Methods and systems for upgrading heavy oil using catalytic hydrocracking and thermal coking

• US 9,644,157 B2
• Filed: 07/30/2012
• Issued: 05/09/2017
• Est. Priority Date: 07/30/2012
• Status: Active Grant

• Current Assignee: Hydrocarbon Technology & Innovation, LLC
• Original Assignee: Headwaters Heavy Oil, LLC (Seven Group Holdings Limited)
• Inventors: Harris, Everette, Gendler, Jeffrey
• Primary Examiner(s): Stein, Michelle
• Application Number:
  US13/561,479
• Publication Number:
  US 20140027344A1
• Time in Patent Office: 1,744 Days
• 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 upgraded material use a colloidal or molecular catalyst dispersed within heavy oil feedstock, pre-coking hydrocracking reactor, separator, and 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 with the colloidal or molecular catalyst, as compared to a conventional hydrocracking process or a conventional thermal coking process.

Claims

1. A method for hydroprocessing a heavy oil feedstock to increase production of upgraded liquid hydrocarbon products and reduce coke formation, the method comprising:

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

C. (650°

F.), including asphaltenes or other coke forming precursors, and a colloidal or molecular catalyst formed in situ within and dispersed throughout the heavy oil feedstock;

introducing the heavy oil feedstock and hydrogen into a pre-coking hydrocracking reactor;

hydrocracking the heavy oil feedstock at hydrocracking conditions to cause fragmentation of larger hydrocarbon molecules into smaller molecular fragments having a fewer number of carbon atoms and form hydrocarbon free radicals from the heavy oil feedstock, the colloidal or molecular catalyst catalyzing upgrading reactions between hydrogen and the hydrocarbon free radicals to yield an upgraded material, the upgrading reactions reducing the quantity of asphaltenes or other coke forming precursors by at least 20%, increasing the hydrogen to carbon ratio in the upgraded material, and decreasing the boiling points of hydrocarbons in the upgraded material compared to the heavy oil feedstock;

transferring the upgraded material, together with residual colloidal or molecular catalyst and hydrogen, to a separator to separate gaseous and volatile fractions from a liquid hydrocarbon fraction, the liquid hydrocarbon fraction comprising residual catalyst metal;

introducing at least a portion of the liquid hydrocarbon fraction and residual catalyst metal into one or more coking reactors and causing thermal-cracking of the liquid hydrocarbon fraction to form upgraded hydrocarbon products and coke;

separating the coke from the upgraded hydrocarbon products; and

further processing the upgraded hydrocarbon products to form further processed hydrocarbons and without recycling any further processed hydrocarbons to the hydrocracking reactor.

2. The method as in claim 1, wherein the separator comprises a hot separator.

3. The method as in claim 1, wherein the separator comprises a distillation tower.

4. The method as in claim 1, wherein the separator comprises a hot separator and a distillation tower.

5. The method as in claim 1, wherein the portion of the liquid hydrocarbon fraction introduced into the coking reactor comprises a vacuum reduced crude.

6. The method as defined in claim 1, the pre-coking hydrocracking reactor comprising at least one of a slurry phase reactor, an ebullated bed reactor, or a fixed bed reactor.

9. The method as in claim 1, wherein the one or more coking reactors comprise one or more delayed coking reactors, fluid coking reactors, or Flexicoking®

reactors.

10. The method as defined in claim 1, wherein the heavy oil feedstock comprises at least about 10 wt % asphaltenes or other coke forming precursors.

11. The method as in claim 1, the upgrading reactions reducing the quantity of asphaltenes or other coke forming precursors by at least 40 wt %.

12. The method as in claim 1, the upgrading reactions reducing the quantity of asphaltenes or other coke forming precursors by at least 60 wt %.

13. The method as in claim 1, the method converting at least 60 wt % of hydrocarbons having a boiling point of at least 524°

C. (975°

F.).

14. The method as in claim 1, the method converting at least 70 wt % of hydrocarbons having a boiling point of at least 524°

C. (975°

F.).

15. The method as in claim 1, the method converting at least 80 wt % of hydrocarbons having a boiling point of at least 524°

C. (975°

F.).

16. The method as in claim 1, wherein the method converts at least 85 wt % of hydrocarbons having a boiling point of at least 524°

C. (975°

F.).

17. The method as in claim 1, wherein the method yields at least 80 wt % of C4+hydrocarbons and a boiling point of less than about 524°

C. (975°

F.).

18. The method as in claim 1, wherein the method reduces coke formation by at least 25 wt % compared to coking in the absence of hydrocracking catalyzed by the molecular or colloidal catalyst.

