IP Library Granted Patent US 9,169,448
Granted Patent B2
US 9,169,448 · App. 13/451,030 · Granted Oct 27, 2015

In-situ hydrogenation of aromatic compounds for heavy oil upgrading

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Quick Facts
Patent No.
US 9,169,448
App. No.
13/451,030
Granted
Oct 27, 2015
Kind
B2
Abstract

A method for upgrading a heavy oil includes: disposing a catalyst comprising rhodium and a support in a heavy oil environment, the heavy oil environment including a heavy oil comprising an aromatic compound; introducing hydrogen; and hydrogenating the aromatic compound with the catalyst and hydrogen to upgrade the heavy oil to upgraded oil. A method for converting an asphaltene includes: disposing a supported catalyst in a composition comprising an asphaltene, the supported catalyst being a low temperature catalyst; introducing hydrogen; and hydrogenating the asphaltene to convert the asphaltene into a hydrogenated asphaltene.

Claims (47)

1. A method for upgrading a heavy oil, the method comprising:

disposing a catalyst comprising rhodium and a support in a heavy oil environment, the heavy oil environment including a heavy oil comprising an aromatic compound;

introducing hydrogen; and

hydrogenating the aromatic compound with the catalyst and hydrogen to upgrade the heavy oil to provide an upgraded oil;

wherein the rhodium comprises rhodium nanoparticles supported on the support;

and wherein the support comprises hydroxyapatite, fluoroapatite, chloroapatite, bromoapatite, or a combination comprising at least one of the foregoing,

wherein the aromatic compound is asphaltene; and

wherein the method further comprises adjusting a temperature, pressure, and pH of the heavy oil environment to exfoliate particles of the aromatic compound in response to hydrogenating the aromatic compound.

2. The method of claim 1 , wherein the catalyst is rhodium nanoparticles supported on nanocrystalline hydroxyapatite.

3. The method claim 1 , wherein the catalyst is dispersed in a fluid prior to disposing the catalyst in the heavy oil environment.

4. The method of claim 3 , wherein the fluid comprises propane, butane, pentane, dimethyl sulfoxide, tetrahydrofuran, o-dioxane, m-dioxane, p-dioxane, dimethoxyethane, n-methyl-pyrrolidone, n,n-dimethylacetamide, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, dimethylformamide, hexamethylphosphoramide, nitromethane, or a combination comprising at least one of the foregoing.

5. The method of claim 1 , wherein disposing the catalyst further comprises disposing the catalyst on gravel particles in gravel pack, proppant, filter, sand screen, fluid, or a combination comprising at least one of the foregoing.

6. The method of claim 1 , further comprising disposing, in the heavy oil environment, a catalyst promoter which includes a metal, surfactant, or a combination comprising at least one of the foregoing.

7. The method of claim 1 , wherein the upgraded oil comprises hydrogenated asphaltene.

8. The method of claim 1 , wherein the heavy oil environment comprises downhole, a refinery, pre-refinery facility, production zone, formation, reservoir, or a combination comprising at least one of the foregoing.

9. The method of claim 8 , further comprising producing the upgraded oil, wherein hydrogenating occurs prior to producing the upgraded oil.

10. The method of claim 8 , further comprising producing the heavy oil, wherein hydrogenating occurs subsequent to producing the heavy oil.

11. The method of claim 1 , wherein hydrogenating the aromatic compound is at a temperature from 20° C. to 1500° C.

12. The method of claim 1 , wherein the pressure of hydrogen is from 3 atm to 40 atm.

13. The method of claim 1 , wherein hydrogenating the aromatic compound is at a total pressure from 3 atm to 250 atm.

14. The method of claim 1 , wherein the upgraded oil has a greater API gravity than that of the heavy oil.

15. The method of claim 1 , wherein the API gravity of the upgraded oil is greater than that of the heavy oil by at least three degrees.

16. The method of claim 1 , wherein the viscosity of the upgraded oil is less than that of the heavy oil.

17. A method for converting an asphaltene, the method comprising:

disposing a supported catalyst in a composition comprising an asphaltene, the supported catalyst being a low temperature catalyst;

introducing hydrogen; and

hydrogenating the asphaltene to convert the asphaltene into a hydrogenated asphaltene, wherein the supported catalyst comprises rhodium nanoparticles supported on a support; and wherein the support comprises hydroxyapatite, fluoroapatite, chloroapatite, bromoapatite, zeolite, or a combination comprising at least one of the foregoing;

wherein introducing hydrogen comprises generating hydrogen in-situ, or a combination comprising generating hydrogen in-situ and injection hydrogen gas;

wherein generating hydrogen in-situ comprises subjecting a target to sonic energy, pyrolysis, or a combination comprising at least one of the foregoing; and

wherein the target comprises a metal hydride comprising one or more of the following: NaA 1 H 4 ; LiA 1 H 4 ; Li 3 A 1 H 6 ;

LiNa 2 A 1 H 6 ; Ca(A 1 H 4 ) 2 ; MgH 2 LiBH 4 ; NaBH 4 ; Ca(BH 4 ) 2 ; or Mg(BH 4 ) 2 .

18. A method for converting an asphaltene, the method comprising:

disposing a catalyst in a composition comprising an asphaltene;

introducing hydrogen; and

hydrogenating the asphaltene to convert the asphaltene into a hydrogenated asphaltene,

wherein introducing hydrogen comprises generating hydrogen in-situ; and

wherein generating hydrogen in-situ comprises:

in-situ combustion of a hydrocarbon; or

pyrolysis of a hydrocarbon by heating the hydrocarbon using electric resistive heating, induction heating, or a combination comprising at least one of the foregoing; or

reacting a metal with a fluid.

19. The method of claim 18 , wherein the catalyst is a supported low temperature catalyst having an activity effective to hydrogenate the asphaltene at a temperature of 25° C.

20. The method of claim 18 , wherein generating hydrogen in-situ comprises in-situ combustion of a hydrocarbon.

21. The method of claim 18 , wherein generating hydrogen in-situ comprises pyrolysis of a hydrocarbon by heating the hydrocarbon using electric resistive heating, induction heating, or a combination comprising at least one of the foregoing.

22. The method of claim 18 , wherein generating hydrogen in-situ comprises reacting a metal with a fluid.

23. The method of claim 22 , wherein the metal is aluminum, iron, magnesium, zinc, or a combination comprising at least one of the foregoing.

24. The method of claim 22 , wherein the fluid is brine, acid, or a combination comprising at least one of the foregoing.

25. The method of claim 18 , wherein the catalyst is a supported catalyst comprising rhodium nanoparticles supported on a support comprising hydroxyapatite, fluoroapatite, chloroapatite, bromoapatite, zeolite, or a combination comprising at least one of the foregoing.

Assignments (3)
CHANGE OF NAME Recorded Jun 23, 2022
From: BAKER HUGHES, A GE COMPANY, LLC
To: BAKER HUGHES HOLDINGS LLC
Reel/Frame 060791/0629 →
CHANGE OF NAME Recorded Apr 5, 2022
From: BAKER HUGHES INCORPORATED
To: BAKER HUGHES, A GE COMPANY, LLC
Reel/Frame 059613/0709 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 26, 2012
From: MAZYAR, OLEG A.
To: BAKER HUGHES INCORPORATED
Reel/Frame 028442/0967 →