IP Library Granted Patent US 6,878,655
Granted Patent B2
US 6,878,655 · App. 10/251,139 · Granted Apr 12, 2005

Method and apparatus for the regeneration of hydrocarbon synthesis catalysts

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Quick Facts
Patent No.
US 6,878,655
App. No.
10/251,139
Granted
Apr 12, 2005
Kind
B2
Abstract

The present invention is generally related towards the regeneration of hydrocarbon synthesis catalysts. In particular, the present invention is directed towards the regeneration of deactivated Fischer-Tropsch type catalysts using a two step process wherein the catalyst is first prepared using a dry gas and then regenerated using a hydrogen rich gas. The regeneration process is carried out at temperatures and pressures that are generally different than the operating temperatures and pressures for a typical hydrocarbon synthesis reaction.

Claims (110)

1. A process for treating catalyst slurry having a CO conversion value from a synthesis reactor wherein said catalyst slurry comprises water comprising:

(a) contacting a catalyst slurry with a stripping gas at a pressure equal to or lower than the synthesis reactor operating pressure wherein at least a portion of the water is removed from the catalyst slurry; and

(b) contacting said catalyst slurry in step (a) with a hydrogen containing gas under conditions and for a period of time sufficient to increase the CO conversion value of the catalyst slurry.

2. The process according to claim 1 wherein the stripping gas is contacted with the catalyst slurry at a temperature from about 200° C. to about 350° C. and a pressure from about 25 psia to about 450 psia.

3. The process according to claim 1 wherein the stripping gas is contacted with the catalyst slurry at a temperature from about 210° C. to about 250° C. and a pressure from about 50 psia to about 200 psia.

4. The process according to claim 1 wherein the stripping gas is contacted with the catalyst slurry at a temperature from about 210° C. to about 250° C. and a pressure from about 50 psia to about 125 psia.

5. The process according to claim 1 wherein the stripping gas comprises less than about 10 mole percent water.

6. The process according to claim 5 wherein the stripping gas comprises less than about 10 mole percent carbon monoxide.

7. The process according to claim 1 wherein the stripping gas comprises less than about 5 mole percent water.

8. The process according to claim 1 wherein the stripping gas comprises less than about 1 mole percent water.

9. The process according to claim 1 wherein step (a) is carried out in a Fischer-Tropsch synthesis reactor.

10. The process according to claim 1 wherein the hydrogen containing gas is contacted with the catalyst slurry at a temperature from about 220° C. to about 350° C. and a pressure from about 25 psia to about 450 psia.

11. The process according to claim 1 wherein the hydrogen containing gas is contacted with the catalyst slurry at a temperature from about 250° C. to about 330° C. and a pressure from about 50 psia to about 200 psia.

12. The process according to claim 1 wherein the hydrogen containing gas is contacted with the catalyst slurry at a temperature from about 250° C. to about 330° C. and a pressure from about 50 psia to about 125 psia.

13. The process according to claim 1 wherein the hydrogen containing gas comprises less than about 10 mole percent water.

14. The process according to claim 13 wherein the hydrogen containing gas comprises less than about 10 mole percent carbon monoxide.

15. The process according to claim 1 wherein the hydrogen containing gas comprises less than about 5 mole percent water.

16. The process according to claim 1 wherein the hydrogen containing gas comprises less than about 1 mole percent water.

17. The process according to claim 1 wherein step (b) is carried out in a Fischer-Tropsch synthesis reactor.

18. The process according to claim 1 wherein the synthesis reactor is a Fischer-Tropsch reactor.

19. The process according to claim 1 wherein the catalyst comprises a metal selected from the group consisting of Group 8, 9, 10 metals and mixtures thereof.

20. The process according to claim 1 wherein the catalyst comprises cobalt.

21. The process according to claim 1 wherein step (b) is carried out at a higher temperature than the operating temperature of said synthesis reactor.

22. The process according to claim 1 wherein both step (a) and (b) are carried out at a higher temperature than the operating temperature of said synthesis reactor.

23. The process according to claim 1 wherein step (a) is carried out at a pressure lower than the synthesis reactor operating pressure.

