Systems and methods for hydroprocessing heavy oil

• US 10,118,146 B2
• Filed: 11/17/2016
• Issued: 11/06/2018
• Est. Priority Date: 04/28/2004
• Status: Active Grant

• Current Assignee: Hydrocarbon Technology & Innovation, LLC
• Original Assignee: Hydrocarbon Technology & Innovation, LLC
• Inventors: Lott, Roger K., Lee, Lap-Keung
• Primary Examiner(s): ROBINSON, RENEE E
• Application Number:
  US15/354,230
• Publication Number:
  US 20170066978A1
• Time in Patent Office: 719 Days
• 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 system and method for preparing and conditioning a heavy oil feedstock for hydroprocessing in a hydroprocessing system includes forming metal sulfide catalyst particles in situ within the heavy oil feedstock. The metal sulfide catalyst particles are formed in situ by (1) premixing a catalyst precursor with a hydrocarbon diluent to form a diluted precursor mixture, (2) mixing the diluted precursor mixture with the heavy oil feedstock 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 feedstock to form metal sulfide catalyst particles in situ in the heavy oil feedstock. The in situ formed metal sulfide catalyst particles catalyze beneficial upgrading reactions between the heavy oil feedstock and hydrogen and eliminates or reduces formation of coke precursors and sediment.

Claims

1. A system for preparing and conditioning a heavy oil feedstock for hydroprocessing in a hydroprocessing system, 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; and

a heater, downstream from the second mixing vessel and upstream from a hydroprocessing reactor and/or that comprises the hydroprocessing reactor, and which heats the conditioned feedstock and 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.

2. The system of claim 1, 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.

3. The system of claim 1, wherein the heavy oil feedstock comprises at least about 95% by weight of hydrocarbons having a boiling point of at least about 524°

C.

4. The system of claim 1, wherein the catalyst precursor is oil soluble.

5. The system of claim 1, wherein the hydrocarbon diluent comprises at least one of hydrocarbon oil, vacuum gas oil, decant oil, cycle oil, or light gas oil.

6. The system of claim 1, 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, naphthenic acid, pentacarbonyl, or hexacarbonyl.

7. The system of claim 1, wherein the catalyst precursor comprises at least one of molybdenum 2-ethylhexanoate, molybdenum naphthenate, molybdenum hexacarbonyl, vanadium octoate, vanadium naphthenate, or iron pentacarbonyl.

8. The system of claim 1, 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.

9. The system of claim 1, 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.

10. The system of claim 1, 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.

11. The system of claim 1, 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.

12. The system of claim 1, 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.

13. The system of claim 1, 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.

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

15. The system of claim 1, 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.

16. The system of claim 1, 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.

17. The system of claim 16, wherein the colloidal or molecular catalyst particles are less than about 100 nm in size.

18. A system for preparing and conditioning a heavy oil feedstock for hydroprocessing in a hydroprocessing system, comprising:

a first mixing vessel 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, 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 pre-heater, downstream from the second mixing vessel and upstream of a hydroprocessing reactor of the hydroprocessing system, configured to receive and heat 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.

19. The system of claim 18, 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.

20. The system of claim 18, wherein the catalyst precursor is selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthenate, molybdenum hexacarbonyl, vanadium octoate, vanadium naphthenate, and iron pentacarbonyl.

21. The system of claim 18, 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.

22. A system for preparing and conditioning a heavy oil feedstock for hydroprocessing in a hydroprocessing system, 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 oil-soluble catalyst precursor decomposes to form a diluted precursor mixture comprising mixture products of the oil-soluble 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 oil-soluble catalyst precursor decomposes to form a conditioned feedstock comprising mixture products of the oil-soluble catalyst precursor, the hydrocarbon diluent, and the heavy oil feedstock; and

a 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.

23. The system of claim 22, 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.

24. The system of claim 22, 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.

25. The system of claim 22, wherein the in situ formed metal sulfide catalyst particles comprise colloidal or molecular catalyst particles less than 1 micron in size.

26. A method for preparing and conditioning a heavy oil feedstock for hydroprocessing in a hydroprocessing system, comprising:

providing a catalyst precursor, a hydrocarbon diluent, and a heavy oil feedstock separate from the hydrocarbon diluent;

in a first mixing vessel, 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;

in a second mixing vessel, downstream from the first mixing vessel, 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; and

in a heater, downstream from the second mixing vessel and upstream from a hydroprocessing reactor, heating the conditioned feedstock and decomposing 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.

27. A method for preparing and conditioning a heavy oil feedstock for hydroprocessing in a hydroprocessing system, comprising:

in a first mixing vessel, receiving a catalyst precursor and a hydrocarbon diluent and mixing 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;

in a second mixing vessel, downstream from the first mixing vessel, receiving the diluted precursor mixture and a heavy oil feedstock and mixing 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

in a pre-heater, downstream from the second mixing vessel and upstream of a hydroprocessing reactor, 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.

28. A method for preparing and conditioning a heavy oil feedstock for hydroprocessing in a hydroprocessing reactor, comprising:

preparing 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, the metal sulfide catalyst particles being formed from an oil-soluble catalyst precursor in situ within the heavy oil feedstock by;

in a first mixing vessel, receiving and mixing a hydrocarbon diluent and the oil-soluble catalyst precursor below a temperature at which the oil-soluble catalyst precursor decomposes to form a diluted precursor mixture comprising mixture products of the oil-soluble catalyst precursor and the hydrocarbon diluent;

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

in a heater, downstream from the second mixing vessel, heating 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.