Oxidizers for carbon dioxide-based fracturing fluids

Patent metadata

Field	Value
Publication number	US-11499090-B2
Application number	US-202016936215-A
Country	US
Kind code	B2
Filing date	Jul 22, 2020
Priority date	Jul 24, 2019
Publication date	Nov 15, 2022
Grant date	Nov 15, 2022

Abstract

A method for treating kerogen in a subterranean zone which includes the use of supercritical carbon dioxide or emulsions of liquid carbon dioxide and an aqueous fluid. The carbon dioxide or emulsions can further include oxidizers. The oxidizers can include inorganic oxidizers or organic oxidizers, for example an oxidizer including an organic cation and an oxidizing anion. Additional additives such as polymers, crosslinkers, clay inhibitors, scale inhibitors and corrosion inhibitors can further enhance the efficiency of the kerogen-treating carbon dioxide or emulsion.

First claim

What is claimed is:

1. A method for treating kerogen or organic matter in a subterranean zone, the method comprising placing a composition in the subterranean zone, the composition comprising:
supercritical carbon dioxide (CO 2 ); and
a fluid comprising an oxidizer, wherein the fluid is an aqueous fluid, and wherein the composition comprises an emulsion of supercritical carbon dioxide and the aqueous fluid, wherein the supercritical carbon dioxide and the fluid comprising the oxidizer are mixed to form the emulsion before placing the composition in the subterranean zone,
wherein the oxidizer comprises a cation and an anion, and the cation comprises a fluorinated organic cation.

2. The method of claim 1 , further comprising alternating placing the composition in the subterranean zone with placing a second fluid in the subterranean zone.

3. The method of claim 1 , wherein the anion comprises at least one of chlorate or bromate.

4. The method of claim 1 , wherein the cation comprises at least one of an ammonium ion, a butylammonium ion, a dibutylammonium ion, a tributyl ammonium ion, or a tetrabutylammonium ion.

5. The method of claim 1 , wherein the cation comprises at least one of: an ammonium ion substituted with alkyl or phenyl groups; bis(triphenylphosphine)iminium; or tetraphenylphosphinium.

6. The method of claim 1 , where the cation comprises a cationic heterocycle.

7. The method of claim 6 , wherein the cationic heterocycle is at least one of pyridinium, pyrrolidinium, pyrazolium, or imidazolium.

8. The method of claim 1 , wherein an external phase of the emulsion comprises the aqueous fluid and an internal phase of the emulsion comprises the supercritical CO 2 .

9. The method of claim 1 , wherein the emulsion comprises hydrophobic particles to stabilize the emulsion.

10. The method of claim 1 , wherein an external phase of the emulsion comprises the supercritical CO 2 and an internal phase of the emulsion comprises the aqueous fluid.

11. The method of claim 1 , wherein the aqueous fluid comprises an inorganic oxidizer.

12. The method of claim 11 , wherein the inorganic oxidizer comprises at least one of bromate, chlorate, chlorite, persulfate, perborate, percarbonate, hypochlorite, nitrite, nitrate, perchlorate, or peroxide.

13. The method of claim 1 , wherein the emulsion comprises an organic oxidizer.

14. The method of claim 1 , wherein the emulsion is stabilized by surfactants or particles.

15. The method of claim 1 , further comprising flowing the composition into the subterranean zone with a fracturing fluid.

16. The method of claim 15 , wherein the fracturing fluid comprises at least one of a polymer, a crosslinker, a breaker, a surfactant, a scale inhibitor, a corrosion inhibitor, or a flowback aid.

17. The method of claim 15 , further comprising flowing the composition and the fracturing fluid with proppants.

18. The method of claim 1 , wherein the subterranean zone comprises carbonate rock or sandstone rock comprising organic matter.

19. The method of claim 1 , wherein:
the cation comprises a member selected from the group consisting of tetrabutylammonium bromate, tributylammonium bromate, dibutylammonium bromate, butylammonium bromate, tetrabutylammonium chlorate, bis(triphenylphosphine)iminium bromate, pyridinium bromate; and
the cation is made by a double displacement reaction.

20. A method for treating kerogen or organic matter in a subterranean zone, the method comprising placing a composition in the subterranean zone, the composition comprising:
supercritical carbon dioxide (CO 2 ); and
a fluid comprising an oxidizer, wherein the fluid is an aqueous fluid, and wherein the composition comprises an emulsion of carbon dioxide and the aqueous fluid, wherein an external phase of the emulsion comprises the supercritical CO 2 and an internal phase of the emulsion comprises the aqueous fluid, and wherein the supercritical carbon dioxide and the fluid comprising the oxidizer are mixed to form the emulsion before placing the composition in the subterranean zone,
wherein:
the oxidizer comprises a cation and an anion;
the anion comprises at least one of chlorate or bromate;
the cation comprises a member selected from the group consisting of tetrabutylammonium bromate, tributylammonium bromate, dibutylammonium bromate, butylammonium bromate, tetrabutylammonium chlorate, bis(triphenylphosphine)iminium bromate, pyridinium bromate; and
the cation is made by a double displacement reaction.

21. A method for treating kerogen or organic matter in a subterranean zone, the method comprising placing a composition in the subterranean zone, the composition comprising:
supercritical carbon dioxide (CO 2 ); and
a fluid comprising an oxidizer, wherein the fluid is an aqueous fluid, and wherein the composition comprises an emulsion of supercritical carbon dioxide and the aqueous fluid, wherein the supercritical carbon dioxide and the fluid comprising the oxidizer are mixed to form the emulsion before placing the composition in the subterranean zone,
wherein:
the oxidizer comprises a cation and an anion;
the cation comprises a member selected from the group consisting of tetrabutylammonium bromate, tributylammonium bromate, dibutylammonium bromate, butylammonium bromate, tetrabutylammonium chlorate, bis(triphenylphosphine)iminium bromate, pyridinium bromate; and
the cation is made by a double displacement reaction.

Assignees

• Saudi Arabian Oil Co

Inventors

• Schipper Desmond
• Hull Katherine Leigh
• Saini Rajesh Kumar
• Abousleiman Younane N

Classifications

• E21B43/263

  using explosives · CPC title

• C09K8/80

  Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open · CPC title

• C09K8/703

  Foams · CPC title

• Y02P20/54

  using solvents, e.g. supercritical solvents or ionic liquids · CPC title

• C09K8/035

  Organic additives · CPC title