1. PyNe -- Glasgow WP 2H Biorefinery Tony Bridgwater and Doug Elliott September 20, 2006

2. 2 Presentation Organization Biorefinery basics Biorefinery concepts TEA for Biorefineries

3. 3 An Example of a Current Biorefinery Corn Wet Mill starchcorn oil corn gluten meal corn gluten feed food & industrial starches hydrolysis glucose fuel ethanol High fructose corn syrup sorbitol foodstuffs pharma. polyolsisosorbide hydrogenation Other sweeteners citric acid lysine xanthangums itaconicacid & other fermentation products industrial oils lactic acid PLA polymers resins & plastics applications polyesters surfactants pharmaceuticals deicers solvents coatings glycerol food oils feed oils Corn Wet Mill starchcorn oil corn gluten meal corn gluten feed food & industrial starches hydrolysis glucose fuel ethanol fermentation sorbitol foodstuffs pharma. polyolsisosorbide hydrogenation citric acid lysine xanthangums itaconicacid & other fermentation products industrial oils lactic acid PLA polymers resins & plastics applications polyesters surfactants pharmaceuticals deicers solvents coatings glycerol food oils feed oils T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005

4. 4 Current Ethanol Process CornDry GrindLiquefactionScarification Fermentation Primary Distillation Rectifier Molecular Sieves Centrifuge Triple Effect Evaporator DDG Dryer DDG Animal Feed Ethanol Solids 50% EtOH 95% EtOH 100% EtOH Liquids Water Recycle Solids T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005

5. 5 Strategies for Creating Additional Value Modify dry mills to include a quick steeping process that allows germ recovery Add an intermediate filtration process to recovery non-starch derived sugars (hemicellulose) Develop new fermentations for utilization of five carbon sugars (itaconic acid, succinic acid, etc) Develop new chemistry to produce value added products from hemi-cellulose (sugar alcohols, polyols) Include an energy component-pyrolyze “DDG or modified DDG” to produce bio-oil T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005

6. 6 The Holistic Ethanol Facility CornQuick SteepScarification Filtration Fermentation Ethanol Recovery Molecular Sieves “Fiber”Hydrolysis New DDG Animal Feed Ethanol Starch EtOH 95% EtOH 100% EtOH Germ Separation Fermentation Catalytic Conversions Pyrolysis Fuel/Power EG, PG Glycerol, Etc Itaconic Succinic, Etc Oil T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005

7. 7 Possible Future Biorefinery Lignocellulosic Biomass HydrolysisFermentation UpgradingPyrolysis Ethanol Fuel Distillation Products lignin sugars bio-oil Additional Biomass Motor Fuel D.J. Stevens, PyNe, 2005 Heat, electricity

8. 8 The Potential Role of Pyrolysis Part of a Petroleum Refinery Biomass first would be converted to bio-oil, possibly at distributed locations at small scale Bio-oil can be partially upgraded by catalytic hydrotreatment at larger scale in proximity of a petroleum refinery Upgraded bio-oil then would be co-fed with petroleum feedstocks through a catalytic process to produce conventional refinery product slate The global petroleum industry is showing more interest From the Department of Energy perspective, this is a medium-term approach

9. 9 Pyrolysis/Petroleum Biorefinery Distributed Lignocellulosic Biomass Upgrading and Refining with Petroleum Fast Pyrolysis Products Motor Fuel bio-oil transport

10. 10 Overall Biorefining Concept Yrjö Solantausta, 14.3.2006, VTT

11. 11 The Potential Role of Pyrolysis Stand-alone facilities Small size makes economics of fuel production difficult May be more appropriate for heat and power applications High-value specialty chemicals may provide the economic driver Unlikely to gain strong support from Department of Energy in the U.S. because of current focus on petroleum displacement, but Department of Agriculture is interested

12. 12 Concept of a Biorefinery D. Radlein, Fast Pyrolysis Handbook, 1999 Pyrolyzer Fuel Gas Char Converter Bio-oil AshActivated carbon Biomass Anhydrosugars Hydrolysis & Fermentation Reaction Separation Catalytic Reforming NH 3 lime alcohol water Ethanol Slow Release Fertilizers (N, Ca, Zn, Fe...) Noxolene™ (NOx reduction) BioLime™ (NOx/SOx reduction) Fuel Enhancers Flavor Chemicals Chemicals Flavors Adhesives Diesel/boiler Fuel Specialty Synthesis Gas Hydrogen

13. Biomass Refinery Concept D. Meier Biomass Fractionation Fibers Cellulose Hemicellulose Lignin direct use in situ treatment post treatment direct use PHENOLS alcohols water (NCW, steam)

14. 14 Biomass Refinery Concept D. Meier Biomass Fractionation Fibers Cellulose Hemicellulose Lignin direct use in situ treatment post treatment direct use PHENOLS alcohols water (NCW, steam)

