Sustainable Biofuels A Small Step towards Carbon Management

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1 Energy Technology Division Sustainable Biofuels A Small Step towards Carbon Management Raghubir Gupta and David Dayton Energy Technology Division RTI International Research Triangle Park, NC April 2014 RTI International is a trade name of Research Triangle Institute.

2 RTI International Turning Knowledge Into Practice Developing advanced process technologies for energy applications by partnering with industry leaders One of the world s leading research organizations Syngas Carbon Capture Natural Gas Industrial Water Biofuels

3 Photosynthesis - Biomass Production

4 Gasoline (cars & trucks) The Challenge - Transportation Fuels 140 bgy Diesel (on-road, rail) Aviation (jet fuel) 43 bgy 25 bgy 19.5 MM barrels/day 71% for Transportation Energy Independence and Security Act of 2007 Raised CAFE fuel efficiency standards for cars to 35 mpg by 2020 Minimum standard of 27.5 mpg for domestic passenger vehicles Set new efficiency standards for electric household devices (appliances, battery chargers, freezers, motors, light bulbs, etc.) Established a new renewable fuel standard: 9 billion gallons/yr in billion gallons/yr by 2022, of which 21 billion gallons must be cellulosic Biofuels must deliver a 20% lifecycle greenhouse gas reduction Annual Transportation Fuels Use (2008)

5 Biomass to biofuels -- a complex supply chain Biomass-to-Biofuels Supply Chain Source EERE Office of Biomass Program 2007 Multi-Year Program Plan Feedstock Supply Feedstock Logistics Agricultural Residues corn stover, cereal straws Energy Crops -Woody and Perennial Herbaceous Forest Resources - Existing and Repurposed Pulp and Paper and Forest Products Mills Industrial and Other Wastes Algae Biofuel Production Biochemical Thermochemical Gasification Pyrolysis Hydrothermal/Liquifaction Aqueous Phase Processing Biofuels Distribution Biofuels Utilization Bulk Distribution Infrastructure Retail Marketing Network Vehicles Technology Development and Deployment Engineering Economics Risk Management Other Considerations Sustainability Water Greenhouse Gas Emissions Policy and Regulatory Mandates/subsidies Financial Markets

6 Biofuels Technology Pathways Feedstock Deconstruction Intermediate Product Upgrading Cellulosic Feedstocks Agricultural Residues Forest Resources Energy Crops Municipal Solid Waste Algae Biochemical Conversion Gasification Pyrolysis/Direct Liquefaction Open Pond Close Bioreactor Sugars Syngas Bio-oil Source: Bioenergy Technologies Office Replacing the Whole Barrell, DOE/EE-0920 July 2013 Fermentation Catalysis Fermentation Catalysis Catalysis Transesterification Bio-products Ethanol Advanced Biofuels Gasoline Diesel Jet Fuel Biodiesel

7 Biochemical Conversion CO 2 Feedstock Supply Pretreatment/ Deconstruction Hydrolysis Sugars & Intermediates C6/C5 Fermentation Product Recovery (distillation) Ethanol Butanol Agricultural Residues Woody Biomass Grasses/Straws Concentrated or dilute acid Ammonia Fiber Expansion (AFEX) Warm or Hot Water Washing Enzymatic Catalytic Boiler Residual Lignin Heat & Power

8 N2-free dry gas concentration, vol% Tar concentration, g/nm3 Fe, Co, Ru Oxosynthesis Co, Rh CuZnO-Based CuCo-Based MoS2-Based Cu, Ag (TIGAS, MTG, MTO) Carbonylation Zeolite Rh-based HPA/ Zeolite Thermochemical Conversion - Gasification Feed Processing & Handling Biomass Gasification Syngas Cleanup Syngas Conditioning Catalytic Fuel Synthesis Advanced Biofuels Hydrogen Carbon Monoxide Methane Carbon Dioxide Ethane Ethylene Tar Conc. Benzene conc Diesel Waxes Gasoline Olefins Fischer-Tropsch Ethanol Gasoline Olefins Syngas CO + H 2 CuZnO-Based Methanol CH 3 OH Al2O3/ Zeolite/HPA DME CH 3 OCH :30 16:30 17:30 18:30 19:30 20:30 21:30 22:30 23:30 Time, HH:MM Indirect Biomass Gasification in a 50 kg/hr bubbling fluid bed gasifier 10 Aldehydes Alcohols Mixed Alcohols Formaldehyde Acetic Acid Catalytic Syngas Conversion to Fuels and Chemicals Methyl Acetate

