IMPROVED EFFICIENCY IN THE TREATMENT OF INDUSTRIAL WASTEWATERS

1 IMPROVED EFFICIENCY IN THE TREATMENT OF INDUSTRIAL WASTEWATERS Prof. Ulla Lassi University of Oulu/Kokkola University Consortium Chydenius Kokkola Material Week, KMW, 24.9.2014

CONTENT 2 1. Introduction 2. Advancedd catalytic ti oxidation methods in the treatmentt t of industrial i wastewaters 3. Chemical precipitation as a method for mine water treatment 4. Industrial residues as novel (ad)sorbents for the heavy metal removal from wastewaters for the removal of nitrates and phoshates for sulphate removal 5. Conclusions Prof. Ulla Lassi Kokkola Material Week, KMW, 24.9.2014

RESEARCH GROUP OF APPLIED CHEMISTRY Totally 27 researchers Main projects on that topic : Researchers in the field of water treatment: MSc M.Sc. (Chem.) Hanna Runtti Moniwater/Tekes 2009-2011 Valokata/Tekes 2008-2010 2010 M.Sc. (Chem.) Sari Tuomikoski (defense AOPI/Academy of Finland, 2012-2016 14.11.2014) Teollisuuden jätevesien käsittely, 2009- M.Sc. (Eng.) Laura Rahikka SULKA/EU, 2012-2014 MSc M.Sc. (Chem.) Tero Luukkonen Several projects with industry M.Sc. (Chem.) Emma-Tuulia Tolonen M.Sc. (Chem.) Anne Heponiemi M.Sc. (Eng.) Ville Kuokkanen B.Sc. (Chem.) Mikko Niskanen B.Sc. (Chem.) Sara Lopez Senior researchers: D.Sc. Pekka Tynjälä (advisor, until 1.5.2014) D.Sc. Tao Hu D.Sc. Saïd Azalim (until 31.12.2013) DSc D.Sc. Jaakko Rämö (advisor) D.Sc. Teija Kangas (advisor) Prof. Ulla Lassi

SOME EXAMPLES OF INDUSTRIAL CO-OPERATION OPERATION

SOME EXAMPLES OF INDUSTRIAL CO-OPERATION OPERATION Industrial collaboration: Cabb Oy (Kemfine), Kemira, Snellman, Eskopuu, UPM, Stora Enso, JP Analysis, Yara, Sachtleben Pigments, Freeport, PAC Solution, Rautaruukki, Outokumpu, Talvivaara, Keliber, Gasek, Arizona Chemical, OWA etc. Some significant references of industrial co-operation: operation: HEPONIEMI, A., RAHIKKA, L., KUOKKANEN, T. & LASSI. U. (2011) Catalytic oxidation of industrial wastewater under mild conditions, Topics in Catalysis, vol. 54, 1034-1041. LUUKKONEN, T, HUKKANEN, R., PELLINEN, J., RÄMÖ, J. & LASSI, U. (2012) Reduction of total organic carbon in recovery bil boiler make-up with ih activated carbon filter, PowerPlantPl Chemistry 14(2): 112-119. KUOKKANEN, V., LASSI, U., KUOKKANEN, T. & RÄMÖ, J. (2013) Recent applications of electrocoagulation on treatment of water and wastewater A review, Green and Sustainable Chemistry, 3, 89-121. KILPIMAA (TUOMIKOSKI), S. RUNTTI, H., KANGAS, T., LASSI, U. & KUOKKANEN, T. (2014) Removal of phosphate and nitrate over a modified carbon residue from biomass gasification, Chemical Engineering Research and Design (in press) RUNTTI, H., KILPIMAA (TUOMIKOSKI), S., KANGAS, T., LASSI, U., KUOKKANEN, T. & RÄMÖ, J. (2014) Activated carbon residue from biomass gasification as an adsorbent for the removal of iron(ii), copper(ii) and nickel(ii) ions, Journal of Water Process Engineering (in press) TOLONEN, E., SARPOLA, A., RÄMÖ, J. & LASSI, U. (2014) Chemosphere 117, 419-424.

