1 Expertise of the scientific community in the Languedoc-Roussillon region agriculture energy Green technologies environmental monitoring evaluation methods products water & waste Number 16
2 AGROPOLIS INTERNATIONAL agriculture food biodiversity environment Agropolis International brings together institutions of research and higher education in Montpellier and Languedoc- Roussillon in partnership with local communities, companies and regional enterprises and in close cooperation with international institutions. This scientific community has one main objective the economic and social development of Mediterranean and tropical regions. Agropolis International is an international space open to all interested socioeconomic development stakeholders in fields associated with agriculture, food production, biodiversity, environment and rural societies. Agropolis is an international campus devoted to agricultural and environmental sciences. There is significant potential for scientific and technological expertise: more than 2,200 scientists in over 80 research units in Montpellier and Languedoc-Roussillon, including 300 scientists conducting research in 60 countries. Agropolis International is structured around a broad range of research themes corresponding to the overall scientific, technological and economic issues of development: Agronomy, cultivated plants and cropping systems Animal production and health Biodiversity and Aquatic ecosystems Biodiversity and Land ecosystems Economics, societies and sustainable development Environmental technologies Food: nutritional and health concerns Genetic resources and integrative plant biology Grapevine and Wine, regional specific supply chain Host-vector-parasite interactions and infectious diseases Modelling, spatial information, biostatistics Water: resources and management Agropolis International promotes the capitalization and enhancement of knowledge, personnel training and technology transfer. It is a hub for visitors and international exchanges, while promoting initiatives based on multilateral and collective expertise and contributing to the scientific and technological knowledge needed for preparing development policies. 2
3 Research skills of Montpellier and the Languedoc-Roussillon region in the field of green technologies A growing awareness of the need to preserve the environment has increasingly led to the desire to develop intervention techniques and methods aimed at reducing pollution or, more generally, environmental impact, thus generating new areas of activity. The scientific community gathered by Agropolis International has taken up the research issues raised by the development of these new approaches and new investigation fields. The purpose of this Dossier is to outline the areas of expertise it has been able to develop, both in the field of agricultural techniques as such and in water and waste recycling and recovery (beyond the pollution mitigation aspects), product enhancement in the form of new bio-based materials, and new forms of bioenergy. This research is not solely confined to the development of new technologies but has a broader scope, taking in as well product and process evaluation and eco-design, industrial or territorial ecology, and environmental monitoring. This Dossier also presents the joint efforts of the research and business communities, in particular through competitiveness clusters, to promote the development and dissemination of innovations to spur economic development. The topics presented in this issue are of particular concern to the nine research units or teams that have made environmental technologies an essential part of their work, comprising some 150 senior scientists and 100 doctoral students. Foreword for sustainable development Topics covered by the research teams and innovation partners for agriculture Bio-based products and materials Water and waste recycling and recovery Bioenergy Assessment methods: Life cycle analysis, eco-design, industrial and territorial ecology Environmental monitoring Innovation stakeholders mobilize around green technologies Training at Agropolis International 44 List of acronyms and abbreviations 46 Cover & chapters: from Irish_design Shutterstock The information contained in this dossier is valid as of 01/12/
4 Foreword for sustainable development D id you know? Ten years ago the term green technologies or environmental technologies was almost unknown. The concept was formalized in 2004 by the European Community in its Environmental Technologies Action Plan (ETAP) *, which defines environmental technologies as: that set of technologies that provide the same service as conventional technologies but have less impact on the environment (including renewable energy); end-of-pipe technologies: pollution and waste treatment; pollution measurement technologies. Another important point is that the concept of green technologies does not merely pertain to technological objects, but includes all processes, products and services that make for greater environmental efficiency. The formalization of that concept, and the European and national development plans that ensued, helped drive a minor revolution in the field of design/production and consumption, paving the way for hitherto neglected innovations and affording opportunities for growth. The result has been increasing integration of ecodesign methods into product design and development processes, not only through the search of technological approaches or raw materials whose use is not so heavy from the environmental standpoint, but also through system management optimization; which has now become possible thanks to information technology (smart grids). Another result has been the reclassification of much waste, which is now looked at as a source of raw materials from which valuable compounds (e.g., phosphates from sewage) or energy may be obtained. At the level of development (especially for industrial zones) or process creation (e.g. for treatment), the crux of this new vision is an attempt to re-use byproducts and waste as near at hand as possible in a circular economy