Photocatalytic Production and Use of Conjugated Linoleic Acid-Rich Soy Oil A Proctor & VP Jain Department of Food Science, Univeristy of Arkansas, Fayetteville, AR, USA. Conjugated linoleic acid (CLA) (cis/trans; trans/cis)) is a product of rumen fermentation that has been shown to have anti-carcinogenic, anti-atherosclerotic and anti-mutagenic properties. However, it is found naturally only in dairy and bovine meat products which are also a source of undesirable saturated dietary fat. Alternative means of obtaining CLA by chemical synthesis and fermentation have been explored but involve extensive purification steps and use of reagents with variable yields and CLA quality. We have developed a 'greener' technology to produce high-CLA soy oil(~20%)by u.v. photo-isomerization of oil alpha linoleic acid to CLA at 22 C, using only an iodine catalyst. Although the CLA cis/trans and trans/cis isomer content was much greater than found in dairy and beef products, the majority of the CLA isomers produced were trans/trans, which also have valuable nutraceutical properties. The cis/trans and trans/cis isomers are the initial products of photisomerization but rapidly form the more thermodynamically stable trans/trans isomers. There was little indication of lipid oxidation during processing that is probably due to the conversion of alpha linoleic acid which is highly prone to oxidation. The iodine can be removed from the soy oil by conventional adsorption processing without CLA loss. The oil was used in frying operations make high-CLA potato crisps (chips), whose oil content was similar to that of the fresh oil. Future will address reducing the processing time, identification of possible minor iodo-compounds and study of the apparent improved oxidative stability of the novel high CLA/ low alpha linoleic soy oil. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Polymeric and Low Molecular Weight Hydrophobic Chemicals Produced by Microorganisms from Renewables A Steinbuchel Institut fur Molekulare Mikrobiologie und Biotechnologie, Munster, Germany. Microorganisms are capable of synthesizing a wide range of hydrophobic substances which often serve as reserve compounds for carbon and energy and are accumulated as inclusion bodies in the cells. Most bacteria are able to accumulate lipophilic storage compounds as inclusion bodies in the cytoplasm. Whereas members of most genera synthesize hydrophobic polymers belonging to poly(hydroxyalkanoic acids) (PHA), accumulation of triacylglycerols (TAGs) and wax esters (WE) occurs in some Gram-negative bacteria like Acinetobacter sp. and in most actinomycetes like Rhodococcus opacus, Streptomyces coelicolor or Mycobacterium tuberculosis. The key enzymes of TAGs and WE synthesis are promiscuous wax ester synthases/acyl-CoA:diacylglycerol acyltransferases (WS/DGAT), whereas PHAs are synthesized by unspecific PHA synthases. Since WS/DGAT is a very unspecific enzyme, which transfers the acyl-moiety of various acyl-CoA thioesters to many different alcohols and other hydroxylated compounds and even to thiols, a wide range of different lipids may be synthesized by these enzymes in vivo in engineered bacteria. Similarily, PHA synthases are capable of polymerizing a wide range of different hydroxyfatty acids and even mercaptofatty acis yielding polyoxoesters or polythioesters, respectively. Such bacteria are therefore useful catalysts for conversion of renewable resources provided by agriculture or forestry as well as of residual compounds derived from the latter into polymers and lipids for technical applications in various areas. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Biobased Resins and Plastics J van Haveren, CG Boeriu & A van der Bent Sustainable Chemistry & Technology, Wageningen University and Research, The Netherlands. The importance of renewable resources to current and particularly future society is rapidly gaining recognition. E.g., in 2005, the Dutch government complied with the advice of the 'Board for Renewable Resources' (translated from Dutch) to strive for a major replacement of fossil oil and gas by renewable resources. For chemicals and chemical materials, the aim is to realize a replacement of 25% by 2030. In the current situation, only about 5% of all products generated by the chemical industry are biobased. Obviously, closing this gap will require major R&D efforts at both the fundamental and applied level. During the last decades, most R&D on biobased materials was focused on creating materials that are readily biodegradable. The new biobased economy drivers (depletion of cheap fossil oil and gas, global warming, etc) now emphasize the importance of durable high performance biobased materials. At the Sustainable Chemistry & Technology Group of Wageningen University and Research, we focus primarily on the development of chemical building blocks, chemicals and materials that are derived from carbohydrates, fatty acids and proteins. Hereto, organic & polymer chemistry, biopolymer science & technology and biocatalysis are used. In the presentation, general concepts for both the chemical and enzymatical production of fine chemicals and polymers will be covered, as well as specific examples such as engineering plastic resins, resins for decorative paints and powder coatings, and polymer matrices for the targeted delivery of drugs. These examples illustrate the growing potential of renewable resources as feedstock for chemical products. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Commercialisation of Biofuel Industry in Africa: a Review B Amigun [1], R Sigamoney [2] & H von Blottnitz [1] [1] Environmental Process System Engineering Research Unit, Department of Chemical Engineering, University of Cape Town, Rondebosch, South Africa; [2] Research Group I 'Future Energy and Mobility Structures', Wuppertal Institute for Climate Environment Energy, Postfach 100 480, Wuppertal, Germany. Energy is a key factor in industrial development and in providing vital services that increase prosperity and improve the quality of life. However, its production, use, and byproducts have resulted in major pressures on the environment, both from a resource use (depletion) and pollution point of view. The decoupling of energy use from development represents a major challenge of sustainable development. The long-term aim is for development and prosperity to continue through gains in energy efficiency rather than increased consumption and a transition towards the environmentally friendly use of renewable resources. The production of modern, clean biomass-derived fuel in the African continent is the only long-term environmentally sustainable solutions to future energy demand. A plethora of barriers, however continue to slow its development and commercialization despite the availability of biomass resources, increase in the price of conventional fuel and their rising demand compared to the dwindling convertible currency earning and rising evidence of climate change. Amongst these is the lack of a good understanding and application of key concepts of cost estimation-a key to successful project which impacts both the project profitability and influences the technical solutions. Existing methods have limited applicability and on many occasions disappointing accuracy because of the inappropriate nature of the estimating techniques. The problems of inaccessibility, pollution and unaffordability of energy which is regarded as an integral part of our existence can be alleviated through the development and commercialization of alternative energy sources. Understanding the economics of biofuel industry is crucial in realising eventual commercialisation. This presentation provides knowledge-based review for expanding (commercialization) of biomass-derived fuel (biofuel) through improved understanding of its economics. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Epoxidation of alpha-Pinene Mediated by Cobalt(III) Catalysts R Chakrabarty [1], BK Das [1] & JH Clark [2] [1] Department of Chemistry, Gauhati University, Guwahati, India; [2] Green Chemistry Centre of Excellence, Department of Chemistry, University of York, York, UK Use of renewable natural products as feedstocks in the production of chemicals is considered as the first step in greening the life cycle of chemical products. Terpenes, which are widely distributed in nature, are of particular importance from the fact that their oxidation products find use as the starting materials for fragrance, flavour and therapeutic agents. The bicyclic terpenes - alpha- and beta-pinene - occur in wood turpentine which can be obtained from the resinous sap of pine, tea, cedar and other trees and also from orange peel oil and many fragrances. Thus, oxyfunctionalisation of alpha-pinene is an important reaction. Herein we describe the use of a cubane-like Co(III) complex (B) as an autoxidation catalyst favouring the formation of the epoxidised product under environmentally benign conditions. The cluster complex B with R = CH3, Co4(O)4(O2CCH3)4(py)4 has been examined as a catalyst for the autoxidation of alpha-pinene under homogeneous as well as heterogeneous conditions. Homogeneous air oxidation of alpha-pinene under atmospheric pressure results in high selectivity for alpha-pinene oxide in preference over allylic oxidation products. The selectivity for alpha-pinene oxide at the highest conversion of 81% (TON = 2,520) observed at 100 deg C is 68%. A heterogeneous catalyst prepared by immobilizing the above complex on chemically modified hexagonal mesoporous silica (HMS-CH2CH2CO2H) also favours the epoxidation pathway in aplha-pinene autoxidation giving alpha-pinene oxide, verbenol and verbenone as the main products. At 100 deg C, 72% selectivity towards aplha-pinene oxide is observed at 81.5% substrate conversion in a liquid phase reaction.

Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Choosing Future Platform Molecules - a User Perspective RJ Crawford Unilever R&D, Port Sunlight, UK. As well as contributing to a more sustainable industrial base the expansion of renewable chemistry and the realisation of the bio-refinery concept represents a great opportunity for both industry and consumers. Platform molecules are the link between feedstock and end-product so it is important that we have a good understanding of both end-use requirements as well as production technology. Successful Platform Molecules will service many end-user requirements and it follows that a collaborative approach will most efficiently select the best ones. Existing chemical supply and use has developed together over many years to become an efficient and inter-dependent set of industries. To speed the development of new chemical process technology we should look therefore not just to the replacement of existing chemical functions (where price competition will be most severe) but also to the exploitation of the properties of Platform Molecules and their derivatives to offer new and advantageous functions. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

The Role of Non-Food Crops as a Bioresource Brian Edmunds Director of Springdale Renewable Energy, Springdale Group, UK Springdale Group is a group of businesses entirely dedicated to the detailed and thorough exploitation of non-food crops as a bioresource. The activities of the group can be broadly categorised as plant breeding, seed multiplication, commercial field production, field mechanisation, crop processing, packaging, logistics, marketing, research and development. These areas of operation will be further detailed in activities specific to the three main types of product the group promotes these being industrial oils (including nutraceuticals and pharamaceuticals) fibres and energy. Springdale's involvement for example in the use of plant oils for lubricants and fuels, plant fibres for construction and composites and biomass for energy production will be described. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Valuing Ecosystem Services: Biofuels C Perrings Global Institute of Sustainability, Arizona State University, Arizona, USA. Recent research on biofuels suggests that they are not cost-competitive with fossil fuels at current prices. This raises the question of what factors should be taken into account in deciding whether it is nevertheless socially optimal to support biofuels production. Evaluating alternative ways of delivering energy in terms of the direct and indirect (environmental) costs of production provides one approach. It gives us a measure of the social cost effectiveness of the alternatives. A second approach considers the efficiency of biofuels production in terms of social opportunity cost of the ecosystem resources involved. The Millennium Ecosystem Assessment has drawn attention to many ecosystem services that have hitherto been ignored in the analysis of agricultural systems. Taking these into account significantly raises the hurdle on biofuels. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

New Cereal Based Bio-Refinery: New Initiatives C Rupp-Dahlem Roquette Freres, Lestrem, France. Vegetal-based chemistry is definitively one of the most promising approaches to achieve sustainable development for the future. Vegetal-based chemistry is the use of renewable raw materials from vegetal agriculture, such as corn, to produce for example bio-ethanol for energy, building blocks for the commodities, specialties and fine chemicals markets and biopolymers for plastics. This vegetal-based chemistry is supported by industrial (or white) biotechnology, using new biological systems for the production of such chemical entities. An example of this vegetal-based chemistry is the current corn bio-refinery, which implements biological and chemical reaction steps to produce a wide range of products including starch, glucose, sorbitol and some sorbitol derivatives like isosorbide. This new concept of biorefinery is financially supported in France by the Industrial Innovation Agency (AII) whose objectives are to select significant, innovative programmes (minimum 50 million euros per programme). One of the first programmes selected by this Agency is the BioHub(trademark)programme. The target of the BioHub(trademark)programme is to develop cereal based chemical products to the point where they are sustainable substitutes for fossil origin products. The BioHub(trademark) programme has federated a consortium of European Industrial Companies and Scientists. Some of these projects covered in the BioHub(trademark) programme are described in more detail as follows : Isosorbide as a substitute for diols for polyesters; Dimethyl Isosorbide as a green solvant. The BioHub(trademark)initiative is an excellent example of European collaboration between new biotech. start-up, medium and large enterprises and scientists. Such collaboration is necessary to enable the chemical industry to become more sustainable. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Renewables: Time for Priority to Develop Building Blocks for the Chemical Industry CV Stevens Department of Organic Chemistry, Faculty of Bioscience Engineering, Ghent University, Gent, Belgium. In the last decade, renewable resources are getting more attention in view of their positive effects on the sustainability of processes, the reduction of the greenhouse gas emissions and the opportunities to develop biofuels. Especially, the research and the production of bio-ethanol and biodiesel is the major topic when talking about renewables. However, the production of biomaterials and bio-based building blocks, which will be the major challenge in the long run, is getting much less attention. Therefore, it is essential to invest more attention to study the production of bio-materials and building blocks for the future in a multidisciplinary way. Major chemical companies are aware of this challenge and started to make structural changes and to set up divisions to look at the potential of renewable resources, however the small and medium sized enterprises will face difficulties to make the switch for their products, especially in view of the REACH regulation. Integral valorization and vertical integration in the production of industrial crops will have to be further developed in order to build up biorefineries in agricultural areas with a good accessibility. Further, two examples of fundamental research topics related to renewable resources will be discussed. Inulin, the polydisperse reserve polysaccharide from chicory, has been modified by carbamoylation and esterification in organic solvents to develop a variety of modified inulin derivatives from which the interfacial and emulsion stabilizing properties were determined. The medium and long chain acylated/carbamoylated inulin derivatives, with low degrees of substitution (DS), showed a good to very good reduction of the interfacial tension which makes these biopolymers interesting in the field of biodegradable emulsifying agents. Inutec SP1 has been developed in collaboration with industry as a new and high performing emulsifying agent for the cosmetic industry, as well as for the latex industry. Undecenoic acid derived from castor oil has been dimerised to a polyfunctional building block of which the reactivity and usefulness is now being evaluated. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Business Sustainability: 21st Century Leadership Mr Dan Gross Wal-Mart's Alternative Fuels Sustainability Value Network Use Dan Gross, Operations Manager, will discuss Wal-Mart's strategy on meeting the challenges of conducting business in the 21st century. He will talk about the company's business sustainability strategy and its efforts regarding renewable resources, all the while saving money for its customers. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Issues Arising in Use of Biomass Derived Materials for Energy and Industry Dr David Turley Agricultural and Rural Strategy Team, Central Science Laboratory, York, UK. The returning interest in use of crop-derived materials as feedstocks for energy production, industrial materials and chemistry, as well as in traditional uses in pharmacology and health and well being, is leading to an expansion in demand for non-food crops. In some cases these may be existing arable crops used to produce oil, starch and sugar, in other cases they may be native crops developed for specialist uses (e.g. for fibre), or in other cases non-native species introduced to fulfil specific needs (eg biomass for energy). In each case there will be differing impact on the farming environment and a trade off in terms of impacts due to differences in crop management. There are increasing concerns about the impacts that such rapid change could have on the environment. The rapid development of liquid biofiel markets is leading to a rapid expansion in oil crops, both in the EU and in tropical oil production - with concerns over the intensity of arable cropping and loss of uncultivated land, and in loss of important habitats to palm oil plantation. This paper will review the drivers currently influencing development of non-food crops and will assess the impacts on land availability and the issues of increasing competition on land for food and non-food uses. The issues and concerns arising from such changes will be highlighted but also the potential gains and contributions that non-food crops can make to issues such as reducing greenhouse gas emissions and socio-economic impacts such as retaining land in agricultural production and increasing opportunities for rural employment. These issues will be illustrated by current case studies and examples in different market sectors, along with discussion of how use of biorenewables from plants might be managed to maintain consumer and market confidence. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

