| JPH10128063 | TREATMENT OF VOLATILE ORGANIC HALOGEN COMPOUND-CONTAINING GAS AND DEVICE THEREFOR |
| WO/2009/013540 | CATALYST |
| JPS52120293 | CATALYSTS FOR OXIDATION AND REDUCTION |
ALHAMED YAHIA A (SA)
AL-ZAHRANI AABDULRAHIM A (SA)
DAOUS MOHAMMAD A (SA)
KHAMIS AHMAD A (SA)
AL-HAZMI MOHAMMED H (SA)
| WO2000013791A1 | 2000-03-16 | |||
| WO1999016546A1 | 1999-04-08 | |||
| WO1998032524A1 | 1998-07-30 | |||
| WO1996014153A1 | 1996-05-17 |
| US4191846A | 1980-03-04 |
| CLAIMS What is claimed is: 1. A dehydrogenation catalyst composition comprising: a) a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; b) a gold compound; c) one or more transition metal compounds. 2. The composition of claim 1, wherein the oxide of cerium comprises Ce02. 3. The composition of claim 2, wherein the Ce02 is present in an amount from about 40.0 wt% to about 85 wt%. 4. The composition of claim 2, wherein the Ce02 is present in an amount from about 45 wt% to about 80 wt%. 5. The composition of claim 2, wherein the Ce02 is present in an amount from about 50.0 wt% to about 75.0 wt%. 6. The composition of claim 2, wherein the Ce02 is present in an amount from about 50.0 wt% to about 60.0 wt%. 7. The composition of claim 2, wherein the Ce02 is present in an amount of about 55.0 wt%. 8. The composition of any of claims 1-7, wherein the oxide of titanium comprises Ti02. 9. The composition of claim 8, wherein the Ti02 is present in an amount from about 0.1 wt% to about 30 wt%. 10. The composition of claim 8, wherein the Ti02 is present in an amount from about 2.5 wt% to about 25 wt%. 11. The composition of claim 8, wherein the Ti02 is present in an amount from about 5.0 wt% to about 25.0 wt%. 12. The composition of claim 8, wherein the Ti02 is present in an amount from about 10.0 wt% to about 25.0 wt%. 13. The composition of claim 8, wherein the Ti02 is present in an amount from about 15.0 wt% to about 25.0 wt%. 14. The composition of claim 8, wherein the Ti02 is present in an amount from about 17.5 wt% to about 22.5 wt%. 15. The composition of claim 8, wherein the Ti02 is present in an amount of about 20.0 wt%. 16. The composition of any of claims 1-15, wherein the oxide of zirconium comprises Zr02. 17. The composition of claim 16, wherein the Zr02 is present in an amount from about 5.0 wt% to about 40.0 wt%. 18. The composition of claim 16, wherein the Zr02 is present in an amount from about 7.5 wt% to about 35 wt%. 19. The composition of claim 16, wherein the Zr02 is present in an amount from about 10.0 wt% to about 30.0 wt%. 20. The composition of claim 16, wherein the Zr02 is present in an amount from about 15.0 wt% to about 30.0 wt%. 21. The composition of claim 16, wherein the Zr02 is present in an amount from about 20.0 wt% to about 30.0 wt%. 22. The composition of claim 16, wherein the Zr02 is present in an amount from about 22.5 wt% to about 27.5 wt%. 23. The composition of claim 16, wherein the Zr02 is present in an amount of about 25.0 wt%. 24. The composition of claim 1, wherein the oxide of cerium comprises Ce02; wherein the oxide of titanium comprises Ti02; and wherein the oxide of zirconium comprises Zr02. 25. The composition of claim 25, wherein the Ce02 is present in an amount from about 50.0 wt% to about 60.0 wt%; wherein the Ti02 is present in an amount from about 15.0 wt% to about 25.0 wt%; and wherein the Zr02 is present in an amount from about 20.0 wt% to about 30.0 wt%. 26. The composition of claim 25, wherein the Ce02 is present in an amount of about 55.0 wt%; wherein the Ti02 is present in an amount of about 20.0 wt%; and wherein the Zr02 is present in an amount of about 25.0 wt%. 27. The composition of claim 1, wherein the cerium and zirconium comprise an oxide of the formula ZrxCey02; wherein x has a value of about 0.30 to about 0.99; wherein y has a value of about 0.50 to about 0.01; and wherein the sum of x and y is about 1.00. 28. The composition of claim 1, wherein the cerium and zirconium comprise an oxide of the formula ZrxCey02; wherein x has a value of about 0.35 to about 0.97; wherein y has a value of about 0.55 to about 0.03; and wherein the sum of x and y is about 1.00. 29. The composition of claim 1, wherein the cerium and zirconium comprise an oxide of the formula ZrxCey02; wherein x has a value of about 0.40 to about 0.95; wherein y has a value of about 0.60 to about 0.05; and wherein the sum of x and y is about 1.00. 30. The composition of any of claims 1-29, wherein the gold content of the composition is from about 0.1 wt% to about 5.0 wt%. 31. The composition of claim 30, wherein the gold content of the composition is from about 0.1 wt% to about 2.0 wt%. 32. The composition of claim 30, wherein the gold content of the composition is from about 0.1 wt% to about 1.0 wt%. 33. The composition of claim 30, wherein the gold content of the composition is from about 0.5 wt% to about 1.5 wt%. 34. The composition of claim 30, wherein the gold content of the composition is about 1.0 wt%. 35. The composition of any of claims 1-34, wherein the gold comprises one or more oxides. 36. The composition of any of claims 1-35, wherein the gold particles are of a size less than about 10 nm. 37. The composition of any of claims 1-35, wherein the gold particles are of a size less than about 8 nm. 38. The composition of any of claims 1-35, wherein the gold particles are of a size less than about 6 nm. 39. The composition of any of claims 1-35, wherein the gold particles are from about 2 nm to about 10 nm. 40. The composition of any of claims 1-35, wherein the gold particles are from about 2 nm to about 8 nm. 41. The composition of any of claims 1-35, wherein the gold particles are from about 3 nm to about 6 nm. 42. The composition of any of claims 1-41, wherein the transition metal comprises tin. 43. The composition of claim 42, wherein the tin is present in an amount from about 0.1 wt% to about 0.5 wt%, or about 0.2 wt% to about 0.5 wt%. 44. The composition of claim 42, wherein the tin is present in an amount from about 0.2 wt% to about 0.4 wt%. 45. The composition of claim 42, wherein the tin is present in an amount from about 0.2 wt% to about 0.3 wt%. 46. The composition of claim 42, wherein the tin is present in an amount of about 0.2 wt% 47. The composition of claim 42, wherein the tin is present in an amount of about 0.3 wt%. 48. The composition of claim 42, wherein the tin is present in an amount of about 0.4 wt%. 49. The composition of claim 42, wherein the tin is present in an amount of about 0.5 wt%. 50. The composition of any of claims 1-49, wherein the transition metal salt is present in an amount from about 0.1 wt% to about 2.0 wt%. 51. The composition of claim 50, wherein the transition metal salt is present in an amount from about 0.1 wt% to about 1.0 wt%. 52. The composition of claim 50, wherein the transition metal salt comprises iron. 53. The composition of claim 52, wherein the iron is in the form of Fe(III). 54. The composition of claim 52, wherein the iron is in the form of Fe(II). 55. The composition of any of claims 1-54, wherein the dehydrogenation catalyst composition is the calcination product of a mixture of a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; a tin compound; and one or more transition metal compounds. 56. A dehydrogenation catalyst prepared by calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce02, Ti02, and Zr02. 57. The product of claim 56, wherein calcining is carried out at a temperature from about 100 °C to about 600 °C. 58. The product of claim 57, wherein calcining is carried out at a temperature from about 400 °C to about 600 °C. 59. The product of claim 57, wherein calcining is carried out at a temperature from about 500 °C to about 600 °C. 60. The product of claim 56, wherein calcining is carried out at a temperature of about 550 °C. 61. The product of any of claims 57-60, wherein calcining is carried out in the presence of an oxygen flow or air flow. 62. The product of claim 61, wherein calcining is carried out in the presence of an oxygen flow. 63. The product of claim 61, wherein calcining is carried out in the presence of an air flow. 64. The product of claim 56, further comprising the steps of preparing the mixture: a) dispersing a transition metal salt with Ce02, Ti02, and Zr02; and b) dispersing a gold salt with the material comprising the transition metal salt, Ce02, Ti02, and Zr02, wherein the steps of preparing the mixture occur prior to calcining. 65. The product of claim 64, wherein dispersing is impregnation, precipitation, deposition-precipitation, co-precipitation, or incipient wetness impregnation. 66. The product of claim 64, wherein dispersing is impregnation, precipitation, deposition-precipitation or co-precipitation. 67. The product of claim 64, wherein dispersing is impregnation, precipitation, or depo sition-precipitation . 68. The product of claim 64, wherein dispersing is impregnation, or precipitation. 69. The product of claim 64, wherein dispersing is impregnation. 70. The product of claim 69, wherein the impregnation is carried out in aqueous solution at a temperature from about 55 °C to about 75 °C. 71. The product of claim 69, wherein the impregnation is carried out in aqueous solution at a temperature from about 60 °C to about 70 °C. 72. The product of claim 69, wherein the impregnation is carried out in aqueous solution at a temperature of about 65 °C. 73. The product of any of claims 65-72, further comprising dispersing a tin salt with the material comprising the Ce02, Ti02, and Zr02. 74. The product of any of claims 65-73, wherein the aqueous solution has a pH from about 7.0 to about 12.0, or about 8.0 to about 10.5. 75. The product of claim 73, wherein the pH of the aqueous solution is adjusted using alkaline compounds. 76. The product of claim 73, wherein the pH of the aqueous solution is adjusted using magnesium citrate, barium carbonates, hydroxides or ammonia, or a mixture thereof. 77. A method of preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce02, Ti02, and Zr02. 78. The method of claim 77, wherein calcining is carried out at a temperature from about 100 °C to about 600 °C. 79. The method of claim 78, wherein calcining is carried out at a temperature from about 400 °C to about 600 °C. 80. The method of claim 78, wherein calcining is carried out at a temperature from about 500 °C to about 600 °C. 81. The method of claim 78, wherein calcining is carried out at a temperature of about 550 °C. 82. The method of any of claims 78-81, wherein calcining is carried out in the presence of an oxygen flow or air flow. 83. The method of claim 82, wherein calcining is carried out in the presence of an oxygen flow. 84. The method of claim 82, wherein calcining is carried out in the presence of an air flow. 85. A method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of: a) providing an alkane; b) providing a dehydrogenation catalyst comprising: i) a porous carrier comprising cerium, titanium, and zirconium ii) a gold compound; iii) a tin compound; and iv) one or more transition metal compounds; c) heating the alkane in the presence of the dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene. 86. The method of claim 85, wherein the alkane is selected from ethane, propane, or butane, or a mixture thereof. 87. The method of claim 85, wherein the alkane is selected from ethane, or propane, or a mixture thereof. 88. The method of claim 86, wherein the alkane is propane. 89. The method of claim 85, wherein the alkene is selected from ethene, propene, or butane, or a mixture thereof. 90. The method of claim 85, wherein the alkene is selected from ethene, or propene, or a mixture thereof. 91. The method of claim 90, wherein the alkene is propene. 92. The method of claim 85, wherein the heating is at a temperature from about 400 °C to about 600 °C. 93. The method of claim 92, wherein the heating is at a temperature from about 500 °C to about 600 °C. 94. The method of claim 85, further comprising the step of heating the dehydrogenation catalyst at a temperature from about 400 °C to about 600 °C in the presence of a mixture of oxygen and helium prior to the providing of the dehydrogenation catalyst. 95. The method of claim 94, wherein the heating is at about 500 °C. 96. The method of claim 94, wherein the heating is at about 550 °C. 97. The method of claim 85, further comprising providing hydrogen and helium. 98. The method of claim 85, wherein the dehydrogenation catalyst has the composition of any of claims 1-51. 99. The method of claim 85, wherein the dehydrogenation catalyst is the product of the process of any of claims 56-76. 100. A dehydrogenation catalyst composition comprising: a) a porous carrier comprising Ce02 in an amount from about 50.0 wt% to about 60.0 wt%; Ti02 in an amount from about 15 wt% to about 25 wt%; and Zr02 in an amount from about 20.0 wt% to about 30.0 wt%; b) a gold compound in an amount from about 0.1 wt% to about 2.0 wt%; c) a tin compound in an amount from about 0.1 wt% to about 0.5 wt%; and d) one or more transition metal compounds in an amount from about 0.1 wt% to about 2.0 wt%. 101. A dehydrogenation catalyst composition comprising: a) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount from about 17.5 wt% to about 22.5 wt%; and Zr02 in an amount from about 22.5 wt% to about 27.5 wt%; b) a gold compound in an amount from about 0.1 wt% to about 1.0 wt%; c) a tin compound in an amount from about 0.2 wt% to about 0.5 wt%; and d) one or more transition metal compounds in an amount from about 0.1 wt% to about 1.0 wt%. 102. A dehydrogenation catalyst composition comprising: a) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount of about 20.0 wt%; and Zr02 in an amount of about 20 wt%; b) a gold compound in an amount of about 1.0 wt%; c) a tin compound in an amount of about 0.3 wt%; and d) one or more transition metal compounds in an amount from about 0.1 wt% to about 1.0 wt%. 103. A dehydrogenation catalyst composition comprising: a) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount of about 20.0 wt%; and Zr02 in an amount of about 20 wt%; b) a gold compound in an amount of about 1.0 wt%; c) a tin compound in an amount of about 0.3 wt%; and d) iron in an amount from about 0.1 wt% to about 1.0 wt%. 