of Chemical and Biomolecular Engineering, Universidad de Cantabria, Avda. Los Castros s/n, Santander, Cantabria, Spain; *corresponding author: tel , Topic 3. Applied Chemical Engineering The ability to efficiently separate CO 2 from other light gases has received a great deal attention aiming at reducing greenhouse gas emissions. Membrane technology is seen as a green alternative to energy-intensive amine scrubbing in CO 2 removal from post-combustion processes evaluated either in a single or two-stage system using commercial polymer membranes [1]. Beyond the transport properties, the development of water resistant and thermal and mechanical stable membrane materials would allow working in a wider range of operating conditions to optimize the CO 2 separation in post-combustion. In this work, the study of a two-stage process membrane separation process with recirculation for CO 2 capture in a coal-fired power plant is evaluated. Different membrane materials with selected permselectivity properties are proposed in each stage in order to achieve 90% CO 2 removal efficiency and > 95% CO 2 purity at the exit. In the first stage, a membrane of permeability around 1000 Barrer and low selectivity is proposed. The membrane material chosen for this stage is hybrid chitosan- [Emim][Ac] ionic liquid. Chitosan is the second most abundant polymer from natural resources, containing amine and hydroxyl groups in the solid polymer structure, which makes it attractive for CO 2 /N 2 separation, also in the presence of humidity [2]. [Emim][Ac]- based supported membranes have been previously studied in our laboratory, in the range K, with high permeability and selectivity, but their liquid state may lack of stability in the long term [3]. Hybrid [Emim][Ac] - chitosan membranes have been explored as a means of combining synergic effects of the high solubility and flexibility of the dispersed phase and the processability and hydrophilicity of the polymer to improve membrane fabrication and performance in flue gas separation processes. For the second stage, a membrane material with selectivity higher than 20 and temperatures above 50ºC to avoid the use of a second heat exchanger is proposed. In this case, mixed matrix membranes from poly(1- trimethylsilyl-1propyne) (PTMSP) and small-pore zeolite crystalline particles are prepared in the laboratory that fulfill these conditions. PTMSP polymer is the highest permeable polymer known due to its high free volume, and the addition of small pore zeolites with high molecular sieving properties greatly enhances the selectivity [4]. The large permselectivity of these membranes is expected lead to a smaller membrane area thus reducing costs. The overall cost of the membrane-based system can be estimated using commercially available membranes economic data, and compared with current commercial amine absorption system. Acknowledgements This work is partially based on a concept from Eliot S. Gerber (U.S.A.), for which he is gratefully acknowledged. The authors are also grateful for the financial support from the Spanish Ministry of Economy and Competitiveness (MINECO) under projects ENE and CTQ C. C. C. also acknowledges the Ministry for the Ramón y Cajal grant (RYC ) at the Universidad de Cantabria. References [1] H. Zhai, and E. S. Rubin. Envir. Sci. Tech., 2013, 47, [2] L. A. El-Azzami and E. A. Grulke. J. Polym. Sci. Pol. Phys., 2007, 45, [3] E. Santos, J. Albo, A. Irabien. J. Membr. Sci., 2014, 452, 277. [4] C. Casado-Coterillo, J. Soto, M. T. Jimaré, S.Valencia, A. Corma, C. Téllez, J. Coronas. Chem. Eng. Sci., :

323 LOGIC BASED ALGORITHMS FOR THE INTEGRATION OF DIFFERENT MODELS IN THE SYNTHESIS OF CHEMICAL PROCESSES: APPLICATION TO THE DESIGN OF A POWER UTILITY PLANT N. Quirante and J.A. Caballero. Institute of Chemical Processes Engineering. University of Alicante, P.O. 99, E Alicante, Spain. Telephone Fax Abstract Scientific topic: Process and Product Engineering. Generalized Disjunctive Programming (GDP) is becoming increasingly popular as a solution technique for optimization problems involving discrete decisions, and it has been widely applied in design or retrofit of chemical processes. However, when a mathematical programming approach is used to synthesize a chemical process usually rely on shortcut or aggregated models in an attempt of capturing the essential of the model while the problem is maintained in a tractable size. However, under some situations the shortcut models are not accurate enough and important deviations are produced from the actual behavior. On another side, modular process simulators include robust and reliable models with special tailored algorithms to each unit process including specialized initialization procedures, but they have an input-output (grey box) structure that makes difficult their inclusion in a gradient based optimization environment. The major difficulties when solving a synthesis problem based on a superstructure approach, formulated as an MINLP and developed in a modular process simulator (Hysys, Aspen, ChemCad, etc), are first that some variables can take zero values (in the initial relaxed problem) if some of the variables in the superstructure take a zero value, or when the variables related to the non-existing units are forced to be equal to zero. In a process simulator this could produce a large set of different errors (that depend both on the process simulator and the unit operation considered). Secondly, some complex unit operations include numerical noise which makes difficult to calculate accurate derivatives. And third, in a given iteration, non-existing units are evaluated unnecessarily wasting calculation time. In this work we present a superstructure based algorithm, with the following characteristics: 1. Surrogate models (based in kriging interpolation) substitute unit operations from which it is difficult (or even impossible) calculate accurate derivatives. 2. Non noisy (or slightly noisy) units are maintained in the process simulator, and therefore rigorously calculated. 3. A logic based outer approximation (L-OA) algorithm is used to solve the problem. The major advantage of the L-OA algorithm is that only solve feasible NLP problems. In that way, we can fix lower and upper bounds for all the variables and avoid the zero flow problems. Besides, non-existing units in a given iteration are ignored reducing the size of the NLP and which makes the algorithm numerically more efficient. The complete synthesis of a Utility Plant is used as a motivating example. The superstructure, inspired in the previous work by Bruno et al. 1, includes: a gas turbine (through a kriging surrogate model generated from Aspen Hysys data); boilers at different pressures; four vapor head levels; steam turbines between all vapor levels with and without lateral extraction; vacuum turbines (with or without lateral extraction) and a deaerator. All of them rigorously simulated using the process simulator Aspen Hysys. Reference 1. Bruno JC, Fernandez F, Castells F, Grossmann IE. A Rigorous MINLP Model for the Optimal Synthesis and Operation of Utility Plants. Chemical Engineering Research and Design. 1998;76(3): Acknowledgements The authors wish to acknowledge the financial support by the Spanish Ministry of Economy and Competitiveness (CTQ C02-02).