15. 15 BIOREFINERY CONCEPT Fast pyrolysis Wet fuels Mixed fuels Woody biomass waste wood, Acacia bark, agro- biomasses, constr. wood Extractives Solvent extraction Biodiesel Aqueous phase Steam reformation H2 for fuel cells Lignin phase Alcohol addition, solids removal Fuel oils, Diesel fuels Hydrolysis, fermentation Bio-ethanol for fuel cells Thermal cracking/ Catalytic hydrotreatment Char Process energy Steam activation Activated carbon Optional hydrolysis Lignans Anja Oasmaa, 2005, VTT

16. Forschungszentrum Karlsruhe in der Helmholtz-Gemeinschaft ITC-CPV HE FW fast pyrolysis biomass preparation liquid fuel synthesis rail transport from many pyrolysis plants to large, central plant for syngas generation and use entrained flow gasification gas cleaning electricity generation Different biomass and carbon feedstocks bio-oil/char -slurry lignocellulosic biomass: wood, straw, hay.... fossil fuel: other biomass: coal... starch, oil... pulverised coal coal/water slurry organic waste: paper, plastics, dung... synthesis products: synfuel, chemicals, H 2 electricity low T heat O2O2 CO 2 special chemicals

17. 17 SummarySummary Numerous opportunities involving: incorporation into sugar biorefinery incorporation into a petroleum refinery stand-alone with chemical, fuel, and power production incorporation into a gasification and synthesis plant Pyrolysis demonstration will lead to biorefinery Product separation and recovery is a major hurdle Finding the right niche is key

18. PyNe -- Glasgow Progress in Biorefinery Case studies Max Lauer and Doug Elliott September 20, 2006

19. 19 The Potential Role of Pyrolysis Part of a sugars-based biorefinery based on residue pyrolysis for fuel and, perhaps, products Part of a Petroleum Refinery with distributed production and centralized processing Stand-alone facilities with distributed production and centralized processing and refining or true stand-alone with or without fractionation and product processing Incorporation into a gasification and chemical/fuel synthesis plant

20. 20 TEA of Pyrolysis Biorefinery What process concept (or concepts?) Single concept in depth, or Comparison of several concepts Technical or Technoeconomic Detailed mass and energy balance only, or M&E balance to allow capital & operating cost estimate What methods? What level of detail?

21. 21 Biorefinery Concepts to be Evaluated The following institutions agreed to provide the relevant information for the concepts listed below, and these would form the basis of an evaluation exercise. USDA - compare pyrolysis to combustion in ethanol plants IWC – pre-separation concept and pyrolyse products (lignin), maximise by-products and chemicals from the process, particularly phenols FZK – bio-slurry gasification + synthesis PNNL - Distributed pyrolysis to central refinery for upgrading and integration BTG – direct gasification of bio-oil in existing gasifier + synthesis Aston – Speciality chemicals and fuels Rodim – Chemicals and animal pharmaceuticals and fertiliser JR - Pyrolysis + CHP stand-alone ECN – comparison with biomass gasification routes

22. 22 Biorefinery Concepts to be Evaluated Chemicals as primary product IWC – pre-separation concept and pyrolyse products (lignin), maximise by-products and chemicals from the process, particularly phenols Aston – Speciality chemicals and fuels Rodim – Chemicals and animal pharmaceuticals and fertiliser Fuels as primary product FZK – bio-slurry gasification + synthesis BTG – direct gasification of bio-oil in existing gasifier + synthesis ECN – comparison with biomass gasification routes PNNL - Distributed pyrolysis to central refinery for upgrading and integration USDA - compare pyrolysis to combustion in ethanol plants JR - Pyrolysis + CHP stand-alone Template Block flowsheet starting with biomass input – maybe as bio-oil, using all products in some way and minimising waste production Outline mass balance through „blocks“ Capital costs Product costs

23. 23 Biorefinery Concepts to be Evaluated Chemicals as primary product 1.Speciality chemicals and/or separation of biomass components Transport fuels as primary product 2.Bio-oil for transport fuels via gasification and FT and/or methanol 3.Bio-oil (hydro) de-oxygenation for transport fuels Reference case 4.Power and heat Process a.Template for specifications and bio-oil costs b.Block flowsheet starting with biomass (industrial sawmill waste ISW) input, using all products in some way and minimising waste production, to give end products c.Outline mass balance through „blocks“. Size d.Capital costs e.Product costs How and when? Small working groups, Email, Draft (a) & (b) & (c) by end 2006 to DCE Small meetings if needed (d) & (e) TBD but NOT after next TNet meeting Group meeting 2007 FT 20,000bbl/d=3000t/d Biomass 2,000t/d = 660,000t/y AU, IWC, UN, USDA ECN, FZK, BTG, VUT, PNNL, VTT, UT, AU, CF JR, NTNU, UF, USDA @ JR Define ISW @ JR

24. 24 Biorefinery Concepts to be Evaluated FACTS FT single train 20,000bbl/d = 3000t/d diesel = ca 12,000t/d biomass USA Biomass 2,000t/d = 660,000t/y EU Biomass 300 t/d = 100,000 t/y Choren planning 1,000,000 t/y for gasification + FT SIZE OF BIOMASS PROCESSING PLANTS for consideration Small = 200 t/d input dry biomass Large = 2000 t/d input dry biomass = 400 MWth input = 160 MWe SIZE OF intermediate fuel products dependent of biomass input, e.g. partially refined product to refinery SIZE OF FT 12,000 bbl/d output diesel production Upgraded bio-oil hydrotreater = 6000 bbl/d diesel = 800 t/d diesel