104. A dehydrogenation catalyst composition comprising: a) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount of about 20.0 wt%; and Zr02 in an amount of about 20 wt%; b) a gold compound in an amount of about 1.0 wt%; c) a tin compound in an amount of about 0.3 wt%; and d) Fe(II) in an amount from about 0.1 wt% to about 1.0 wt%. 105. A dehydrogenation catalyst composition comprising: a) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount of about 20.0 wt%; and Zr02 in an amount of about 20 wt%; b) a gold compound in an amount of about 1.0 wt%; c) a tin compound in an amount of about 0.3 wt%; and d) Fe(III) in an amount from about 0.1 wt% to about 1.0 wt%. 106. A method for the preparation of propene by catalytic dehydrogenation, the method comprising the steps of: a) providing propane; b) providing a dehydrogenation catalyst comprising: i) a porous carrier comprising Ce02, Ti02, and Zr02; ii) a gold compound; iii) a tin compound; and iv) one or more transition metal compounds; c) heating propane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene. 107. A method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of: a) providing an alkane; b) providing a dehydrogenation catalyst comprising: i) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount from about 17.5 wt% to about 22.5 wt%; and Zr02 in an amount from about 22.5 wt% to about 27.5 wt%; ii) a gold compound in an amount from about 0.1 wt% to about 2.0 wt%; iii) a tin compound in an amount from about 0.1 wt% to about 0.5 wt%; and iv) one or more transition metal compounds in an amount from about 0.1 wt% to about 2.0 wt%; c) heating the alkane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene. 108. A method for the preparation of propene by catalytic dehydrogenation, the method comprising the steps of: a) providing propane; b) providing a dehydrogenation catalyst comprising: i) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount from about 17.5 wt% to about 22.5 wt%; and Zr02 in an amount from about 22.5 wt% to about 27.5 wt%; ii) a gold compound in an amount from about 0.1 wt% to about 2.0 wt%; iii) a tin compound in an amount from about 0.1 wt% to about 0.5 wt%; and iv) one or more transition metal compounds in an amount from about 0.1 wt% to about 2.0 wt%; c) heating propane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene. 109. A method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of: a) providing an alkane; b) providing a dehydrogenation catalyst comprising: i) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount from about 17.5 wt% to about 22.5 wt%; and Zr02 in an amount from about 22.5 wt% to about 27.5 wt%; ii) a gold compound in an amount from about 0.1 wt% to about 1.0 wt%; iii) a tin compound in an amount from about 0.2 wt% to about 0.5 wt%; and iv) one or more transition metal compounds in an amount from about 0.1 wt% to about 1.0 wt%; c) heating the alkane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene. 110. A method for the preparation of propene by catalytic dehydrogenation, the method comprising the steps of: a) providing propane; b) providing a dehydrogenation catalyst comprising: i) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount from about 17.5 wt% to about 22.5 wt%; and Zr02 in an amount from about 22.5 wt% to about 27.5 wt%; ii) a gold compound in an amount from about 0.1 wt% to about 1.0 wt%; iii) a tin compound in an amount from about 0.2 wt% to about 0.5 wt%; and iv) one or more transition metal compounds in an amount from about 0.1 wt% to about 1.0 wt%; c) heating propane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene. 111. A method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of: a) providing an alkane; b) providing a dehydrogenation catalyst comprising: i) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount of about 20 wt%; and Zr02 in an amount of about 25 wt%; ii) a gold compound in an amount of about 1.0 wt%; iii) a tin compound in an amount of about 0.3 wt%; and iv) or more transition metal compounds in an amount from about 0.1 wt% to about 1.0 wt%; c) heating the alkane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene. 112. A method for the preparation of propene by catalytic dehydrogenation, the method comprising the steps of: a) providing propane; b) providing a dehydrogenation catalyst comprising: i) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount of about 20 wt%; and Zr02 in an amount of about 25 wt%; ii) a gold compound in an amount of about 1.0 wt%; iii) a tin compound in an amount of about 0.3 wt%; and iv) or more transition metal compounds in an amount from about 0.1 wt% to about 1.0 wt%; c) heating propane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene. 113. A method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of: a) providing an alkane; b) providing a dehydrogenation catalyst comprising: i) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount of about 20 wt%; and Zr02 in an amount of about 25 wt%; ii) a gold compound in an amount of about 1.0 wt%; iii) a tin compound in an amount of about 0.3 wt%; and iv) iron in an amount from about 0.1 wt% to about 1.0 wt%; c) heating the alkane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene. 114. A method for the preparation of propene by catalytic dehydrogenation, the method comprising the steps of: a) providing propane; b) providing a dehydrogenation catalyst comprising: i) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount of about 20 wt%; and Zr02 in an amount of about 25 wt%; ii) a gold compound in an amount of about 1.0 wt%; iii) a tin compound in an amount of about 0.3 wt%; and iv) iron in an amount from about 0.1 wt% to about 1.0 wt%; c) heating propane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene. 115. A method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of: a) providing an alkane; b) providing a dehydrogenation catalyst comprising: i) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount of about 20 wt%; and Zr02 in an amount of about 25 wt%; ii) a gold compound in an amount of about 1.0 wt%; iii) a tin compound in an amount of about 0.3 wt%; and iv) Fe(II) in an amount from about 0.1 wt% to about 1.0 wt%; c) heating the alkane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene. 116. A method for the preparation of propene by catalytic dehydrogenation, the method comprising the steps of: a) providing propane; b) providing a dehydrogenation catalyst comprising: i) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount of about 20 wt%; and Zr02 in an amount of about 25 wt%; ii) a gold compound in an amount of about 1.0 wt%; iii) a tin compound in an amount of about 0.3 wt%; and iv) Fe(II) in an amount from about 0.1 wt% to about 1.0 wt%; c) heating propane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene. 117. A method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of: a) providing an alkane; b) providing a dehydrogenation catalyst comprising: i) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount of about 20 wt%; and Zr02 in an amount of about 25 wt%; ii) a gold compound in an amount of about 1.0 wt%; iii) a tin compound in an amount of about 0.3 wt%; and iv) Fe(III) in an amount from about 0.1 wt% to about 1.0 wt%; c) heating the alkane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene. 118. A method for the preparation of propene by catalytic dehydrogenation, the method comprising the steps of: a) providing propane; b) providing a dehydrogenation catalyst comprising: i) a porous carrier comprising Ce02 in an amount of about 55 wt%; Ti02 in an amount of about 20 wt%; and Zr02 in an amount of about 25 wt%; ii) a gold compound in an amount of about 1.0 wt%; iii) a tin compound in an amount of about 0.3 wt%; and iv) Fe(III) in an amount from about 0.1 wt% to about 1.0 wt%; c) heating propane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene. |
FIELD OF INVENTION
[0001] The present invention relates to a dehydrogenation catalyst composition comprising: a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; a tin compound; and one or more transition metal compounds. In one aspect, present invention relates to a dehydrogenation catalyst composition comprising: a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; and one or more transition metal compounds. In various further aspects, the invention relates to the products of the disclosed methods of preparing the dehydrogenation catalyst composition. In various aspects, the disclosed dehydrogentation catalyst compositions can be used to prepare alkenes from the corresponding alkanes in a caatalytic dehydrogenation reaction.
BACKGROUND OF THE INVENTION
[0002] Propylene is a raw material used in important industrial processes including the production of polypropylene, acrylic acid, acrylonitrile, cumene and others. According to a recent study, propylene demand is expected to increase 4.7% annually up to the year 2015. The need for propylene increases faster than the need for ethylene. Catalytic processes for the dehydrogenation of propane are of major interest for industries as a potential source of propylene. Therefore, the development of economic and effective catalysts for propane dehydrogenation is an important goal.
[0003] Existing metal catalysts for propane dehydrogenation are predominantly Pt- based catalysts supported on oxide carriers. Sn, Ga, Zn, La, K, Na, and In are commonly used as promoters for the Pt-containing catalysts. The carriers of these catalysts are oxides such as alumina, chromia, silica, titania, ceria, zirconia, or magnesia or a mixture of any of the aforementioned oxides. Other metals including Pd, Ru, Pd/Ag, Ir, and Re have also been studied as catalysts for propane dehydrogenation.
[0004] The known supported metal catalysts for industrial propane dehydrogenation suffer from several disadvantages. Namely, they require high working temperatures (up to 700 °C) and a cyclic regime with short duration of the working cycle while offering only a moderate degree of conversion and low selectivity. Thus, in order to substantially improve catalyst performance it is necessary for additional catalysts to be developed that overcome these shortcomings.
SUMMARY OF THE INVENTION
[0005] In one aspect, the invention relates to a dehydrogenation catalyst composition comprising:
a) a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium;
b) a gold compound;
c) a tin compound; and
d) one or more transition metal compounds.
[0006] In a further aspect, the dehydrogenation catalyst composition is the calcination product of a mixture of a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; a tin compound; and one or more transition metal compounds.
[0007] In a further aspect,the invention relates to a dehydrogenation catalyst prepared by calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 .
[0008] In one aspect, the invention relates to a dehydrogenation catalyst composition comprising:
a) a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium;
b) a gold compound; and
c) one or more transition metal compounds.
[0009] In a further aspect, the invention relates to a dehydrogenation catalyst prepared by calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 .
[0010] In a further aspect, the invention relates to a method of preparing a
dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 .
[0011] In a further aspect, the invention relates to a method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of:
a) providing an alkane; b) providing a dehydrogenation catalyst comprising:
i) a porous carrier comprising cerium, titanium, and zirconium ii) a gold compound;
iii) a tin compound; and
iv) one or more transition metal compounds;
c) heating the alkane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene.
[0012] In a further aspect, the invention relates to a method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of:
a) providing an alkane;
b) providing a dehydrogenation catalyst comprising:
v) a porous carrier comprising cerium, titanium, and zirconium vi) a gold compound; and
vii) one or more transition metal compounds;
c) heating the alkane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene.
[0013] While aspects of the present invention can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of skill in the art will understand that each aspect of the present invention can be described and claimed in any statutory class. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is in no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The accompanying figures, which are incorporated in and constitute a part of this specification, illustrate several aspects and together with the description serve to explain the principles of the invention. [0015] Figures 1A and IB shows representative x-ray diffraction (XRD) data for the unused catalyst 1.0Au-1.0Fe-1.0Sn/55.0CeO 2 -25.0ZrO 2 -20.0TiO 2 .
[0016] Figure 2A and 2B shows representative XRD data for the used catalyst l.OAu- 1.0Fe-1.0Sn/55.0CeO 2 -25.0ZrO 2 -20.0TiO 2 .
[0017] Figure 3 shows representative x-ray photoelectron spectroscopy (XPS) data indicating the quantity of Au found within 1-12 nm of the unused catalyst l.OAu-l.OFe- 1.0Sn/55.0CeO 2 -25.0ZrO 2 -20.0TiO 2 sample surface. The most intense peak is due to emission from the 4f level of the Au atoms. Mg impurities can also be observed. These impurities are most likely due to the addition of Mg citrate during catalyst preparation to control the pH of the media.
[0018] Figure 4 shows representative XPS data indicating the quantity of O found within 1-12 nm of the unused catalyst 1.0Au-1.0Fe-1.0Sn/55.0CeO 2 -25.0ZrO 2 -20.0TiO 2 sample surface. The most intense peak is due to emission from the Is level of the O atoms.
[0019] Figure 5 shows representative XPS data indicating the quantity of Ti found within 1-12 nm of the unused catalyst 1.0Au-1.0Fe-1.0Sn/55.0CeO 2 -25.0ZrO 2 -20.0TiO 2 sample surface. The most intense peak is due to emission from the 2p level of the Ti atoms.