324 OPTIMIZATION OF CHEMICAL PROCESSES USING CHEMICAL SIMULATORS AND MACHINE LEARNING ALGORITHMS J. Javaloyes*, N. Quirante, R. Ruiz-Femenia and J. A. Caballero University of Alicante, PO 99, E Alicante, Spain Telephone: Fax: * Scientific topic: Process and Product Engineering Chemical process simulators is a widespread powerful tool used by chemical engineers for a variety of applications ranging from material and energy calculations on complex flowsheet to evaluating different design alternatives to estimate the economic feasibility and environmental impact. There are many commercial simulators which include a wide variety of unit operations, with especially suited numerical methods developed for the convergence and with detailed thermodynamic fluid packages. However, although these software packages are a great tool for process simulation (in steady state and dynamic) and design problems, there are still significant shortcomings when are used in optimization problems. Most commonly optimization problems in process systems engineering involve discrete and continuous variables. The mixed-integer programming provides a powerful framework to model and solve this kind of problems. However, some important difficulties arises when we try to optimize a chemical process using process simulators and derivative-based solvers, due to the modular architecture of the process simulators, in which the different blocks (processing units) are black box models for the users, and usually there is no access to the original code and derivative information is not available. Derivative-free optimization algorithms (DFO) can be used when derivative information is not available. This combination (process simulators - DFO) is interesting, and provides good results in an acceptable computationally time for small to medium dimensionality problems (up to ten independent variables). Another possibility when the objective function and/or some constraints are represented by noisy implicit black box functions it is to generate surrogate models. Although these models have a lack of physical sense, are compact, computationally cheap to evaluate and can be optimized using derivative-based methods. In this work we implemented a modified version of the original Automated Learning of Algebraic Models for Optimization (ALAMO) algorithm proposed by A. Cozad, et al. [1] to build accurate and low-complexity surrogate models to ensure the tractability in the further optimization stage. These models are built as a linear combination of a subset of basis functions chosen from a larger set of potential basis functions. Thus, the objective is to calculate the regression coefficients (model parameters) and determine which the best subset functions is. The ALAMO algorithm is based on the ordinary least-squares regression problem to obtain the model parameters. The authors perform a series of reformulations and simplification steps leading to a MILP problem, and use the corrected Akaike information criterion to measure the model fitness and its complexity. Then, the surrogate model is improved automatically by the smart selection of new sample points (adaptive sampling algorithm). See [1] for detailed description of the algorithm. Moreover by solving first a LP obtained from the original MILP problem, it is possible to check which potential basis functions exhibit the highest contributions. Thus, we are able to reduce the initial library and improve the performance of the algorithm. The capability of the proposed algorithm was proven with several chemical process flowsheets with different number of independent variables. All these processes involve distillation columns, given the importance and complexity of these units. The objective function was to minimize the Total Annual Cost of the processes. Results highlight the ability of the algorithm to deal with medium size problems (up to ten degrees of freedom). It is worth to mention that, although the surrogate models are more computationally expensive to built compared to other methods (such as kriging), further optimization is less complex and faster, allowing to use global optimization solvers as BARON. Further work includes combining this method with others for obtaining surrogate models, to replace the more complex units of a superstructure developed in a process simulator, and use derivative-based solvers (such as the logic based outer approximation) in the optimization stage. References 1. Alison Cozad, Nikolaos V. Sahinidis and David C. Miller. Learning Surrogate Models for Simulation-Based Optimization. AIChE Journal, 2014; Vol. 60, No. 6, Acknowledgments This work was supported by the Ministry of Economy and Competitiveness (Spain). CTQ C02-02.

