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The present invention relates to catalysts for the production of hydrogen using the water gas shift reaction and the carbon dioxide reforming of hydrocarbon-containing fuels. The catalysts nickel and/or copper on a ceria/zirconia support, where the support is prepared using a surfactant templating m

The present invention relates to catalysts for the production of hydrogen using the water gas shift reaction and the carbon dioxide reforming of hydrocarbon-containing fuels. The catalysts nickel and/or copper on a ceria/zirconia support, where the support is prepared using a surfactant templating method. The invention also includes processes for producing hydrogen, reactors and hydrogen production systems utilizing these catalysts.

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What is claimed is: 1. A water gas shift reaction (WGSR) catalyst for the production of hydrogen from an input gas stream comprising H2O and carbon monoxide comprising a catalytically effective amount of nickel and/or copper, or an oxide thereof, dispersed on a support, wherein the support comprise

What is claimed is: 1. A water gas shift reaction (WGSR) catalyst for the production of hydrogen from an input gas stream comprising H2O and carbon monoxide comprising a catalytically effective amount of nickel and/or copper, or an oxide thereof, dispersed on a support, wherein the support comprises a mixed bi-metal oxide and the support is prepared using a surfactant templating method. 2. The WGSR catalyst according to claim 1 comprising: (a) an oxide support comprising a first oxide selected from the group consisting of zeolites and oxides of cerium (Ce), silicon (Si), thorium (Th), magnesium (Mg), yttrium (Y), lanthanum (La), zirconium (Zr), aluminum (Al), titanium (Ti), hafium (Hf), niobium (Nb), tantalum (Ta), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), molybdenum (Mo), tungsten (W), rhenium (Re), rhodium (Rh), antimony (Sb), bismuth (Bi), manganese (Mn), gallium (Ga), strontium (Sr) and barium (Ba), and a second oxide selected from the group consisting of zeolites and oxides of cerium (Ce), silicon (Si), thorium (Th), magnesium (Mg), yttrium (Y), lanthanum (La), zirconium (Zr), aluminum (Al), titanium (Ti), hafium (Hf), niobium (Nb), tantalum (Ta), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), molybdenum (Mo), tungsten (W), rhenium (Re), rhodium (Rh), antimony (Sb), bismuth (Bi), manganese (Mn), gallium (Ga), strontium (Sr) and barium (Ba), wherein the ratio of amount of first oxide to second oxide is in the range of about 50:50 to about 70:30 and the first and second oxides are different; and (b) about 1 to about 10 wt % of one or more metals, or oxides thereof, dispersed on the oxide support, wherein the one or more metals are selected from the group consisting of copper, nickel and mixtures thereof, wherein the support is prepared using a surfactant templating method. 3. The catalyst according to claim 2, wherein the first oxide is selected from the group consisting of zeolites and oxides of cerium (Ce), silicon (Si), thorium (Th), magnesium (Mg), yttrium (Y), lanthanum (La), zirconium (Zr) and aluminum (Al), and the second oxide is selected from selected from the group consisting of zeolites and oxides of cerium (Ce), silicon (Si), thorium (Th), magnesium (Mg), yttrium (Y), lanthanum (La), zirconium (Zr) and aluminum. 4. The catalyst according to claim 3, wherein the oxide support comprises CeO2 (ceria) as the first oxide, and ZrO2 (zirconia) as the second oxide. 5. The catalyst according to claim 1, comprising both copper and nickel, each being present in an amount in the range of from about 1 to about 5 wt %. 6. The catalyst according to claim 5, wherein the copper and nickel are present in an amount in the range of from about 3 to about 5 wt %. 7. The catalyst according to claim 1, represented by the formula NiyCuz[AxB(1-x)]O2, wherein x is in the range of about 0.5 to about 0.7, y and z represent the weight percent of Ni and Cu, respectively, and are each, independently, in the range of about 1 to about 5% and A and B are independently selected from the group consisting of Ce, Si, Th, Mg, Y, La, Zr, Al, Ti, Hf, Nb, Ta, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mo, W, Re, Rh, Sb, Bi, Mn, Ga, Sr and Ba, with the proviso that A does not equal B. 8. The catalyst according to claim 7, wherein y and z are each, independently, in the range of about 3 to about 5, x is about 0.5 and A is Ce and B is Zr. 9. The catalyst according to claim 7, wherein A and B are present in a ratio A:B in the range of about 70:30 to about 50:50. 