[0020] Figure 6 shows representative XPS data indicating the quantity of Zr found within 1-12 nm of the unused catalyst 1.0Au-1.0Fe-1.0Sn/55.0CeO 2 -25.0ZrO 2 -20.0TiO 2 sample surface. The most intense peak is due to emission from the 3d level of the Zr atoms.
[0021] Figure 7 shows representative XPS data indicating the quantity of Ce found within 1-12 nm of the unused catalyst 1.0Au-1.0Fe-1.0Sn/55.0CeO 2 -25.0ZrO 2 -20.0TiO 2 sample surface. The most intense peak is due to emission from the 3d level of the Ce atoms.
[0022] Figure 8 shows a representative TEM image of unused catalyst l.OAu-l.OFe- 1.0Sn/55.0CeO 2 -25.0ZrO 2 -20.0TiO 2 . High magnification (235 kX) images were recorded in conventional imaging mode. The image shows that the powders are essentially comprised of finely divided material in the form of clusters. Each cluster consists of entangled tape-like structures, each strand being 5-10 nm in width.
[0023] Figure 9A-D shows representative surface area of the unused non-promoted Au catalyst.
[0024] Figure 10 shows representative overall propane yield of dehydrogenation of C 3 H 8 experiments performed using non-promoted gold-containing catalysts. The non- promoted gold-containing catalyst is 1.0Au/33.3CeO 2 -33.3ZrO 2 -33.3TiO 2 , which is described in Table 1. Ex. A was a fresh sample, while Ex. B-D were after regenerations of the same sample. (GHSV was 3804, temperature was 575°C, Feed composition ratio of C 3 H 8 : H 2 :N2 was 1:0.5:5.5.)
[0025] Figure 11 shows selectivity of propane formation over formation of other hydrocarbons of dehydrogenation experiments performed using non-promoted gold- containing catalysts. (The non-promoted gold-containing catalyst is 1.0Au/33.3CeO 2 - 33.3Zr0 2 -33.3Ti0 2 , which is described in Table 1. Ex. A was a fresh sample, while Ex. B-D were after regenerations of the same sample. GHSV was 3804, temperature was 575°C, Feed composition ratio of C3¾: H 2 :N 2 was 1:0.5:5.5.)
[0026] Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or can be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
DETAILED DESCRIPTION OF THE INVENTION
[0027] The present invention can be understood more readily by reference to the following detailed description of the invention and the Examples included therein.
[0028] Before the present compounds, compositions, articles, devices, and/or methods are disclosed and described, it is to be understood that they are not limited to specific synthetic methods unless otherwise specified, or to particular reagents unless otherwise specified, as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, example methods and materials are now described.
[0029] Moreover, it is to be understood that unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of embodiments described in the specification.
[0030] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited.
DEFINITIONS
[0031] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term "comprising" can include the embodiments
"consisting of and "consisting essentially of." Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined herein.
[0032] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a polycarbonate poly" includes mixtures of two or more polycarbonate polymers.
[0033] As used herein, the term "combination" is inclusive of blends, mixtures, alloys, reaction products, and the like.
[0034] As used herein, the terms "about" and "at or about" mean that the amount or value in question can be the value designated some other value approximately or about the same. It is generally understood, as used herein, that it is the nominal value indicated +10% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is "about" or "approximate" whether or not expressly stated to be such. It is understood that where "about" is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.
[0035] Ranges can be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, a further aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms a further aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about" that particular value in addition to the value itself. For example, if the value "10" is disclosed, then "about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
[0036] References in the specification and concluding claims to parts by weight of a particular element or component in a composition denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.
[0037] As used herein, the term "effective amount" refers to an amount that is sufficient to achieve the desired modification of a physical property of the composition or material. For example, an "effective amount" of polyester refers to an amount that is sufficient to achieve the desired improvement in the property modulated by the formulation component, e.g., improved impact strength and flow-ability, under applicable test conditions and without adversely affecting other specified properties. The specific level in terms of wt% in a composition required as an effective amount will depend upon a variety of factors including the amount and type of polycarbonate, amount and type of impact modifier, amount and type of talc, and end use of the article made using the composition.
[0038] A weight percent (wt. %) of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included. [0039] As used herein, the terms "optional" or "optionally" means that the
subsequently described event or circumstance can or can not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
[0040] The term "metal oxide" refers to compositions comprising the metal oxide, which may or may not further comprise the corresponding metal hydroxides and/or waters of hydration. Thus, a "metal oxide" refers qualitatively to compositions wherein an elemental analysis reveals the presence of the relevant metal (in one or more valence states) and oxygen.
[0041] The term "catalytic dehydrogenation" refers to a dehydrogenation reaction that occurs over a heterogeneous catalyst as described herein.
[0042] The term "heterogeneous catalyst" refers to a calcined product of a gold compound, a tin compound, and one or more transition metal compounds on a porous support. In one aspect, the catalyst is a catalytic composition comprising a gold compound, a tin compound, and one or more transition metal compounds (or the corresponding salt) of the formula:
(Au) a (M 1 ) b (Sn) c
wherein a is 0.1 to 5, preferably 0.1 to 1, b is 0.1 to 2, preferably 0.1 to 1, c is 0.1 to 0.5, preferably 0.3, and M 1 is iron, or cobalt, or a combination comprising at least one of the foregoing metals.
[0043] The metals in the calcined catalyst or in the support are not limited to any particular valence state. These metals can be present in the catalyst or support in any possible positive oxidation for the metal species.
[0044] Various porous materials that can be used as the support include, for example, zirconia (zirconium oxide, Zr0 2 ), titania (titanium oxide, Ti0 2 (anatase or rutile)), ceria (cerium oxide, Ce0 2 ), aluminosilicates, silica (silicon dioxide, Si0 2 ), alumina, (aluminum oxide, A1 2 0 3 (acidic or neutral)), zinc oxide, magnesia (magnesium oxide, MgO), niobium oxide, tin oxide, and combinations comprising at least one or more of the foregoing materials. Aluminosilicates, for example, can include various zeolites such as the SBA series of zeolites, for example, SBA-11, SBA-12, and SBA-15. Other exemplary types of zeolites include mordenite, ZSM-5, L-zeolite, faujasite, ferrierite, and chabazite. In one specific embodiment, the support is zirconia.
[0045] In a further aspect, the porous support is a microporous or a mesoporous material. Mesoporous supports have a pore size of greater than or equal to about 10 to about 100 angstroms, and the microporous supports have a pore size of less than or equal to about 10 angstroms, as determined by BET measurements.
[0046] The surface area of the supported heterogeneous catalyst is influenced by both the support and catalyst. For example, it has been found that pure zirconium oxyhydroxide dried at 120 °C showed a surface area of about 330 m per gram. After calcination at 800 °C, the surface area decreased to 10 m per gram. Addition of catalyst to the support can increase the surface area in some embodiments. Without wishing to be bound by theory, this might be explained by the catalyst interacting with the zirconia support to inhibit sintering and stabilizing the tetragonal phase of zirconia, which leads to an increase in surface area.
However, higher loadings of catalyst can cause the formation of crystalline metal oxide such as tungsten oxide that can plug the pores and decrease the specific surface area.
[0047] The amount of gold used in the heterogeneous catalyst varies, depending on the type of support, the desired activity of the heterogeneous catalyst, and like consideration. For example, in one aspect the total amount of gold is 0.1 wt % to 5.0 wt %, based on the weight of the support. In a further aspect, the total amount of gold is 0.1 wt % to 2.0 wt %, based on the weight of the support. In a still further aspect, the total amount of gold is 0.1 wt % to 1.0 wt %, based on the weight of the support.
[0048] The amount of tin used in the heterogeneous catalyst varies, depending on the type of support, the desired activity of the heterogeneous catalyst, and like consideration. For example, in one aspect the total amount of tin is 0.1 wt % to 0.5 wt %, based on the weight of the support. In a further aspect, the total amount of tin is 0.2 wt % to 0.2 wt %, based on the weight of the support. In a still further aspect, the total amount of tin is 0.3 wt. %, based on the weight of the support.
[0049] The amount of transition metal used in the heterogeneous catalyst varies, depending on the type of support, the desired activity of the heterogeneous catalyst, and like consideration. For example, in one aspect the total amount of transition metal is 0.1 wt % to 2.0 wt %, based on the weight of the support. In a further aspect, the total amount of transition metal is 0.1 wt % to 1.0 wt %, based on the weight of the support.
[0050] The term "supported catalyst" refers to a catalyst which contains a carrier on which the catalytically active component(s) of a heterogeneous catalyst is deposited.
[0051] The term "promoted catalyst" refers to a catalyst which is expected to provide improvement in one or more of the properties of the catalyst, e.g., selectivity, activity, conversion, stability and yield as compared to a catalyst not containing the promoter, e.g. non-promoted.
[0052] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valence filled by a bond as indicated, or a hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group. Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this invention belongs.
[0053] Each of the materials disclosed herein are either commercially available and/or the methods for the production thereof are known to those of skill in the art.
[0054] The following abbreviations are used herein.
[0055] Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order.
Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of embodiments described in the specification.
[0056] It is understood that the compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.
CATALYST COMPOSITIONS
[0057] In one aspect, the invention provides a method for preparing a
dehydrogenation catalyst composition.
[0058] In one aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; a tin compound; and one or more transition metal compounds .
[0059] In a further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising Ce0 2 , an oxide of titanium, and an oxide of zirconium; a gold compound; a tin compound; and one or more transition metal compounds. In a still further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising Ce0 2 present in an amount from about 50.0 wt% to about 75.0 wt%., an oxide of titanium, and an oxide of zirconium; a gold compound; a tin compound; and one or more transition metal compounds.
[0060] In a further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of cerium, Ti0 2 , and an oxide of zirconium; a gold compound; a tin compound; and one or more transition metal compounds. In a still further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of cerium, Ti0 2 present in an amount from about 5.0 wt% to about 20.0 wt%., and an oxide of zirconium; a gold compound; a tin compound; and one or more transition metal compounds.
[0061] In a further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and Zr0 2 ; a gold compound; a tin compound; and one or more transition metal compounds. In a still further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and Zr0 2 present in an amount from about 10.0 wt% to about 30.0 wt%.; a gold compound; a tin compound; and one or more transition metal compounds.
[0062] In a further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of titanium, and cerium and zirconium comprise an oxide of the formula Zr x Ce y 0 2 ; wherein x has a value of about about 0.40 to about 0.95; wherein y has a value of about 0.60 to about 0.05; and wherein the sum of x and y is about 1.00; a gold compound; a tin compound; and one or more transition metal compounds
[0063] In a further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au content of the composition is from about 0.1 wt% to about 5.0 wt%; a tin compound; and one or more transition metal compounds. In a still further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au content of the composition is from about 0.1 wt% to about 2.0 wt%; a tin compound; and one or more transition metal compounds. In yet a further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au content of the composition is from about 0.1 wt% to about 1.0 wt%; a tin compound; and one or more transition metal compounds. In an even further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au comprises one or more oxides; a tin compound; and one or more transition metal compounds.
[0064] In a further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; a tin compound wherein the Sn is present in an amount from about 0.1 wt% to about 0.5 wt%; and one or more transition metal compounds. In a still further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; a tin compound wherein the Sn is present in an amount from about 0.2 wt% to about 0.4 wt%; and one or more transition metal compounds. In yet a further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; a tin compound wherein the Sn is present in an amount of about 0.3 wt%; and one or more transition metal compounds.
[0065] In a further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; a tin compound; and one or more transition metal compounds wherein the transition metal salt is present in an amount from about 0.1 wt% to about 2.0 wt%. In a further aspect, the invention provides a heterogeneous catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; a tin compound; and one or more transition metal compounds wherein the transition metal salt is present in an amount from about 0.1 wt% to about 1.0 wt%.
[0066] In one aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; and one or more transition metal compounds .
[0067] In a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising Ce0 2 , an oxide of titanium, and an oxide of zirconium; a gold compound; and one or more transition metal compounds. In a still further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising Ce0 2 present in an amount from about 40.0 wt% to about 85.0 wt%., an oxide of titanium, and an oxide of zirconium; a gold compound; and one or more transition metal compounds. In yet a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising Ce0 2 present in an amount from about 50.0 wt% to about 75.0 wt%., an oxide of titanium, and an oxide of zirconium; a gold compound; and one or more transition metal compounds. In an even further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising Ce0 2 present in an amount from about 50.0 wt% to about 60.0 wt%., an oxide of titanium, and an oxide of zirconium; a gold compound; and one or more transition metal compounds. In a still further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising Ce0 2 present in an amount of about 55.0 wt% , an oxide of titanium, and an oxide of zirconium; a gold compound; and one or more transition metal compounds.