325 ANALYSIS OF THE IMPROVING IN CONVENTIONAL DISTILLATION COLUMNS TROUGH THE OPTIMAL DESIGN OF EQUIVALENT INTERNALLY HEAT-INTEGRATED DISTILLATION COLUMNS Juan A. Reyes-Labarta*, J. Javaloyes, N. Quirante, and J. A. Caballero University of Alicante, PO 99, E Alicante, Spain Telephone: Fax: * Scientific topic: Process and Product Engineering With the aim to improve the energy performance of the conventional distillation columns, this work introduces a systematic method for the optimal and rigorous design of internally heat-integer distillation columns (HIDiC) by means of combining a derivative-free optimization algorithm (the particle swarm optimizer) and a chemical process simulator. HIDiC are based on the combination of direct vapor recompression scheme and the heat integration between the rectifying and stripping sections [1]. Figure 1 shows the basic flowsheet of a HIDiC with a single heatintegrated exchange column. In this distillation system the rectifying and the stripping sections are physically separated by the feed tray. Moreover, a compression station is needed to increase the temperature of the rectifying section to allow the heat transfer from the rectifying to the stripping section. The compression ratio plays a very important role in HIDiC [2], and should be enough to provide a positive temperature driving force between both sections (at lees 10 ºC). This kind of distillation schemes are a feasible way to save energy especially suited for the separation of close-boiling mixtures, which leads to a very difficult separation, and/or low operating temperature systems. Figure 1. Internally heat-integer distillation system flowsheet. The design and economic optimization of HIDiC involves the selection of the number of trays of each section, the total number of intermediate heat exchanger and their optimal location (discrete decisions), as well as the total amount of heat transferred and the pressure ratio between both diabatic sections (continuous variables). The proposed approach take into account the above mentioned design parameters to minimize the total annual cost (TAC) of the system. The model is solved in two levels. The PSO algorithm and objective function (TAC) equations are included as explicit equations in the model (implemented in Matlab). And the product specifications and HIDiC process are solved at the level of process simulator (Aspen Hysys). These two software packages are connected via ActiveX/COM libraries. Comparative studies between conventional distillation columns and HIDiC were performed in order to prove the capabilities of this methodology using different separation mixtures such as benzene/toluene/ p - xylene or propylene/propane. Results shows that the proposed methodology is capable to find good solutions, and HIDiC are more energy efficiency than the conventional columns for the mixtures under study, especially when boiling points are quite close. References 1. Suphanit, B. Design of internally heat-integrated distillation column (HIDiC): Uniform heat transfer area versus uniform heat distribution. Energy 2010, 35, Nakaiwa, M.; Huang, K.; Naito, K.; Endo, A.; Akiya, T.; Nakane, T.; Takamatsu, T. Parameter Analysis and Optimization of Ideal Heat Integrated Distillation Columns. Comput. Chem. Eng. 2001, 25, Acknowledgments This work was supported by the Ministry of Economy and Competitiveness (Spain). CTQ C02-02.

326 DETERMINING THE BEST POSSIBLE OPERATION PARAMETERS TO MINIMIZE WATER CONTENTS IN ORDER TO MAXIMIZE THE DESIRED MEA PRODUCT STREAM R. Naeem Al-Hazmi SABIC Riyadh KSA, (M) +966 (0) , (T) +966 (1) , (F) +966 (1) , (E) Applied Chemical Engineering, Process and Product Engineering, Process Modelling, Simulation and Optimization, Ethanolamine plant at Saudi Kayan is designed to produce Mono Ethanolamine, Di-Ethanolamine and Tri- Ethanolamine. Currently, the plant is running normal at about 110% load of the total capacity. The aim of this work is to determine the best possible operating parameters to minimize water contents in order to maximize the desired MEA product stream. In order to accomplish this target, the simulation model has been developed using Aspen simulation model for several cases to ensure validity of the model as following: A) developed a simulation model using PFD data at load 100% to validate the model B) developed a simulation model using actual plant data at load 110% to verify the model validation. The match was found to be excellent. Results of the simulation indicate the water contents can be reduced. This work expected to be implemented on the plant. Water content can be minimized at bottom stream of drying column by adjusting reboiler duty and bottom stream flow rate.; therefore the water content in the MEA product of MEA column will be reduced up to 0.03 wt% as shown in the mass balance. Also amount of water in MEA product could be minimized up to 0.02 and 0.04 if basket has been added into MEA column at load 100 and 110% respectively. Two patents have been filed using this work. Applied Chemical Engineering SK MEA Purity/ Performance Chemical Revision DRAFT 1

327 CHARACTERIZATION OF POWDER COMPOUNDS BY USING EXPERIMENTAL AND MOLECULAR SIMULATION STUDIES Z. Ozturk #1, D.A. Kose #2, B. Ozturk#2 and A. Asan#1 #1Hitit University, Faculty of Engineering, Chemical Engineering Department, Corum, 19030, Turkey. #2Hitit University, Faculty of Arts and Sciences, Chemistry Department, Corum, 19030, Turkey. Process and Product Engineering To solve basic characteristics of the powder compounds are very difficult because their single crystal could not be formed by the way only powder XRD peaks could be collected. Powder XRD data has limited information for the crystal structure of the compounds. In recent years using the increased algorithms to investigate characteristics of the compounds are not enough alone. Additional experimental analysis could help to determine structure more accurate [1]. Combined characterization of the compounds decreases spent time and increases the quality of the characterization process [2-3]. Teraftalic acid, 1,10 phenantroline and Cu(II) building blocks are used to construct new mix ligand organometallic compounds which is codded as ZOMOF-01, is a kind of metal organic framework (MOF) structured compound. The compound was prepared by room temperature synthesize method and then TGA/DTA, elemental analysis, solid state UV-NIR-vis and powder XRD analysis realized. After that, molecular structure determined by using experimental analysis. But it was not enough to show mechanical and thermodynamic properties of the compound so the Grand Canonical Metropolis Monte Carlo Metropolis GCMC) simulations are used to calculate and to construct crystal structure and mechanical/thermodynamic properties of the compound. Reflex and Forcite modules of Materials Studio 6.0. At the first, PXRD peaks were processed and used for indexing. After that determined molecule from experimental investigations was imported to the unit cell which was constructed by using indexing outcomes with Reflex module. Rietweld optimization of the crystal structure was realized to optimize structure to have XRD peaks as like experimental PXRD. At last, Forcite module was used to calculate other characteristics such like thermodynamics and mechanical. References [1] H. Chen and S. L. Lin, J Mater Sci, vol. 49, pp , [2] R. Kitaura, F. Iwahori, R. Matsuda, S. Kitagawa, Y. Kubota, M. Takata and T. C. Kobayashi, Inorg. Chem., vol. 43, pp , [3] Y. Zhao, Y.-H. Kim, A. C. Dillion, M. J. Heben and S. B. Zhang, Phys. Rev. Lett., vol. 94, p , 2005.

