IP Library Granted Patent US 11,214,729
Granted Patent B2
US 11,214,729 · App. 16/552,540 · Granted Jan 4, 2022

Re-crosslinking particle gel for CO

Inventors: Yifu Long (Rolla, MO); Baojun Bai (Rolla, MO); Thomas P. Schuman (Rolla, MO)
Assignee: The Curators of the University of Missouri
C09K8/588C09K8/594E21B33/138E21B43/164
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Quick Facts
Patent No.
US 11,214,729
App. No.
16/552,540
Granted
Jan 4, 2022
Kind
B2
Abstract

The present invention generally relates to the composition of particle gels for CO 2 -EOR and CO 2 storage. More particularly, CO 2 resistant particle gels are provided that can re-crosslink at subterranean conditions. These particle gels can be deployed to improve the conformance of CO 2 flooding, CO 2 huff-puff, or Water-Alternative-Gas (WAG). The applications may also involve CO 2 storage, such as the blocking of CO 2 leakage and similar CO 2 processing.

Claims (40)

1. A swellable composition for controlling fluid flow, said swellable composition comprising a polymer matrix, a first crosslinker, and a second crosslinker, wherein said polymer matrix comprises a first monomer having a re-crosslinking moiety, a second monomer having an acid resistance moiety, and a third monomer having a CO 2 -phillic moiety.

2. The swellable composition of claim 1 , wherein said swellable composition is in the form of a particulate gel.

3. The swellable composition of claim 1 , wherein said first monomer comprises a water-soluble carboxylic acid and said second monomer comprises a water-soluble cationic monomer.

4. The swellable composition of claim 1 , wherein said first monomer comprises N-isopropylacrylamide, N,N-diethylacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, acryloyl morpholine, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethylacrylate, dimethylaminoethyl methacrylate, maleic anhydride, N-vinyl pyrrolidone, vinyl acetate, N-vinyl formamide, or combinations thereof,

wherein said second monomer comprises sodium vinylsulfonate, potassium vinylsulfonate, sodium phenyl vinyl sulfate, potassium phenyl vinyl sulfate, sodium vinyl sulfate, 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt, potassium vinyl sulfate, or combinations thereof, and

wherein said third monomer comprises vinyl benzoate, benzyl vinyl formate, vinyl acetate, ethyl vinyl ether, methyl vinyl ether, vinylidene fluoride, lactic acid, lactic acid cyclic dimer, glycolic acid, glycolide, hexamethylcyclotrisiloxane, 1H,1H,2H,2H-perfluorooctyl methacrylate, or combinations thereof.

5. The swellable composition of claim 1 , wherein said first monomer comprises an acrylamide or a derivative thereof,

wherein said second monomer comprises 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt, and

wherein said third monomer comprises vinyl acetate.

6. The swellable composition of claim 1 , wherein said first crosslinker comprises methylene bisacrylamide, diallylamine, triallylamine, divinyl sulfone, diethyleneglycol diallyl ether, or combinations thereof.

7. The swellable composition of claim 6 , wherein said second crosslinker comprises Cr(III)-acetate, Cr(III)-propionate, Zr(IV)-acetate, Zr(IV)-lactate, or combinations thereof.

8. The swellable composition of claim 1 , further comprising one or more additives, wherein said additives comprise silica particles, fibers, an oxygen scavenger, or combinations thereof.

9. The swellable composition of claim 1 , wherein said polymer matrix comprises at least 40 mole percent of said first monomer based on the total mole content of said first monomer, said second monomer, and said third monomer;

wherein said polymer matrix comprises at least 0.5 mole percent and less than 50 mole percent of said second monomer based on the total mole content of said first monomer, said second monomer, and said third monomer;

wherein said polymer matrix comprises at least 1 mole percent and less than 50 mole percent of said third monomer based on the total mole content of said first monomer, said second monomer, and said third monomer.

10. The swellable composition of claim 9 , wherein said swellable composition comprises at least 80 weight percent of said polymer matrix.

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

(a) polymerizing said first monomer, said second monomer, and said third monomer in the presence of said first crosslinker and said second crosslinker to form 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.

12. The method of claim 11 , wherein said polymerizing of step (a) occurs at a temperature of 20 to 200° C.

13. The method of claim 11 , wherein said polymerizing of step (a) comprises ultrasonication.

14. A method of altering or controlling a fluid present in a subterranean environment comprising:

(a) introducing a swellable composition according to claim 1 into said subterranean environment so that said swellable composition contacts said fluid,

wherein said polymer matrix comprises a plurality of crosslinkable polymer chains and

at least a portion of said second crosslinker is interspersed among said crosslinkable polymer chains;

(b) allowing said second crosslinker to associate with said crosslinkable polymer chains upon exposure to said fluid to thereby form a swollen composition; and

(c) at least partially controlling the flow of said fluid within said subterranean environment with said swollen composition.

15. The method of claim 14 , wherein said fluid comprises water or a brine solvent.

16. The method of claim 14 , wherein said subterranean environment comprises a well, pipeline, or fracture.

17. The method of claim 14 , wherein said swellable composition is in the form particles having an initial average particle size prior to said introducing of step (a) and said swollen composition is in the form of particles having a second average particle size, and

wherein said second average particle size that is at least 5 times greater than that of said initial average particle size.

18. The method of claim 14 , wherein said first monomer comprises N-isopropylacrylamide, N,N-diethylacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, acryloyl morpholine, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethylacrylate, dimethylaminoethyl methacrylate, maleic anhydride, N-vinyl pyrrolidone, vinyl acetate, N-vinyl formamide, or combinations thereof,

wherein said second monomer comprises sodium vinylsulfonate, potassium vinylsulfonate, sodium phenyl vinyl sulfate, potassium phenyl vinyl sulfate, sodium vinyl sulfate, 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt, potassium vinyl sulfate, or combinations thereof, and

wherein said third monomer comprises vinyl benzoate, benzyl vinyl formate, vinyl acetate, ethyl vinyl ether, methyl vinyl ether, vinylidene fluoride, lactic acid, lactic acid cyclic dimer, glycolic acid, glycolide, hexamethylcyclotrisiloxane, 1H,1H,2H,2H-perfluorooctyl methacrylate, or combinations thereof.

19. The method of claim 14 , wherein said first monomer comprises an acrylamide or a derivative thereof,

wherein said second monomer comprises 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt, and

wherein said third monomer comprises vinyl acetate.

20. The method of claim 19 , wherein said first crosslinker comprises methylene bisacrylamide, diallylamine, triallylamine, divinyl sulfone, diethyleneglycol diallyl ether, or combinations thereof, and

wherein said second crosslinker comprises Cr(III)-acetate, Cr(III)-propionate, Zr(IV)-acetate, Zr(IV)-lactate, or combinations thereof.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 19, 2019
From: LONG, YIFU; BAI, BAOJUN; SCHUMAN, THOMAS
To: THE CURATORS OF THE UNIVERSITY OF MISSOURI
Reel/Frame 050430/0762 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 27, 2019
From: LONG, YIFU; BAI, BAOJUN; SCHUMAN, THOMAS
To: THE CURATORS OF THE UNIVERSITY OF MISSOURI
Reel/Frame 050184/0431 →
Continuity (2)
Provisional Application 62725610 · Aug 31, 2018
Related Publication 20200071601A1 · Mar 5, 2020
Cited By (1)
US 12,534,663