Systems for hydroprocessing heavy oil

• US 9,605,215 B2
• Filed: 12/03/2013
• Issued: 03/28/2017
• Est. Priority Date: 04/28/2004
• Status: Active Grant

• Current Assignee: Headwaters Heavy Oil, LLC (Seven Group Holdings Limited)
• Original Assignee: Headwaters Heavy Oil, LLC (Seven Group Holdings Limited)
• Inventors: Lott, Roger K., Lee, Lap Keung
• Primary Examiner(s): ROBINSON, RENEE E
• Application Number:
  US14/095,698
• Publication Number:
  US 20140093433A1
• Time in Patent Office: 1,211 Days
• US Class Current: 1/1
• CPC Class Codes: B01J 8/08 with moving particles with fluidised particles B01J8/18
• CPC Class Codes: B01J 8/22 gas being introduced into the liquid
• CPC Class Codes: B01J 8/226 internally, i.e. the particles rotate within the vessel
• CPC Class Codes: C10G 2300/1033 Oil well production fluids
• CPC Class Codes: C10G 2300/107 Atmospheric residues having a boiling point of at least about 538 °C
• CPC Class Codes: C10G 2300/1077 Vacuum residues
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/206 Asphaltenes
• CPC Class Codes: C10G 2300/4056 Retrofitting operations
• CPC Class Codes: C10G 2300/70 Catalyst aspects
• CPC Class Codes: C10G 2300/703 Activation
• CPC Class Codes: C10G 2300/802 Diluents
• CPC Class Codes: C10G 45/04 characterised by the catalyst used
• CPC Class Codes: C10G 45/16 suspended in the oil, e.g. slurries
• CPC Class Codes: C10G 45/34 characterised by the catalyst used
• CPC Class Codes: C10G 45/46 characterised by the catalyst used
• CPC Class Codes: C10G 45/56 with moving solid particles
• CPC Class Codes: C10G 47/06 Sulfides
• CPC Class Codes: C10G 47/26 suspended in the oil, e.g. slurries
• CPC Class Codes: C10G 49/005 Inhibiting corrosion in hydrotreatment processes
• CPC Class Codes: C10G 49/12 : suspended in the oil, e.g. slurries
• CPC Class Codes: C10G 65/00 : Treatment of hydrocarbon oils by two or more hydrotreatment processes only
• CPC Class Codes: C10G 65/02 : plural serial stages only
• CPC Class Codes: C10G 67/08 : including acid treatment as the refining step in the absence of hydrogen

Abstract

A hydroprocessing system involves introducing heavy oil and in situ formed metal sulfide catalyst particles, or a catalyst precursor capable of forming metal sulfide catalyst particles in situ within the heavy oil, into a hydroprocessing reactor. The metal sulfide catalyst particles are formed in situ by 1) premixing a catalyst precursor with a hydrocarbon diluent to form a precursor mixture, 2) mixing the precursor mixture with heavy oil to form a conditioned feedstock, and 3) heating the conditioned feedstock to decompose the catalyst precursor and cause or allow metal from the precursor to react with sulfur in the heavy oil to form the metal sulfide catalyst particles in situ in the heavy oil. The in situ formed metal sulfide catalyst particles catalyze beneficial upgrading reactions between the heavy oil and hydrogen and eliminates or reduces formation of coke precursors and sediment.

Claims

1. A system for hydroprocessing heavy oil, comprising:

a hydroprocessing reactor comprised of;

a reaction chamber operating at hydroprocessing conditions;

an input port through which heavy oil is fed into the reaction chamber;

an output port through which upgraded hydrocarbon material is withdrawn from the reaction chamber;

a liquid hydrocarbon phase within the reaction chamber comprised of heavy oil and upgraded hydrocarbon material;

metal sulfide catalyst particles dispersed in the liquid hydrocarbon phase; and

a gaseous phase comprised of hydrogen gas dispersed in the liquid hydrocarbon phase; and

an in situ catalyst formation system comprised of;

a catalyst precursor;

a hydrocarbon diluent;

a heavy oil feedstock separate from the hydrocarbon diluent;

