OXYGEN MEMBRANE CATALYTIC FUEL REFORMING NETL SECA Fuel Processing Workshop Pittsburgh, Pennsylvania December 6, 2005 Michael V. Mundschau and Jarrod A. Benjamin Eltron Research Inc. 4600 Nautilus Court South, Boulder, CO 80301-3241

OUTLINE Introduction Facilities at Eltron Research Inc. Background - Membrane Methane Reforming Diesel Fuel Reforming Perovskite Catalysts Phase I Results Future Goals Conclusions/Summary ELTRON RESEARCH INC. Slide 2

ACKNOWLEDGMENT U.S. Department of Energy Contract Number: DE-FG02-05ER84394 DOE SBIR Program ELTRON RESEARCH INC. Slide 3

FACILITIES AT ELTRON RESEARCH INC. Main Workspace Instrument Room - XRD SEM/EDX Ceramic Processing Ovens Ceramic Processing Lab Machine Shop ELTRON RESEARCH INC. Slide 4

MEMBRANE TESTING UNITS HIGH-PRESSURE MEMBRANE TESTING UNITS Tests to 17.2 bar (250 psi) differential pressure at 8001000°C for oxygen transport membranes. Tests to 70 bar (1000 psi) 300450°C for hydrogen transport membranes. ELTRON RESEARCH INC. Slide 5

HIGH PRESSURE REACTOR FutureGen Goals: Tests to 1000 psi (70 bar) differential pressure for hydrogen transport membranes under water-gas shift conditions (H2, CO, CO2, steam). Clean-up of coal-derived hydrogen. ELTRON RESEARCH INC. Slide 6

PEROVSKITE MEMBRANE FOR REFORMING METHANE INTO H2 + CO Porous Perovskite with methane steam reforming catalysts Methane and steam streamed past porous layer Air streamed past slotted side Dense Perovskite oxygen transport layer Slotted air side Present catalysts designed for steam reforming of natural gas. Not suitable for diesel fuel. Phase I research is designing and testing catalysts for reforming of diesel fuel. ELTRON RESEARCH INC. Slide 7

DIRECT PARTIAL OXIDATION OF METHANE THROUGH A STEAM REFORMING STEP Steam Reforming CH4 + H2O (g) CO + 3H2 H = +206.1 kJ mol-1 Hydrogen Oxidation H2 + O (ad) H2O (g) H = -241.8 kJ mol-1 Oxygen Dissociation ½ O2 O (ad) ________________________________________________________________________ Net Partial Oxidation CH4 + ½ O2 CO + 2H2 H = -35.7 kJ mol-1 ELTRON RESEARCH INC. Slide 8

AMBIENT PRESSURE DIESEL FUEL REFORMER Commercial D-2 Diesel Fuel (Conoco-Phillips) used >200 ppm S Tube furnace reactors operated 9001000oC Steam and oxygen added to suppress carbon Gases contained in cabinet and vented ELTRON RESEARCH INC. Slide 9

T <900oC favors C, CH4, CO2, H2O T >900oC favors H2, CO T <900oC favors C, CH4, CO2, H2O ELTRON RESEARCH INC. Slide 10

STABLE SULFIDES WHICH FORM TO POISON COMMON CATALYSTS NiS m.p. 797oC Cu2S 1100oC PdS d. 950oC La2S3 2150oC FeS 1199oC RuS2 1000oC ZnS b.p. 1185oC WS2 1250oC Ag2S 825oC US >2000oC Ce2S3 2100oC PtS2 250oC CoS >1116oC IrS2 300oC MoS2 BaS 1200oC MgS SrS ELTRON RESEARCH INC. Slide 11

Catalytic activity of transition-metal sulphides for hydrodesulphurization of dibenzothiophene. (After Whittingham & Chianelli, 1980.) ELTRON RESEARCH INC. Slide 12

THERMODYNAMIC STABILITIES OF METAL SULFIDES Most metals will form stable sulfides when exposed to H2S. Pt and Ir may remain metallic at high T. Co, Mo, W, Ag, Cu and Fe can remain metallic at 1000oC if H2 : H2S ratio kept >1000 : 1. Ce, Ca, Sr, Ba, Mg, Mn, and Zn form very stable sulfides. ELTRON RESEARCH INC. Slide 13

Adapted from Henrich and Cox. PEROVSKITE STRUCTURE A Cations - large black spheres B Cations - small black spheres Oxygen Anions - white and grey spheres O2- A-Site Cation B-Site Cation Adapted from Henrich and Cox. Mobile lattice oxygen acts as oxidant. Surface vacancies adsorb O2, H2O. ELTRON RESEARCH INC. Slide 14

PEROVSKITE CATALYSTS Upper: Single phase perovskite; Lower: Two phase perovskite ELTRON RESEARCH INC. Slide 15

X-Ray Diffraction of Stable Perovskite Catalyst ELTRON RESEARCH INC. Slide 16

Second Strategy: Decompose Perovskite to Form Dispersed Metal Catalyst on Refractory Oxide Support ELTRON RESEARCH INC. Slide 17

Fuel Exhaust as a Function of Time; 1000C; 4 Steam to Carbon; 0 Fuel Exhaust as a Function of Time; 1000C; 4 Steam to Carbon; 0.3 O2 to Carbon; F01 Catalyst Bed; No Wall Catalyst; D-2 Commercial Diesel Fuel: >200 ppm S ELTRON RESEARCH INC. Slide 18

Fuel Exhaust as a Function of Time; 1000C; 4 Steam to Carbon; 0 Fuel Exhaust as a Function of Time; 1000C; 4 Steam to Carbon; 0.3 O2 to Carbon; K15 Catalyst Bed; No Wall Catalyst; D-2 Commercial Diesel Fuel; >200 ppm S ELTRON RESEARCH INC. Slide 19

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FUTURE GOALS - PHASE II Integrate new steam reforming/partial oxidation catalysts with perovskite oxygen transport membrane materials. Continue methods for suppression of carbon Fast fuel injection Inert perovskite coatings in cool zones (300-800oC) Addition of oxygenated fuel, O2, H2O, CO2 Optimize multiple-phase perovskite catalysts. ELTRON RESEARCH INC. Slide 21

SUMMARY AND CONCLUSIONS Perovskite-based catalysts designed and tested for reforming of diesel fuel into H2+CO. Catalysts designed for stability at 1000oC. Thermodynamics used to guide operating conditions for suppressing formation of carbon and undesired sulfides. ELTRON RESEARCH INC. Slide 22