APPARATUS AND SYSTEMS FOR UPGRADING HEAVY OIL USING CATALYTIC HYDROCRACKING AND THERMAL COKING

• US 20150361360A1
• Filed: 08/26/2015
• Published: 12/17/2015
• Est. Priority Date: 07/30/2012
• Status: Active Grant

• Current Assignee: Headwaters Heavy Oil, LLC (Seven Group Holdings Limited)
• Original Assignee: Headwaters Heavy Oil, LLC (Seven Group Holdings Limited)
• Inventors: HARRIS, EVERETTE, GENDLER, JEFFREY
• Granted Patent: US 9,969,946 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B01J 23/28 Molybdenum
• CPC Class Codes: B01J 27/043 with iron group metals or platinum group metals
• CPC Class Codes: B01J 27/047 with chromium, molybdenum, tungsten or polonium
• CPC Class Codes: B01J 27/051 Molybdenum
• CPC Class Codes: B01J 35/50 characterised by their shape or configuration
• CPC Class Codes: B01J 35/66 Pore distribution
• CPC Class Codes: B01J 35/69 bimodal
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/086 Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
• CPC Class Codes: B01J 37/20 Sulfiding
• CPC Class Codes: C10B 55/00 Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material cracking oils C10G
• CPC Class Codes: C10B 57/045 containing mineral oils, bitumen, tar or the like or mixtures thereof
• CPC Class Codes: C10G 2300/206 Asphaltenes
• CPC Class Codes: C10G 47/12 Inorganic carriers
• CPC Class Codes: C10G 69/06 including at least one step of thermal cracking in the absence of hydrogen
• CPC Class Codes: C10G 9/005 Coking (in order to produce liquid products mainly)

Abstract

Methods and systems for hydroprocessing heavy oil feedstocks to form an upgraded material involve the use of a colloidal or molecular catalyst dispersed within a heavy oil feedstock, a pre-coking hydrocracking reactor, a separator, and a coking reactor. The colloidal or molecular catalyst promotes upgrading reactions that reduce the quantity of asphaltenes or other coke forming precursors in the feedstock, increase hydrogen to carbon ratio in the upgraded material, and decrease boiling points of hydrocarbons in the upgraded material. The methods and systems can be used to upgrade vacuum tower bottoms and other low grade heavy oil feedstocks. The result is one or more of increased conversion level and yield, improved quality of upgraded hydrocarbons, reduced coke formation, reduced equipment fouling, processing of a wider range of lower quality feedstocks, and more efficient use of supported catalyst if used in combination with the colloidal or molecular catalyst, as compared to a conventional hydrocracking process or a conventional thermal coking process.

Claims

1. A hydroprocessing system for hydroprocessing a heavy oil feedstock to form coke and upgraded hydrocarbon products, comprising:

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

C. and a colloidal or molecular catalyst dispersed throughout the feedstock;

a pre-coking hydrocracking reactor configured to heat or maintain the heavy oil feedstock at a hydrocracking temperature together with hydrogen and convert at least a portion of higher boiling hydrocarbons in the heavy oil feedstock to lower boiling hydrocarbons and thereby form an upgraded material, the pre-coking hydrocracking reactor comprised of (i) an inlet port at a bottom of the reactor into which the heavy oil feedstock and hydrogen are introduced and (ii) an outlet port at a top of the reactor from which the upgraded material, colloidal or molecular catalyst, and hydrogen are withdrawn;

a separator configured to separate gaseous and volatile fractions from a liquid hydrocarbon fraction in the upgraded material, the separator being comprised of (i) an inlet through which the upgraded material is introduced into the separator, (ii) a first outlet through which the gaseous and volatile fractions are withdrawn, and (iii) a second outlet through which the liquid hydrocarbon fraction is withdrawn;

one or more coking reactors configured to receive and process the liquid hydrocarbon fraction from the separator; and

a separator configured to remove coke from a liquid hydrocarbon product.

2. The hydroprocessing 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 hydroprocessing system of claim 1, wherein the heavy oil feedstock comprises at least about 10 wt % asphaltenes or other coke forming precursors.