a first mixing vessel configured to receive the catalyst precursor and the hydrocarbon diluent and mix them below a temperature at which a significant portion of the catalyst precursor decomposes to form a diluted precursor mixture comprising mixture products of the catalyst precursor and the hydrocarbon diluent;

a second mixing vessel, downstream from the first mixing vessel and upstream from the hydroprocessing reactor, configured to receive the diluted precursor mixture and the heavy oil feedstock and mix them prior to heating to a temperature at which a substantial portion of the catalyst precursor decomposes to form a conditioned feedstock comprising mixture products of the catalyst precursor, the hydrocarbon diluent, and the heavy oil feedstock; and

a heater, downstream from the second mixing vessel and upstream from the hydroprocessing reactor and/or that forms part of the hydroprocessing reactor, that heats the conditioned feedstock to decompose the catalyst precursor so that metal from the decomposed catalyst precursor reacts with sulfur in the heated feedstock to form metal sulfide catalyst particles in situ within the heated feedstock.

3. A system as in claim 1 or 2, wherein the heavy oil feedstock comprises at least one of heavy crude oil, oil sand bitumen, atmospheric tower bottoms, vacuum tower bottoms, resid, visbreaker bottoms, coal tar, heavy oil from oil shale, or liquefied coal.

4. A system as in claim 1 or 2, wherein the heavy oil feedstock comprises at least about 95% by weight of hydrocarbons having a boiling point of at least about 524°

C.

5. A system as in claim 1 or 2, wherein the catalyst precursor is oil soluble.

6. A system as in claim 5, wherein the hydrocarbon diluent comprises at least one of hydrocarbon oil, vacuum gas oil, decant oil, cycle oil, or light gas oil.

7. A system as in claim 1 or 2, wherein the catalyst precursor comprises at least one transition metal and at least one organic moiety comprising or derived from octanoic acid, 2-ethylhexanoic acid, naphthalic acid, pentacarbonyl, or hexacarbonyl.

8. A system as in claim 7, wherein the catalyst precursor comprises at least one of molybdenum 2-ethylhexanoate, molybdenum naphthanate, molybdenum hexacarbonyl, vanadium octoate, vanadium naphthanate, or iron pentacarbonyl.

9. A system as in claim 1 or 2, wherein the first mixing vessel is configured to receive and mix the hydrocarbon diluent and the catalyst precursor at a temperature in a range of about 25°

C. to about 250°

C., wherein the second mixing vessel is configured to receive and mix the diluted precursor mixture and the heavy oil feedstock at a temperature in a range of about 25°

C. to about 350°

C., and wherein the heater is configured to receive and heat the conditioned feedstock to a temperature in a range of about 275°

C. to about 450°

C.

10. A system as in claim 1 or 2, wherein the first mixing vessel is configured to receive and mix the hydrocarbon diluent and the catalyst precursor at a temperature in a range of about 50°

C. to about 200°

C., wherein the second mixing vessel is configured to receive and mix the diluted precursor mixture and the heavy oil feedstock at a temperature in a range of about 50°

C. to about 300°

C., and wherein the heater is configured to receive and heat the conditioned feedstock to a temperature in a range of about 300°

C. to about 440°

C.

11. A system as in claim 1 or 2, wherein the first mixing vessel is configured to receive and mix the hydrocarbon diluent and the catalyst precursor at a temperature in a range of about 75°

C. to about 150°

C., wherein the second mixing vessel is configured to receive and mix the diluted precursor mixture and the heavy oil feedstock at a temperature in a range of about 75°

C. to about 250°

C., and wherein the heater is configured to receive and heat the conditioned feedstock to a temperature in a range of about 375°

C. to about 420°

C.

12. A system as in claim 1 or 2, wherein the first mixing vessel is configured to receive and mix the diluent and the catalyst precursor for a time period in a range of about 1 second to about 20 minutes, and wherein the second mixing vessel is configured to receive and mix the diluted precursor mixture and the heavy oil feedstock for a time period in a range of about 1 second to about 20 minutes.