New Catalytic Materials from Renewable Resources DJ Macquarrie Department of Chemistry, Green Chemistry Centre of Excellence, University of York, York, UK. The development of clean chemical technologies is essential if we are to effect efficient conversion of raw materials to the vast array of products required by modern society. A major area of importance in this respect is the use of catalytic processes, in particular heterogeneous catalysis, allowing for simpler recovery of catalyst and product. It is important, but often overlooked, that the catalyst itself must be derived from renewable and sustainable sources. This presentation give an overview of work at York designed to produce novel materials from biological sources which function as highly effective catalysts for the conversion of a range of molecules into important product types. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Simulation for Product Selection in Developing Potential Biorefineries DS Pertiwi & PN Sharratt Chemical Engineering and Analytical Science, University of Manchester, Manchester, United Kingdom. Biorefineries have been increasingly investigated since about a decade ago. They are envisioned as part of the infrastructure to replace oil refineries as oil runs out. There have been some innovative findings to employ renewables as alternative raw materials, but more demonstration projects are needed to show the process feasibility. There are several problem levels that should be considered in selecting potential biorefineries, e.g raw material selection, process and product selections, and eventually equipment selection. The whole integrated process should be projected to be the best biorefinery in economic and technical aspects and must be environmentally friendly. A simplified process simulation for biorefinery assessment has been proposed in this study using solver in the Microsoft Excel software. A case study has been used as an example. This study emphasises the product selection, taking into account the economic aspects (based on the operational costs of known process technology). The environmental aspect was quantified by calculating the amount of remaining feed and potential waste. A number of scenarios are analysed to identify the relativity between product slate, product value, and the implication of technologies deployed in the biorefinery. The outcome of the assessment is found to be sensitive to product value and process yield/efficiency. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Green Chemistry Approaches to Biodiesel and Propanediol GA Kraus & VSY Lin Chemistry, Iowa State University, Ames, IA. The idea of a biorefinery is modeled after the oil refinery wherein petroleum is converted into gasoline, oil, and monomers such as ethylene and propylene. They produce high volume chemicals (such as gasoline and diesel), plus a number of low volume, high value materials. Unlike petroleum refineries, corn grain and soy biorefineries are in their early stages of development. For biorefineries to be successful on a long-term basis, they must produce: 1) high volume fuels such as ethanol or biodiesel; and, 2) a portfolio of high value products and chemicals. In the soy processing plant, the soy protein is separated from the oil. Some soy processors then convert the soybean oil into biodiesel by treating the oil with methanol and a catalyst. We have developed catalysts for this conversion that are heterogeneous, recyclable, and significantly lower the cost of manufacturing biodiesel. The by-product of this reaction is glycerol, a hygroscopic triol. Glycerol must be converted into higher-value chemicals that can replace petrochemicals. One such chemical could be 1,3-propanediol (PDO), which is used in textiles and fabrics, such as DuPont's Sorona. Another is acrolein, a three-carbon monomer for plastics and polyurethanes. A third is propylene glycol which is used as an antifreeze and an airplane de-icer. Center for Catalysis researchers have evaluated an ionic hydrogenation reaction to convert glycerol into 1,3-propanediol (PDO). A porous silicon material derived from waste silicon chips is an effective reagent to convert glycerol into 1,3-propanediol. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Renewable Energies: The Future of Energy? Transition to Post-Fossil-Energies Gerhard Isenberg The Environmental Academy, (Die Umwelt Akademie), Munich, Germany. Increasing energy demand will also in the next decades mainly be covered by fossil energies. Limited resources esp. of hydro-carbons will require solutions to close the expected gap between increasing demand and available resources. These requirements will be supported by fossil-energy-influenced augmenting of green-house-gas-emissions. Besides energy saving and most efficient use of energy the challenge will be the development and market introduction of renewable energies 'just in time'. Fossil based energy-supply will under long-term-aspects not be sustainable. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Bioenergy H Shapouri Department of Agriculture, Office of Energy Policy and New Uses, Washington, USA. Ethanol is the most widely produced biofuel. Since 2004, biofuels production took off across the globe because of the high world prices of crude oil signaling a new trend. Energy Information Administration (EIA) projects that the high prices of crude oil to continue during the 2006-2030 along with price instability an important feature of the oil market. Responding to such an outlook, countries are planning to reduce their oil import dependency. Currently more than 50 countries produce biofuels but the longer the high oil price persists, more countries are expected to enter the production market. Those countries with large agricultural resources will be the prime player in expanding production. For most farmers in these countries diverting the supply to a new demand outlet means an increase in price. The key commodity players for the production of ethanol and/or biodiesel are corn and soybean oil in the United States, sugar and soybean oil in Brazil, rapeseed oil in Europe, and palm oil in Malaysia. Another growing market for biobased products is in industrial use. Currently, feedstock prices are competing with crude oil products, creating new opportunities for biobased products. Feedstock can be used for the production of polymers, chemicals, solvents, adhesives, lubricants, paints etc. With the multiplicity of demand, the future of biofuel plants is expected to become more complex. These plants will convert starch, oil, and biomass materials to chemical building blocks such as hydrogen, methanol, and lactic and other organic acids. To produce the chemical building blocks, biomass materials are converted to sugar, such as glucose, fructose, xylose, arabinose, lactose, or sucrose, or they are converted to synthesis gas such as hydrogen and methane. Building blocks could be processed to secondary chemicals and refined products, which could be used in transportation, textiles, environment, communications, housing, recreation, and health and hygiene. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Chemistry and Sustainable Energy Dr Jeff Hardy Royal Society of Chemistry. Factors such as high oil and gas prices, fears over security of supply and a need to cut carbon emissions have resulted in energy sitting at the top of political agenda's worldwide. Is it possible in modern society to satisfy an ever-growing demand for energy whilst actively reducing anthropogenic carbon emissions? What role will the chemical sciences play in delivering this scenario? The Royal Society of Chemistry has played an active role in the recent energy review in the UK and continues play a proactive role in the continuing energy debate. This presentation will examine present and future energy technologies through the eyes of a chemist and will seek to demonstrate that the chemical sciences underpin almost all energy technology options. In particular the presentation will examine nuclear power, carbon capture and storage technologies, gas and coal to liquid technology, renewable power, biomass, transportation and the basis of the hydrogen economy. Is there a technological silver bullet that will meet energy demands and address climate change? Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Oil Seed Engineering to Reduce Petroleum Dependence J Grushcow Linnaeus Plant Sciences Inc. Current trends driving demand for bio-products include concerns for the environment, GHG reduction and the cost and availability of petroleum. This presentation explores how new the tools of molecular biology can deliver value added feed stocks for industrial purposes that can substitute for a variety of petroleum products. Canada is a world leader in agriculture and in particular in the area of oil seed production with an average of over 10 million acres under production each year. Unfortunately, prices for commodity seed oils have been trending steadily down for the last 20 years. These new oilseed products promise to deliver significant value added at the farm gate while at the same time providing products that lessen the impact on our environment. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

European Policy and Biofuel J Lovett [1], M Poudyal [1], B Datta [2], G Ceddia [3], C De Lucia [3] & R Luque [4] [1] Centre for Ecology, Law and Policy, Departments of Environment, Social Policy and Politics, University of York, York, UK; [2] Department of Economics, University of York, York, UK; [3] Environment Department, University of York, York, UK; [4] Green Chemistry Centre of Excellence, Department of Chemistry, University of York, York, UK. There is now a general scientific consensus that observed trends in global warming are caused by anthropogenic emissions of greenhouse gases (GHG). Initial precautionary concern about the impacts of GHG led to the development in 1992 of the United Nations Framework Convention on Climate Change which in turn resulted in the 1997 Kyoto Protocol as a means by which the problem could be tackled. As scientific certainty grows there is a stronger political will to face the realities of climate change. In 2002 the European Union ratified the Kyoto Protocol and in a speech in 2004 the British Prime Minster, Tony Blair, said that the challenge of global warming is so far-reaching in its impact and irreversible in its destructive power, that it alters radically human existence. In the same speech, the PM emphasised the potential for scientific innovation as a means of countering GHG emissions. Biodiesel is one such innovation and in recognition of its potential the European Union passed a directive setting targets for its use in 2003. Neither these targets nor the Kyoto targets have been met. Moreover, increasing concern has been raised over issues such as the effect on biodiversity of planting extensive areas of biodiesel feedstock, particularly in developing countries. Further policy complications arise from political instability in countries with major oil reserves and the rise of China and India as newly industrialising nations. Nonetheless, the reality of global warming, finite oil resources and rising oil prices mean that renewable sources of energy will have an important role to play with benefits for new markets, employment, less reliance on raw material imports and reduction of pollution. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Biotechnology and our Material Future Dr John Pierce Director of DuPont CR&D, Wilmington, USA. The use of biotechnology for the production of chemicals and materials of industrial value is beginning to emerge as a major economic force. Driven by continuing improvements in the efficiency of agricultural production, which provides the necessary raw materials, and the exploding knowledge base of DNA structure and biotechnological tools, the biological production of very large volumes of important chemicals and materials from renewable resources is becoming a reality. These materials are finding use in energy, transportation, clothing, housing, in short, in all the major industries that utilize chemicals and materials. Despite the impressive advances, we are just beginning to learn how to incorporate biological principles into truly multidisciplinary approaches with engineering, chemistry, physics, and material sciences-disciplines with long, successful histories of innovation. As we do so, we will improve our capacity to utilize renewable resources and renewable concepts in the production of materials, and will take a major step toward ensuring a sustainable future. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Acetic-Fatty Anhydrides to Increase Wood Stability J Peydecastaing & C Vaca_Garcia LCAi, Ensiacet, Toulouse, France. Dissymmetric acetic-fatty anhydrides synthesized from fatty acids and acetic anhydride, are very reactive molecules towards cellulose and wood. By this way, both acetyl and acyl groups are easily grafted on the natural biopolymers of the wood cell wall. They ensure covalent bonding of a plurality of aliphatic chains on said materials. Their high reactivity is due to the dissymmetry of the molecule made of a short acetic chain and a long aliphatic chain. The amphiphilic character of the molecule improves their efficiency to penetrate and react with wood components. After reaction wood shows waterproofing and dimensional stability. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

The Chemistry and/or Economics of Biomass Conversion JP Lange Shell Global Solutions, Amsterdam, The Netherlands. Governments across the world are stimulating the valorisation of local biomass to secure the energy supply, reduce the CO2 emissions and support the rural economy. A 1st generation of fuels and chemicals are presently produced from high-value sugars and oils. Meanwhile, a 2nd generation, based on cheaper and more abundant lignocellulosic feedstock, is being developed. The present paper could review (1) the typical chemistries and processes required for converting lignocellulose and/or (2) the manufacturing economics of biomass conversion. As for the chemistry of lignocellulose conversion, we will show the need to 'deoxygenate' the biomass to produce biofuels with good energy density and fuel compatibility. We will then review the main conversion routes by discussing the basic chemistry involved and presenting one emerging process for illustration. These routes include

• the pyrolysis to char, bio-crude or gas, illustrated by BtG's process for wood pyrolysis,

• the gasification to syngas and its subsequent conversion to alkanes or methanol, illustrated by BtL process developed jointly by CHOREN and Shell,

• the hydrolysis to sugars and their fermentation or chemical derivatives (e.g. ethanol, biogas, glycols and levulinic acid), illustrated by Iogen's process for lignocellulosic ethanol.

The economics of the biomass conversion processes discussed above could be discussed to illustrate why the production costs of biofuels typically amount to $60-120/barrel of oil equivalent. Influential economic factors include

• the price and conversion efficiency of the biomass, which determine the overall feed cost,

• the energy efficiency and scale of the process, which affects the cost of the plant, and

• the value of the product, which increase in the order of: bio-crude < transportation fuels < power < chemicals.

Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Biorefinery, the Bridge Between Agriculture and Chemistry J Sanders Department of Valorization of Plant Production Chains, Wageningen University and Research Centre, Wageningen, The Netherlands. Economic factors, such as costs increases of oil, connected to the depletion of mineral resources, and environmental considerations, such as the negative impact of CO2 emissions, has led to interest in the use of renewable resources as feedstocks for transportation fuels, energy (heat and electricity) and chemical products. When used in combination with environmentally sound production and processing techniques, the use of biomass can be seen as a sustainable alternative to conventional feedstocks. In the Netherlands a Governmental Committee on Renewable Resources has designed a plan how to substitute 30% of the Dutch fossil raw materials by biomass in the year 2030. Obviously a lot of the biomass will have to come from abroad, but strategies to optimize the use of the biomass that is already used every year might limit the additional area to about the size of the Netherlands. Other European countries having less import of biomass at the moment, but more agricultural area available, might solver their biomass availability in other ways. Production of chemicals might take advantage of the biomass structure in a much better way than the production of fuels or electricity from biomass can do. The production of chemicals from biomass saves more fossil energy than producing just energy from biomass! This is reflected by sound economic advantages as well in raw material cost as in investment costs. To develop technologically sustainable routes, the whole chain of biomass production, i.e. from cultivation and harvest, its (pre)-treatment and conversion to products should be considered. Biorefinery opens the way towards the production of bulk chemicals and thereby obtaining the highest value from biomass by knowledge intensive technologies that can be patented. Several examples will be shown amongst others the fractionation of grass, sugarbeet, Cassava. Some amino acids are very suitable starting materials for highly functionalised petrochemicals. Economical production routes of chemicals from biomass require large-scale substitution of bulk chemicals and connection to current approaches and facilities (process integration) of the petrochemical industries to convert crude oil into chemical building blocks. Protein will be an abundant 'waste' product from the boost in production of transportation fuels. Ethanol from wheat and corn and biodiesel from rape and palm will supply an additional amount of protein around 100 million tonnes/year if these biofuels will substitute 10% of the fuel demand. Genetic modification of plants will increase the potential of biomass to chemicals because of increase of the concentrations of the actually present biochemicals that can serve as precursors for bulk chemicals. Also it will be addressed that small scale (pre) processing of the biomass can give advantages over large scale processing because of less transportation costs but also because of the opportunity to use process-integrations that can not be used on large scale. These integrations will yield high efficiencies of energy utilization but can be improved on social or organisational levels. The biorefinery of biomass will offer new economic opportunities for the Agriculture and the Chemical industry by the production of a world of chemicals, transportation fuels and energy. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Fuel Pellets as an Energy Resource M Arshadi Unit of Biomass Technology & Chemistry, Swedish University of Agricultural Sciences, Umea, Sweden. A wood pellets a small hard piece of bio-energy. Wood pellets are an energy rich alternative to oil and other fossil fuels. The raw material is sawdust from mostly pine and spruce. It is possible to produce fuel pellets in small scale, medium scale and large-scale facilities. Since the raw material for wood pellets production are used also in paper mill to produce paper and also will be used in large scale ethanol production from cellulose material in the near future, it is a urgent needs of new alternative to sawdust for pellets production. There are several other new raw materials which can be used in fuel pellets production such as willow, bark, cotton, olive seeds, straw, reed canary grass, peat and etc. In a wood pellets production process the raw material is dried to about 5-15 % moisture content and then ground into a fine powder. The powder then pressed through cylindrical holes in a pellets matrix (dies) to make short sticks which called pellets. The pellets are now in optimal form for extended storage without any lose of quality and transport compare to sawdust which have a moisture content of 45-55 % and needs lots of places to store it and also will be changed by microbial and chemical activities during storage. The pellets then will be delivered in bulk by train and boat and also in large or small sacks to consumer. Pellets then will be burned in a pellets furnace to produce heat in small-scale and large-scale facilities. Ash content from pellets burning is less than 0.5 %. Today more than one million tons of wood pellets are produced in Sweden per year. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Right Honourable Michael Meacher, MP House of Commons, London, UK The huge potential for renewables to fill the looming energy gap is greatly underestimated. As the world fast approached peak oil in 5-10 years time, renewable sources of energy, at this stage particularly windpower, have more than enough capacity to meet the entire electricity generation requirement of the three main continental blocs - the US, the EU and China. There is an urgent need to tackle the barriers hindering the development of renewables, particularly the lobbying power of the big vested interests. Much more can and should be done to provide a more favourable fiscal climate, especially by phasing out the inbuilt subsidies for fossil fuels. More R&D is also needed to counter the problem of intermittency. In particular, Government support should be strongly focused on development of decentralised energy systems, especially microgeneration plant for individual households. Biomass also has enormous potential. The first-generation comprises various grain and vegetable crops. Harvested for their sugar, starch or oil content, sugar cane and palm oil currently produce the most litres of fuel per hectare. By contrast the next-generation of biofuel feedstock comprises cellulose-rich organic material, which is harvested for its total biomass. It includes not only woody crops and tall perennial grasses, but also the organic portion of municipal solid waste. But key problems remain. In the most optimistic scenarios, bioenergy could provide for more than twice current global energy demand, without competing with food production, forest protection programmes, and biodiversity. In the least favourable scenarios however, bioenergy could supply only a fraction of current energy use by 2050. Also if biofuels are produced with heavy inputs of fossil energy, they have the potential to generate as much or more greenhouse gas emissions as petroleum fuels do. Ultimately, net energy per hectare, after deducting energy input, will be the most important measure from a resource perspective. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Agresidue and Industrial Fiber Crops as Papermaking Fibers M Lewis, W McKean & M Wetzel Paper Science and Engineering Department, University of Washington Seattle, WA USA. The opportunities for utilization of agresidue or industrial crops are numerous. The fibers from many of these opportunities still need to be used for papermaking. Wheat straw is a viable agresidue, which can be used in papermaking. The recovery process in pulping of wheat straw has been an issue due to silica content. A method of atmospherically pulping has been found to yield high quality fibers and eliminating the need for a recovery cycle and still generating a series of hemicellulose and lignin to feed forward into a biorefinery system. Most industrial fiber crops have not shown the papermaking characteristics that wood has. Arundo donax however is a high biomass producer, which has been run successfully in traditional pulp mills. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Tailoring Ionic Liquids for Biocatalysis and Bioprocesses NC Bruce CNAP, Department of Biology, University of York, York, UK. Ionic liquids hold significant promise as tuneable media for bioprocesses, due to the enormous number of structural solvent permutations that can be envisaged. We have developed an integrated approach to the selection of ionic liquids for enzyme-catalysed reactions, embracing both fundamental and practical considerations, with the aim of developing a 'rule book' for the design of optimized solvents for individual classes of enzyme. Functionalized alkanolammonium cations provide a versatile template for the development of biocompatible ionic liquids. These materials may be prepared at very low cost and high purity from readily available bulk precursors, in an entirely waste-free process. They retain the 'traditional' advantages of ionic liquids, being non-volatile, non-flammable and exceptionally powerful solvents, whilst offering the additional benefits of reduced viscosity, low toxicity and complete biodegradability. Information about the properties of these new ionic liquids and potential applications for biocatalysis and bioprocessing will be presented. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Industrial Biocatalysts for the bio-based economy Biorefinery development & Biocatalysis Dr Pauline Teunissen Genencor International BV Genencor has been interested in the concept of biorefineries since the mid 1980's, particularly with the possibility of processing biomass enzymatically. Biorefineries can potentially use multiple feedstocks to produce multiple products. The ability to use multiple feedstocks is taking advantage of supply/demand of feedstocks. This presentation will focus on two types of biorefineries for the fuel ethanol industry: glucose production from starch feedstocks and the production of fermentable sugars from cellulosic wastes. Technologies, opportunities and challenges will be discussed. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Green Extraction and Reactions in Supercritical CO2. R Marriott Botanix Ltd. The application of supercritical and liquid CO2 to carry out selective extraction of a wide range of molecules and groups of molecules is well established for some products but is less well known for many others. As this is now a mature technology a review of current industrial applications and potential new applications will be given focussing on those areas where conventional solvent extraction has been completely replaced and new applications where the use of extraction with CO2 could bring technical and environmental benefits. Supercritical CO2 has also been adopted as a reaction medium and some industrial processes have already been established. However one of the ultimate applications of supercritical and liquid CO2 is catalysis of reactions using biocatalysts either in the form of whole cells or isolated enzymes. A number of these applications will be presented and the future potential and barriers to the use of this technology discussed. Finally the use of a combination of selective extraction and biocatalytic reactions to create a unique biorefinery will be explored. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

