Heavy oil hydroprocessing with Group VI metal slurry catalyst

Abstract

A process for the preparation of a dispersed Group VIB metal sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting aqueous ammonia and a Group VIB metal compound, such as molybdenum oxide or tungsten oxide, to form water soluble compounds such as aqueous ammonium molybdates or tungstates. The aqueous ammonium molybdates or tungstates are sulfided at a relatively low temperature with hydrogen sulfide without feed oil. The slurry stream is then passed through a separator and ammonia is flashed and separated from the system, leaving a separator residue slurry. The separator residue slurry is then mixed with feed oil, hydrogen and hydrogen sulfide and sulfided at a relatively high temperature to produce a dispersed molybdenum sulfide or tungsten sulfide catalyst of high hydroprocessing activity. The catalyst slurry and feed oil can then be passed to a hydroprocessing reactor.

Description

Claims

1. A process comprising the preparation of a dispersed Group VIB metal sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting ammonia and a Group VIB metal compound in water to form an aqueous ammonium Group VIB metal compounds, reacting said aqueous ammonium Group VIB metal compounds with hydrogen sulfide essentially in the absence of feed oil in a low temperature sulfiding step at a temperature in the range 70.degree. to 350.degree. F., continuing the reaction of aqueous ammonium Group VIB metal compound with hydrogen sulfide in an intermediate temperature sulfiding step at a temperature in the range 180.degree. to 700.degree. F. which is higher than the temperature in said low temperature sulfiding step and essentially without feed oil, withdrawing an aqueous effluent stream from said intermediate temperature sulfiding step, passing said effluent stream to a separator zone, removing ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil and hydrogen sulfide to a high temperature sulfiding step at a temperature in the range 500.degree. to 750.degree. F. which is higher than the temperature in said intermediate temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, and withdrawing from said high temperature sulfiding step an aqueous-oil slurry containing dispersed Group VIB metal sulfide slurry catalyst.

2. The process of claim 1 wherein said residence time is at least 0.3 hours.

3. The process of claim 1 wherein said residence time is at least 0.4 hours.

4. The process of claim 1 wherein said residence time is at least 0.5 hours.

5. The process of claim 1 wherein said feed oil is a crude oil.

6. The process of claim 1 wherein said feed oil is a heavy crude oil.

7. The process of claim 1 wherein said feed oil is a residual oil.

8. The process of claim 1 wherein said feed oil is a refractory heavy distillate.

9. A process comprising the preparation of a dispersed Group VIB metal sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting ammonia and a Group VIB metal compounds in water to form an aqueous ammonium Group VIB metal compounds, reacting said aqueous ammonia Group VIB metal compounds with hydrogen sulfide in a low temperature sulfiding step at a temperature in the range 70.degree. to 350.degree. F. substantially in the absence of feed oil, withdrawing an aqueous effluent stream from said low temperature sulfiding step, passing said aqueous effluent stream to a separator zone, removing ammonia from said effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil, hydrogen and hydrogen sulfide to a high temperature sulfiding step operated at a temperature in the range 500.degree. to 750.degree. F. which is higher than the temperature in said low temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, and withdrawing an aqueous-oil slurry containing dispersed Group VIB metal sulfide slurry catalyst.

10. A process comprising the preparation of a dispersed Group VIB metal sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting a thiosubstituted Group VIB metal ammonium compound, water, and hydrogen sulfide substantially in the absence of feed oil in a zone at a low temperature in the range 70.degree. to 350.degree. F., withdrawing an aqueous effluent stream from said low temperature zone, passing said effluent stream to a separator zone, removing ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil, hydrogen and hydrogen sulfide to a high temperature sulfiding zone at a temperature in the range 500.degree. to 750.degree. F., the residence time in each of said sulfiding zones being at least 0.02 hours and removing an aqueous-oil slurry containing dispersed Group VIB metal sulfide catalyst.

11. A process comprising the preparation of a dispersed molybdenum sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting ammonia and a molybdenum compound in water to form aqueous ammonium molybdates, reacting said aqueous ammonium molybdates with hydrogen sulfide essentially in the absence of feed oil in a low temperature sulfiding step at a temperature in the range of 70.degree. to 350.degree. F., continuing the reaction with hydrogen sulfide in an intermediate temperature sulfiding step at a temperature in the range 180.degree. to 700.degree. F. essentially in the absence of feed oil, said intermediate temperature sulfiding step operated at a temperature which is higher than the temperature in said low temperature sulfiding step, withdrawing an aqueous effluent stream from said intermediate temperature sulfiding step, passing said effluent stream to a separator zone, removing ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil, hydrogen and hydrogen sulfide to a high temperature sulfiding step at a temperature in the range 500.degree. to 750.degree. F. which is higher than the temperature in said intermediate temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, and withdrawing from said high temperature sulfiding step an aqueous-oil slurry containing dispersed molybdenum sulfide slurry catalyst.

