USRE37789EExpiredUtility

Regenerating zeolitic cracking catalyst

Assignee: PHILLIPS PETROLEUM COPriority: Nov 17, 1980Filed: May 13, 1996Granted: Jul 16, 2002

Est. expiryNov 17, 2000(expired)· nominal 20-yr term from priority

Inventors:Brent J. Bertus Harold W. Mark John S. Roberts Arnold M. Schaffer

B01J 38/18B01J 29/166Y10S502/521C10G 11/182B01J 38/10B01J 29/90C10G 11/05

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Claims

Abstract

A method for countering the adverse effect of contaminating metals on a crystalline aluminosilicate catalyst comprising contacting the catalyst with a reducing gas under suitable conditions.In a preferred embodiment, the catalyst contains antimony.

Claims

exact text as granted — not AI-modified

What is claimed is:

1. In a process for the catalytic cracking of a hydrocarbon feed wherein said feed is contacted with a crystalline zeolite aluminosilicate cracking catalyst containing at least one contaminating metal selecting from the group consisting of nickel, vanadium, and iron under cracking conditions and at least a portion of said cracking catalyst is periodically regenerated by contact with a combustion supporting gas under regeneration conditions and at least a portion of the regenerated catalyst is employed in the catalytic cracking of hydrocarbon feed, the improvement consisting essentially of contacting at least a portion of said regenerated catalyst with a reducing gas under conditions suitable for countering effects of contaminating metals thereon to produce a passivated catalyst and employing at least a portion of said reduced passivated catalyst in cracking said hydrocarbon feed.

2. A process according to claim 1 wherein said cracking catalyst is contacted with said reducing gas at a temperature in the range of about 850° F. to about 1300° F.

3. A process according to claim 2 wherein said reducing gas comprises hydrogen.

4. A process according to claim 3 wherein said hydrocarbon feed contains at least one of nickel and vanadium.

5. A process according to claim 4 wherein the catalyst that is contacted with said hydrogen contains antimony.

6. A process according to claim 5 wherein the antimony is applied to the catalyst in the form of antimony tris(O,O-dipropyl phosphorodithioate).

7. A process according to claim 5 wherein said antimony is applied to the catalyst by antimony tris(O,O-dipropyl phosphorodithioate) dissolved in the hydrocarbon feed.

8. A process according to claim 2 wherein the catalyst that is contacted with said reducing gas contains antimony.

9. A process according to claim 2 wherein said reducing gas comprises at least one gas selected from the group consisting of carbon monoxide, hydrogen, propane, methane, and ethane.

10. A process according to claim 9 2 wherein said reducing gas comprises regenerator off gases.

11. A process according to claim 9 2 wherein said reducing gas comprises light gases from the catalytic cracker.

12. A method for passivating a crystalline zeolite alumino-silicate-containing catalyst utilized to crack hydrocarbon feedstock to lower molecular weight products in a reaction zone where the feedstock contains at least two metal comtaminants selected from the class consisting of nickel, vanadium, and iron and where at least some of the metal contaminants become deposited on the catalyst, which comprises passing the catalyst after regeneration, through a reduction zone maintained at a temperature of 600° to 704° C. for a time sufficient to at least partially passivate the metal contaminants on the catalyst, a reducing environment maintained in the reduction zone by the addition to the reduction zone of a material selected from the class consisting of hydrogen, carbon monoxide, and mixtures thereof, said passivated catalyst thereafter passing to said reaction zone without further processing.

13. In a hydrocarbon cracking process wherein:
A. hydrocarbon feedstock containing at least two metal contaminates contaminants selected from the class consisting of nickel, vanadium, and iron is passed into a cracking zone having a crystalline zeolite alumino-silicate-containing cracking catalyst therein at cracking conditions to form cracked hydrocarbon products and wherein coke and metal contaminants are deposited on the catalyst; and
B. the coke and metal contaminated catalyst is passed to a regeneration zone maintained at regeneration conditions having a regeneration gas passing therethrough whereby at least a portion of the coke is removed from the catalyst, the improvement which comprises passing the catalyst from the regeneration zone through a reduction zone maintained at a temperature of 600° C. to 704° C. whereby the metal contaminants are at least partially passivated prior to the catalyst being returned to the reaction cracking zone, a reducing atmosphere maintained in the reduction zone by the addition to the reduction zone of a material selected from the class consisting of hydrogen, carbon monoxide, and mixtures thereof, said catalyst passing without further processing from the reduction zone to the cracking zone.

