Scale-up of Hydrogen Transport Membranes for IGCC and FutureGen Plants

Eltron Research & Development Scale-up of Hydrogen Transport Membranes for IGCC and FutureGen Plants Presented by Paul J. Grimmer Eltron Research Inc. Boulder, CO 80301 May 17, 2006 This presentation does not contain any proprietary or confidential information. #PD13 Slide 1 Eltron Research & Development Overview Technical Targets Low-cost H2 production system to produce CO2 and H2 from coalderived synthesis gas Demonstrate in 220 lb H2 /day unit Design for 4 ton/day unit Tolerant to syn gas contaminants Partners NORAM Engineering CoorsTek Praxair Timeline Project start date: 1 Oct 2005 Project end date: 30 Sep 2010 5% percent complete Budget ($000) Total project funding: $15,300 DOE share: $12,240 Contractor share: $ 3,060 Funding received in FY05:$ 0 Funding for FY06: $ 966 Barriers Addressed Reducing hydrogen cost Hydrogen production from diverse pathways Hydrogen of sufficient purity for fuel cells DOE Contract DE-FC26-05NT42469 Slide 2 Eltron Research & Development Objectives Continue Vision 21 project for high-throughput, lowcost H2 separation system: scale-up and improve tolerance to contaminants (S, Hg, etc.) Determine optimum mechanical configuration (tube vs. plate; metal vs. cermet) based on manufacturability, cost & performance of membrane and system Scale up membrane & system from 0.45 lb/day of H2 using lab gases to 220 lb/day in coal-derived syn gas Integrate membrane design into a 4 ton/day H2 production unit Determine optimum process design & cost and compare vs. other systems Slide 3 Eltron Research & Development Advances in Past Year Process Design and Cost Estimating 1,000 psi ∆P across membrane Elimination of sweep gas Outlet Pressure up to 270 psi Initial testing of Sulfur tolerance to 200 ppm Excellent results of integrating Water-Gas Shift into membrane reactor (separately funded SBIR project) Slide 4 Eltron Research & Development Current Performance Results 99.999%+ H2 selectivity consistently Demonstrated 1,000 psi ∆P Demonstrated 270 psi permeate pressure (limited by experimental setup) 11 months continuous operation in a simulated synthesis gas stream containing H2, CO, CO2 and H2O (steam) Eltron H2 flux = 423 ml/min-cm2 (Pd = 15, Pd-Cu alloy = 8) Flux rates validated by DOE NETL Slide 5 Eltron Research & Development Recent Flux Data Feed : 60%H2-40%He Temperature: 380/400 °C ·cm -2 STP) 180 160 140 120 100 80 60 40 20 0 0 200 400 600 800 1000 Increasing Feed Pressure, Permeate pressure = 18 psig Increasing Permeate Pressure, Feed Pressure = 450 psig Sieverts' Law H 2 Permeation (mL·min -1 P f1/2- P s1/2(Pa 1/2) Outlet pressure ranged from 0 – 275 psig Sieverts’ Law deviation – gas phase diffusion limited (reactor configuration) not membrane limited Slide 6 Eltron Research & Development Membrane Long-Term Stability under WGS Conditions 1.4E-07 1.2E-07 1.0E-07 8.0E-08 6.0E-08 4.0E-08 2.0E-08 0.0E+00 0 50 100 150 200 250 300 Eltron HTM Pd Membrane ·s -1·Pa -0.5 ) 340 C with a feed containing 41.4%H2 , 37.3%H2 O, 3.3%CO and 17.8% CO 2 and a Cu/ZnO guard bed o Hydrogen permeability (mol·m -1 T ime (Days) • One of few known membrane studies that was conducted for 11 months under a simulated WGS conditions. • Still about five times better than Pd membrane after one year operation. Slide 7 Eltron Research & Development Vision 21 Process Modeling Results (NORAM) 35 TPD H2 Separator Unit Tubular Heat Exchanger Type Geometry $21K Capital / TPD H2 x8 = 265 TPD H2 FutureGen Total Incremental System Cost ~ $23 M Includes membrane cost, separator assembly / installation, gas cleaning, H2 cooling For Comparison PSA ~ $41M Source: ASME VIII, Div. 1, Section UHX Slide 8 Eltron Research & Development Sulfur Tolerance of an Alloy Catalyst 8.0E-09 Hydrogen Permeability (mol·m-1·s-1·Pa-0.5) 7.0E-09 6.0E-09 5.0E-09 40%H2, 20ppm H2S @ 440oC 40%H2, 100ppm H2S @ 440oC 4.0E-09 3.0E-09 60%H2, 20ppm H2S @ 320oC 2.0E-09 1.0E-09 0.0E+00 0 20 40 60 80 100 120 140 160 180 200 Time (Hours) • Several alloy catalysts display a good stability