328 TEACHING EXPERIENCES IN CHEMICAL ENGINEERING: EVALUATION, DESIGN AND SET-UP OF VLE EXPERIMENTS OF AMINE-BASED SOLVENTS FOR CCS CAPTURE F. Vega, M. Rodríguez, B. Navarrete, B. Alonso-Fariñas Chemical and Environmental Engineering Department, School of Engineering, University of Seville, C/ Camino de los Descubrimientos s/n Seville, Spain, phone: (+34) Scientific Topic: 3.3 New tools in Chemical Engineering Education Abstract A new teaching methodology that complement current theoretical and practical teaching in Chemical Engineering has been proposed. The target is to meet the educational challenges proposed by EHEA, basically, changing teacher role as transmitter of knowledge, self-learning and training in skills which enable it to practice. This methodology can lead to change theoretical learning and sort out problems with practical learning closer to reality. Students are required to understand of engineering and optimization of processes that are currently essential for academics in this field. The new methodology is based on developing tasks directed by the tutor with a working group of 4 to 6 students, in order to meet with a global objective proposed by the tutors during the first class. In this case, Vapour-Liquid Equilibrium (VLE) determination for amine-co2-water system was proposed as a topic to be evaluated by the pupils. The aim of the proposed project is to design and erected a lab-scale plant that can be used to obtain those curves for potential solvents applied in post-combustion capture [1,2]. Initial work has involved conceptual evaluation of different design options found in the literature, previously selected by tutors. Basic design calculations, development of construction drawings, P&ID, mounting specifications, operation manual were discussed during the face sessions. Subsequently, the tasks involved assembly and operation of the lab-scale plant in order to determine VLE curves for most-common amine-based solvents, which were forward compare with references to validate the apparatus design. The new teaching methodology let students to develop competences such as working in groups and solving real engineering problems, accomplishing traditional teaching methodologies in Chemical Engineering. Students has met the proposed challengers, concluding with the installation and commissioning of a lab-scale plant. The experience of the working group has been excellent, with the activity a success from the educational point of view. Pupils have shown great interest throughout the course, promoted by the idea of applying the knowledge acquired during their studies to develop an idea and turn it into a real problem. 1. References [1] P. W. J. Derks, H. B. S. Dijkstra, J. A. Hogendoorn, and G. F. Versteeg. American Institute of Chemical Engineers 2005; 51(8): [2] S. Park, C. Shim, H. Lee, K. Lee. Fluid Phase Equilibria 1997; 134:

329 Design of control algorithms for predetermined response Barberà, E IQS School of Engineering, Via Augusta, 390, Barcelona Tel: , Fax: , 3.3. Chemical Engineering Education Introduction The aplication of Ragazzini method (1) allows the controller design from the model of the behavior of the complete system. In this work, it is tried to design controllers who cause that the response of the system is a ramp followed by a step of setpoint value, smoothing the exigencies of dead beat algorithms (2). Methods The desired system response to unitary step input is a ramp with n intervals until arriving at final value. x(0) = 0 x(1) = 1/n x(2) = 2/n... x(n-1) = (n-1)/n x(n) = 1... Considering that the system input is a unitary step and the possible existence of a dead time equivalent to N periods of sampling, the system transfer function desired is: K(z) z N 1 z z n 1 z (n 1) 1 Results A ramp of three intervals, n=3, is fixed for a process with unit gain, time constant, τ, of 10 and dead time, N, of 3. In this case, the controller transfer function is: 1 z (z) z z z 7 6 3z 3z z 1 7 D 3 The grafic response of controlled variable verifies that this controller fullfils all the design conditions. Conclusions 198 normalized first order with dead time (FOPDT) processes (3, 4, 5) have been evaluated with periods of sampling periods, T: 0.02, 0,05, 0,1 and 0,2 seconds and different values of the ramp intervals (n=1 to 4, except for T=0.02, n= 1 to 10). In all cases good results have been verified. Despite the results, this design procedure has some inconvenients: - MODEL: a very good process model is needed, the quality of the response is very sensible to the errors in the model. - MANIPULATED VARIABLE: excessively great values of the manipulated variable are needed when a fast answer is desired. - DISTURBANCES: the response to input of disturbances is very slow References: (1) Ragazzini, J.R.; Franklin, G.F.: Sampled-Data Control Systems, McGraw-Hill, New York, N.Y., 1958 (2) Barberà, E.; Amorós, X.: "Algoritmos de control digital directo. Control Deadbeat", Afinidad, 40, 29-32, Enero Febrero 1983 (3) Barberà, E.: Procesos de primer orden con tiempo muerto (FOPDT): Un nuevo procedimiento para el ajuste de controladores PI y PID, Laboratorios y proveedores, (150), 53, marzo-abril, 2006 (4) Barberà, E.: Comparación entre diferentes procedimientos de ajuste de controladores PID. I. Valores máximos de la variable controlada y de la señal reguladora. Afinidad, 70, 242-5, octubre-desembre 2013 (5) Barberà, E.: Comparación entre diferentes procedimientos de ajuste de controladores PID. II. Márgenes de ganancia y de fase y comportamiento como regulador. Afinidad, 70, 246-9, octubre-desembre

