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CONFERENCE HANDBOOK
RENEWABLE RESOURCES & BIOREFINERIES CONFERENCE6th – 8th September, 2006
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CONTENTSPage:
Delegate Information 4
VenueConference SecretariatRegistrationConference BadgesCar ParkingBedrooms
Conference Information 5
Meals & RefreshmentsSocial Events
Venue Facilities 6
PostBedroomsEmergency ProceduresReporting Accidents/IncidentsUrgent MessagesPhotocopying & Faxing FacilitiesBanksShopsBusesSports Facilities
Campus Map 7
Sponsors & Exhibitors 8
Exhibition Floor Plan 9
Exhibitors & Sponsors 10 - 13
Preliminary Programme 14 - 16
Speaker Abstracts 17 - 26
Poster Abstracts 27 - 37
Notes 38 - 40
We are delighted that you will be able to join usfor the conference at the University of York andtrust that you will have an enjoyable meeting.We hope that the information provided in thisdocument will help you get the most out ofyour time at the conference.
Venue
University of York Heslington York YO10 5DDTel: +44 (0) 1904 430000www.yorkconferencepark.com
Conference Secretariat
Kathryn Foster Procon Conferences Ltd Tattersall House East Parade Harrogate HG1 5LTTel: +44 (0) 1423 564488Fax: +44 (0) 1423 [email protected]
Registration
The registration desk will be situated in theGoodricke Dining Room on Wednesday andthereafter the registration desk will be situatedin the Exhibition Centre and will be open as follows:
Wednesday 6th September 14.00 – 19.00Thursday 7th September 08.00 – 18.00Friday 8th September 08.00 – 13.30
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DELEGATE INFORMATIONPlease ensure that you wear your ConferenceBadge at all times for security reasons.
Conference Badges:Delegate BlueExhibitors YellowRed Speakers/VIPsGreen Organisers/helpers
Car Parking
Cars may be parked in Campus Central, West,South or North car parks. Parking permits areavailable from the Conference Secretariat. If youhave not already purchased a parking permit,please contact the Secretariat using the contactdetails provided. Delegates with a pre-purchased parking permit must completethe information on their permit and display itover the front rear view mirror throughout theconference.
Please do not park in the staff car parks,as you will be asked to move your vehicle.
Bedrooms
Please see your booking confirmation for detailsof your allocated residence. Residential delegates can check in as follows:
James College Residents Please collect your keys from Goodricke CollegeReception. Tel +44 (0) 1904 433100
Meals
Breakfast – Residential delegates can take breakfast in the Roger Kirk Centre between 07.30 and09.00 hours each day.
Tea/Coffee Breaks – These will be served alongside the Exhibition in the Exhibition Centre
Lunch – These will be served alongside the Exhibition in the Exhibition Centre
Beer & Buffet on Wednesday 6th September – The beer tasting and buffet dinner will be heldin the Exhibition Centre from 19.00 - 22.00 hours.
Gala Dinner on Thursday 7th September - The Formal Conference Dinner will take placefrom 19.30 hours at the National Railway Museum. Coaches will be provided to the NRM and willbe returned to the University at the end of the night.
Drinks Reception on Friday 8th September – The drinks reception will take place alongside theExhibition in the Exhibition Centre from 15.30 hours – 18.00 hours.
Exhibition Opening Time
Wednesday 6th September 19.00 – 22.00Thursday 7th September 09.00 – 18.00Friday 8th September 09.00 – 18.00
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CONFERENCEINFORMATION
Post
All mail directed to you whilst staying at the Universityshould be addressed to: ‘Renewable Resources &Biorefineries Conference, Room P/T003, ExhibitionCentre, University of York, Heslington,York,YO10 5DD’
Bedrooms
Delegates may check in from 1400 hours on the day ofarrival. On the day of departure you are asked to vacateyour room by 0930 hours and return your keys to reception. Please note that there will be a charge of £10for any keys/swipecards not returned. Please note that allaccommodation is non smoking.
Luggage storage is available throughout the conference inGoodricke College. Please ask at Goodricke Reception.
All residential delegates are allocated a single study bedroom with en-suite facilities. All rooms have a 13 ampsocket and a shaver point, a hairdryer and an alarm clock.Rooms are serviced daily, beds made, bins emptied andwashbasins cleaned.Visitors are provided with a welcomepack containing soap and shower gel, cups and two towels. Coffee, tea, sugar and milk sachets are providedalong with a kettle in each room. Please remember toreturn your key to reception at the end of the conference.
Emergency Procedures
Visitors are required to familiarise themselves with theUniversity’s Emergency Procedures, which are displayedin each bedroom and in the main entrances to eachbuilding.
Reporting Accidents/Incidents
Should an accident, criminal act or suspicious incidentoccur on University premises it must be reported withoutdelay to the Security Centre (01904 434444) and in anemergency on 0800 433333. Internal calls to the SecurityCentre can be made on extension 4444 and extension3333 for emergencies.
For medical attention, please contact the porter/securitycentre. Each reception is equipped with a first aid box andSecurity staff are on duty 24 hours a day.
Urgent Messages
The 24 hour (urgent only) telephone number for theUniversity is 01904 430000. Callers must state the nameof the conference and asked to be put through to theBiorefineries Registration Desk. The fax number for the
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VENUE FACILITIESConference is 01904 434423. The recipients name andevent title and dates of the conference must be clearlystated. In an extreme emergency visitors can be contactedvia the Security Centre on 01904 434444.
There are coin boxes and card phones in each college foroutgoing calls. Private lines can be arranged on request,however these need to be booked well in advance.
Photocopying and Faxing Facilities
These are available in the Conference Support Office inP/T003 of the Exhibition Centre. This is staffed from 0815hours to 1715 hours weekdays and 0830 hours until 1700hours on weekends.
Banks
Barclays, Lloyds, HSBC and NatWest have branches nearby in Heslington Village, all with cash dispensingmachines.
HSBC Bank and the Co-op Bank have a cash –dispenseroutside Vanburgh College and Goodricke College respectively.
Shops
There is a Post Office in Heslington Village. The MarketSquare near Vanburgh College includes a supermarket,bookshop and other retail outlets.
Buses to York Centre
There is a regular bus service operating betweenHeslington Campus and York Centre (Route 4) at 10minute intervals from Monday to Saturday between 0800hours and 1800 hours. In the evening the service isreduced to half hourly intervals. Sunday service is hourly.Bus stops are located at close intervals along bothHeslington Lane and University Road.
Sports Facilities
The University has an extensive range of sports facilities.These will be open to delegates throughout the conference at a cost of £6 per hour. The opening hours are0800 hours to 2200 hours and inductions are available bybooking in advance. The induction will be waived if youalready have membership of a gym.
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CAMPUS MAP
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SPONSORS & EXHIBITORSThe University of York and the members of the Organising Committee would like
to thank the following organisations for their generous support of this Conference and Exhibition:
Green Chemistry Centre of ExcellenceUniversity of York
University of York
University of Gent
John H Wiley & Sons
Murgitroyd & Company
Royal Society of Chemistry
Enterprise & Innovation OfficeUniversity of York
Science City York
National Industrial Symbiosis Programme (NISP)
York Science Park ( Innovation Centre) Ltd
Central Science Laboratory
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Poster
Display
Poster
Display
Trade
Exhibition
Company Name: John Wiley & SonsContact Name: Kate JeromeAddress: The Atrium, Southern Gate, Chichester, PO19 8SQEmail: [email protected]: +44 (0) 1243 770179 Fax: +44 (0) 1243 770154
Visit Wiley at their Stand to pick up your free journal copies of:
The Journal of Chemical Technology and Biotechnology. Essential reading in all aspects of industrial and sustainabletechnologies. www.interscience.wiley.com/jctb
The Journal of the Science of Food and Agriculture. For the latest research in food science and agriculture.www.interscience.wiley.com/jsfa
Plus 20% discount* off all Wiley book titles on display (*discount valid up to 1 month post event).
Browse our complete range of book titles at www.wiley.com/chemistry
Company Name: Murgitroyd & CompanyContact Name: Douglas DrysdaleAddress: IT Centre,York Science Park, Heslington,York,YO10 5DGTel: 01904 567696
Murgitroyd & Company is one of Europe's larger firms of patent and trade mark attorneys, with over a total complement of 200, including over 70 technical staff, operating from 9 European offices.
Chemistry, Biotechnology and the Life Sciences are central to our practice, and our strong Chemical and Life Sciencesteam assists our clients, be they a university or global corporation, to build foundations of robust intellectual property todrive commercialisation and maximise investment return.
Company Name: Enterprise and Innovation Office, University of YorkContact Name: Andrew Tingey, Business Development ManagerAddress: The Innovation Centre,York Science Park,York,YO10 5DGEmail: [email protected]: 01904 435101 Fax: 01904 435101
The Enterprise and Innovation Office at the University of York makes the world class research base of the Universitymore accessible for real impact on the economy and the public good. All members of the team have recent businessand public sector experience and strong academic qualifications. The office is dedicated to working closely with companies and the public sector regionally, nationally and internationally, and builds long term strategic relationshipsfor mutual benefit.
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EXHIBITORS & SPONSORS
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Company Name: Royal Society of ChemistryContact Name: Dr Jeff HardyAddress: Burlington House, Piccadilly, London, W1J 0BAEmail: [email protected]: 0207 440 3395 Fax: 0207 734 1227
The RSC is the largest organisation in Europe for advancing the chemical sciences. Supported by a worldwide networkof 43,000 members and an international publishing business, our activities span education, conferences, science policyand the promotion of chemistry to the public.
The RSC regards the chemical sciences as critical to sustainable development.
The RSC Environment, Sustainability and Energy Forum provides leadership on health & safety, environmental chemistry, toxicology, hazard management, green chemical technology, energy and sustainability.
Company Name: Green Chemistry Centre of Excellence for IndustryContact Name: Dr Ashley WilsonAddress: Green Chemistry Centre, Department Of Chemistry,
University Of York, Heslington,York YO10 5DDEmail: [email protected]: 01904 432578 Fax: 01904 432705
Biodiesel Manufacturing Demonstrator Unit
The manufacture of biodiesel (methyl ester) directly from crops of used oils recovered from food manufacturingprocesses, is vital to the UK’s sustainable biofuel programme.
The Environment Agency (York) have sponsored Green Chemistry for Industry to build and exhibit a model biodieselmanufacturing plant for demonstration at exhibitions and conferences. The demonstrator will promote the use ofbiodiesel to motorists but also encourage farmers to consider growing biodiesel feedstocks.
Company Name: Green Chemistry Centre of ExcellenceContact Name: Professor James ClarkAddress: Green Chemistry Centre of Excellence, DepartmentOf Chemistry,University Of York, Heslington,York YO10 5DDEmail: [email protected]: 01904 432559 Fax: 01904 432705
Green Chemistry Centre of Excellence
The York Green Chemistry Centre is the first multidisciplinary academic organisation dedicated to creating genuinelysustainable supply chains for chemical and related products. The Centre will promote green chemistry solutions to themanifold chemical-related problems and challenges for the 21st century by working in partnership with manufacturers,producers, retailers and consumers. The Centre brings together industrial collaboration with research, education andthe promotion of green chemistry.
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Company Name: The National Industrial Symbiosis Programme (NISP)Contact Name: Malcolm Bailey Address: NISP Yorkshire, & Humber, Po Box 75, Grimsby, DN41 8WZEmail: [email protected]: 01469 569920 Fax: 01469 561113
The National Industrial Symbiosis Programme (NISP) is a FREE business opportunity programme that delivers bottom line, environmental and social benefits to its members and is the first industrial symbiosis initiative in the worldto be launched on a national scale.
Sometimes referred to as the advent of a second industrial revolution, industrial symbiosis asks businesses and otherorganisations to embrace new ideas, principles and technologies in the search for sustainable solutions to achieve economic success.
Committed to connecting industry and creating opportunity, NISP brings together companies from all business sectorswith the aim of improving cross industry resource efficiency. What makes NISP different to other resource efficiencyinitiatives is that it deals with all types of resource – materials, energy, water and supports the sharing of assets,logistics and expertise.
The Yorkshire & Humber programme is particularly committed to the active development of renewable resources andto the biorefinery concept through supply chain collaboration.
Company Name: Science City YorkContact Name: Steph MorrisAddress: 20 George Hudson Street,York,YO1 6WREmail: [email protected]: 01904 5544532 Fax: 01904 554429
Science City York is a government-funded organisation that provides a range of business and education support servicesto help the creation and growth of science and technology-based enterprises in York and North Yorkshire.The focus of its activities is in three technology-based sectors: bioscience, health and the environment; IT and digitalmedia; and creative, arts and heritage technologies.Science City York was launched in 1998 as a partnership between the City of York Council and the University of York.