[0068] In a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, Ti0 2 , and an oxide of zirconium; a gold compound; and one or more transition metal compounds. In a still further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, Ti0 2 present in an amount from about 0.1 wt% to about 30.0 wt%., and an oxide of zirconium; a gold compound; and one or more transition metal compounds. In yet a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, Ti0 2 present in an amount from about 2.5 wt% to about 25.0 wt%., and an oxide of zirconium; a gold compound; and one or more transition metal compounds. In an even further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, Ti0 2 present in an amount from about 5.0 wt% to about 25.0 wt%., and an oxide of zirconium; a gold compound; and one or more transition metal compounds. In a still further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, Ti0 2 present in an amount from about 10.0 wt% to about 25.0 wt%., and an oxide of zirconium; a gold compound; and one or more transition metal compounds. In yet a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, Ti0 2 present in an amount from about 15.0 wt% to about 25.0 wt%., and an oxide of zirconium; a gold compound; and one or more transition metal compounds. In an even further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, Ti0 2 present in an amount from about 17.5 wt% to about 22.5 wt%., and an oxide of zirconium; a gold compound; and one or more transition metal compounds. In a still further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, Ti0 2 present in an amount of about 20.0 wt% , and an oxide of zirconium; a gold compound; and one or more transition metal compounds.
[0069] In a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and Zr0 2 ; a gold compound; and one or more transition metal compounds. In a still further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and Zr0 2 present in an amount from about 5.0 wt% to about 40.0 wt%.; a gold compound; and one or more transition metal compounds. In yet a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and Zr0 2 present in an amount from about 7.5 wt% to about 35.0 wt%.; a gold compound; and one or more transition metal compounds. In an even further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and Zr0 2 present in an amount from about 10.0 wt% to about 30.0 wt%.; a gold compound; and one or more transition metal compounds. In a still further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and Zr0 2 present in an amount from about 15.0 wt% to about 30.0 wt%.; a gold compound; and one or more transition metal compounds. In yet a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and Zr0 2 present in an amount from about 20.0 wt% to about 30.0 wt%.; a gold compound; and one or more transition metal compounds. In an even further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and Zr0 2 present in an amount from about 22.5 wt% to about 27.5 wt%.; a gold compound; and one or more transition metal compounds. In a still further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and Zr0 2 present in an amount of about 25.0 wt%; a gold compound; and one or more transition metal compounds.
[0070] In a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising Ce0 2 , Ti0 2 , and Zr0 2 ; a gold compound; and one or more transition metal compounds. In a still further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising Ce0 2 present in an amount of about 55.0 wt%, Ti0 2 present in an amount of about 20.0 wt%, and Zr0 2 present in an amount of about 25.0 wt%; a gold compound; and one or more transition metal compounds.
[0071] In a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of titanium, and cerium and zirconium comprise an oxide of the formula Zr x Ce y 0 2 ; wherein x has a value of about 0.30 to about 0.99; wherein y has a value of about 0.50 to about 0.01; and wherein the sum of x and y is about 1.00; a gold compound; and one or more transition metal compounds. In a still further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of titanium, and cerium and zirconium comprise an oxide of the formula Zr x Ce y 0 2 ; wherein x has a value of about 0.35 to about 0.97; wherein y has a value of about 0.55 to about 0.03; and wherein the sum of x and y is about 1.00; a gold compound; and one or more transition metal compounds. In yet a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of titanium, and cerium and zirconium comprise an oxide of the formula Zr x Ce y 0 2 ; wherein x has a value of about 0.40 to about 0.95; wherein y has a value of about 0.60 to about 0.05; and wherein the sum of x and y is about 1.00; a gold compound; and one or more transition metal compounds
[0072] In a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au content of the composition is from about 0.1 wt% to about 5.0 wt%; and one or more transition metal compounds. In a still further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au content of the composition is from about 0.1 wt% to about 2.0 wt%; and one or more transition metal compounds. In yet a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au content of the composition is from about 0.5 wt% to about 1.5 wt%; and one or more transition metal compounds. In an even further aspect, the invention provides a
dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au content of the composition is about 1.0 wt%; and one or more transition metal compounds. In an even further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au comprises one or more oxides; and one or more transition metal compounds.
[0073] In a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au particles are of a size less than about 10 nm; and one or more transition metal compounds. In a still further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au particles are of a size less than about 8 nm; and one or more transition metal compounds. In yet a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au particles are of a size less than about 6 nm; and one or more transition metal compounds. In an even further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au particles are from about 2 nm to about 10 nm; and one or more transition metal compounds. In a still further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au particles are from about 2 nm to about 8 nm; and one or more transition metal compounds. In yet a further aspect, the invention provides a
dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound wherein the Au particles are from about 3 nm to about 6 nm; and one or more transition metal compounds.
[0074] In a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; and one or more transition metal compounds wherein the transition metal salt is present in an amount from about 0.1 wt% to about 2.0 wt%. In a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; and one or more transition metal compounds wherein the transition metal salt is present in an amount from about 0.1 wt% to about 1.0 wt%.
[0075] In a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; and one or more transition metal compounds wherein the transition metal salt comprises tin. In a still further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; and one or more transition metal compounds wherein the transition metal salt comprises iron. In yet a further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; and one or more transition metal compounds wherein the transition metal salt comprises iron in the form of Fe(III). In an even further aspect, the invention provides a dehydrogenation catalyst comprising a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; and one or more transition metal compounds wherein the transition metal salt comprises iron in the form of Fe(II). [0076] In one aspect, the invention provides a dehydrogenation catalyst prepared by calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 . In a still further aspect, the invention provides a dehydrogenation catalyst prepared by calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out at a temperature from about 100 °C to about 600 °C. In yet a further aspect, the invention provides a dehydrogenation catalyst prepared by calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out at a temperature from about 400 °C to about 600 °C. In an even further aspect, the invention provides a dehydrogenation catalyst prepared by calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out at a temperature of about 550 °C. In a still further aspect, the invention provides a dehydrogenation catalyst prepared by calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Z r0 2 , wherein calcining is carried in the presence of an oxygen or air flow. In yet a further aspect, the invention provides a dehydrogenation catalyst prepared by calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out in the presence of an oxygen flow. In an even further aspect, the invention provides a dehydrogenation catalyst prepared by calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out in the presence of an air flow.
[0077] In a further aspect, the invention provides a dehydrogenation catalyst prepared by calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , further comprising the steps of preparing the mixture:
a. dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
b. dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ,
wherein the steps of preparing the mixture occur prior to calcining. In a still further aspect, dispersing is impregnation, precipitation, deposition-precipitation, co-precipitation, or incipient wetness impregnation. In yet a further aspect, dispersing is impregnation, precipitation, deposition-precipitation or co-precipitation. In an even further aspect, dispersing is impregnation, precipitation, or deposition-precipitation. In a still further aspect, dispersing is impregnation, or precipitation. In yet a further aspect, dispersing is
impregnation. In an even further aspect, impregnation is carried out in aqueous solution at a temperature from about 55 °C to about 75 °C. In a still further aspect, impregnation is carried out in aqueous solution at a temperature from about 60 °C to about 70 °C. In yet a further aspect, impregnation is carried out in aqueous solution at a temperature of about 65 °C. In an even further aspect, the aqueous solution has a pH from about 7.0 to about 12.0. In a still further aspect, the pH of the aqueous solution is from about 8.0 to about 10.5. In yet a further aspect, the pH of the aqueous solution is adjusted using alkaline compounds. In an even further aspect, the pH of the aqueous solution is adjusted using magnesium citrate, barium carbonates, hydroxides or ammonia, or a mixture thereof.
[0078] In one aspect, the invention provides a dehydrogenation catalyst composition comprising a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount from about 17.5 wt% to about 22.5 wt%; and Zr0 2 in an amount from about 22.5 wt% to about 27.5 wt%; a gold compound in an amount from about 0.1 wt% to about 1.0 wt%; and one or more transition metal compounds in an amount from about 0.1 wt% to about 1.0 wt%.In one aspect, the invention provides a dehydrogenation catalyst composition comprising a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20.0 wt%; and Zr0 2 in an amount of about 20 wt%; a gold compound in an amount of about 1.0 wt%; and one or more transition metal compounds in an amount from about 0.1 wt% to about 1.0 wt%.
[0079] In one aspect, the invention provides a dehydrogenation catalyst composition comprising a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20.0 wt%; and Zr0 2 in an amount of about 20 wt%; a gold gold compound in an amount of about 1.0 wt%; and tin in an amount from about 0.1 wt% to about 1.0 wt%.
[0080] In one aspect, the invention provides a dehydrogenation catalyst composition comprising a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20.0 wt%; and Zr0 2 in an amount of about 20 wt%; a gold compound in an amount of about 1.0 wt%; and iron in an amount from about 0.1 wt% to about 1.0 wt%.
[0081] In one aspect, the invention provides a dehydrogenation catalyst composition comprising a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20.0 wt%; and Zr0 2 in an amount of about 20 wt%; a gold compound in an amount of about 1.0 wt%; and Fe(II) in an amount from about 0.1 wt% to about 1.0 wt%.
[0082] In one aspect, the invention provides a dehydrogenation catalyst composition comprising a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20.0 wt%; and Zr0 2 in an amount of about 20 wt%; a gold gold compound in an amount of about 1.0 wt%; and Fe(III) in an amount from about 0.1 wt% to about 1.0 wt%.
METHODS OF MAKING CATALYST COMPOSITION
[0083] In one aspect, the invention provides a method for preparing a
dehydrogenation catalyst composition.
[0084] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 . In a still further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out at a temperature from about 100 °C to about 600 °C. In yet a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out at a temperature from about 400 °C to about 600 °C. In an even further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out at a temperature from about 500 °C to about 600 °C. In a still further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out at a temperature of about 550 °C.
[0085] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out in the presence of an oxygen flow or air flow. In a still further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out in the presence of an oxygen flow. In yet a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out in the presence of an air flow.
[0086] In one aspect, the invention provides a method for preparing a
dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ;
b) dispersing a tin salt with the material comprising the gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ; and
c) dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ,
wherein the steps of preparing the mixture occur prior to calcining.
[0087] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above comprising the steps of preparing the mixture:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ;
b) dispersing a tin salt with the material comprising the gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ; and
c) dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 .
[0088] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ;
b) dispersing a tin salt with the material comprising the gold salt, Ce0 2 , Ti0 2 , and
Zr0 2 ; and
c) dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ,
wherein dispersing is impregnation, precipitation, deposition-precipitation, co-precipitation, or incipient wetness impregnation and wherein the steps of preparing the mixture occur prior to calcining.
[0089] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture: a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ;
b) dispersing a tin salt with the material comprising the gold salt, Ce0 2 , Ti0 2 , and
Zr0 2 ; and
c) dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ,
wherein dispersing is impregnation, and wherein the steps of preparing the mixture occur prior to calcining.
[0090] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ;
b) dispersing a tin salt with the material comprising the gold salt, Ce0 2 , Ti0 2 , and
Zr0 2 ; and
c) dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ,
wherein dispersing is impregnation, wherein the impregnation is carried out in aqueous solution at a temperature from about 55 °C to about 75 °C, and wherein the steps of preparing the mixture occur prior to calcining.
[0091] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ;
b) dispersing a tin salt with the material comprising the gold salt, Ce0 2 , Ti0 2 , and
Zr0 2 ; and
c) dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ,
wherein dispersing is impregnation, wherein the impregnation is carried out in aqueous solution at a temperature of about 65 °C, and wherein the steps of preparing the mixture occur prior to calcining.
[0092] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; b) dispersing a tin salt with the material comprising the gold salt, Ce0 2 , Ti0 2 , and
Zr0 2 ; and
c) dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ,
wherein dispersing is impregnation, wherein the impregnation is carried out in aqueous solution with a pH from about 8.0 to about 10.5, and wherein the steps of preparing the mixture occur prior to calcining.
[0093] In one aspect, the invention provides a method for preparing dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 .
[0094] In a further aspect, the invention provides a method for preparing
dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out at a temperature from about 100 °C to about 600 °C. In a still further aspect, the invention provides a method for preparing dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out at a temperature from about 400 °C to about 600 °C. In yet a further aspect, the invention provides a method for preparing dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out at a temperature from about 500 °C to about 600 °C. In an even further aspect, the invention provides a method for preparing dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out at a temperature from about 100 °C to about 600 °C. In a still further aspect, the invention provides a method for preparing dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out at a temperature of about 550 °C.
