2005 OBP Bi-Annual Peer Review TC Platform Analysis Overview Richard Bain Thermochemical Platform November 14-16

Overview Budget Nexant – Sulfur Removal PNNL – Alcohols Separations Princeton – Black Liquor Gasification for fuels UOP – Refinery Analysis Partners Provide performance and cost data to Integrated Biorefinery models Provide research direction and focus through technoeconomic and environmental evaluation addressing technical barriers Set goals/targets Measure progress. Analysis Objective

Thermo Chemical R&D Feedstock R&D Biochemical R&D Products R&D Integrated Biorefinery Corn Wet Mill Improvements Corn Dry Mill Improvements Agricultural Residue Processing Energy Crops Pulp&Paper Mill Improvements Forest Products Mill Improvements Corn Other Grains Corn Stover Wheat Straw Rice Straw Perennial Grasses Woody Crops Mill Wastes Wood Mill Wastes Wood Fiber Conversion DDG Conversion Biomass & Lignin Gasification Systems-level demonstration& validation of technologies to improve corn wet milling facilities using corn grain feedstock by 2008 Systems-level demonstration& validation of technologies to improve corn dry milling facilities using corn grain feedstock by 2008 Systems-level demonstration& validation of technologies to utilize agricultural residue feedstocks in existing or new facilities by2009 Systems-level demonstration& validation of technologies to utilize perennial crops in existing or new facilities by2012 Systems-level demonstration& validation of technologies to improve pulp&paper mill facilities and/or produce additional products from wood by 2012 Systems-level demonstration& validation of technologies to improve forest products mill facilities and/or produce additional products by2012 Biomass & Lignin Gasification Biomass & Lignin Gasification Biomass & Lignin Gasification Biomass Pyrolysis Strategic fit with Pathways

The (Fully) Integrated Biorefinery An effective integrated biorefinery must include biological and thermochemical conversion Maximize efficiency of biomass (and land) utilization by producing fuels thermochemically and biologically

Potential Biorefinery Products Biorefinery ProductTarget Product MarketComment Mixed AlcoholsEthanol, existing alcohols markets Ethanol is largest component of mixed alcohol and can enter U.S. ethanol market. Higher alcohols are high-value byproducts. FT Liquids - NaphthaMotor GasolineFT naphtha is upgradeable to gasoline blendstock. Co-produced with FT distillate. FT Liquids – DistillateDistillate FuelHigh cetane, sulfur-free diesel blendstock. Co-produced with FT naphtha. FT Liquids – WaxesWaxes Potential high-value co-product, but wax production in the US is declining. Can crack wax to make more distillate and naphtha. Renewable DieselDistillate FuelProduced by hydrotreating of fatty acids. Also called Green Diesel Dimethyl Ether (DME)Distillate or LPG Blendable with LPG to 20-25%. Diesel engine use requires fueling infrastructure changes – centrally fueled fleet vehicles are potential near-term market. Pyrolysis Oil – NaphthaMotor GasolineUpgrading of lignin fraction Pyrolysis Oil - DistillateDistillateUpgrading of lignin fraction. Co-produced with naphtha fraction Methanol Methanol as chemical intermediate (e.g., for olefins) is most promising market, since fuel use (MTBE) is in decline in U.S. Hydrogen Market is growing, mainly for use in refineries (captive market) Ammonia Among the largest commodity chemicals

Targets – End Products Ethanol from Thermochemical Mixed Alcohols

Targets – Syngas Intermediate DOE program targets based on intermediate syngas price to track progress toward reducing technical barriers Decrease in syngas price due to increased yields, decreased capital costs, & efficiency gains (2025)(2010)

Targets – Tied with Research Current Goal Results from NREL’s PDU tar reformer Goal case yield is increased & capital cost is less Potential Impact of Reformer Efficiency on Syngas Price Attaining research goals = reduction in syngas price

Ethanol via bioconversion Corn Stover 2,000 dMT/day Ethanol 198,400 gpd Lignin-rich Residue 600 dMT/day Steam & Power Gas-Fired CHP Plant Syngas Production Synthesis Chemical Alcohols 11,800 gpd n-Propanol 9,100 gpd n-Butanol 11,800 gpd Amyl/Hex Alcohols Biomass Residues/ Pyrolysis Oils 1,205 dMT/day Syngas Ethanol 98,000 gpd Ethanol 296,400 gpd Products from sugars will be made in both the stand-alone sugars biorefinery and in this Advanced Ethanol Biorefinery. Sugars Based Biorefinery