14. The process of claim 13 further comprising the steps of:
A. analyzing the amount of metal contaminants on the catalyst, and
B. adding to the reaction cracking a hydrocarbon feedstock containing a predetermined amount of a contaminant metal.

15. The process of claim 14 wherein the metal contaminant added to the cracking zone is selected from the class consisting of vanadium and iron.

16. The process of claim 13 further comprising the addition of a passivation agent selected from the class consisting of antimony, tin, bismuth, and manganese to further passivate the catalyst.

17. In a hydrocarbon cracking process wherein:
A. hydrocarbon feedstock containing at least two metal contaminates contaminants selected from the class consisting of nickel, vanadium and iron is passed into a reaction zone having a crystalline zeolite alumino-silicate-containing cracking catalyst therein at cracking conditions to form cracked hydrocarbon products and wherein coke and metal contaminants are deposited on the catalyst;
B. the coke and metal contaminated catalyst is passed from the reaction zone to a regeneration zone maintained at regeneration conditions having a regenerating gas passing therethrough to remove at least a portion of the coke from the catalyst, the improvement which comprises:
i. passing the catalyst from the regeneration zone through a reduction zone maintained at a temperature within the range of about 600° C. to about 704° C. in the presence of hydrogen, carbon monoxide, or mixtures thereof to passivate the metal contaminants on the catalyst; and
ii. passing the catalyst from the reduction zone to the reaction zone without further processing.

18. A method for passivating a cracking catalyst comprising crystalline zeolite aluminosilicate utilized to crack hydrocarbon feedstock to lower molecular weight products in a reaction zone, wherein the feedstock contains at least one metal contaminant selected from the class consisting of nickel, vanadium, and iron and wherein at least some of the metal contaminants become deposited on the catalyst, which comprises passing the catalyst after regeneration through a reduction zone maintained at a temperature sufficient to at least partially passivate the metal contaminants on the catalyst, maintaining the catalyst in the reduction zone for a time sufficient to at least partially passivate the metal contaminates contaminants on the catalyst, wherein the reduction environment is maintained in the reduction zone by the addition to the reduction zone of a material selected from the class consisting of hydrogen, carbon monoxide, and mixtures thereof, said passivated catalyst thereafter passing to said reaction zone without further processing in the reduced state.

19. In a hydrocarbon cracking process wherein:
A. hydrocarbon feedstock containing at least one metal contaminates contaminant selected from the class consisting of nickel, vanadium, and iron is passed into a reaction zone containing a cracking catalyst comprising crystalline zeolite aluminosilicate under cracking conditions to form cracked hydrocarbon products and wherein coke and metal contaminants are deposited on the catalyst; and
B. the coke and metal contaminated catalyst is passed to a regeneration zone maintained at regeneration conditions having a regeneration gas passing therethrough whereby at least a portion of the coke is removed from the catalyst, the improvement which consists essentially of passing the catalyst from the regeneration zone through a reduction zone maintained at a temperature sufficient to at least partially passivate the metal contaminants on the catalyst, maintaining the catalyst in the reduction zone for a time sufficient to at least partially passivate the metal contaminants on the catalyst, a reducing atmosphere being maintained in the reduction zone by the addition to the reduction zone of a material selected from the class consisting of hydrogen, carbon monoxide, and mixtures thereof, and passing at least a portion of said reduced passivated catalyst in the reduced state to the reaction zone.

20. The process of claim 19 wherein the reduction zone is maintained at a temperature in the range of about 600° C. to about 704° C.

21. In a hydrocarbon cracking process wherein a hydrocarbon feedstock is passed into a reaction zone containing a cracking catalyst comprising crystalline zeolite aluminosilicate that is contaminated with at least one metal contaminant selected from the group consisting of nickel, vanadium, and iron and coke and said metal contaminated catalyst is passed to a regeneration zone maintained at regeration regeneration conditions having a regeneration gas passing therethrough whereby at least a portion of the coke is removed from the catalyst and regenerated catalyst is recycled back to the reaction zone, the improvement consisting essentially of passing the catalyst from the regeneration zone through a reduction zone containing a reducing gas maintained at a temperature sufficient to at least partially passivate the metal contaminants on the catalyst, maintaining the catalyst in the reduction zone for a time sufficient to at least partially passivate the metal contaminants on the catalyst, and recycling reduced the thus passivated catalyst in the reduced state to the reaction zone.