25. PyNe -- Glasgow Round Robin on Lignin Pyrolysis Dietrich Meier and Doug Elliott September 20, 2006

26. 26 Round Robin Participants Which laboratories? list of potential participants at Lille Feedstock requirements What kind? many potential sources How much? depends on the laboratory method Time line Acquire feedstock Distribute feedstock Perform tests Collect data Submit report

27. 27 Potential Round Robin Participants LaboratoryProcess Aston UniversityFluid bed, TGA, Py-GCMS Forschungszentrum Karlsruhe (FZK)Fluid bed, screw feed ECNFluid bed University of NapoliBatch University of TwenteFluid bed USDA-Eastern Regional Research CenterFluid bed, TGA BFH-Institute for Wood ChemistryFluid bed, EF National Renewable Energy Lab (NREL)Fluid bed Pacific Northwest National Lab (PNNL)Analytical, TGA, Fluid bed VTT-Technical Research Centre of FinlandPy-GC-AED CIRAD-ForêtAnalytical Institut Français du Pétrole (IFP)TGA, Analytical,

28. 28 Potential Round Robin Participants LabProcess AstonFluid bed (150, 300, 1000g/h), TGA (10mg), Py-GCMS (0.1mg) FZKFluid bed, screw feed (10000g/h) ECNFluid bed ( NapoliBatch, fluid bed (10g?) TwenteFluid bed (1000g/h) USDAFluid bed (1000g/h), TGA BFHFluid bed (150, 5000g/h), PyGC (0.1mg), microbatch (20mg) NRELFluid bed (10000g/h) PNNLAnalytical, TGA (10mg), Fluid bed (100g/h) VTTPy-GC-AED (0.1mg) CIRADAnalytical, fluid bed (1000g/h) IFPTGA (10mg), Analytical,

29. 29 Potential Lignin Sources for Round Robin MeadWestvaco Indulin AT – precipitated Kraft lignin (softwood) Lignol (Alcell) Organosolve lignin Variable biomass source potential IOGEN EtOH residue (straw lignocellulosic) International Lignin Institute Others Sigma Aldrich (sulfur-free) Borregard (kraft lignin or lignosulfonates, both with sulfur) STFI (Swedish pulp & paper institute), kraft lignin

30. 30 Lignin Source MeadWestvaco www.meadwestvaco.com pulping lignin products several grades sulfonated Kraft lignins – REAX and KRAFTSPERSE sulfonated sulfite lignin – POLYFON unsulfonated Kraft lignin – Indulin -AT: 5% moisture, 6.5 pH (15% aq) 3% ash, 97% lignin -C: 5% moisture, 10.2 pH (15% aq) commercial products, readily available in most quantities

31. 31 Lignin Source Lignol (Alcell process) – Bridgwater/Elliott organosolve hardwood lignin Michael Rushton, Vancouver, BC, Canada kilogram quantities available signed agreement by each researcher no third party distribution no publication without permission – source attributed no chemical analysis without permission – data shared inform Lignol of patenting efforts involving Lignol lignin joint ownership of jointly developed IP mutual confidentiality recipient pays cost of shipping, duties, etc. many potential biomass types in the future

32. 32 Lignin Source Iogen – Elliott ligno-cellulosic EtOH residue Ron R. Paradis, VP EtOH and Byproduct Marketing not responsive

33. 33 Lignin Source ENEA-Trisaia -- Chiaramonti steam explosion, alkali extracted, acid precipitated Dr. Braccio and Dr. Zimbardi 1 kg lignin available for round robin tests they would ship the lignin they would like to know some details like what kind of tests and who would carry them out

34. 34 Lignin Source Abengoa – Prins biorefinery residue Viorel Duma, Chesterfield, MO, USA a few hundred kilos available at a time start up this winter 30% dry solids (could be treated (?) to reduce moisture for pyrolysis) lignin content of 60%, balance fiber and ash less interesting alternative -- dry purified lignin product

35. 35 Lignin Source Aldrich Chemical www.sigma-aldrich.com Several grades, commercially available low sulfonate, alkali $0.30-0.40/g hydrolytic $1.20-1.60/g organosolve $0.60-1.00/g 100s of gram quantities

36. 36 Lignin Source Lignoboost -- Meier/Elliott pulping residue lignin Per Tomani, STFI-Packforsk AB, Stockholm sulfur content depends on method, but typically 1-3% several hundred kilos of product available they need to know more of purpose of testing

37. 37 Lignin Source Swedish Energy Agency – Bridgwater organosolve enzyme acid

38. 38 Other Potential Lignin Sources for Round Robin Lignin without sulfur Baltic hydrolysis ILI Genencor enzyme hydrolysis lignin Mondi Sulfur containing lignin Kraft lignin (Borregard?)