Company Name: York Science ParkContact Name: Tracey SimmAddress: Innovation Way, Heslington,York,YO10 5DGEmail: [email protected]: +44 (0) 1904 435100 Fax: +44 (0) 1904 435135
Located within the University of York campus this 21 acre Business Park facilitates technology transfer and businessdevelopment by providing knowledge-based enterprises with purpose built facilities and direct links to the University.
There are over 100,000 sq ft of specialist facilities including the Innovation, Bio and IT Centres, making York the first UKScience Park to offer dedicated IT, bio and knowledge based incubation space on a single site supporting the development of start up, growth stage companies and big corporations alike.
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Company Name: Central Science LaboratoryContact Name: Melvyn Askew Address: Sand Hutton,York,YO41 1LZEmail: [email protected]: : +44 (0) 1904 462300 Fax: +44 (0) 1904 462029
CSL is the UK’s foremost public sector laboratory, underpinning agriculture, environment and food. It’s a world-classfacility with a worldwide business portfolio in public and private sectors, providing research, consultancy and servicingfunctions. As an Executive Agency of Department of Environment, Food & Rural Affairs, it was launched officially 10years ago, being developed from a number of well-established laboratories.
Company Name: Faculty of Bioscience Engineering Contact Name: Professor Chris Stevens Address: Faculty of Bioscience Engineering,Ghent University, Belgium Email: [email protected]: : +32 926 45957 Fax: +32 926 46243
The Faculty of Bioscience Engineering at the University of Ghent in Belgium contains a number of academic departments working on diverse aspects of Agricultural Science, Engineering, Biotechnology and related areas.The departments of Organic Chemistry and Molecular Biotechnology are especially active in the use of RenewableResources. Ghent hosted the first International Conference on Renewable Resources and Biorefineries in 2005 and have collaborated on the planning of this event in York.
Wednesday 6th September 2006
Thursday 7th September 2006
Time
15.30 – 17.00
17.00 – 19.00
19.00 – 22.00
Lecture Room – P/X001
Plenary Lectures
Right Honourable Michael Meacher MP, UK
Dr Wiktor RaldowHead of the New and Renewable Energy Sources Unit for the European Commision
Dr Uma ShaankerUniversity of Agricultural Sciences Bangalore, India
Tyler ElmSenior Director, Corporate Strategy, Wal-Mart Stores, Inc. (Via Video Link)
Exhibition Open, Beer Tasting and Buffet in Exhibition Centre, with Exhibition viewing time
Time
08.00
09.00 – 09.40
09.40 – 10.25
10.25 – 10.45
10.45 – 12.00 Session 1 (continued)
Professor George KrausIowa State University, USA
Dr Ray MarriotBotanix Ltd, UK
Dr Birinchi DasGauhati University, India
Poster / Exhibition Viewing Time - Lunch
Session 2 (continued)
Justin AdamsDirector - Long Term Technology Group
Technology, BP, UK
J P LangeShell Global Solutions, The Netherlands
12.00 – 13.30
Lecture Room – P/X001Lecture Room – P/L001
Keynote LectureP/X001
Dr John PierceDirector of Dupont Central Research Biological Sciences
Session 1Platform Molecules & Green Chemistry
Professor Colin WebbThe University of Manchester, UK
Dr Bob CrawfordDiscovery Platform Director Unilever
Research & Development, UK
Session 2Biofuels / Bioenergy
Jon VicaryDirector, Manco Energy Ltd, UK
Bamikole AmigunAdo-Ekiti University, Nigeria
Exhibition Viewing Time – Coffee Break
Registration - Goodricke College
Registration Open in Exhibition Centre
PRELIMINARY PROGRAMME
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Professor James H ClarkSession Chair
Simon NewtonSession Chair Professor Chris Stevens
Professor James H ClarkSession Chair Professor Chris Stevens
Professor James H ClarkSession Chair
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Thursday 7th September 2006 (Continued)
Time
Session 5Fermentation and Metabolic Engineering
Professor Wim SoetaertFaculty of Bioscience Engineering, Ghent
University, Belgium
Dr A JainBiotechnology, ICFAI University, Delhi, India
Dr Pauline TeunissenManager Grain Processing Applications &
Technical Support, Genencor International B.V.
Session 6Biopolymers (& Fibres) / Biomaterials
Professor Dr Alexander SteinuchelUniversity of Munster, Germany
Professor Vladimir StrelkoNational Academy of Sciences of Ukraine,
Kiev, Ukraine
Mark LewisManager, Program Operations, College of
Forest Resources, University of Washington
Lecture Room – P/X001Lecture Room – P/L001
Session 3Biorefineries
Professor Johan SandersWageningen University, The Netherlands
Dr Srinivas KilambiPresident, Bio Refinery
Reliance Industries Limited, India
Dr Rafael LuqueDepartment Of Chemistry,The University Of York, UK
Dr Jeff HardyManager Environment, Sustainability and
Energy Forum, Royal Society of Chemistry, UK
Session 4 Biofuels / Bioenergy
Dr John LovettEnvironment Department,
University of York, UK
Dr David TurleyCentral Science Laboratory,York, UK
Dr Pasquale PazienzaEconomics Department, University
of Foggia, Foggia, Italy
Investment speaker to confirmed
Professor Ian GrahamSession Chair Mr David Turley
Professor Wim SoetaertSession Chair Dr Chris Henshall
13.30 – 14.00 Keynote Lecture
Dr Steffen DaebelerVice-Managing Director, Agency for Renewable Resourses (FNR), Germany
Dr Chris HenshallSession Chair
14.00 – 15.30
Exhibition Viewing Time – Afternoon Tea Break15.30 – 16.00
16.00 – 17.30
Keynote LectureP/X001
Dr Hosein ShapouriUSDA / Office of Energy Policy and New Uses, USA
17.30 – 18.00
Dr Andrew TingeySession Chair
Conference Dinner at National Railway Museum19.30 – 23.00
Friday 8th September 2006
Time
Session 9Young Researchers
Miss DS PertiwiUniversity of Manchester, Manchester, UK
Mr J PeydesastaingENSCIAET, Toulouse, France
Mr Robin WhiteDepartment of Chemistry
University of York,York, UK
Session 10Chemical Products
Professor Chris StevensFaculty of Bioscience Engineering,
Ghent University, Belgium
Jack GrushcowPresident, Linnaeus Plant Sciences Inc.
Dr Joe MazzaPacific Agri-food Research Centre, Canada
Lecture Room – P/X001Lecture Room – P/L001
Session 7- P/X001Bioresources 1
Clifford SpencerChairman, Springdale Group, UK
Professor W PraznikBOKU - University of Natural Resources &
Applied Life Sciences Vienna, Austria
Christophe Rupp-DahlemRoquette Freres, France
Session 8 - P/L001Bioresources 2
Dr Mehrdad ArshadiSwedish University of Agricultural Sciences,
Umea, Sweden
Professor Andy ProctorUniversity of Arkansas, USA
Dr SF CurlingBiocomposites Centre, Bangor, Wales, UK
Dr Andrew TingeySession Chair Dr Alistair Boxall
Dr Jeremy TomkinsonSession Chair Professor Chris Stevens
09.00 – 09.30 Keynote Lecture
Gerhard IsenbergFormerly DaimlerChrysler
Professsor James H ClarkSession Chair
09.30 – 10.30
10.30 – 10.50
10.50 – 12.00
Keynote LectureP/X001
Professor Charles PerringsProfessor of Environmental Economics & Environmental Management,
Arizona State University, USA
13.30 – 14.00
Session Chair
Final Reception15.30 – 18.00
Exhibition Viewing Time – Coffee Break
Poster / Exhibition Viewing Time - Lunch(including poster session by MRes in Clean Chemical Technology students)
12.00 – 13.30
Professsor Wim SoetaertSession Chair
Session 11Biocatalysis
Professsor Neil BruceCNAP, University of York, UK
Professor Lene LangeNovozymes, Director, Molecular
Biotechnology
Session 10Chemical Products (Continued)
Dr Duncan MacquarrieUniversity of York, UK
Dr A Van Der BentAgrotechnology and Food Sciences Group,
Wageningen UR, The Netherlands
14.00 – 15.00
Professsor Wim Soetaert Dr Alistair Boxall
15.00 – 15.30 Closing remarks
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SPEAKER ABSTRACTSPlenary LecturesWednesday 6 September 17:00 – 19:00 PX/001
Right Honourable Michael Meacher, MPHouse of Commons, London, UK.
The huge potential for renewables to fill the looming energy gapis greatly underestimated. As the world fast approached peak oilin 5-10 years time, renewable sources of energy, at this stage particularly windpower, have more than enough capacity to meetthe entire electricity generation requirement of the three maincontinental blocs - the US, the EU and China.There is an urgent need to tackle the barriers hindering thedevelopment of renewables, particularly the lobbying power ofthe big vested interests. Much more can and should be done toprovide a more favourable fiscal climate, especially by phasingout 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 developmentof decentralised energy systems, especially microgeneration plantfor 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 andpalm oil currently produce the most litres of fuel per hectare.By contrast the next-generation of biofuel feedstock comprisescellulose-rich organic material, which is harvested for its totalbiomass. It includes not only woody crops and tall perennialgrasses, 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, forestprotection programmes, and biodiversity. In the least favourablescenarios however, bioenergy could supply only a fraction of current energy use by 2050. Also if biofuels are produced withheavy inputs of fossil energy, they have the potential to generateas much or more greenhouse gas emissions as petroleum fuelsdo. Ultimately, net energy per hectare, after deducting energyinput, will be the most important measure from a resource perspective.
Dr Wiktor Raldow Head of the New and Renewable Energy Sources Unit forthe European Commission
Dr Uma Shaanker University of Agricultural Sciences Bangalore, India
Tyler ElmSenior Director, Corporate StrategyWal-Mart Stores, Inc. (Via Video Link)
Keynote LectureThursday 7 September09:00 – 09:40PX/001
Dr John PierceBiotechnology and our material futureDirector of DuPont CR&D, Wilmington, USA.The use of biotechnology for the production of chemicals andmaterials of industrial value is beginning to emerge as a majoreconomic force. Driven by continuing improvements in the efficiency of agricultural production, which provides the necessaryraw materials, and the exploding knowledge base of DNA structure and biotechnological tools, the biological production ofvery large volumes of important chemicals and materials fromrenewable resources is becoming a reality. These materials arefinding 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 learnhow to incorporate biological principles into truly multidisciplinary approaches with engineering, chemistry,physics, and material sciences-disciplines with long, successfulhistories of innovation. As we do so, we will improve our capacity to utilize renewable resources and renewable concepts inthe production of materials, and will take a major step towardensuring a sustainable future.
Session 1: Platform Molecules and Green ChemistryThursday 7 September09:40 – 12:00PL/001
Dr Bob CrawfordDiscovery Platform DirectorUnilever Research &Development, UK
A1Epoxidation of alpha-pinene mediated by cobalt(III) catalystsR 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, UKUse 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 arewidely distributed in nature, are of particular importance from thefact 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 andmany fragrances. Thus, oxyfunctionalisation of alpha-pinene isan important reaction. Herein we describe the use of a cubane-like Co(III) complex (B) as an autoxidation catalystfavouring the formation of the epoxidised product under
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environmentally benign conditions. The cluster complex B withR = CH3, Co4(O)4(O2CCH3)4(py)4 has been examined as acatalyst for the autoxidation of alpha-pinene under homogeneous as well as heterogeneous conditions.Homogeneous air oxidation of alpha-pinene under atmosphericpressure results in high selectivity for alpha-pinene oxide inpreference over allylic oxidation products. The selectivity foralpha-pinene oxide at the highest conversion of 81% (TON =2,520) observed at 100 deg C is 68%. A heterogeneous catalystprepared by immobilizing the above complex on chemicallymodified 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% selectivitytowards aplha-pinene oxide is observed at 81.5% substrate conversion in a liquid phase reaction.
S1Green Extraction and Reactions in Supercritical CO2.R MarriottBotanix Ltd.The application of supercritical and liquid CO2 to carry out selective extraction of a wide range of molecules and groups ofmolecules is well established for some products but is less wellknown for many others. As this is now a mature technology areview of current industrial applications and potential new applications will be given focussing on those areas where conventional solvent extraction has been completely replacedand new applications where the use of extraction with CO2 couldbring technical and environmental benefits. Supercritical CO2has also been adopted as a reaction medium and some industrial processes have already been established. However oneof the ultimate applications of supercritical and liquid CO2 iscatalysis of reactions using biocatalysts either in the form ofwhole cells or isolated enzymes. A number of these applicationswill be presented and the future potential and barriers to the useof this technology discussed. Finally the use of a combination ofselective extraction and biocatalytic reactions to create a uniquebiorefinery will be explored.
