Advances in dehydrogenation catalysis

• US 6,417,135 B1
• Filed: 03/22/2000
• Issued: 07/09/2002
• Est. Priority Date: 08/27/1999
• Status: Expired due to Term

• Current Assignee: Indorama Ventures Oxides, LLC
• Original Assignee: Huntsman Petrochemical LLC (Huntsman Corporation)
• Inventors: Dyroff, David R.
• Primary Examiner(s): Bell, Mark L.
• Assistant Examiner(s): Hailey, Patricia L.
• Application Number:
  US09/533,278
• Time in Patent Office: 839 Days
• Field of Search: 502/20, 502/325-328, 502/330-339, 502/313, 502/308, 502/317
• US Class Current: 502/325
• CPC Class Codes: B01J 23/40 of the platinum group metals
• CPC Class Codes: B01J 35/31 Density
• CPC Class Codes: B01J 35/32 Bulk density
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/635 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/647 2-50 nm
• CPC Class Codes: B01J 35/651 50-500 nm
• CPC Class Codes: B01J 35/66 Pore distribution
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 2521/04 Alumina
• CPC Class Codes: C07C 2523/42 Platinum
• CPC Class Codes: C07C 2523/44 Palladium
• CPC Class Codes: C07C 2523/46 Ruthenium, rhodium, osmium or iridium
• CPC Class Codes: C07C 5/3337 of the platinum group

Abstract

Provided herein are supported catalysts and processes useful in the dehydrogenation of hydrocarbons. Catalysts made according to the invention possess a unique pore size distribution which provides a favorable balance of selectivity, activity, and thermal stability. In a preferred form of the invention, catalysts made in accordance of the invention are regenerable. Detergent range paraffins may be converted to monoolefins using a catalyst and process provided by the invention.

Claims

1. A regenerable catalyst useful in the dehydrogenation of hydrocarbons, said catalyst comprising a primary catalytic component that comprises one or more elements selected from the group consisting of:

platinum, rhodium, iridium, palladium, ruthenium, and osmium deposited on a solid support comprising porous alumina, wherein said regenerable catalyst has a surface area greater than 100 m²/g, a volume of pores with diameters below 60 Angstrom units that is less than 0.05 cm³/g, a volume of pores with diameters in the range of 60-350 Angstrom units that is greater than 0.50 cm³/g, and wherein the volume of pores with diameters in the range of 60-350 Angstrom units is greater than about 70% of the total contained pore volume.

2. A catalyst according to claim 1 wherein said primary catalytic component comprises platinum.

3. A catalyst according to claim 1 wherein the packed bulk density is greater than about 0.50 g/cm ³.

4. A catalyst according to claim 3 wherein said primary catalytic component comprises platinum.

5. A catalyst according to claim 1 wherein the volume of pores with diameters in the range of 60-350 Angstrom units is greater than about 75% of the total contained pore volume.

6. A catalyst according to claim 5 wherein said primary catalytic component comprises platinum.

7. A catalyst according to claim 5 wherein the packed bulk density is greater than about 0.50 g/cm³.

8. A catalyst according to claim 7 wherein said primary catalytic component comprises platinum.

9. A catalyst according to claim 1 in which -the primary catalytic component is present in an amount between 0.01 and 3.00% by weight based on the total weight of the catalyst, including every hundredth percentage therebetween.

10. A catalyst according to claim 9 wherein said primary catalytic component comprises platinum.

11. A catalyst according to claim 3 in which the primary catalytic component is present in an amount between 0.01 and 3.00% by weight based on the total weight of the catalyst, including every hundredth percentage therebetween.

12. A catalyst according to claim 11 wherein the volume of pores with diameters in the range of 60-350 Angstrom units is greater than about 75% of the total contained pore volume.

13. A catalyst according to claim 1 wherein the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 50% of the length of the first cycle.

14. A catalyst according to claim 1 wherein the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 35% of the length of the first cycle.

15. A catalyst according to claim 1 wherein the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 20% of the length of the first cycle.

16. A catalyst according to claim 1 wherein the primary catalytic component comprises a mixture of at least two different elements selected from the group consisting of:

platinum, palladium, rhodium, ruthenium, iridium, and osmium.

17. A catalyst according to claim 1 in which the catalyst exists in the form of spheroids having diameters in the range of between 1.0 millimeters and 4.0 millimeters, including every tenth millimeter therebetween.

18. A catalyst according to claim 1 in which the catalyst exists in the form of an extrudate with its longest length dimension in the range of between 1.0 millimeters and 10.0 millimeters, including every tenth millimeter therebetween.