approach: industrial ecology, or a way of applying the concept of environmental technology in a given territory. On the consumer side, people are becoming more aware of the environmental impact of the goods and services they use, and an actual market is emerging. Thus, to protect consumers from greenwashing (a marketing technique whereby products are given an artificial veneer of greenness ) and ensure that they can actually shop in an ecoinnovative way, it is essential for scientifically valid environmental assessment methods to be devised. The development of green technologies is a challenge that the Agropolis scientific community has striven to take up in its specific fields, namely agrobiological processes and land use management, relying on the support of the EcoTech-LR regional platform and the strength and vitality of the region s research efforts. Prof. Véronique Bellon-Maurel, Deputy Director of Strategy and Research at IRSTEA, Director of the EcoTech-LR regional platform * European Commission, Stimulating technologies for sustainable development: an environmental technologies action plan of the European Union. COM (2004) 38, 28 January
5 INRA-LBE Photobioreactors for controlled production of microalgae. 5
6 Topics covered by the research teams and innovation partners (November 2012) T he various research units and teams and innovation partners appearing in the text of this dossier are shown in the table below. 1. for agriculture 2. Bio-based products and materials 3. Water and waste recycling and recovery 4. Bioenergy 5. Assessment methods: Life cycle analysis, eco-design, industrial and territorial ecology 6. Environmental monitoring The Page column shows where the introductory text on the unit or partner appears. The red dot ( ) shows the topic in which the unit or partner primarily pursues its activities, while the black dots ( ) indicate topics they are also involved in. Units page UMR ITAP - Information/Technologies/Environmental Analysis/Agricultural Processes (Montpellier SupAgro/IRSTEA) Director: Tewfi k Sari, tewfi UMR IATE - Agro-polymer Engineering and Emerging Technologies (CIRAD/INRA/Montpellier SupAgro/UM2) Director: Hugo de Vries, IAM Team - Engineering and Macromolecular Architectures UMR ICGM - Institut Charles Gerhardt, Montpellier (ENSCM/CNRS/UM2/UM1) IAM Team Director: Jean-Jacques Robin, ICGM Director: François Fajula, UPR CMGD Materials Research Centre (EMA) Director: José-Marie Lopez Cuesta, / mines-ales.fr UMR IEM European Membrane Institute (ENSCM/CNRS/UM2) Director: Philippe Miele, UPR Recycling and Risk (CIRAD) Director: Jean-Marie Paillat, UR LBE Laboratory of Environmental Biotechnology (INRA) Director: Jean-Philippe Steyer, www4.montpellier.inra.fr/narbonne UR Biomass & Energy (CIRAD) Director: Rémy Marchal, UPR LGEI Laboratory for Industrial Environment Engineering and Natural and Industrial Risks (EMA) Director: Miguel Lopez-Ferber, ELSA cluster Environmental Lifecycle and Sustainability Assessment (IRSTEA/CIRAD/EMA/Montpellier SupAgro/INRA) Contact: Véronique Bellon-Maurel,
7 Standardized digestibility tests for various types of waste, to estimate the potential quantity of recoverable methane. INRA-LBE Innovation stakeholders page Institute of Excellence for Carbon-free Energy (IEED) Greenstars Contact: Jean-Philippe Steyer, www4.montpellier.inra.fr/narbonne/ EcoTech LR Platform Contact: Véronique Bellon-Maurel, DERBI Competitiveness cluster Development of Renewable Energy/Building/Industry President: André Joffre Director: Gilles Charier, WATER competitiveness cluster President: Michel Dutang Director General: Jean-Loïc Carré, / Qualiméditerranée competitiveness cluster President: Guillaume Duboin Director: Isabelle Guichard, Risks competitiveness cluster Territorial risk and vulnerability management President: Joël Chenet Director: Richard Biagioni, Trimatec competitiveness cluster President: Jérôme Blancher Contact: Laura Lecurieux-Belfond, BIOÉNERGIESUD Network Offi cer in charge: Aurélie Beauchart, / Transferts LR President: Christophe Carniel Director: Anne Lichtenberger, Green ntechnologies 7
8 for agriculture 8 Develop green technologies for sustainable agricultural production In order to design green technologies for more sustainable agro- and bioprocesses and for environmentrelated services, the Joint Research Unit (UMR) Information- Technologies-Environmental Analysis-Agricultural Processes (UMR ITAP, Montpellier SupAgro/ IRSTEA) develops scientific and technical baselines for: Characterization of agroecosystems through the development of optical sensors (mainly hyperspectral artificial vision and near-infrared spectroscopy). Because of the special properties of the environments being studied (optically scattering media, objects with identical spectral characteristics, presence of water), the research topics include the understanding of radiation-matter interaction and data processing methods (chemometrics, analysis of hyperspectral images). Modelling for agroenvironmental decision-making through the development of decision support systems to diagnose system condition or through the implementation of lower-impact precision farming approaches. Various methodologies are under review: fuzzy logic, discrete event systems, geostatistics. The chosen implementation field is winegrowing. The main team UMR ITAP Information/Technologies/Environmental Analysis/Agricultural Processes (Montpellier SupAgro/IRSTEA) 27 scientists Other team involved in this topic UPR Recycling and Risk (CIRAD) 13 scientists Reduction in pesticide pollution through a study of spraying techniques, from the nozzle to the transport of pesticides over an entire watershed or territory, making use of unique experimental means. As a reference centre for the assessment of pesticide application technologies, keen to reduce their impact on the environment and human health, it hosts a team from the Institut Français de la Vigne et du Vin (IFV) [French Vine and Wine Institute], with whom it is working closely under the ECOPHYTO 2018 plan. Eco-assessment and eco-design through the development of tools to evaluate the