12. The process of claim 11 wherein said feed oil is hydroprocessed in said high temperature sulfiding step.

13. The process of claim 11 including passing said aqueous-oil slurry containing dispersed molybdenum sulfide slurry catalyst to a hydroprocessing step.

14. The process of claim 13 wherein said hydroprocessing step is operated at a temperature higher than the temperature in said high temperature sulfiding step.

15. The process of claim 11 wherein said low temperature sulfiding step is operated at a temperature in the range 130.degree. to 180.degree. F.

16. The process of claim 11 wherein said intermediate temperature sulfiding step is operated at a temperature in the range 300.degree. to 550.degree. F.

17. The process of claim 11 wherein said residence time is at least 0.1 hours.

18. The process of claim 11 wherein said molybdenum compound is molybdenum oxide.

19. The process of claim 11 wherein said step of reacting ammonia with said molybdenum compound is performed at a temperature of 33.degree. to 350.degree. F.

20. The process of claim 11 wherein said step of reacting ammonia with said molybdenum compound is performed at a temperature of 120.degree. to 180.degree. F.

21. The process of claim 11 wherein said step of reacting ammonia with said molybdenum compound is performed at a pressure of 0 to 400 psig.

22. The process of claim 11 wherein said step of reacting ammonia with said molybdenum compound is performed at a pressure of 0 to 10 psig.

23. The process of claim 11 wherein said step of reacting ammonia with said molybdenum compound employs an NH.sub.3 /Mo weight ratio of 0.1 to 0.6.

24. The process of claim 11 wherein said step of reacting ammonia with said molybdenum compound employs an NH.sub.3 /Mo weight ratio of 0.15 to 0.3.

25. The process of claim 11 wherein said low temperature sulfiding step employs a hydrogen/hydrogen sulfide blend.

26. The process of claim 11 wherein in said low temperature sulfiding step the ratio of H.sub.2 S to Mo is greater than 2.7 SCF H.sub.2 S/lb Mo.

27. The process of claim 11 wherein in said low temperature sulfiding step the ratio of H.sub.2 S to Mo is greater than 12 SCF H.sub.2 S/lb Mo.

28. The process of claim 11 wherein said residence time is at least 0.2 hours.

29. The process of claim 11 wherein in said low temperature sulfiding step the hydrogen sulfide partial pressure is 3 to 400 psi.

30. The process of claim 11 wherein in said low temperature sulfiding step the hydrogen sulfide partial pressure is 150 to 250 psi.

31. The process of claim 11 wherein said ammonia separating step is performed by cooling and depressurizing said aqueous effluent stream.

32. The process of claim 11 including continuous agitation to maintain solids in dispersion.

33. The process of claim 11 wherein said dispersed molybdenum sulfide is molybdenum disulfide.

34. A process comprising the preparation of a dispersed molybdenum sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting ammonia and a molybdenum compound in water to form aqueous ammonium molybdate, reacting said aqueous ammonium molybdate with hydrogen sulfide in a low temperature sulfiding step at a temperature in the range 70.degree. to 350.degree. F. substantially in the absence of feed oil, withdrawing an aqueous effluent stream from said low temperature sulfiding step, passing said aqueous effluent stream to a separator zone, separating ammonia from said effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil, hydrogen and hydrogen sulfide to a high temperature sulfiding step at a temperature between 500.degree. and 750.degree. F., the residence time in each of said sulfiding steps being at least 0.02 hours, and withdrawing an aqueous-oil slurry containing dispersed molybdenum sulfide slurry catalyst.

35. The process of claim 34 wherein said low temperature sulfiding step is operated at a temperature in the range 130 to 180.degree. F.

36. The process of claim 34 wherein said residence time is at least 0.1 hours.

37. The process of claim 34 wherein said molybdenum compound is molybdenum oxide.

38. A process comprising the preparation of a dispersed molybdenum sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting thiosubstituted ammonium molybdate, water, and hydrogen sulfide substantially in absence of hydrocarbon oil in a low temperature sulfiding step at a temperature in the range 180.degree. to 700.degree. F., withdrawing an aqueous effluent stream from said low temperature sulfiding step, passing said effluent stream to a separator zone, separating ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil, hydrogen and hydrogen sulfide to a high temperature sulfiding step at a temperature in the range 500.degree. to 750.degree. F. which is higher than the temperature in said low temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, and recovering an aqueous-oil slurry containing dispersed molybdenum sulfide catalyst.