The Generation of Novel Biomaterial Based Stationary Phases & Their Application in Chromatography RJ White & JH Clark Green Chemistry Centre of Excellence, Department of Chemistry, University of York, UK. The majority of chromatographic systems exploit silica based stationary phases, affording little scope for recycling and unappreciable biodegradability. By comparison starch is one of the most renewable / biodegradable resources available. At present it is highly under utilised in terms of typical chemical applications, with its main use being in the food, paper and adhesives sectors1. Chromatography relies upon the interactions of compounds dissolved in a flowing mobile phase with a stationary material or phase. There remains the need for new stationary phase materials having different and potentially improved separating characteristics when compared to the silica equivalent, with a surface polarity between that of silica and reverse phase silica. There is also the added driver to develop materials that present new exciting, enhanced separation profiles as a result of a low micropore to mesopore ratio, which are based on renewable starting materials and that present a decreased environmental burden after use. Expanded and chemically modified renewable starches and other carbohydrate-based materials potentially fulfill the criteria described above. Presenting a chemically active surface open to modification, these carbohydrate-based materials will be used in typical chromatographic applications and manipulated to form novel monolith columns, which in them self present a number of advantages2. The poster aims to demonstrate the preparation, modification and utility of such novel stationary phases in chromatography. References: [1] (a)'Economics of Starch Production in the UK', G. Entwistle et al., Industrial Crops & Products, 1998, 7, 175 (b) 'Starch, and Modified Starches as Support Materials and Catalysts', PhD Thesis, J. J. E. Hardy, University of York, 2001 [2] 'Comparison of the efficiency of microparticulate and monolithic capillary columns', S. Eeltink et al., J. Sep. Sci., 2004, 27, 1431 Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Platform Chemical Production from Low Cost Sustainable Raw Materials R Luque [1], JH Clark [1], TJ Farmer [1], DJ Macquarrie [1], C Du [2], CSK Lin [2], R Wang [2] & C Webb [2] [1] Chemistry Department, Green Chemistry Centre of Excellence, The University of York, York, UK; [2] Satake Centre for Grain Process Engineering, School of Chemical Engineering and Analytical Science, The University of Manchester, Manchester, UK. Depletion of petroleum and escalating environmental concerns create a need for novel sustainable routes for the production of commodity and specialty products with similar or advanced properties as compared to petrochemically derived one. Nowadays, renewable agricultural carbohydrates and exploitation of biological systems emerge as the main stream towards greener chemical production. For this reason, the biorefinery concept fits perfectly and it is proposed as an alternative to the petroleum-based industry. Indeed, the establishment of sustainable processing will be dependent on the development of integrated processes that converts renewable raw materials to value-added products. Development of pilot processing concept requires a multidisciplinary approach which involves cereal processing, chemical engineering and green chemistry. Objective of our research focuses on the development of low environmental impact synthetic methodologies for production of value-added succinic acid derivatives. Succinic acid is recovered from a complex multi-step processing technology that involves three stages of bioprocess, namely upstream processing, bioreaction and downstream processing. Selection of succinic acid as a highly promising platform molecule can be strengthened by recent reports from the US Department of Energy1,2. For the green chemical transformation of succinic acid into value-added derivatives, we intend to work within strict criteria using heterogeneous catalysis (where catalysts are required), benign reaction media, minimal use of auxiliaries and minimal energy requirements (with application of microwave irradiation). 1 Paster, M., Pellegrino, J. and Carole, T.M., 2003, Industrial Bioproducts: Today and Tomorrow, Report Number Columbia, Maryland). 2 Petersen, G. and Werpy, T., 2004, Top Value Added Chemicals From Biomass, Report Number USA). Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Characterisation of Gel Properties of Hemicellulose Derived from Timber SF Curling [1], CAS Hill [1] & P Fowler [2] [1] School of Agricultural and Forestry Science, University of Wales Bangor, United Kingdom; [2] Biocomposites Centre, Bangor, Wales, United Kingdom. Timber can be used as a sustainable source for process chemicals, silvichemicals and as a source of chemical feedstocks. Research should be directed towards materials with exploitable properties and high intrinsic value in the market place, a role that undegraded hemicelluloses may fulfill. Mechanical refining followed by mild alkaline extraction has been shown to be effective, at a laboratory scale, of extracting a hemicellulose gel from sitka spruce. To enable exploitation of the hemicellulose, various forms of the gel have been characterised and are detailed. Possible uses are also discussed. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Creating New Energy Platforms for Reliance Bio-Refinery SK Shrivastava, S Kilambi, PK Sarode, S Japtiwale & S Bhowmik Reliance Industries Limited, Navi Mumbai, India. Energy consumption has increased exponentially over the last 2 decades as the world economy has grown and more countries have become industrialized. Crude oil, a non-renewable resource, has been the major source to meet the increased energy demand so far. The limited crude oil supply will be exhausted in the near future if oil consumption continues to increase at its current rate. As the national economies are dependant on oil, the consequences of inadequate oil availability could be severe. Therefore, there is a great global interest in exploring alternative renewable & sustainable energy sources such as Biofuels, Solar, Wind, Geothermal etc. Biofuels are derived from following sources: Bio-Ethanol from fermentable carbohydrates (e.g. sugar crops, fodder beet, fruits, grains, cassava, sweet potato/sorghum etc). Bio-Diesel from various edible and non-edible oils (Palm, rapeseed, coconut, soya, jatropha etc) Bio-Ethanol from Cellulosic materials (corn stover, wheat/rice straws, bagasse, vegetable biomass etc) Presently Bio-Ethanol is manufactured globally via either grain route or sugar route, which is a part of human food chain. Some third world countries are still facing problems regarding sourcing of food for the people. Hence Reliance is planning to set up Bio-Refinery which would use the agro-energy synergy and convergence to generate India's second Green & Black (Food + Energy) revolution. The focus will be to bring in an era of scientific, corporate organized farming in India which will result in 2 to 3 times enhanced yield of grains, sugars and also cellulosic biomass. Grains and sugars will be dedicated for human consumption while part of the biomass will be used for animal feed and majority as the source of biofuels such as ethanol, butanol, MTHF, Hydrogen etc. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Industrial and Energetic Use of Biomass in Europe and Germany Dr Steffen Daebeler Vice-Managing Director, Fachagentur Nachwachsende Rohstoffe e.V. (FNR), Gülzow, Germany. The total area of the EU-25 is 397.3 million ha, from which 98.4 million ha (25%) are arable land and 148 million ha (37%) are forest. Germany has a total area of 35.7 million ha, from which 11.8 million (33%) ha are arable land and 10.5 million ha (29%) are forest. The cultivation of renewable raw materials for bioproducts and bioenergy in Germany has significantly increased: from 291.000 ha in 1993, to 510.000 in 1998, to 1,4 million ha in 2005. The share of the agricultural area used for non-food crops in Germany is far more than in the EU. Thus, the share of non-food cropland in 1998 was in the EU-15 1.5% whereas in Germany a share of 4.4% was reached. In 2002 roughly 56 million m3 domestic wood were used in Germany, whereas about three third are used for wood and wood-derived products and one third are used as bioenergy. Currently, about 17 million tons of petrochemical and 2 million tons of renewable raw materials are used in the German chemical industry, i.e. roughly 10% of the raw materials are RRM. Bioenergy is an imported area for the use of biomass. About 286 PJ/a (2004) energy are currently bioenergy in Germany. The R&D and market launch funding regarding to renewable resources is coordinated at the federal level in Germany by the Agency for Renewable Resources on behalf of the Federal Ministry of Consumer Protection, Food and Agriculture (BMVEL). The main task of the FNR is the technical and administrative R&D project supervision. Furthermore, the FNR organises symposiums and participates in fairs in order to promote the use of RRM. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Bioresources for Human Well-Being: Promises and Challenges R Uma Shaanker [1] & KN Ganeshaiah [2] [1] Department of Crop Physiology, University of Agricultural Sciences, Bangalore, India; [2] Department of Genetics and Plant Breeding, University of Agricultural Sciences, Bangalore, India. In the recent past, following the convention on biological diversity, biological resources have come to be regarded as a precious but untapped capital of any country. Consequently, the last few years have witnessed an unprecedented interest in cataloguing, and conserving the valuable biodiversity of a country. The recent emphasis on use of bioresources for biorefineries, ranging from bioenergy to biomaterials has only further heightened these interests and concerns. But the successful use of bioresources, especially from the perspectives of mega-diverse countries such as India, Brazil etc lies in knowing what bioresources exist, and where. Equally important is also to characterise and understand, the potential that bioresources hold for a range of goods and services for human well being. All these are however very daunting, and need novel approaches to deal with. In India, for instance, efforts are on to develop an exhaustive digital library of bioresources that can provide spatially explicit distribution maps of each one of the plant and animal resources. The digital inventory can not only guide the targeted exploration but also in the sustainable use of the bioresources. The challenge of using bioresources requires the development of algorithms that can successfully prospect for a given biomaterial or for a functional goal. Newer predictive tools that hasten bioprospecting could greatly encourage the use of bioresources. In my lecture I shall dwell on the promises and challenges that bioresources hold for mining biologically important compounds. I shall especially draw on some of the recent studies at our laboratory that have addressed the documentation and utilization of bioresources. Finally, I shall present an overall strategy that addresses the utilization and conservation of bioresources with specific reference to India. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Novel Carbonaceous and Inorganic Catalysts for Proton Transfer Reactions V Strelko [1], J Clark [2], S Tennison [3] & V Budarin [2] [1] Institute of Sorption and Problems of Endoecology, Kiev, Ukraine; [2] Green Chemistry Centre of Excellence, University of York, UK; [3] MAST Carbon, UK. It is well known that oxidized carbons contain the surface functional groups of carboxyl and phenol types with mobile proton. Having applied the potentiometric to determine the acidity of surface groups in carboxylic cationites and oxidized carbons of various types we have shown that the acidity of such groups in carbons, produced from fruit shells far exceeds (pK~2) the acidity of carboxylic cationites (pK~2.5). It is likely due to the fact that pi-electrons of oxygen atoms, forming the surface groups in carbon, are very much delocated by the pi-conjugated system of the graphite-like planes. It reduced the effective negative charge on oxygen and, as a result, the mobility of proton increases and, therefore, -OH and -COOH groups become more acidic. It is worth to be noted that in the case of synthetic oxidized carbons, which possess much more perfect (almost without defects) structure of pi-conjugation in the system of graphitic planes, the acidity of surface group even more (pK~1) as far as in this case the delocalisation of electrons (pi-electrons of oxygen) is mostly expressed. To understand the general principles of catalysis by oxidized carbons in reactions of etherification we studied in details kinetics and mechanism of synthesis of butyl acetate in gaseous phase in the wide range of temperatures (150-450 oC) using the H+-modifications of oxidized carbons, as well as reaction of hydrolysis for some ethers and lipids. In the presentation the data about new 'sol-gel' method for synthesis of spherically granulated porous titanium and zirconium oxides as well prepared on their base by sulfatation new catalysts of proton transfer with controlled porosity and surface chemistry are introduced. It is also presented results, which demonstrate the prospective application of these materials in reaction of fine organic synthesis (pharmaceutical) and re-etherification of vegetable oils (biodiesel). Renewable Resource & Biorefineries conference, York, 6-8th September 2006

Starch glucans: Molecular and Supermolecular Characteristics in Aqueous Systems W Praznik [1], R Loeppert [1] & A Huber [2] [1] Department of Chemistry, BOKU - University of Natural Resources & Applied Life Science Vienna, Vienna, Austria; [2] KFUG - Karl-Franzens Univ. Graz, IfC - Inst. f. Chem., Graz, Austria. Starch glucans in aqueous media tend to form supermolecular structures which hardly may be distinguished from constituting individual polymer molecules. However, these aggregates are not covalently bound but dynamically H-bond fixed and any time the result of varying kind and magnitude of applied stress to the aqueous glucan system. Hence, typically observed structures rather are due to interaction phenomena than to individual molecule mass and geometry. As modern absolute analytical approaches, in particular light scattering techniques, are dominated by minor contents of supermolecular components obtained results primarily reflect present aggregates and additionally come up with high fluctuations. An approach which is independent on supermolecular structures – quantitative labeling of the unique terminal hemiacetal groups on each glucan molecule combined with determination of mass and molar glucan concentrations - provides information on de facto molecular dimensions of individual starch glucans. Combination of SEC-separation with detection of refractive index (mass), fluorescence (labeled hemiacetals), scattering intensity (apparent molar mass of aggregates) and viscosity (excluded volume) provides distributions of molecular and supermolecular starch glucan characteristics, finally. Results from different starch glucans such as non-branched alpha(1,4)-glucan (amylose synthesized by potato phosphorylase), short chain branched glucan (alpha-amylase hydrolized waxy maize starch) and a mix of non/long chain branched and short chain branched glucans (native potato starch) will be presented and discussed. In particular, the influence of different solvent system on obtained apparent molar mass distribution will be illustrated. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

MEMORE - Metabolic Modelling of E. coli for the Production of Chemicals from Renewable Resources W Soetaert [1], P Vanrolleghem [2], R Cunin [3], JJ Heijnen [4], K Rumbold [1] & E Vandamme [1] [1] Laboratory of Industrial Microbiology and Biocatalysis, Ghent University, Ghent, Belgium; [2] Department of Applied Mathematics, Biometrics and Process Control, Ghent University, Ghent, Belgium; [3] Department of Microbiology, Free University of Brussels, Brussels, Belgium; [4] Department of Biotechnology, Delft University of Technology, Delft, The Netherlands. Metabolic engineering is a key technology for industrial biotechnology, which has its industrial and technological basis in the carbohydrate processing industry, fermentation industry and chemical industry. The MEMORE project aims to provide the tools and know-how to significantly speed up and improve metabolic engineering in E. coli. It aims to develop a dynamic mathematical model of the central metabolism, in which all major metabolic fluxes are described and can be used for simulation. Kinetic data is collected from dedicated chemostat fermentations and substrate pulse experiments. This allows to analyse the dynamic behaviour of the cellular metabolism by analysis of its intracellular metabolites. The determination of intracellular metabolites is performed by LC-MS/MS analysis. The data obtained by this means is used for calibration and parameter estimation of the dynamic model. E. coli is the preferred micro-organism for metabolic studies as its central metabolism (glycolysis, citrate cycle, pentose phosphate cycle) is very well characterised. The construction of a dynamic metabolic model that has the ability to accurately predict cellular metabolism under different fermentation conditions would be extremely valuable in many areas of industry. If one can predict the optimal fermentation conditions and required genetic make-up of a micro-organism for production of a particular industrially important product, this will allow for rapid and cost-effective development of these micro-organisms. After having developed the methodology and the metabolic model of the central metabolism of E. coli, this will be put to the test by designing an E. coli strain that overproduces succinate. In this process, succinate is produced by fermentation from renewable resources, plants that have fixed CO2 during their growth. Moreover, the succinate fermentation itself is a CO2-fixing technology, turning CO2 into succinate. The production of succinate from glucose thus has a significant impact on the greenhouse effect, a core issue for sustainable development. Renewable Resource & Biorefineries conference, York, 6-8th September 2006

POSTER ABSTRACTS Platform Molecules and Green Chemistry P1 Utilisation of Glycerol from Biodiesel feed-stocks: Microwave-assisted Chlorodehydroxylation to give a crucial intermediate in Epichlorohydrin manufacture MC Reid, JH Clark, DJ Macquarrie, R Luque & SW Breeden Green Chemistry Centre of Excellence, The University of York, York, UK. Despite typically being associated with dirty pollution creating processes, chlorinations may ironically prove to be useful in developing new low-energy and low-waste green chemical methodology. More specifically chlorodehydroxylations, where a hydroxyl group is replaced by a chlorine atom in an organic substrate, could allow polyhydroxylated platform molecules (typically byproducts of the biodiesel and related biorefinery processes) to be reused therefore giving them added value. Here we describe our recent endeavors to integrate enhancedmicrowave activation effects and catalysis on reaction of glycerol with aqueous HCl in an effort to yield an intermediate necesary in epichlorohydrin synthesis. This intermediate is itself currently used in epoxy resin and other predominately petrochemically based manufacturing products/processes of crucial economic importance. So far, we have not found any reports in the literature regarding the use of microwave activation effects in conjunction with new grafted heterogeneous catalysts in this reaction, both of which will contribute to speeding up the desired reaction allowing faster reaction times together with greater energy and atom-efficiency. Another green feature of this work is reaction performance in a solventless environment, resulting in further reducing waste. Additionally use of heuristic green chemistry problem solving methods through enabling tools such as metrics and informatics will be discussed through application of our work to glycerol and other platform molecules such as 3-hydroxypropionic acid and lactic acid. P5 Adding value to wheat straw through integrated exploitation of high-value wax products H Li [1], FEI Deswarte [1], JH Clark [1] & JJE Hardy [2] [1] Green Chemistry Centre, Department of Chemistry, University of York, York, UK; [2] Royal Society of Chemistry, London, UK. Wheat (Triticum aestivum) occupies the largest land area of all arable crops in the United Kingdom. However, with a harvest index approximating to 50%, a considerable proportion of the dry matter produced (straw) is currently of little commercial use in many parts of the UK. Estimates suggest that four to five million tonnes per annum of wheat straw are effectively treated as waste in the United Kingdom. To remain competitive, especially if free trade continues worldwide, there is a need to add value to this straw. Recent research undertaken at the Green Chemistry Centre at the University of York, has demonstrated that a selective and complete extraction of wheat straw waxes can be achieved by benign supercritical carbon dioxide. In addition, isolation of high value fractions including polycosanols, sterols (both of which show significant industrial potential as cholesterol lowering nutraceuticals), odd-numbered long chain alkanes (typically acting as insect semiochemicals) and waxes with different physical properties, can be extracted by tuning the extraction

conditions. As part of a successful industrial collaboration with Botanix Ltd (an extraction company), the Clean Technology centre has scaled up the extraction to 75 Kg of straw which extracted sufficient quantities of materials for product testing and further green chemical modifications. This low environmental impact technology would represent an initial process step in a Biorefinery supplied with low value agro-residues. 1 Deswarte, F.E.I., Clark, J.H., Hardy, J.J.E. and Rose, P., the fractionation of valuable wax products from wheat straw using CO2, Green Chem., 8 (2006) 39-4 2 Clark, J.H., Deswarte, F.E.I. and Hardy J.J.E., International patent application P112649WO, 2006. P6 Development of novel bioreactors for synthesis/hydrolysis of optically pure bioactive peptides A Bacheva [1] & DJ Macquarrie [2] [1] Department of Chemistry, MV Lomonosov Moscow State University, Moscow, Russia; [2] Green Chemistry Centre of Excellence, Department of Chemistry, University of York, York, UK. The development of synthetic procedures which require mild processing conditions and simple isolation of products is a major goal in the development of the chemistry of renewable resources. We are interested in developing continuous reactors for the synthesis of short peptides using enzymes such as subtilisin, which is capable of peptide synthesis or hydrolysis, depending on the conditions. This requires the ability to form enzyme-containing films or particles which can be coated / packed into a continuous reactor, through which the reactant solution can be flowed. Our approach is based on the use of chitosan as an enzyme support, and the formation of chitosan-subtilisin composites. Chitosan is an ideal support material for this work, as it is renewable, cheap (derived from a waste product from fishing and food production) and forms films, beads and fibres easily, although from acidic solution. In order to form active composite materials, we have developed a non-acidic route to making films containing enzyme, which allows the enzyme to survive the film / bead forming step without loss of activity. Initial catalytic results indicate that the composite materials can show excellent activity when used in conventional reactors. We have found that the activity is strongly dependent on the methodology applied to crosslink the composites and therefore impart mechanical stability. This aspect of the project is currently underway along with studies aimed at fixing the catalysts to continuous reactors.