environmental and social impact of products, processes and industries based on life cycle assessment (LCA). The chosen areas of study are water and land use management. This UMR formed the kernel of the Environmental Lifecycle and Sustainability Assessment cluster (ELSA, cf. p. 32), France s largest group of LCA researchers. It is also part of LabEx Agro and the regional platform Environmental technologies for agro-bioprocesses (EcoTech-LR, cf. p. 43). It works in partnership with French private sector stakeholders such as Pellenc SA, Pellenc ST, Ondalys, Envilys, etc.) and scientific researchers (National Institute of Agricultural Research [INRA], Centre for International Cooperation in Agricultural Research [CIRAD], École des Mines d Alès [EMA], Montpellier Laboratory of Informatics, Robotics and Microelectronics [LIRMM], etc.). Abroad, it has collaborated, in particular, with the Instituto de Investigación y Tecnología Agroalimentaria and the Autonomous University of Barcelona (Spain), the international private group GEOSYS, the Universities of Turin and Florence (Italy), Talca (Chile), Sydney (Australia), the Instituto de Investigaciones Agropecuarias (Chile), Finnish Environment Institute (Finland), etc. The UMR s main scientific facilities include: a 200-m² optical laboratory: optical sensors, spectrometers (ultraviolet (UV)/visible/near-infrared), hyperspectral and multispectral vision test benches; a platform for the study of pesticide sprays and their impacts on the environment and health (1,600 m²): a large-scale experimental wind tunnel; an under-boom patternator; a laser particle sizer and velocity sensor; full metrological gear to evaluate sprayers. an LCA software package; an electronic and mechanical prototyping platform (300 m²). The sanitation system LCA answers the question What environmental costs for what discharge intensity? [ongoing endeavour of ONEMA (French National Agency for Water and Aquatic Environments) and IRSTEA]. Resource consumption Air emissions NH 3 NO X N 2 O CO 2... Waste, sludge, leachate Second discharge to soil, air, water Collection network N, P, ETM, CTO, DBO 5... WWTP Water discharges Performance level
9 Filtration and fertigation station. Subsoiler suitable for duct burial. Patrick Rosique (IRSTEA) & Jean-Marie Lopez (CIRAD) Subsurface drip irrigation a proven innovative solution for field crop irrigation In the face of more and more frequent water shortages and growing environmental degradation, irrigated agriculture must now avoid overuse of water resources as well as water and soil pollution while maintaining excellent performance levels. At the level of the agricultural plot, the subsurface drip irrigation (SDI) technique is a recent innovation adopted for field crops by a growing number of farmers subject to water restrictions. Water and dissolved nitrogen are supplied close to the roots by polyethylene tubing buried 35 to 40 cm deep and equipped with emitters spaced 15 to 50 cm apart that deliver flow rates from 0.5 to 3.0 l/h under a pressure of 0.5 to 1.5 bars. IRSTEA has for some years now been doing agronomic tests to measure the hydraulic and agronomic performance of SDI compared to gun irrigation. After four years operating the equipment, SDI s watering uniformity coefficient remains above 95%. When tested on maize crops, SDI had better agronomic performance than gun irrigation: depending on the gap between tubes (80, 120 or 160 cm), the productivity of irrigation water varies from 3.50 to 4.25 kg of grain produced per m3 of water delivered, as against only 2.70 to 3.20 in the gun irrigation model, or an average improvement of 18%; nitrogen productivity in 2011 (fertigation) was between 30 and 38 kg of grain produced per unit of nitrogen applied, as against only 19 to 23 kg in the case of spraying (+60%). On the economic front, even though some authors concede better performance is obtained, it is recommended, given its relatively high sunk costs (between 3,000 and 5,000/ha), that SDI be introduced only when crops are rotated, with particular attention to whether high-added-value crops (vegetables) are involved. Contact: Patrick Rosique, 9
10 for agriculture R. Cayrol Région Réunion ISARD project greening of agricultural production systems through waste recycling Organic waste products (OWPs) generated through human activity are constantly increasing. Farming produces them in great quantities (livestock, agro-industries). Wastewater production too increases owing to urban growth and denser urban populations. Wastewater or sludge from wastewater treatment is often spread on agricultural land on the outskirts of cities. These OWPs are sources of organic matter that may increase soil fertility and, as a corollary, allow sustainable agricultural production to be carried on. In studying how best to use them, a number of things need to be taken into account, viz. the many types of waste and the wide variation in where they are found and what they can be used for. Composted poultry litter. The ISARD project is developing a comprehensive approach to the integration of applied knowledge in this field. Where it breaks new ground is in considering the organic matter produced by agricultural and other activities. That consideration is at two organizational levels: the first level deals with the OWPs, the soils on which they are used and the crops grown; the processes studied are essentially the biogeochemical cycles; the second level looks at units producing, processing and using organic matter, as well as stakeholder groups; the processes studied are the transformations and flows of organic matter, regulations and costs. At both levels, many tools exist to ensure a timely response to the needs of integrated management. The project makes use of those tools, with the goal of improving them by taking into account the risk/benefit ambiguity and by defining helpful indicators. The project involves nine partners in four areas: the Versailles plain (France), Réunion Island, the Dakar metropolitan area (Senegal), and the Mahajanga region (Madagascar). Its attention to the situation in developing countries affords a more nuanced view of the composition of OWPs, treatment facilities, societal demands and existing regulatory frameworks. Contact: Hervé Saint Macary, Representation of recycling systems in ISARD. Industrial waste/om Animal feed, fertilizer, minerals Pre-processing Agricultural OM LEVEL 1 OBJECTS Urban waste Agricultural OM Gas discharge Infl ow LEVEL 2 - TERRITORY Material flows of value to agriculture Polluant fl ows Advice, guidance, decision support Understanding, diagnosis, indicators Runoff Soil interaction Absorption by plant 10 Leaching