[0095] In a further aspect, the invention provides a method for preparing
dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out in the presence of an oxygen flow or air flow. In a still further aspect, the invention provides a method for preparing dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out in the presence of an oxygen flow. In yet a further aspect, the invention provides a method for preparing dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 wherein calcining is carried out in the presence of an air flow.
[0096] In a further aspect, the invention provides a method for preparing
dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture that is calcined:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ;
b) dispersing a tin salt with the material comprising the gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ; and
c) dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
[0097] In a further aspect, the invention provides a method for preparing
dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture that is calcined:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ;
b) dispersing a tin salt with the material comprising the gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ; and
c) dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation, precipitation, deposition-precipitation, co-precipitation, or incipient wetness impregnation.
[0098] In a further aspect, the invention provides a method for preparing
dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture that is calcined:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ;
b) dispersing a tin salt with the material comprising the gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ; and
c) dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation. [0099] In a further aspect, the invention provides a method for preparing
dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture that is calcined:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ;
b) dispersing a tin salt with the material comprising the gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ; and
c) dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation carried out in aqueous solution at a temperature from about 55 °C to about 75 °C.
[0100] In a further aspect, the invention provides a method for preparing
dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture that is calcined:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ;
b) dispersing a tin salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ; and
c) dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation carried out in aqueous solution at a temperature of about 65 °C.
[0101] In a further aspect, the invention provides a method for preparing
dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture that is calcined:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ;
b) dispersing a tin salt with the material comprising the gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ; and
c) dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation carried out in aqueous solution which has a pH from about 7.0 to about 12.0.
[0102] In a further aspect, the invention provides a method for preparing
dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture that is calcined: a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; b) dispersing a tin salt with the material comprising the gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ; and
c) dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation carried out in aqueous solution which has a pH from about 8.0 to about 10.5.
[0103] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 . In a still further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out at a temperature from about 100 °C to about 600 °C. In yet a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out at a temperature from about 400 °C to about 600 °C. In an even further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out at a temperature from about 500 °C to about 600 °C. In a still further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out at a temperature of about 550 0 C.
[0104] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out in the presence of an oxygen flow or air flow. In a still further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out in the presence of an oxygen flow. In yet a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out in the presence of an air flow.
[0105] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
d) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
e) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ,
[0106] wherein the steps of preparing the mixture occur prior to calcining. In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
d) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
e) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation, precipitation, deposition-precipitation, co- precipitation, or incipient wetness impregnation; and wherein the steps of preparing the mixture occur prior to calcining.
[0107] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
b) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ,
wherein dispersing is impregnation, precipitation, deposition-precipitation or co- precipitation; and wherein the steps of preparing the mixture occur prior to calcining.
[0108] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
b) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ,
wherein the steps of preparing the mixture occur prior to calcining; and wherein dispersing is impregnation, precipitation, or deposition-precipitation. [0109] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
b) dispersing a gold salt with the material comprising the transition metal salt, CeO Ti0 2 , and Zr0 2 ,
wherein dispersing is impregnation, or precipitation; and wherein the steps of preparing the mixture occur prior to calcining.
[0110] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
d) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
e) dispersing a gold salt with the material comprising the transition metal salt, CeO Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation; and wherein the steps of preparing the mixture occur prior to calcining.
[0111] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
d) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
e) dispersing a gold salt with the material comprising the transition metal salt, CeO Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation; wherein the impregnation is carried out in aqueous solution at a temperature from about 55 °C to about 75 °C; and wherein the steps of preparing the mixture occur prior to calcining.
[0112] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
b) dispersing a gold salt with the material comprising the transition metal salt, CeO Ti0 2 , and Zr0 2 , wherein dispersing is impregnation; wherein the impregnation is carried out in aqueous solution at a temperature from about 60 °C to about 70 °C; and wherein the steps of preparing the mixture occur prior to calcining.
[0113] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
d) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
e) dispersing a gold salt with the material comprising the transition metal salt, , Ce0 2 , Ti0 2 , and Zr0 2 ,
wherein dispersing is impregnation; wherein the impregnation is carried out in aqueous solution at a temperature of about 65 °C; and wherein the steps of preparing the mixture occur prior to calcining.
[0114] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
b) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ,
wherein dispersing is impregnation; wherein the impregnation is carried out in aqueous solution with a pH from about 7.0 to about 12.0; and wherein the steps of preparing the mixture occur prior to calcining.
[0115] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
d) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
e) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation; wherein the impregnation is carried out in aqueous solution with a pH from about 8.0 to about 10.5; and wherein the steps of preparing the mixture occur prior to calcining.
[0116] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture: a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
b) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ,
wherein dispersing is impregnation; wherein the impregnation is carried out in aqueous solution with a pH from about 8.0 to about 10.5; wherein the pH of the aqueous solution is adjusted using alkaline compounds; and wherein the steps of preparing the mixture occur prior to calcining.
[0117] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
b) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ,
wherein dispersing is impregnation; wherein the impregnation is carried out in aqueous solution with a pH from about 8.0 to about 10.5; wherein the pH of the aqueous solution is adjusted using magnesium citrate, barium carbonates, hydroxides or ammonia, or a mixture thereof; and wherein the steps of preparing the mixture occur prior to calcining.
[0118] In one aspect, the invention provides a method for preparing a
dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 .
[0119] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out at a temperature from about 100 °C to about 600 °C. In a still further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out at a temperature from about 400 °C to about 600 °C. In yet a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out at a temperature from about 500 °C to about 600 °C. In an even further aspect, the invention provides a method for preparing dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out at a temperature from about 100 °C to about 600 °C. In a still further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out at a temperature of about 550 0 C.
[0120] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out in the presence of an oxygen flow or air flow. In a still further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out in the presence of an oxygen flow. In yet a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 , wherein calcining is carried out in the presence of an air flow.
[0121] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture that is calcined:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and b) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 .
[0122] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture that is calcined:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and b) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation, precipitation, deposition-precipitation, co-precipitation, or incipient wetness impregnation. [0123] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture that is calcined:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
b) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation.
[0124] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture that is calcined:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
b) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation carried out in aqueous solution at a temperature from about 55 °C to about 75 °C.
[0125] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture that is calcined:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
b) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation carried out in aqueous solution at a temperature of about 65 °C.
[0126] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture that is calcined:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and
b) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation carried out in aqueous solution which has a pH from about 7.0 to about 12.0. [0127] In a further aspect, the invention provides a method for preparing a dehydrogenation catalyst composition as described above further comprising the steps of preparing the mixture that is calcined:
a) dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ; and b) dispersing a gold salt with the material comprising the transition metal salt, Ce0 2 , Ti0 2 , and Zr0 2 ;
wherein dispersing is impregnation carried out in aqueous solution which has a pH from about 8.0 to about 10.5.
USES OF CATALYST COMPOSITIONS
[0128] In one aspect, the invention provides a method for preparing an alkene by catalytic dehydrogenation, the method comprising the steps of:
a) providing an alkane;
b) providing a dehydrogenation catalyst comprising:
i) a porous carrier comprising cerium, titanium, and zirconium ii) a gold compound;
iii) a tin compound; and
iv) one or more transition metal compounds;
c) heating the alkane in the presence of a dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene.
[0129] In one aspect, the invention provides a method for preparing an alkene by catalytic dehydrogenation, the method comprising the steps of:
a) providing an alkane;
b) providing a dehydrogenation catalyst comprising:
i. a porous carrier comprising cerium, titanium, and zirconium ii. a gold compound; and
iii. one or more transition metal compounds;
c) heating the alkane in the presence of a dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene.
[0130] In a further aspect, the invention provides a method for preparing an alkene by catalytic dehydrogenation as described above wherein the alkane is selected from ethane, propane, and butane. In a still further aspect, the invention provides a method for preparing an alkene by catalytic dehydrogenation as described above wherein the alkane is propane.
[0131] In a further aspect, the invention provides a method for preparing an alkene by catalytic dehydrogenation as described above wherein the alkene is selected from ethane, propene, and butene. In a still further aspect, the invention provides a method for preparing an alkene by catalytic dehydrogenation as described above wherein the alkene is propene.
[0132] In a further aspect, the invention provides a method for preparing an alkene by catalytic dehydrogenation as described above wherein the heating is at a temperature from about 400 °C to about 600 °C. In a still further aspect, the invention provides a method for preparing an alkene by catalytic dehydrogenation as described above wherein the heating is at a temperature from about 500 °C to about 600 °C. In yet a further aspect, the invention provides a method for preparing an alkene by catalytic dehydrogenation as described above wherein the heating is at a temperature from about 400 °C to about 600 °C.
[0133] In a further aspect, the invention provides a method for preparing an alkene by catalytic dehydrogenation as described above further comprising the step of heating the dehydrogenation catalyst at a temperature from about 400 °C to about 600 °C in the presence of a mixture of oxygen and helium prior to the providing of the dehydrogenation catalyst. In a still further aspect, the invention provides a method for preparing an alkene by catalytic dehydrogenation as described above further comprising the step of heating the
dehydrogenation catalyst at a temperature from about 400 °C to about 600 °C in the presence of a mixture of oxygen and helium prior to the providing of the dehydrogenation catalyst wherein the heating is at about 500 °C.
[0134] In a further aspect, the invention provides a method for preparing an alkene by catalytic dehydrogenation as described above further comprising providing hydrogen and helium.
[0135] In one aspect, the invention provides a method for preparing propene by catalytic dehydrogenation, the method comprising the steps of:
a) providing propane;
b) providing a dehydrogenation catalyst comprising:
i) a porous carrier comprising cerium, titanium, and zirconium ii) a gold compound; and
iii) one or more transition metal compounds; c) heating propane in the presence of a dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene.
[0136] In a further aspect, the invention provides a method for preparing propene by catalytic dehydrogenation as described above wherein the heating is at a temperature from about 400 °C to about 600 °C. In a still further aspect, the invention provides a method for preparing propene by catalytic dehydrogenation as described above wherein the heating is at a temperature from about 500 °C to about 600 °C. In yet a further aspect, the invention provides a method for preparing propene by catalytic dehydrogenation as described above wherein the heating is at a temperature from about 400 °C to about 600 °C.
[0137] In a further aspect, the invention provides a method for propene by catalytic dehydrogenation as described above further comprising the step of heating the
dehydrogenation catalyst at a temperature from about 400 °C to about 600 °C in the presence of a mixture of oxygen and helium prior to the providing of the dehydrogenation catalyst. In a still further aspect, the invention provides a method for preparing propene by catalytic dehydrogenation as described above further comprising the step of heating the
dehydrogenation catalyst at a temperature from about 400 °C to about 600 °C in the presence of a mixture of oxygen and helium prior to the providing of the dehydrogenation catalyst wherein the heating is at about 500 °C.
[0138] In a further aspect, the invention provides a method for preparing propene by catalytic dehydrogenation as described above further comprising providing hydrogen and helium.
[0139] Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present invention. The following examples are included to provide addition guidance to those skilled in the art of practicing the claimed invention. The examples provided are merely representative of the work and contribute to the teaching of the present invention. Accordingly, these examples are not intended to limit the invention in any manner.
[0140] While aspects of the present invention can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of skill in the art will understand that each aspect of the present invention can be described and claimed in any statutory class. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.
[0141] Throughout this application, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which this pertains. The references disclosed are also individually and specifically incorporated by reference herein for the material contained in them that is discussed in the sentence in which the reference is relied upon. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided herein can be different from the actual publication dates, which can require independent confirmation.
EXAMPLES
[0142] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the catalysts, compounds, compositions, articles, devices and/or methods claimed herein are made and evaluated, and are intended to be purely exemplary of the invention and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric.
[0143] There are numerous variations and combinations of reaction conditions, e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions.
[0144] Several methods for preparing the catalysts of this invention are illustrated in the following Examples. Starting materials and the requisite intermediates are in some cases commercially available, or can be prepared according to literature procedures or as illustrated herein. [0145] The following exemplary catalysts of the invention were synthesized. The Examples are provided herein to illustrate the invention, and should not be construed as limiting the invention in any way.
1. PREPARATION OF INTERMEDIATE I
[0146] 2.2 g of Fe 3 (N0 3 ) 3 -9H 2 0 was dissolved in 192 cm 3 of distilled water heated to 65 ° C. Then the support mixture consisting of 43.49 g Ce0 2 , 12.18 g Zr0 2 and 6.70 g Ti0 2 that was preliminary dried at 110 °C for 4 hours was added. The impregnation process of Fe salt lasts for 180 min. at 65 °C under intensive mixing. At this time the obtained material was washed several times with hot distillated water and dried at 110 °C for 12 hours.