S2Green Chemistry Approaches to Biodiesel and PropanediolGA Kraus & VSY LinChemistry, Iowa State University, Ames, IA.The idea of a biorefinery is modeled after the oil refinery wherein petroleum is converted into gasoline, oil, and monomerssuch as ethylene and propylene. They produce high volumechemicals (such as gasoline and diesel), plus a number of lowvolume, high value materials. Unlike petroleum refineries, corngrain and soy biorefineries are in their early stages of development. For biorefineries to be successful on a long-termbasis, they must produce: 1) high volume fuels such as ethanol orbiodiesel; 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 thesoybean oil into biodiesel by treating the oil with methanol and a
catalyst. We have developed catalysts for this conversion that areheterogeneous, recyclable, and significantly lower the cost ofmanufacturing biodiesel. The by-product of this reaction is glycerol, a hygroscopic triol. Glycerol must be converted intohigher-value chemicals that can replace petrochemicals. One suchchemical 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 thirdis propylene glycol which is used as an antifreeze and an airplanede-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 siliconchips is an effective reagent to convert glycerol into 1,3-propanediol.
Session 2: Biofuels and Bio-energyThursday 7 September09:40 – 12:00PX/001
Jon VicaryDirector, Manco Energy Ltd, UK
Justin AdamsDirector – Long Term Technology Group Technology, BP,UK
A2Commercialisation of biofuel industry in Africa: a reviewB Amigun [1], R Sigamoney [2] & H von Blottnitz [1][1] Environmental Process System Engineering ResearchUnit, Department of Chemical Engineering, University ofCape Town, Rondebosch, South Africa; [2] Research GroupI 'Future Energy and Mobility Structures', WuppertalInstitute for Climate Environment Energy, Postfach 100 480,Wuppertal, Germany.Energy is a key factor in industrial development and in providingvital services that increase prosperity and improve the quality oflife. However, its production, use, and byproducts have resulted inmajor 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 developmentand prosperity to continue through gains in energy efficiencyrather than increased consumption and a transition towards theenvironmentally friendly use of renewable resources.The production of modern, clean biomass-derived fuel in theAfrican 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 demandcompared to the dwindling convertible currency earning and rising evidence of climate change. Amongst these is the lack of agood understanding and application of key concepts of cost estimation-a key to successful project which impacts both theproject profitability and influences the technical solutions.Existing methods have limited applicability and on many occasions disappointing accuracy because of the inappropriatenature of the estimating techniques. The problems of inaccessibility, pollution and unaffordability of energy which isregarded as an integral part of our existence can be alleviatedthrough the development and commercialization of alternativeenergy sources. Understanding the economics of biofuel industryis crucial in realising eventual commercialisation.
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This presentation provides knowledge-based review for expanding (commercialization) of biomass derived fuel (biofuel)through improved understanding of its economics.
S3The Chemistry and/or Economics of biomass conversionJP LangeShell Global Solutions, Amsterdam, The Netherlands.Governments across the world are stimulating the valorisation of local biomass to secure the energy supply, reducethe CO2 emissions and support the rural economy. A 1st generation of fuels and chemicals are presently produced fromhigh-value sugars and oils. Meanwhile, a 2nd generation, basedon cheaper and more abundant lignocellulosic feedstock, isbeing developed. The present paper could review (1) the typicalchemistries and processes required for converting lignocelluloseand/or (2) the manufacturing economics of biomass conversion.As for the chemistry of lignocellulose conversion, we will showthe need to 'deoxygenate' the biomass to produce biofuels withgood energy density and fuel compatibility. We will then reviewthe main conversion routes by discussing the basic chemistryinvolved and presenting one emerging process for illustration.These routes include* the pyrolysis to char, bio-crude or gas, illustrated by BtG'sprocess for wood Pyrolysis,* the gasification to syngas and its subsequent conversion toalkanes or methanol, illustrated by BtL process developed jointlyby CHOREN and Shell,* the hydrolysis to sugars and their fermentation or chemicalderivatives (e.g. ethanol, biogas, glycols and levulinic acid),illustrated by Iogen's process for lignocellulosic ethanol.The economics of the biomass conversion processes discussedabove could be discussed to illustrate why the production costs ofbiofuels 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 thecost of the plant, and* the value of the product, which increase in the order of: bio-crude < transportation fuels < power < chemicals.
Keynote LectureThursday 7 September 13:30 – 14:00PX/001
Dr Steffen DaebelerIndustrial and energetic use of Biomass in Europe andGermanyVice-Managing Director, Fachagentur NachwachsendeRohstoffe e.V. (FNR), Gülzow, Germany.The total area of the EU-25 is 397.3 million ha, from which 98.4million ha (25%) are arable land and 148 million ha (37%) areforest. Germany has a total area of 35.7 million ha, from which11.8 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 significantlyincreased: 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 fornon-food crops in Germany is far more than in the EU. Thus, theshare of non-food crop land 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-derivedproducts and one third are used as bioenergy.
Currently, about 17 million tons of petrochemical and 2 milliontons of renewable raw materials are used in the German chemicalindustry, i.e. roughly 10% of the raw materials are RRM.Bioenergy is an imported area for the use of biomass. About 286PJ/a (2004) energy are currently bioenergy in Germany.The R&D and market launch funding regarding to renewableresources is coordinated at the federal level in Germany by theAgency for Renewable Resources on behalf of the FederalMinistry of Consumer Protection, Food and Agriculture (BMVEL).The main task of the FNR is the technical and administrative R&Dproject supervision. Furthermore, the FNR organises symposiumsand participates in fairs in order to promote the use of RRM.
Session 3: BiorefineriesThursday 7 September14:00 – 15:30PL/001
A3Creating new energy platforms for reliance bio-refinerySK Shrivastava, S Kilambi, PK Sarode, S Japtiwale & SBhowmikReliance Industries Limited, Navi Mumbai, India.Energy consumption has increased exponentially over the last 2decades as the world economy has grown and more countrieshave become industrialized. Crude oil, a non renewable resource,has been the major source to meet the increased energy demandso far. The limited crude oil supply will be exhausted in the nearfuture 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 alternativerenewable & sustainable energy sources such as Biofuels, Solar,Wind, Geothermal etc. Biofuels are derived from followingsources: Bio-Ethanol from fermentable carbohydrates (e.g. sugarcrops, fodder beet, fruits, grains, cassava, sweet potato/sorghumetc). Bio-Diesel from various edible and non-edible oils (Palm,rapeseed, coconut, soya, jatropha etc) Bio-Ethanol from Cellulosicmaterials (corn stover, wheat/rice straws, bagasse, vegetable biomass etc) Presently Bio-Ethanol is manufactured globally viaeither grain route or sugar route, which is a part of human foodchain.Some third world countries are still facing problems regardingsourcing of food for the people. Hence Reliance is planning to setup Bio-Refinery which would use the agro-energy synergy andconvergence 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 resultin 2 to 3 times enhanced yield of grains, sugars and also cellulosicbiomass. Grains and sugars will be dedicated for human consumption while part of the biomass will be used for animalfeed and majority as the source of biofuels such as ethanol,butanol, MTHF, Hydrogen etc.
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A4Platform Chemical Production from Low Cost SustainableRaw MaterialsR 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 ofExcellence, The University of York, York, UK; [2] SatakeCentre for Grain Process Engineering, School of ChemicalEngineering and Analytical Science, The University ofManchester, Manchester, UK.Depletion of petroleum and escalating environmental concernscreate a need for novel sustainable routes for the production ofcommodity and specialty products with similar or advancedproperties as compared to petrochemically derived one.Nowadays, renewable agricultural carbohydrates and exploitation of biological systems emerge as the main streamtowards 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 bedependent 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 ourresearch focuses on the development of low environmentalimpact synthetic methodologies for production of value-addedsuccinic acid derivatives. Succinic acid is recovered from a complex multi-step processing technology that involves threestages of bioprocess, namely upstream processing, bioreactionand downstream processing. Selection of succinic acid as a highly promising platform molecule can be strengthened byrecent 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 criteriausing heterogeneous catalysis (where catalysts are required),benign reaction media, minimal use of auxiliaries and minimalenergy requirements (with application of microwave irradiation).1 Paster, M., Pellegrino, J. and Carole, T.M., 2003, IndustrialBioproducts: Today and Tomorrow, Report Number Columbia,Maryland).2 Petersen, G. and Werpy, T., 2004, Top Value Added ChemicalsFrom Biomass, Report Number USA).
S4Chemistry and Sustainable EnergyDr HardyRoyal 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 growingdemand for energy whilst actively reducing anthropogenic carbon emissions? What role will the chemical sciences play indelivering this scenario? The Royal Society of Chemistry hasplayed an active role in the recent energy review in the UK andcontinues 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 todemonstrate that the chemical sciences underpin almost all energy technology options. In particular the presentation willexamine 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 andaddress climate change?
S5Biorefinery, the bridge between agriculture and chemistryJ SandersDepartment of Valorization of Plant Production Chains,Wageningen University and Research Centre, Wageningen,The Netherlands.Economic factors, such as costs increases of oil, connected to thedepletion of mineral resources, and environmental considerations, such as the negative impact of CO2 emissions, hasled to interest in the use of renewable resources as feedstocks fortransportation fuels, energy (heat and electricity) and chemicalproducts. When used in combination with environmentally soundproduction and processing techniques, the use of biomass can beseen as a sustainable alternative to conventional feedstocks.In the Netherlands a Governmental Committee on RenewableResources has designed a plan how to substitute 30% of theDutch fossil raw materials by biomass in the year 2030. Obviouslya lot of the biomass will have to come from abroad, but strategiesto optimize the use of the biomass that is already used every yearmight limit the additional area to about the size of theNetherlands. 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 biomassstructure in a much better way than the production of fuels orelectricity from biomass can do.The production of chemicals frombiomass saves more fossil energy than producing just energy frombiomass! This is reflected by sound economic advantages as wellin raw material cost as in investmentcosts.To develop technologically sustainable routes, the whole chain ofbiomass 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 bulkchemicals and thereby obtaining the highest value from biomass by knowledge intensive technologies that can be patented. Several examples will be shown amongst others thefractionation of grass, sugarbeet, Cassava. Some amino acids arevery suitable starting materials for highly functionalized petrochemicals. Economical production routes of chemicals frombiomass require large scale substitution of bulk chemicals andconnection to current approaches and facilities (process integration) of the petrochemical industries to convert crude oilinto 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 palmwill supply an additional amount of protein around 100 milliontonnes/year if these biofuels will substitute 10% of the fueldemand.Genetic modification of plants will increase the potential of biomass to chemicals because of increase of theconcentrations ofthe actually present biochemicals that can serve as precursors forbulkchemicals. Also it will be addressed that small scale (pre)processing of the biomass can give advantages over large scaleprocessing because of less transportation costs but also because ofthe opportunity to use process-integrations that can not be usedon large scale. These integrations will yield high efficiencies ofenergy utilization but can be improved on social or organisational levels. The biorefinery of biomass will offer neweconomic opportunities for the Agriculture and the Chemicalindustry by the production of a world of chemicals, transportationfuels and energy.
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Session 4: Policy and Investment IssuesThursday 7 September 14:00 – 15:30PX/001
Dr Jon Lovett Environment Department, University of York, UK
A5Issues arising in use of biomass derived materials for energy and industryD Turley Agricultural and Rural Strategy Team, Central ScienceLaboratory, York, UK.The returning interest in use of crop-derived materials as feedstocks for energy production, industrial materials andchemisty, as well as in traditional uses in pharmacology andhealth and well being, is leading to an expansion in demand fornon-food crops. In some cases these may be existing arable cropsused to produce oil, starch and sugar, in other cases they may benative crops developed for specialist uses (e.g. for fibre), or inother cases non-native species introduced to fulfil specific needs(eg biomass for energy). In each case there will be differingimpact on the farming environment and a trade off in terms ofimpacts due to differences in crop management. There areincreasing concerns about the impacts that such rapid changecould have on the environment.The rapid development of liquidbiofiel markets is leading to a rapid expansion in oil crops, bothin the EU and in tropical oil production - with concerns over theintensity of arable cropping and loss of uncultivated land, and inloss 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 onland availability and the issues of increasing competition on landfor food and non-food uses.The issues and concerns arising from such changes will behighlighted but also the potential gains and contributions thatnon-food crops can make to issues such as reducing greenhousegas emissions and socio-economic impacts such as retaining landin agricultural production and increasing opportunities for ruralemployment. 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 bemanaged to maintain consumer and market confidence.
A6Is an excise tax on bio-diesel economically acceptable? Adiscussion.Dr De Lucia Caterina [1] & Dr Pazienza Pasquale [2][1] Environment Department, University of York, York, UK;[2] Economics Department, University of Foggia, Foggia,Italy.The aim of this paper is to discuss the validity of subsidizing theconsumption of bio-diesel fuels in terms of public health expenditures re-allocation due to improvements in health (respiratory diseases). We compare actual effects on healthcaused by SO2 and NO2 emissions of oil fuels and bio-dieselfuels for a panel of European countries. Current literature suggests an increase of NO2 is offset by a substantial decrease inSO2 emissions when bio-diesel consumption is adopted. Basedon this evidence we argue in favour to the adoption of financialincentives to bio-diesel production / consumption rather than theexisting use of excise taxes.