330 EL SISTEMA DE GESTIÓN DE LA CALIDAD: DESDE EL DISEÑO DE ASIGNATURAS HASTA LAS AUDITORÍAS. IMPLICACIÓN DE LOS ALUMNOS J. Giménez (1), M. Cruells, N. Escaja, J. Fernández, J.A. Garrido, M. Llauradó, A. Roca, L. Rodríguez, M.Ll. Sagristà, C. Navarro, J.O. Bernad, C. Escobar (1) Department of Chemical Engineering. Faculty of Chemistry. Universitat de Barcelona. C/ Martí i Franquès, Barcelona. Spain. Phone FAX Scientific topic: 3.3. Chemical Engineering Education Actualmente, todos los grados universitarios deben tener implantado un Sistema de Gestión de la Calidad (SGC). El objetivo final de este SGC es la mejora continua y, dado que es obligatorio implementarlo, hay que intentar aprovechar todas sus posibilidades de manera que pueda ayudar en la tarea docente. A modo de ejemplo se van a comentar a continuación las posibilidades que brindan algunos de los elementos del SGC. Centrémonos en los grados y en dos procesos básicos como son la docencia propiamente dicha y la movilidad del estudiante. Empezando por los procedimientos, algunos de ellos desarrollan las etapas de la labor docente: diseño de la asignatura, planificación e impartición y evaluación. Disponer de esos procedimientos simplifica mucho la labor del profesor. Quedan muy claras las responsabilidades del personal implicado en las distintas etapas y se asegura una mayor homogeneidad en la preparación de las asignaturas, cosa que repercute en la mejora de la docencia. Se podría decir lo mismo de la movilidad del estudiante, para lo cual se dispone de procedimientos que describen los procesos de realización de prácticas externas y de movilidad nacional e internacional. Ello simplifica la labor de los tutores y de los alumnos y garantiza un mejor control del desarrollo de estos procesos. Aparte de los procesos básicos, en cualquier SGC tienen mucha importancia los procesos de análisis y mejora. A través de ellos y de las herramientas que proporcionan, es posible hacer el seguimiento de todos los procesos incluidos en el SGC y detectar errores, disfunciones y debilidades, cuyo análisis lleva a las acciones pertinentes para intentar subsanarlos, con lo cual se entra ya en la dinámica de la mejora continua. En esta línea, el Comité de la Calidad (CC) de la Facultad de Química de la UB, independientemente de las encuestas institucionales de la universidad, ha elaborado encuestas propias como herramientas para analizar los laboratorios involucrados en la docencia (satisfacción del usuario) y necesidades de las empresas (satisfacción de cliente). Para la evaluación de la satisfacción de los usuarios, desde hace más de 10 años, al final de cada turno de prácticas de laboratorio, los alumnos y los profesores cumplimentan una encuesta que evalúa distintos aspectos de la docencia práctica: instalaciones del laboratorio, material y equipos, elementos de seguridad, desarrollo de la labor docente, etc. Los resultados han permitido detectar deficiencias en los laboratorios que han podido ser subsanadas, y quizá con más celeridad de lo habitual, debido posiblemente a la presión de las encuestas. Así mismo, han resultado decisivas para implementar la cultura de la seguridad, del respeto al medio ambiente y de la calidad en los laboratorios docentes de la facultad. Para evaluar la satisfacción del cliente, ya en el año 2007 se envió una encuesta a más de 150 empresas (respondieron 51), en la cual se les pedía su opinión acerca de los conocimientos que los egresados debían tener sobre diversos temas: operaciones de laboratorio, procesos químicos, tratamiento de datos, gestión de calidad, medio ambiente y seguridad, planificación del trabajo, gestión de la información y del tiempo, etc. Aparte de valorar la formación clásica, las empresas valoraban mucho los conocimientos en gestión (de información, calidad, medio ambiente y seguridad). A partir de estos resultados, se introdujeron modificaciones en los planes de estudios de los nuevos grados. Dicha encuesta ha sido revisada recientemente y está previsto enviarla de nuevo a lo largo de este año. Otro aspecto interesante de los procesos de análisis y mejora es el de las auditorías. A través de un proyecto de innovación docente, el CC ha puesto en marcha unas auditorías en las que los estudiantes actúan como auditores de los laboratorios docentes de la facultad. En el curso , participaron 53 estudiantes, los cuales, después de una breve formación, actuaron como auditores en 30 auditorías en prácticamente todos los laboratorios de la Facultad, con la participación del orden de 60 estudiantes y 30 profesores como interlocutores de los laboratorios auditados. Se auditaron 19 grupos de prácticas y diferentes asignaturas prácticas correspondientes a los tres grados (Química, Ingeniería Química e Ingeniería de Materiales) y a los distintos departamentos de la Facultad. Como punto fundamental, los estudiantes han trabajado competencias transversales relacionadas con la ética, capacidad de expresión oral y escrita, capacidad de diálogo, capacidad de liderazgo, análisis e interpretación de datos y gestión de la calidad. Por tanto, esta herramienta del SGC se ha mostrado muy útil en la labor docente. Quizá esta última frase podría ser la conclusión más importante de este trabajo. El SGC no debe verse como un elemento para aumentar la burocracia sino como una herramienta útil para la simplificación y mejora de la actividad docente.