13. A system as in claim 1 or 2, wherein the first mixing vessel is configured to receive and mix the diluent and the catalyst precursor for a time period in a range of about 1 second to about 5 minutes, and wherein the second mixing vessel is configured to receive and mix the diluted precursor mixture and the heavy oil feedstock for a time period in a range of about 1 second to about 10 minutes.

14. A system as in claim 1 or 2, wherein the first mixing vessel is configured to receive and mix the diluent and the catalyst precursor for a time period in a range of about 1 second to about 5 minutes, and wherein the second mixing vessel is configured to receive and mix the diluted precursor mixture and the heavy oil feedstock for a time period in a range of about 1 second to about 3 minutes.

15. A system as in claim 1, wherein the heater is positioned upstream from the hydroprocessing reactor so as to form at least a portion of the metal sulfide catalyst particles in situ in the heated feedstock and upstream from the hydroprocessing reactor.

16. A system as in claim 1 or 2, wherein the system is configured so that at least a portion of the metal sulfide catalyst particles are formed in situ within the hydroprocessing reactor.

17. A system as in claim 1 or 2, wherein the system is configured so that the in situ formed metal sulfide catalyst particles comprise colloidal or molecular catalyst particles less than 1 micron in size.

18. A system as in claim 17, wherein the colloidal or molecular catalyst particles are less than about 100 nm in size.

19. A system as in claim 1 or 2, wherein the hydroprocessing reactor is a slurry phase reactor in which the in situ formed metal sulfide catalyst particles are the sole or primary hydroprocessing catalyst within the slurry phase reactor.

20. A system as in claim 1 or 2, wherein the hydroprocessing reactor is an ebullated bed reactor that operates using a dual catalyst system comprising a supported ebullated bed catalyst within an expanded catalyst zone within the reaction chamber and the in situ formed metal sulfide catalyst particles dispersed throughout the reaction chamber, including supported catalyst-free zones above and below the expanded catalyst zone.

21. A system as in claim 20, wherein the in situ formed metal sulfide catalyst particles extend the useful life of the supported ebullated bed catalyst compared to an ebullated bed reactor operating in the absence of the in situ formed metal sulfide catalyst particles.

22. A system as in claim 1 or 2, wherein the hydroprocessing reactor is a fixed bed reactor that operates using a dual catalyst system comprising a supported fixed bed catalyst and the in situ formed metal sulfide catalyst particles.

23. A system as in claim 22, wherein the in situ formed metal sulfide catalyst particles extending the useful life of the supported fixed bed catalyst compared to a fixed bed reactor operating in the absence of the in situ formed metal sulfide catalyst particles.

24. A system as in claim 1 or 2, wherein the hydroprocessing reactor is configured to operate at a conversion level of at least 65%.

25. A system as in claim 1 or 2, wherein the hydroprocessing reactor is configured to operate at a conversion level of at least 75%.

26. A system as in claim 1 or 2, wherein the hydroprocessing reactor is configured to operate at a conversion level of at least about 80%.

27. A system as in claim 1 or 2, further comprising a separator, downstream from the hydroprocessing reactor, configured to receive and separate the upgraded hydrocarbon material into a gaseous and lower boiling fraction and a higher boiling liquid fraction containing residual metal sulfide catalyst particles.

28. A system as in claim 27, further comprising a second hydroprocessing reactor, downstream from the separator, configured to receive and convert the higher boiling liquid fraction into a second upgraded hydrocarbon material.

29. A system as in claim 27, further comprising a conduit configured to recycle a portion of the higher boiling liquid fraction and the residual metal sulfide catalyst particles back to the hydroprocessing reactor.