10. The catalyst according to claim 9, wherein the A:B ratio is about 60:40 to about 50:50. 11. The catalyst according to claim 1, represented by a formula selected from the group consisting of: Ni(3)Cu(5)[Ce0.70Zr0.30]O2; Ni(5)Cu(3)[Ce0.70Zr0.30]O2; Ni(3)Cu(5)[Ce0.50Zr0.50]O2; and Ni(5)Cu(3)[Ce0.50Zr0.50]O2. 12. The catalyst according to claim 11, which is Ni(3)Cu(5) [Ce0.50Zr0.50]O2. 13. The catalyst according to claim 1, in a form selected from the group consisting of tablet, extrudate, pellet, bead, cylinder, hollow cylinder, powder, washcoat composition deposited on monolith substrate, high mechanical strength particulate and high heat capacity particulate. 14. A reactor comprising a catalyst according to claim 1. 15. The reactor according to claim 14, comprising a reactor inlet, a reaction chamber and a reactor exhaust outlet. 16. A method of preparing a WGSR catalyst according to claim 1 comprising (a) preparing a mixed bi-metal oxide support using a surfactant templating method; and (b) dispersing a catalytically effective amount of nickel and/or copper, or an oxide thereof, on the support. 17. The method according to claim 16, further comprising step (c) in which the WGSR catalyst is shaped into a form. 18. The method according to claim 17, wherein the form of the WGSR catalyst is selected from the group consisting of tablet, extrudate, pellet, bead, cylinder, hollow cylinder, powder, washcoat composition deposited on monolith substrate, high mechanical strength particulate and high heat capacity particulate. 19. The method according to claim 16, wherein the surfactant templating method in (a) comprises: (i) combining aqueous solutions of metal oxide precursors, with an aqueous solution of at least one surfactant; (ii) stirring the combination; (iii) adding a base to adjust the pH of the combined solutions to about 10 to about 13 to produce a slurry comprising precipitated support; (iv) allowing said slurry to sit at elevated temperatures; (v) isolating the precipitated support from the slurry; and (vi) optionally washing said isolated support to remove residual solvent. 20. The method according to claim 19, wherein the combined solution is mixed at room temperature. 21. The method according to claim 20, wherein the combined solution is mixed for about 60 to 120 minutes. 22. The method according to claim 19, wherein the base is ammonia. 23. The method according to claim 19, wherein the pH of the combined solution is adjusted to about 11 to about 12. 24. The method according to claim 19, wherein the precipitate is separated from the slurry by filtration. 25. The method according to claim 19, wherein the slurry is heated to elevated temperatures of about 80 to 100° C. in (iv). 26. The method according to claim 19, wherein the slurry is heated for about 1 to 10 days in (iv). 27. The method according to claim 19, wherein the pH of the slurry is readjusted by the addition of a further amount of a base after (iv). 28. The method according to claim 19, wherein the slurry is cooled prior to isolation of the support in (v). 29. The method according to claim 19, wherein the surfactant is an oligomeric surfactant or a tetraalkyl ammonium salt. 30. The method according to claim 29, wherein the oligomeric surfactant is a co-polymer of the formula (EO)a—(PO)b-(EO)c, in which EO is a hydrophilic polyethylene oxide block and PO is a polypropylene oxide block (EO), and wherein a, b, and c are independently selected from integers between 1 to 100. 31. The method according to claim 30, wherein the molar ratio of metal oxide precursors to the oligomeric surfactant is about 2.5 to 3.0. 32. The method according to claim 29, wherein the tetraalkyl ammonium salt is selected from alkyltrimethyl ammonium chloride, alkyltrimethyl bromide and alkyltrimethyl ammonium hydroxide. 33. The method according to claim 32, wherein the alkyl group has six to eighteen carbon atoms. 34. The method according to claim 32, wherein the molar ratio of metal oxide precursors to the tetraalkylammonium salt is about 0.7 to 0.9. 35. The method according to claim 16, wherein the dispersion of the nickel and/or copper on the mixed bi-metal support is done using incipient impregnation, deposition-precipitation, decantation or co-precipitation. 36. A process for producing hydrogen, comprising contacting an input gas stream comprising H2O and carbon monoxide with a WGSR catalyst above 300° C., wherein the WGSR catalyst is a catalyst according to claim 1. 