331 EL JUEGO DE ROL COMO HERRAMIENTA EN LA ENSEÑANZA DE LA INGENIERÍA QUÍMICA J. Giménez, M. Vicente Department of Chemical Engineering. Faculty of Chemistry. Universitat de Barcelona. C/ Martí i Franquès, Barcelona. Spain. Phone FAX Scientific topic: 3.3. Chemical Engineering Education El hecho de tener implementados sistemas de gestión, representa, hoy en día, un valor añadido para las empresas. Es por ello que muchas de ellas trabajan con las ISO 9001, ISO 14001, OHSAS 18001, etc. Por estas razones, en el Máster en Ingeniería Química de la Universidad de Barcelona, se trabajan los sistemas de gestión. La idea central de los sistemas de gestión y su objetivo principal es la mejora continua. En definitiva se basa en el conocido Plan Do Check Act y en la conocida pirámide de la gestión: Política Manual Procedimientos Registros y formularios Análisis y mejora. En lo que hace referencia a los sistemas de gestión medioambiental, se acostumbra a tomar como referencia las normas ISO y/o la EMAS (Reglamento CE 1221/2009). Para hacerse una idea, quizá baste con indicar los apartados que constituyen la ISO (en la EMAS son muy parecidos): Política Ambiental, Planificación (aspectos ambientales, requisitos legales, objetivos), Implementación y operación (funciones, responsabilidad, competencia, formación, comunicación, documentación, control operacional, etc.), Verificación (seguimiento, no conformidad, acción correctiva y acción preventiva, auditoría interna, etc.), Revisión por la dirección. A la vista de todos estos apartados, la aplicación de estos sistemas de gestión requiere toda una estructura documental pero también tienen una parte técnica importante. La cuestión sería parecida para la implementación de los sistemas de gestión de seguridad y salud donde habría que sustituir los aspectos ambientales por la evaluación de riesgos. Al analizar la ISO (o EMAS o ISO 9001 u OHSAS 18001) se observa que afecta a todos los niveles y a todas las personas de la organización. Por tanto, será necesario que todas ellas participen de su contenido y se sientan integradas. Un aspecto a considerar es el relacionado con la interpretación que se pueda hacer de distintos aspectos de los sistemas de gestión. Es obvio que los puntos de vista de empresario, operarios, jefe de planta, jefe de mantenimiento, responsable de seguridad (acostumbra también a ser el responsable de medio ambiente y calidad), técnicos de la administración, etc. serán muy diversos. Cada uno de ellos tiene objetivos e intereses diferentes que, más de una vez, pueden chocar y que, por tanto, requerirán una cierta habilidad negociadora para conseguir que todos los intereses sean viables en un grado razonable y aceptable para todos. Desde el punto de vista docente, los sistemas de gestión pueden ser un tema muy importante en la formación del alumno puesto que le obligan a tener una visión global de las cosas, a integrar conocimientos que ha ido adquiriendo en distintas disciplinas y a trabajar de manera documentada y ordenada. Otra cosa es la explicación de todo ello a los alumnos y cómo se consigue captar su interés y su motivación. La clase magistral puede ser útil para dar una visión general de todo el tema e insistir en algunos conceptos importantes como el de la mejora continua. Una vez hecho esto, entrar a explicar punto por punto un sistema de gestión puede convertirse en algo muy árido. Por tanto, habrá que buscar vías alternativas. Entre ellas, el juego de roles puede aportar soluciones ya que permite que cada uno adopte un papel que debe defender, lo cual obliga a cada estudiante a saber qué corresponde a su papel y, por tanto, a entrar a fondo en aquellos aspectos del sistema de gestión ligados con su papel. Además, el hecho de tener que discutir luego su posición con la de otros compañeros también mejora algunas de sus competencias. Los roles a asignar serían: empresario, operario, jefe de planta, responsable de seguridad y técnico de la administración. Para enmarcar estos roles, se puede elegir una empresa, real o imaginaria, relacionada con el sector químico. Una vez tiene asignado su papel, tomando como base la ISO y la EMAS, cada estudiante define las implicaciones que conlleva su rol (preparación del manual, definición del mapa de procesos, legislación que debería conocer, documentos que debería conocer y redactar, indicadores, acciones correctivas y preventivas, cuestionarios de auditoría, etc.). En definitiva, habrán elaborado parte de la documentación de un sistema de gestión y habrán adquirido conciencia de lo que significa la mejora continua, cosa que les puede ser útil en su vida profesional posterior. Los estudiantes deben ser capaces de asimilar las responsabilidades e implicaciones que conlleva su rol y saber negociar y defender los propios intereses frente a otras personas, interiorizando su rol, desde una postura ética, dialogante y comprensiva. Con ello, mejoran en habilidades y competencias tales como sentido de la responsabilidad, flexibilidad, capacidad de comunicación, capacidad de negociación, trabajo en equipo, etc.

