OTM - An Advanced Oxygen Technology for IGCC

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1 OTM - An Advanced Oxygen Technology for IGCC Ravi Prasad, Jack Chen, Bart van Hassel, John Sirman, James White, Eric Shreiber, Joe Corpus, Joshua Harnanto San Francisco, Oct 30, 2002 Gasification Technologies

2 Use of Oxygen in IGCC Oxygen is the preferred oxidant Reduced costs for gasifier, heat recovery, acid gas removal Enhanced potential for CO 2 sequestration But added cost for ASU O2 supply options: Cryogenic: Most mature & commercial PSA: Small-medium sizes Polymeric Membranes: Small, low purity OTM: Emerging breakthrough technology

3 Why OTM? Oxygen Purity (%) Cryo PSA Poly Mem Process Temperature (C) OTM High operating temperature enables efficient integration with IGCC

4 OTM = Oxygen Transport Membrane Mixed Conductor Transport Mechanism Ion Migration High Pressure Air O 2 Bulk Charge Diffussion Dissociation Transfer -- Adsorption Charge Transfer Recombination Low Pressure Oxygen Electron e- OTM Migration Desorption Bulk Diffussion Oxides of Metals Oxygen Ion & Electron Transport Produces Pure O2 High T Operation ( C) Pressure Driven Oxygen Separation

Integrated Technology Program Element Fabrication

5 Praxair s Integrated OTM Approach Systems Engineering Process Engineering Materials Synthesis Integrated Technology Program Element Fabrication Powder Production Thin Film Development Over 25 Development Partners

6 OTM Integration in IGCC Basis for Assessment Illinois #6 coal as feedstock Westinghouse 501G gas turbine Anchor point for all calculations : ~272 MW power output from GT Shell technology used for gasification O 2 production: Advanced Cryo: Advanced cryo tailored for IGCC OTM integrated with GT OTM+SOFC Integrated with GT OTM with steam integration

7 IGCC with OTM and SOFC Air Gas Turbine Flue Gas Steam Cycle Steam Extracted Air Clean Syngas Coal Gasification & Clean-up Steam & Water Exchange Sulfur Air SOFC BFW N 2 O 2 OTM Supplemental Compressor BFW

8 Cost and Efficiency of Power Generation via IGCC Cost of Electricity (mils/kwh) Cryo OTM OTM+SOFC $800/kW $400/kW Efficiency (% HHV) Cryo OTM OTM integration integration with with IGCC IGCC produces produces significant significant benefits benefits to to environment environment and and consumer consumer OTM OTM+SOFC

9 Project Plan Joint DOE/Praxair program objective: Commercialize OTM membranes for IGCC Applications Phase1: Material development Composite OTM development Proof of concept in multi-element pilot reactor Phase2: Manufacturing of full size elements Development of specialized components Engineering validation in larger pilot reactor Phase3: Pre-commercial demonstration

10 OTM Materials Options O = Fluorite, AO 2 Perovskites, ABO 3 e - Dual Phase Pyrochlores, A 2 B 2 O 7 Brownmillerite A 2 B 2 O 5

11 Evolution of Advanced OTM Materials O2 Flux (% Hurdle Rate) OTM1 OTM2 OTM3 Relative Strength OTM1 OTM2 OTM3 Generation of Material Generation of Material Simultaneous improvement of flux & strength is a significant accomplishment

12 Components of Praxair s High Performance Composite OTM Low resistance Substrates Gas Tight Films Flow Rate, CC/Sec Generation 2 Al 2 O 3 Generation 1 Leak Rate [cc/sec] 1.E-04 1.E-05 1.E-06 1.E-07 1.E-08 1.E-09 1.E-10 1.E-11 Target Leak Rate E Year 1 Year 2 Year 3 Differential Pressure, PSI Ultra low leak rates achieved in a single firing step

13 PSC: Commercial Technology for OTM Powder Production Conventional Y 2 O 3 Y 1 Ba 2 Cu 3 Ox BaCO3 CuO Calcination CuO Y2O3 Advanced Process Each particle is an intimate mixture of Y 2 O 3, CuO, BaCO 3 Calcination Y 1 Ba 2 Cu 3 O 7 Y 2 Ba 1 Cu 1 O 5 Ba 2 CO 3 Micro-scale stoichiometry control Well suited for complex, multi-cation chemistries Highly flexible - Over 400 mixed oxide compositions made

14 Element Fabrication Praxair has access to fabrication technology from Amoco BP Statoil Westinghouse Praxair & its partners have fabricated and tested a wide range of element geometries Plates, monoliths, tubes. Final selection is based on many considerations

15 Assessment of Element Geometry Attribute Tubular Planar Monolith Sealing Best Difficult Very Difficult Manifolding Easier Difficult Very Difiicult Could be self Strength Self Supporting Not self supporting supporting Existing Technology Existing technology Multiple Options Very Difficult for Fabrication for small size Most advanced for any size Difficult for large size large size Scaleup Easy Difficult Very Difficult Mnf Yield on Low for complex High Functional Element geometry Low Area/Volume Ratio Medium High Very High Thermal Management Easy Fair Difficult Replacement Single tube Entire stack Entire Monolith Tubular Variants: Preferred configuration

16 Praxair Technology for Large OTM Elements Unique semi works manufacturing facility operational

17 Seal Technology Development at Praxair Leak (% target maximum) 100% 80% 60% 40% 20% 0% Commercial Target Maximum Hours Temperature ( C) Leak (% target maximum) 100% 80% 60% 40% 20% 0% Commercial Target Maximum Cycle # Temperature ( C) 100 Product O2 Purity (%)

18 Multi-Element Pilot Reactor 0.2 TPD capacity Pilot plant producing high purity O2 using composite tubes Target Flux demonstrated Life test in progress

19 Advances in OTM Technology at Praxair O2 Flux (% of Target) C C C C % of target flux 150C lower temperature 6x flux improvement Oxygen purity > 99.5% Successful hr life 275psi & 900C Thin Film Membrane Stable flux performance No membrane degradation 10 thermal cycles (25-900C at 275 psi) achieved with no degradation He Purged Un- Purged

20 Summary Ceramic membranes offer potential for low cost oxygen Lowest capital cost, power consumption, and oxygen cost 2-7% gain in efficiency COE reduction of 8-15% Project has made substantial progress 120% of commercial flux achieved High pressure cyclable seals & gas tight membranes 99.5%+ O 2 purity reached at 275 psi P Multi-element pilot system operational Pilot and pre-commercial demonstrations are essential steps to commercialization

Oxy-Fuel Combustion Using OTM For CO 2 Capture from Coal Power Plants

2nd Workshop International Oxy-Combustion Research Network Hilton Garden Inn Windsor, CT, USA 25th and 26th January 2007 Hosted by: Alstom Power Inc. PRESENTATION - 11 Oxy-Fuel Combustion Using OTM For