with a 40% H2 stream containing 20 ppmv of H2S. • Emerging warm-gas cleaning technology can clean sulfur impurity below 2 ppmv. Slide 9 Eltron Research & Development Progress Towards DOE FutureGen Targets Performance Criteria Flux (sccm/cm2/100 psi ∆P) Operating Temperature (oC) S Tolerance (ppmv) System Cost ($/ft2) ∆P Operating Capability (psi) Carbon Monoxide Tolerance Hydrogen Purity (%) Stability/Durability (years) Permeate Pressure (psi) 2005 Target 50 400-700 N/A 1000 100 Yes 95 1 N/A 2010 Target 100 300-600 2 500 400 Yes 99.5 3 N/A 2015 Target 150 250-500 20 <250 800-1000 Yes 99.99 >5 N/A Current Eltron Membrane 160 300-400 20 (early) <200 1,000 Yes >99.999 0.9 270 Slide 10 Eltron Research & Development Simplified Project Schedule Scale Up Hydrogen Transport Membranes for IGCC and FutureGen Coal to Hydrogen Production Plants FY2006 Design/Build 1.3 lb/day H2 Sep Unit Improved Membrane Components Develop Methods of Low-Cost Membrane Manufacturing Process Economic Analysis Develop & Test & Optimize Impurity Management System Design / Build / Test 5.5 lb/day PDU Design / Build / Test 220 lb/day Subscale Engineering Prototype Design 4 tpd Field Demonstration Unit FY2007 FY2008 FY2009 FY2010 Qtr 1 Qtr 2 Qtr 3 Qtr 4 Qtr 1 Qtr 2 Qtr 3 Qtr 4 Qtr 1 Qtr 2 Qtr 3 Qtr 4 Qtr 1 Qtr 2 Qtr 3 Qtr 4 Qtr 1 Qtr 2 Qtr 3 Qtr 4 DOE Contract #DE-FC26-05NT42469 Slide 11 Eltron Research & Development Slide 12 Eltron Research & Development Hydrogen Transport Across Eltron’s Membrane H-H H-H Hydrogen H-H Dissociation H H H H-H H-H H-H H H-H Hydrogen Transport Membrane Material Diffusion of Hydrogen in Dissociated Form H Layers of Hydrogen Dissociation Catalyst H H H H HH Recombination and Desorption of H2 Slide 13 Eltron Research & Development Sputtering System for Membrane Catalyst Deposition Slide 14 Eltron Research & Development Material Focus – FY06 Top/Bottom Catalyst Layer Increased sulfur tolerance (alloys) [top layer] Optimal application to bulk membrane (CVD, Electroplating, Electroless, Sputtering) Tubular vs. Plate Bulk Membrane Diffusional barriers with top/bottom layers Cost reduction (cermets) [with CoorsTek] Slide 15 Eltron Research & Development Process Design Focus – FY06 Eltron System Staged WGS/HTM optimum balance Number of stages Permeate pressure per stage Membrane size (hence throughput) per stage Heat management issues (if any) Operability Start-up, shutdown, run-times Refined Capital & Operating Cost Estimation Comparison to Other H2 &/or CO2 Systems Pressure Swing Absorption Post-combustion amine scrubbing Note – Above with NORAM & Praxair Slide 16 Eltron Research & Development Simplified Flowsheet Staged WGS / HTM System Maximum H 2 and CO2 Production Synthesis Gas 1,000 psig 300°C CO2 to Sequestration Steam 950 psig 400°C > 96% CO2 (ex H O) 2 WGS HTM HTM 1 2 HTM WGS HTM HTM 2 3 1 H2 5 psig HTM WGS HTM 3 1 H2 HTM HTM 2 3 H2 HTM V -10 psig H2 Compr Compr H2 60 psig H2 H2 Compr H2 H2 H2 H2 to Fuel or Export 200 psig > 96% Recovery Slide 17 Eltron Research & Development Integrated WGS / HTM Conversion “Beyond Equilibrium” 100 90 F81-34A B 100 90 80 CO Conversion (%) 70 60 50 40 30 20 10 0 0 Feed (mol%) H2 47.8% CO2 6.2% CO 7.8% H2O 38.2% 70 60 50 40 30 H2 O/CO = 4.9, GHSV = 2000/h, Temperature: 380 C 20 40 60 80 100 o 20 CO conversion H2 productivity 120 140 10 0 Differential Pressure Across Membrane (psig) Slide 18 Hydrogen Productivity (%) 80 Eltron Research & Development Challenge for Funding Contract between Eltron & DOE is for first 2 years only. Last 3 years will be committed after a replacement subcontractor has been identified. Eltron is in discussions for participation with 25+ companies including coal and energy producers, technology providers, E&C’s, gasifier providers, turbine manufacturers and materials suppliers. Eltron will likely propose to accelerate the program to skip the 5.5 lb/day unit and add a functioning 4 ton/day unit (instead of the current paper design) when the new partner(s) is finalized. Slide 19 Eltron Research & Development Summary Eltron’s membrane continues to show stable, high