9 Syngas Utilization Chemicals Chemical Looping Fe 3 O 4 + CO 3FeO + CO 2 3FeO + H 2 O Fe 3 O 4 + H 2 Hydrogen Methanation CO + 3H 2 CH 4 + H 2 O Methane (SNG) Methanol Synthesis CO + 2H 2 CH 3 OH CO 2 + 3H 2 CH 3 OH + H 2 O CO + H 2 O CO 2 + H 2 Clean Syngas H 2, CO, CO 2 Building Blocks for Fuels and Chemicals Dimethyl Ether Synthesis 2CH 3 OH CH 3 OCH 3 + H 2 O LPG and Diesel Fuel Transportation Fuels Fischer-Tropsch Synthesis 2nH 2 + nco (-CH 2 -) + nh 2 O Gasoline and Diesel Mixed Alcohol Synthesis 2nH 2 + nco C n H 2n+1 OH + (n-1)h 2 O Ethanol and Gasoline Additive LPG and Gasoline

10 Thermochemical Conversion Pyrolysis Biomass (White Oak) Proximate Analysis (wt %) Baseline Bio-Oil Baseline Char Gas (15%) ~500 C T? 1 atm Pyrolysis 1 atm Vapor-Phase Biomass Vapors Upgrading 70% 80% volatiles Hot Gas Filtration 10-15% Fixed C % Ash Biomass Pyrolysis ~25 C C 50% Quench 1 atm H 5% C O 40% 1 atm N <1% S <0.5% < 0.5 sec T? Liquid-Phase Cellulose 40% P? Upgrading Hemicellulose 35% Lignin 25% Char (15%) Reagents: H 2, ROH, H 2 O, O 2,other? Fuels & Chemicals Petroleum Refinery Petrochemical Plant Biorefinery Liquid Bio-oil Intermediate Low TAN Low viscosity stable Volatile Matter Fixed Carbon Ash HHV (BTU/lb) Ultimate Analysis (wt%) C H O N S Ash

11 Catalytic Fast Pyrolysis Technology Options In-situ Ex-situ Cost target: $3.00 gal -1 by 2022 Largest cost contributors: feedstock and capital Technology is much less developed than pyrolysis/hydrotreating Diesel and Jet fuels are more desirable.

12 Catalytic Biomass Pyrolysis State-of-Technology Current State-of-the-Art Biomass (C in ) Gas CO, CO 2 C x H y (C 2 ) H 2 H 2 O, CO 2 H 2 H 2 O, CO 2 Flash Pyrolysis Char (C 1 ) Mild Hydrotreating Coke (C 3 ) Hydroprocessing Coke (C 4 ) Biofuel (C out ) Primary Technical Objectives Maximize biofuel output Minimize external H 2 consumption Reduce process complexity Maximize heat integration RTI s Translational Technology Biomass (C in ) Gas CO, CO 2 C x H y H 2 (C B ) Catalytic Pyrolysis Char + Coke (C A ) H 2 H 2 O, CO 2 Hydroprocessing Coke (C C ) Biofuel (C out ) Technical Barriers to Overcome Utilize H 2 produced in-situ Reduce oxygen content of biocrude Improve bio-crude thermal stability to maximize energy recovery Minimize coke formation C B < C 2 C A << C 1 +C 3 C C C 4

13 Catalytic Upgrading of Biocrude Intermediates to Hydrocarbons Feedstocks Woody biomass Switchgrass Corn Stover Conversion Technology Catalytic Biomass Pyrolysis Upgrading Technology Hydroprocessing Advanced Biofuels Diesel (F-76) Jet Fuel (JP-5, JP-8) Integrate novel catalytic biomass pyrolysis step with hydroprocessing step Optimize the catalytic biomass pyrolysis process to achieve high degree of deoxygenation, while maximizing the biocrude yield Improve bio-crude thermal stability Evaluate the impact of bio-crude quality in the hydroprocessing step Minimize hydrogen demand of the integrated process and maximize biofuels yields Leveraging $4.0 M DOE/EERE funding to develop, design and operate small integrated pilot system RTI s 1 TPD Biomass Unit