FY05 Tasks State of syngas technology/update Equipment design and costs – design & cost detail for gas clean up, air separation unit, and modular systems (work with Nexant) Potential of ethanol from mixed alcohols (gasification of biomass and subsequent conversion to ethanol from mixed alcohols) Effect of oxygen purity on direct gasification (examine different oxygen purities then compare indirectly-heated LP gasification to directly heated HP gasification) Energy densification of distributed biomass (energy requirements and cost of delivering pyrolysis oil and biomass in various forms) Cost-benefit assessment of biorefineries making fuels from black liquor – Princeton University/Navigant/IPST-Georgia Tech/ Politecnico di Milano Opportunities for Bio-renewables in petroleum refineries – UOP/NREL/PNNL

Equipment Design & Costs Task Gas Cleanup Design and Cost Estimates Detailed design and costs for low pressure & high pressure gas clean up & conditioning designs cyclones syngas Scrubber Tar reformer Syngas cooling Water To treatment LO-CAT Sulfur Amine CO2 Syngas compression ZnO bed For LP case

O 2 Purity & Direct versus Indirect Gasification Task ParameterIndirect BCLDirect GTI PressureLow pressure (25 psia)High pressure ( psia) Feeding systemFeed screw conveyorPressurized lock hoppers with feed screw conveyor Syngas compressionAdditional compression neededNo additional compression Heat supply - two vessels (gasifier/combustor) with a circulating medium - air for combustion - one vessel - oxygen blown thus ASU is needed Raw syngas quality/properties - more tar - more char - more CO - lower H 2 :CO ratio - higher heating value - more CO 2 - higher H 2 :CO ratio - lower heating value but higher gasifier efficiency because mass flow of dry gas is higher Operating cost - lower - same Capital cost - lower - 25% higher Biofuel product yield - same - 3% higher

Energy Densification Task total delivered cost on an energy equivalent basis ($/GJ) for transport distances of 0 – 200 miles for: - wood chip delivery with drying at end use site - delivery of dried wood chips - delivery of pelletized wood - delivery of corn stover cubes - delivery of pyrolysis oil Small Distributed Systems 100 ton per day

Forest Biorefinery Analysis Objective Complete a detailed design and cost-benefit assessment of biorefineries making synthetic fuels from black liquor (BL) and wood residues at U.S. Kraft pulp mills; reference mill case-study approach; assess potential energy and environmental impacts for the industry and the country. Activities to date Screened and prioritized biorefinery products for detailed analysis. Developed modeling tools for process design/simulation, mill-integration analysis, financial analysis, and cost-benefit evaluation. Heat and mass balances developed for two fuel products (F-T liquids and DME), ongoing for third product (mixed alcohols), and planned (pending additional funding) for fourth product (methanol as a chemical intermediate). Scoping analysis ongoing for low-temperature BLG to identify most promising mill integration and biorefinery products. Financial/environmental cost-benefit spreadsheet model under development. Initial discussions with engineering company for capital cost estimates. Analytical Team Eric Larson – Princeton University Ryan Katofsky – Navigant Consulting Stefano Consonni – Politecnico di Milano Kristiina Lisa – IPST/Georgia Tech Jim Frederick – IPST/Georgia Tech

Opportunities for Bio-renewables in Petroleum Refineries Evaluate the economics for use of Biorenewables in Oil Refineries ( Based on $40/bbl crude) Uncover attractive near and long term Opportunities for Biorenewables in Oil Refineries - Proof of Principle Experiments to Confirm Ideas Goal Activities Production of Renewable (green) Diesel Upgrading of Pyrolysis Oils Separation into Lignin and Aqueous Fractions Upgrading of Lignin Fraction Team UOP/NREL/PNNL

Renewable Diesel H2

FY05 Milestones Milestone type Task / Milestone Description Completion Date DBiomass syngas to product design report1/31/05 DEnergy densification of distributed biomass4/15/05 D Effect of oxygen purity on direct-fired gasification & comparison to indirect gasification 9/30/05 E Potential of thermochemical ethanol from mixed alcohols 10/31/05 J Complete a technical and economic evaluation to validate the cost of syngas from biomass suitable for producing a fuel product. 3/31/05 6/30/05 9/30/05

Future Work - FY06 State of syngas technology/update Dry or CO 2 reforming versus steam reforming – potential economic & environmental benefits Sugars/Thermochemical Integrated Biorefinery (cost shared with strategic analysis) Cost-benefit assessment of biorefineries making fuels from black liquor Lignocellulosic Biomass Fermentation Catalysis Syngas Production Sugar Production Ethanol Products: propanol, butanol other alcohols Lignin-rich Residues Low Quality Residues CHP Distillation CO2