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

• US 20140027344A1
• Filed: 07/30/2012
• Published: 01/30/2014
• Est. Priority Date: 07/30/2012
• Status: Active Grant

• Current Assignee: Hydrocarbon Technology & Innovation, LLC
• Original Assignee: Headwaters Technology Innovation, LLC
• Inventors: Harris, Everette, Gendler, Jeffrey
• Granted Patent: US 9,644,157 B2
• Time in Patent Office: Days
• US Class Current: 208/61
• 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;

heating or maintaining the heavy oil feedstock at a hydrocracking temperature 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 or other coke forming precursors, 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;

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

separating the coke from the upgraded hydrocarbon products.

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 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.

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

12. The method as in claim 1, the upgrading reactions reducing the quantity of asphaltenes or other coke forming precursors by at least 20 wt %.

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

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

15. 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.).

16. 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.).

17. 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.).

18. 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.).

19. 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.).

20. 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.

21. 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.

22. The method as defined in claim 21, the hydrocarbon oil diluent comprising at least one of vacuum gas oil, decant oil, cycle oil, or light gas oil.

23. The method as defined in claim 21, 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.

24. The method as defined in claim 23, the at least one transition metal comprising one or more of Mo, Ni, Co, W, V or Fe.

25. The method as defined in claim 21, 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.

26. The method as defined in claim 21, the ratio of catalyst precursor composition to hydrocarbon oil diluent being in a range of about 1:

100 to about 1;

5.

27. The method as defined in claim 21, 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.

28. The method as defined in claim 21, 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.

29. The method as defined in claim 21, 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.

30. The method as defined in claim 21, 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.

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.

31. 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 that heats or maintains the heavy oil feedstock at a hydrocracking temperature together with hydrogen in order to 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 that separates gaseous and volatile fractions from a liquid hydrocarbon fraction in the upgraded material, the separator 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; and

one or more coking reactors configured to receive and process the liquid hydrocarbon fraction, the one or more coking reactors comprising one or more delayed coking reactors, fluid coking reactors, or Flexicoking®

reactors.

32. The hydroprocessing system according to claim 31, further comprising a second pre-coking hydrocracking reactor downstream of the pre-coking hydrocracking reactor, wherein the second pre-coking hydrocracking reactor further upgrades the upgraded material to form a further upgraded material to be 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.

33. The hydroprocessing system according to claim 31, further comprising a second pre-coking hydrocracking reactor downstream from the separator and a second separator downstream from the second pre-coking hydrocracking reactor, wherein the second pre-coking hydrocracking reactor upgrades the liquid hydrocarbon fraction from the separator to form a further upgraded material to be introduced into the second separator that separates gaseous and volatile fractions from a liquid hydrocarbon fraction in the further upgraded material.