332 INNOVATIVE TOOLS FOR DRIVING THE SELF-LEARNING OF CHEMICAL ENGINEERING STUDENTS C. Negro, A. Blanco, E. Fuente, M.C. Monte *, D. Hermosilla, A. Tijero, N. Merayo, I. Latour, L. Cortijo, H. Barndök, L. Blanco. Chemical Engineering Department Complutense University of Madrid. Faculty of Chemistry Avda. Compltense s/n Madrid, Spain, * Tel : , * Fax: * Chemical Engineering Education 1. Introduction Since the European Higher Education Area (EHEA) has been implemented, the students are the protagonists of the learning process and the self-learning is one of their main activities. This has required modifying the learning methodology of the students, and providing them with new tools according to the new requirements and challenges that they must overcome. Among other capacities, they must be able to solve problems in Chemical Engineering and to prepare high quality scientific reports. This work presents some tools that have been developed at the Chemical Engineering Department of the Complutense of Madrid University to drive the selflearning of their students. 2. Results 2.1. Tools for self-evaluation A collection of initial self-evaluation tests related to the unsoundness of required basic knowledge as, for example, tests about the use of equilibrium diagrams, or about mass and energy balances, has been developed to overcome the learning difficulties of students. Furthermore, a collection of self-evaluation tests for the subject Process Engineering, implemented by a quiz maker software, are presented. On the other hand, a case study presentation that allows the students interacting to select the best reactor to carry out a chemical reaction has been prepared. As example, the ammonia production by the Haber Bosch process has been selected. The students must work with different reactors by using a simulation program, as Aspen Plus, to decide which one is the best selection. They can learn how their decisions affect the process. A tutorial about Aspen Plus has been also prepared to guide them carrying out the simulation Tools for self-sufficient learning in reporting research The quality of the scientific reports can be increased notably if the students have the appropriate tools to help them to identify the main faults and to remind them some considerations to take account. To accomplish this objective, a protocol to become students in reviewers of their scientific reports, with a template and a check-list for helping them in reviewing the scientific report was developed and it is presented. Furthermore, the reviewing among each other helps them to detect and be aware on the deficiencies of their own works and it gives them the opportunity of correct the reports before submitting them. In addition, some tools were developed to help the students in elaborating the scientific reports: a template for the elaboration of the reports, several tutorials (Aspen, Excel, Sigmaplot), and a guide notes and state of the art searching guide. Ackowledgements The authors wish to thank the University Complutense of Madrid for supporting the Project for Innovation and Improving Teaching Quality (PIMCD 2013) Design of Innovative Tools for the Performance of Transversal and Specific Capabilities of Process Engineering (Ref.: PIMCD-UCM-303).

333 SOFTWARE TO DESIGN LIQUID PHASE IDEAL REACTORS: CASES FOR TEACHING PURPOSES A. Durán, J.M. Monteagudo*, C. Loarces Department of Chemical Engineering, Grupo IMAES, Escuela Técnica Superior de Ingenieros Industriales, Universidad de Castilla-La Mancha, Avda. Camilo José Cela 3, Ciudad Real (Spain). Fax: Phone: , ext: Scientific Topic (3.3 New Tools in Chemical Engineering Education). A simulation software has been developed using Visual Basic.NET in order to calculate conversion and temperature profiles with time for liquid phase ideal reactors: discontinuous batch reactor (BR) and continuously stirred tank reactor (CSTR). The software employs the Simpson's rule for the numerical approximation of definite integrals and the forth order Runge-Kutta method for the approximation of solutions of differential equations corresponding to mass and energy balances. An attractive interface will be appealing to the users in different graphics. The software is limited to reactions with order 0, 1 and 2 and with the same number of moles entering and leaving the reactor. Different examples are implemented in order to quantify the efficiency of reactors. A cost analysis is also added for simple first order reactions in BR. In order to foment a critical, constructive and participatory view, students can be asked to use the software to test with different input values relating the heat exchanger, such as overall coefficient, temperature or transfer area, to show the results from these evaluations in figures and to propose a possible improvement in a typical device. Fig.1. Input data screen for a not isothermal/not adiabatic batch reactor. Fig. 2. Results from execution

334 Degradation of boscalid in waste water by AOP ozonation and heterogeneous photocatalysis. Study and comparison of treatments. C.AYRAL 1*, P. DESTRAC 1, C.ANDRIANTSIFERANA 1, F. BENOIT-MARQUIE², M- H.MANERO 1, C. JULCOUR 1, H. DELMAS 1 1 Université de Toulouse; INPT, UPS; Laboratoire de Génie Chimique UMR CNRS , Allée Emile Monso, F Toulouse, France ² IMRCP Interactions Moléculaires et Réactivité Chimique et Photochimique Avenue Edouard Belin BP Toulouse Cedex 4 *mail at Topic: Chemical Engineering for Sustainable Development: Environmental Technology and Risk Analysis. Advanced Technique for Effluent Treatment In an environmental context, the presence of micropollutants in wastewater is problematic. One of the current major challenges is to develop new water treatment to eliminate such pollutants. Our project fits into this context by investigating the degradation of a recently marketed pesticide: boscalid. Boscalid [2-chloro-N(4 -chlorobiphenyl-2-yl)-nicotinamide] is a fungicide mainly used in the last treatment before harvest fruit. Despite the low water solubility of boscalid (4.64 mg/l at 25 C), the disposal of fruit washing effluents becomes a problem due to the potential ecotoxicity and environmental persistence of this molecule. Very few studies exist on the degradation of boscalid and there is thus a critical need for efficient treatment techniques to address this issue. In this work, we study and compare the degradation of boscalid by two advanced oxidation processes (AOPs): ozonation and photocatalysis. Such techniques generate very active and non-selective oxidant species: hydroxyl radicals. For monitoring of the pesticide concentration, different analytical techniques have been developed and optimized: HPLC-DAD, HPLC-MS and UV spectrometry. To better compare the AOPs, the experiments are performed in the same semi-batch reactor, treating one liter of boscalid solution. Regarding heterogeneous photocatalysis, several parameters have been investigated: boscalid concentration, type of TiO 2 -based catalyst either in the form of nanopowder or supported onto quartz coverslip or zeolite extrudates. The oxidations kinetics of these different configurations are compared. At the beginning of oxidation, the initial concentration is 100 µg/l of boscalide. After 200 minutes, nearly 20% of boscalid is degraded in the case of catalyst TiO 2 /Quartz, degradation reached 40% with TiO 2 /zeolite. For ozonation, two concentrations of boscalid have been studied: C = 1 µg/l and C = 100 µg/l. Comparison of these kinetic of ozonation shows the degradation is slower if the pesticide is one hundred times more concentrated. These preliminary results indicate that ozonation and heterogeneous photocatalysis can be suitable treatments for boscalid contaminated waters.