24. The process according to claim 23 wherein step (a) is carried out at a pressure at least 20 psia lower than the synthesis reactor operating pressure.

25. The process according to claim 23 wherein step (a) is carried out at a pressure from about 50 psia to about 125 psia provided the synthesis reactor operating pressure is greater than about 145 psia.

26. The process according to claim 1 wherein step (b) is carried out at a pressure lower than the synthesis reactor operating pressure.

27. The process according to claim 26 wherein step (b) is carried out at a pressure at least 20 psia lower than the synthesis reactor operating pressure.

28. The process according to claim 26 wherein step (b) is carried out at a pressure from about 50 psia to about 125 psia provided the synthesis reactor operating pressure is greater than about 145 psia.

29. A process for treating a catalyst slurry having a CO conversion value from a synthesis reactor comprising:

(a) transferring at least a portion of the catalyst slurry to an intermediate vessel;

(b) transferring at least a portion of the catalyst slurry from step (a) to a regeneration vessel;

(c) contacting at least a portion of the catalyst slurry with a stripping gas at a pressure equal to or lower than the synthesis reactor operating pressure and under conditions and for a period of time sufficient to remove at least a portion of the water; and

(d) contacting at least a portion of the catalyst slurry with a hydrogen containing gas under conditions and for a period of time sufficient to increase the CO conversion value of the catalyst slurry.

30. The process according to claim 29 wherein the stripping gas is contacted with the catalyst slurry at a temperature from about 200° C. to about 350° C. and a pressure from about 25 psia to about 450 psia.

31. The process according to claim 29 wherein the stripping gas is contacted with the catalyst slurry at a temperature from about 210° C. to about 250° C. and a pressure from about 50 psia to about 200 psia.

32. The process according to claim 29 wherein the stripping gas is contacted with the catalyst slurry at a temperature from about 210° C. to about 250° C. and a pressure from about 50 psia to about 125 psia.

33. The process according to claim 29 wherein the stripping gas comprises less than about 10 mole percent water.

34. The process according to claim 33 wherein the stripping gas comprises less than about 10 mole percent carbon monoxide.

35. The process according to claim 29 wherein the stripping gas comprises less than about 5 mole percent water.

36. The process according to claim 29 wherein the stripping gas comprises less than about 1 mole percent water.

37. The process according to claim 29 wherein step (c) is carried out in a synthesis reactor.

38. The process according to claim 29 wherein the hydrogen containing gas is contacted with the catalyst slurry at a temperature from about 220° C. to about 350° C. and a pressure from about 25 psia to about 450 psia.

39. The process according to claim 29 wherein the hydrogen containing gas is contacted with the catalyst slurry at a temperature from about 250° C. to about 330° C. and a pressure from about 50 psia to about 200 psia.

40. The process according to claim 29 wherein hydrogen containing gas is contacted with the catalyst slurry at a temperature from about 270° C. to about 320° C. and a pressure from about 50 psia to about 125 psia.

41. The process according to claim 29 wherein the hydrogen containing gas comprises less than about 10 mole percent water.

42. The process according to claim 41 wherein the hydrogen containing gas comprises less than about 10 mole percent carbon monoxide.

43. The process according to claim 29 wherein the hydrogen containing gas comprises less than about 5 mole percent water.

44. The process according to claim 29 wherein the hydrogen containing gas comprises less than about 1 mole percent water.

45. The process according to claim 29 wherein step (d) is carried out in a synthesis reactor.

46. The process according to claim 29 wherein the synthesis reactor is a Fischer-Tropsch reactor.

47. The process according to claim 29 wherein the catalyst comprises a metal selected from the group consisting of Group 8, 9, 10 metals and mixtures thereof.

48. The process according to claim 29 wherein the catalyst comprises cobalt.

49. The process according to claim 29 wherein step (d) is carried out at a higher temperature than the operating temperature of said synthesis reactor.

50. The process according to claim 29 wherein both step (c) and (d) are carried out at a higher temperature than the operating temperature of said synthesis reactor.

51. The process according to claim 29 wherein the intermediate vessel and the regeneration vessel are the same vessel.

52. The process according to claim 29 wherein the stripping process of step (c) is carried out in the intermediate vessel.