P7 In search of green solvents for aromatic industry: the case of hydrofluoro ethers A Gonzalvez, C Raynaud & T Talou Agro-industrial chemistry lab, INPT-ENSIACET, Toulouse, France. Due to the future application of the european directive REACH, the aromatic industry must search for safe and environmentally friendly organic solvents to replace the widely used hexan or its recent substitute cyclohexan. In the same time, research laboratories in flavors and fragrances have to replace dichloromethane, as it is classified as CMR. According to the Green Chemistry concept, supercritical carbon dioxide appears to be the genuine green solvent but its use requires specifically

designed and expensive pilot plants. At the same time, the cosmetics industry has begun to use hydrofluoro ethers mainlydue to their safety and because they are not classified as VOC according to US regulation. In the present paper, the extractive potentials of two hydrofluoro ethers, methoxynonafluorobutane and ethoxynonafluorobutane were compared to those of hexan and cyclohexan for the obtention of resinoids from various medieval aromatic plants (aka: forgotten plants). Two plants, Helichrysum italicum and Galium odoratum, were particularly investigated as they are used respectively as alimentary condiment in roman cuisine and aromatic base of the Luxemburg national drink (Maitrank). Extractions were performed by maceration for 1, 4 and 8 hours of dry plants (flowers or leaves) at 25 degC. Before analysis, absolutes were obtained by extraction with ethanol of resinoids followed by a cold filtration in order to remove fats, waxes and dyes. Complementary hydrodistillations were performed on the same plants in order to obtain the corresponding essential oils. All aromatic extracts obtained were analyzed by GC-MS-Olfactometry in order to identify their key flavor compounds and sensorially evaluated by a senior flavorist. The first results showed that both hydrofluorothers gave similar extraction yields as hexan, a solvent recovery by distillation up to 80%, and aromatic extracts rich in top notes, particularly searched by flavorists when hexan and cyclohexan extracted mainly heart and back notes. P8 Novel catalysts based on renewable resources - starch and chitosan-based catalysts for the synthesis of fine chemicals DJ Macquarrie [1], JJE Hardy [1], AJ Deveaux [1], K Milkowski [1], JH Clark [1], S Doi [1], S Hubert [1], R Luque [1], M Bandini [2] & A Bacheva [3] [1] Green Chemistry Centre of Excellence, Department of Chemistry, University of York, York, UK; [2] Dipartimento di Chimica 'G. Ciamician', Università di Bologna, Bologna, Italy; [3] Department of Chemistry, M V Lomonosov Moscow State University, Moscow, Russia. Polymer-supported catalysts have long been successfully applied in synthetic chemistry.The ease of separation and reuse is a major advantage in clean synthesis. However, petrochemically derived polymers, which make up the vast majority of this class of supports, have problems of sustainability and biodegradability. We have worked on both starch and chitosan as renewable, biodegradable support materials for catalysts, and this presentation will outline our work here. Expanded starch can be functionalised with acid and basic sites, leading to very active catalysts which can be recovered and reused. Chitosan can be functionalised to give supported transition metal based catalysts, wich have proved to be active in a series of reactions. In many cases activity is as good or better than existing systems, although significant differences in behaviour can sometimes be seen. for example, in the Suzuki coupling of aryl bromides and aryl boronic acids, excellent reactivity is seen at high temperatures, whereas at lower temperatures, protodeborylation is the dominant process. This contrasts with silica-based systems where deborylation is a relatively minor pathway. Chitosan can be easily prepared in bead form or as films, and this allows the attachment of supported catalysts to reactor walls, or packed beds of catalyst, giving promise for continuous reactor systems.

P9 Additives for the preparation of alkenyl succinic anhydrides (ASA) of vegetable origin F Stefanoiu, C Cecutti, C Vaca Garcia & E BorredonLaboratory of Agro-Industrial Chemistry, INP-Ensiacet, Toulouse, France. In the preparation of alkenyl succinic anhydrides (ASA), additives or a mixture of additives were used to improve the yield of the product and to reduce side-reactions. ASA are obtained by ene-reaction between an enophile molecule, maleic anhydride (MAH), and an unsaturated molecule, which is usually an olefin or, in our case, oleic or linoleic moieties. Our objective was to synthesize and to characterize new vegetable ASA obtained from high oleic sunflower methyl esters in the presence of a small amount of an additive that inhibits side-reactions. The latter, observed in the preparation of ASA, include the polymerization of MAH, the copolymerization of methyl esters and MAH, the oligomerization of methyl esters, the retroene-reaction, and the thermal decomposition of MAH and ASA. Such ASA can be effective to replace petrochemical ASA in numerous applications: surfactants, wood treatment chemicals or paper sizing agents. The considered vegetable ASA are original according to their terminal ester moiety and to the double bond located in the middle of the alkene chain. We studied the influence of additives on the yield and some properties of the adduct: colour, viscosity. The amount of each additive was approx. 0.1-10 mol% of the amount of MAH, the most effective being phenothiazine.We observed less effective results with vegetable ASA when compared to petrochemical ASA. The difference in behaviour can be justified by the fact that these inhibitors are generally employed for shorter chains (C12- C14) than those of the vegetable ASA (C18). Moreover, the color and viscosity would depend also on the degradation of thermo sensitive molecules of vegetable origin. The authors thank ONIDOL (France) for funding.

Biofuels and Bio-energy P2 Effect of carbonization conditions on the physical properties of biochar produced from apicot stone D Ozcimen & A Ersoy-Mericboyu Chemical Engineering Department, Istanbul Technical University, Maslak-Istanbul, Turkey. Among renewable energy resources biomass has an important role. Apricot stone is a valuable agroindustrial by-product that is available biomass resource in Turkey. In this study, carbonization experiments has been conducted on the samples of apricot stones to determine the effects of carbonization variables such as heating rate, particle size and sweep gas flow rate on the physical properties of biochar. A statistical design technique was applied by use of a two-level factorial design matrix to interpret experimental results. Carbonization conditions were selected by considering the following variables: heating rate (5 K/min, 20 K/min), particle size (0.250-0.355 mm,1-1.4 mm) and nitrogen gas flow rate (0, 1000 cc/min). All experiments were performed at a temperature of 550 K and in Jenkner type fixed bed carbonization retort. The char porosity %, total intruded volume (cc/g) and mean pore diameter of biochars were found to vary between %5-62, 0.05-0.73 (cc/g) and 16.6-546 (nm), respectively. The char porosity and total intruded volume values are decreased significantly with an increase in particle size and increased with the increase in heating rate. The sweep gas

flowrate has the lowest effect on the porosity properties of biochar. Amprical relations between the char porosity and carbonization conditions were also developed. Keywords: Biomass, apricot stone, biochar, carbonization, factorial design. P3 Evaluation of grapeseed as a biofuel source D Ozcimen & A Ersoy-Mericboyu Chemical Engineering Department, Istanbul Technical University, Maslak-Istanbul, Turkey. Most of fruit stones, seeds and shells can be used as a resource of carbonization and pyrolysis for production of alternative fuels, chemicals and charcoals. Especially for conventional fossil fuels, new and renewable fuels have the properties of being the major alternatives. In this study, carbonization experiments has been conducted on the samples of grapeseed to determine the effects of carbonization variables such as temperature, sweep gas flow rate and heating rate on the bio-oil yields. A statistical design technique was applied by use of a two-level factorial design matrix to interpret experimental results. Process conditions were selected according to a two-level factorial design matrix considering the following variables: temperature (723 K, 823 K), nitrogen gas flow rate (0 and 1000 cc/min) and heating rate (5 and 20 K/min). All experiments were performed at average particle size of 0.377 mm. The carbonization process was carried out in Jenkner type fixed bed retort. It was found that the liquid yields of samples changed depending on the process conditions. Amprical relations between the bio-oil yield and the process conditions were developed. Bio-oil yield of grapeseed increased with the increasing temperature, nitrogen gas flowrate and heating rate. Bio-oil was characterized and presented as a biofuel resource. Keywords: Biomass, bio-oil, grapeseed, carbonization, factorial design. P4 Selection of Saccharomyces cerevisiae strains for bioethanol production C Parra, M Rodriguez, E Araque, J Freer & J Baeza Renewable Resources Laboratory, Biotechnology Center, Universidad de Concepción, Concepción, Chile. Simultaneous fermentation and saccharification processes of lingocellulosic material requires the utilization of microorganisms capable of working al high temperatures, and consequently the selection of S. cerevisiae strains capable of fermenting sugars at temperatures above 40 degC with a high ethanol yield has become a necessity. In the present study, twelve strains of S. cerevisiaewere grown at 35, 40, 42 and 45 degC in agar plate. All the strains grew at 35 and 40 degC; only two of them grew at 42 degC and none at 45 degC. A small amount of pure yeasts were passed to a liquid medium, and incubated at 35, 40 and 42 degC. At 35 degC, no statistically significant differences were detected in biomass production or ethanol yield. Final ethanol yields were above 80% of the theoretical in all cases (based on the hexoses content). At 40 degC and 24 h, ethanol yield of 12% was achieved for three strains, 45% for other two, and 60-80% for six of them. Only one of the strains grew at 42 degC, producing ethanol with a 50% yield at 48 h. The five strains that grew at 40 degC and with an ethanol yield greater than 70% were submitted to two acclimatization treatments and the growth and ethanol production at 40 and 42 degC were evaluated. After acclimatization, one pure strain of yeast (IR2) was isolated. KEY WORDS Saccharomyces cerevisiae, bioethanol, biomass thermotolerant.

P21 Optimizing the Size of Anaerobic Digesters E Ghafoori & PC Flynn Department of Mechanical Engineering, University of Alberta, Edmonton, AB, Canada. Anaerobic digestion of manure to produce power in farm or feedlot based units as well as centralized plants is evaluated for two settings in Alberta, Canada: a mixed farming area, Red Deer County, and an area of concentrated beef cattle feedlots, Lethbridge County. Centralized plants transport manure to the plant and digestate back to the source CFO, an added cost relative to farm or feedlot based plants, but gain from the economy of scale in plant capital and operating cost. A centralized plant drawing manure from 61 sources in the mixed farming area, at a manure yield of 34 dry tonne year-1 ha-1 could produce 6.5 net MW of power at a cost of $218 MWh-1. No individual CFO in the mixed farming area, including a 7,500 head beef cattle feedlot, can produce power at a lower cost with a farm or feedlot based unit. A centralized plant drawing manure from 560,000 beef cattle in Lethbridge County, at a manure yield of 280 dry tonne year-1 ha-1, can produce power at a cost of $138 MWh-1. In Lethbridge County, An individual feedlot larger than 40,000 head of beef cattle could produce power at a lower cost than the centralized plant. Commercial processes to recover concentrated nutrients and a dischargeable water stream from digestate are not available. However, we analyze the theoretical impact of digestate processing based on a capital cost of 2/3 of the AD plant itself. Digestate processing shifts the balance in favor of centralized processing, and a feedlot would need to be larger than 250,000 head to produce power at a lower cost than a centralized plant. Power from biogas has a high cost relative to current power prices and to the cost of power from other large scale renewable sources. Power from biogas would need to be justified by other factors than energy value alone, such as phosphate, pathogen or odor control.