2. PREPARATION OF INTERMEDIATE II
[0147] 0.11 g of SnCl 2 -2H 2 0 was dissolved in hot distilled water with addition of HC1, if necessary. The solution was added to distilled water heated to 65 °C and the volume adjusted to 192 cm . Then the support with preliminary deposited Fe dried at 110 °C for 4 hours was added. The impregnation process of Fe salt lasts for 180 min. at 65 °C under intensive mixing. At this time the obtained material was washed several times with hot distillated water and dried at 110 °C for 12 hours.
3. GENERAL ROUTE FOR PREPARATION OF GOLD-CONTAINING CATALYST
[0148] 0.29 g HAuCl 4 -H 2 0 was dissolved in 192 cm 3 of distilled water heated to 65 °C and the support impregnated with Fe or Sn salts under intensive mixing was added. The pH of the solution was adjusted by the addition of a solution of Mg(C 6 Hs0 7 ) 2 -14H 2 0. The impregnation process of Au salt lasts for 90 min. at 65 °C under intensive mixing. The precipitate was filtered, and washed several times with distillated water, to complete removal of the CI- and N0 3 - ions. The obtained material was then dried at 110 °C for 4 hours and calcined at 550 °C for 12 hours.
4. GENERAL ROUTE FOR REGENERATION OF GOLD-CONTAINING CATALYST
[0149] Deactivated catalysts were regenerated in the reactor where the reaction was carried out. After the reaction was stopped, the catalyst was slowly cooled down to 250 °C in a hydrogen flow of 50 cm /min. Once the catalyst had cooled, the hydrogen was replaced by a nitrogen flow of 50 cm /min. The nitrogen flow was kept for 90 min. At this time, the nitrogen was replaced by a mixture of 0 2 :N 2 = 1.0: 99.0. This treatment was maintained for 60 min. The gas mixture was then changed to 0 2 :N 2 = 5.0: 95.0. The temperature was increased to 400 °C at a ramping rate of 10 °C/min and held at this temperature for 60 min. Then, the temperature was increased to 500 °C at a ramping rate of 10 °C/min and held at this temperature for 60 min. The composition of the regeneration mixture was changed to 0 2 :N2 = 20.0: 80.0. At this time, the regeneration mixture was replaced by pure oxygen, which was passed through the reactor at 500 °C for 30 min. The end of the regenerating process was estimated by the absence of C0 2 in effluent gases.
[0150] The reactor was then cooled down to 100 °C and flushed with nitrogen for 2 hrs. Regenerated catalysts were then reduced following the procedure described below.
5. GENERAL ROUTE FOR REDUCTION OF GOLD-CONTAINING CATALYST
[0151] Upon loading the sample into the reactor, the sample was flushed with nitrogen at a flow rate of 50 cm 3 /min. The temperature of the reactor was raised to 120 °C and maintained for 2 hrs before being increased at a rate of 3 °C/min. The temperature continued to be increased until it reached 200 °C. At this time 5% of the nitrogen flow was replaced by hydrogen. From this point on, as the temperature increased, the percentage of hydrogen was increased by 5% at 50 °C intervals. When the reactor temperature reached 575 °C, the nitrogen flow was stopped completed. The reduction was carried out at this temperature for 3 hrs in pure hydrogen. At this time, the catalyst was deemed ready for testing.
6. REPRESENTATIVE CATALYSTS
[0152] Table 1 below lists specific catalysts prepared by the methods described above and in the experimental examples below. The catalysts in Table 1 were synthesized with methods identical or analogous to those shown herein. The requisite starting materials were commercially available, described in the literature, or readily synthesized by one skilled in the art of organic synthesis.
7. X-RAY DIFFRACTION ANALYSIS
[0153] Table 2 below lists XRD data for specific Au-Fe-promoted catalysts. XRD data was determined using an EQUINOX 1000 (Inel, France) with Cu (Ka) radiation (λ^Ο.154056 nm) at a setting of 30 kV and 30 mA. The catalysts in Table 2 were synthesized with methods identical or analogous to those described herein. Table 2
Parameter of the
Catalyst Phase composition (wt%) Crystallites (nm)
unit cell (A)
Ceo.75Zro.25O2 - 63 9
Ce/Zr/Ti/Fe/Au
Ti0 2 - 36 14 a = 5,356 unused proba 5
Au - 1
Ce/Zr/Ti/Fe/Au Ceo.75Zro.25O2 -62 9
used proba 9 Ti0 2 - 37 13 a = 5,354
Au - 1
8. X-RAY PHOTOELECTRON SPECTROSCOPIC ANALYSIS
[0154] Table 3 below lists XPS data for specific carriers and gold promoted and non- promoted catalysts as well as the experimentally determined concentrations of the elements present on the surface of the catalyst. All values are listed as a %. XPS data was determined using an ultra-high vacuum multi-technique surface analysis system (XSAM 800
spectrometer) operating at base pressures of 10-10 bar range. A standard X-ray source with Al-Ka (1486.6 eV) was used to irradiate the sample surface. The analysis chamber was maintained at 5x10-9 bar during all measurements. As the standard practice in XPS studies, the adventitious hydrocarbon Cls line (284.6 eV) corresponding to C-C bond has been used as binding energy reference for charge correction. Fe is undeterminable using this technique. All values are listed as a %. The catalysts in Table 2 were synthesized with methods identical or analogous to those described herein.
9. MOSSBAUER SPECTROSCOPIC ANALYSIS
[0155] Table 4 below lists Mossbauer spectral data for Au-Fe-promoted catalysts was obtained by Wissenschaftliche Elektronik GmbH, Germany. The Mossbauer spectra of both catalysts have an optimal fit using the two quadrupole doublets model. The determined hyperfine parameters of two sets of doublet lines can be assigned to ultradisperse hematitelike a-Fe 2 0 3 particles (D < 10 nm) with superparamagnetic (SPM) behavior. It is know that when the magnetic anistropy barrier (KV) (where K is the anisotropy constant and V is the particle volume) is smaller or comparable to the average thermal energy (Ε ¾ ) of the particles (KV <v Eth), the magnetic moment flips so rapidly that the effective moment during the time of measurement becomes zero. This causes the collapse of a six-line pattern to a
superparamagnetic doublet. The presence of the gradient of the electric field surrounding the iron nuclei (high value of QS) means that the distortion of the symmetry for the neighbor changes. That might be a result from the location of the iron nuclei in the polyhedral buildup from ligands of a different chemical nature. In this case, the core-shell model can be applied to explain the presence of two quadrupole doublets. They belong to iron ions from the "core" and the interface ("shell layers") of nanoparticles. The doublet component with lower QS belongs to iron ions from the "core" of the particles. The doublet component with larger QS can be assigned to interface (from the "shell" layers) ferric ions. The lower symmetry in the environment of "surface" iron ions results in a change in the electric field gradient and thereofre in a shift of the QS value. The obtained ratio of ther elative weights of these core doublets to shell quadrupole doublets, corresponding to the "inner" and "outer" iron ions, is 1 : 1 for the first sample, while for the second sample it is 1 : 1.06. From the obtained spectra detailed herein, it follows that all iron ions are in the Fe 3+ state. They are octahedral in coordination with oxygen atoms as their closest neighbors.
[0156] The formed iron oxide phase with nano dimensions is in a super paramagnetic state. Therefore, according to the used model, the hematite-like particle size is below D = 5 nm. The ratio between two doublets shows that the iron oxide particles have the diameter of about 5 nm and 4 nm for the two samples, correspondingly.
[0157] Mossbauer spectral data was determined using by Wissenschaftliche
Elektronik GmbH, Germany. The catalysts in Table 4 were synthesized with methods identical or analogous to those described herein. Table 4
Sample QS G Hematite particle
(mm/s) (%) size (nm)
1.OAu.1.0Fe 2 O 3 /5.5CeO2.2.5ZrO2.2TiO2 5.0
Doublet 1 - Fe 3+ oh , Fe 2 0 3 -core 0.775 50
Doublet 2 - Fe 3+ oh, Fe 2 0 3 -shell 1.216 50
1.OAu.1.0Fe 2 O 3 .1.0SnO 2 /5.5CeO 2 .2.5ZrO 2 .2TiO 2 4.0
Doublet 1 - Fe 3+ oh , Fe 2 0 3 -core 0.871 47
Doublet 2 - Fe 3+ oh, Fe 2 0 3 -shell 1.173 53
10. DEHYDROGENATION OF PROPANE
[0158] The catalytic activity of the catalysts prepared according to the methods described above in propane dehydrogenation were measured in a Microactivity-Reference (PID Eng & Tech, Madrid, Spain) automated catalytic system. A quartz flow reactor with i.d. = 6 mm containing 0.5 - 1 g of catalyst mixed with 1 g quartz sand (mesh size 12 - 25) was used. The reaction temperature was varied in the interval 500 - 600 °C and measured by a thermocouple located in the catalyst bed. The Gas Hourly Space Velocity (GHSV) of the reacting gas C 3 ¾ : H 2 : He = 1: 1:5 was varied between 1900 to 3800 h "1 . Before use the catalyst was treated with a mixture of oxygen and He at 500 °C for two hours. At this time the catalysts were reduced to the temperature of the reaction for 2 hours.
[0159] The inlet and outlet reaction composition was analyzed by gas chromatograph with PID and HWD detectors.
11. ACTIVITY OF CATALYSTS IN THE DEHYDROGENATION OF PROPANE
[0160] Table 5 below lists specific carriers and Gold non-promoted catalysts as well as the experimentally determined catalytic properties in the dehydrogenation of propane. The catalyst activity was determined using the Microactivity-Reference (PID Eng & Tech, Madrid, Spain) automated catalytic system as described above. The catalysts in Table 5 were synthesized with methods identical or analogous to those described herein.
Table 5
C 3 H 8 Total C 3 ¾ HC
T GHSV
No. Catalyst Conv. Select. Yield select.
(°C)
(%) (%) (%) (%)
Ce0 2 -Zr0 2 -Ti0 2 Carrier
1 33.3Ce0 2 -33.3Zr0 2 -33.3Ti0 2 550 3800 5.5 28.1 1.5 94.8
Gold non-promoted
1.0Au/33.3CeO 2 -33.3ZrO 2 -
2 3800 6.9 51.2 3.5 93.5
33.3Ti0 2
575
1.0Au/33.3CeO 2 -33.3ZrO 2 -
3 3800 8.0 50.6 3.6 95.2
33.3Ti0 2
Average at 575 °C 3800 7.5 50.9 3.6 94.4
[0161] Table 6 below lists Au-Fe-Sn promoted catalysts as well as the experimentally determined catalytic properties in the dehydrogenation of propane. The catalyst activity was determined using the Microactivity-Reference (PID Eng & Tech, Madrid, Spain) automated catalytic system as described above. The catalysts in Table 6 were synthesized with methods identical or analogous to those described herein.
Table 6
C3H8 Total C3H6 HC
T GHSV
No. Catalyst Conv. Select. Yield select.
(°C) (h- 1 )
(%) (%) (%) (%)
1.OAu- 1.OFe- 1.OSn/55.0CeO 2 -
4 500 3800 2.25 42.2 0.73 97.4
25.0ZrO 2 -20.0TiO 2
1.OAu- 1.OFe- 1.OSn/55.0CeO 2 -
5 3800 6.74 52.0 3.72 97.4
25.0ZrO 2 -20.0TiO 2
550
1.OAu- 1.OFe- 1.OSn/55.0CeO 2 -
6 3800 18.3 40.3 7.6 90.3
25.0ZrO 2 -20.0TiO 2
Average at 550 °C 3800 12.5 46.2 5.7 93.9
1.OAu- 1.OFe- 1.OSn/55.0CeO 2 -
1 1900 49.9 27.5 12.4 77.3
25.0ZrO 2 -20.0TiO 2
1.OAu- 1.OFe- 1.OSn/55.0CeO 2 -
2 1900 46.3 28.3 12.5 79.5
25.0ZrO 2 -20.0TiO 2
1.OAu- 1.OFe- 1.OSn/55.0CeO 2 -
7 3800 24.1 49.1 11.9 71.2
25.0ZrO 2 -20.0TiO 2
575
1.OAu- 1.OFe- 1.OSn/55.0CeO 2 -
8 3800 28.3 43.5 12.2 93.0
25.0ZrO 2 -20.0TiO 2
1.OAu- 1.OFe- 1.OSn/55.0CeO 2 -
9 3800 31.2 43.2 13.6 89.2
25.0ZrO 2 -20.0TiO 2
1.OAu- 1.OFe- 1.OSn/55.0CeO 2 -
10 3800 34.1 40.7 14.4 90.7
25.0ZrO 2 -20.0TiO 2
Average at 575 °C 3167 35.7 38.7 12.8 83.5
1.OAu- 1.OFe- 1.OSn/55.0CeO 2 -
11 3800 34.5 40.7 14.1 9.7
25.0ZrO 2 -20.0TiO 2
1.OAu- 1.OFe- 1.OSn/55.0CeO 2 -
3 600 1900 47.6 36.0 13.8 83.7
25.0ZrO 2 -20.0TiO 2
1.OAu- 1.OFe- 1.OSn/55.0CeO 2 -
12 3800 49.2 36.1 16.1 84.3
25.0ZrO 2 -20.0TiO 2
Average at 600 °C 3167 43.8 37.6 14.7 59.2
[0162] Table 7 below lists Au-Co-Sn promoted catalysts as well as the experimentally determined catalytic properties in the dehydrogenation of propane. The catalyst activity was determined using the Microactivity-Reference (PID Eng & Tech, Madrid, Spain) automated catalytic system as described above. The catalysts in Table 7 were synthesized with methods identical or analogous to those described herein. Table 7
C3H8 Total C3H6 HC
T GHSV
No. Catalyst Conv. Select. Yield select.
