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PyNe -- Glasgow

PyNe -- Glasgow . WP 2H Biorefinery Tony Bridgwater and Doug Elliott September 20, 2006. Presentation Organization. Biorefinery basics Biorefinery concepts TEA for Biorefineries. An Example of a Current Biorefinery. Corn Wet Mill. Corn Wet Mill. corn gluten . corn gluten . corn gluten.

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PyNe -- Glasgow

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

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

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

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

  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 5

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

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

  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 8

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

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

  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 11

  12. Concept of a Biorefinery Hydrolysis & Fermentation Biomass Ethanol Anhydrosugars Slow Release Fertilizers (N, Ca, Zn, Fe ...) NH3 Reaction Pyrolyzer Bio-oil Noxolene™ (NOx reduction) Reaction BioLime™ (NOx/SOx reduction) lime Fuel Gas Reaction Fuel Enhancers Flavor Chemicals alcohol Char Converter Chemicals Flavors Separation water Adhesives Diesel/boiler Fuel Specialty Ash Activated carbon Separation Catalytic Reforming Synthesis Gas Hydrogen D. Radlein, Fast Pyrolysis Handbook, 1999 12

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

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

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

  16. Different biomass and carbon feedstocks other biomass: lignocellulosic biomass: organic waste: fossilfuel: wood, straw, hay .... paper, plastics, dung ... starch, oil ... coal ... biomass preparation fastpyrolysis special chemicals bio-oil/char -slurry rail transport from many pyrolysis plants to large, central plant for syngasgeneration and use O2 pulverised coalcoal/water slurry entrained flow gasification CO2 gas cleaning liquid fuel synthesis synthesis products: synfuel, chemicals, H2 low T heat electricity generation electricity

  17. Summary • 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 17

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

  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 19

  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? 20

  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 21

  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 22

  23. Biorefinery Concepts to be Evaluated AU, IWC, UN, USDA ECN, FZK, BTG, VUT, PNNL, VTT, UT, AU, CF JR, NTNU, UF, USDA @ JR Define ISW @ JR Chemicals as primary product • Speciality chemicals and/or separation of biomass components Transport fuels as primary product • Bio-oil for transport fuels via gasification and FT and/or methanol • Bio-oil (hydro) de-oxygenation for transport fuels Reference case • Power and heat Process • Template for specifications and bio-oil costs • Block flowsheet starting with biomass (industrial sawmill waste ISW) input, using all products in some way and minimising waste production, to give end products • Outline mass balance through „blocks“. Size • Capital costs • 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 23

  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 24

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

  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 26

  27. Potential Round Robin Participants 27

  28. Potential Round Robin Participants 28

  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 29

  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 30

  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 31

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

  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 33

  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 34

  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 35

  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 36

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

  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?) 38

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