Claims
- 1. A method for producing a hydrogen-rich gas which comprises:
contacting a CO-containing gas with a water gas shift catalyst in the presence of water at a temperature of not more than about 450° C., wherein the water gas shift catalyst comprises: a) Pt, its oxides or mixtures thereof, b) at least one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, their oxides and mixtures thereof, and c) at least one of Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Pd, La, Ce, Pr, Nd, Sm, Eu, their oxides and mixtures thereof.
- 2. The method according to claim 1, wherein the CO-containing gas is a syngas.
- 3. The method according to claim 1, wherein the water gas shift catalyst comprises at least one of Li, Na, K, their oxides and mixtures thereof.
- 4. The method according to claim 3, wherein the water gas shift catalyst comprises Fe, its oxides or mixtures thereof.
- 5. The method according to claim 3, wherein the water gas shift catalyst is selected from the group consisting of
Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Zr, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and La, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Y, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mo, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mn, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, Zr, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof; and Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof.
- 6. The method according to claim 1, wherein the water gas shift catalyst is supported in a carrier selected from alumina, zirconia, titania, ceria, magnesia, lanthania, niobia, zeolite, perovskite, silica clay, yttria, iron oxide or mixtures thereof.
- 7. The method according to claim 6, wherein the water gas shift catalyst comprises at least one of Li, Na, K, their oxides or mixtures thereof.
- 8. The method according to claim 7, wherein the water gas shift catalyst comprises Fe, its oxides or mixtures thereof.
- 9. The method according to claim 7, wherein the supported water gas shift catalyst is selected from:
Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof and Zr, its oxides or mixtures thereof on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and La, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Y, its oxides or mixtures thereof on Al2O3; Pt, its oxides or mixtures thereof. Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof and Mo, its oxides or mixtures thereof on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof. Na, its oxides or mixtures thereof and Co, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof and Mn, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, Zr, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2; and Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2.
- 10. The method according to claim 9, wherein the Al2O3 is γ-Al2O3.
- 11. The method according to claim 6, wherein the carrier comprises at least one member selected from the group consisting of iron oxide zirconia, titania and ceria.
- 12. The method according to claim 11, wherein the carrier comprises zirconia.
- 13. The method according to claim 1, wherein the CO-containing gas is contacted with the water gas shift catalyst at a temperature ranging from about 150° C. to about 450° C.
- 14. The method according to claim 13, wherein the CO-containing gas is contacted with a water gas shift catalyst at a temperature ranging from more than about 350° C. to up to about 450° C.
- 15. The method according to claim 13, wherein the CO-containing gas is contacted with a water gas shift catalyst at a temperature ranging from about 250° C. to up to about 350° C.
- 16. The method according to claim 13, wherein the CO-containing gas is contacted with a water gas shift catalyst at a temperature ranging from about 150° C. to up to about 250° C.
- 17. The method according to claim 1, wherein the CO-containing gas is contacted with the water gas shift catalyst at a pressure of no more than about 75 bar.
- 18. The method according to claim 17, wherein the CO-containing gas is contacted with the water gas shift catalyst at a pressure of no more than about 50 bar.
- 19. The method according to claim 17, wherein the CO-containing gas is contacted with the water gas shift catalyst at a pressure of no more than about 15 bar.
- 20. The method according to claim 17, wherein the CO-containing gas is contacted with the water gas shift catalyst at a pressure of no more than about 1 bar.
- 21. The method according to claim 1, wherein the water gas shift catalyst comprises about 0.01 wt. % to about 10 wt. %, with respect to the total weight of all catalyst components plus the support material, of each Group 8, 9 or 10 element present in the water gas shift catalyst.
- 22. The method according to claim 21, wherein the water gas shift catalyst comprises about 0.01 wt. % to about 2 wt. % of each Group 8, 9 or 10 element present in the water gas shift catalyst.
- 23. The method according to claim 22, wherein the water gas shift catalyst comprises about 0.05 wt. % to about 0.5 wt. % of each Group 8, 9 or 10 element present in the water gas shift catalyst.
- 24. The method according to claim 1, wherein the water gas shift catalyst comprises about 0.05 wt. % to about 20 wt. %, with respect to the total weight of all catalyst components plus the support material, of each lanthanide element present in the water gas shift catalyst.
- 25. A catalyst for catalyzing the water gas shift reaction comprising:
a) Pt, its oxides or mixtures thereof, b) at least one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, their oxides and mixtures thereof, and c) at least one of Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Pd, La, Ce, Pr, Nd, Sm, Eu, their oxides and mixtures thereof.
- 26. The catalyst according to claim 25, wherein the catalyst comprises at least one of Li, Na, K, their oxides and mixtures thereof.
- 27. The catalyst according to claim 26, wherein the catalyst comprises Fe, its oxides or mixtures thereof.