11 Photo from MorgueFile A decision workflow to reduce fungicide treatments on grapevines A workflow is a model of a working process, generally taking the form of a software package or information system. The Mildium workflow was developed by INRA, UMR Vineyard Health and Agroecology (INRA, Bordeaux Sciences Agro) and the French National Research Institute of Science and Technology for Environment and Agriculture (IRSTEA, UMR ITAP). It sets out how to decide whether, and when, a fungicide against powdery mildew should be applied. The decision-making process was mapped using the Statecharts computer language. The decision is based on information collected for specific vegetative stages on the plot and on an expert assessment of local bioclimatic risk. Over a number of years, in various regions, the experiments done under the Mildium workflow have shown that the system is effective in reducing pesticide treatments at plot level (by 30 to 50% depending on the diseases and situations encountered). That result was obtained by comparing the treatments done and the health status of a plot managed under Mildium and those of a similar plot, nearby, that was managed in a conventional manner by the same establishment. As a modelling specialist, UMR ITAP was also involved in experiments with its partners on how best to benefit from feedback and guide theoretical choices with respect to formal representation. It is also working with Arvalis to develop workflows for fungicide protection in wheat. Specification Objectives The Mildium workflow provides plot-level decision support. Research is underway on how to manage an entire operation. The workflow process also involves knowledge consolidation. In providing a service that reduces the number of crop protection applications, the workflow acts as an environmental technology suited to a sustainable approach to agriculture. Contact: Olivier Naud, Strategic principles broken down into tactical phases based on epidemiology and expertise Automation (workflow) & variables The Mildium workflow reduces pesticide treatments on grapevines. Tactical and thresholds described in phases POD 11
12 Bio-based products and materials 12 Physical, physicochemical and biotechnological means of processing agromolecules, agro-polymers or complex matrices The goal of the Agro-polymer Engineering and Emerging Technologies UMR (UMR IATE, CIRAD/INRA/Montpellier SupAgro/ UM2) is to help increase knowledge of the functionalities of plant products and their constituents, to improve their performance in food and non-food uses. It conducts research on physical, physicochemical and biotechnological means of processing agro-molecules, agropolymers and complex matrices, in an effort to understand the impact of these changes, at different The main team IAM team Engineering and Macromolecular Architectures ICGM - Institut Charles Gerhardt, Montpellier UMR CNRS 5253 (ENSCM/CNRS/UM2/UM1) 60 scientists UMR IATE Agro-polymer Engineering and Emerging Technologies (CIRAD/INRA/Montpellier SupAgro/UM2) 49 scientists UPR CMGD Materials Research Centre (EMA) 40 scientists...continued on page 14 scales, on structures and target functionalities. Its research activities are organized into five complementary multidisciplinary and multi-scale areas: Fractioning of agroresources Structuring of agro-polymers under stress and powder reactivity Matter transfers and reactions in food/packaging systems Microbial biotechnology and lipid and agro-polymer Knowledge representation and reasoning to improve food quality and safety These research foci are concerned with green technologies in terms of a way of acquiring knowledge to design, develop and manage eco-efficient procedures for biomass deconstruction to produce polymers, useful molecules and synthons from which to regenerate biomaterials. The research is based on two platforms and several technical support centres: The plant fractioning platform * (low to intermediate moisture) focuses mainly on primary processing of cereals and lignocellulosic biomass and on forming materials from agropolymers. It operates in two stages: first, mechanical separation and sorting of raw plant materials (mills, grinders ), then forming of materials by reconstruction and assembly under pressure (kneading, rolling ). The LipPol-Green ** platform (an international partnership) offers scientific support and very highlevel instruments for studies at the interface between plant science and environmental chemistry, in the fields of lipid biotechnology, physical chemistry of polymers and the exploration and use of plants molecular diversity, to produce molecules, materials and fuels from biomass. UMR IATE is a participant in the 3BCAR Carnot Institute (Bioenergy, Biomaterials and Biomolecules from Renewable Carbon) and LabEx Agro and is also involved in many partnerships, both academic and industrial (Alland & Robert, Panzani, BASF, Michelin ), in particular with partners from the countries of the South: The European project ECOefficient BIOdegradable Composite Advanced Packaging ( ) seeks to supply the food industries with flexible, biodegradable packaging (funded by the 7 th Framework Programme for Technological Research and Development [FPTRD]. Since 2008, research activities on natural rubber in Southeast Asia have been carried on under the aegis of the platform Hevea Research Programme in Partnership. The METAGLYC 2 project (German fund to finance renewable resources, ) is developing new ways of obtaining glycerol derivatives by chemical catalysis and biocatalysis.