19. A catalyst according to claim 1 wherein the surface area is within the range of 135 to 150 m²/g, including every integral m²/g therebetween, the volume of pores with diameters below 60 Angstrom units is less than 0.02 cm³/g, the volume of pores with diameters in the range of 60-350 Angstrom units is in the range of 0.60-0.80 cm³/g, including every hundredth cm³/g therebetween, and the volume of pores with diameters in the range of 60-350 Angstrom units is greater than 80% of the total contained pore volume.

20. A catalyst useful in the dehydrogenation of hydrocarbons, said catalyst comprising:

a) a primary catalytic component that comprises one or more elements selected from the group consisting of;

platinum, rhodium, iridium, palladium, ruthenium, and osmium deposited on a porous alumina catalyst support, and

b) an acidity control component comprising at least one element selected from the group consisting of the alkali metals and the alkaline earth metals deposited upon said support,

wherein said catalyst has a surface area greater than 100 m²/g, a volume of pores with diameters below 60 Angstrom units that is less than 0.05 cm³/g, a volume of pores with diameters in the range of 60-350 Angstrom units that is greater than 0.50 cm³/g, and wherein the volume of pores with diameters in the range of 60-350 Angstrom units is greater than about 70% of the total contained pore volume.

21. A catalyst according to claim 20 wherein the volume of pores with diameters in the range of 60-350 Angstrom units is greater than about 75% of the total contained pore volume.

22. A catalyst according to claim 20 wherein the packed bulk density is greater than 0.50 g/cm³.

23. A catalyst according to claim 21 wherein the packed bulk density is greater than 0.50 g/cm³.

24. A catalyst according to claim 20 wherein said acidity-control component is present in an amount between 0.001 and 1.000% by weight based on the total weight of the catalyst, including every thousandth percentage therebetween.

25. A catalyst according to claim 24 wherein the packed bulk density is greater than 0.50 g/cm³.

26. A catalyst according to claim 20 wherein the acidity control component is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium.

27. A catalyst according to claim 26 wherein the acidity control component is potassium.

28. A catalyst according to claim 26 wherein the added acidity control component is potassium and is present in an amount in the range of about 0.10% to 0.60% by weight based upon the total weight of the finished catalyst, including every hundredth percentage therebetween.

29. A catalyst according to claim 22 wherein said acidity control component is present in an amount between 0.001 and 1.000% by weight based on the total weight of the catalyst, including every thousandth percentage therebetween.

30. A catalyst according to claim 29 wherein the acidity control component is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium.

31. A catalyst according to claim 30 wherein the acidity control component is potassium.

32. A catalyst according to claim 30 wherein the added acidity control component is potassium and is present in an amount in the range of about 0.10% to 0.60% by weight based upon the total weight of the finished catalyst, including every hundredth percentage therebetween.

33. A catalyst according to claim 20 wherein said catalyst is regenerable.

34. A catalyst according to claim 20 wherein said primary catalytic component comprises platinum and said acidity control component comprises one or more elements selected from the group consisting of:

lithium, sodium, potassium, rubidium, and cesium.

35. A catalyst according to claim 20 wherein the catalyst is regenerable and the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 50% of the length of the first cycle.

36. A catalyst according to claim 20 wherein the catalyst is regenerable and the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 35% of the length of the first cycle.

37. A catalyst according to claim 20 wherein the catalyst is regenerable and the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 20% of the length of the first cycle.

38. A catalyst according to claim 20 in which the catalyst exists in the form of spheroids having diameters in the range of between 1.0 millimeters and 4.0 millimeters, including every tenth millimeter therebetween.

39. A catalyst according to claim 20 in which the catalyst exists in the form of an extrudate with its longest length dimension in the range of between 1.0 millimeters and 10.0 millimeters, including every tenth millimeter therebetween.

40. A catalyst according to claim 20 in which the acidity control agent is a mixture of at least two elements selected from the group consisting of:

the alkali metals and alkaline earth metals.

41. A catalyst according to claim 20 wherein the surface area is within the range of 135 to 150 m²/g, including every integral m²/g therebetween, the volume of pores with diameters below 60 Angstrom units is less than 0.02 cm³/g, the volume of pores with diameters in the range of 60-350 Angstrom units is in the range of 0.60-0.80 cm³/g, including every hundredth cm³/g therebetween, and the volume of pores with diameters in the range of 60-350 Angstrom units is greater than 80% of the total contained pore volume.

42. A catalyst according to claim 20 further comprising an activator component selected from the group consisting of:

scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, silver, lanthanum, hafnium, tantalum, tungsten, rhenium, and gold deposited upon said support and wherein the activator component is present in an amount between 0.10% and 5.00% by weight based upon the total weight of the finished catalyst, including every hundredth percentage therebetween.