Investment Speaker to be confirmed
Session 5: Fermentation and MetabolicEngineeringThursday 7 September 16:00 – 17:30PL/001
Prof Wim SoetaertFaculty of Bioscience Engineering, Ghent University,Belgium
A7Pilot scale optimization of phytase production byAspergillus niger in solid state fermentationA JainBiotechnology, ICFAI University, Dehradun, India.Pilot scale optimization of phytase production by Aspergillusniger in solid state fermentation A wild type soil isolate ofAspergillus niger was used to produce extracellular phytase inpilot scale solid state fermentation unit.The strain was acclimatized to grow on wheat bran (WB) as solenutrient source. The optimum fermentation conditions weredetermined to be substrate moistened with tap water 28degreescelcius, 90% or more relative humidity and 4 days incubation. Thefungal strain produced two phytases with pH optima 1.8 and 5.0respectively. Both the enzymes were stable upto 60 degrees celcius. For direct use of the fermented mass in the poultry feedwe initially harvested the enzyme before it reached the maximumactivity to avoid sporulation.Later on we developed a medium whereby a part of wheat branwas replaced by soybean meal (SM) or groundnut oil cake (GOC).The latter proved to be a good supplement for increasing enzymeactivity and more importantly it delayed the sporulation which isconsidered to be because of high oleic acid content of groundnuts.To a mixture of WB and GOC addition of glucose and ammoniumnitrate further increased enzyme activity without sporulation,reproducibly.Key words: Solid state fermentation, Aspergillus niger, Delayedsporulation, Phytase, Pilot scale production, Phytic acid, Wheatbran, Groundnut oil cake.
Dr Pauline TeunissenManager Grain Processing Applications& TechnicalSupport,Genencor International B.V.
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Session 6: Biopolymers (& Fibres) / BiomaterialsThursday 7 September16:00 – 17:30PX/001
S6Polymeric and low molecular weight hydrophobic chemicals produced by microorganisms from renewablesA Steinbuchel Institut fur Molekulare Mikrobiologie undBiotechnologie, Munster, Germany.Microorganisms are capable of synthesizing a wide range ofhydrophobic substances which often serve as reserve compoundsfor carbon and energy and are accumulated as inclusion bodies inthe cells. Most bacteria are able to accumulate lipophilic storagecompounds 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 keyenzymes of TAGs and WE synthesis are promiscuous wax estersynthases/acyl-CoA:diacylglycerol acyltransferases (WS/DGAT),whereas PHAs are synthesized by unspecific PHA synthases.Since WS/DGAT is a very unspecific enzyme, which transfersthe acyl-moiety of various acyl-CoA thioesters to many differentalcohols and other hydroxylated compounds and even to thiols,a wide range of different lipids may be synthesized by theseenzymes in vivo in engineered bacteria. Similarily, PHA synthases are capable of polymerizing a wide range of differenthydroxyfatty acids and even mercaptofatty acis yielding polyoxoesters or polythioesters, respectively. Such bacteria aretherefore useful catalysts for conversion of renewable resourcesprovided by agriculture or forestry as well as of residual compounds derived from the latter into polymers and lipids fortechnical applications in various areas.
S7Novel carbonaceous and inorganic catalysts for proton transfer reactionsV 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 suchgroups in carbons, produced from fruit shells far exceeds (pK~2)the acidity of carboxylic cationites (pK~2.5). It is likely due to thefact that pi-electrons of oxygen atoms, forming the surfacegroups in carbon, are very much delocated by the pi-conjugatedsystem of the graphite-like planes. It reduced the effective negative charge on oxygen and, as a result, the mobility of protonincreases and, therefore, -OH and -COOH groups become moreacidic.It is worth to be noted that in the case of synthetic oxidized carbons, which possess much more perfect (almost withoutdefects) structure of pi-conjugation in the system of graphiticplanes, the acidity of surface group even more (pK~1) as far as inthis case the delocalisation of electrons (pi-electrons of oxygen) ismostly expressed. To understand the general principles of catalysis by oxidized carbons in reactions of etherification westudied in details kinetics and mechanism of synthesis of buthyl
acetate in gaseous phase in the wide range of temperatures (150-450 oC) using the H+-modifications of oxidized carbons, aswell as reaction of hydrolysis for some ethers and lipids. In thepresentation the data about new 'sol-gel' method for synthesis ofspherically granulated porous titanium and zirconium oxides aswell prepared on their base by sulfatation new catalysts of protontransfer with controlled porosity and surface chemistry are introduced. It is also presented results, which demonstrate theprospective application of these materials in reaction of fineorganic synthesis (pharmaceutical) and reetherification of vegetable oils (biodiesel).
Mark Lewis ManagerProgram Operations, College of Forest Resources,University of Washington
Keynote LectureThursday 7 September 17:30 – 18:00P/X001
Dr Hosein ShapouriUSDA/Office of Energy Policy and New Uses, USA
Keynote LectureFriday 8 September09:00 – 09:30PX/001
Gerhard IsenbergThe Environmental Academy, (Die Umwelt Akademie),Munich, Germany.Increasing energy demand will also in the next decades mainly becovered by fossil energies.Limited resources esp. of hydro-carbonswill require solutions to close the expected gap between increasing demand and available resources. These requirementswill be supported by fossil-energy-influenced augmenting ofgreen-house-gas-emissions.Besides energy saving and most efficient use of energy the challenge will be the development andmarket introduction of renewable energies 'just in time'. Fossilbased energy-supply will under long-term-aspects not be sustainable.
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Session 7: Bioresources 1Friday 8 September 09:30- 10:30PX/001
Clifford Spencer Chairman, Springdale Group, UK
S8Starch glucans: Molecular and SupermolecularCharacteristics in Aqueous Systems
W Praznik [1], R Loeppert [1] & A Huber [2][1] Department of Chemistry, BOKU - University of NaturalResources & 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 supermolecularstructures which hardly may be distinguished from constitutingindividual polymer molecules. However, these aggregates are notcovalently bound but dynamically H-bond fixed and any time theresult of varying kind and magnitude of applied stress to theaqueous glucan system. Hence, typically observed structuresrather are due to interaction phenomena than to individual molecule mass and geometry. As modern absolute analyticalapproaches, in particular light scattering techniques, are dominated by minor contents of supermolecular componentsobtained results primarily reflect present aggregates and additionally come up with high fluctuations. An approach whichis independent on supermolecular structures - quantitative labeling of the unique terminal hemiacetal groups on each glucan molecule combined with determination of mass andmolar glucan concentrations - provides information on de facto molecular dimensions of individual starch glucans.Combination of SEC-separation with detection of refractiveindex (mass), fluorescence (labeled hemiacetals), scatteringintensity (apparent molar mass of aggregates) and viscosity(excluded volume)provides distributions of molecular and supermolecular starch glucan characteristics, finally. Results fromdifferent starch glucans such as non-branched alpha(1,4)-glucan(amylose synthesized by potato phosphorylase), short chainbranched glucan (alpha-amylase hydrolized waxy maize starch)and a mix of non/long chain branched and short chain branchedglucans (native potato starch) will be presented and discussed.In particular, the influence of different solvent system onobtained apparent molar mass distribution will be illustrated.
S9New Cereal based Bio-refinery: new initiativesC Rupp-DahlemRoquette Freres, Lestrem, France.Vegetal-based chemistry is definitively one of the most promisingapproaches to achieve sustainable development for the future.Vegetal-based chemistry is the use of renewable raw materialsfrom vegetal agriculture, such as corn, to produce for examplebio-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 theproduction of such chemical entities. An example of this vegetal-based chemistry is the current corn bio-refinery, whichimplements biological and chemical reaction steps to produce awide range of products including starch, glucose, sorbitol andsome sorbitol derivatives like isosorbide. This new concept ofbiorefinery is financially supported in France by the IndustrialInnovation Agency (AII) whose objectives are to select
significant, innovative programmes (minimum 50 million eurosper programme). One of the first programmes selected by thisAgency is the BioHub(trademark)programme. The target of theBioHub(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 IndustrialCompanies and Scientists. Some of these projects covered in theBioHub(trademark) programme are described in more detail asfollows : Isosorbide as a substitute for diols for polyesters ;Dimethyl Isosorbide as a green solvant.The BioHub(trademark)initiative is an excellent example ofEuropean collaboration between new biotech. start-up, mediumand large enterprises and scientists. Such collaboration is necessary to enable the chemical industry to become more sustainable.
Session 8: Bioresources 2Friday 8 September 09:30 – 10:30PL/001
A8Photocatalytic production and use of conjugated linoleicacid-rich soy oilA Proctor & VP JainDepartment of Food Science, Univeristy of Arkansas,Fayetteville, AR, USA.Conjugated linoleic acid (CLA) (cis/trans; trans/cis)) is a productof 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 bovinemeat products which are also a source of undesirable saturateddietary fat. Alternative means of obtaining CLA by chemicalsynthesis and fermentation have been explored but involve extensive purification steps and use of reagents with variableyields 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 wasmuch greater than found in dairy and beef products, the majorityof the CLA isomers produced were trans/trans, which also havevaluable nutraceutical properties. The cis/trans and trans/cis isomers are the initial products of photisomerization but rapidlyform the more thermodynamically stable trans/trans isomers.There was little indication of lipid oxidation during processingthat is probably due to the conversion of alpha linoleic acid whichis highly prone to oxidation. The iodine can be removed from thesoy oil by conventional adsorption processing without CLA loss.The oil was used in frying operations make high-CLA potatocrisps (chips), whose oil content was similar to that of the freshoil. Future will address reducing the processing time,identification of possible minor iodo-compounds and study of theapparent improved oxidative stability of the novel high CLA/ lowalpha linoleic soy oil.
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S10Determination of Volatile Organic Compounds EmittedFrom Softwood Pellets During StorageM ArshadiSwedish University of Agricultural Sciences, Unit ofBiomass Technology & Chemistry, Umea, Sweden.Today more than one million tons of wood pellets are producedin Sweden per year. Despite their advantages it has been shownthat during storage, volatile organic compounds (VOCs) areformed due to self-heating and auto-oxidation of lipids. Whenthe lipids in wood materials are subjected to auto-oxidation,odorous compounds such as aldehydes and carboxylic acids areformed. These compounds can lead to a bad smell and otherquality problems, contributing to an unsatisfied consumer. Todetect and minimize the amount of the compounds which areresponsible for these quality disturbances in pellets production,we have used a full factorial experimental design in a large-scalepellets production company. By this method we have been ableto change process parameters in a rational and systematic wayand detect where in the production chain these undesired compounds have been formed.Pellets produced by different process parameters have differentqualities which allow us to identify the most optimal processparameters in order to make pellets with the best quality.Fuel pellets made from fresh and stored Norway spruce and Scotspine sawdust were produced and investigated for the emission ofVOC. The measurements were performed using emission chambers placed in an oven in order to simulate the high temperatures that occur during storage. A large amount of air waspumped through the pellets and samples were taken consecutively throughout a several hour period to establish anemission profile.An absorptions sampling technique followed by HPLC/UV andMS detection analyses made identification of the aldehydes possible. Our investigations illustrated that wood pellets madefrom stored sawdust generate less VOC than pellets made fromfresh sawdust. We found that pellets made from spruce sawdustemit less VOC than pellets made from pine sawdust. We alsodetermined the impact of other process parameters on pelletsquality.
A9Characterisation of Gel Properties of Hemicellulosederived from TimberSF Curling [1], CAS Hill [1] & P Fowler [2][1] School of Agricultural and Forestry Science, Universityof Wales Bangor, United Kingdom; [2] BiocompositesCentre, Bangor, Wales, United Kingdom.Timber can be used as a sustainable source for process chemicals,silvichemicals and as a source of chemical feedstocks. Researchshould be directed towards materials with exploitable propertiesand 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 gelfrom sitka spruce. To enable exploitation of the hemicellulose,various forms of the gel have been characterised and are detailed.Possible uses are also discussed.
Session 9: Young Researchers Friday 8 September 10:50 – 12:00PL/001
A10Simulation for Product Selection in Developing PotentialBiorefineriesDS Pertiwi & PN SharrattChemical Engineering and Analytical Science, University ofManchester, Manchester, United Kingdom.Biorefineries have been increasingly investigated since about adecade ago. They are envisioned as part of the infrastructure toreplace oil refineries as oil runs out. There have been some innovative findings to employ renewables as alternative rawmaterials, but more demonstration projects are needed to showthe process feasibility.There are several problem levels that should be considered inselecting potential biorefineries, e.g raw material selection,process and product selections, and eventually equipment selection. The whole integrated process should be projected to bethe best biorefinery in economic and technical aspects and mustbe environmentally friendly. A simplified process simulation forbiorefinery assessment has been proposed in this study usingsolver in the Microsoft Excel software. A case study has been usedas 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 theamount of remaining feed and potential waste. A number of scenarios are analysed to identify the relativity between productslate, product value, and the implication of technologies deployedin the biorefinery. The outcome of the assessment is found to besensitive to product value and process yield/efficiency.