13 POMEWISO project solvent-free membrane preparation from biopolymers Porous polymeric membranes for use in water treatment are developed on an industrial scale from synthetic polymers dissolved in an organic solvent (acetone, DMF, NMP...). Porosity is generated by a phase inversion process, usually induced by immersion of the homogeneous polymer solution in a bath of non-solvent (water). Apart from the fact that the raw material is derived from a non-renewable land resource, large amounts of organic solvents are used, with the risk of generating environmental pollution and health problems. The goal of the POMEWISO project (an IEM/IRSTEA collaboration) is to develop a new porous membrane production process that relies on clean, green chemistry, (i) using polymers from natural rather than synthetic resources and (ii) substituting water (the solvent for water-soluble polymers) for traditional organic solvents. Hence, the scientific problem is to fine-tune the process of developing membranes from different water-soluble polymers (polyvinyl alcohol [PVA], cellulose ethers, chitosan) with a low critical solution temperature (LCST), thereby controlling their morphological and functional properties. Once the phase inversion is induced by increasing the temperature (TIPS-LCST procedure), crosslinking of the polymer chains will be necessary to strengthen the film thus formed. This crosslinking will preferably be done by irradiation or heat treatment to avoid the use of chemical crosslinkers. T LCST Diphasic Monophasic Spinodal region Spinodal curve Influence of temperature rise during the TIPS-LCST process. Binodal region Binodal curve A multi-scale analysis will be conducted to better understand the phenomena of phase separation, structure growth, and the final morphology of the membranes as well as their filtration properties. The experimentation will be done using light scattering methods, optical microscopy, near-infrared and confocal Raman spectroscopy, and dead-end filtration. It should be possible, using a modelling approach and solving the modified Cahn-Hilliard equation, to predict the evolution of structures over time until the final morphology is obtained. φ vol Contact: Denis Bouyer, The STOCKACTIF project of the French National Research Agency (ANR) (biomaterials & energy programme, ) is looking at active storage of biomass to facilitate industrial processing. The SPECTRE project (international France-Mexico Programme Blanc [non-thematic programme], ) focuses on the evaluation and control of industrial biotechnology procedures. The 3BCAR PEACE project (with the Environmental Biotechnology Laboratory [LBE], ) is studying the effect of cell wall composition and thermomechanical pre-treatment techniques on the efficiency of the conversion of model biomass into energy products. The project on Epoxidation of Polyphenols by a Chemo-enzymatic Approach is aimed at obtaining bio-based epoxy resins (with UMR Science For Oenology, [INRA, Montpellier SupAgro, UM1], Various projects supported by the LipPol-Green and Plant Product Processing platforms. * iate_plateforme_fractionnement_des_vegetaux_v3.pdf ** Monomers to polymers: integrated solutions for synthetic materials The Engineering and Macromolecular Architectures (IAM) team of the Institut Charles Gerhardt of Montpellier (ICGM), UMR CNRS 5253 (ENSCM/ CNRS/UM2/UM1) has since its inception been developing a chemistry based on the synthesis of controlled-architecture polymers, macromonomers, telechelic oligomers, graft or block copolymers, and telomers. In particular, the team has been studying particular applications of such telomers as reactive oligomers in photocrosslinkable compounds or as additives for coatings, surfactants or composite matrices, etc., all applications where low viscosities and controlled reactivities are sought. The IAM team, whose core endeavour is the application of organic chemistry to polymers, is recognized for its expertise in developing integrated technological solutions for materials synthesis, from monomers to polymers, in order to offer solutions for highperformance applications. For many years, too, it has been developing a chemistry based on simple and clean processes (emulsion polymerization, supercritical fluids ) and on sustainable development (biodegradable polymers, polymer recycling, optimum use of agricultural resources ). The team is also recognized for its expertise in macromolecular chemistry involving the heteroatoms Si, P and F. The bio-based polymers theme was begun more recently, based on laboratory skills in polycondensation, thiol-ene chemistry and chain polymerization. One of the objectives of the current work is to replace dangerous molecules with biobased ones in the development of polyurethanes, phenol-formaldehyde resins, epoxy resins and unsaturated polyesters. The scientific issues involved relate to the use of renewable resources through the development of a reduction chemistry process that will enable the use of oxygenated raw materials and the development of depolymerization techniques (natural polymers such as chitosan, lignin, etc., often have very high 13
14 GreenResins project new bio-based epoxy resins free of bisphenol A Diagram of the production of bio-based epoxy resins from tannin-derived catechin. Because of their versatility and ease of use, epoxy resins are very widely used. They include a great variety of materials with a wide range of physical properties. However, they are mostly derived from bisphenol A (BPA), a compound classified as CMR (carcinogenic, mutagenic and reprotoxic). The GreenResins project involves the use of natural, non-toxic aromatic and polyaromatic compounds derived from renewable resources as reagents for use in developing thermosetting epoxy resins as a BPA substitute. Bio-based products and materials The source of these natural phenolic compounds is tannins from forestry or viticulture by-products, so there is no competition with food crops. Among the phenolic compounds being studied by the IAM (ICGM) team, in collaboration with the UMR Science for Oenology (INRA, Montpellier SupAgro et UM1), is catechin, a molecule with four phenolic groups. Catechin is epoxidized with epichlorohydrin. The phenols in catechin s two aromatic rings display different levels of reactivity, leading to two products: one molecule with four epoxy groups and a cyclized by-product with two epoxy groups. The average functionality is 2.7 epoxy groups per molecule. The mixture is used unpurified to prepare epoxy resins with amine hardeners since both products obtained are functionalized and contribute to network development. Resins derived from functionalized natural compounds possess thermal and mechanical properties comparable to those of conventional fossil-fuel-derived resins such as the diglycidyl ether of BPA. The possibility of obtaining bio-based aromatic resins that are more rigid and perform better than aliphatic resins is what distinguishes this work, which won the 2010 Pollutec Award for innovative environmental techniques. Contacts: Sylvain