43. A catalyst useful in the dehydrogenation of hydrocarbons, said catalyst comprising:

a) a primary catalytic component that comprises one or more elements selected from the group consisting of platinum, rhodium, iridium, palladium, ruthenium, and osmium deposited on a porous alumina catalyst support, and

b) an activator component comprising one or more elements selected from the group consisting of;

scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, silver, lanthanum, hafnium, tantalum, tungsten, rhenium, and gold deposited upon said support,

wherein said catalyst has a surface area greater than 100 m²/g, a volume of pores with diameters below 60 Angstrom units that is less than 0.05 cm³/g, a volume of pores with diameters in the range of 60-350 Angstrom units that is greater than 0.50 cm³/g, and wherein the volume of pores with diameters in the range of 60-350 Angstrom units is greater than about 70% of the total contained pore volume.

44. A catalyst according to claim 43 wherein the volume of pores with diameters in the range of 60-350 Angstrom units is greater than about 75% of the total contained pore volume.

45. A catalyst according to claim 43 wherein the packed bulk density is greater than 0.50 g/cm³.

46. A catalyst according to claim 43 wherein said activator component comprises at least one element selected from the group consisting of copper, silver, and gold.

47. A catalyst according to claim 43 wherein said activator component comprises at least one element selected from the group consisting of copper, silver, and gold, and wherein the packed bulk density is greater than 0.50 g/cm³.

48. A catalyst according to claim 43 wherein said activator component is present in an amount between 0.10 and 5.00% by weight based on the total weight of the catalyst, including every hundredth percentage therebetween.

49. A catalyst according to claim 43 wherein said activator component is present in an amount between 0.10 and 5.00% by weight based on the total weight of the catalyst, including every hundredth percentage there between, and wherein the packed bulk density is greater than 0.50 g/cm³.

50. A catalyst according to claim 46 wherein said activator component is copper.

51. A catalyst according to claim 50 wherein said activator component is present in an amount in the range of 1.00% to 3.00% by weight based upon the total weight of the catalyst, including every hundredth percentage therebetween.

52. A catalyst according to claim 43 wherein said primary catalytic component comprises platinum.

53. A catalyst according to claim 52 wherein said activator component comprises at least one element selected from the group consisting of:

copper, silver, and gold.

54. A catalyst according to claim 43 wherein the catalyst is regenerable and the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 50% of the length of the first cycle.

55. A catalyst according to claim 43 wherein the catalyst is regenerable and the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 35% of the length of the first cycle.

56. A catalyst according to claim 43 wherein the catalyst is regenerable and the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 20% of the length of the first cycle.

57. A catalyst according to claim 43 in which the catalyst exists in the form of spheroids having diameters in the range of between 1.0 millimeters and 4.0 millimeters, including every tenth millimeter therebetween.

58. A catalyst according to claim 43 in which the catalyst exists in the form of an extrudate with its longest length dimension in the range of between 1.0 millimeters and 10.0 millimeters, including every tenth millimeter therebetween.

59. A catalyst according to claim 43 wherein the surface area is within the range of 135 to 150 m²/g, including every integral m²/g therebetween, the volume of pores with diameters below 60 Angstrom units is less than 0.02 cm³/g, the volume of pores with diameters in the range of 60-350 Angstrom units is in the range of 0.60-0.80 cm³/g, including every hundredth cm³/g therebetween, and the volume of pores with diameters in the range of 60-350 Angstrom units is greater than 80% of the total contained pore volume.

60. A catalyst according to claim 43 wherein the primary catalytic component comprises a mixture of at least two different elements selected from the group consisting of:

platinum, rhodium, iridium, palladium, ruthenium, and osmium.

61. A catalyst according to claim 43 further comprising an acidity control component disposed on said support, wherein the acidity control component includes at least one element selected from the group consisting of:

lithium, sodium, potassium, rubidium, cesium, and francium.

62. A catalyst according to claim 61 wherein the primary catalytic component comprises platinum;

the acidity control component is selected from the group consisting of;

lithium, sodium, and potassium; and

the activator component is selected from the group consisting of;

copper, silver, and gold.

63. A catalyst useful in the dehydrogenation of hydrocarbons, said catalyst comprising:

a) a primary catalytic component that comprises one or more elements selected from the group consisting of;

platinum, rhodium, iridium, palladium, ruthenium, and osmium deposited on a porous alumina catalyst support;

b) an activator component comprising one or more elements selected from the group consisting of;

scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, silver, lanthanum, hafnium, tantalum, tungsten, rhenium, and gold deposited upon said support; and

c) an acidity control component comprising at least one element selected from the group consisting of the alkali metals and the alkaline earth metals deposited upon said support,

wherein said catalyst has a surface area greater than 100 m²/g, a volume of pores with diameters below 60 Angstrom units that is less than 0.05 cm³/g, a volume of pores with diameters in the range of 60-350 Angstrom units that is greater than 0.50 cm³/g, and wherein the volume of pores with diameters in the range of 60-350 Angstrom units is greater than about 70% of the total contained pore volume.