4. The hydroprocessing system of claim 1, wherein the pre-coking hydrocracking reactor comprises at least one of a slurry phase reactor, an ebullated bed reactor, or a fixed bed reactor.

5. The hydroprocessing system of claim 1, wherein the pre-coking hydrocracking reactor is a slurry phase reactor including (i) an inlet port at a bottom of the slurry phase reactor into which the heavy oil feedstock and hydrogen are introduced and (ii) an outlet port at a top of the slurry phase reactor from which the upgraded material, colloidal or molecular catalyst, and hydrogen are withdrawn.

6. The hydroproces sing system of claim 5, the slurry phase reactor further comprising a recycle channel, a recycling pump, and a distributor grid plate.

7. The hydroprocessing system of claim 1, wherein the separator comprises a hot separator.

8. The hydroprocessing system of claim 1, wherein the separator comprises a distillation tower.

9. The hydroprocessing system of claim 1, wherein the separator comprises a hot separator and a distillation tower.

10. The hydroprocessing system of claim 1, wherein the liquid hydrocarbon fraction from the separator and introduced into the one or more coking reactors comprises a vacuum reduced crude.

11. The hydroprocessing system of claim 1, wherein the one or more coking reactors comprise one or more delayed coking reactors, fluid coking reactors, or Flexicoking®

reactors.

12. The hydroprocessing system of claim 1, the system comprising a single pre-coking hydrocracking reactor configured to receive and process the liquid hydrocarbon fraction from the separator.

13. The hydroprocessing system of claim 1, the system comprising:

a pre-coking hydrocracking reactor configured to receive and process the liquid hydrocarbon fraction from the separator to form the upgraded material; and

a second pre-coking hydrocracking reactor downstream of the first pre-coking hydrocracking reactor, wherein the second pre-coking hydrocracking reactor is configured to further upgrade the upgraded material prior to being introduced into the separator, the second hydrocracking reactor comprising at least one of a slurry phase reactor, an ebullated bed reactor, or a fixed bed reactor.

14. The hydroprocessing system of claim 1, further comprising:

a secondary pre-coking hydrocracking reactor downstream from the separator; and

a secondary separator downstream from the secondary pre-coking hydrocracking reactor,

wherein the second pre-coking hydrocracking reactor is configured to upgrade the liquid hydrocarbon fraction from the separator to form a further upgraded material to be introduced into the secondary separator, which is configured to separate gaseous and volatile fractions from a liquid hydrocarbon fraction in the further upgraded material.

15. The hydroprocessing system of claim 1, the pre-coking hydrocracking reactor being configured to perform upgrading reactions that reduce the quantity of asphaltenes or other coke forming precursors by at least 20 wt %.

16. The hydroprocessing system of claim 1, the pre-coking hydrocracking reactor being configured to perform upgrading reactions that reduce the quantity of asphaltenes or other coke forming precursors by at least 40 wt %.

17. The hydroprocessing system of claim 1, the pre-coking hydrocracking reactor being configured to perform upgrading reactions that reduce the quantity of asphaltenes or other coke forming precursors by at least 60 wt %.

18. The hydroprocessing system of claim 1, the hydroprocessing system being configured to convert at least 60 wt % of hydrocarbons having a boiling point of at least 524°

C. (975°

F.).

19. The hydroprocessing system of claim 1, the hydroprocessing system being configured to convert at least 70 wt % of hydrocarbons having a boiling point of at least 524°

C. (975°

F.).

20. The hydroprocessing system of claim 1, the hydroprocessing system being configured to convert at least 80 wt % of hydrocarbons having a boiling point of at least 524°

C. (975°

F.).

21. The hydroprocessing system of claim 1, the hydroprocessing system being configured to convert at least 85 wt % of hydrocarbons having a boiling point of at least 524°

C. (975°

F.).

22. The hydroprocessing system of claim 1, the hydroprocessing system being configured to yield at least 80 wt % of C4+ hydrocarbons and a boiling point of less than about 524°

C. (975°

F.).

23. The hydroprocessing system of claim 1, the hydroprocessing system being configured to reduce coke formation by at least 25 wt % compared to coking in the absence of hydrocracking catalyzed by the molecular or colloidal catalyst.