Caillol, Bernard Boutevin, & Hélène Fulcrand, Comparative thermal and mechanical properties of resins prepared from the diglycidyl ether of BPA and from tannins. Sample T g ( C) T d5 ( C) T d30 ( C) Char 800 (%) Swelling (%) Soluble (%) Storage Modulus (Gpa) Glassy region Rubbery region DGEBA DGEBA 25 GEC tannins 50 DGEBA 50 GEC tannins molar masses, making it impossible to use them directly), a return to polycondensation rather than free radical polymerization to make the best use of biomass reactive functions (acid, alcohol ) and the development of reliable access Other teams working in this area UMR IEM European Membrane Institute (ENSCM/CNRS/UM2) 50 scientists UR LBE Laboratory of Environmental Biotechnology (INRA) 16 scientists paths to compensate for changes in biomass composition. Thus, new ways of accessing bio-based epoxy resins based on tannins from forestry or viticulture by-products have been developed. In addition, the IAM team has developed new reactive functional synthons from vegetable oils and fatty acids bearing amine, alcohol or acid functions that give access to new bio-based polymers (polyurethanes, polyesters ). Many industrial collaborations are underway, with national and international companies. In 2010, the team was awarded the Pollutec award Innovative Techniques for the Environment (cf. project GreenResins). Life cycle assessment of polymers and composites: integration of materials from recycling and renewable resource channels into the development of innovative materials The Materials Research Centre (Internal Research Unit [UPR], CMGD) is one of three internal laboratories of the École des Mines d Alès (EMA), which is a national public administration (EPA) reporting to the Ministry of Industry. Because it places great emphasis on relations with the economic sector, CMGD is part of the M.IN.E.S. Carnot Institute (Innovative Methods for Business and Society), which brings together all French Écoles des Mines
15 and their research association, ARMINES. The Centre is involved in various competitiveness clusters and maintains academic and industrial collaborations at the national and international level through European projects, projects funded by the Environment and Energy Management Agency (ADEME), ANR and FUI. CMGD is structured into two research departments, namely Advanced Polymer Materials (MPA) and Civil Engineering Materials and Structures (MSGC). Materials life cycle assessment is central to the concerns of both departments, for with the implementation of European directives to promote endof-life product recycling, advances are being made in the development of ever more efficient identification and sorting technologies, which may soon enable online identification of both plastics and their additives. Thus, CMGD researchers are supporting the development of, on the one hand, prototype sorting equipment, and on the other hand high-performance plastic alloys that can be made from high-purity materials reclaimed from sorting. Moreover, the growing global demand for energy, the need to find an alternative to fossil energy resources that are being depleted, and society s determination to reduce the environmental impacts of human activity and its carbon footprint are driving the partial or full integration of renewable resources (concept of bio-basing) into materials development. The compostability of materials is an added benefit now being worked on and which, provided collection channels are available, should allow for better end-of-life waste management. Thus, CMGD researchers are trying to remove many scientific and technological obstacles in order to turn these products to account in various application areas, such as packaging, agriculture, transport and building. CMGD covers many disciplines, including chemistry, physical chemistry, mechanics and process engineering. In addition to a platform for the processing of polymers and concrete materials, it has a platform for materials characterization (mechanical, thermal and thermomechanical tests under standard conditions, fire resistance tests, aging tests, scanning electron microscope observations in environmental mode, X-ray diffraction, chemical and physicochemical analysis ). M. Maugenet Innobat Materials and eco-construction Joinery strips of polyester/flax biocomposite. In the building sector, needs arise at two levels: first, to meet market expectations for greener products by paying attention to sustainable development objectives, and second, to comply with the Grenelle de l Environnement by making use of more energy-efficient materials to reduce buildings energy consumption, using renewable resources, recycling waste and reducing non-recyclable waste. Thus, CMGD has since 2010 been working with the IAM (ICGM) team on a project funded by ADEME and supported by the Montpellier-area INNOBAT company, which won a JEC Innovation Award in This project is designed to develop a new material for joinery profiles, inasmuch as none of the traditional materials now used (wood, polyvinyl chloride [PVC], aluminium and polyester/glass composite) can meet the upcoming 2012 and 2020 thermal regulations while achieving the required level of mechanical performance level and meeting the architectural criteria, all with a lower environmental impact. The new material is a pultruded composite with a thermosetting matrix derived in whole or in part from plant waste from the timber and wine industries and from continuous plant fibres. The project addresses many R&D issues: synthesis and formulation of thermosetting resins (epoxy and/ or unsaturated polyester) derived in whole or in part from plant waste; preparation of flax plant fibres together with batch analysis and homogenization and possibly surface treatment of fibres; adaptation of formulas (resin reactivity, fibre tensile strength) to the pultrusion procedure; benchmarking of mechanical and thermal performance, fire retardancy and in-service ageing (humidity, temperature, UV exposure). Prototypes are currently available and marketing is planned soon. Contacts: Anne Bergeret, & Michel Maugenet, For further information: 15