A11Acetic-fatty anhydrides to increase wood stabilityJ Peydecastaing & C Vaca_GarciaLCAi, Ensiacet, Toulouse, France.Dissymmetric acetic-fatty anhydrides synthesized from fatty acidsand acetic anhydride, are very reactive molecules towards cellulose and wood. By this way, both acetyl and acyl groups areeasily grafted on the natural biopolymers of the wood cell wall.They ensure covalent bonding of a plurality of aliphatic chains onsaid materials. Their high reactivity is due to the dissymmetry ofthe molecule made of a short acetic chain and a long aliphaticchain. The amphiphilic character of the molecule improves theirefficiency to penetrate and react with wood components. Afterreaction wood shows waterproofing and dimensional stability.
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A12The Generation of Novel Biomaterial Based StationaryPhases & Their Application in ChromatographyRJ White & JH ClarkGreen Chemistry Centre of Excellence, Department ofChemistry, 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 mostrenewable / biodegradable resources available. At present it ishighly 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 orphase. There remains the need for new stationary phase materials having different and potentially improved separatingcharacteristics when compared to the silica equivalent, with asurface polarity between that of silica and reverse phase silica.There is also the added driver to develop materials that presentnew exciting, enhanced separation profiles as a result of a lowmicropore to mesopore ratio, which are based on renewablestarting materials and that present a decreased environmentalburden after use.Expanded and chemicallymodified renewable starches and othercarbohydrate-based materials potentially fulfil the criteriadescribed above. Presenting a chemically active surface open tomodification, these carbohydrate-based materials will be used intypical chromatographic applications and manipulated to formnovel monolith columns, which in them self present a number ofadvantages2. 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 etal., Industrial Crops & Products, 1998, 7, 175(b) 'Starch, and Modified Starches as Support Materials andCatalysts', 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
Session 10a: Chemical ProductsFriday 8 September10:50 – 12:00PX/001
S11Oil seed engineering to reduce petroleum dependenceJ GrushcowLinnaeus Plant Sciences Inc.Current trends driving demand for bio-products include concerns for the environment, GHG reduction and the cost andavailability of petroleum. This presentation explores how new thetools of molecular biology can deliver value added feed stocks forindustrial purposes that can substitute for a variety of petroleumproducts.Canada is a world leader in agriculture and in particular in thearea of oil seed production with an average of over 10 millionacres under production each year. Unfortunately, prices for commodity seed oils have been trending steadily down for thelast 20 years. These new oilseed products promise to deliver significant value added at the farm gate while at the same timeproviding products that lessen the impact on our environment.
A13Renewables: Time for Priority to develop Building Blocks forthe Chemical IndustryCV StevensDepartment of Organic Chemistry, Faculty of BioscienceEngineering, Ghent University, Gent, Belgium.In the last decade, renewable resources are getting more attentionin 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 theproduction of bio-ethanol and biodiesel is the major topic whentalking about renewables. However, the production of biomaterials and bio-based building blocks, which will be the majorchallenge 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 ina multidisciplinary way. Major chemical companies are aware ofthis challenge and started to make structural changes and to setup 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 inview of the REACH regulation.Integral valorization and vertical integration in the production ofindustrial crops will have to be further developed in order to buildup biorefineries in agricultural areas with a good accessibility.Further, two examples of fundamental research topics related torenewable resources will be discussed.Inulin, the polydisperse reserve polysaccharide from chicory, hasbeen modified by carbamoylation and esterification in organicsolvents to develop a variety of modified inulin derivatives fromwhich the interfacial and emulsion stabilizing properties weredetermined. The medium and long chain acylated/carbamoylatedinulin derivatives, with low degrees of substitution (DS), showeda good to very good reduction of the interfacial tension whichmakes these biopolymers interesting in the field of biodegradableemulsifying 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 latexindustry. Undecenoic acid derived from castor oil has beendimerised to a polyfunctional building block of which the reactivity and usefulness is now being evaluated.
Dr Joe MazzaPacific Agri-Food Research Centre, Canada
Keynote LectureFriday 8 September 13:30 – 14:00PX/001
Professor Charles PerringsProfessor of Environmental Economics & EnvironmentalManagement, Arizona State University, USA
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Session 10b: Chemical Products Friday 8 September14:00 – 15:00PX/001
S12New Catalytic Materials from Renewable ResourcesDJ MacquarrieDepartment of Chemistry, Green Chemistry Centre ofExcellence, University of York, York, UK.The development of clean chemical technologies is essential if weare to effect efficient conversion of raw materials to the vast arrayof 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 recoveryof catalyst and product. It is important, but often overlooked, thatthe catalyst itself must be derived from renewable and sustainable sources.This presentation give an overview of work atYork designed to produce novel materials from biological sourceswhich function as highly effective catalysts for the conversion ofa range of molecules into important product types.
A14Biobased resins and plasticsJ van Haveren, CG Boeriu & A van der BentSustainable Chemistry & Technology, WageningenUniversity and Research, The Netherlands.The importance of renewable resources to current and particularly future society is rapidly gaining recognition. E.g., in2005, the Dutch government complied with the advice of the'Board for Renewable Resources' (translated from Dutch) tostrive for a major replacement of fossil oil and gas by renewableresources. For chemicals and chemical materials, the aim is torealize a replacement of 25% by 2030. In the current situation,only about 5% of all products generated by the chemical industryare biobased. Obviously, closing this gap will require major R&Defforts at both the fundamental and applied level. During the lastdecades, most R&D on biobased materials was focused on creating materials that are readily biodegradable. The newbiobased economy drivers (depletion of cheap fossil oil and gas,global warming, etc) now emphasize the importance of durablehigh performance biobased materials.At the Sustainable Chemistry & Technology Group ofWageningen University and Research, we focus primarily on thedevelopment of chemical building blocks, chemicals and materials that are derived from carbohydrates, fatty acids andproteins. 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 becovered, as well as specific examples such as engineering plasticresins, resins for decorative paints and powder coatings, andpolymer matrices for the targeted delivery of drugs. These examples illustrate the growing potential of renewable resourcesas feedstock for chemical products.
Session 11: BiocatalysisFriday 8 September 14:00 – 15:00PL/001
S13Tailoring ionic liquids for biocatalysis and bioprocessesNC BruceCNAP, 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 solventpermutations that can be envisaged. We have developed an integrated approach to the selection of ionic liquids for enzymecatalysed reactions, embracing both fundamental and practicalconsiderations, with the aim of developing a 'rule book' for thedesign of optimized solvents for individual classes of enzyme.Functionalized alkanolammonium cations provide a versatiletemplate 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 ofionic liquids, being non-volatile, non-flammable and exceptionally powerful solvents, whilst offering the additionalbenefits of reduced viscosity, low toxicity and completebiodegradability. Information about the properties of these newionic liquids and potential applications for biocatalysis and bioprocessing will be presented.
Professor Lene Lange Novozymes, Director, Molecular Biotechnology
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POSTER ABSTRACTSPlatform Molecules and Green Chemistry
P1Utilisation of Glycerol from Biodiesel feed-stocks:Microwave-assisted Chlorodehydroxylation to give a crucial intermediate in Epichlorohydrin manufactureMC Reid, JH Clark, DJ Macquarrie, R Luque & SWBreedenGreen Chemistry Centre of Excellence, The University ofYork, York, UK.Despite typically being associated with dirty pollution creatingprocesses, chlorinations may ironically prove to be useful indeveloping new low-energy and low-waste green chemicalmethodology. More specifically chlorodehydroxylations, where ahydroxyl group is replaced by a chlorine atom in an organic substrate, could allow polyhydroxylated platform molecules (typically byproducts of the biodiesel and related biorefineryprocesses) to be reused therefore giving them added value. Herewe describe our recent endeavors to integrate enhanced-microwave activation effects and catalysis on reaction of glycerolwith aqueous HCl in an effort to yield an intermediate necesaryin 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 anyreports in the literature regarding the use of microwave activationeffects in conjunction with new grafted heterogeneous catalystsin this reaction, both of which will contribute to speeding up thedesired reaction allowing faster reaction times together withgreater energy and atom-efficiency. Another green feature of thiswork is reaction performance in a solventless environment,resulting in further reducing waste. Additionally use of heuristicgreen chemistry problem solving methods through enablingtools such as metrics and informatics will be discussed throughapplication of our work to glycerol and other platform moleculessuch as 3-hydroxypropionic acid and lactic acid.
P5Adding value to wheat straw through integrated exploitation of high-value wax productsH 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 ofChemistry, London, UK.Wheat (Triticum aestivum) occupies the largest land area of allarable crops in the United Kingdom. However, with a harvestindex approximating to 50%, a considerable proportion of the drymatter produced (straw) is currently of little commercial use inmany parts of the UK.Estimates suggest that four to five million tonnes per annum ofwheat straw are effectively treated as waste in the UnitedKingdom. 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 atthe University of York, has demonstrated that a selective andcomplete extraction of wheat straw waxes can be achieved bybenign supercritical carbon dioxide. In addition, isolation of highvalue fractions including polycosanols, sterols (both of whichshow significant industrial potential as cholesterol loweringnutraceuticals), 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 withBotanix Ltd (an extraction company), the Clean Technology centre has scaled up the extraction to 75 Kg of straw whichextracted sufficient quantities of materials for product testing andfurther green chemical modifications.This low environmental impact technology would represent aninitial 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 usingCO2, Green Chem., 8 (2006) 39-42 Clark, J.H., Deswarte, F.E.I. and Hardy J.J.E., International patentapplication P112649WO, 2006.
P6Development of novel bioreactors for synthesis/hydrolysisof optically pure bioactive peptidesA Bacheva [1] & DJ Macquarrie [2][1] Department of Chemistry, MV Lomonosov MoscowState University, Moscow, Russia; [2] Green ChemistryCentre of Excellence, Department of Chemistry, Universityof York, York, UK.The development of synthetic procedures which require mild processing conditions and simple isolation of products is a majorgoal 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 onthe conditions. This requires the ability to form enzyme-containing films or particles which can be coated /packed into a continuous reactor, through which the reactantsolution 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 andfood production) and forms films, beads and fibres easily,although from acidic solution. In order to form active compositematerials, we have developed a non-acidic route to making filmscontaining enzyme, which allows the enzyme to survive the film/ bead forming step without loss of activity.Initial catalytic results indicate that the composite materials canshow excellent activity when used in conventional reactors. Wehave found that the activity is strongly dependent on the methodology applied to crosslink the composites and thereforeimpart mechanical stability. This aspect of the project is currentlyunderway along with studies aimed at fixing the catalysts to continuous reactors.
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P7In search of green solvents for aromatic industry: the caseof hydrofluoro ethersA Gonzalvez, C Raynaud & T TalouAgro-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 environmentallyfriendly organic solvents to replace the widely used hexan or itsrecent substitute cyclohexan. In the same time, research laboratories in flavors and fragrances have to replacedichloromethane, as it is classified as CMR. According to theGreen Chemistry concept, supercritical carbon dioxide appears tobe the genuine green solvent but its use requires specificallydesigned 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 VOCaccording to US regulation.In the present paper, the extractive potentials of two hydrofluoroethers, methoxynonafluorobutane and ethoxynonafluorobutanewere compared to those of hexan and cyclohexan for the obtention of resinoids from various medieval aromatic plants(aka: forgotten plants). Two plants, Helichrysum italicum andGalium odoratum, were particularly investigated as they are usedrespectively 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 ofdry plants (flowers or leaves) at 25 degC. Before analysis,absolutes were obtained by extraction with ethanol of resinoidsfollowed by a cold filtration in order to remove fats, waxes anddyes. Complementary hydrodistillations were performed on thesame 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. Thefirst results showed that both hydrofluorothers gave similarextraction yields as hexan, a solvent recovery by distillation up to80%, and aromatic extracts rich in top notes, particularly searchedby flavorists when hexan and cyclohexan extracted mainly heartand back notes.
P8Novel catalysts based on renewable resources - starch andchitosan-based catalysts for the synthesis of fine chemicalsDJ Macquarrie [1], JJE Hardy [1], AJ Deveaux [1], KMilkowski [1], JH Clark [1], S Doi [1], S Hubert [1], RLuque [1], M Bandini [2] & A Bacheva [3][1] Green Chemistry Centre of Excellence, Department ofChemistry, University of York, York, UK; [2] Dipartimentodi Chimica 'G. Ciamician', Università di Bologna, Bologna,Italy; [3] Department of Chemistry, M V LomonosovMoscow State University, Moscow, Russia.Polymer-supported catalysts have long been successfully appliedin synthetic chemistry.The ease of separation and reuse is a majoradvantage in clean synthesis. However, petrochemically derivedpolymers, 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 befunctionalised with acid and basic sites, leading to very activecatalysts which can be recovered and reused. Chitosan can befunctionalised to give supported transition metal based catalysts,wich have proved to be active in a series of reactions. In manycases activity is as good or better than existing systems, althoughsignificant differences in behaviour can sometimes be seen. forexample, 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 wheredeborylation is a relatively minor pathway. Chitosan can be easily prepared in bead form or as films, and this allows theattachment of supported catalysts to reactor walls, or packed bedsof catalyst, giving promise for continuous reactor systems.