39. The process of claim 38 wherein said thiosubstituted ammonium molybdate is an ammonium oxythiomolybdate.

40. The process of claim 38 wherein said thiosubstituted ammonium molybdate is ammonium tetrathiomolybdate.

41. The process of claim 38 wherein said molybdenum sulfide is molybdenum disulfide.

42. The process of claim 38 wherein said ammonia separating step is performed by cooling and depressurizing said aqueous effluent stream.

43. A process comprising the preparation of a dispersed tungsten sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting ammonia and a tungsten compound in water to form aqueous ammonium tungstates, reacting said aqueous ammonium tungstates with hydrogen sulfide in a low temperature sulfiding step at a temperature in the range 70.degree. to 350.degree. F. essentially in the absence of feed oil, continuing the reaction with hydrogen sulfide in an intermediate temperature sulfiding step at a temperature in the range 180.degree. to 700.degree. F. essentially in the absence of feed oil, said intermediate temperature sulfiding step operated at a temperature higher than the temperature in said low temperature sulfiding step, withdrawing an aqueous effluent stream from said intermediate temperature sulfiding step, passing said effluent stream to a separator step, separating ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue together with hydrocarbon oil, hydrogen and hydrogen sulfide to a high temperature sulfiding step operated at a temperature in the range 500.degree. to 750.degree. F. which is higher than the temperature in said intermediate temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, and withdrawing from said high temperature sulfiding step an aqueous-oil slurry containing dispersed tungsten sulfide catalyst.

44. The process of claim 43 wherein said tungsten compound is tungsten oxide.

45. The process of claim 43 wherein said dispersed tungsten sulfide is tungsten disulfide.

46. The process of claim 43 wherein said step of reacting said ammonia with said tungsten compound is performed at a temperature of 33.degree. to 350.degree. F.

47. The process of claim 43 wherein said step of reacting ammonia with said tungsten compound is performed at a temperature of 120.degree. to 180.degree. F.

48. The process of claim 43 wherein said step of reacting ammonia with said tungsten compound is performed at a pressure of 0 to 400 psig.

49. The process of claim 43 wherein said step of reacting ammonia with said tungsten compound is performed at a pressure of 0 to 10 psig.

50. The process of claim 43 wherein said step of reacting ammonia with said tungsten compound employs an NH.sub.3 /W weight ratio of 0.03 to 0.31.

51. The process of claim 43 wherein said step of reacting ammonia with said tungsten employs an NH.sub.3 /W weight ratio of 0.05 to 0.25.

52. The process of claim 43 wherein said low temperature sulfiding step employs a hydrogen/hydrogen sulfide blend.

53. The process of claim 43 wherein in said low temperature sulfiding step the ratio of H.sub.2 S/W is greater than 1.4 SCF H.sub.2 S/lb W.

54. The process of claim 43 wherein in said low temperature sulfiding step the ratio of H.sub.2 S/W is greater than 6.3 SCF H.sub.2 S/lb W.

55. The process of claim 43 wherein in said low temperature sulfiding step the temperature is 130.degree. to 180.degree. F.

56. The process of claim 43 wherein said residence time is at least 0.2 hours.

57. The process of claim 43 wherein in said low temperature sulfiding step the hydrogen sulfide partial pressure is 3 to 400 psi.

58. The process of claim 43 wherein in said low temperature sulfiding zone the hydrogen sulfide partial pressure is 150 to 250 psi.

59. The process of claim 43 wherein said ammonia separating step is performed by cooling and depressurizing said aqueous effluent stream.

60. The process of claim 43 including continuous agitation to maintain solids in dispersion.

61. The process of claim 43 wherein said residence time is at least 0.3 hours.

62. A process comprising the preparation of a dispersed tungsten sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting thiosubstituted ammonium tungstate, water and hydrogen sulfide substantially without feed oil in a sulfiding step at a low temperature in the range 180.degree. to 700.degree. F., withdrawing an aqueous effluent stream from said low temperature sulfiding step, passing said effluent stream to a separator zone, separating ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue with feed hydrocarbon oil, hydrogen and hydrogen sulfide to a sulfiding step at a high temperature in the range 500.degree. to 750.degree. F. which is above the temperature in said low temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, and recovering an aqueous-oil slurry containing dispersed tungsten sulfide catalyst.