16 Bio-based products and materials Controlled lifetime biocomposites The first generations of bio-based plastics were mainly targeted for short-lived applications such as packaging. Today, the demand has changed. What industry needs now are bio-based plastics with functionality at least equivalent to those of the current petrochemical-based plastics as regards barrier effect and mechanical, chemical and thermal resistance over the material s life cycle. There is a broad consensus to that effect in the scientific community. Thus, CMGD has been at the forefront of these developments. Beginning with foamed starch packaging for undemanding usage conditions, it went on to develop films and solid or foamed materials based on polylactic acid (PLA), a polymer obtained by fermentation of corn starch, less sensitive to moisture than starch and with better mechanical properties. The COLIBIO project (COntrolled LIfetime BIOcomposites), funded by ANR and accredited by the Trimatec competitiveness cluster, aims to develop a biocomposite with very good mechanical and thermal properties, whose useful life can be controlled, to meet the requirements of the automobile industry. The idea was to reinforce a PLA-based matrix with glass fibres that would break down under normal composting conditions (temperature, ph, humidity); the scientific and technological obstacles were the ability to keep the biocomposite functioning with a high level of mechanical performance throughout its service life and to ensure end-of-life degradation. Suitable biodegradable glass-fibre formulations were thus developed and the durability of the PLA/glass biocomposites under biomimetic conditions during use and at end of life was studied. It emerged that there is a strong interdependence between the alkalinity of the glasses and their mechanical behaviour under conditions simulating accelerated service use (immersion in water at 65 C) and the rate of their mineralization in soil, which may be accompanied by soil acidification. Contact: Anne Bergeret, Stress (MPa) Resilience (kj/m²) biodegradable PLA/fibreglass biocomposites (various glass formulations) non-biodegradable PLA/fibreglass biocomposite Conservation of properties from baseline state (%) Degree of conservation of mechanical performance ( stress, elongation, resilience) of biodegradable and nonbiodegradable PLA/fibreglass biocomposites after ageing under conditions simulating accelerated service use (24 hours immersion in water at 65 C) Elongation (%) mg CO 2 / g C in the composite No soil acidificaton Time (days) 4.24 PLA matrix Heavy soil acidificaton Mineralization rates in soil simulating end of life of biodegradable PLA/fibreglass biocomposites under different levels of soil acidification. École des Mines d Alès CMGD 16 École des Mines d Albi, centre RAPSODEE Bioplastics-based nanostructured materials Scanning electron microscope view of a PHBV/clay bionanocomposite foam made by extrusion assisted by supercritical CO 2. In 2006, in order to be more responsive to calls for proposals and enhance its ability to perform contract research in partnership with industry, the M.IN.E.S. Carnot Institute established a NanoMines group, with some fifty researchers from the various French Écoles des Mines working on the nanostructures topic. The aim is to bring out synergies between research teams by combining multidisciplinary skills in such areas as the development of nanomaterials, their characterization, modelling and application testing. In this context, in 2011, CMGD and the RAPSODEE Centre of the École des Mines d Albi undertook a project to develop bionanocomposites made up of nanoparticles in a bioplastic matrix, to control and improve the matrix s properties. Production of these bionanocomposites by supercritical fluid extrusion (CO 2 ) enables nanoparticles to disperse throughout the matrix, forming a foam without the use of chemical agents, while at the same time making the material lighter and more insulating.
17 The BIORARE project Winner of the Investments for the Future national call for Biotechnologies and Bioresources The BIORARE project (bioelectrosynthesis to refine residual waste, IRSTEA/Chemical Engineering Laboratory French National Centre for Scientific Research/LBE-INRA/Suez- Environnement) focuses on how to use the concept of microbial electrosynthesis to biologically refine waste and effluents. This recent discovery could eventually enable the production of high-added-value molecules from the organic matter and energy in waste. CO 2 e - Effluent CO 2 e - e - e - Gas Organic molecules Bioelectrochemical systems technology would be used to channel the metabolic reactions of the bioprocess into the production of building-block molecules with high added value for use in green chemistry. The organic material is oxidized in a first compartment by complex biomass, which transfers electrons to an anode. The electrons then go to the cathode, where they are used in a biological reduction reaction. By regulating the potential at the cathode to a value derived from a theoretical calculation (Nernst Law), one can artificially create thermodynamic conditions that will allow only certain reactions to occur. Waste DCO Anode C + Cathode Electroactive microbes CO 2 CO 2 T. Bouchez Principle of the microbial bioelectrosynthesis system used in the BIORARE project. These microbial bioelectrosynthesis systems maintain a physical separation between a dirty compartment containing the organic material to be processed and a clean compartment where the desired molecules are synthesized, metabolic fluxes are channelled, and oxidation reactions at the cathode are selected by regulating the potential. Development of a detailed specification for the application of microbial electrosynthesis to the biorefining of organic waste requires the key components to be determined, together with the relevant specifications for a projected industrial development strategy. The scientific and technical basis of microbial electrosynthesis will be firmed up, then the relationship between the operating conditions and the molecules actually synthesized will be validated experimentally. Multidisciplinary approaches will be combined to better understand and identify the technological potential of these systems. Environmental assessment of strategies linking these systems to existing industrial installations will be carried out based on reference scenarios that will identify the environmentally sensitive components and provide guidance for technical and industrial choices. An analysis of economic, societal and regulatory factors will bring future industrial development strategies into better focus. A detailed specification for the implementation of microbial electrosynthesis systems for organic waste biorefining will be developed and related measures for the protection of intellectual property will be taken as necessary. Contact: Nicolas Bernet, The bioplastic matrix used in this project is a biodegradable polymer derived from microorganisms that belongs to the polyhydroxyalkanoate (PHA) family, specifically poly(3- hydroxybutyrate-co-3-hydroxyvalerate (PHBV). The matrix was reinforced with montmorillonite clay nanoparticles at a low uptake rate (less than 3% by mass). Incorporation of the clay significantly improved the matrix s mechanical and thermal properties and its fire resistance and helped control its biodegradation. The foams obtained have a porosity of up to 50%; the cell size homogeneity has yet to be improved through a study of the operating parameters of the process. Contacts: Nicolas Le-Moigne, & Martial Sauceau, For further information: Transmission electron microscope view of clay dispersal in a PHBV/clay bionanocomposite foam. École des Mines d Alès CMGD 17