P9Additives for the preparation of alkenyl succinic anhydrides (ASA) of vegetable originF Stefanoiu, C Cecutti, C Vaca Garcia & EBorredonLaboratory of Agro-Industrial Chemistry, INP-Ensiacet, Toulouse, France.In the preparation of alkenyl succinic anhydrides (ASA), additivesor a mixture of additives were used to improve the yield of theproduct 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 olefinor, in our case, oleic or linoleic moieties.Our objective was to synthesize and to characterize new vegetable ASA obtained from high oleic sunflower methyl estersin 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 ofmethyl esters and MAH, the oligomerization of methyl esters, theretroene-reaction, and the thermal decomposition of MAH andASA.Such ASA can be effective to replace petrochemical ASA innumerous applications: surfactants, wood treatment chemicalsor 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 someproperties of the adduct: colour, viscosity. The amount of eachadditive was approx. 0.1-10 mol% of the amount of MAH, themost effective being phenothiazine. We observed less effectiveresults with vegetable ASA when compared to petrochemicalASA. The difference in behaviour can be justified by the fact thatthese inhibitors are generally employed for shorter chains (C12-C14) than those of the vegetable ASA (C18). Moreover, the colorand viscosity would depend also on the degradation of thermosensitive molecules of vegetable origin. The authors thankONIDOL (France) for funding.
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Biofuels and Bio-energy
P2Effect of carbonization conditions on the physical proper-ties of biochar produced from apicot stoneD Ozcimen & A Ersoy-MericboyuChemical Engineering Department, Istanbul TechnicalUniversity, Maslak-Istanbul, Turkey.Among renewable energy resources biomass has an importantrole. Apricot stone is a valuable agroindustrial by-product that isavailable biomass resource in Turkey. In this study, carbonizationexperiments has been conducted on the samples of apricotstones to determine the effects of carbonization variables such asheating rate, particle size and sweep gas flow rate on the physical properties of biochar. A statistical design technique wasapplied by use of a two-level factorial design matrix to interpretexperimental results. Carbonization conditions were selected byconsidering the following variables: heating rate (5 K/min, 20K/min), particle size (0.250-0.355 mm,1-1.4 mm) and nitrogengas flow rate (0, 1000 cc/min).All experiments were performed at a temperature of 550 K and inJenkner type fixed bed carbonization retort. The char porosity %,total intruded volume (cc/g) and mean pore diameter of biocharswere found to vary between %5-62, 0.05-0.73 (cc/g) and 16.6-546(nm), respectively. The char porosity and total intruded volumevalues are decreased significantly with an increase in particle sizeand increased with the increase in heating rate. The sweep gasflowrate has the lowest effect on the porosity properties ofbiochar. Amprical relations between the char porosity and carbonization conditions were also developed.Keywords: Biomass, apricot stone, biochar, carbonization,factorial design.
P3Evaluation of grapeseed as a biofuel sourceD Ozcimen & A Ersoy-MericboyuChemical Engineering Department, Istanbul TechnicalUniversity, Maslak-Istanbul, Turkey.Most of fruit stones, seeds and shells can be used as a resource ofcarbonization 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 majoralternatives. In this study, carbonization experiments has beenconducted on the samples of grapeseed to determine the effectsof carbonization variables such as temperature, sweep gas flowrate and heating rate on the bio-oil yields. A statistical designtechnique was applied by use of a two-level factorial designmatrix 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 1000cc/min) and heating rate (5 and 20 K/min).All experiments were performed at average particle size of 0.377mm. The carbonization process was carried out in Jenkner typefixed bed retort. It was found that the liquid yields of sampleschanged depending on the process conditions. Amprical relationsbetween 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, factorialdesign.
P4Selection of Saccharomyces cerevisiae strains for bioethanolproductionC Parra, M Rodriguez, E Araque, J Freer & J BaezaRenewable Resources Laboratory, Biotechnology Center,Universidad de Concepción, Concepción, Chile.Simultaneous fermentation and saccharification processes of lingocellulosic material requires the utilization of microorganismscapable of working al high temperatures, and consequently theselection of S. cerevisiae strains capable of fermenting sugars attemperatures above 40 degC with a high ethanol yield hasbecome a necessity. In the present study, twelve strains of S.cerevisiaewere grown at 35, 40, 42 and 45 degC in agar plate. Allthe strains grew at 35 and 40 degC; only two of them grew at 42degC and none at 45 degC. A small amount of pure yeasts werepassed to a liquid medium, and incubated at 35, 40 and 42 degC.At 35 degC, no statistically significant differences were detected inbiomass production or ethanol yield. Final ethanol yields wereabove 80% of the theoretical in all cases (based on the hexosescontent). At 40 degC and 24 h, ethanol yield of 12% was achievedfor three strains, 45% for other two, and 60-80% for six of them.Only one of the strains grew at 42 degC, producing ethanol witha 50% yield at 48 h.The five strains that grew at 40 degC and withan 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 WORDSSaccharomyces cerevisiae, bioethanol, biomass thermotolerant.
P21Optimizing the Size of Anaerobic DigestersE Ghafoori & PC FlynnDepartment of Mechanical Engineering, University ofAlberta, Edmonton, AB, Canada.Anaerobic digestion of manure to produce power in farm or feedlot based units as well as centralized plants is evaluated fortwo settings in Alberta, Canada: a mixed farming area, Red DeerCounty, and an area of concentrated beef cattle feedlots,Lethbridge County. Centralized plants transport manure to theplant and digestate back to the source CFO, an added cost relativeto farm or feedlot based plants, but gain from the economy ofscale in plant capital and operating cost. A centralized plant drawing manure from 61 sources in the mixed farming area, at amanure yield of 34 dry tonne year-1 ha-1 could produce 6.5 netMW of power at a cost of $218 MWh-1. No individual CFO in themixed farming area, including a 7,500 head beef cattle feedlot, canproduce power at a lower cost with a farm or feedlot based unit.A centralized plant drawing manure from 560,000 beef cattle inLethbridge County, at a manure yield of 280 dry tonne year-1 ha-1, can produce power at a cost of $138 MWh-1. In LethbridgeCounty, An individual feedlot larger than 40,000 head of beef cattle could produce power at a lower cost than the centralizedplant. Commercial processes to recover concentrated nutrientsand 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 250,000head to produce power at a lower cost than a centralized plant.Power from biogas has a high cost relative to current power pricesand to the cost of power from other large scale renewable sources.Power from biogas would need to be justified by other factorsthan energy value alone, such as phosphate, pathogen or odorcontrol.
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P23Degradation of biodiesels at elevated temperaturesMS Stark, A Neal & MRG SmethurstDepartment of Chemistry, University of York, York, UK.Biodiesel production is currently increasing, in response to environmental concerns and policies such as the EuropeanUnion 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 itmay 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 thesmooth 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 attemperatures 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 byperoxyl radicals, and the reaction of the resultant alkoxyl speciesto form ketones or alcohols of the starting material, or decomposition to form aldehyde or alkane fragments.
P24Saccharification and fermentation of Pinus radiata D.Donand Acacia dealbata wood chips pretreated by bio-organosolv processC Muñoz [1], A Berlin [2], R Mendonca [1], J Baeza [1], JSaddler [2] & J Freer [1][1] Renewable Resources Laboratory, Biotechnology Center,University of Concecpcion, Concepcion, Chile; [2] ForestProducts Biotechnology, Faculty of Forestry, The Universityof British Columbia, Vancouver, Canada.Wood chips from Pinus radiata and Acacia dealbata werebiotreated by white-rot fungi, Ceriporiopsis subvermispora andGanoderma australe, respectively. Sterilized wood chips wereinoculated with 500 mg fugal mycelium/kg wood and incubatedfor 30 days at 25 degC and 55% RH. Decayed and untreatedwood chips were delignified by an organosolv process(ethanol:water 60:40, 200 degC, 1 h) to produce pulps with lowlignin content. Prepared pulps underwent sequential hydrolysisand 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) wereused 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%) comparedto pulps produced from untreated wood chips (~80% glucan and14% lignin). Pulps obtained from biotreated A. dealbata showedalso higher glucan content (~94%) and lower lignin content(~2%) than pulps produced from untreated wood (~90% glucanand 5% lignin). The enzymatic hydrolysis (SHF) of untreated andbiotreated P. radiata yielded glucan-to-glucose conversion ~55%and 100%, respectively. In the case of A. dealbata, the glucan-to-glucose conversion was 100% for both control and biotreatredpulps. Ethanol yield in SHF of control and biotreated P. radiatapulps was 25%-38% and 49-55% theoretical yield, respectively,while for control and biotreated A. dealbata pulps the ethanolyield was 58%-62% and 61%-69%, respectively.The SSF of untreated and biotreated P. radiata organosolv pulpsyielded 4%-10% and 53%-65% ethanol, respectively, and 67%-77% and 78-%-82% for untreated and biotreated A. dealbataorganosolv 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.
P28Ecological gradation of energy in a pond ecosystemManjunath IyerDepartment of EC & CSE, Bangalore University, Bangalore,India.There exists a self-similarity in the concentration of the organismsalong the depth of the pond. It originates as a result of a kind ofdifferential feedback from the bottom of the pond to the surface[1]. The flow of energy towards the bottom of the pond would becontrolled by the (ratio of) the gas mixture that flows towards thesurface. This control mechanism would have far reaching impacton the photosynthesis as well as the readjustment of the concentration of the organisms through aquatic movement.As the consequence of the differential feedback, many interestingproperties would be imparted to the ecosystem. The ecosystembecomes more and more predictive. Analysis shows that, greaterthe depth of the pond, better would be the predictability.Meaning, in a deep pond ecosystem, the degree of adaptabilitywould be better. Any environmental changes would be reflectedand responded fast compared to a shallow pond ecosystem.The predictability provides better controllability. If a certain set oforganisms at a specific depth vanishes or move out, the deeppond ecosystem can still sustain and quickly reconfigures.Such a change would mean drastic for a small pond leaving it incrisis. A better understanding of the control mechanism can provide techniques for the survivability of small pond ecosystemsAnother interesting outcome of the differential feedback is theabstraction or gradation. The biological activities involving energygeneration and consumption become abstract with depth. Thereexists a mathematical relation in the abstractions of different levels. It is interesting to see that the gap between different levelsincreases 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 andprocess, ISMB 2006 (accepted)
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Biocatalysis
P18Biocatalyst Catalysts for Sustainable ChemistryUnderstanding the interaction of functionalised supportswith enzymesS Narayanaswamy [1], HR Hazel [2], DJ Macquarrie [1], JHClark [1] & NC Bruce [2][1] Green Chemistry Centre of Excellence, Dept ofChemistry, University of York, York,UK; [2] CNAP, Dept ofBiology, University of York, UK.The goal of Green Chemistry is to develop sustainable technologies to produce the desired products with minimalchemical waste. This requires the use of renewable raw materialsand transformations under very mild conditions. Immobilizedenzymes are emerging as new heterogeneous biocatalysts,resulting in improved performance in activity, and stability andfacilitating separation of enzymes. Earlier immobilizations madeuse of polymers as supports, which often reduced the activity ofenzymes .We have initially made use of mesoporous material-SBA-15: dueto its larger pore size and thermal stability . Our current enzymeof interest is Glucose Oxidase because of its high stability underextreme conditions . Our initial work has shown that using SBA-15 functionalised supports can lead to an increased activitydepending on the surface chemistry. We intend to use GlucoseOxidase to predict the interactions and therefore to design bettersupports 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 usingvinyl groups. It therefore appears that different functional groupsare 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 isalso being investigated. Starch and enzymes (proteins) are bothmacromolecules, so it would be interesting to understand thechemical and biological interactions between them. Meanwhile,the ease of forming films makes chitosan unique for bio-fabrication of enzymes. These films are intended to be used inmicroreactors.
P26Industrial Biotechnology and the MDG'sB VersterDept 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 systemis education and the establishment of infrastructure in ruralSouthern Africa.The system comprises three components:1) A grid of microorganism growth, biotechnologically developedto 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 productseparation, with filter-air cooling and nutrient supply.The system can be fixed to rooftops, or provide shade underwhich crops can be grown. As it is a sealed system, it does notrequire water. This system is designed for rural use in semi-aridto arid areas, with a low water requirement and low maintenance. It shows promise for bio-hydrogen production, aswell 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 isdesigned at present to be a slow-growth system, to cope with lownutrient (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 electricitygrids, in areas where healthcare and education is at a minimum.The eventual goal of this system is the sustainability of severalsmall 'farming' communities, where the 'crops' are these bio-grids, that do not require much water or other input, whilebeing able to produce diverse products, from biofuels for domesticuse, to pharmaceutical precursors, to biomaterials for use in thetextile industry.Advantages:Cheap, basic technology.Large scope for development and specialization.Alternative technology to fermentation.