335 BENEFITS OF ASPEN PLUS AND ASPEN HYSYS SOFTWARE FOR CHEMICAL ENGINEERING BACHELOR THESIS E. Díez 1, J.C. Domínguez 1, R. Miranda 1, I. Moraleja 2, M. Oliet 1, A. Rodríguez 1, V. Alonso 1, P. Yustos 1, J.M. Toledo 1, Y. Madrid 2, M.T. Pérez-Corona 2, E. García-Carpintero 1, M. Hipólito 3, E. Escriche 3, M. Collado 1 1. Departamento de Ingeniería Química, Facultad de CC. Químicas 2. Departamento de Química Analítica, Facultad de CC. Químicas 3. Biblioteca Complutense, Facultad de CC. Químicas Universidad Complutense de Madrid, Avda. Complutense s/n, 28040, Madrid, Spain. Scientific Topic: 3: Applied Chemical Engineering. 3.3: Chemical Engineering education Chemical Engineering degree covers a wide range of disciplines related to chemical processes such as transport phenomena, chemical kinetics, reaction engineering or process control and design. Although all of them are deeply taught as individual courses along the four-year curriculum of the degree, the final bachelor thesis (BS) is crucial for a global assessment of all the acquired competences [1]. This work is part of an innovation and development in education project that is carried out by an interdisciplinary team of different departments of the Faculty of Chemistry at Complutense University of Madrid. The main objective of the project is to provide necessary tools for the students of Chemical Engineering to appropriately develop their final bachelor thesis. The project comprises two main sections: the first one will be an online open course, which will include several lectures describing the bullet points to be considered for the preparation and dissertation of a BS Thesis; the second one will be a compilation of useful tools related to specific subjects that can be used in different stages of the elaboration of a BS Thesis, such as software simulators, word processors, spreadsheets, literature management software, scientific literature searchers, chemical and physical properties data bases, etc. In particular, this work specifically deals with the use of commercial simulation software such as Aspen Plus and Aspen Hysys. In the Chemical Engineering degree of Complutense University of Madrid [2], the BS Thesis consists on designing a section of an industrial process from the beginning; it includes a feasibility study, mass and energy balances, both functional and mechanical equipment design, and the correspondent safety, environmental and economic analyses. The core of this thesis is to solve the mass and energy balances on one hand, and to accurately calculate the functional and mechanical parameters of the involved equipment on the other hand. To achieve these goals, Aspen Plus or Aspen Hysys simulation programs have demonstrated to be extremely useful [3]. Both simulators are commonly employed within the Chemical Industry to design unit operations, such as distillation or extraction, but also chemical reaction operations that involve, for example, plug-flow or continuous stirred-tank reactors. The two of them are capable of solving both mass and energy balances around a single apparatus or a group of apparatus. Besides, as they have implemented the appropriate design equations, they allow calculating their main functional parameters of an equipment. Therefore, according to previously said, the aim of this communication is to show the usefulness of both simulation programs in the view of elaborating a chemical engineering BS Thesis. This will be carried out by means of a help guide that will display their main applications as well as their main strengths and weaknesses. The first part of the proposed help guide is a brief introduction that will serve as starting point to get used to the software. Its main body is a detailed description of how to simulate the different operations (distillation columns, heat exchangers, chemical reactors ); this is important because the main characteristic of a simulation program is having specific blocks to simulate the most important unit operations as well as chemical reaction equipment. This section includes how to introduce the input data, what kind of output of information can be obtained but also how to draw conclusions from this information. Finally, the last section will deal with specific applications such as solid or polymer management. Literature [1] C. Lipson, How to write a BA Thesis: a practical guide from your first ideas to your finished paper; The University of Chicago Press: Chicago & London, [2] https://quimicas.ucm.es/tfg (accessed June, 2014). [3] (accessed June, 2014). Acknowledgements. The authors gratefully acknowledge the financial support of the project: Curso abierto de ayuda para la elaboración del Trabajo Fin de Grado en los Grados en Química e Ingeniería Química, Proyecto de Innovación y Mejora de la Calidad Docente Nº 37, Universidad Complutense de Madrid, 2014.

336 THE INTEGRATION OF A MATHEMATICAL-THERMODINAMIC MODEL IN THE SIMULATION OF A RECTIFICATION PROCESS BY A PACKED COLUMN. A PRACTICAL CASE AS A FORMATIVE TOOL Marrero, P.; Ríos, R.; de la Nuez, I.; Fernández, L, Ortega, J. Laboratorio de termodinámica, Parque Científico-Tecnológico, Campus de Tafira. Las Palmas de Gran Canaria, 35017, Spain , Experimentation is one of the main activities in the educational field in chemical engineering. But, if further experimentation is linked to a theoretical approach, taking into account the basis for such pr