20 30 40 50 Preparation of catalysts for catalytic wet oxidation Preparation of support 0 10 by sol-gel method S2 Ce(NO 3 ) 3,6 H 2 O Zr(OC 3 H 7 ) 3 7 water S1 C 3 H 7 OH S2 solution 2 was added to solution 1 drop-wise at RT under vigorous stirring S1 Ce 0.2 Zr 0.8 O 2 Ce 0.85 Zr 0.25 O 2 Dried in oven at 120 C C for 12h Heat treatment at 650 C for 5h 60 C Evaporation in a sand bath at 60 C for 1 hour Remark: CeO 2 and ZrO 2 commercial catalysts (Sigma-Aldrich) Advanced oxidation processes in industrial wastewater treatment (AOPI)

Preparation of catalysts for catalytic wet oxidation Impregnation of active metals to the supports Rotary evaporator AgNO 3 + Acidic water + support Ag/ZrO 2 Ag/CeO 2 Ag/Ce 0.2 Zr 0.8 O 2 Ag/Ce 0.85 Zr 0.25 O 2 Time 4h Speed 25% Temperature 40 C Dried in oven at 120 C for 12h The target metal content for silver 2.5 wt -%. Heat treatment at 650 C for 5h & reduced at 350 C for 3h Advanced oxidation processes in industrial wastewater treatment (AOPI)

CERIUM OXIDE BASED CATALYSTS FOR WET AIR OXIDATION OF BISPHENOL A (BPA) 8 in the production of polycarbonate and epoxy resins adhesives protective coatings powder paints etc. organic effluents Temperature 130-200 C Pressure 5-50 bar Homogeneous catalysts Metal salts (Cu, Fe) Heterogeneous catalysts method for refractory Carbon b materials (AC, CNT) Transition metals (Cu, Mn, Co, Cr, V, Ti) induce feminization in several Supported noble metals animals and possibly humans Active metal (0.1-5 wt%): Pt, Ru, Ir, Ag Supports: CeO 2, TiO 2, ZrO 2, Al 2 O 3, SiO 2

CWAO OF BISPHENOL A 9 Sample volume 160 ml BPA 60 mg l -1 Temperature 160 C Pressure of air 20 bar Reaction time 180 min Catalyst concentration 4 g l -1 sol-gel method wet impregnation (w), complexation (c) Ag/CeO 2 (Sigma Aldrich)w Ag/Ce 0.85 Zr 0.15 O 2 w & c Ag/Ce 0.2 Zr 0.8 O 2 w & c Pt/CeO 2 w Pt/Ce 0.8Ti 0.2O 2w Pt/Ce 0.2 Ti 0.8 O 2 w

Toxicity measurements with model compounds Assay Target Important p53 protein Cell stress Semiquantitative (immunoblotting) Reactive oxygen species Comet assay Oxidative stress DNA damage ROS induce macromolecular (DNA,,p protein, lipids) damage Detects DNA-breaks MTT-assay Cell viability Detects mitochondrial damage Caspase-3 activity Apoptosis Enzyme not present in all cell lines Selected methods for molecular toxicity Pump Intervillous flow Maternal reservoir Maternal venous flow PLACENTA L LOBULE Fetal venous flow Fetal arterial flow Fetal reservoir O /CO 2 N /CO 2 2 2 Pump Placental perfusion equipment In co-operation with Prof. Kirsi Vähäkangas, University of Eastern Finland (toxicity) and Prof. Riitta Keiski (photocatalysis)

Toxicity measurements with model compounds Assay Bisphenol A MCF-7 Diuron MCF-7 Phthalic anhydride MCF-7 BeWo Bewo Bewo Perfluorooctanoic acid MTT X X X X X X - Propidium X - - - X - - iodide & digitonin ROS - - - - Comet assay - X - X - - p53 X - - - X - Phospho-p53 X - - - X - - Sphere assay X - X - - - In co-operation with Prof. Kirsi Vähäkangas, University of Eastern Finland (toxicity) and Prof. Riitta Keiski (photocatalysis)