37. The process according to claim 36, wherein the input gas stream further comprises CO2, H2 and a hydrocarbon fuel. 38. The process according to claim 37, wherein the input gas stream is contacted with a WGSR catalyst at a temperature between about 300° C. and about 700° C. 39. A carbon dioxide reforming (CDR) catalyst for the production of hydrogen from an input gas stream comprising a hydrocarbon fuel and carbon dioxide comprising a catalytically effective amount of nickel, or an oxide thereof, dispersed on a support, wherein the support comprises a mixed bi-metal oxide and the support is prepared using a surfactant templating method. 40. The carbon dioxide reforming (CDR) catalyst according to claim 39 comprising: (a) an oxide support comprising a first oxide selected from the group consisting of zeolites and oxides of cerium (Ce), silicon (Si), thorium (Th), magnesium (Mg), yttrium (Y), lanthanum (La), zirconium (Zr), aluminum (Al), titanium (Ti), hafium (Hf), niobium (Nb), tantalum (Ta), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), molybdenum (Mo), tungsten (W), rhenium (Re), rhodium (Rh), antimony (Sb), bismuth (Bi), manganese (Mn), gallium (Ga), strontium (Sr) and barium (Ba), and a second oxide selected from the group consisting of zeolites and oxides of cerium (Ce), silicon (Si), thorium (Th), magnesium (Mg), yttrium (Y), lanthanum (La), zirconium (Zr), aluminum (Al), titanium (Ti), hafium (Hf), niobium (Nb), tantalum (Ta), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), molybdenum (Mo), tungsten (W), rhenium (Re), rhodium (Rh), antimony (Sb), bismuth (Bi), manganese (Mn), gallium (Ga), strontium (Sr) and barium (Ba), wherein the ratio of amount of first oxide to second oxide is in the range of about 95:5 to about 50:50 and the first and second oxides are different; and (b) about 1 to about 5 wt % of nickel, or an oxide thereof, dispersed on the oxide support; wherein the support is prepared using a surfactant templating method. 41. The catalyst according to claim 40, wherein the first oxide is selected from the group consisting of zeolites and oxides of cerium (Ce), silicon (Si), thorium (Th), magnesium (Mg), yttrium (Y), lanthanum (La), zirconium (Zr) and aluminum (Al), and the second oxide is selected from the group consisting of zeolites and oxides of cerium (Ce), silicon (Si), thorium (Th), magnesium (Mg), yttrium (Y), lanthanum (La), zirconium (Zr) and aluminum. 42. The catalyst according to claim 41, wherein the first oxide is an oxide of cerium and the second oxide is an oxide of zirconium. 43. The catalyst according to claim 39, comprising about 5 wt % nickel. 44. The catalyst according to claim 39, further comprising 0 to about 1 wt % of an alkali metal, or an oxide thereof. 45. The catalyst according to claim 44, wherein the alkali metal is selected from the group consisting of potassium, cesium and sodium. 46. The catalyst according to claim 44, represented by the formula Ni-M[AxB(1-x)]O2, wherein M is an alkali metal in an amount of 0 to about 1 wt %, x is in the range of about 0.5 to about 0.9, and A and B are independently selected from the group consisting of Ce, Si, Th, Mg, Y, La, Zr, Al, Ti, Hf, Nb, Ta, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mo, W, Re, Rh, Sb, Bi, Mn, Ga, Sr and Ba, with the proviso that A does not equal B. 47. The catalyst according to claim 46, wherein M is in an amount of 0 wt %, x is about 0.6 and A is Ce and B is Zr. 48. The catalyst according to claim 46, wherein A and B are present in a ratio A:B in a range of about 90:10 to about 50:50. 49. The catalyst according to claim 48, wherein the A:B ratio is about 92:8 to about 60:40. 50. The catalyst according to claim 39, represented by a formula selected from the group consisting of: Ni[Ce0.50Zr0.50]O2; Ni[Ce0.60Zr0.40]O2; Ni[Ce0.68Zr0.32]O2; Ni[Ce0.78Zr0.22]O2; Ni[Ce0.85Zr0.15]O2; and Ni[Ce0.92Zr0.08]O2. 51. The catalyst according to claim 50 which is Ni[Ce0.60Zr0.40]O2. 52. The catalyst according to claim 39, wherein the catalyst is stable at a gas hourly space velocity (GHSV) of equal or less than 91200 ml/(h·g-cat) at 600° C., 121200 ml/(h·g-cat) at 650° C., and 302400 ml/(h·g-cat) at 700° C. 53. The catalyst according to claim 39, in a form selected from the group consisting of tablet, extrudate, pellet, bead, cylinder, hollow cylinder, powder, washcoat composition deposited on monolith substrate, high mechanical strength particulate and high heat capacity particulate. 54. A reactor comprising a catalyst according to claim 39. 55. The reactor according to claim 54, comprising a reactor inlet, a reaction chamber and a reactor exhaust outlet. 56. A method of preparing a CDR catalyst according to claim 39 comprising (a) preparing a mixed bi-metal oxide support using a surfactant templating method; and (b) dispersing a catalytically effective amount of nickel and/or copper, or an oxide thereof, on the support. 