Options for Renewable Hydrogen Technologies Robert J. Evans Electric and Hydrogen Technologies & Systems Energy & Agricultural Carbon Utilization Athens, Georgia June 11-12, 2004
Presentation Outline Hydrogen Overview Biomass Feedstocks Direct Production Gasification Storable Intermediates Bio-Oil Oil Steam Reforming Co-products: Bio-Carbon
Benefits of a Hydrogen Economy Energy Security Can be produced from domestic sources Environmental Pollutants from mobile sources eliminated Emissions from stationary H 2 production sites easier to control Greenhouse gas emissions significantly reduced Economic R&D can help the global economy Biomass Hydro Wind Solar Nuclear Oil Coal Natural Gas With Carbon Sequestration HIGH EFFICIENCY & RELIABILITY ZERO/NEAR ZERO EMISSIONS Conventional H 2 Production Steam Reforming: CH 4 + H 2 O 3H 2 + CO Water Gas Shift: CO + H 2 O CO 2 + H 2 Carbon Gasification: C + H 2 O CO + H 2 Transportation Distributed Generation
Hydrogen Delivery Distributed generation Centralized generation and delivery
Renewable Hydrogen Production Photoelectrochemical hydrogen production from water Photobiological hydrogen production using algae Hydrogen production from biomass Solar thermal hydrogen production Co-production of electricity and hydrogen from renewable technologies, e.g., wind - electrolysis
Biomass Feedstocks 6 CO 2 +6 H 2 O C 6 H 12 O 6 +6 O 2 sunlight Economic Potential : 15% of the world s energy by 2050. Fischer and Schrattenholzer, Biomass and Bioenergy 20 (2001) 151-159. Crop residues Forest residues Energy crops Animal waste Municipal waste Million Dry tons 12 9 6 3 0 Georgia Biomass Feedstock Supply ~150 PJ of H2 energy 5% of GA energy use? Ag Residue 2000 2010 2020 2030 2040 2050 Issues: Biomass Availability and Costs Total
Biomass Feedstocks Composition and Form Moisture and Energy content Feeding Issues Supplies Transportation Costs vs. Economy of Scale Distribution Transport of Biomass or Hydrogen? Costs Difficult to Compete with NGSR Without Credits
Traditional Facility Location Biomass Facility Location Discrete Suppliers Economies of Scale Courtesy of M. Realff, Ga Tech Continuously-distributed Supply Transportation Intensive Economies of Scope
Dollars 30 25 20 15 10 Qualitative Behavior of Total Costs for Processing Fixed Biomass Quantity Increasing with facility size Facility Transportation Total 5 0 0 50 100 150 200 250 300 Volume throughput Courtesy of M. Realff, Ga Tech
H 2 from Biomass Potential H 2 : the Inevitable Fuel of the Future Biomass is Renewable Zero Net CO 2 Impact Potential for Near Term Renewable H 2 Deployment Challenges No Completed Technology Demonstrations Low Yield of H 2 Not competitive with Natural Gas Steam Reforming Requires Appropriate H 2 Storage and Utilization Scenarios
Possible Development Scenario: Biomass H 2 Near Term Mid Term Long Term Biomass Waste Biomass Pyrolysis/ SR Coproducts Cofeed NG + Energy Crops + Gasification + C Seqest. + Adv. Coal + Biomass Refineries Hydrogen On-Site Prod Hythane NG, Electrol. + Storage + Dist. Gen. + Fuel Cells + Hydrogen Economy
Biomass and H 2 Energy Pathways Thermal Biological Physical Excess air Partial air No Air Pretreatment Combustion Gasification Pyrolysis Fermentation Hydrolysis (Heat & Pressure) CH 4 Heat (CO 2 + H 2 O) Fuel Gases (CO + H 2 ) Liquids/ Vapors Ethanol Liquids H 2 Traditional uses: Food, Feed, Fiber, and Wood Products
Vapor H 2 O CO CO 2 Primary Secondary Tertiary Oxygenates Low P Furans, Phenols, BTX Ketenes, Olefins PAH s H 2 O CO CO 2 H 2 O H 2 CH 4 CO CO 2 PM Solid Biomass Char Soot Pyrolysis Severity
Pyrolysis products, wt % Liquid Char Gas Fast Pyrolysis 75% 12% 13% Moderate temperature Fast heating rate Short residence time Slow Pyrolysis 30% 35% 35% Low temperature Slow heating rate Long residence time Gasification 5% 10% 85% High temperature Long residence time
Gasification Direct Production Thermal / Steam / Oxygen Syn Gas Processing: Catalysis and Separation Supercritical Conversion Wet Biomass Pyrolysis to Hydrogen and Carbon Biological Conversion