- 28. The catalyst according to claim 26, wherein the catalyst is selected from the group consisting of:
Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Zr, its oxides or mixtures thereof, Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and La, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Y, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mo, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mn, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, Zr, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof; and Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof.
- 29. The catalyst according to claim 25, further comprising a support selected from alumina, zirconia, titania, ceria, magnesia, lanthania, niobia, zeolite, perovskite, silica clay, yttria, iron oxide or mixtures thereof.
- 30. The catalyst according to claim 29, wherein the catalyst comprises at least one of Li, Na, K, their oxides and mixtures thereof.
- 31. The catalyst according to claim 29, wherein the catalyst comprises Fe, its oxides, or mixtures thereof.
- 32. The catalyst according to claim 30, wherein the supported catalyst is selected from:
Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Zr, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and La, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Y, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mo, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mn, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, Zr, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2; and Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2.
- 33. The catalyst according to claim 32, wherein the Al2O3 is γ-Al2O3.
- 34. The catalyst according to claim 25, wherein the catalyst comprises about 0.01 wt. % to about 10 wt. %, with respect to the total weight of all catalyst components plus the support material, of each Group 8, 9 or 10 element present in the catalyst.
- 35. The catalyst according to claim 34, wherein the catalyst comprises about 0.01 wt. % to about 2 wt. % of each Group 8, 9 or 10 element present in the catalyst.
- 36. The catalyst according to claim 35, wherein the catalyst comprises about 0.05 wt. % to about 0.5 wt. % of each Group 8, 9 or 10 element present in the catalyst.
- 37. The catalyst according to claim 25, wherein the catalyst comprises about 0.05 wt. % to about 20 wt. %, with respect to the total weight of all catalyst components plus the support material, of each lanthanide element present in the catalyst.
- 38. A catalyst for catalyzing the water gas shift reaction comprising:
a) Pt, its oxides or mixtures thereof; b) at least one of V, Zr, their oxides and mixtures thereof; and c) at least one of Ti, Mo, Co, their oxides and mixtures thereof.
- 39. The catalyst according to claim 38, wherein the catalyst further comprises Na, its oxides or mixtures thereof.
- 40. A method for producing a hydrogen-rich syngas which comprises:
contacting a CO-containing gas with a water gas shift catalyst in the presence of water at a temperature of not more than about 450° C., wherein the water gas shift catalyst comprises: a) Pt, its oxides or mixtures thereof; b) at least one of V, Zr, their oxides and mixtures thereof, and c) at least one of Ti, Mo, Co, their oxides and mixtures thereof.
- 41. The method according to claim 40, wherein the water gas shift catalyst further comprises Na, its oxides or mixtures thereof.
- 42. A method of preparing a catalyst comprising the steps of
applying Li and Fe containing precursors to a surface; calcining the Li and Fe containing surface to a temperature of between about 600° C. and about 900° C. to form a treated surface; applying a Pt containing precursor to the treated surface.
- 43. A method according to claim 42, wherein Na is impregnated onto the treated surface after the calcination step.
- 44. A method according to claim 42, wherein the temperature is about 700° C.
- 45. A fuel processing system for generation of a hydrogen-rich gas from a hydrocarbon or substituted hydrocarbon fuel, the fuel processing system comprising:
a fuel reformer for converting a fuel reactant stream comprising a hydrocarbon or a substituted hydrocarbon fuel to a reformed product stream comprising carbon monoxide and water, the fuel reformer having an inlet for receiving the reactant stream, a reaction chamber for converting the reactant stream to the product stream and an outlet for discharging the product stream; a water gas shift reactor for effecting a water gas shift reaction at a temperature of less than about 450° C., the water gas shift reactor comprising an inlet for receiving a water gas shift feed stream comprising carbon monoxide and water from the product stream of the fuel reformer, a reaction chamber comprising the water gas shift catalyst of claim 25, the water gas shift catalyst being effective for generating hydrogen and carbon dioxide from the water gas shift feed stream and an outlet for discharging the resulting hydrogen-rich gas; and a temperature controller adapted for maintaining the temperature of the reaction chamber of the water gas shift reactor at a temperature of less than about 450° C.
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims benefit from earlier filed U.S. Provisional Application No. 60/434,682, filed Dec. 20, 2002, which is incorporated herein in its entirety by reference for all purposes. The present application also incorporates by reference PCT International Patent Application No. ______ entitled “Platinum-Alkali/Alkaline-Earth Catalyst Formulations For Hydrogen Generation” naming as inventors Hagemeyer et al. (Attorney Docket No. 708000601PCT) filed on the same date as the present application.
Provisional Applications (1)
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Number |
Date |
Country |
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60434682 |
Dec 2002 |
US |