P23 Degradation of biodiesels at elevated temperatures MS Stark, A Neal & MRG Smethurst Department of Chemistry, University of York, York, UK. Biodiesel production is currently increasing, in response to environmental concerns and policies such as the European Union Biofuels Directive, which has set the target of 5.75 % biofuel use by 2010 in the EU. This increase in biodiesel consumption raises the issue of its stability to autoxidative degradation, both during storage and, particularly, use, where it may experience elevated temperatures and oxidise to form molecules that affect its key physical characteristics such as viscosity, or form deposits or varnishes that adversely affect the smooth running of the engine by fouling fuel lines or injectors. Therefore, to improve understanding of biodiesel degradation, the autoxidation of methyl oleate (methyl cis-octadec-9-enoate), a major component of biodiesel, has been studied in detail at temperatures representative of those experienced in an engine (130 - 190 degC). Products are identified and reaction mechanisms proposed to account for their formation; the dominant reaction is the epoxidation of the C=C double bond by peroxyl radicals, and the reaction of the resultant alkoxyl species to form ketones or alcohols of the starting material, or decomposition to form aldehyde or alkane fragments. P24 Saccharification and fermentation of Pinus radiata D.Don and Acacia dealbata wood chips pretreated by bio-organosolv process C Muñoz [1], A Berlin [2], R Mendonca [1], J Baeza [1], J

Saddler [2] & J Freer [1] [1] Renewable Resources Laboratory, Biotechnology Center, University of Concecpcion, Concepcion, Chile; [2] Forest Products Biotechnology, Faculty of Forestry, The University of British Columbia, Vancouver, Canada. Wood chips from Pinus radiata and Acacia dealbata were biotreated by white-rot fungi, Ceriporiopsis subvermispora and Ganoderma australe, respectively. Sterilized wood chips were inoculated with 500 mg fugal mycelium/kg wood and incubated for 30 days at 25 degC and 55% RH. Decayed and untreated wood chips were delignified by an organosolv process (ethanol:water 60:40, 200 degC, 1 h) to produce pulps with low lignin content. Prepared pulps underwent sequential hydrolysis and fermentation (SHF) or simultaneous saccharification and fermentation (SSF). Cellulase (Celluclast 1.5L, 20 FPU/g glucan) and beta-Glucosidase (Novozym 188, 40 CBU/g glucan) were used for enzymatic hydrolysis of pulps and Saccharomyces cerevisiae for hexose fermentation of sugar hydrolyzates. Pulps produced from biotreated P. radiata showed a higher glucan content (~90%) and lower lignin content (~8%) compared to pulps produced from untreated wood chips (~80% glucan and 14% lignin). Pulps obtained from biotreated A. dealbata showed also higher glucan content (~94%) and lower lignin content (~2%) than pulps produced from untreated wood (~90% glucan and 5% lignin). The enzymatic hydrolysis (SHF) of untreated and biotreated P. radiata yielded glucan-to-glucose conversion ~55% and 100%, respectively. In the case of A. dealbata, the glucan-toglucose conversion was 100% for both control and biotreatred pulps. Ethanol yield in SHF of control and biotreated P. radiata pulps was 25%-38% and 49-55% theoretical yield, respectively, while for control and biotreated A. dealbata pulps the ethanol yield was 58%-62% and 61%-69%, respectively. The SSF of untreated and biotreated P. radiata organosolv pulps yielded 4%-10% and 53%-65% ethanol, respectively, and 67%- 77% and 78-%-82% for untreated and biotreated A. dealbata organosolv pulps, respectively. The bio-organosolv pretreatment produces pulps with high glucan and low lignin content that are easily hydrolyzable following both SHF and SSF process schemes. The bio-organosolv pulps produced from untreated wood. Keywords: Pinus radiata, Acacia dealbata , Ceriporiopsis subvermispora , Ganoderma australe, bio-organosolv pulping, bioethanol. P28 Ecological gradation of energy in a pond ecosystem Manjunath Iyer Department of EC & CSE, Bangalore University, Bangalore, India. There exists a self-similarity in the concentration of the organisms along the depth of the pond. It originates as a result of a kind of differential feedback from the bottom of the pond to the surface [1]. The flow of energy towards the bottom of the pond would be controlled by the (ratio of) the gas mixture that flows towards the surface. This control mechanism would have far reaching impact on the photosynthesis as well as the readjustment of the concentration of the organisms through aquatic movement. As the consequence of the differential feedback, many interesting properties would be imparted to the ecosystem. The ecosystem becomes more and more predictive. Analysis shows that, greater the depth of the pond, better would be the predictability. Meaning, in a deep pond ecosystem, the degree of adaptability would be better. Any environmental changes would be reflected and responded fast compared to a shallow pond ecosystem. The predictability provides better controllability. If a certain set of

organisms at a specific depth vanishes or move out, the deep pond ecosystem can still sustain and quickly reconfigures. Such a change would mean drastic for a small pond leaving it in crisis. A better understanding of the control mechanism can provide techniques for the survivability of small pond ecosystems Another interesting outcome of the differential feedback is the abstraction or gradation. The biological activities involving energy generation and consumption become abstract with depth. There exists a mathematical relation in the abstractions of different levels. It is interesting to see that the gap between different levels increases with depth. Each level is dominated by a kind of organism bring in the gradation in the ecosystem. References: 1. Manjunath.R, Self- similar models for biological system and process, ISMB 2006 (accepted)

Biocatalysis P18 Biocatalyst Catalysts for Sustainable Chemistry Understanding the interaction of functionalised supports with enzymes S Narayanaswamy [1], HR Hazel [2], DJ Macquarrie [1], JH Clark [1] & NC Bruce [2] [1] Green Chemistry Centre of Excellence, Dept of Chemistry, University of York, York,UK; [2] CNAP, Dept of Biology, University of York, UK. The goal of Green Chemistry is to develop sustainable technologies to produce the desired products with minimal chemical waste. This requires the use of renewable raw materials and transformations under very mild conditions. Immobilized enzymes are emerging as new heterogeneous biocatalysts, resulting in improved performance in activity, and stability and facilitating separation of enzymes. Earlier immobilizations made use of polymers as supports, which often reduced the activity of enzymes . We have initially made use of mesoporous material-SBA-15: due to its larger pore size and thermal stability . Our current enzyme of interest is Glucose Oxidase because of its high stability under extreme conditions . Our initial work has shown that using SBA-15 functionalised supports can lead to an increased activity depending on the surface chemistry. We intend to use Glucose Oxidase to predict the interactions and therefore to design better supports for enzymes. In contrast, to the reports of Zhao and co-workers , showing higher yield in vinyl functionalised supports, our initial studies have revealed a lower yield using vinyl groups. It therefore appears that different functional groups are required for optimal activity, with different types of enzyme. A low adsorption for enzyme onto non-functionalised supports, further demonstrates the importance of organic groups on supports. The use of expanded starch and chitosan as supports is also being investigated. Starch and enzymes (proteins) are both macromolecules, so it would be interesting to understand the chemical and biological interactions between them. Meanwhile, the ease of forming films makes chitosan unique for biofabrication of enzymes. These films are intended to be used in microreactors. P26 Industrial Biotechnology and the MDG's B Verster Dept of Biology, Univeristy of York, York, UK. A system is introduced that makes use of a low ecological impact, low maintenance, multi-use system. The first goal of the system

is education and the establishment of infrastructure in rural Southern Africa. The system comprises three components: 1) A grid of microorganism growth, biotechnologically developed to produce biomaterials, most probably through use of photosynthesis. 2) Sun-follower technology to best capture sunlight for photosynthetic utilization. 3) Sealed environment, containing the bio-grid, enabling product separation, with filter-air cooling and nutrient supply. The system can be fixed to rooftops, or provide shade under which crops can be grown. As it is a sealed system, it does not require water. This system is designed for rural use in semi-arid to arid areas, with a low water requirement and low maintenance. It shows promise for bio-hydrogen production, as well as carbon sequestration and can be modified for waste catalysis, like water remediation and sewage treatment. Why the MDG's? This system can be modified to produce food, although it is designed at present to be a slow-growth system, to cope with low nutrient (CO2 and water) supply, and enable low maintenance. It aids in education in biosciences, while producing an opportunity for entrepreneurship. It is a first step towards infrastructure in communities that are isolated from electricity grids, in areas where healthcare and education is at a minimum. The eventual goal of this system is the sustainability of several small 'farming' communities, where the 'crops' are these bio-grids, that do not require much water or other input, while being able to produce diverse products, from biofuels for domestic use, to pharmaceutical precursors, to biomaterials for use in the textile industry. Advantages: Cheap, basic technology. Large scope for development and specialization. Alternative technology to fermentation. Biopolymers (fibres) / Biomaterials P10 A new star(ch) is born: Starbon Acids and their uses as catalysts VL Budarin, JH Clark, TJ Farmer, R Luque & DJ Macquarrie Green Chemistry Centre of Excellence, Department of Chemistry, The University of York, York, UK. Mesoporous carbonaceous materials have an outstanding potential in many different applications such as adsorption, medicine and catalysis.1 Recently, we have reported the synthesis of a new form of mesoporous carbon, named Starbon, obtained after low temperature carbonization of expanded starch.2 Such starch derived mesoporous materials have several tunable properties including surface properties (ranging from hydrophilic to hydrophobic surfaces) which can be easily controlled by the degree of carbonization (from 200 to 700C) and the possibility of their use as supports for catalysis. Due to this diversity of surface functional groups, starbons can be easily modified. In this sense, simple treatment of the Starbon material with sulfuric acid gave a solid acid catalyst that has promising properties in the catalysis field. Indeed, low surface-area sulfonated aromatic materials have recently been reported as effective solid acid catalysts.3 In our preliminary experiments, we have screened a wide range of reactions including esterifications of different acids (succinic, fumaric and levulinic, among them), acylations of substituted alcohols and amines as well as alkylations of substituted benzenes (i.e. xylenes) with arylchlorides, obtaining, in general,

interesting results in terms of catalytic activity and selectivity to each one of the desired products, depending on the conditions. Of note are the comparative studies carried out with some other water-tolerant solid acid materials such as sulphated zirconias, clays and zeolitic materials, in which slower reaction rates and worse selectivities/conversions for the target products were found under the same reaction conditions. 1 a) S. U. Song, S. I. Lee,Y. K. Chung, Angew. Chem., Int. Ed., 2000, 39, 4158; b) D. C. Ko, J. F. Porter, G. Makay, Chem. Eng. Sci., 2000, 55, 5819; 2 V. Budarin, J. H. Clark, J. J. E. Hardy, R. Luque, K. Milkowski, S. J. Tavener, A. J.Wilson, Angew. Chem. Int. Ed., 45, In press, DOI:10.1002/anie.200600460. 3 M. Toda, A. Takagaki, M. Onamura, J. N. Kondo, S. Hayashi, K. Domen, M. Hara, Nature, 2005, 438, 178.

P11 New materials based on renewable polysaccharide polymers VL Budarin, JH Clark, FEI Deswarte, S Doi, JJE Hardy, AJ Hunt, DJ Macquarrie, K Milkowski, OJ Samuel & R White Green Chemistry Centre of Excellence, Department of Chemistry, University of York, York, UK. Natural polysaccharide polymers, such as starch, cellulose and chitin represent a carbon neutral, non-toxic, biodegradable and abundant resource comprising the majority of biomass. They are widely utilised in food as well as a wide range of non-food applications. The outstanding environmental performance along with low cost and widespread availability of these polymers have attracted research into a variety of applications at Green Chemistry Centre of Excellence at York such as novel starch-based plastics for a variety of applications. Moreover, the inherently high degree of functionality of these polysaccharides make them potentially attractive surface-active materials. The nitrogen functionality, for example, has been utilised to produce successful heterogeneous catalysts and Chitosan's biocompatible nature allowed enzyme heterogenisation. However, the wider exploitation of these materials is restricted by the naturally low porosities limiting the availability of active sites. Researchers at York have developed a range of novel porous starch or cellulose based materials utilising novel microwave, ultrasound and supercritical fluids technologies in the expansion process. The expanded materials have been applied as supports for heterogeneous catalysts for a variety of chemical transformations with activities comparable to commercial systems. Additionally, post or in-situ surface modification of the polysaccharides generated materials with excellent absorption and release characteristics applicable in remediation, filters and pharm aceutical or agricultural absorption-release matrices. They have also been successfully applied as stationary phases in gas and liquid chromatography enabling, for example, the use of less toxic eluting solvents and potentially the separation of chiral compounds. Expanded starches have also been utilised in synthesis of further novel compounds. Acid catalysed low temperature pyrolysis yielded a family of carbonaceous materials with tuneable porosities and surface and bulk characteristics applicable to catalysis and chromatography. The expanded starch matrix has also been utilised in the synthesis of novel porous composite materials with different surface characteristics and improved thermal stability P13 Switchable Adhesives for Carpet Tiles JH Clark & PS Shuttleworth

Green Chemistry Centre of Excellence, Department of Chemistry, University of York, York, UK. The carpet tile market in the UK is fifteen million meters squared with over 90% of this going to landfill after use. This represents on an unacceptable level of waste and future legislation will force manufacturers to recycle used tiles. The current manufacturing process for the production of carpet tiles involves the use of powerful adhesives to bind the base (e.g. PVC) and fibre components (e.g. nylon 6, 6). This approach inhibits separation and does not adequately facilitate recycling of the individual components. The use of novel switchable adhesives made from starch based materials potentially presents an exciting alternative to conventional materials. Through modification (physical or chemical) the desired properties (i.e. hydrophobicity) can be imparted, resulting in a starch based material which can ultimately be deconstructed under an external stimulus (e.g. Acidic or Basic treatment) achieving separation of the component parts and hence enabling recycling. The poster will aim to demonstrate and discuss some potential methods for the production of starch-based plastics and adhesives. These will include:-

The hydrolysis of starch and product analysis

The esterification of starch - To increasing hydrophobicity - Enhancement of thermal stability, (an important parameter for plastic and adhesive applications) - Decreasing melt temperature for use as hot-melt adhesives - Modifying rheological flow properties Furthermore, the extrusion processing of starch and the route to forming Thermoplastic Starch (TPS) will also be discussed.