2. A system for hydroprocessing heavy oil, comprising:

a catalyst precursor;

a hydrocarbon diluent;

a heavy oil feedstock separate from the hydrocarbon diluent;

a first mixing vessel configured for receiving and mixing the catalyst precursor with the hydrocarbon diluent below a temperature at which a significant portion of the catalyst precursor decomposes to form a diluted precursor mixture comprising mixture products of the catalyst precursor and the hydrocarbon diluent;

a second mixing vessel, downstream from the first mixing vessel, configured for receiving and mixing the diluted precursor mixture with the heavy oil feedstock without heating to a temperature at which a substantial portion of the catalyst precursor decomposes to form a conditioned feedstock comprising mixture products of the catalyst precursor, the hydrocarbon diluent, and the heavy oil feedstock;

a pre-heater, downstream from the second mixing vessel, configured for receiving and heating the conditioned feedstock to decompose the catalyst precursor so that metal from the decomposed catalyst precursor reacts with sulfur in the heated feedstock to form metal sulfide catalyst particles in situ within the heated feedstock; and

a hydroprocessing reactor, downstream from the pre-heater, comprised of a reaction chamber operating at hydroprocessing conditions, an input port configured for introducing the heated feedstock and in situ formed metal sulfide catalyst particles into the reaction chamber, and an output port for withdrawing upgraded hydrocarbon material formed within the reaction chamber.

30. A system for hydroprocessing heavy oil, comprising:

a hydroprocessing reactor configured to operate at hydroprocessing conditions and being comprised of a reaction chamber, an input port for feeding heavy oil into the reaction chamber, and an output port for withdrawing upgraded hydrocarbon material from the reaction chamber;

a first mixing vessel upstream from the hydroprocessing reactor configured to receive a catalyst precursor and a hydrocarbon diluent and mix them below a temperature at which a significant portion of the catalyst precursor decomposes to form a diluted precursor mixture comprising mixture products of the catalyst precursor and the hydrocarbon diluent;

a second mixing vessel, downstream from the first mixing vessel and upstream from the hydroprocessing reactor, configured to receive the diluted precursor mixture and a heavy oil feedstock separate from the hydrocarbon diluent and mix them without heating to a temperature at which a substantial portion of the catalyst precursor decomposes to form a conditioned feedstock comprising mixture products of the catalyst precursor, the hydrocarbon diluent, and the heavy oil feedstock; and

a heater, downstream from the second mixing vessel and upstream from hydroprocessing reactor and/or that forms part of the hydroprocessing reactor, for receiving and heating a conditioned feedstock to decompose a catalyst precursor and cause or allow metal from the decomposed catalyst precursor to react with sulfur in a heated feedstock to form metal sulfide catalyst particles in situ within the heated feedstock.

31. A system as in claim 30, wherein the catalyst precursor is oil soluble and wherein the hydrocarbon diluent comprises at least one of hydrocarbon oil, vacuum gas oil, decant oil, cycle oil, or light gas oil.

32. A system as in claim 31, wherein the catalyst precursor is selected from the group of molybdenum 2-ethylhexanoate, molybdenum naphthanate, molybdenum hexacarbonyl, vanadium octoate, vanadium naphthanate, and iron pentacarbonyl.

33. A system as in claim 30, wherein the first mixing vessel is configured to receive and mix the hydrocarbon diluent and the catalyst precursor for a time period in a range of about 1 second to about 5 minutes, and wherein the second mixer is configured to receive and mix the diluted precursor mixture and the heavy oil feedstock for a time period in a range of about 1 second to about 10 minutes.

34. A system as in claim 30, wherein the heater is positioned upstream from the hydroprocessing reactor and configured to form metal sulfide catalyst particles in situ upstream from the hydroprocessing reactor.

35. A system as in claim 30, wherein the heater forms part of the hydroprocessing reactor so as to form metal sulfide catalyst particles in situ within the hydroprocessing reactor.

36. A system as in claim 30, wherein the system is configured to form metal sulfide catalyst particles comprising colloidal or molecular catalyst particles less than 1 micron in size.

37. A system as in claim 30, wherein the hydroprocessing reactor is a slurry phase reactor in which metal sulfide catalyst particles formed in situ in the heavy oil are the sole or primary hydroprocessing catalyst within the slurry phase reactor.

38. A system as in claim 30, wherein the hydroprocessing reactor is an ebullated bed reactor configured to operate using a dual catalyst system comprised of a supported ebullated bed catalyst within an expanded catalyst zone of the reaction chamber and metal sulfide catalyst particles formed in situ in the heavy oil are dispersed throughout the reaction chamber, including supported catalyst-free zones above and below the expanded catalyst zone.