18 Bio-based products and materials GreenCoat project new bio-based polyurethanes from vegetable oils Polyurethanes are among the best-selling polymers in the world, ranking 6th; world production is over 14 Mt. They are useful in many areas of everyday life, including thermal insulation and coatings. They are traditionally produced by reacting an isocyanate with a polyol oligomer. While the isocyanate is almost exclusively derived from petrochemical feedstocks, the polyol can be derived from renewable resources. However, most isocyanate compounds are highly toxic or even CMR (carcinogenic, mutagenic and reprotoxic) and are on the SIN list (Substitute It Now! REACH, Annex XVII). The initial aim of the GreenCoat project is to develop new bio-based polyols, derived from vegetable oil, with new properties. A subsequent goal is to develop isocyanate-free bio-based polyurethanes from glycerol. Thiol-ene (TEC) Vegetable oils 1. Transesterifi cation or amidifi cation 2. TEC Fatty acids and esters Transesterifi cation Glycerin Glycerin carbonate Bio-based polyols are synthesized from vegetable oil or from fatty acids or esters through thiol-ene coupling on the double bonds of the fatty chains. The thiol used has one or more alcohol functions. The addition reaction is carried out with neither solvent nor initiator, under UV; the yield is quantitative. This technology produces bio-based polyols with widely varying structure and functionality. The development of isocyanate-free bio-based polyurethanes relies on the cyclocarbonate ring-opening reaction mediated by primary amines. Thus, the IAM (ICGM) team has produced oligomers bearing dicyclocarbonate functions from glycerol carbonate. Reacting these oligomers with diamines produces isocyanate-free bio-based polyurethanes. In both cases, the bio-based polyurethanes obtained have properties similar to those of fossil-fuel-derived polyurethanes and can be used in coatings, binders, paints, etc. This project has received funding from ANR Matepro and is being conducted in collaboration with the Organic Polymers Chemistry Laboratory (Bordeaux) and the Résipoly and SEG companies. Contacts: Sylvain Caillol, Rémi Auvergne, & Bernard Boutevin, Diagram of bio-based polyurethane production from vegetable oil and derivatives. Synthesis by thiol-ene coupling of new bio-based polyols from vegetable oils. Glycerol Isocyanate-free bio-based polyurethane production. 18
19 Biodegradable packaging developed under the project. EcoBioCAP project Eco-efficient Biodegradable Composite Advanced Packaging Over the past ten years, many types of biodegradable food packaging have been developed, the main goal being to imitate petrochemical plastics; however, no real evaluation has been done of their environmental benefits, economic viability or potential impact on the quality and safety of packaged foods. These packaging systems quickly bogged down, especially in the food industry, as a result of a number of major controversies (diversion of food resources, overly complicated recycling/ recovery routes, for example). A more holistic, systemic approach is needed in developing such biodegradable packaging in order to restore the trust and consumers and users and to pique their interest. The European EcoBioCAP project aims to supply European Union food industries with modular biodegradable packaging tailored to the requirements of perishable foodstuffs, with direct benefits for the environment and for European consumers in terms of food quality and safety. This new generation of packaging will be based on the multi-scale development of composite structures all of whose constituent parts will be from food industry by-products. UM2/INRA Production techniques and all the properties of the materials developed in the course of the project will be optimized through demonstration activities with industrial partners before industrial use is begun. The EcoBioCAP technology will be made available to all industry players through development of a decision support tool. Finally, outreach activities will be undertaken, not just to inform the scientific community of the project results, but also to make sure consumers and end-users know the benefits of such biodegradable packaging and how to use it. The EcoBioCAP project has a budget of 4.2 million, financed by Europe (to the tune of 3 million over four years under the seventh Framework Programme for Research and Development. It brings together 16 partners from eight different countries, including six private companies. Contact: Nathalie Gontard, For further information: 19
20 Water and waste recycling and recovery 20 Seeking durable materials and membrane processes The European Membrane Institute (UMR IEM, ENSCM- CNRS-UM2), founded in 1998, is an internationally-recognized reference laboratory for membrane materials and processes. Its research objectives are in keeping with a multidisciplinary and multi-scale approach: the development and characterization of novel membrane materials; their implementation in membrane processes having applications in, for example, sewage treatment, gas separation, and biotechnology as it relates to food and health sciences. The main teams UMR IEM European Membrane Institute (ENSCM/CNRS/UM2) 50 scientists UPR Recycling and Risk (CIRAD) 13 scientists UR LBE Laboratory of Environmental Biotechnology (INRA) 16 scientifiques...continued on page 22 IEM comprises three research departments: design of membrane materials and multifunctional systems; polymer interfaces and physical chemistry; membrane process engineering. The Institute s green-technologyrelated activities are based on process intensification and have three main foci, with the general objectives of increasing process efficiency and moving towards sustainability (less consumption of energy and solvents, waste minimization, optimum resource use): development of multifunctional reactors combining different functions within the same technology; development of new processes, new materials for use in traditional processes, or new operating conditions; use of modelling to gain a better understanding of reaction and transfer mechanisms, which can then be used to improve the efficiency of existing processes. The work the Institute carries out under this approach, through the activities of its Membrane Process Engineering department, relates mainly to: the use of bio-based products and materials: the development of membranes from bio-polymers; the development of biodegradable membranes; fractionation for by-product recovery; water and waste recycling and recovery: effluent concentration and production of pure and ultra-pure water; degradation of pollutants in wastewater using membranes combined with photocatalysed biological or physico-chemical reactions; sorption; a combination of membranes and enzymatic reactions. Regional collaborations have been put in hand, in particular with the ELSA cluster (cf. p. 32), to integrate LCA and eco-design aspects into research projects dealing with the development of new processes for the solvent-free production of membrane materials (ANR POMEWISO project, cf. p. 13) or the implementation of intensive processes combining membranes and sorption on functionalized polymers (ANR Copoterm Copolymers for Water Treatment and Metal Recovery ).