RESULTS FROM CWAO OF BPA 12 100 80 a) 100 80 b) BPA remova al [%] 60 60 40 Ag/CeO 2 w Ag/Ce 0.85 Zr 0.15 O 2 w 40 20 Ag/Ce 0.2 Zr 0.8 O 2 w 20 Pt/CeO 2 Ag/Ce 0.85 Zr 0.15 O 2 c Pt/Ce 0.8 Ti 0.2 O 2 0 Ag/Ce 0.2 Zr 0.8 O 2 c Pt/Ce 0.2 Ti 0.8 O 2 0 0 20 40 60 80 100 120 140 160 180 200 0 20 40 60 80 100 120 140 160 180 200 Oxidation time [min] Oxidation time [min] BPA removal as a function of oxidation time with Ag (a) and Pt catalysts (b). Both Ag and Pt catalysts were active in the removal of BPA from wastewaters Adding of silver has no effect on the catalytic activity Too low active metal content (leaching of the Ag) Highest removal of BPA (97 %) with Pt/CeO 2 and Pt/Ce 0.8 Ti 0.2 O 2 catalysts BPA remova al [%] Heponiemi, Azalim, Hu, Lassi (2014) Cerium oxide based catalysts for wet air oxidation of bisphenol A, Topics in Catalysis (submitted) Heponiemi, Azalim, Hu, Lassi (2014) Catalytic wet air oxidation of bisphenol A with platinum catalysts supported on cerium and cerium-titanium oxides, Applied Catalysis B: Environmental (submitted)

RESULTS 13 Catalytic oxidation is an efficient method for the treatment of ww with high organic concentration, e.g. pharmaceutical industry Catalytic reaction mechanism and kinetics has to be known, carboxylic acids areformed as intermediates t (rds) Catalytic treatment of industrial ww affects also the toxicity and biodegradability of these compounds, which is currently studied

MINE WATER TREATMENT WITH CHEMICAL PRECIPITATION 14 SULKA-project (Sulphur Compounds in Mining Operations Environmental Impact Assessment, Measurement and Emission Abatement) Our response in WP6: Treatment of mine waters The enhancement of lime precipitation p for sulphate removal from mine waters is investigated Lime precipitation is also used as a pretreatment step before other treatment methods such as adsorption which is also studied for sulphate and metals removal from mine waters (so called hybrid method) http://www.oulu.fi/sites/default/files/content/poster_sulka.pdf 10.10.2014

CHEMICAL PRECIPITATION USING LIME AND POLYMERS 15 Different coagulants and flocculants are studied for the improvement of the settling characteristics of the sludge Precipitation experiments are done using the jar test Modelling of chemical precipitation is done by MINEQL+ software Tolonen, E-T., Tynjälä, P., Runtti, H., Luukkonen, T, Rämö, J. & Lassi, U. (2013), Mine water treatment with chemical precipitation using milk of lime and polymers, In: Proceedings of WaRes conference, August 15th Oulu, Finland (Eds. E. Pongracz and H. Pruikkonen), pp. 129-131..

16 CHEMICAL PRECIPITATION USING BY-PRODUCTS By-products from quicklime manufacturing have been tested successfully for mine water treatment as low-cost substitutes for commercial lime products All tested by-products removed over 99 % of Al, As, Cd, Co, Cu, Fe, Mn, Ni, Zn from AMD All tested by-products removed approximately 60 % of sulphate from AMD Tolonen, E-T., Sarpola, A., Hu, T., Rämö, J., Lassi, U. Chemosphere 117 (2014), 419-424.