Biopolymers (fibres) / Biomaterials
P10A new star(ch) is born: Starbon Acids and their uses as catalystsVL Budarin, JH Clark, TJ Farmer, R Luque & DJ MacquarrieGreen Chemistry Centre of Excellence, Department ofChemistry, 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 synthesisof a new form of mesoporous carbon, named Starbon, obtainedafter low temperature carbonization of expanded starch.2 Suchstarch derived mesoporous materials have several tunable properties including surface properties (ranging from hydrophilicto hydrophobic surfaces) which can be easily controlled by thedegree of carbonization (from 200 to 700C) and the possibility oftheir use as supports for catalysis. Due to this diversity of surfacefunctional groups, starbons can be easily modified. In this sense,simple treatment of the Starbon material with sulfuric acid gave asolid acid catalyst that has promising properties in the catalysisfield. Indeed, low surface-area sulfonated aromatic materials haverecently 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 toeach one of the desired products, depending on the conditions.Of note are the comparative studies carried out with some otherwater-tolerant solid acid materials such as sulphated zirconias,clays and zeolitic materials, in which slower reaction rates andworse selectivities/conversions for the target products were foundunder 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.
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P11New materials based on renewable polysaccharide polymersVL Budarin, JH Clark, FEI Deswarte, S Doi, JJE Hardy, AJHunt, DJ Macquarrie, K Milkowski, OJ Samuel & R WhiteGreen Chemistry Centre of Excellence, Department ofChemistry, University of York, York, UK.Natural polysaccharide polymers, such as starch, cellulose andchitin represent a carbon neutral, non-toxic, biodegradable andabundant resource comprising the majority of biomass. They arewidely utilised in food as well as a wide range of non-food applications.The outstanding environmental performance along with low costand widespread availability of these polymers have attractedresearch into a variety of applications at Green Chemistry Centreof Excellence at York such as novel starch-based plastics for avariety of applications. Moreover, the inherently high degree offunctionality of these polysaccharides make them potentiallyattractive surface-active materials. The nitrogen functionality, forexample, has been utilised to produce successful heterogeneouscatalysts and Chitosan's biocompatible nature allowed enzyme heterogenisation. However, the wider exploitation of these materials is restricted by the naturally low porosities limiting theavailability of active sites. Researchers at York have developed arange of novel porous starch or cellulose based materials utilising novel microwave, ultrasound and supercritical fluidstechnologies in the expansion process.The expanded materials have been applied as supports for heterogeneous catalysts for a variety of chemical transformationswith 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 pharmaceutical or agricultural absorption-release matrices. They havealso been successfully applied as stationary phases in gas and liquid chromatography enabling, for example, the use of less toxiceluting solvents and potentially the separation of chiral compounds.Expanded starches have also been utilised in synthesis of furthernovel compounds. Acid catalysed low temperature pyrolysisyielded a family of carbonaceous materials with tuneable porosities and surface and bulk characteristics applicable to catalysis and chromatography. The expanded starch matrix hasalso been utilised in the synthesis of novel porous compositematerials with different surface characteristics and improvedthermal stability
P12Refining and Successive Functionality Control ofLignocellulosics.Phase-separation systemMASA Funaoka, KG Mikame & MT AoyagiDepartment of Environmental Science and Technology,Graduate School of Bioresources, Mie University, Tsu, Mie,Japan.Lignin is a natural polymer with very complicated network structures.The complexity is due to the presence of building units(phenylpropanes) with reactive substituents and randominterunit linkages. The originally designed process includes thephase-separative reaction system composed of phenol derivatives and concentrated acid. The concentrated acid is a solvent for carbohydrates, and works as a catalyst for the fragmentation and phenolation of lignin, and phenol derivativesact as phenolation agents, a barrier to minimize the attack of acidon the lignin, and a solvent for the lignin fractions. Through thisprocess, native lignins are converted quantitatively to a new typeof lignin-based polymer (lignophenols) composed mainly ofbis(aryl)propane type units. The selective grafting of monomeric
phenol derivatives to C1-positions of propane units leads to theformation of new phenylpropane units between grafted phenolicunits and lignin propane units, resulting in a dramatic change ofthe original lignin functions.The characteristic units in lignophenols, bis(aryl) propane-2-O-aryl ethers, can be used asswitching devices for the structural control: the phenoxide ions ofgrafted phenols readily attack the electron deficient C2 nucleophilically, resulting in the cleavage of C2-aryl ether linkageswith the exchange of phenolic functionality from C1-graftednuclei to lignin nuclei. Since this type of neighboring group participation is very quantitative, the functionality of lignophenolscan strictly be adjusted by the frequency control of C2-attackablephenolic nuclei (switching devices) within the molecules.New application fields of lignophenols are shown below:Recyclable composites with cellulose, biopolyesters, and inorganicmaterials (glasses, metals), Raw materials for recyclable polymers,Detachable adhesives, Switching devices for material recycling,Electromagnetic shielding materials, Carbon molecular sievingmembranes, Enzyme supports for bioreactors and affinity chromatography, Adsorbents for proteins and metals, Performancecontrol agents for lead-acid battery and enzymes, Photoresists,Antioxidants, UV barriers, Solar cell sensitized with lignophenols.
P13Switchable Adhesives for Carpet TilesJH Clark & PS ShuttleworthGreen Chemistry Centre of Excellence, Department ofChemistry, University of York, York, UK.The carpet tile market in the UK is fifteen million meters squaredwith over 90% of this going to landfill after use. This represents onan unacceptable level of waste and future legislation will forcemanufacturers to recycle used tiles. The current manufacturingprocess 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 separationand does not adequately facilitate recycling of the individual components.The use of novel switchable adhesives made from starch basedmaterials potentially presents an exciting alternative to conventional materials. Through modification (physical or chemical) the desired properties (i.e. hydrophobicity) can beimparted, resulting in a starch based material which can ultimately be deconstructed under an external stimulus (e.g. Acidicor Basic treatment) achieving separation of the component partsand hence enabling recycling.The poster will aim to demonstrate and discuss some potentialmethods for the production of starch-based plastics and adhesives. These will include:-
l
The hydrolysis of starch and product analysisl
The esterification of starch- To increasing hydrophobicity- Enhancement of thermal stability, (an important parameter forplastic and adhesive applications)- Decreasing melt temperature for use as hot-melt adhesives- Modifying rheological flow propertiesFurthermore, the extrusion processing of starch and the route toforming Thermoplastic Starch (TPS) will also be discussed.
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P14The Generation of Novel Biomaterial Based StationaryPhases & Their Application in ChromatographyRJ White & JH ClarkGreen Chemistry Centre of Excellence, Department ofChemistry, 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 ofthe most renewable / biodegradable resources available. At present it is highly under utilised in terms of typical chemicalapplications, 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 orphase. There remains the need for new stationary phase materials having different and potentially improved separatingcharacteristics when compared to the silica equivalent, with asurface polarity between that of silica and reverse phase silica.There is also the added driver to develop materials that presentnew exciting, enhanced separation profiles as a result of a lowmicropore to mesopore ratio, which are based on renewablestarting materials and that present a decreased environmentalburden after use. Expanded and chemically modified renewablestarches and other carbohydrate-based materials potentially fulfil the criteria described above. Presenting a chemically activesurface open to modification, these carbohydrate-based materialswill be used in typical chromatographic applications and manipulated to form novel monolith columns, which in them selfpresent a number of advantages2. The poster aims to demonstrate the preparation, modification and utility of suchnovel stationary phases in chromatography.References:[1] (a)'Economics of Starch Production in the UK', G. Entwistle etal., Industrial Crops & Products, 1998, 7, 175(b) 'Starch, and Modified Starches as Support Materials andCatalysts', 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
P29Molecular Structure and Dimension of Xylan from VariousSourcesW Praznik [1], R Loeppert [1], K Zangger [2] & A Huber [2][1] Department of Chemistry, BOKU - University of NaturalResources & 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 molecularcharacteristics in terms of unimer-composition, molar mass andexcluded volume distributions. As well destructive as non-destructive techniques were applied, in particular: totalhydrolysis and TLC-analysis for identification of constituting carbohydrates, NMR for identification of specific functionalitiesin non-hydrolized xylans and SEC-multiple detection to obtainmolar mass distribution and excluded volume distribution.Molar mass distribution of investigated wood xylans from WolfCellulosics and beech range between 500 and 30 000 grams permol with mean molar mass in terms of Mw in the range of 10 000grams 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 to240 000 grams per mol were present resulting in even highermean molar mass of Mw 36 000 grams per mol. Compared toxylan of oat bran with significantly higher dp-components with
molar masses up to 500 000 grams per mol and mean molar massof Mw 85 000 grams per mol. Furthermore, there is evidence of atleast two populations in the molar mass distribution indicatingxylan 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 moietieswith varying amount of acetyl- and methyl-groups linked to sugarmoieties such as arabinose, mannose, galactose, and glucuronicand galacturonic acid.
Bioresources
P15Renewable Industrial Materials From TreesSK Badamali, F Bouxin, V Budarin, K Milkowski, FEIDeswarte & JH Clark, Green Chemistry Centre ofExcellence, 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 treesand 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 approximately75% of the felled tree (e.g. leaves, bark, small branches, off-cut,etc). There is therefore a need to identify innovative applicationsfor forestry species.In this context, Sitka Spruce (Picea sitchensis) was selected as thetree species to be studied in the course of this project, as it a verycommon and low value tree in the UK.Essential oils with excellent microbial activities were isolated fromSitka Spruce bark using environmentally-friendly methodologies(i.e. supercritical carbon dioxide extraction). Expanded cellulosematerials with surface area up to 140m2/g have been producedusing ultrasound and successfully used a chromatographic media,catalytic supports and adsorbents. Finally, Catalytic oxidativehydrolysis systems and microwave heating technology with aim toproducing a portfolio of substituted aromatic compounds fromlignin were examined.The poster will generally discussed the potential of adding valueto trees through extraction of secondary metabolites prior toexploitation of the structural components (i.e. cellulose andlignin).
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P16Enzyme-assisted Aqueous Processing as the Front-end to aSoybean BiorefineryBP Lamsal & LA JohnsonCenter for Crops Utilization Research, Iowa StateUniversity, Ames, IA, USA.A biorefinery is cluster of bio-based industries producing chemicals, fuels, power, products and materials. We envision asoybean biorefinery processing soybeans into value-added products for food, feed, biomaterials and bioenergy, similar tocorn wet milling. Enzyme-assisted Aqueous ExtractionProcessing (AEP) holds promises as the front-end to such abiorefinery. AEP, which uses water as an extraction medium, isan alternative to hexane extraction for processing soybeans.Because of increasing environmental and safety issues associated with hexane extraction of oil, AEP is being evaluatedfor extracting oil from oil-bearing plant materials.The challenges are: the need for mechanical treatment to rupture cells and facilitate water washing; disruption of oleosinprotein 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 becomesemulsified by protein and lecithin.Extruding full-fat soy flakes into water and enzyme-assisted AEPwith 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 exposedsites for easy enzyme attack, enhancing extraction. Protease alsoacted on olesin to facilitate more oil release. Hydrolyzed proteinswere more soluble in aqueous medium, resulting in higher protein extraction yield. Extruding full-fat soy flakes prior toenzyme-assisted AEP was key to increasing oil extraction and toincreasing oil droplet size in the cream fraction. Larger oildroplets in the cream phase favored coalescence yielding morefree oil. The cream fraction was heated to 95 degC for 5 h, frozenat -deg20C and thawed, and treated with various deemulsification agents. Heating did not break the emulsion butfreezing-thawing, Agent A, and Agent B recovered 86, 68, and73% of the total oil, respectively.
P17Integrating Recovery of Plant-made Pharmaceuticals into aBiorefineryD Octaviani, N Vignaux, S Fox & L JohnsonCenter for Crops Utilization Research, Iowa StateUniversity, Ames, IA, USA.Advances in molecular biology allow development of recombinant proteins in corn to produce pharmaceuticals andindustrial enzymes. In addition to providing a natural storagesystem, easy scale-up, established production practices and highyield to cost ratio, this production system can be integrated intoa biorefinery where biofuels and biobased products are produced.Corn expressing recombinant Dog Gastric Lipase (rDGL) fortreating cystic fibrosis patients was used as a model where therecombinant protein is expressed in endosperm. A dry-millingmethod was developed to separate corn tissues into a germ-richfraction containing most of the oil and water-soluble protein andan endosperm-rich fraction containing most of the rDGL. Fourdegermers 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 oilyield to mass yield of the germ-rich fraction relative to the sameratio in the endosperm-rich fraction. The drum degermer recovered 74% of the total oil in 23% of the total mass while theendosperm fraction contained only 22% of the total oil.The drum
degermer gave the highest germ DMI (3.2) and lowest endospermDMI (0.32). As a reference, hand-dissected kernels gave 6.9 germDMI and 0.12 endosperm DMI. Only degermer type affected DMI;moisture and percent recycle did not have significant effects. Thedrum degermer recovered 89% rDGL activity in 70.4% of the totalmass 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 theendosperm fraction before the fermenting the starch to fuelethanol and the germ fraction is used to produce biodiesel.