22. A method according to claim 21 wherein said reducing gas consists essentially of at least one gas selected from the group consisting of carbon monoxide, hydrogen, propane, methane, and ethane.

23. A method according to claim 22 further comprising analyzing the amount of metal contaminants on the contaminated catalyst and adding to the reaction zone a hydrocarbon feedstream containing vanadium, nickel, and iron.

24. A method according to claim 22 further including monitoring the composition of the metal contaminants on said catalyst and combining said recycled catalyst with a hydrocarbon feedstream containing vanadium, nickel, and iron.

25. A method according to claim 24 wherein the major portion of said metal contaminant comprises nickel.

26. A method according to claim 24 wherein the reduction zone is maintained at a temperature of 454° C. to 704° C. to at least partially passivate said metal contaminant.

27. A process according to claim 26 wherein the temperature in the reduction zone is maintained within the range of about 600° C. to about 704° C.

28. A process according to claim 27 further comprising the addition of a passivation agent selected from the class consisting of antimony, tin, bismuth, and manganese to further passivate the catalyst.

29. A method for passivating adverse effects of metal contaminants on a cracking catalyst consisting essentially of a crystalline zeolite aluminosilicate containing at least one metal selected from the group consisting of nickel, vanadium, and iron which comprises passing the catalyst after regeneration through a reduction zone maintained at a temperature sufficient to at least partially passivate the metal contaminants on the catalyst, maintaining the catalyst in the reduction zone for a time sufficient to at least partially passivate the metal contaminants on said catalyst, wherein the reducing environment is maintained in the reduction zone by the addition to the reduction zone of a reducing gas, wherein the reduced thus passivated catalyst is passed to the cracking zone, and said reduced catalyst and is combined with a hydrocarbon feedstream containing nickel, vanadium and iron.

30. A method according to claim 29 wherein the composition of the metal contaminates contaminants on said catalyst is monitored.

31. A method according to claim 30 wherein said reducing gas consists essentially of at least one gas selected from the group consisting of carbon monoxide, hydrogen, propane, methane, and ethane.

32. A method according to claim 31 wherein the reduction zone temperature is maintained at a temperature of 454° C. to 704° C. to at least partially passivate said metal contaminants on said catalyst.

33. A method for passivating a crystalline zeolite alumino-silicate-containing catalyst which has been utilized to crack hydrocarbon feedstock to lower molecular weight products in a reaction zone where the feedstock contains at least one metal contaminant selected from the class consisting of nickel, vanadium, and iron and where at least some of the metal contaminant becomes deposited on the catalyst, which consists essentially of exposing the catalyst after regeneration to a reducing environment maintained at a temperature in the range of about 454° C. to about 704° C. for a time sufficient to counter adverse effects of said contaminating metals on said catalyst, said reducing environment being maintained by a material selected from the class consisting of hydrogen, carbon monoxide, and mixtures thereof, and passing at least a portion of said reduced the thus passivated catalyst back to said reaction zone.

34. In a hydrocarbon cracking process wherein:
A. hydrocarbon feedstock containing at least one metal contaminant selected from the class consisting of nickel, vanadium, and iron is passed into a reaction zone containing a cracking catalyst comprising crystalline zeolite aluminosilicate under cracking conditions to form cracked hydrocarbon products and wherein coke and metal contaminants are deposited on the catalyst; and
B. the coke and metal contaminated catalyst is subjected to regeneration with a regenerating gas whereby at least a portion of the coke is removed from the catalyst, the improvement which consists essentially of subjecting catalyst resulting from the regeneration to a reducing atmosphere at a temperature in the range of about 454° C. to about 704° C. so as to counter adverse effects of said contaminating metals on said catalyst, and passing at least a portion of said reduced the thus passivated catalyst back to said reaction zone.

