IP Library › Granted Patent US 12,247,156
Granted Patent B2
US 12,247,156 · App. 17/791,619 · Granted Mar 11, 2025

Re-crosslinkable particle for conformance control and temporary plugging

Inventors: Yifu Long (Rolla, MO); Bowen Yu (Rolla, MO); Baojun Bai (Rolla, MO); Thomas Schuman (Rolla, MO)
Assignee: The Curators of the University of Missouri
C09K8/426
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Quick Facts
Patent No.
US 12,247,156
App. No.
17/791,619
Granted
Mar 11, 2025
Kind
B2
Abstract

The present invention generally relates to the composition of particle gels for conformance control, well drilling and well treatments. More particularly, this invention relates to swellable polymer particle gels that can re-crosslink, i.e., reassociate and self-heal, at subterranean conditions. These particle gels can be deployed to improve the conformance of water flooding of especially matrix bypass events (MBEs), that are also known as void space conduits. Moreover, these particle gels can be deployed for controlling the water production and increasing of petroleum recovery. The inventive particles can also be deployed as diverter for well stimulation.

Claims (34)

1. A swellable composition for controlling fluid flow, said swellable composition comprising a polymer matrix comprising:

polymer chains crosslinked by a crosslinking agent, said polymer chains including:

a first monomer selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide, N-tert-butylacrylamide, N-ethylacrylamide, N-hydroxyethyl acrylamide, N-isopropylacrylamide, N, N-diethylacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, N,N-dimethylacrylamide, and N-vinyl formamide; and

a second monomer selected from the group consisting of sulfonates, sulfates, phosphates, and 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt; and

a re-crosslinking agent embedded within the polymer matrix and chosen from an aminated alginate, chitosan, aminated chitosan, a dextran amine, aminated cellulose, aminated guaran, or complexes thereof with a multivalent metal ion.

2. The swellable composition of claim 1 , wherein said monomer comprises a sodium or potassium salt of vinylsulfonate, vinyl sulfate, phenyl vinyl sulfonate, phenyl vinyl sulfate, and/or vinyl phosphate.

3. The swellable composition of claim 1 , wherein said polymer chains further comprise a monomer comprising diallyldimethylammonium chloride, (3-(methacryloylamino) propyl) trimethyl ammonium chloride, (2-(methacryloyloxy) ethyl) trimethyl ammonium chloride, vinylbenzyl trimethyl ammonium chloride, dimethylaminoethylacrylate methyl chloride quaternary salt, dimethylaminoethylacrylate benzyl chloride quaternary salt, and/or dimethylaminoethylmethacrylate methyl chloride quaternary salt.

4. The swellable composition of claim 1 , wherein said polymer chains further comprise a monomer comprising hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethylacrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEM), alkyl esters, a-olefins, vinyl alkylates, vinyl alkyl ethers, N-vinyl amides, and/or alkyl aromatics.

5. The swellable composition of claim 1 , wherein said re-crosslinking agent is chitosan or aminated chitosan.

6. The swellable composition of claim 1 , wherein said crosslinking agent comprises a divinyl monomer.

7. The swellable composition of claim 6 , wherein said crosslinking agent comprises methylene bisacrylamide, divinyl sulfone, diethyleneglycol diallyl ether, or combinations thereof.

8. The swellable composition of claim 7 , wherein said crosslinking agent comprises methylene bisacrylamide.

9. The swellable composition of claim 1 , wherein said crosslinking agent comprises diacrylyl tertiary amide, diacrylylpiperazine, diallyltartardiamide, dihydroxyethylene-bis-acrylamide, bis-acrylylcystamine, trimethylolpropane trimethacrylate, propyleneglycol triacrylate, tripropyleneglycol diacrylate, allyl methacrylate, triethyleneglycol dimethacrylate, tetrahydrofurfuryl methacrylate, trimethylolpropane triacrylate, or combinations thereof.

10. The swellable composition of claim 1 , wherein said crosslinking agent comprises a multifunctional crosslinker.

11. The swellable composition of claim 10 , wherein said crosslinking agent comprises pentaerythritol triacrylate, 1,5 pentane diol dimethacrylate, pentaerythritol triallylether, or combinations thereof.

12. The swellable composition of claim 1 , further comprising one or more additives, wherein said one or more additives comprise a chelating agent, a rheological modifier, a nanomaterial, a biocide, an oxygen scavenger, or combinations thereof.

13. The swellable composition of claim 12 , wherein said one or more additives comprises a chelating agent and/or an oxygen scavenger.

14. The swellable composition of claim 1 , wherein said polymer matrix is substantially free of CO 2 -philic moieties.

15. A method of forming the swellable composition of claim 1 , said method comprising:

(a) polymerizing said monomer in the presence of said crosslinking agent and said re-crosslinking agent to form said polymer matrix and embed said re-crosslinking agent within said polymer matrix;

(b) drying said polymer matrix to form a dried polymer matrix; and

(c) grinding said dried polymer matrix to form said swellable composition.

16. The method of claim 15 , wherein said polymerizing of step (a) occurs at a temperature of at least 20° C. and/or less than 200° C.

17. The method of claim 15 , wherein said polymerizing of step (a) comprises ultrasonication.

18. The method of claim 17 , wherein said ultrasonication occurs for at least 10 minutes and/or less than 6 hours.

19. The method of claim 15 , wherein said polymerizing of step (a) occurs for at least 1 hour and/or less than 18 hours.

20. A method of forming a gel formation in a target zone of a subterranean environment, said method comprising:

(a) dispersing the swellable composition of claim 1 into a carrier fluid, thereby causing said swellable composition to swell; and

(b) introducing said carrier fluid comprising said swellable composition into said target zone having a temperature of at least 50° C., thereby causing said re-crosslinking agent to react with said monomer and form said gel formation.

21. The method of claim 20 , wherein said carrier fluid is selected from the group consisting of fresh water, produced water, sea water, brine, and drilling fluid.

22. The method of claim 20 , wherein said subterranean environment is selected from the group consisting of wells and pipelines.

23. The method of claim 20 , wherein said target zone is selected from the group consisting of fractures, conduits, lost-circulation zones, cavernous formations, high-permeability zones, wellbores, and perforations.

24. The method of claim 20 , wherein said swellable composition is in the form of particles having an initial average particle size prior to said contact and wherein upon contact with said fluid, said particles swell to a second average particle size that is at least about 5 times greater than that of the initial average particle size.

25. The method of claim 24 , wherein said particles exhibit less than about 20 percent decrease in volume after exposure to said subterranean environment for 1 day.

Continuity (1)
Related Publication 20230055352A1 · Feb 23, 2023
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