53. The process according to claim 52 wherein the stripping process of step (d) is carried out in the regeneration vessel.

54. The process according to claim 53 wherein the catalyst slurry is continuously circulated between the intermediate and regeneration vessels for a period of time sufficient to treat the catalyst slurry.

55. The process according to claim 29 wherein the stripping process of step (c) is carried out in the regeneration vessel.

56. The process according to claim 29 wherein step (c) is carried out at a pressure lower than the synthesis reactor operating pressure.

57. The process according to claim 56 wherein step (c) is carried out at a pressure at least 20 psia lower than the synthesis reactor operating pressure.

58. The process according to claim 56 wherein step (c) is carried out at a pressure from about 50 psia to about 125 psia provided the synthesis reactor operating pressure is greater than about 145 psia.

59. The process according to claim 29 wherein step (d) is carried out at a pressure lower than the synthesis reactor operating pressure.

60. The process according to claim 59 wherein step (d) is carried out at a pressure at least 20 psia lower than the synthesis reactor operating pressure.

61. The process according to claim 59 wherein step (d) is carried out at a pressure from about 50 psia to about 125 psia provided the synthesis reactor operating pressure is greater than about 145 psia.

62. A process for converting a hydrocarbon-containing feed gas to liquid hydrocarbon products comprising:

(a) reacting the hydrocarbon-containing gas and an oxygen-containing gas in a syngas reactor under conditions effective to produce a syngas stream;

(b) reacting at least a portion of the syngas stream of step (a) in a synthesis reactor under conditions effective to produce liquid and gaseous hydrocarbon products and water, wherein the syngas is contacted with a synthesis catalyst slurry and at least a portion of said catalyst is at least partially deactivated as a result;

(c) contacting at least a portion of the deactivated catalyst slurry from step (b) with a stripping gas at a pressure equal to or lower than the synthesis reactor operating pressure and under conditions effective for removing at least a portion of the water from the catalyst slurry; and

(d) contacting at least a portion of the stripped catalyst slurry in step (c) with a hydrogen containing gas under conditions and for a period of time sufficient to at least partially re-activate the catalyst slurry.

63. The process according to claim 62 wherein the stripping gas is contacted with the catalyst slurry at a temperature from about 200° C. to about 350° C. and a pressure from about 25 psia to about 450 psia.

64. The process according to claim 62 wherein the stripping gas is contacted with the catalyst slurry at a temperature from about 210° C. to about 250° C. and a pressure from about 50 psia to about 200 psia.

65. The process according to claim 62 wherein the stripping gas is contacted with the catalyst slurry at a temperature from about 210° C. to about 250° C. and a pressure from about 50 psia to about 125 psia.

66. The process according to claim 62 wherein the stripping gas comprises less than about 10 mole percent water.

67. The process according to claim 62 wherein the stripping gas comprises less than about 5 mole percent water.

68. The process according to claim 62 wherein the stripping gas comprises less than about 1 mole percent water.

69. The process according to claim 62 wherein step (c) is carried out in a Fischer-Tropsch synthesis reactor.

70. The process according to claim 62 wherein the stripping gas comprises less than about 10 mole percent carbon monoxide.

71. The process according to claim 62 wherein the hydrogen containing gas is contacted with the catalyst slurry at a temperature from about 220° C. to about 350° C. and a pressure from about 25 psia to about 450 psia.

72. The process according to claim 62 wherein the hydrogen containing gas is contacted with the catalyst slurry at a temperature from about 250° C. to about 330° C. and a pressure from about 50 psia to about 200 psia.

73. The process according to claim 62 wherein the hydrogen containing gas is contacted with the catalyst slurry at a temperature from about 270° C. to about 320° C. and a pressure from about 50 psia to about 125 psia.

74. The process according to claim 62 wherein the hydrogen containing gas comprises less than about 10 mole percent water.

75. The process according to claim 74 wherein the hydrogen containing gas comprises less than about 10 mole percent carbon monoxide.

76. The process according to claim 62 wherein the hydrogen containing gas comprises less than about 5 mole percent water.

77. The process according to claim 62 wherein the hydrogen containing gas comprises less than about 1 mole percent water.

