1. 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

2. 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

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

4. 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

5. 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

6. 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

7. 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

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

9. 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

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

11. 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

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

13. 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

14. 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

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

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

17. Second Strategy: Decompose Perovskite to Form Dispersed Metal Catalyst on Refractory Oxide Support
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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; F01 Catalyst Bed; No Wall Catalyst; D-2 Commercial Diesel Fuel: >200 ppm S
ELTRON RESEARCH INC. Slide 18

19. 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

20. ELTRON RESEARCH INC. Slide 20

21. 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 ( oC)
Addition of oxygenated fuel, O2, H2O, CO2
Optimize multiple-phase perovskite catalysts.
ELTRON RESEARCH INC. Slide 21

22. 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