Chemical Products including Oleochemicals
P19Biobased Chemicals: today, not tomorrow. The valorisationof functionalized chemicals from biomass resources compared to the conventional fossil production routeB BrehmerValorization of Plant Production Chains, WageningenUniversity and Research Centre, Wageningen, TheNetherlands.It is proposed that already today, by utilising existing, recentlydeveloped and developing technology, it is economically advantageous for many chemicals to derive from biomass, in particular the functionalized chemicals. The only way to validatethis conjecture is to develop a complete comparative life cycleanalysis. 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 optimumroute with the best production options along the whole production chain while determining any possible limiting factors.Using this tool, a systematic production matrix relating severallogical source crops and a few key chemicals of varying derivativelevels can be created and compared to the conventional fossilroutes. Combined with economic considerations and some unambiguous environmental factors, the investigation will provideall the information relevant to the industry. The goal is to create anobjective and reliable simulation system ratifying the economicand environmental feasibility of exploiting biobased chemicalstoday and indicate the steps necessary for further improvement.
P20The Forest Biorefinery ConceptCAS Hill [1] & SF Curling [2][1] School of Agricultural and Forest Sciences, University ofWales, Bangor, UK; [2] School of Agricultural and ForestSciences, University of Wales, Bangor, UK.Although there has been a great deal of interest in the use ofagricultral resources for the production of industrial chemicalfeedstocks, rather less has been directed at the use of forestresources for this purpose. Forest resources have a number ofadvantages 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 theuse of forest-based reources for producing various silvichemicalsand biopolymers with some historical and contemporary casestudies.
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P25Selectivity in microbial transformation of some xenobioticsubstancesO 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 fewxenobiotic substances, either to produce industrially useful derivatives or to test the capability of these microorganisms tomineralize them selectively. The following strains, Pseudomonasaeruginosa, Rhodotorula sp., Yarrowia lipolytica, isolated fromheavily 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 oftheir population, and, after 24 h, the following aromatic and heteroaromatic compounds, as single substance or as mixturedissolved in ethanol, were inoculated to obtain a final concentration of 1%: Naphthalene, 1- and 2-methylNaphthalene, 1,2-dimethyl Naphthalene, Indole, 5-methylIndole, Quinoline and 8-methyl Quinoline. The mixture was analyzed at regular intervals, up to 30 days, by using differenttechniques, including B.O.D. measures. The results of this workhave shown different biotransformation behaviour of the threestrains in the presence of aromatic and heteroaromatic substratesand the influence of minor modifications in the structure of thexenobiotic compounds on the microbial activity. Synergic and/orinhibitory effects were found when a mixture of added substances or a microbial consortium was used. The interestingstructure selectivity, found in this work, might be perhaps usefulin the treatment of tar fractions to obtain purer single high valuehydrocarbons. Some products, due to a partial biotransformationof indole derivatives, were isolated and the determination of theirstructures is currently in progress. A production of oxygenatedfatty acids and of biosurfactants, that might have a large industrial impact, was always observed, so indicating that theirmanufacture is not related only to make the xenobiotic compounds bioavailable for the strain.
P27Enhancement of Solar Energy Efficiency for DrinkingWater DisinfectionG 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 tohuman beings worldwide.Over one billion people each year areexposed to unsafe drinking water due to poor source waterquality 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 employedin countries like Pakistan are needed. Chemical disinfectionoptions such as chlorine and iodine treatment require chemicalsthat must be purchased. These chemicals can be expensive andalso have a limited shelf life. Physical treatment options such asboiling, UV treatment, and filtering require materials that maynot be easily acquired or purchased. One alternative drinkingwater treatment method that has been proposed is solar disinfection, a process that is simple and easily utilized. Thephotoactivity of titanium dioxide has been meticulously investigated to demonstrate its bactericidal ability. P25 Degussa
Titanium Dioxide (80% anatase and 20% rutile) was used as theprimary source of Titanium particles during our study. This powder was coated by silver particles and both materials weretested in dark and sunlight for E.coli inactivation. The results demonstrated that Ag-TiO2's exceptional bactericidal abilityagainst normal sunlight. The acquired data also showed thatinactivation kinetics of Ag-TiO2 with respect to bare TiO2 at various elapsed time. TiO2 and Ag-TiO2 in suspension andimmobilized form showed no significant difference. The resultsclearly showed that solar energy efficiency is enhanced for Ag-TiO2 as compared to bare TiO2. It was noted that E.coliwasprobably inactivated by two different photocatalytic mechanisticpathways, possibly free or surface-bound hydroxyl radicals andreactive oxygen species (H2O2).
MRes Session
P30Glycerol and Succinic Acid as Platform Molecules fromBiomassD VandenBurg, C Chukwuogo & J ClarkGreen Chemistry Centre, Department of Chemistry,University of York, Heslington, England.In the context of vanishing fossil resources, biomass represents thebest way in which Man can continue to meet his increasing needfor chemical products. Many useful chemicals can be derived fromplants; 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 buildingblocks of current and future chemical products) easily obtainedfrom biomass. These were chosen based on their chemical utilityand expected value. Of these, we have looked at glycerol and succinic acid as a case study, since we believe that they best showthe versatility, importance and innovation that platform moleculesrepresent.Unrefined glycerol has been used as an additive for many years insectors such as the cosmetic and pharmaceutical industry. Beingone of the major effluent streams from biodiesel synthesis (itselfan hugely important advance in Green Chemistry) GreenChemists have been looking at adding value to this importantmolecule. 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 toform biodegradable nylon analogues.Succinic acid and its primary derivatives are in great demand foruses as diverse as polymer production to de-icing technology [2].The current oil based synthesis of succinic acid is highly wastefuland involves chemicals harmful to the environment. Using bioreactor technology it is now possible to produce high qualitysuccinnic acid from the waste generated by the corn and paperindustries [3]. We anticipate that many commercially importantmolecules will be derived from succinic acid, (THF can be easilyderived 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. Werpyand G.Petersen 2004.[2] www.wisibiorefine.org[3] Chemicals and Materials from Renewable Resources, J.Bozell,ACS, 2001
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P31Bioethanol: production and usesTL Malkin & SE HaleGreen Chemistry Centre of Excellence, University of York,York, UK.The majority of ethanol is produced from crude oil in a directhydration 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 degreesCelsius and passed over a phosphoric acid catalyst.The process isundesirable from a green perspective as it uses high temperaturesand pressures and creates large amounts of waste.A greener solution is to produce the ethanol from renewableresources: carbohydrates such as starch and cellulose can behydrolysed to simple sugars and then further converted toethanol by fermentation. To begin with a pretreatment opens thestructure of biomass making it susceptible to hydrolysis by concentrated or dilute H2SO4. The fermentation process takesplace using enzymes and then the ethanol is recovered by fractional distillation.Biomass energy contributes 9-13 % of the global energy supplywhich accounts for 45 ± 10 EJ per year (2004).[1] Worldbioethanol production was 31 GL in 2001 with the major producers America and Brazil, contributing 62 % of it. Americarelies on corn while Brazil produces bioethanol from sugarcaneunder the national program 'ProAlcool'. The program has beensuccessful as 13 billion litres of ethanol are produced saving 220000 barrels of gasoline imports per day. 5 million cars run on purebioethanol now in Brazil.Within the UK, British Sugar has placed a contract with a designfirm in the race for the UK's first bioethanol plant. A pilot schemein Somerset is using the Ford Focus Flexi-Fuel Vehicle that runson 85% bioethanol.We question whether this is enough to counter act the rapidlydecreasing amount of fossil fuels and feel the UK should followmore closely Brazils example.[1] B. Dale and S. Kim, Biomass and Bioenergy, 2004, 26, 361
P32Process Intensification using Spinning Disc Reactors(SDRs)SD Blore & JH WestellGreen Chemistry Centre of Excellence, University of York,York, UK.With increasing demand for reactors that provide not only greaterenergy efficiency, but also the benefits of Just-In-Time (JIT) production, preventing both waste and the risk of storage, manytypes of continuous reactors have been developed in an attemptto meet the requirements of the many types of chemical reactionsthey apply to. One such reactor is the Spinning Disc Reactor(SDR), a small (less than one cubic metre) reactor that is capableof 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 inplant inventory, as a standalone reactor requires no extensivepipe work (the reactor forms only 20% of typical chemical plantproduction costs) with energy also being saved as the SDR canperform a reaction as much as 1,000 times faster than a batchreactor, with mass and heat transfer rates improved 10 and 15fold respectively. SDRs often operate with little or no solvent, andwhere more than one reactor is required; they can be set up torelease the first stage product straight onto a second disc. Evenmore promising is the ability of the disc itself to act as a supportbed for catalysts where they are also needed.The technology has now been used not only to produce bulkchemicals, but also in the production of pharmaceuticals,polymers and even ready meals for major supermarkets.
P33CO2 Sequestration as a method of Greenhouse GasAbatementBA Lanigan & VS PugnetGreen Chemistry Centre, Department of Chemistry,University of York, York, UK.Since the start of the industrial revolution, the atmospheric CO2concentration has increased by 40%, most of it released since 1945.If the emission levels continue at the current rate, by the year 2050we will have effectively doubled the pre-industrial concentrations.As CO2 is a greenhouse gas, the rise in atmospheric levels hasbeen 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 inthe commitment period of 2008 to 2012. Given our high degree ofreliance on fossil fuels (roughly 85% of commercial energy use),and the difficulties (technical, economic and social) of large scaleuse of alternative options (like nuclear and renewables), the ability to use fossil energy while avoiding CO2 emissions is apotentially attractive alternative that needs to be carefully studied.The purpose of CO2 capture is to produce a concentrated streamof 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.
P34Chitin: Application, Modification and ExtractionJW Comerford & MA NeesamGreen Chemistry Centre of Excellence, University of York,York, UK.This poster presentation reviews the extraction and applications ofthe 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 thepotential to provide a cheap and large quantity of renewable polymeric material, especially in coastal regions or areas with ahigh throughput of crustacean shell waste. Currently a smallindustry, chitin refining is expected to increase in the foreseeablefuture in order to replace petrochemical derived products, aspetrochemical feedstocks diminish and the demand for newimproved materials increases. For instance, chitin could be usedfor pollution remediation, as its structure has many sites able tobind to various metals as well as many organic pollutants. Chitincould 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 bedescribed; these include the classic extraction, as well as novelenvironmentally friendly extractions not currently practiced, suchas biological isolation using enzymes.The conversion of chitin to chitosan and further functionilisationof the resulting material, using methods such as ultrasound, willbe discussed.Finally, the tremendous potential of modified and native chitin willbe highlighted.
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P35Bioresources For Greener Surfactants: A Case Study OfAlkylpolyglucisides (Apg)F Mabiki & Z JiankunGreen Chemistry Centre of Excellence, Department ofChemistry, University of York, York, UK; Bioresources are raw material derived from living organisms. Themain suppliers of bio resources may include the conventionalrenewable resource industries such as agriculture, forestry,marine, various organic residues and also bio-residuals generated from existing conversion and manufacturing processesCarbohydrates are promising bioresources towards more environmentally friendly and greener surfactants. The amphiliccompounds, which offers wide applications due to their ability tointeract with all the interfaces. Alkylypolyglucosides (APGs) arethe surfactants purely made from bioresources, their preparationprocess is quit simple and greener, cost effective even at largescale, and they socially acceptable as they are increasingly used.APGs are prepared from carbohydrate resources, which mayinclude starches such as wheat, corn, potatoes, any monomericform of carbohydrates, and the fatty acid sources such as fattyalcohol from coconut or palm oil, tallow, rapeseed depending ofthe desired alkyl chain length. As surfactants they are used infoods, micro-emulsions, detergent and cleaners, personal careproducts, textiles, pesticides, and other daily used house holdproducts, because they exhibits favorable dermatological properties, reduce the irritant effects of surfactant combinations,completely biodegradable, both aerobically/anaerobically andprimarily/ultimately.They are less toxic than other conventional surfactants, they haveno pronounced inverse solubility vs. temperature as normal non-ionic surfactants and also they are more lipophilic comparesto their petrochemical based surfactants counter parts. APGs aremost promising surfactants for future as well as today's technological development. However, there are challenging areasfor the sustainable development of the APG surfactants includesmaximum crop use, production of pure APG surfactants, energyminimization during preparation and use, and the greener preparation procedures. Despite these challenges, they are stillthe most promising surfactants for today's as well as future sustainability.
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