IP Library Granted Patent US 11,292,959
Granted Patent B2
US 11,292,959 · App. 16/739,434 · Granted Apr 5, 2022

Compositions and methods for delayed crosslinking in hydraulic fracturing fluids

Inventors: Christopher Waller (Houston, TX); Kirk E. Wells (Sugar Land, TX); Trinh Tran (Manvel, TX); Pablo Munoz (Katy, TX)
Assignee: ChampionX USA Inc.
C09K8/685C09K8/528C09K8/602C09K8/605C09K8/887C09K8/90E21B33/138E21B37/06C09K2208/12C09K2208/26
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Quick Facts
Patent No.
US 11,292,959
App. No.
16/739,434
Granted
Apr 5, 2022
Kind
B2
Abstract

Disclosed herein are compositions and methods for delaying crosslinking of aqueous crosslinkable polymers such as polysaccharides in injectable compositions for hydraulic fracturing and related applications. The compositions and methods provide delayed crosslinking at high temperatures and pressures, such as those encountered by hydraulic fracturing compositions injected into subterranean environments. Compositions include injectable solutions comprising a competing agent that is a reaction product of a dialdehyde having 2 to 4 carbon atoms with a non-polymeric cis-hydroxyl compound. Provided are methods of making and using delayed-crosslinking compositions comprising crosslinker compositions containing zirconium complexes and the competing agents.

Claims (34)

1. A method comprising:

combining and reacting in water a dialdehyde having 2 to 4 carbon atoms with a non-polymeric cis-hydroxyl compound to form a competing agent solution comprising a competing agent, wherein the competing agent solution does not comprise a zirconium complex or a borate;

optionally adjusting a pH of the competing agent solution to about 6.0 to about 6.5;

combining a zirconium (IV) compound and an alkanolamine in one or more solvents to form a crosslinker composition comprising a zirconium complex; and

combining the competing agent solution and the crosslinker composition to form a delayed-crosslinking composition.

2. The method of claim 1 , wherein the method further comprises:

combining the delayed-crosslinking composition, a water source, and a crosslinkable polymer to form an injectable solution;

injecting the injectable solution into a subterranean reservoir; and

recovering a hydrocarbon from the reservoir.

3. The method of claim 2 , wherein a temperature within the subterranean reservoir is about 40° C. to 180° C.

4. The method of claim 2 , the method further comprising adding one or more proppants to the injectable solution prior to the injecting.

5. The method of claim 1 , wherein a molar ratio of the competing agent to the zirconium complex is from 1:3 to 2:9.

6. The method of claim 1 , wherein the alkanolamine is triethanolamine and the zirconium (IV) compound is zirconium tetra(n-propoxide).

7. The method of claim 1 , wherein the dialdehyde is glyoxal.

8. The method of claim 1 , wherein the non-polymeric cis-hydroxyl compound is sorbitol.

9. The method of claim 1 , wherein the dialdehyde and the non-polymeric cis-hydroxyl compound are combined and reacted in water in about a 1:1 molar ratio of the dialdehyde to the non-polymeric cis-hydroxyl compound.

10. The method of claim 1 , wherein the non-polymeric cis-hydroxyl compound is a C3 to C7 sugar alcohol selected from erythritol, threitol, pentaerythritol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, glycerol, and any combination thereof.

11. The method of claim 1 , wherein the temperature of the crosslinking composition is maintained between about 15° C. and about 70° C. during the combining the zirconium (IV) compound and the alkanolamine.

12. The method of claim 1 , wherein the crosslinker composition is maintained at a temperature of from about 35° C. to about 40° C. for 90 to 150 minutes after the combining the zirconium (IV) compound and the alkanolamine.

13. The method of claim 2 , wherein the crosslinkable polymer is a polysaccharide.

14. The method of claim 2 , wherein the crosslinkable polymer is carboxymethyl hydroxypropyl guar.

15. The method of claim 2 , wherein the water source comprises a produced water, tap water, groundwater, surface water, seawater, wastewater, or any combination thereof.

16. A method comprising:

combining and reacting in water a dialdehyde having 2 to 4 carbon atoms with a non-polymeric cis-hydroxyl compound to form a competing agent solution comprising a competing agent, wherein the competing agent solution does not comprise a zirconium complex or a borate;

optionally adjusting a pH of the competing agent solution to about 6.0 to about 6.5;

combining the competing agent solution, a water source, and a polysaccharide to form a reactive premix.

17. The method of claim 16 , wherein the water source excludes one or more reactive species.

18. The method of claim 16 , the method further comprising:

combining a zirconium (IV) compound and an alkanolamine in one or more solvents to form a crosslinker composition comprising a zirconium complex;

combining the crosslinker composition and the reactive premix to form an injectable solution;

injecting the injectable solution into a subterranean reservoir; and

recovering a hydrocarbon from the reservoir.

19. The method of claim 18 , wherein the crosslinker composition is maintained at a temperature of about 35° C. to about 40° C. for 90 to 150 minutes after the combining the zirconium (IV) compound and the alkanolamine.

20. The method of claim 16 , wherein the dialdehyde and the non-polymeric cis-hydroxyl compound are combined and reacted in water in about a 1:1 molar ratio of the dialdehyde to the non-polymeric cis-hydroxyl compound.

Assignments (7)
RELEASE OF SECURITY INTEREST IN PATENTS Recorded Jul 17, 2025
From: JPMORGAN CHASE BANK, N.A.
To: CHAMPIONX LLC; APERGY ESP SYSTEMS, LLC; APERGY BMCS ACQUISITION CORP; HARBISON-FISCHER, INC.; NORRIS RODS, INC.,; NORRIS RODS, INC.,; NORRISEAL-WELLMARK, INC.; PCS FERGUSON, INC.; QUARTZDYNE, INC.; US SYNTHETIC CORPORATION
Reel/Frame 072004/0019 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 19, 2024
From: CHAMPIONX USA INC.
To: CHAMPIONX LLC
Reel/Frame 067768/0888 →
RELEASE OF SECURITY INTEREST Recorded Jun 7, 2022
From: BANK OF AMERICA, N.A.
To: CHAMPIONX USA INC.
Reel/Frame 060304/0267 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 10, 2020
From: ECOLAB USA INC.
To: CHAMPIONX USA INC.
Reel/Frame 053749/0001 →
SECURITY INTEREST Recorded Jun 5, 2020
From: CHAMPIONX USA INC.
To: JPMORGAN CHASE BANK, N.A.
Reel/Frame 053250/0001 →
SECURITY INTEREST Recorded Jun 5, 2020
From: CHAMPIONX USA INC.
To: BANK OF AMERICA, N.A.
Reel/Frame 052848/0368 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 10, 2020
From: WALLER, CHRISTOPHER; WELLS, KIRK E.; TRAN, TRINH; MUNOZ, PABLO
To: ECOLAB USA INC.
Reel/Frame 051478/0558 →