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Fuel Processing Perspective

Richard Bellows IFC/Hydrogen Source NSF Workshop on Low Temperature (PEM) Fuel Cells Vision: A single reactor to convert hydrocarbons into high purity H2-rich feed offering high efficiency, low volume, low cost, durability and rapid start-up. State-of the- Art: Multi-reactor alpha-prototype capabilities demonstrated, second generation designs in progress. Significant gaps in cost, life, especially in transport applications. Issues: - Impurity Mitigation – Several reactors needed to control fuel cell poisons: CO, “S”, etc. - Catalyst Activity/Cost – Noble metals expensive in transportation applications - System Complexity – Multiple reactors, each at different temperature. - Control Complexity – Critical control variables impossible or expensive to measure - Transient Control – Multiple steady states in ATR and PROX poorly understood Strategies: - New materials, especially catalysts and/or adsorbents and membranes - WGS - New concepts to eliminate components - WGS membrane reactors - New understanding: PROX selectivity mech., low temp. WGS, multiple steady states ---New control strategies: Predictive control algorithms, new sensors, stable designs

Targets/Performance & Gaps
Specification
Scale (kWe) Fuel FPS Cost ($/kWe) FPS Volume (L/kWe) FPS Weight (kg/kWe) Durability (hr.)
Start-up/transient (min.)

Transportation 40-90 gasoline 15-20 ~1 ~1 3-6k 1 / 0.1

Commerce/Resid 1-250 Natural gas 300-500 ~20 ~20 40k 5-120

Projected Designs
done done Uncertain New materials ~2 ~2 ~1k new materials 5-25

Fuel Processor Impurity Control S.O.A.
• State of Art
– S, CO, NH3, HC’s, (others – ions etc.)
• WGS
– Traditional HTS, LTS – Temperature trajectory controlled – Higher activity, non-pyrophoric catalysts

• PrOx
– Noble metal – Reactor designs: multi-stage adiabatic / catalyzed heat exchangers

• Sulfur adsorption
– HDS (hydro-desulfurization) – Liquid phase removal – Gas phase (ZnO bed)

• H2 separation
– Pd membranes – PSA

• Carbon Formation
– Steam / carbon, oxygen / carbon – reforming temperature

• WGS

Impurity Control Research Issues – Performance and Durability

– Size reduction – Efficiency / CO reduction & conversion

• PrOx
– – – – Noble metal Selectivity, complexity Response – transients & start-up Control - sensors

• Sulfur adsorption
– Size – Equilibrium limitations (ZnO with H2O); high temperature – sensor

• H2 separation
– – – – Pd membranes - cost Compatibility with ATR due to pressure differential Sulfur tolerance PSA complexity

• Carbon formation
– O/C, Steam/C – equilibrium & catalyst interactions

Technical Approaches and Agenda
– WGS
• Size reduction – higher catalyst activity • Integral membrane to shift equilibrium (CO2, H2)

– PrOx
• Non-noble metal catalysts • Modeling, transient control • Remove from system (HT membranes, anode catalysts, H2 separation)

– Sulfur adsorption
• • • • High capacity sorbents Sulfur tolerant catalysts (low T sulfur removal/sorption) Regenerable adsorbents Sulfur sensor - detection at ppb levels

– H2 separation

• Non-Pd membranes (or v. low Pd) • High flux, low P differential • NH3, HC’s, CO

– Other impurity adsorbents

Catalyst Research
• Issues in current Fuel Processing Catalysts
– Low Activity of present Low Temp Shift (LTS) – Low impurity tolerance (S) of LTS – Low-selectivity of PROX (multi stage Reactor)

Strategies
• WGS
– – – – – Non-noble metal catalysts and novel supports Sulfur tolerant Highly active below 250 C Stable in reformate gas, wide temp window Mechanistic studies

PROX
• Fundamental understanding of selectivity • New non-noble metal catalyst formulations

New Catalyst/Reactor Concepts
• Membrane Reactor (s)
– New low temp ATR catalyst with or w/o membrane – High temp shift catalyst (450-550C) plus H2 selective membrane

Challenges
• Membrane Reactor- Must match catalyst activity to H2 flux through membrane: shift catalyst should have high activity in presence of high CO2 concentration. Requires sulfur tolerant catalysts

Control Systems
• Issues
– – – – – – – – Responsive to reduce lag time Durable Minimal Drift Sensitive to key impurities (S, CO) Massflow for feed Control Excursions High Temp Valves/Sensors (H2 Compatible) Dynamic Modeling

Approaches
• Develop model to study transient behavior (start-up & shut down). • Develop CO and Sulfur sensors with rapid response at elevated temperatures. • Flow Sensors • Feedback control on power output/on demand power. • Other gases: CO2, N2, HC, NH3, to improve performance.

Recommendations
• Identify existing requirements and test existing products to identify limitations. • Develop model to integrate appropriate sensors. • Develop new or improved sensors where needed. • Develop dynamic model to control fuel processing system.

Fuel Processing Novel Concepts
• Membrane reactors
– Oxygen separation / enrichment – CO, CO2, N2, H2

• Low temperature fuel processing
– H2 generation at < 400 C or less

• Example new concepts
– – – – – Plasmas Micro-channel TIMFR – Thermally Integrated Multi-Functional Reactors SEMPOR – Solid Electrolyte Membrane Partial Oxidation Reactors Others