35. A process for the cracking of a hydrocarbon feedstock comprising contacting said feedstock under cracking conditions in a cracking zone with a used cracking catalyst prepared by a process consisting essentially of (1) starting with a contaminated cracking catalyst comprising crystalline zeolite alumino-silicate wherein said contaminants comprise carbon and at least one metal contaminant selected from the group consisting of nickel, vanadium, and iron, (2) exposing said contaminated cracking catalyst in an oxidation step to a combustion-supporting gas under conditions sufficient to result in combustion of carbon contaminant, and (3) then exposing the resulting catalyst in a reduction step to a reducing gas under conditions suitable for countering adverse effects of said contaminating metals, said process being further characterized by the fact that the contaminated cracking catalyst is not subjected to oxidation or removal of contaminating metals subsequent to the reduction step.

36. A process according to claim 35 wherein said cracking is conducted to a temperature in the range of about 800° F. to about 1200° F.

37. A process according to claim 36 wherein cracking catalyst is periodically removed from said cracking zone and exposed in an oxidation step to a combustion-supporting gas under conditions sufficient to result in combustion of carbon thereon, and then the resulting catalyst is exposed in a reduction step to a reducing gas under conditions suitable for countering adverse effects of said contaminating metals, and catalyst from the reducing step is recycled to the cracking zone.

38. A process according to claim 36 wherein cracking catalyst is periodically removed from said cracking zone and exposed in an oxidation step at a temperature in the range of about 950° F. to 1500° F. to a combustion-supporting gas under conditions sufficient to result in combustion of carbon thereon, and then the resulting catalyst is exposed in a reduction step to a reducing as gas at a temperature in the range of about 850° F. to about 1300° F. under conditions sufficient to counter adverse effects of said contaminating metals, and catalyst from the reducing step is recycled to the cracking zone.

39. A process according to claim 38 wherein said reducing gas comprises gases resulting from the combustion of carbon on said contaminated catalyst, said gases comprising carbon monoxide and said hydro-carbon feedstock contains 1.2 weight percent sulfur.

40. A process according to claim 39 wherein said contaminated catalyst contains at least one metal selected from the group consisting of antimony, tin, bismuth, and manganese.

41. A process according to claim 40 wherein said contaminated catalyst contains about 0.005 to about 10 weight percent antimony.

42. A process according to claim 41 38 wherein said hydrocarbon feedstock comprises at least one metal selected from the group consisting of nickel, vanadium, and iron in concentrations within the following ranges:

Nickel
0.02-100 ppm

Vanadium
0.02-500 ppm

Iron
0.02-500 ppm.

43. A process according to claim 41 38 wherein the starting contaminated cracking catalyst contains 38 ppm nickel, 58 ppm vanadium, and 85 ppm iron.

44. A process according to claim 41 38 wherein said hydrocarbon feedstock comprises at least one component selected from the group consisting of heavy residual and topped crude.

45. A process according to claim 41 38 wherein said reducing gas comprises hydrogen.

46. In a process for the catalytic cracking of a hydrocarbon feed wherein said feed is contacted with a crystalline zeolite alumino-silicate cracking catalyst under cracking conditions and at least a portion of said cracking catalyst is periodically regenerated by contact with a combustion-supporting gas under regeneration conditions and at least a portion of the regenerated catalyst is employed in the catalytic cracking of the hydrocarbon feed and wherein the cracking catalyst becomes contaminated by at least one metal selected from the group consisting of nickel, iron, vanadium, and copper, the improvement comprising contacting at least a portion of the regenerated catalyst with a reducing gas under conditions suitable for reducing the adverse effects of contaminating metals thereon and recycling the resulting catalyst to the cracking zone without any intermediate oxidation or removal of the contaminating metal.

47. A process according to claim 46 wherein said cracking catalyst becomes contaminated with nickel.

48. A process according to claim 46 wherein nickel is the major metal contaminant of the group consisting of nickel, iron, vanadium, and copper.

49. A process according to claim 46 wherein nickel and vanadium make up the major portion of the contaminants on said catalyst.

50. A process according to claim 1 wherein said cracking catalyst contains at least one contaminant metal selected from the group consisting of nickel and vanadium.

51. A process according to claim 4 wherein the amount of nickel in the hydrocarbon feed, if present, is in the range of 0 . 02 to 100 ppm and the amount of vanadium in the hydrocarbon feed, if present, is in the range of 0 . 02 to about 500 ppm and the amount of hydrogen employed in the reducing step is in the range of about 0 . 1 to about 20 standard cubic feed per minute per pound of said contaminant metal in the catalyst.