(°C) (h- 1 )
(%) (%) (%) (%)
1.OAu- 1.OCo- 1.0Sn/55.0CeO 2 -
13 1900 30.3 15.2 4.6 70.5
25.0ZrO 2 -20.0TiO 2
1.OAu- 1.OCo- 1.0Sn/55.0CeO 2 -
14 3800 29.7 21.2 6.6 85.3
25.0ZrO 2 -20.0TiO 2
1.0Au/33.3CeO 2 -33.3ZrO 2 -
16 575 3800 6.9 51.2 3.5 93.5
33.3Ti0 2
1.0Au/33.3CeO 2 -33.3ZrO 2 -
17 3800 8.0 50.6 3.6 95.2
33.3Ti0 2
1.0Au/33.3CeO 2 -33.3ZrO 2 -
18 3800 6.6 59.1 3.9 79.3
33.3Ti0 2
Average at 575 °C 3420 16.3 39.5 4.4 84.8
1.OAu- 1.OCo- 1.0Sn/55.0CeO 2 -
15 600 1900 49.2 13.5 6.7 63.1
25.0ZrO 2 -20.0TiO 2
[0163] Set forth below are some embodiments of the catalyst composition and processes disclosed herein.
[0164] Embodiment 1: A dehydrogenation catalyst composition comprising: a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; and one or more transition metal compounds.
[0165] Embodiment 2: The composition of Embodiment 1, wherein the oxide of cerium comprises Ce0 2 .
[0166] Embodiment 3: The composition of Embodiment 2, wherein the Ce0 2 is present in an amount from about 40.0 wt% to about 85 wt%.
[0167] Embodiment4: The composition of Embodiment 2, wherein the Ce0 2 is present in an amount from about 45 wt% to about 80 wt%.
[0168] Embodiment 5: The composition of Embodiment 2, wherein the Ce0 2 is present in an amount from about 50.0 wt% to about 75.0 wt%.
[0169] Embodiment 6: The composition of Embodiment 2, wherein the Ce0 2 is present in an amount from about 50.0 wt% to about 60.0 wt%.
[0170] Embodiment 7: The composition of Embodiment 2, wherein the Ce0 2 is present in an amount of about 55.0 wt%.
[0171] Embodiment 8: The composition of any of Embodiments 1-7, wherein the oxide of titanium comprises Ti0 2 .
[0172] Embodiment 9: The composition of Embodiment 8, wherein the Ti0 2 is present in an amount from about 0.1 wt% to about 30 wt%. [0173] Embodiment 10: The composition of Embodiment 8, wherein the Ti0 2 is present in an amount from about 2.5 wt% to about 25 wt%.
[0174] Embodiment 11: The composition of Embodiment 8, wherein the Ti0 2 is present in an amount from about 5.0 wt% to about 25.0 wt%.
[0175] Embodiment 12: The composition of Embodiment 8, wherein the Ti0 2 is present in an amount from about 10.0 wt% to about 25.0 wt%.
[0176] Embodiment 13: The composition of Embodiment 8, wherein the Ti0 2 is present in an amount from about 15.0 wt% to about 25.0 wt%.
[0177] Embodiment 14: The composition of Embodiment 8, wherein the Ti0 2 is present in an amount from about 17.5 wt% to about 22.5 wt%.
[0178] Embodiment 15: The composition of Embodiment 8, wherein the Ti0 2 is present in an amount of about 20.0 wt%.
[0179] Embodiment 16: The composition of any of Embodiments 1-15, wherein the oxide of zirconium comprises Zr0 2 .
[0180] Embodimentl7: The composition of Embodiment 16, wherein the Zr0 2 is present in an amount from about 5.0 wt% to about 40.0 wt%.
[0181] Embodiment 18: The composition of Embodiment 16, wherein the Zr0 2 is present in an amount from about 7.5 wt% to about 35 wt%.
[0182] Embodiment 19: The composition of Embodiment 16, wherein the Zr0 2 is present in an amount from about 10.0 wt% to about 30.0 wt%.
[0183] Embodiment 20: The composition of Embodiment 16, wherein the Zr0 2 is present in an amount from about 15.0 wt% to about 30.0 wt%.
[0184] Embodiment 21: The composition of Embodiment 16, wherein the Zr0 2 is present in an amount from about 20.0 wt% to about 30.0 wt%.
[0185] Embodiment 22: The composition of Embodiment 16, wherein the Zr0 2 is present in an amount from about 22.5 wt% to about 27.5 wt%.
[0186] Embodiment 23: The composition of Embodiment 16, wherein the Zr0 2 is present in an amount of about 25.0 wt%.
[0187] Embodiment 24: The composition of Embodiment 1, wherein the oxide of cerium comprises Ce0 2 ; wherein the oxide of titanium comprises Ti0 2 ; and wherein the oxide of zirconium comprises Zr0 2 .
[0188] Embodiment 25: The composition of Embodiment 25, wherein the Ce0 2 is present in an amount from about 50.0 wt% to about 60.0 wt%; wherein the Ti0 2 is present in an amount from about 15.0 wt% to about 25.0 wt%; and wherein the Zr0 2 is present in an amount from about 20.0 wt% to about 30.0 wt%.
[0189] Embodiment 26: The composition of Embodiment 25, wherein the Ce0 2 is present in an amount of about 55.0 wt%; wherein the Ti0 2 is present in an amount of about 20.0 wt%; and wherein the Zr0 2 is present in an amount of about 25.0 wt%.
[0190] Embodiment 27: The composition of Embodiment 1, wherein the cerium and zirconium comprise an oxide of the formula Zr x Ce y 0 2 ; wherein x has a value of about 0.30 to about 0.99; wherein y has a value of about 0.50 to about 0.01; and wherein the sum of x and y is about 1.00.
[0191] Embodiment 28: The composition of Embodiment 1, wherein the cerium and zirconium comprise an oxide of the formula Zr x Ce y 0 2 ; wherein x has a value of about 0.35 to about 0.97; wherein y has a value of about 0.55 to about 0.03; and wherein the sum of x and y is about 1.00.
[0192] Embodiment 29: The composition of Embodiment 1, wherein the cerium and zirconium comprise an oxide of the formula Zr x Ce y 0 2 ; wherein x has a value of about 0.40 to about 0.95; wherein y has a value of about 0.60 to about 0.05; and wherein the sum of x and y is about 1.00.
[0193] Embodiment 30: The composition of any of Embodiments 1-29, wherein the Au content of the composition is from about 0.1 wt% to about 5.0 wt%.
[0194] Embodiment 31: The composition of Embodiment 30, wherein the Au content of the composition is from about 0.1 wt% to about 2.0 wt%.
[0195] Embodiment 32: The composition of Embodiment 30, wherein the Au content of the composition is from about 0.1 wt% to about 1.0 wt%.
[0196] Embodiment 33: The composition of Embodiment 30, wherein the Au content of the composition is from about 0.5 wt% to about 1.5 wt%.
[0197] Embodiment 34: The composition of Embodiment 30, wherein the Au content of the composition is about 1.0 wt%.
[0198] Embodiment 35: The composition of any of Embodiments 1-34, wherein the Au comprises one or more oxides.
[0199] Embodiment 36: The composition of any of Embodiments 1-35, wherein the Au particles are of a size less than about 10 nm.
[0200] Embodiment 37: The composition of any of Embodiments 1-35, wherein the Au particles are of a size less than about 8 nm. [0201] Embodiment 38: The composition of any of Embodiments 1-35, wherein the Au particles are of a size less than about 6 nm.
[0202] Embodiment 39: The composition of any of Embodiments 1-35, wherein the Au particles are from about 2 nm to about 10 nm.
[0203] Embodiment 40: The composition of any of Embodiments 1-35, wherein the Au particles are from about 2 nm to about 8 nm.
[0204] Embodiment 41: The composition of any of Embodiments 1-35, wherein the Au particles are from about 3 nm to about 6 nm.
[0205] Embodiment 42: The composition of any of Embodiments 1-41, wherein the transition metal comprises tin.
[0206] Embodiment 43: The composition of Embodiment 42, wherein the tin is present in an amount from about 0.1 wt% to about 0.5 wt%, or about 0.2 wt% to about 0.5 wt%.
[0207] Embodiment 44: The composition of Embodiment 42, wherein the tin is present in an amount from about 0.2 wt% to about 0.4 wt%.
[0208] Embodiment 45: The composition of Embodiment 42, wherein the tin is present in an amount from about 0.2 wt% to about 0.3 wt%.
[0209] Embodiment 46: The composition of Embodiment 42, wherein the tin is present in an amount of about 0.2 wt%
[0210] Embodiment 47: The composition of Embodiment 42, wherein the tin is present in an amount of about 0.3 wt%.
[0211] Embodiment 48: The composition of Embodiment 42, wherein the tin is present in an amount of about 0.4 wt%.
[0212] Embodiment 49: The composition of Embodiment 42, wherein the tin is present in an amount of about 0.5 wt%.
[0213] Embodiment 50: The composition of any of Embodiments 1-49, wherein the transition metal salt is present in an amount from about 0.1 wt% to about 2.0 wt%.
[0214] Embodiment 51: The composition of Embodiment 50, wherein the transition metal salt is present in an amount from about 0.1 wt% to about 1.0 wt%.
[0215] Embodiment 52: The composition of Embodiment 50, wherein the transition metal salt comprises iron.
[0216] Embodiment 53: The composition of Embodiment 52, wherein the iron is in the form of Fe(III). [0217] Embodiment 54: The composition of Embodiment 52, wherein the iron is in the form of Fe(II).
[0218] Embodiment 55: The composition of any of Embodiments 1-54, wherein the dehydrogenation catalyst composition is the calcination product of a mixture of a porous carrier comprising an oxide of cerium, an oxide of titanium, and an oxide of zirconium; a gold compound; a tin compound; and one or more transition metal compounds.
[0219] Embodiment 56: A dehydrogenation catalyst prepared by calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 .
[0220] Embodiment 57: The product of Embodiment 56, wherein calcining is carried out at a temperature from about 100 °C to about 600 °C.
[0221] Embodiment 58: The product of Embodiment 57, wherein calcining is carried out at a temperature from about 400 °C to about 600 °C.
[0222] Embodiment 59: The product of Embodiment 57, wherein calcining is carried out at a temperature from about 500 °C to about 600 °C.
[0223] Embodiment 60: The product of Embodiment 56, wherein calcining is carried out at a temperature of about 550 °C.
[0224] Embodiment 61: The product of any of Embodiments 57-60, wherein calcining is carried out in the presence of an oxygen flow or air flow.
[0225] Embodiment 62: The product of Embodiment 61, wherein calcining is carried out in the presence of an oxygen flow.
[0226] Embodiment 63: The product of Embodiment 61, wherein calcining is carried out in the presence of an air flow.
[0227] Embodiment 64: The product of Embodiment 56, further comprising the steps of preparing the mixture: dispersing a transition metal salt with Ce0 2 , Ti0 2 , and Zr0 2 ;
dispersing a tin salt with the material comprising the gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ; and dispersing a gold salt with the material comprising the transition metal salt, gold salt, Ce0 2 , Ti0 2 , and Zr0 2 ; wherein the steps of preparing the mixture occur prior to calcining.
[0228] Embodiment 65: The product of Embodiment 64, wherein dispersing is impregnation, precipitation, deposition-precipitation, co-precipitation, or incipient wetness impregnation.
[0229] Embodiment 66: The product of Embodiment 64, wherein dispersing is impregnation, precipitation, deposition-precipitation or co-precipitation. [0230] Embodiment 67: The product of Embodiment 64, wherein dispersing is impregnation, precipitation, or deposition-precipitation.