78. The process according to claim 62 wherein step (d) is carried out in a Fischer-Tropsch synthesis reactor.

79. The process according to claim 62 wherein the synthesis reactor is a Fischer-Tropsch reactor.

80. The process according to claim 62 wherein the catalyst comprises a metal selected from the group consisting of Group 8, 9, 10 metals and mixtures thereof.

81. The process according to claim 62 wherein the catalyst comprises cobalt.

82. The process according to claim 62 wherein step (c) is carried out at a higher temperature than the operating temperature of said synthesis reactor.

83. The process according to claim 62 wherein both step (c) and (d) are carried out at a higher temperature than the operating temperature of said synthesis reactor.

84. The process according to claim 62 wherein step (c) is carried out at a pressure lower than the synthesis reactor operating pressure.

85. The process according to claim 84 wherein step (c) is carried out at a pressure at least 20 psia lower than the synthesis reactor operating pressure.

86. The process according to claim 84 wherein step (c) is carried out at a pressure from about 50 psia to about 125 psia provided the synthesis reactor operating pressure is greater than about 145 psia.

87. The process according to claim 62 wherein step (d) is carried out at a pressure lower than the synthesis reactor operating pressure.

88. The process according to claim 87 wherein step (d) is carried out at a pressure at least 20 psia lower than the synthesis reactor operating pressure.

89. The process according to claim 87 wherein step (d) is carried out at a pressure from about 50 psia to about 125 psia provided the synthesis reactor operating pressure is greater than about 145 psia.

90. A process for treating catalyst slurry having a CO conversion value from a synthesis reactor wherein said catalyst slurry comprises water comprising contacting the catalyst slurry with a hydrogen containing gas at a pressure equal to or lower than the synthesis reactor operating pressure for a period of time sufficient to increase the CO conversion value of the catalyst slurry wherein said hydrogen containing gas comprises less than about 10 mole % water and less than about 33 mole % carbon monoxide.

91. The process according to claim 90 wherein the hydrogen containing gas comprises less than about 5 mole % water.

92. The process according to claim 90 wherein the hydrogen containing gas comprises less than about 1 mole % water.

93. The process according to claim 90 wherein the hydrogen containing gas is contacted with the catalyst slurry at a temperature from about 220° C. to about 350° C. and a pressure from about 25 psia to about 450 psia.

94. The process according to claim 90 wherein the hydrogen containing gas is contacted with the catalyst slurry at a temperature from about 220° C. to about 330° C. and a pressure from about 50 psia to about 200 psia.

95. The process according to claim 90 wherein the hydrogen containing gas is contacted with the catalyst slurry at a temperature from about 220° C. to about 300° C. and a pressure from about 50 psia to about 125 psia.

96. The process according to claim 90 wherein the synthesis reactor is a Fischer-Tropsch reactor.

97. The process according to claim 90 wherein process for treating the catalyst slurry is carried out at a pressure at least 20 psia lower than the synthesis reactor operating pressure.

98. The process according to claim 90 wherein the process for treating the catalyst slurry is carried out at a pressure at a pressure from about 50 psia to about 125 psia provided the synthesis reactor operating pressure is greater than about 145 psia.

99. The process according to claim 90 wherein the hydrogen containing gas comprises less than about 20 mole % carbon monoxide.

100. The process according to claim 90 wherein the hydrogen containing gas comprises less than about 10 mole % carbon monoxide.

Assignments (4)
CONFIRMATORY DEED OF ASSIGNMENT EFFECTIVE DEC. 31, 2017 Recorded Jan 28, 2021
From: CLARIANT CORPORATION
To: CLARIANT INTERNATIONAL LTD.
Reel/Frame 055160/0912 →
MERGER Recorded Jan 27, 2021
From: SUD-CHEMIE INC.
To: CLARIANT CORPORATION
Reel/Frame 055139/0688 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 10, 2011
From: CONOCOPHILLIPS COMPANY
To: SUD-CHEMIE INC.
Reel/Frame 025931/0938 →
MERGER Recorded Jan 26, 2005
From: CONOCO INC.
To: CONOCOPHILLIPS COMPANY
Reel/Frame 015623/0721 →