52. A process according to claim 3 wherein the feed that is contacted with the reduced catalyst contains at least one contaminating metal selected from nickel and vanadium, the amount of each such contaminating metal being at least about 0 . 02 ppm, and the regenerated cracking catalyst is contacted with said reducing gas at a temperature in the range of about 850 ° F. to about 1300 ° F. for a time of about 0 . 05 minutes to about two hours before being recycled for employment in the catalytic cracking of hydrocarbon feed and the amount of hydrogen employed in the reducing step is in the range of about 0 . 1 to about 20 standard cubic feet per minute per pound of said contaminant metal in the catalyst.

53. A process according to claim 2 wherein said reducing gas comprises at least one propane, methane, and ethane.

54. A process according to claim 2 wherein said reducing gas comprises carbon monoxide.

55. A process according to claim 46 wherein said cracking catalyst becomes contaminated by at least one metal selected from the group consisting of nickel and vanadium and said reducing gas comprises at least one of hydrogen, methane, ethane, and propane.

56. In a cracking process wherein a hydrocarbon feed is contacted with a cracking catalyst in a cracking step in a cracking zone at a temperature in the range of about 800 ° F. to about 1200 ° F., said cracking catalyst comprising crystalline zeolite aluminosilicate that is contaminated with at least one contaminating metal selected from the group consisting of nickel and vanadium, and at least a portion of the cracking catalyst is periodically removed from the cracking zone and subjected to a regeneration step involving contact with a combustion supporting gas at a temperature in the range of about 950 ° F. to about 1500 ° F. in a regeneration zone to result in the combustion of carbon existing on said cracking catalyst, and at least a portion of the thus regenerated catalyst is recycled for reuse in the cracking step, the improvement consisting essentially of countering adverse effects of said contaminating metals on the regenerated catalyst by removing at least a portion of the regenerated catalyst from the regeneration zone and subjecting said removed regenerated catalyst to a passivation step involving contact with hydrogen at a temperature in the range of about 850 ° F. to about 1300 ° F. and then recycling at least a portion of the catalyst that was subjected to said passivation step to the cracking zone without any intermediate oxidation or removal of contaminating metals from the product of the passivation step.

57. A process for cracking a hydrocarbon feedstock comprising contacting a hydrocarbon feedstock with a cracking catalyst comprising crystalline zeolite aluminosilicate containing at least one contaminating metal selected from the group consisting of nickel, vanadium, and iron in a cracking zone to effect cracking of the hydrocarbon feedstock, periodically removing at least a portion of said cracking catalyst from the cracking zone and sending said removed catalyst to a regeneration zone in which carbon is oxidized and thereby removed from said catalyst, at least a portion of the thus regenerated catalyst is removed from the regeneration zone and subjected to a passivation step in a passivation zone by contacting said regenerated catalyst with at least one gas selected from the group consisting of hydrogen, methane, ethane, and propane at passivation reaction conditions, and then at least a portion of the thus passivated catalyst is recycled to the cracking zone without any intermediate oxidation or removal of contaminating metals.

58. A process according to claim 57 wherein said hydrocarbon feedstock contains at least one metal contaminant selected from the group consisting of nickel and vanadium.

59. A process according to claim 58 wherein said passivation reaction conditions include a temperature in the range of about 850 ° F. to about 1300 ° F.

60. A process according to claim 58 wherein said passivation reaction conditions include a temperature in the range of about 850 ° F. to about 1300 ° F.

61. A process according to claim 59 wherein said gas includes hydrogen.

62. A process according to claim 12 where hydrogen is employed in the reduction zone.

63. A process according to claim 13 where hydrogen is employed in the reduction zone.

64. A process according to claim 17 where hydrogen is employed in the reduction zone.

65. A process according to claim 18 where hydrogen is employed in the reduction zone.

66. A process according to claim 19 where hydrogen is employed in the reduction zone.

67. A process according to claim 21 wherein the reducing gas comprises hydrogen.

68. A process according to claim 29 wherein the reducing gas comprises hydrogen.

69. A process according to claim 33 wherein hydrogen is employed in the reducing environment.

70. A process according to claim 34 wherein hydrogen is employed in said reducing atmosphere.

71. A process according to claim 46 wherein said reducing gas comprises hydrogen.

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