P14 The Generation of Novel Biomaterial Based Stationary Phases & Their Application in Chromatography RJ White & JH Clark Green Chemistry Centre of Excellence, Department of Chemistry, University of York, UK. The majority of chromatographic systems exploit silica based stationary phases, affording little scope for recycling and unappreciable biodegradability. By comparison starch is one of the most renewable / biodegradable resources available. At present it is highly under utilised in terms of typical chemical applications, with its main use being in the food, paper and adhesives sectors1. Chromatography relies upon the interactions of compounds dissolved in a flowing mobile phase with a stationary material or phase. There remains the need for new stationary phase materials having different and potentially improved separating characteristics when compared to the silica equivalent, with a surface polarity between that of silica and reverse phase silica. There is also the added driver to develop materials that present new exciting, enhanced separation profiles as a result of a low micropore to mesopore ratio, which are based on renewable starting materials and that present a decreased environmental burden after use. Expanded and chemically modified renewable starches and other carbohydrate-based materials potentially fulfil the criteria described above. Presenting a chemically active surface open to modification, these carbohydrate-based materials will be used in typical chromatographic applications and manipulated to form novel monolith columns, which in them self present a number of advantages2. The poster aims to demonstrate the preparation, modification and utility of such novel stationary phases in chromatography. References:

[1] (a)'Economics of Starch Production in the UK', G. Entwistle et al., Industrial Crops & Products, 1998, 7, 175 (b) 'Starch, and Modified Starches as Support Materials and Catalysts', PhD Thesis, J. J. E. Hardy, University of York, 2001 [2] 'Comparison of the efficiency of microparticulate and monolithic capillary columns', S. Eeltink et al., J. Sep. Sci., 2004, 27, 1431 P29 Molecular Structure and Dimension of Xylan from Various Sources W Praznik [1], R Loeppert [1], K Zangger [2] & A Huber [2] [1] Department of Chemistry, BOKU - University of Natural Resources & Applied Life Science Vienna, Vienna, Austria; [2] KFUG - Karl-Franzens Univ. Graz, IfC - Inst. f. Chem., Graz, Austria. Xylans from different sources are investigated upon molecular characteristics in terms of unimer-composition, molar mass and excluded volume distributions. As well destructive as non-destructive techniques were applied, in particular: total hydrolysis and TLC-analysis for identification of constituting carbohydrates, NMR for identification of specific functionalities in non-hydrolized xylans and SEC-multiple detection to obtain molar mass distribution and excluded volume distribution. Molar mass distribution of investigated wood xylans from Wolf Cellulosics and beech range between 500 and 30 000 grams per mol with mean molar mass in terms of Mw in the range of 10 000 grams per mol and polydispersity index close to 10. Broad distributions even were found for wood xylan from birch, however, more high-dp components with molar masses up to 240 000 grams per mol were present resulting in even higher mean molar mass of Mw 36 000 grams per mol. Compared to xylan of oat bran with significantly higher dp-components with molar masses up to 500 000 grams per mol and mean molar mass of Mw 85 000 grams per mol. Furthermore, there is evidence of at least two populations in the molar mass distribution indicating xylan populations of oat bran differing in conformation. Due to NMR and structure analysis the investigated samples consist of a backbone of beta(1,4)-linked xylopyranose moieties with varying amount of acetyl- and methyl-groups linked to sugar moieties such as arabinose, mannose, galactose, and glucuronic and galacturonic acid. Bioresources P15 Renewable Industrial Materials From Trees SK Badamali, F Bouxin, V Budarin, K Milkowski, FEI Deswarte & JH Clark, Green Chemistry Centre of Excellence, Department of Chemistry, University of York, York, UK. Trees are an integral part of the UK's landscape and rural economy. Unfortunately, the economic benefits provided by trees and their by-products (e.g. timber) have declined in recent years. Standing timber price has plummeted to a 25 year low. In addition, the forestry industry in Britain currently discards approximately 75% of the felled tree (e.g. leaves, bark, small branches, off-cut, etc). There is therefore a need to identify innovative applications for forestry species. In this context, Sitka Spruce (Picea sitchensis) was selected as the tree species to be studied in the course of this project, as it a very common and low value tree in the UK. Essential oils with excellent microbial activities were isolated from Sitka Spruce bark using environmentally-friendly methodologies (i.e. supercritical carbon dioxide extraction). Expanded cellulose materials with surface area up to 140m2/g have been produced using ultrasound and successfully used a chromatographic media,

catalytic supports and adsorbents. Finally, Catalytic oxidative hydrolysis systems and microwave heating technology with aim to producing a portfolio of substituted aromatic compounds from lignin were examined. The poster will generally discussed the potential of adding value to trees through extraction of secondary metabolites prior to exploitation of the structural components (i.e. cellulose and lignin).

P16 Enzyme-assisted Aqueous Processing as the Front-end to a Soybean Biorefinery BP Lamsal & LA Johnson Center for Crops Utilization Research, Iowa State University, Ames, IA, USA. A biorefinery is cluster of bio-based industries producing chemicals, fuels, power, products and materials. We envision a soybean biorefinery processing soybeans into value-added products for food, feed, biomaterials and bioenergy, similar to corn wet milling. Enzyme-assisted Aqueous Extraction Processing (AEP) holds promises as the front-end to such a biorefinery. AEP, which uses water as an extraction medium, is an alternative to hexane extraction for processing soybeans. Because of increasing environmental and safety issues associated with hexane extraction of oil, AEP is being evaluated for extracting oil from oil-bearing plant materials. The challenges are: the need for mechanical treatment to rupture cells and facilitate water washing; disruption of oleosin protein molecules, which stabilizes the oil in the seed; separation of emulsified oil from the aqueous fractions; and limited recovery of free oil because the oil released becomes emulsified by protein and lecithin. Extruding full-fat soy flakes into water and enzyme-assisted AEP with 0.5% w/w endo-protease extracted 88% of total oil and 77% of total protein. Extruding denatured protein and sequestered oil. Protease treatment was effective because denaturation exposed sites for easy enzyme attack, enhancing extraction. Protease also acted on olesin to facilitate more oil release. Hydrolyzed proteins were more soluble in aqueous medium, resulting in higher protein extraction yield. Extruding full-fat soy flakes prior to enzyme-assisted AEP was key to increasing oil extraction and to increasing oil droplet size in the cream fraction. Larger oil droplets in the cream phase favored coalescence yielding more free oil. The cream fraction was heated to 95 degC for 5 h, frozen at -deg20C and thawed, and treated with various deemulsification agents. Heating did not break the emulsion but freezing-thawing, Agent A, and Agent B recovered 86, 68, and 73% of the total oil, respectively. P17 Integrating Recovery of Plant-made Pharmaceuticals into a Biorefinery D Octaviani, N Vignaux, S Fox & L Johnson Center for Crops Utilization Research, Iowa State University, Ames, IA, USA. Advances in molecular biology allow development of recombinant proteins in corn to produce pharmaceuticals and industrial enzymes. In addition to providing a natural storage system, easy scale-up, established production practices and high yield to cost ratio, this production system can be integrated into a biorefinery where biofuels and biobased products are produced. Corn expressing recombinant Dog Gastric Lipase (rDGL) for treating cystic fibrosis patients was used as a model where the recombinant protein is expressed in endosperm. A dry-milling method was developed to separate corn tissues into a germ-rich fraction containing most of the oil and water-soluble protein and

an endosperm-rich fraction containing most of the rDGL. Four degermers were evaluated (drum-type degermer, attrition mill, impact mill, disk mill, and roller mill), at two corn moisture contents (15 and 21%) and two recycles (7 and 15%). We developed the concept of Dry Milling Index (DMI) to evaluate dry-milling systems wherein DMI was the ratio of oil yield to mass yield of the germ-rich fraction relative to the same ratio in the endosperm-rich fraction. The drum degermer recovered 74% of the total oil in 23% of the total mass while the endosperm fraction contained only 22% of the total oil.The drum degermer gave the highest germ DMI (3.2) and lowest endosperm DMI (0.32). As a reference, hand-dissected kernels gave 6.9 germ DMI and 0.12 endosperm DMI. Only degermer type affected DMI; moisture and percent recycle did not have significant effects. The drum degermer recovered 89% rDGL activity in 70.4% of the total mass containing only 26% of the total oil. Recovery of recombinant proteins in corn could be integrated into a biorefinery wherein the recombinant protein is extracted from the endosperm fraction before the fermenting the starch to fuel ethanol and the germ fraction is used to produce biodiesel. Chemical Products including Oleochemicals P19 Biobased Chemicals: today, not tomorrow. The valorisation of functionalized chemicals from biomass resources compared to the conventional fossil production route B Brehmer Valorization of Plant Production Chains, Wageningen University and Research Centre, Wageningen, The Netherlands. It is proposed that already today, by utilising existing, recently developed and developing technology, it is economically advantageous for many chemicals to derive from biomass, in particular the functionalized chemicals. The only way to validate this conjecture is to develop a complete comparative life cycle analysis. As opposed to a traditional LCA, the 'multicriterion' developed here will revolve around energy flows and process efficiency in terms of exergy. The aim is to assess the optimum route with the best production options along the whole production chain while determining any possible limiting factors. Using this tool, a systematic production matrix relating several logical source crops and a few key chemicals of varying derivative levels can be created and compared to the conventional fossil routes. Combined with economic considerations and some unambiguous environmental factors, the investigation will provide all the information relevant to the industry. The goal is to create an objective and reliable simulation system ratifying the economic and environmental feasibility of exploiting biobased chemicals today and indicate the steps necessary for further improvement. P20 The Forest Biorefinery Concept CAS Hill [1] & SF Curling [2] [1] School of Agricultural and Forest Sciences, University of Wales, Bangor, UK; [2] School of Agricultural and Forest Sciences, University of Wales, Bangor, UK. Although there has been a great deal of interest in the use of agricultral resources for the production of industrial chemical feedstocks, rather less has been directed at the use of forest resources for this purpose. Forest resources have a number of advantages over the use of industrial crops. The material is essentially non-seasonal with potential for harvesting the standing crop throughout the year. Furthermore the levels of

production can be forecast many years in advance leading to stability in production. This paper will explore the potential for the use of forest-based reources for producing various silvichemicals and biopolymers with some historical and contemporary case studies.

P25 Selectivity in microbial transformation of some xenobiotic substances O Piccolo [1, 2], D Montin [2], E Argese [3] & G Dondo [4] [1] Studio Consulenza Scientifica,Sirtori, Italy; [2] Department of Chemistry, Ca' Foscari University, Venice, Italy; [3] Department of Environmental Sciences, Ca' Foscari University, Venice, Italy; [4] Analisi & Controlli srl, Genoa, Italy. Aim of this work was a preliminary investigation of the behaviour of some microbial cultures in the presence of a few xenobiotic substances, either to produce industrially useful derivatives or to test the capability of these microorganisms to mineralize them selectively. The following strains, Pseudomonas aeruginosa, Rhodotorula sp., Yarrowia lipolytica, isolated from heavily contaminated soil or from mixtures of fuels by Analisi & Controlli srl, were chosen as cheap and representative microorganisms, which are often present in hydrocarbon polluted environments. Microbial cultures were grown on specific broths, that permitted a rapid and efficient increase of their population, and, after 24 h, the following aromatic and heteroaromatic compounds, as single substance or as mixture dissolved in ethanol, were inoculated to obtain a final concentration of 1%: Naphthalene, 1- and 2-methyl Naphthalene, 1,2-dimethyl Naphthalene, Indole, 5-methyl Indole, Quinoline and 8-methyl Quinoline. The mixture was analyzed at regular intervals, up to 30 days, by using different techniques, including B.O.D. measures. The results of this work have shown different biotransformation behaviour of the three strains in the presence of aromatic and heteroaromatic substrates and the influence of minor modifications in the structure of the xenobiotic compounds on the microbial activity. Synergic and/or inhibitory effects were found when a mixture of added substances or a microbial consortium was used. The interesting structure selectivity, found in this work, might be perhaps useful in the treatment of tar fractions to obtain purer single high value hydrocarbons. Some products, due to a partial biotransformation of indole derivatives, were isolated and the determination of their structures is currently in progress. A production of oxygenated fatty acids and of biosurfactants, that might have a large industrial impact, was always observed, so indicating that their manufacture is not related only to make the xenobiotic compounds bioavailable for the strain. P27 Enhancement of Solar Energy Efficiency for Drinking Water Disinfection G Raza [1], A Hameed [2] & T Bhatti [3] [1] Department of Microbiology, Quaid-I-Azam University, Islamabad, Pakistan; [2] Quaid-I-Azam University, Islamabad, Pakistan; [3] Pinstech, Islamabad, Pakistan. Contaminated drinking water poses a major health threat to human beings worldwide.Over one billion people each year are exposed to unsafe drinking water due to poor source water quality and lack of adequate water treatment that results in several diseases. The lack of adequate drinking waters in developing countries is a continually growing problem due to population increases and increased demands on source waters. Therefore, water disinfection methods that are easily employed in countries like Pakistan are needed. Chemical disinfection

options such as chlorine and iodine treatment require chemicals that must be purchased. These chemicals can be expensive and also have a limited shelf life. Physical treatment options such as boiling, UV treatment, and filtering require materials that may not be easily acquired or purchased. One alternative drinking water treatment method that has been proposed is solar disinfection, a process that is simple and easily utilized. The photoactivity of titanium dioxide has been meticulously investigated to demonstrate its bactericidal ability. P25 Degussa Titanium Dioxide (80% anatase and 20% rutile) was used as the primary source of Titanium particles during our study. This powder was coated by silver particles and both materials were tested in dark and sunlight for E.coli inactivation. The results demonstrated that Ag-TiO2's exceptional bactericidal ability against normal sunlight. The acquired data also showed that inactivation kinetics of Ag-TiO2 with respect to bare TiO2 at various elapsed time. TiO2 and Ag-TiO2 in suspension and immobilized form showed no significant difference. The results clearly showed that solar energy efficiency is enhanced for Ag-TiO2 as compared to bare TiO2. It was noted that E.coliwas probably inactivated by two different photocatalytic mechanistic pathways, possibly free or surface-bound hydroxyl radicals and reactive oxygen species (H2O2). MRes Session P30 Glycerol and Succinic Acid as Platform Molecules from Biomass D VandenBurg, C Chukwuogo & J Clark Green Chemistry Centre, Department of Chemistry, University of York, Heslington, England. In the context of vanishing fossil resources, biomass represents the best way in which Man can continue to meet his increasing need for chemical products. Many useful chemicals can be derived from plants; indeed many man-made chemicals have been modifications and mimics of natural products. Recently the U.S. Department of Energy [1] published a report highlighting 12 key 'platform molecules' (molecules that can serve as the building blocks of current and future chemical products) easily obtained from biomass. These were chosen based on their chemical utility and expected value. Of these, we have looked at glycerol and succinic acid as a case study, since we believe that they best show the versatility, importance and innovation that platform molecules represent. Unrefined glycerol has been used as an additive for many years in sectors such as the cosmetic and pharmaceutical industry. Being one of the major effluent streams from biodiesel synthesis (itself an hugely important advance in Green Chemistry) Green Chemists have been looking at adding value to this important molecule. Chemicals such as 1,5 propane diol and propane glycol, can be easily produced from glycerol by fermentation methods. Work is also being done into using glycerol-derived chemicals to form biodegradable nylon analogues. Succinic acid and its primary derivatives are in great demand for uses as diverse as polymer production to de-icing technology [2]. The current oil based synthesis of succinic acid is highly wasteful and involves chemicals harmful to the environment. Using bioreactor technology it is now possible to produce high quality succinnic acid from the waste generated by the corn and paper industries [3]. We anticipate that many commercially important molecules will be derived from succinic acid, (THF can be easily derived from succinic acid and so may be seen as a sustainable solvent for the future).