Gasification / Water-Gas Shift Indirect Biomass + Energy CO + H 2 + CH 4 + CO + H 2 O CO 2 + H 2 BCL/FERCO - Low Pressure, Indirectly Heated Direct CH 1.46 O.56 + 0.22 O 2 CO + 0.73 H 2 + Energy Biomass Syngas 15.4 Wt. % CO + H 2 O CO 2 + H 2 Theo. yield Overall: CH 1.46 O.56 + 0.22 O 2 +H 2 O CO 2 + 1.73H 2 IGT - High Pressure O2 Blown
Single-Stage Steam Gasification H 2 H 2 +CO + CH4 + CO 2 + H 2 O + Tar + Biomass Steam Gasification 850-1000 o C Char Steam
Indirect Gasification Heat + Sand Char + Sand
BCL CFB Indirect Gasification + Steam Reforming Biomass Gasification 0.2 MPa 830 C CO + H 2 +CO 2 + CH 4 H 2 + CO 2 + CO Catalytic H2O Reforming 3.5 MPa 850 C Compression 91 C HT Shift 3 MPa 370 C LT Shift 2.5 MPa 200 C PSA H 2
Storable Intermediates Pyrolysis Oils Steam Reforming Coproducts Biomass Fractionation Streams Methanol & Ethanol On-board Reforming Methane from Anaerobic Digestion Pyrolysis and Reforming Options
Biomass Pyrolysis The thermal decomposition of biomass Heat No Oxygen Products Gas Liquid: Bio-Oil + H 2 O Solid: Char Proportions depend on Heating Rate, Temperature, Pressure, time
Pyrolysis Biomass + Energy Bio-oil + Char + Gas E.g., 66 wt.% bio-oil Yield Steam Reforming of Bio-oil Bio-oil + H 2 O CO + H 2 CO + H 2 O CO 2 + H 2 CH 1.9 O 0.7 + 1.26 H 2 O CO 2 + 2.21 H 2 Maximum yield: 17.2 g H/100 g bio-oil (11.2% based on wood) Process conditions: 850ºC, fluidized supported nickel catalyst
Pyrolysis Process Concept Biomass PYROLYSIS Bio-Carbon Bio-oil SEPARATION Co-products Phenolic Intermediates H 2 O CATALYTIC STEAM REFORMING H 2 (and CO 2 ) e.g., Resins Octane additives Fine Chemicals
Oil 49 H 2 O CO 2 Biomass 100 Gas 5 Reforming 850 o C H2 8 Pyrolysis H 2 O 23 CO 400-500 o C C 12 Char 23 Activation 850 o C
Eprida s Approach Biocarbon-Based Fertilizers Inside Formations Formation of Ammonium Bicarbonate Inside the 15min Char Interior
Overall Project Goals Demonstrate the production of hydrogen from biomass by pyrolysis steam reforming for $2.90/kg by 2010 Barriers: Vapor Conditioning Catalyst Development and Regeneration Reactor Configuration Heat Integration Deployment: H2 + Co-products Milestone: Verify advanced catalysts and reactor configuration for fluid bed reforming of biomass pyrolysis liquid at pilot scale (500 kg H2/day) with catalyst attrition rates < 0.01%/day. 4Q, 2009
Fluid Bed Catalytic Reformer
Problem: Catalyst Attrition Liquid/Gas/Solid Feedstock 850 C Fluidized Catalyst Steam Hydrogen & Co-Products Catalyst fines Courtesy of Kim Magrini, NREL
Blakely Georgia Site Sept 2002
Biomass [100] Phase 3 System 1000 hr run Pyrolysis bio-oil [33] Eductor Filter Preheater Flue Gas? Super Heater Steam Char [35] Compressor Reformer Filter CH 4 Dryer H 2 + CO 2 + Condenser Accumulator Engine H 2 Pressure Swing Adsorption CO 2 + H 2 O
Economics Plant-gate H2 selling price ($/kg) 3.0 2.5 2.0 1.5 1.0 0.5 - Major assumptions: 15% after-tax IRR 20 year plant life n th plant 4,500 cars/day 15,000 cars/day Gasification/reforming MACRS depreciation 90% capacity factor Equity financed 22,500 cars/day 4,500 15,000 cars/day cars/day Pyrolysis/reforming, with coproduct (adhesives)
Co-Product Integration Gasification / Shift Conversion Economically unfavorable compared to NGSR except for very low cost biomass and potential environmental incentives Co-products needed for Today s economics Peanut Hulls Activated Carbon + H2 +CO2 Adhesives + H2 +CO2 The analysis shows that the co-product approach yields hydrogen in the price range of $9 - $12/GJ
Acknowledgements DOE Hydrogen Fuel Cells & Infrastructure Technologies Program NREL Team: Esteban Chornet, Stefan Czernik, Carolyn Elam, Calvin Feik, Rick French, Cathy Gregoire-Padro, Kim Magrini, Yves Parent, Joe Patrick, Steve Phillips Georgia Team: Clark Atlanta University, Yaw Yeboah Eprida Inc: Danny Day Enviro-Tech Enterprises Inc: Denis McGee Georgia Tech: Matthew Realff UGA Dale Threadgill, KC Das IEA colleagues: Suresh Babu, GTI, John Bremmer, Aston University,