39. A system as in claim 30, wherein the hydroprocessing reactor is a fixed bed reactor configured to operate using a dual catalyst system comprising a supported fixed bed catalyst and metal sulfide catalyst particles formed in situ in the heavy oil.

40. A system as in claim 30, further comprising a separator, downstream from the hydroprocessing reactor, configured to separate an upgraded hydrocarbon material into a gaseous and lower boiling fraction and a higher boiling liquid fraction containing residual metal sulfide catalyst particles.

41. A system as in claim 40, further comprising a second hydroprocessing reactor, downstream from the separator, configured to receive and convert a higher boiling liquid fraction into a second upgraded hydrocarbon material.

42. A system as in claim 41, further comprising a conduit configured to recycle a portion of a higher boiling liquid fraction containing residual metal sulfide catalyst particles back to the hydroprocessing reactor.

43. A system for hydroprocessing heavy oil, comprising:

a heavy oil feedstock comprised of hydrocarbons having a boiling point greater than 343°

C. and metal sulfide catalyst particles dispersed in the heavy oil feedstock and having been formed from an oil-soluble catalyst precursor in situ within the heavy oil feedstock;

a first mixing vessel configured to receive the oil-soluble catalyst precursor and a hydrocarbon diluent separate from the heavy oil feedstock and mix them below a temperature at which a significant portion of the catalyst precursor decomposes to form a diluted precursor mixture comprising mixture products of the catalyst precursor and the hydrocarbon diluent;

a second mixing vessel, downstream from the first mixing vessel, configured to receive the diluted precursor mixture and the heavy oil feedstock and mix them without heating to a temperature at which a substantial portion of the catalyst precursor decomposes to form a conditioned feedstock comprising mixture products of the catalyst precursor, the hydrocarbon diluent, and the heavy oil feedstock;

a pre-heater, downstream from the second mixing vessel, configured to heat the conditioned feedstock so as to decompose the oil-soluble catalyst precursor, cause or allow metal from the decomposed catalyst precursor to react with sulfur in the heavy oil feedstock, and form the metal sulfide catalyst particles in situ within the heavy oil feedstock; and

a hydroprocessing reactor configured to receive the heavy oil feedstock containing the in situ formed metal sulfide catalyst particles and form an upgraded hydrocarbon material, the metal sulfide catalyst particles catalyzing reactions between hydrogen and hydrocarbon free radicals within the hydroprocessing reactor while reducing or eliminating formation of coke precursors and sediment.

44. A system as in claim 43, wherein the first mixing vessel is configured to mix the diluent and the oil-soluble catalyst precursor for a time period in a range of about 1 second to about 10 minutes, and wherein the second mixing vessel is configured to mix the diluted precursor mixture with the entirety of the heavy oil feedstock for a time period in a range of about 1 second to about 5 minutes.

45. A system as in claim 43, wherein the first mixing vessel is configured to mix the diluent and oil-soluble catalyst precursor for a time period in a range of about 1 second to about 5 minutes, and wherein the second mixing vessel is configured to mix the diluted precursor mixture with the entirety of the heavy oil feedstock for a time period in a range of about 1 second to about 3 minutes.

46. A system as in claim 43, wherein the in situ formed metal sulfide catalyst particles comprise colloidal or molecular catalyst particles less than 1 micron in size.

47. A system as in claim 43, wherein the hydroprocessing reactor is a slurry phase reactor in which the in situ formed metal sulfide catalyst particles are the sole or primary hydroprocessing catalyst within the slurry phase reactor.

48. A system as in claim 43, wherein the hydroprocessing reactor is an ebullated bed reactor that operates using a dual catalyst system comprised of a supported ebullated bed catalyst within an expanded catalyst zone of the reaction chamber and the in situ formed metal sulfide catalyst particles dispersed throughout the reaction chamber, including supported catalyst-free zones above and below the expanded catalyst zone.

49. A system as in claim 43, wherein the hydroprocessing reactor is a fixed bed reactor that operates using a dual catalyst system comprising a supported fixed bed catalyst and the in situ formed metal sulfide catalyst particles.