[0231] Embodiment 68: The product of Embodiment 64, wherein dispersing is impregnation, or precipitation.
[0232] Embodiment 69: The product of Embodiment 64, wherein dispersing is impregnation.
[0233] Embodiment 70: The product of Embodiment 69, wherein the impregnation is carried out in aqueous solution at a temperature from about 55 °C to about 75 °C.
[0234] Embodiment 71: The product of Embodiment 69, wherein the impregnation is carried out in aqueous solution at a temperature from about 60 °C to about 70 °C.
[0235] Embodiment 72: The product of Embodiment 69, wherein the impregnation is carried out in aqueous solution at a temperature of about 65 °C.
[0236] Embodiment 73: The product of any of Embodiments 65-72, further comprising dispersing a tin salt with the material comprising the Ce0 2 , Ti0 2 , and Zr0 2 .
[0237] Embodiment 74: The product of any of claims 65-73, wherein the aqueous solution has a pH from about 7.0 to about 12.0, or about 8.0 to about 10.5.
[0238] Embodiment 75: The product of Embodiment 73, wherein the pH of the aqueous solution is adjusted using alkaline compounds.
[0239] Embodiment 76: The product of Embodiment 73, wherein the pH of the aqueous solution is adjusted using magnesium citrate, barium carbonates, hydroxides or ammonia, or a mixture thereof.
[0240] Embodiment 77: A method of preparing a dehydrogenation catalyst composition comprising the step of calcining a mixture comprising a gold salt, a tin salt, one or more transition metal salts, Ce0 2 , Ti0 2 , and Zr0 2 .
[0241] Embodiment 78: The method of Embodiment 77, wherein calcining is carried out at a temperature from about 100 °C to about 600 °C.
[0242] Embodiment 79: The method of Embodiment 78, wherein calcining is carried out at a temperature from about 400 °C to about 600 °C.
[0243] Embodiment 80: The method of Embodiment 78, wherein calcining is carried out at a temperature from about 500 °C to about 600 °C.
[0244] Embodiment 81: The method of Embodiment 78, wherein calcining is carried out at a temperature of about 550 °C. [0245] Embodiment 82: The method of any of Embodiments 78-81, wherein calcining is carried out in the presence of an oxygen flow or air flow.
[0246] Embodiment 83: The method of Embodiment 82, wherein calcining is carried out in the presence of an oxygen flow.
[0247] Embodiment 84: The method of Embodiment 82, wherein calcining is carried out in the presence of an air flow.
[0248] Embodiment 85: A method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of: providing an alkane; providing a dehydrogenation catalyst comprising: a porous carrier comprising cerium, titanium, and zirconium a gold compound; a tin compound; and one or more transition metal compounds; heating the alkane in the presence of the dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene.
[0249] Embodiment 86: The method of Embodiment 85, wherein the alkane is selected from ethane, propane, or butane, or a mixture thereof.
[0250] Embodiment 87: The method of Embodiment 85, wherein the alkane is selected from ethane, or propane, or a mixture thereof.
[0251] Embodiment 88: The method of Embodiment 86, wherein the alkane is propane.
[0252] Embodiment 89: The method of Embodiment 85, wherein the alkene is selected from ethene, propene, or butane, or a mixture thereof.
[0253] Embodiment 90: The method of Embodiment 85, wherein the alkene is selected from ethene, or propene, or a mixture thereof.
[0254] Embodiment 91: The method of Embodiment 90, wherein the alkene is propene.
[0255] Embodiment 92: The method of Embodiment 85, wherein the heating is at a temperature from about 400 °C to about 600 °C.
[0256] Embodiment 93: The method of Embodiment 92, wherein the heating is at a temperature from about 500 °C to about 600 °C.
[0257] Embodiment 94: The method of Embodiment 85, further comprising the step of heating the dehydrogenation catalyst at a temperature from about 400 °C to about 600 °C in the presence of a mixture of oxygen and helium prior to the providing of the
dehydrogenation catalyst. [0258] Embodiment 95: The method of Embodiment 94, wherein the heating is at about 500 °C.
[0259] Embodiment 96: The method of Embodiment 94, wherein the heating is at about 550 °C.
[0260] Embodiment 97: The method of Embodiment 85, further comprising providing hydrogen and helium.
[0261] Embodiment 98: The method of Embodiment 85, wherein the
dehydrogenation catalyst has the composition of any of Embodiments 1-51.
[0262] Embodiment 99: The method of Embodiment 85, wherein the
dehydrogenation catalyst is the product of the process of any of Embodiments 56-76.
[0263] Embodiment 100: A dehydrogenation catalyst composition comprising: a porous carrier comprising Ce0 2 in an amount from about 50.0 wt% to about 60.0 wt%; Ti0 2 in an amount from about 15 wt% to about 25 wt%; and Zr0 2 in an amount from about 20.0 wt% to about 30.0 wt%; a gold compound in an amount from about 0.1 wt% to about 2.0 wt%; and one or more transition metal compounds in an amount from about 0.1 wt% to about 2.0 wt%.
[0264] Embodiment 101: A dehydrogenation catalyst composition comprising: a porous carrier comprising Ce0 2 in an amount from 50.0 wt% to about 60.0 wt% (e.g., about 55 wt%); Ti0 2 in an amount from about 17.5 wt% to about 22.5 wt%; and Zr0 2 in an amount from about 20 wt% to about 30 wt% (e.g., about 22.5 wt% to about 27.5 wt%); a gold compound in an amount from about 0.1 wt% to about 2.0 wt% (e.g., about 0.1 wt% to about 1.0 wt%); and one or more transition metal compounds in an amount from about 0.1 wt% to about 1.0 wt%.
[0265] Embodiment 102: A dehydrogenation catalyst composition comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20.0 wt%; and Zr0 2 in an amount of about 20 wt%; a gold compound in an amount of about 1.0 wt%; and one or more transition metal compounds in an amount from about 0.1 wt% to about 1.0 wt%.
[0266] Embodiment 103: A dehydrogenation catalyst composition comprising:a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20.0 wt%; and Zr0 2 in an amount of about 20 wt%; a gold compound in an amount of about 1.0 wt%; and iron in an amount from about 0.1 wt% to about 1.0 wt%. [0267] Embodiment 104: A dehydrogenation catalyst composition comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20.0 wt%; and Zr0 2 in an amount of about 20 wt%; a gold compound in an amount of about 1.0 wt%; and Fe(II) in an amount from about 0.1 wt% to about 1.0 wt%.
[0268] Embodiment 105: A dehydrogenation catalyst composition comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20.0 wt%; and Zr0 2 in an amount of about 20 wt%; a gold compound in an amount of about 1.0 wt%; and Fe(III) in an amount from about 0.1 wt% to about 1.0 wt%.
[0269] Embodiment 106: A method for the preparation of propene by catalytic dehydrogenation, the method comprising the steps of: providing propane; providing a dehydrogenation catalyst comprising: a porous carrier comprising Ce0 2 , Ti0 2 , and Zr0 2 ; a gold compound; and one or more transition metal compounds; heating propane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene.
[0270] Embodiment 107: A method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of: providing an alkane; providing a dehydrogenation catalyst comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount from about 17.5 wt% to about 22.5 wt%; and Zr0 2 in an amount from about 22.5 wt% to about 27.5 wt%; a gold compound in an amount from about 0.1 wt% to about 2.0 wt%; and one or more transition metal compounds in an amount from about 0.1 wt% to about 2.0 wt%; heating the alkane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene.
[0271] Embodiment 108: A method for the preparation of propene by catalytic dehydrogenation, the method comprising the steps of: providing propane; providing a dehydrogenation catalyst comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount from about 17.5 wt% to about 22.5 wt%; and Zr0 2 in an amount from about 22.5 wt% to about 27.5 wt%; a gold compound in an amount from about 0.1 wt% to about 2.0 wt%; and one or more transition metal compounds in an amount from about 0.1 wt% to about 2.0 wt%; heating propane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene.
[0272] Embodiment 109: A method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of: providing an alkane; providing a dehydrogenation catalyst comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount from about 17.5 wt% to about 22.5 wt%; and Zr0 2 in an amount from about 22.5 wt% to about 27.5 wt%; a gold compound in an amount from about 0.1 wt% to about 1.0 wt%; and one or more transition metal compounds in an amount from about 0.1 wt% to about 1.0 wt%; heating the alkane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene.
[0273] Embodiment 110: A method for the preparation of propene by catalytic dehydrogenation, the method comprising the steps of: providing propane; providing a dehydrogenation catalyst comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount from about 17.5 wt% to about 22.5 wt%; and Zr0 2 in an amount from about 22.5 wt% to about 27.5 wt%; a gold compound in an amount from about 0.1 wt% to about 1.0 wt%; and one or more transition metal compounds in an amount from about 0.1 wt% to about 1.0 wt%; heating propane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene.
[0274] Embodiment 111: A method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of: providing an alkane; providing a dehydrogenation catalyst comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20 wt%; and Zr0 2 in an amount of about 25 wt%; a gold compound in an amount of about 1.0 wt%; and or more transition metal compounds in an amount from about 0.1 wt% to about 1.0 wt%; heating the alkane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene.
[0275] Embodiment 112: A method for the preparation of propene by catalytic dehydrogenation, the method comprising the steps of: providing propane; providing a dehydrogenation catalyst comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20 wt%; and Zr0 2 in an amount of about 25 wt%; a gold compound in an amount of about 1.0 wt%; and or more transition metal compounds in an amount from about 0.1 wt% to about 1.0 wt%; heating propane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene.
[0276] Embodiment 113: A method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of: providing an alkane; providing a dehydrogenation catalyst comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20 wt%; and Zr0 2 in an amount of about 25 wt%; a gold compound in an amount of about 1.0 wt%; and iron in an amount from about 0.1 wt% to about 1.0 wt%; heating the alkane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene.
[0277] Embodiment 114: A method for the preparation of propene by catalytic dehydrogenation, the method comprising the steps of: providing propane; providing a dehydrogenation catalyst comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20 wt%; and Zr0 2 in an amount of about 25 wt%; a gold compound in an amount of about 1.0 wt%; and iron in an amount from about 0.1 wt% to about 1.0 wt%; heating propane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene.
[0278] Embodiment 115: A method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of: providing an alkane; providing a dehydrogenation catalyst comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20 wt%; and Zr0 2 in an amount of about 25 wt%; a gold compound in an amount of about 1.0 wt%; and Fe(II) in an amount from about 0.1 wt% to about 1.0 wt%; heating the alkane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene.
[0279] Embodiment 116: A method for the preparation of propene by catalytic dehydrogenation, the method comprising the steps of: providing propane; providing a dehydrogenation catalyst comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20 wt%; and Zr0 2 in an amount of about 25 wt%; a gold compound in an amount of about 1.0 wt%; and Fe(II) in an amount from about 0.1 wt% to about 1.0 wt%; heating propane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene.
[0280] Embodiment 117: A method for the preparation of an alkene by catalytic dehydrogenation, the method comprising the steps of: providing an alkane; providing a dehydrogenation catalyst comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20 wt%; and Zr0 2 in an amount of about 25 wt%; a gold compound in an amount of about 1.0 wt%; and Fe(III) in an amount from about 0.1 wt% to about 1.0 wt%; heating the alkane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of the alkane, thereby yielding an alkene.
[0281] Embodiment 118: A method for the preparation of propene by catalytic dehydrogenation, the method comprising the steps of: providing propane; providing a dehydrogenation catalyst comprising: a porous carrier comprising Ce0 2 in an amount of about 55 wt%; Ti0 2 in an amount of about 20 wt%; and Zr0 2 in an amount of about 25 wt%; a gold compound in an amount of about 1.0 wt%; and Fe(III) in an amount from about 0.1 wt% to about 1.0 wt%; heating propane in the presence dehydrogenation catalyst at a temperature sufficient for dehydrogenation of propane, thereby yielding propene.
[0282] Embodiment 119: The dehydrogenation catalyst composition of any of Embodiments 100 - 105, wherein the transition metal compound comprises a tin compound in an amount from about 0.2 wt% to about 0.5 wt%.
[0283] Embodiment 120: The dehydrogenation catalyst composition of any of Embodiments 100 - 105, wherein the transition metal compound comprises a tin compound in an amount of about 0.3 wt%.
[0284] Embodiment 119: The method of any of Embodiments 106 - 118, wherein the transition metal compound comprises a tin compound in an amount from about 0.2 wt% to about 0.5 wt%.
[0285] Embodiment 120: The method of any of Embodiments 106 - 118, wherein the transition metal compound comprises a tin compound in an amount of about 0.3 wt%.