CONCLUSIONS 17 By-products from quicklime manufacturing can be used for mine water treatment as low-cost substitutes for commercial lime products Over 99% removal of metals (and 60% removal of sulphates) from AMD was obtained Sulphate removal efficiency is limited by gypsum solubility Therefore, some hybrid system is required for sulphate removal Tolonen, E-T., Sarpola, A., Hu, T., Rämö, J., Lassi, U. Chemosphere 117 (2014), 419-424.

INDUSTRIAL RESIDUES AS NOVEL (AD)SORBENTS 19 Development process for utilisation of carbon residue formed in gasification process (wood chips). Sari Tuomikoski: Carbon residues from biomass gasification: Activation, characterization and use as an adsorbent, Doctoral dissertation, 14.11.2014

ADSORPTION EXPERIMENTS 20 Adsorption capacity can be clearly enhanced by chemical (ZnCl 2 ) and physical (CO 2 ) activation or chemical modification (FeCl 3 ) methods Adsorption of heavy metals (e.g. Fe,Cu,Ni), phosphate, nitrate and sulphate were studied Laboratory experiments (batch method) were carried out in order to examine effect of -initialph - initial solution concentration isotherm studies -adsorption time kinetic modeling Isotherm studies Kinetic modeling Error analysis Langmuir Freundlich Dubinin-Raduschevich (D-R) Temk Pseudo-first-order Pseudo-second-order Elovich RMSE

Parameter Unit PACR 1 CACR 2 MCR 3 AC 1 4 AC 2 5 Kinetic model 21 Carbon content % 52.1 61.8 61.0 77.6 91.99 - BET m 2 g -1 590 285 52.4 603 786 - Langmuir Ni removal q m mg g -1-62.9-3.1 - Pseudo-second-order Cu removal q m mg g -1-23.3-4.4 - Pseudo-second-order m Fe removal q m mg g -1-21.4-12.1 - Pseudo-second-order PO 2-4 removal q m mg g -1 30.2 20.5-443 4.43 870 8.70 Pseudo-second-ordersecond order NO 3- removal q m mg g -1 11.2 7.97-10.0 14.6 Pseudo-second-order SO 4 2 removal q m mg g -1 - - 19.5-15.0 Pseudo-second-order 1 PACR: Physically activated carbon residue, 2 CACR: Chemically activated carbon residue, 3 MCR: Chemically modified carbon residue, 4 AC 1: Activated carbon (Merck), 5 AC 2: Activated carbon (Norit). References: Kilpimaa (Tuomikoski), Runtti, Kangas, Lassi, Kuokkanen (2014) Removal of phosphate and nitrate over a modified carbon residue from biomass gasification, Chemical Engineering Research and Design (in press) Kilpimaa i (Tuomikoski), ki) Runtti, Kangas, Lassi, Kuokkanen (2014) Physical activation of carbon residue from biomass gasification: Novel sorbent for the removal of phosphates and nitrates from aqueous solution, Journal of Industrial and Engineering Chemistry (in press). Runtti, Tuomikoski, Kangas, Lassi, Kuokkanen, Rämö (2014) Chemically activated carbon residue from biomass gasification as a sorbent for iron(ii), copper(ii) and nickel(ii) ions, Journal of Water Process Engineering (in press).

CONCLUSIONS 22 Industrial by-products (or waste material) can be modified to low-cost (ad)sorbents for the removal of (heavy) metals and some anions from industrial wastewaters E.g. carbon residues from energy production, silica-based minerals (mine byproducts) and biopolymers (saw dust, peat, straw) are used in our study Modification can be done physically or chemically (addition of functional groups) to increase the selectivity Adsorbents can also be used for passive purification (e.g. closed mines), importance of biodegrability Biodegradation of sorbents enables their future use e.g. as fertilizers

Thank you for your kind attention! More information: http://www.chydenius.fi/tutkimus/soveltava-kemia h tki / k i Contact information: Professor Ulla Lassi, University of Oulu/ Kokkola University Consortium Chydenius email: ulla.lassi@oulu.fi, or ulla.lassi@chydenius.fi tel: +358 400 294 090