[1] Top Value Added Chemicals from Biomass,Volume 1, T.Werpy and G.Petersen 2004. [2] www.wisibiorefine.org [3] Chemicals and Materials from Renewable Resources, J.Bozell, ACS, 2001

P31 Bioethanol: production and uses TL Malkin & SE Hale Green Chemistry Centre of Excellence, University of York, York, UK. The majority of ethanol is produced from crude oil in a direct hydration process.Within this route a highly concentrated ethylene stream is compressed to 7MPa, mixed with H2O, vaporised then heated to a reaction temperature of 300 degrees Celsius and passed over a phosphoric acid catalyst. The process is undesirable from a green perspective as it uses high temperatures and pressures and creates large amounts of waste. A greener solution is to produce the ethanol from renewable resources: carbohydrates such as starch and cellulose can be hydrolysed to simple sugars and then further converted to ethanol by fermentation. To begin with a pretreatment opens the structure of biomass making it susceptible to hydrolysis by concentrated or dilute H2SO4. The fermentation process takes place using enzymes and then the ethanol is recovered by fractional distillation. Biomass energy contributes 9-13 % of the global energy supply which accounts for 45 ± 10 EJ per year (2004).[1] World bioethanol production was 31 GL in 2001 with the major producers America and Brazil, contributing 62 % of it. America relies on corn while Brazil produces bioethanol from sugarcane under the national program 'ProAlcool'. The program has been successful as 13 billion litres of ethanol are produced saving 220 000 barrels of gasoline imports per day. 5 million cars run on pure bioethanol now in Brazil. Within the UK, British Sugar has placed a contract with a design firm in the race for the UK's first bioethanol plant. A pilot scheme in Somerset is using the Ford Focus Flexi-Fuel Vehicle that runs on 85% bioethanol. We question whether this is enough to counter act the rapidly decreasing amount of fossil fuels and feel the UK should follow more closely Brazils example. [1] B. Dale and S. Kim, Biomass and Bioenergy, 2004, 26, 361 P32 Process Intensification using Spinning Disc Reactors (SDRs) SD Blore & JH Westell Green Chemistry Centre of Excellence, University of York, York, UK. With increasing demand for reactors that provide not only greater energy efficiency, but also the benefits of Just-In-Time (JIT) production, preventing both waste and the risk of storage, many types of continuous reactors have been developed in an attempt to meet the requirements of the many types of chemical reactions they apply to. One such reactor is the Spinning Disc Reactor (SDR), a small (less than one cubic metre) reactor that is capable of producing over 1,200 tonnes per annum of chemical product, by continuous process, with a typical selectivity of 95%. The reactor's strengths are also apparent in a 99% reduction in plant inventory, as a standalone reactor requires no extensive pipe work (the reactor forms only 20% of typical chemical plant production costs) with energy also being saved as the SDR can perform a reaction as much as 1,000 times faster than a batch reactor, with mass and heat transfer rates improved 10 and 15 fold respectively. SDRs often operate with little or no solvent, and

where more than one reactor is required; they can be set up to release the first stage product straight onto a second disc. Even more promising is the ability of the disc itself to act as a support bed for catalysts where they are also needed. The technology has now been used not only to produce bulk chemicals, but also in the production of pharmaceuticals, polymers and even ready meals for major supermarkets. P33 CO2 Sequestration as a method of Greenhouse Gas Abatement BA Lanigan & VS Pugnet Green Chemistry Centre, Department of Chemistry, University of York, York, UK. Since the start of the industrial revolution, the atmospheric CO2 concentration has increased by 40%, most of it released since 1945. If the emission levels continue at the current rate, by the year 2050 we will have effectively doubled the pre-industrial concentrations. As CO2 is a greenhouse gas, the rise in atmospheric levels has been directly linked to global warming. The Kyoto Protocol requires nations to cut the emission of greenhouse-gas, including CO2, by at least 5% from 1990 levels in the commitment period of 2008 to 2012. Given our high degree of reliance on fossil fuels (roughly 85% of commercial energy use), and the difficulties (technical, economic and social) of large scale use of alternative options (like nuclear and renewables), the ability to use fossil energy while avoiding CO2 emissions is a potentially attractive alternative that needs to be carefully studied. The purpose of CO2 capture is to produce a concentrated stream of CO2 at high pressure that can readily be transported to a storage site. There are two possibilities for CO2 capture: Extracting it directly from the atmosphere; Extracting it from large stationary sources. This poster focuses on the latter as it is seen as the most promising option. P34 Chitin: Application, Modification and Extraction JW Comerford & MA Neesam Green Chemistry Centre of Excellence, University of York, York, UK. This poster presentation reviews the extraction and applications of the natural polymer chitin. Currently, crustacean waste has to be disposed of according to certain animal waste regulations and with increasing cost of disposal, this is becoming an increasingly unattractive prospect. Chitin, a major structural constituent of crustacean shells, has the potential to provide a cheap and large quantity of renewable polymeric material, especially in coastal regions or areas with a high throughput of crustacean shell waste. Currently a small industry, chitin refining is expected to increase in the foreseeable future in order to replace petrochemical derived products, as petrochemical feedstocks diminish and the demand for new improved materials increases. For instance, chitin could be used for pollution remediation, as its structure has many sites able to bind to various metals as well as many organic pollutants. Chitin could also be used as a renewable catalytic support; the sites mentioned above can be functionalised to support certain catalytic metals. Extraction methods for the isolation of chitin from shells will be described; these include the classic extraction, as well as novel environmentally friendly extractions not currently practiced, such as biological isolation using enzymes. The conversion of chitin to chitosan and further functionilisation of the resulting material, using methods such as ultrasound, will

be discussed. Finally, the tremendous potential of modified and native chitin will be highlighted.

P35 Bioresources For Greener Surfactants: A Case Study Of Alkylpolyglucisides (Apg) F Mabiki & Z Jiankun Green Chemistry Centre of Excellence, Department of Chemistry, University of York, York, UK; Bioresources are raw material derived from living organisms. The main suppliers of bio resources may include the conventional renewable resource industries such as agriculture, forestry, marine, various organic residues and also bio-residuals generated from existing conversion and manufacturing processes Carbohydrates are promising bioresources towards more environmentally friendly and greener surfactants. The amphilic compounds, which offers wide applications due to their ability to interact with all the interfaces. Alkylypolyglucosides (APGs) are the surfactants purely made from bioresources, their preparation process is quit simple and greener, cost effective even at large scale, and they socially acceptable as they are increasingly used. APGs are prepared from carbohydrate resources, which may include starches such as wheat, corn, potatoes, any monomeric form of carbohydrates, and the fatty acid sources such as fatty alcohol from coconut or palm oil, tallow, rapeseed depending of the desired alkyl chain length. As surfactants they are used in foods, micro-emulsions, detergent and cleaners, personal care products, textiles, pesticides, and other daily used house hold products, because they exhibits favorable dermatological properties, reduce the irritant effects of surfactant combinations, completely biodegradable, both aerobically/anaerobically and primarily/ultimately. They are less toxic than other conventional surfactants, they have no pronounced inverse solubility vs. temperature as normal non-ionic surfactants and also they are more lipophilic compares to their petrochemical based surfactants counter parts. APGs are most promising surfactants for future as well as today's technological development. However, there are challenging areas for the sustainable development of the APG surfactants includes maximum crop use, production of pure APG surfactants, energy minimization during preparation and use, and the greener preparation procedures. Despite these challenges, they are still the most promising surfactants for today's as well as future sustainability. Chemical Products including Oleochemicals P36 Synthesis of long chain dicarboxylic acid derivatives from fatty acids R Verhe, L De Buyck & D De Vos Department of Organic Chemistry, Gent University, Gent, Belgium. Metathesis reaction of fatty acid derivatives with a double bound in the long alkyl chain or in the alkoxy chain of the ester function in the presence of a homogeneous bimetallic ruthenium catalyst gives rise to a variety of long chain dicarboxylic acids. Metathesis of methyl oleate produces dimethyl-9-octadecenyl dicarboxylate. Metathesis of allyl oleate only shows reaction in the alkoxy chain producing a C-32 dicarboxylic ester. An identical reaction was observed with the allylamide derivative from oleic acid.

Methyl-10-undecenoate is converted to 2,2,18,18-tetrachloro nonodecaan dicarboxylic acid and into the corresponding diketo dicarboxylic acid via a scheme depicted. The tetrachloro dicarboxylic acid derivative is used in the synthesis of the antibiotic tiromycin. The chlorination in DMF of alkyldiolo cycloalkenes and cycloalkanones also produces long chain chlorinated dicarboxylic acids and the corresponding alpha-ketodicarboxylic acids.

O

XR2

O

X R

O

XR + H2C CH2

R = CH2 CH3n

with n = 15 or 17

X= O or N

R = CH2 CHn-1

with n = 7CH

CH2 CH3n

OR

Bioresources (including carbohydrates) P37 Stability of phytosterols during vegetable oil refining R Verhe, L De Buyck & D De Vos Department of Organic Chemistry, Gent University, Gent, Belgium. Currently, an increased interest is observed for functional minor components naturally present in oils and fats performing a beneficial nutritional effect. In this study organic chemical aspects associated with the influence of processing on tocopherols and phytosterols are presented. During the deodorization process tocopherols are partially volatised and condensed in the deodoriser distillate. However, a tocopherol loss in the tocopherol mass balance during deodorization was observed. The tocopherol loss in the mass balance could be reduced under selected conditions (addition of synthetic antioxidant, stripping with nitrogen gas) suggesting an oxidative degradation of tocopherols during deodorization. The oxidative degradation of tocopherols was confirmed in a model system and the major tocopherol degradation products were identified as epoxy-alpha-tocopherolquinone and alpha-tocopherolquinone. Upon heating of alpha-tocopherol in a triglyceride mixture of triolein and tripalmitin under thermoxidation conditions, epoxy-a-tocopherolquinone and alpha-tocopherolquinone were identified as the main tocopherol degradation products and their concentrations were modelled. In addition, a faster tocopherol oxidation in a more saturated triglyceride matrix was observed, which was explained by a competitive oxidation between tocopherols and unsaturated triglycerides. The mode of refining (chemical versus physical) and the refining conditions have a significant influence on the level of free and esterified phytosterols. In the neutralisation process during chemical refining the free phytosterol content is lowered by 5-25%. Bleaching reduced both the level of free and esterified phytosterols. Only free phytosterols are distillated in the deodorization process and upon physical refining the steryl ester content is increased during deodorization, due to an esterification of free fatty acids and free phytosterols. Biofuels & Bio-energy

P38 Biodiesel: An economically viable petrol-fuel replacement JH Clark [1], B Datta [2], J Lovett [3], R Luque [1] & M Poudyal [3] Affiliations - [1] Department of Chemistry, Green Chemistry Centre of Excellence, University of York, York, UK; [2] Department of Economics and Related Studies, University of York, York, UK; [3] Environment Department, Centre for Ecology, Law and Policy, University of York, York, UK. Biodiesel is a sustainable, non-toxic, biodegradable fuel that is planned to be a major contributor to UK and global CO2-reduction targets. It is essential that the biodiesel life cycle is environmentally sustainable, economically viable, and socially acceptable. The projects' aim is the improvement of the biodiesel production process, economic viability and sustainability through developing greener and cleaner processes. A multidisciplinary team drawn from three York Departments (Environment, Chemistry and Economics) and a leading University in Spain is carrying out preliminary research on key issues including the socio-economic and environmental impacts of land conversion and the use of arable land to grow biodiesel feedstocks, evaluation of effects and importance of government regulatory policy issues involving a full scale theoretical cost-benefit analysis, and on green chemistry technologies to invent a more efficient and environmentally sound production process for biodiesel. Research on green chemistry technologies (supported materials, heterogeneous catalysis, microwave chemistry, etc) in order to replace the alkaline homogeneous catalysts and, increasingly, problems associated to the removal of inorganic salts and glycerol recovery, together with a dynamic economic analysis of the aspects mentioned above seems to be a promising research avenue. Through these studies we will ensure a successful triple bottom line for a better quality and more economically viable biodiesel.