64. A catalyst according to claim 63 wherein the packed bulk density is greater than 0.50 g/cm³.

65. A catalyst according to claim 63 wherein the volume of pores with diameters in the range of 60-350 Angstrom units is greater than about 75% of the total contained pore volume.

66. A catalyst according to claim 63 wherein the primary catalytic component comprises platinum, the acidity control component comprises at least one element selected from the group consisting of:

lithium, sodium, potassium, rubidium, cesium, calcium, and magnesium; and

the activator component comprises at least one element selected from the group consisting of copper, silver, and gold.

67. A catalyst according to claim 63 wherein the catalyst is regenerable and the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 50% of the length of the first cycle.

68. A catalyst according to claim 63 wherein the catalyst is regenerable and the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 35% of the length of the first cycle.

69. A catalyst according to claim 63 wherein the catalyst is regenerable and the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 20% of the length of the first cycle.

70. A catalyst according to claim 63 in which the catalyst exists in the form of spheroids having diameters is in the range of between 1.0 millimeters and 4.0 millimeters, including every tenth millimeter therebetween.

71. A catalyst according to claim 63 in which the catalyst exists in the form of an extrudate with its longest length dimension in the range of between 1.0 millimeters and 10.0 millimeters, including every tenth millimeter therebetween.

72. A catalyst according to claim 63 wherein the surface area is within the range of 135 to 150 m²/g, including every integral m²/g therebetween, the volume of pores with diameters below 60 Angstrom units is less than 0.02 cm³/g, the volume of pores with diameters in the range of 60-350 Angstrom units is in the range of 0.60-0.80 cm³/g, including every hundredth cm³/g therebetween, and the volume of pores with diameters in the range of 60-350 Angstrom units is greater than 80% of the total contained pore volume.

73. A catalyst according to claim 63 wherein:

a) the primary catalytic component comprises platinum;

b) the activator component is selected from the group consisting of copper, silver, and gold, and in which the activator component is present in an amount between 0.10% and 5.00% by weight based on the total weight of the catalyst, including every hundredth percentage therebetween; and

c) the acidity control component is selected from the group consisting of;

alkali metals and alkaline earth metals, and the acidity control component is present in an amount between 0.001% and 1.000% by weight based on the total weight of the catalyst, including every thousandth percentage therebetween.

74. A catalyst according to claim 73 wherein the packed bulk density is greater than 0.50 g/cm^3.

75. A catalyst according to claim 73 which contains between 0.02% and 2.00% of platinum by weight based on the total weight of the catalyst, including every hundredth percentage therebetween.

76. A catalyst according to claim 73 which contains between 0.20% and 1.00% of platinum by weight based on the total weight of the catalyst, including every hundredth percentage therebetween.

77. A catalyst according to claim 73 which contains between 0.40% and 0.70% of platinum by weight based on the total weight of the catalyst, including every hundredth percentage therebetween.

78. A catalyst according to claim 73 wherein said acidity control component is potassium, and wherein the acidity control component is present in an amount between 0.10% and 0.60% by weight based on the total weight of the catalyst, including every hundredth percentage therebetween.

79. A catalyst according to claim 74 which contains between 1.00% and 3.00% of copper by weight based upon the total weight of the catalyst, including every hundredth percentage therebetween.

80. A catalyst according to claim 75 which contains between 1.00% and 3.00% of copper by weight based upon the total weight of the catalyst, including every hundredth percentage therebetween.

81. A catalyst according to claim 73 wherein the catalyst is regenerable and the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 50% of the length of the first cycle.

82. A catalyst according to claim 73 wherein the catalyst is regenerable and the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 35% of the length of the first cycle.

83. A catalyst according to claim 73 wherein the catalyst is regenerable and the cycle length reduction attributable to a first regeneration of the catalyst is not greater than 20% of the length of the first cycle.

84. A catalyst according to claim 73 in which the catalyst exists in the form of spheroids having diameters is in the range of between 1.0 millimeters and 4.0 millimeters, including every tenth millimeter therebetween.

85. A catalyst according to claim 73 in which the catalyst exists in the form of an extrudate with its longest length dimension in the range of between 1.0 millimeters and 10.0 millimeters, including every tenth millimeter therebetween.

86. A catalyst according to claim 73 wherein the surface area is within the range of 135 to 150 m²/g, including every integral m²/g therebetween, the volume of pores with diameters below 60 Angstrom units is less than 0.02 cm³/g, the volume of pores with diameters in the range of 60-350 Angstrom units is in the range of 0.60-0.80 cm³/g, including every hundredth cm³/g therebetween, and the volume of pores with diameters in the range of 60-350 Angstrom units is greater than 80% of the total contained pore volume.