Fuel Cells

1. Fuel Cells Specialized Catalysts for Hydrogen Productionfor Fuel Cell ApplicationsXV FORO DE AVANCES DE LA INDUSTRIA DE LA REFINACIÓN CONFERENCIA TEMÁTICA Fuentes Alternas de Energía 3-Sep-09Jon P. Wagner and Chandra Ratnasamy Presentadopor Alan BirchSüd-Chemie Inc.

2. Outline • Hydrogen catalysts for Fuel Cells • Specialty Reforming Catalysts • Steam reforming • Auto-thermal reforming • Sulfur tolerant catalysts • Specialized Water-Gas Shift Catalysts • Precious metal catalyst • Sulfur tolerant catalysts • Summary

3. Adsorbents and Additives Catalytic Technology Energy and Environment Foundry Products andSpecialty Resins Performance Packaging Air Purification Chemicals Water Treatment Fuel-Cell Technology Petrochemicals Battery Materials Refinery Biotechnology/CRD Olefin Polymerization The Süd-Chemie Group Adsorbents division Catalyst division Süd-Chemie provides worldwide leading material technologies for the most industrial applications including catalysts for environmental, hydrogen production and fuel cell technologies.

4. GlobalHydrogenMarket U.S. RefiningHydrogen Consumptionmillion kg per day Refineries Hydrogen Market Source: 2003, The Innovation Group Terry Higgins, Hart Energy Publishing Hydrogen Production Today • There is substantial Hydrogen production capacity today. • >50 Metric Tons annually, 95% from Natural Gas • Refinery requirements projected to grow by 20-30% over the next 15 years • Süd-Chemie >65 years

5. Hydrogen Production: Transition to Renewables • Developing markets require novel catalyst developments to enable commercialization • Strong motivation to implement “Green” hydrogen production from renewables • Hydrogen as an energy source offers low emissions and high efficiency • Hydrogen based fuel cells can improve energy security and less dependence on hydrocarbon fuels • Süd-Chemie continues committed to be the leader in hydrogen production catalysis in existing and new markets.

6. New Hydrogen Markets • Distributed Hydrogen Generation • On-site production as a cost effective replacement of delivered liquid and compressed hydrogen • Applications: Metal and glass manufacturing, hydrogenation, electronics • Opportunity for Industrial Gas Companies to incrementally expand capacity with nominal investment • Hydrogen for Fuel Cells • Fuel cells offer high efficiency, ultra-low emissions, reliable and point of use electricity generation. • Large stationary fuel cells (100 kW–10 MW): Base load power, waste water, grid support, co-generation efficiencies >80% • Small stationary fuel cells (1-10 kW): residential, back-up, telecommunications • Portable fuel cells (20-500 W): military, battery replacement, plug-less recharging • Automotive fuel cells (50–75 kW): H2 infrastructure required, >2015

7. Hydrocarbon Based Fuel Cells Desulfurization Pre-Reforming Solid Oxide FC Desulfurization Molten Carbonate FC Pre-Reforming Reforming Desulfurization CO Purification PEM FC Direct Methanol FC Methanol PEM FC Hydrogen Catalytic Processes for Fuel Cell Technologies No Fuel Processing required

8. %H2 Temperature, %CO Steam increases hydrogen production and reduces %CO via water-gas shift reaction Reforming Reactions • Partial Oxidation CH4 + 1/2 O2 CO + 2 H2 H = -71 kJ/mole • Autothermal Reforming 2 CH4 + H2O + 1/2 O2 2 CO + 5 H2H = 139 kJ/mole • ATR can be thermal neutral • Steam Reforming CH4 + H2O  CO + 3 H2 H = 210 kJ/mole • Heat and mass transfer limited

9. Hydrocarbon Conversion • Industrial Steam Reforming for Hydrogen Production • Large tubular reformers (10-25 cm ID) with direct firing • Heat and mass transfer limited: High heat flux ~30,000 Btu/ft2/hr • Large catalyst particles are used to limit pressure drop and improve heat transfer

10. Reforming for Fuel Cells Industrial Steam Reforming Thiele Modulus, Steam Reforming: Mass Transfer Limitations

11. Hydrocarbon Conversion for Fuel Cells • Steam Reforming for Fuel Processors CH4 + H2O  CO + 3 H2 H = 210 kJ/mole • High H2 concentration >65% • Heat and mass transfer limited • Small catalyst particles • coated heat exchangers • complex reactors

12. High Activity Steam Reforming Catalysts • Precious metals improve low temperature activity, carbon and sulfur tolerance.