19. The method as defined in claim 1, the colloidal or molecular catalyst in the heavy oil feedstock being formed by:

mixing a hydrocarbon oil diluent and an oil soluble catalyst precursor at a temperature below which a significant portion of the catalyst precursor starts to decompose to form a diluted precursor mixture;

mixing the diluted precursor mixture with a heavy oil feedstock in a manner so as to yield a conditioned feedstock that forms the colloidal or molecular catalyst upon decomposing the catalyst precursor and allowing metal liberated therefrom to react with sulfur liberated from the feedstock; and

heating the conditioned feedstock so as to decompose the catalyst precursor and allow metal liberated from the decomposed catalyst precursor to react with sulfur liberated from the heavy oil feedstock so as to form the colloidal or molecular catalyst.

20. The method as defined in claim 19, the hydrocarbon oil diluent comprising at least one of vacuum gas oil, decant oil, cycle oil, or light gas oil.

21. The method as defined in claim 19, the catalyst precursor comprising 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.

22. The method as defined in claim 21, the at least one transition metal comprising one or more of Mo, Ni, Co, W, V or Fe.

23. The method as defined in claim 19, 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.

24. The method as defined in claim 19, the ratio of catalyst precursor composition to hydrocarbon oil diluent being in a range of about 1:

100 to about 1;

5.

25. The method as defined in claim 19, the hydrocarbon oil diluent and catalyst precursor composition being mixed at temperature in a range of about 25°

C. to about 250°

C., the diluted precursor mixture and heavy oil feedstock being mixed at a temperature in a range of about 25°

C. to about 350°

C., and the conditioned feedstock being heated to a temperature in a range of about 275°

C. to about 375°

C.

26. The method as defined in claim 19, 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.

27. The method as defined in claim 19, the hydrocarbon oil diluent and catalyst precursor composition being mixed for a time period in a range of about 1 second to about 20 minutes, and the diluted precursor mixture and heavy oil feedstock being mixed for a time period in a range of about 1 second to about 20 minutes.

28. The method as defined in claim 19, the hydrocarbon oil diluent and catalyst precursor composition being mixed for a time period in a range of about 20 seconds to about 3 minutes, and the diluted precursor mixture and heavy oil feedstock being mixed for a time period in a range of about 20 seconds to about 5 minutes.

29. The method as defined in claim 1, further comprising processing the upgraded hydrocarbon products downstream from the pre-coking hydrocracking reactor and the one or more coking reactors.

34. The method as in 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.

35. The method as in claim 1, wherein the hydrocracking temperature is in a range of about 395°

C. to about 460°

C., the upgrading reactions reducing the quantity of asphaltenes or other coke forming precursors by at least 20 wt %.

7. The method as in 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.

8. The method as defined in claim 7, the slurry phase reactor further comprising a recycle channel, a recycling pump, and a distributor grid plate.

30. A method for hydroprocessing a heavy oil feedstock to increase production of upgraded liquid hydrocarbon products and reduce coke formation, the method comprising:

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

C. (650°

F.) and including asphaltenes, and a colloidal or molecular catalyst formed in situ within and dispersed throughout the heavy oil feedstock, wherein the heavy oil feedstock is selected from the group consisting of heavy crude oil, oil sand bitumen, atmospheric tower bottoms, vacuum tower bottoms, resid, visbreaker bottoms, coal tar, heavy oil from oil shale, and liquefied coal, with the proviso that the heavy oil feedstock does not comprise coker gas oil;

introducing the heavy oil feedstock and hydrogen into a pre-coking hydrocracking reactor;

hydrocracking the heavy oil feedstock at hydrocracking conditions to cause fragmentation of at least some of the asphaltenes and to form hydrocarbon free radicals from the heavy oil feedstock, the colloidal or molecular catalyst catalyzing upgrading reactions between hydrogen and the hydrocarbon free radicals to yield an upgraded material, the upgrading reactions reducing the quantity of asphaltenes by at least 20%, increasing the hydrogen to carbon ratio in the upgraded material, and decreasing the boiling points of hydrocarbons in the upgraded material compared to the heavy oil feedstock;

transferring the upgraded material, together with residual colloidal or molecular catalyst and hydrogen, to a separator to separate gaseous and volatile fractions from a liquid hydrocarbon fraction, the liquid hydrocarbon fraction comprising residual catalyst metal;

introducing at least a portion of the liquid hydrocarbon fraction and residual catalyst metal into one or more coking reactors and causing thermal-cracking of the liquid hydrocarbon fraction to form upgraded hydrocarbon products and coke;

separating the coke from the upgraded hydrocarbon products, the upgraded hydrocarbon products including coker gas oil; and

further processing an entirety of the upgraded hydrocarbon products, including the coker gas oil, downstream from the pre-coking hydrocracking reactor to form one or more further processed hydrocarbons.

31. The method as defined in claim 30, wherein the heavy oil feedstock consists essentially 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.

32. The method as in claim 30, the upgrading reactions reducing the quantity of asphaltenes by at least 40 wt %.

33. The method as in claim 30, the upgrading reactions reducing the quantity of asphaltenes by at least 60 wt %.

36. The method as in claim 30, wherein the hydrocracking temperature is in a range of about 395°

C. to about 460°

C., the upgrading reactions reducing the quantity of asphaltenes or other coke forming precursors by at least 20 wt %.