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PyNe -- Glasgow WP 2H Biorefinery Tony Bridgwater and Doug Elliott September 20, 2006 Presentation Organization Biorefinery basics Biorefinery concepts TEA for Biorefineries 2 An Example of a Current Biorefinery Corn Wet Mill corn gluten feed corn gluten meal starch corn oil hydrolysis food oils feed oils food & industrial starches glucose industrial oils glycerol hydrogenation fermentation sorbitol • foodstuffs • pharma. polyols deicers solvents coatings isosorbide citric acid lysine xanthan gums itaconic acid & other fermentation products lactic acid fuel ethanol High fructose corn syrup Other sweeteners PLA polymers •resins & plastics applications •polyesters •surfactants •pharmaceuticals T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005 3 Current Ethanol Process Corn Dry Grind Fermentation Primary Distillation Liquefaction 50% EtOH Distillation Rectifier Scarification 95% EtOH Molecular Sieves Solids 100% EtOH Centrifuge DDG Dryer Liquids Triple Effect Evaporator DDG Animal Feed Ethanol Solids Water Recycle T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005 4 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 The Holistic Ethanol Facility Oil Corn Filtration “Fiber” Quick Steep Starch Fermentation EtOH Hydrolysis Germ Separation Ethanol Recovery New DDG Animal Feed Pyrolysis Fermentation Itaconic Succinic, Etc Fuel/Power Catalytic Conversions EG, PG Glycerol, Etc T.A. Werpy, Biorefineries, ACS Mtg, Washington, DC August 31, 2005 Scarification 95% EtOH Molecular Sieves 100% EtOH Ethanol 6 Possible Future Biorefinery Lignocellulosic Biomass Hydrolysis lignin Products sugars Fermentation Heat, electricity Pyrolysis bio-oil Distillation Upgrading Ethanol Fuel Motor Fuel Additional Biomass D.J. Stevens, PyNe, 2005 Products 7 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 Pyrolysis/Petroleum Biorefinery Distributed Lignocellulosic Biomass Fast Pyrolysis bio-oil transport Products Upgrading and Refining with Petroleum Motor Fuel 9 10 Overall Biorefining Concept Hydrocarbon-rich fraction Biomass residues Primary fractionation and liquefaction Lignin-rich fraction Co-processing in conventional petroleum refinery Conventional fuels and chemicals De-oxygenation (blending) Derivatives of hemicelluloses and celluloses Conversion Oxygenated products Process residues Energy production Yrjö Solantausta, 14.3.2006, VTT 10 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 Concept of a Biorefinery Biomass Anhydrosugars NH 3 Pyrolyzer Hydrolysis & Fermentation Reaction Slow Release Fertilizers (N, Ca, Zn, Fe ...) Noxolene™ Bio-oil (NOx reduction) lime Reaction alcohol Reaction water BioLime™ (NOx/SOx reduction) Fuel Gas Char Converter Ethanol Separation Fuel Enhancers Flavor Chemicals Chemicals Flavors Adhesives Ash Activated carbon Separation Diesel/boiler Fuel Specialty Catalytic Reforming Synthesis Gas Hydrogen D. Radlein, Fast Pyrolysis Handbook, 1999 12 Biomass Refinery Concept D. Meier Biomass Fractionation Fibers Cellulose alcohols water (NCW, steam) Lignin direct use Hemicellulose direct use •in situ treatment •post treatment PHENOLS Biomass Refinery Concept D. Meier Biomass Fractionation Fibers Cellulose alcohols water (NCW, steam) Lignin direct use Hemicellulose direct use •in situ treatment •post treatment PHENOLS 14 15 BIOREFINERY CONCEPT Steam activation Char Optional Woody biomass waste wood, Acacia bark, agrobiomasses, constr. wood Process energy Solvent hydrolysis Wet fuels Mixed fuels Activated carbon Extractives extraction Biodiesel Aqueous phase Steam reformation H2 for fuel cells Fast pyrolysis Hydrolysis, fermentation Lignin phase Bio-ethanol for fuel cells Alcohol addition, solids removal Thermal cracking/ Catalytic hydrotreatment Anja Oasmaa, 2005, VTT Fuel oils, Diesel fuels Lignans Forschungszentrum Karlsruhe in der Helmholtz-Gemeinschaft Different biomass and carbon feedstocks fossil fuel: other biomass: coal ... lignocellulosic biomass: wood, straw, hay .... starch, oil ... organic waste: paper, plastics, dung ... biomass preparation fast pyrolysis special chemicals bio-oil/char -slurry rail transport from many pyrolysis plants to large, central plant for syngas generation and use pulverised coal coal/water slurry O2 entrained flow gasification CO2 gas cleaning liquid fuel synthesis synthesis products: synfuel, chemicals, H2 electricity generation low T heat electricity FW FW ITC-CPV HE 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 PyNe -- Glasgow Progress in Biorefinery Case studies Max Lauer and Doug Elliott September 20, 2006 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 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 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 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 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 23 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 PyNe -- Glasgow Round Robin on Lignin Pyrolysis Dietrich Meier and Doug Elliott September 20, 2006 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 Potential Round Robin Participants Laboratory Aston University Forschungszentrum Karlsruhe (FZK) ECN University of Napoli University of Twente USDA-Eastern Regional Research Center BFH-Institute for Wood Chemistry National Renewable Energy Lab (NREL) Pacific Northwest National Lab (PNNL) VTT-Technical Research Centre of Finland CIRAD-Forêt Institut Français du Pétrole (IFP) Process Fluid bed, TGA, Py-GCMS Fluid bed, screw feed Fluid bed Batch Fluid bed Fluid bed, TGA Fluid bed, EF Fluid bed Analytical, TGA, Fluid bed Py-GC-AED Analytical TGA, Analytical, 27 Potential Round Robin Participants Lab Process Aston FZK ECN Napoli Twente USDA Fluid bed (150, 300, 1000g/h), TGA (10mg), Py-GCMS (0.1mg) Fluid bed, screw feed (10000g/h) Fluid bed ( Batch, fluid bed (10g?) Fluid bed (1000g/h) Fluid bed (1000g/h), TGA BFH NREL PNNL VTT CIRAD IFP Fluid bed (150, 5000g/h), PyGC (0.1mg), microbatch (20mg) Fluid bed (10000g/h) Analytical, TGA (10mg), Fluid bed (100g/h) Py-GC-AED (0.1mg) Analytical, fluid bed (1000g/h) TGA (10mg), Analytical, 28 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 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 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 Lignin Source Iogen – Elliott ligno-cellulosic EtOH residue Ron R. Paradis, VP EtOH and Byproduct Marketing not responsive 32 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 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 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 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 Lignin Source Swedish Energy Agency – Bridgwater organosolve enzyme acid 37 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