57. The method according to claim 56, further comprising step (c) in which the CDR catalyst is shaped into a form. 58. The method according to claim 57, wherein the form of the CDR catalyst is selected from the group consisting of tablet, extrudate, pellet, bead, cylinder, hollow cylinder, powder, washcoat composition deposited on monolith substrate, high mechanical strength particulate and high heat capacity particulate. 59. The method according to claim 56, wherein the surfactant templating method in (a) comprises: (i) combining aqueous solutions of metal oxide precursors, with an aqueous solution of at least one surfactant; (ii) stirring the combination; (iii) adding a base to adjust the pH of the combined solutions to about 10 to about 13 to produce a slurry comprising precipitated support; (iv) allowing said slurry to sit at elevated temperatures; (v) isolating the precipitated support from the slurry; and (vi) optionally washing said isolated support to remove residual solvent. 60. The method according to claim 59, wherein the combined solution is mixed at room temperature. 61. The method according to claim 60, wherein the combined solution is mixed for about 60 to 120 minutes. 62. The method according to claim 59, wherein the base is ammonia. 63. The method according to claim 59, wherein the pH of the combined solution is adjusted to about 11 to about 12. 64. The method according to claim 59, wherein the precipitate is separated from the slurry by filtration. 65. The method according to claim 59, wherein the slurry is heated to elevated temperatures of about 80 to 100° C. in (iv). 66. The method according to claim 59, wherein the slurry is heated for about 1 to 10 days in (iv). 67. The method according to claim 59, wherein the pH of the slurry is readjusted by the addition of a further amount of a base after (iv). 68. The method according to claim 59, wherein the slurry is cooled prior to isolation of the support in (v). 69. The method according to claim 59, wherein the surfactant is an oligomeric surfactant or a tetraalkyl ammonium salt. 70. The method according to claim 69, wherein the oligomeric surfactant is a co-polymer of the formula (EO)a—(PO)b-(EO)c, in which EO is a hydrophilic polyethylene oxide block and PO is a polypropylene oxide block (EO), and wherein a, b, and c are independently selected from integers between 1 to 100. 71. The method according to claim 70, wherein the molar ratio of metal oxide precursors to the oligomeric surfactant is about 2.5 to 3.0. 72. The method according to claim 69, wherein the tetraalkyl ammonium salt is selected from alkyltrimethyl ammonium chloride, alkyltrimethyl bromide and alkyltrimethyl ammonium hydroxide. 73. The method according to claim 72, wherein the alkyl group has six to eighteen carbon atoms. 74. The method according to claim 72, wherein the molar ratio of metal oxide precursors to the tetraalkylammonium salt is about 0.7 to 0.9. 75. The method according to claim 56, wherein the dispersion of the nickel and/or copper on the mixed bi-metal support is done using incipient impregnation, deposition-precipitation, decantation or co-precipitation. 76. A process for producing hydrogen, comprising contacting an input gas stream comprising a hydrocarbon fuel and carbon dioxide with a carbon dioxide reforming (CDR) catalyst at a temperature between 550 and 700° C., wherein the CDR catalyst is a catalyst according to claim 39. 77. The process according to claim 76, wherein when the hydrocarbon fuel is natural gas, the hydrocarbon fuel and carbon dioxide are in a molar ratio of about 1:1. 78. A process for producing hydrogen, comprising: contacting a first input gas stream comprising a hydrocarbon fuel and carbon dioxide with a CDR catalyst at a temperature between 550 and 700° C. to produce a first output stream comprising carbon monoxide and hydrogen, wherein the CDR catalyst comprises a catalytically effective amount of nickel, or an oxide thereof, dispersed on a support, wherein the support comprises a mixed bi-metal oxide and the support is prepared using a surfactant templating method; and subsequently contacting the first output gas stream with a WGSR catalyst in the presence of H2O at a temperature above 300° C. to produce a second output stream comprising carbon dioxide and hydrogen, comprises a catalytically effective amount of nickel and/or copper, or an oxide thereof, dispersed on a support, wherein the support comprises a mixed bi-metal oxide and the support is prepared using a surfactant templating method. 79. The process according to claim 78, wherein the second output stream is contacted with a carbon monoxide oxidant.