fluxes using relatively low-cost materials. Contaminant handling, durability, and fabrication are materials focus areas. The project has moved well beyond materials R&D into engineering and cost analysis. Improvements have been made in materials and process design which are leading to additional cost reductions and performance enhancements. The project is on schedule and budget. Slide 20 Eltron Research & Development Back-Up Slides See following slides Slide 21 Eltron Research & Development Response to 2005 Reviewer Comments Lack of focus on durability testing prior to scale up Some sulfur testing has been done with encouraging results Lifetime demonstrated at 11 months to-date Lifetime testing with contaminants is part of the program 100% selectivity and recovery will not be achieved >99.999% selectivity is routinely achieved Recovery will be based on economics which are favored by simplicity and cost of membrane system No economic analysis performed Economics were run after last year’s presentation that show almost a 50% improvement versus PSA The CCP Team calculated that Eltron’s membrane had the potential for 60% cost reduction vs post-combustion amine scrubbing and 40% better than PSA. This was before permeate pressure staging was possible due to discovery of method for higher than atmospheric permeate pressure which reduces costs by another 20%. Slide 22 Eltron Research & Development Recent Publications and Presentations Hydrogen Separation Membranes, A Key to Carbon Sequestration - Energy Frontiers International ( EFI) Conference; "Emerging Energy Technologies: State of the Art - Challenges Ahead", Orlando, FL, Feb 2006 [Paul Grimmer] Membranes for the Purification of Hydrogen Produced from Coal-Derived Water-Gas Shift Mixtures - 22nd Annual International Pittsburgh Coal Conference, Pittsburgh, PA, Sept 2005 [Michael V. Mundschau, Xiaobing Xie, Carl R. Evenson IV, Anthony F. Sammells] Dense Membranes for Methane Conversion to Hydrogen with Carbon Dioxide Sequestration - 7th International Conference on Catalysis in Membrane Reactors, Cetraro - CS, Italy, Sept. 2005 [A. F. Sammells, M. V. Mundschau, X. Xie, C. R. Evenson] Membrane Technologies for Oxygen Production and Hydrogen Separation - International Congress on Membranes and Membrane Processes (ICOM 2005), Seoul, Korea, Aug. 2005 [Arun C. Bose, Phillip A. Armstrong, A. F. Sammells, S. Elangovan] Performance of Palladium Catalysts on Hydrogen Transport Membranes Exposed to Water-Gas Shift Reactants at High Pressure - North American Catalysis Society, 19th North American Meeting, Philadelphia, PA, May 2005 [M.V. Mundschau, X. Xie, A.F. Sammells] Advances in Hydrogen Separation Membrane Technology for the Separation of CO2 and the Purification of Hydrogen Produced from Coal - 30th International Technical Conference on Coal Utilization & Fuel Systems, Clearwater, FL, April 2005 [M.V. Mundschau, X. Xie, A.F. Sammells] Advanced Membranes for the Spontaneous Conversion of Coal to Hydrogen - 21st Annual International Pittsburgh Coal Conference, Osaka, Japan, Sept. 2004 [A.F. Sammells, M.V. Mundschau, X. Xie, C.R. Evenson] Dense Membranes for Separation of H2 from CO2 in High-Pressure Water-Gas Shift Reactors - 7th International Conference on Greenhouse Gas Control Technology, Vancouver, BC, Sept. 2004 [M.V. Mundschau, X. Xie, A.F. Sammells] Oxygen and Hydrogen Transport Membranes for Combined Hydrocarbon Reforming and Hydrogen Separation - 8th International Conference on Inorganic Membranes, Cincinnati, OH, July 2004 [A.F. Sammells, M.V. Mundschau, X. Xie] Simultaneous Hydrocarbon Reforming, Carbon Dioxide Sequestration and Hydrogen Separation Using Dense Inorganic Membranes - Annual Carbon Capture and Sequestration Conference, Alexandria, VA, May 2004 [M.V. Mundschau, X. Xie, C.R. Evenson, A.F. Sammells] Hydrogen and Oxygen Transport Membranes for Spontaneous Conversion of Coal to Hydrogen - 29th International Conference on Coal Utilization and Fuel Systems, Clearwater, FL, April 2004 [A.F. Sammells, M.V. Mundschau, S.E. Roark, T.F. Barton] Slide 23