63. The process of claim 62 wherein said thiosubstituted ammonium tungstate is an ammonium oxythiotungstate.

64. The process of claim 62 wherein said thiosubstituted ammonium tungstate is ammonium tetrathiotungstate.

65. The process of claim 62 wherein said tungsten sulfide is tungsten disulfide.

66. The process of claim 62 wherein said ammonia separating step is performed by cooling and depressurizing said aqueous effluent stream.

67. A process comprising the preparation of a dispersed Group VIB metal sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting ammonia and a Group VIB metal compound in water to form an aqueous ammonium Group VIB metal compound, reacting said aqueous ammonia Group VIB metal compound with hydrogen sulfide in a low temperature sulfiding step at a temperature in the range 70.degree. to 350.degree. F. substantially in the absence of feed oil, withdrawing an aqueous effluent stream from said low temperature sulfiding step, passing said aqueous effluent stream to a separator zone, removing ammonia from said effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil, hydrogen and hydrogen sulfide to an intermediate temperature sulfiding step operated at a temperature in the range 180.degree. to 700.degree. F. which is higher than the temperature in said low sulfiding step and then to a high temperature sulfiding step at a temperature in the range 500.degree. to 750.degree. F. which is higher than the temperature in said intermediate temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, and withdrawing an aqueous-oil slurry containing dispersed Group VIB metal sulfide slurry catalyst.

68. A process comprising the preparation of a dispersed Group VIB metal sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting a Group VIB ammonium compound, water and hydrogen sulfide substantially in the absence of feed oil in a sulfiding step at a low temperature in the range 70.degree. to 350.degree. F. withdrawing an aqueous effluent stream from said low temperature zone, passing said effluent stream to a separator zone, removing ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil, hydrogen and hydrogen sulfide to an intermediate temperature sulfiding step operated at a temperature in the range 180.degree. to 700.degree. F. which is higher than the temperature in said low temperature sulfiding step and then to a high temperature sulfiding step operated at a temperature in the range 500.degree. to 750.degree. F. which is higher than the temperature in said intermediate temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, and removing an aqueous-oil slurry containing dispersed Group VIB metal sulfide catalyst.

69. A process comprising the preparation of a dispersed molybdenum sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting ammonia and a molybdenum compound in water to form aqueous ammonium molybdate, reacting said aqueous ammonium molybdate with hydrogen sulfide in a low temperature sulfiding step in the range 70.degree. to 350.degree. F. substantially in the absence of feed oil, withdrawing an aqueous effluent stream from said low temperature sulfiding step, passing said aqueous effluent stream to a separator zone, separating ammonia from said effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil, hydrogen and hydrogen sulfide to an intermediate temperature sulfiding step operated at a temperature in the range 180.degree. to 700.degree. F. which is higher than the temperature in said low temperature sulfiding step and then to a high temperature sulfiding step operated at a temperature in the range 500.degree. to 750.degree. F. which is higher than the temperature in said intermediate temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, and withdrawing an aqueous oil slurry containing dispersed molybdenum sulfide slurry catalyst.

70. A process comprising the preparation of a dispersed molybdenum sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting ammonium molybdate, water and hydrogen sulfide substantially in the absence of hydrocarbon oil in a low temperature sulfiding step in the range 70.degree. to 350.degree. F., withdrawing an aqueous effluent stream from said low temperature sulfiding step, passing said effluent stream to a separator zone, separating ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil, hydrogen and hydrogen sulfide to an intermediate temperature sulfiding step operated at a temperature in the range 180.degree. to 700.degree. F. which is higher than the temperature in said low temperature sulfiding step and then to a high temperature sulfiding step operated at a temperature in the range 500.degree. to 750.degree. F. which is higher than the temperature in said intermediate temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, and recovering an aqueous-oil slurry containing dispersed molybdenum sulfide catalyst.

71. A process comprising the preparation of a dispersed tungsten sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting an ammonium tungstate compound, water and hydrogen sulfide substantially in the absence of feed oil in a reactor at a low temperature sulfiding zone operated at a temperature in the range 70.degree. to 350.degree. F., withdrawing an aqueous effluent stream from said low temperature reactor, passing said effluent stream to a separator zone, separating ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue with feed hydrocarbon oil, hydrogen and hydrogen sulfide to an intermediate temperature sulfiding step operated at a temperature in the range 180.degree. to 700.degree. F. which is higher than the temperature in said low temperature sulfiding step and then to a high temperature sulfiding zone operated at a temperature in the range 500.degree. to 750.degree. F. which is higher than the temperature in said intermediate temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, and recovering an aqueous-oil slurry containing dispersed tungsten sulfide catalyst.