14 Water + Nutrients + Sunlight Algal Biofuels Flocculant Solvent H 2 CO 2 Utility Power Algae Growth CO 2 +Nutrient recycle Cell Concentration/ Dewatering Oil Extraction Power Production (Anaerobic Digestion + BioGas Combustion) Residual Biomass Hydrotreating Naphtha Advanced Biofuel Gasoline Diesel AD Digestate (co-product) Source: Bioenergy Technologies Office Algal Lipid Upgrading Fact Sheet, DOE/EE-0803 November 2012

15 Life-cycle Assessments State-of-Technology Technoeconomic Analysis GIS-based assessment of optimal feedstock resource potential Land-use change model development Well-to-wheels analysis and expansion of GHG Emissions and Energy Use in Transportation (GREET) model for emerging biofuels production pathways

16 Life-cycle Carbon Emissions from Various Transportation Fuels Source: U.S. Energy Department, Quadrennial Technology Review, September 2011

17 g CO2-e/MJ gasoline Preliminary GHG Analysis for Catalytic Pyrolysis and Upgrading 100 *GHG reductions are relative to GREET 2005 petroleum gasoline baseline of 93.4 g CO2-e/MJ. GHG Reductions > 206% 97% 101% Total Yield > 27 gal/dry ton 48 gal/dry ton 54 gal/dry ton Fuel Use Fuel Distribution Conversion Feedstock Preprocessing Feedstock Transport Feedstock Production Total -250 Ex-Situ, Low Yield Ex-Situ, High Yield In-Situ Lesley Snowden Swan (PNNL) Electricity and fuel yield are the primary GHG drivers for the conversion plant Higher fuel yields mean less off gas to raise steam and generate power (GHG credits)

18 Water NAS Carbon Capture R&D Activities at RTI Post-Combustion Capture Non-Aqueous Solvents Advanced Solid Sorbents Membrane Processes Hybrid Processes Pre-Combustion Capture Sorbents for warm CO 2 removal from syngas Integration of advanced CO 2 capture processes with RTI s Warm Desulfurization Process 18

19 19 RTI International Non-Aqueous Solvents* (Post-CC) RTI s Carbon Capture Technologies Advanced Solid Sorbents* (Post-CC) Water NAS Polymeric Membranes (Pre- & Post-CC) Warm CO 2 Removal from Syngas* (Pre-CC) Advanced sorbents for warm CO 2 removal from syngas Warm desulfurization enabling advanced CC process*

20 Energy Technology Division RTI Warm Syngas Desulfurization Technology Scaleup History TEC Polk 1 Eastman Pilot testing ( ) Eastman Chemical Company 3000hr pilot test, coal-derived syngas > 99.9% removal of H 2 S and COS (< 5 ppmv S) at > 600ºF & > 600 psig Invention (2001) Proprietary Desulfurization Sorbent - R&D 100 Award (2004) Demonstration ( ): Tampa Electric IGCC Plant, Florida $168.8MM DOE funding to design, construct, operate 50 MW e equivalent scale (~20% syngas slip-stream)

21 RTI 50-MWe Warm Syngas Cleanup Demonstration Project - Construction Energy Technology Division Installing Warm Syngas Desulfurization Equipment Installing WGS Reactors Installing Carbon Capture System Site Aerial View Near Completion Completed Construction 50-MWe Demonstration Project

22 CO 2 can be used an oxidant for biomass conversion CO 2 + Char = 2CO CO can be used as a building block for producing fuels and chemicals.

23 Sustainability Key Aspects Water Quantity and Quality Soil Health and Agronomics Feedstocks Conversion Technology Product Distribution Product End Use Climate Change and Air Quality Land Use Biodiversity Promote nutrient and carbon cycling Minimize impact on land and biodiversity Minimize water consumption Minimize air pollution Maximize efficiency Reduce carbon footprint of new facilities Utilize coproducts and fully integrate systems Evaluate air quality impacts Avoid negative impacts on human health

24 This work has been done by this team Raghubir Gupta, Vice President Energy Technology Division RTI International

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