24. The hydroprocessing system of claim 1, further comprising:

a pre-mixer configured to mix a hydrocarbon oil diluent and an oil soluble catalyst precursor at a temperature below a decomposition temperature of the catalyst precursor starts and form a diluted precursor mixture;

a second mixer, downstream from the pre-mixer, configured the mix the diluted precursor mixture with a heavy oil feedstock to yield a conditioned feedstock that is configured to form the colloidal or molecular catalyst upon heating and decomposing the catalyst precursor and allowing metal liberated therefrom to react with sulfur liberated from the feedstock; and

a heater configured to heat the conditioned feedstock, decompose the catalyst precursor, and cause or allow metal liberated from the decomposed catalyst precursor to react with sulfur liberated from the heavy oil feedstock and form the colloidal or molecular catalyst.

25. The hydroprocessing system of claim 24, wherein the hydrocarbon oil diluent comprises at least one of vacuum gas oil, decant oil, cycle oil, or light gas oil.

26. The hydroprocessing system of claim 24, wherein the catalyst precursor comprises at least one transition metal and at least one organic moiety comprising or derived from 3-cyclopentylpropionic acid, cyclohexanebutyric acid, biphenyl-2-carboxylic acid, 4-heptylbenzoic acid, 5-phenylvaleric acid, geranic acid, 10-undecenoic acid, dodecanoic acid, octanoic acid, 2-ethylhexanoic acid, naphthanic acid, pentacarbonyl, or hexacarbonyl.

27. The hydroprocessing system of claim 26, wherein the at least one transition metal comprises one or more of Mo, Ni, Co, W, V or Fe.

28. The hydroprocessing system of claim 24, the catalyst precursor comprising at least one of molybdenum 3-cyclopentylpropionate, molybdenum cyclohexanebutanoate, molybdenum biphenyl-2-carboxylate, molybdenum 4-heptylbenzoate, molybdenum 5-phenylpentanoate, molybdenum geranate, molybdenum 10-undecenoate, molybdenum dodecanoate, molybdenum 2-ethylhexanoate, molybdenum naphthanate, molybdenum hexacarbonyl, vanadium octoate, vanadium naphthanate, or iron pentacarbonyl.

29. The hydroprocessing system of claim 24, the ratio of catalyst precursor composition to hydrocarbon oil diluent being in a range of about 1:

100 to about 1;

5.

30. The hydroprocessing system of claim 24, wherein the pre-mixer is configured to mix the hydrocarbon oil diluent and catalyst precursor composition at temperature in a range of about 25°

C. to about 250°

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

C. to about 350°

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

C. to about 375°

C.

31. The hydroprocessing system of claim 24, wherein the pre-mixer is configured to mix the hydrocarbon oil diluent and catalyst precursor composition at temperature in a range of about 75°

C. to about 150°

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

C. to about 250°

C., and wherein the heater is configured to heat the conditioned feedstock to a temperature in a range of about 310°

C. to about 360°

C.

32. The hydroprocessing system of claim 24, the hydrocarbon oil diluent and catalyst precursor composition being mixed at temperature in a range of about 75°

C. to about 150°

C., the diluted precursor mixture and heavy oil feedstock being mixed at a temperature in a range of about 75°

C. to about 250°

C., and the conditioned feedstock being heated to a temperature in a range of about 310°

C. to about 360°

C.

33. The hydroprocessing system of claim 24, wherein the pre-mixer is configured to mix the hydrocarbon oil diluent and catalyst precursor for a time period in a range of about 1 second to about 20 minutes, and wherein the mixer is configured to mix the diluted precursor mixture and heavy oil feedstock for a time period in a range of about 1 second to about 20 minutes.

34. The hydroprocessing system of claim 24, wherein the pre-mixer is configured to mix the hydrocarbon oil diluent and catalyst precursor for a time period in a range of about 1 second to about 10 minutes, and wherein the mixer is configured to mix the diluted precursor mixture and heavy oil feedstock for a time period in a range of about 1 second to about 10 minutes.