13. Natural Gas with sulfur Sulfur Tolerant Steam Reforming Natural Gas with no sulfur * Courtesy of H2Gen Innovations

14. Sulfur Tolerant ATR of Gasoline * Data provided by Argonne National Laboratory

15. Hydrocarbon Conversion Summary • Steam Reforming • Greatest hydrogen production but heat transfer presents significant challenge • Ru, Ni, Rh catalysts most active • Autothermal Reforming (ATR) • Faster start-up and moderate hydrogen production • Stable combustion and steam reforming required to maximize activity • Catalytic Partial Oxidation (CPOx) • Rapid start-up at the cost of hydrogen production • Higher temperatures required = higher CO

16. Industrial Water Gas Shift Catalysts • High Temp. WGS: Fe/Cr/Cu introduced in the 1950s • Operating Conditions: 310-475 oC, 10-60 barg, SV=3,000-6,000/hr • Requires Activation: Fe2O3 reduced to Fe3O4 • Physically robust, but low activity • Life determined by thermal sintering & physical strength (∆P) • Low Temp. WGS: Cu/Zn/Al introduced in the 1960s • Operating Conditions: 190-300 oC, 10-60 bar, SV=2,000-4,000/hr • Sensitive to oxidation • Requires Activation: CuO reduced to Cuo • Life determined by poisoning • Designed for steady-state operation • with 4-5 year lifetime

17. High Performance Water Gas Shift Catalysts • High Volumetric Activity Required • Precious metal, Pt • Washcoated onto monolithic substrates • Low thermal mass for rapid start-up • Robust Operation • Power load following, transients • Frequent Start/Stop • Poison tolerant • Reduction/Oxidation Tolerant

18. Low Temperature WGS Catalyst–Pt vs Commercial Catalysts Initial Activity • Cu/Zn/Al is much more active than Fe/Cr/Cu • Pt catalyst is more active than commercial catalysts

19. Low Temperature WGS Catalyst–Pt vs Commercial Catalysts Stability • Pt pellet catalyst is more active and stable than commercial Cu/Zn/Al LTS catalyst • Pt based honeycomb catalyst exhibits high activity at high space velocity

20. CO Conversion at 250 oC, SV=41,500/hr 1.6 mm extrusions Pt WGS Catalyst Sulfur Tolerance–Long Term LTS Stability with H2S • Pt WGS stable at low temperature with 10-80 ppb H2S

21. Pt WGS Catalyst Deactivation Modeling • Pt WGS monolith operated in kinetic regime for an extended period of time • Model based on multiple active site sintering • Many start-ups and shut-downs during test • Catalyst activity levels off at 500 hours on stream • Order of deactivation >5 • Safety Factor <2 where n = order of deactivation

22. 120th Start-up / Shut-down Cycle Initial Start-up 0 50 100 Novel Copper Based WGS Catalyst for Transient Operation Desired Attributes • No pre-reduction • Non-pyrophoric • High activity at low temperature (200 oC) • RedOx Stable Significant deactivation… but ~40% volume remains at EQ • Results • Base metal catalyst can withstand multiple start/stop cycles including oxidation.

23. Summary • New Catalyst Developments are Critical to Enabling Distributed Hydrogen Production for Fuel Cells • Integration of catalyst and reactor design important to maximize efficiency and costs • Pt based catalyst are active and stable • New base metal catalysts can withstand start-up and shut-down operation • CO Purification • Selective CO

24. Hydrogen Catalysts of every type, shape and formulation • Precious and base metal • Washcoated on metal, ceramic or foam monoliths • Extruded • Pelletized • Granulated • Custom shapes to optimize your designs

25. Thank You!