High temperature stable gels

• US 5,246,073 A
• Filed: 08/31/1992
• Issued: 09/21/1993
• Est. Priority Date: 08/31/1992
• Status: Expired due to Term

• Current Assignee: Union Oil Company of California (Chevron Corp.)
• Original Assignee: Union Oil Company of California (Chevron Corp.)
• Inventors: Hutchins, Richard D., Dovan, Hoai T., Sandiford, Burton B.
• Primary Examiner(s): Suchfield, George A.
• Application Number:
  US07/940,301
• Time in Patent Office: 386 Days
• Field of Search: 166/294, 166/295, 166/300, 166/305.1, 166/308, 252/8.551, 523/130
• US Class Current: 166/295
• CPC Class Codes: B01J 13/0065 containing an organic phase
• CPC Class Codes: C08F 220/54 Amides , e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
• CPC Class Codes: C08F 8/00 Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C
• CPC Class Codes: C09K 8/512 containing cross-linking agents
• CPC Class Codes: C09K 8/685 containing cross-linking agents
• CPC Class Codes: C09K 8/887 containing cross-linking agents
• CPC Class Codes: C09K 8/94 Foams
• CPC Class Codes: Y10S 507/903 Crosslinked resin or polymer
• CPC Class Codes: Y10S 524/916 Hydrogel compositions
• CPC Class Codes: Y10S 526/932 Thickener or dispersant for aqueous system

Abstract

Gels stable in a subterranean formation at a temperature greater than about 175° F. are formed using, inter alia, a stabilizing agent (e.g., a buffer having a buffering capacity at a pH of at least about 8 and/or a chelating agent).

Claims

1. A method for forming a gel in at least a portion of a subterranean formation, the method comprising the steps of:

(A) injecting a composition into at least a portion of a subterranean formation, the composition comprising (i) an ingredient selected from the group consisting of water soluble, crosslinkable polymers and polymerizable monomers capable of forming a crosslinkable polymer and (ii) water;

(B) injecting a crosslinking agent into at least a portion of the subterranean formation; and

(C) injecting a stabilizing amount of a buffering agent into at least a portion of the subterranean formation, the buffering agent having a buffering capacity at a pH greater than about 8 and being selected from the group consisting of water soluble bicarbonate salts, carbonate salts, phosphate salts, and mixtures thereof,

wherein the subterranean formation is at a temperature of at least about 175°

F.

2. The method of claim 1 wherein at least a portion of steps (A) and (C) are performed prior to step (B).

3. The method of claim 1 wherein the subterranean formation is at a temperature of at least about 300°

F.

4. The method of claim 1 wherein the water soluble, crosslinkable polymer and the crosslinkable polymer formed from the polymerizable monomers are selected from the group consisting of polymethacrylamides, polyacrylamides, acrylic acid-acrylamide copolymers, and acrylic acid-methacrylamide copolymers.

5. The method of claim 4 wherein the water soluble, crosslinkable polymer and the crosslinkable polymer formed from the polymerizable monomers are selected from the group consisting of partially hydrolyzed polymethacrylamides and partially hydrolyzed polyacrylamides.

6. The method of claim 1 wherein the water is hard water.

7. The method of claim 1 wherein the water is sea water.

8. The method of claim 1 wherein the subterranean formation is at a temperature of at least about 200°

F.

9. The method of claim 1 wherein the subterranean formation is at a temperature of at least about 225°

F.

10. The method of claim 1 wherein the subterranean formation is at a temperature of at least about 250°

F.

11. The method of claim 1 wherein the subterranean formation is at a temperature of at least about 275°

F.

12. The method of claim 1 wherein the subterranean formation is at a temperature of at least about 325°

F.

13. The method of claim 1 wherein the subterranean formation is at a temperature of at least about 350°

F.

33. A recovery system comprising;

(a) a subterranean formation;

(b) a well penetrating at least a portion of the subterranean formation; and

(c) a gel located in at least a portion of the subterranean formation, the gel being formed by the method of claim 1.

14. A method for forming a gel in at least a portion of a subterranean formation, the method comprising the step of injecting a composition into at least a portion of a subterranean formation, the composition comprising (A) an ingredient selected from the group consisting of water soluble, crosslinkable polymers and polymerizable monomers capable of forming a corsslinkable polymer, (B) a crosslinking agent, (C) water, and (D) a stabilizing amount of a buffering agent having a buffering capacity at a pH greater than about 8 and selected from the group consisting of water soluble bicarbonate salts, carbonate salts, phosphate salts, and mixtures thereof, wherein the subterranean formation is at a temperature of at least about 175°

F.

15. The method of claim 14 wherein the water comprises a soft water.

16. The method of claim 14 further comprising the steps of injecting a gas into at least a portion of the subterranean formation and injecting one or more ingredients capable of foaming the composition into at least a portion of the subterranean formation.

17. The method of claim 14 further comprising the step of injecting a gas into at least a portion of the subterranean formation, wherein the composition further comprises one or more ingredients capable of foaming the composition.

18. The method of claim 14 wherein the water soluble, crosslinkable polymer and the crosslinkable polymer formed from the polymerizable monomers are selected from the group consisting of polymethacrylamides, polyacrylamides, acrylic acid-acrylamide copolymers, and acrylic acid-methacrylamide copolymers.

34. A recovery system comprising:

(a) a subterranean formation;

(b) a well penetrating at least a portion of the subterranean formation; and

(c) a gel located in at least a portion of the subterranean formation, the gel being formed by the method of claim 14.

35. A recovery system comprising:

(a) a subterranean formation;

(b) a well penetrating at least a portion of the subterranean formation; and

(c) a gel located in at least a portion of the subterranean formation, the gel being formed by the method of claim 17.

19. A method for forming a gel in at least a portion of a subterranean formation, the method comprising the step of injecting a composition into at least a portion of a subterranean formation, the composition comprising (A) an ingredient selected from the group consisting of water soluble, crosslinkable polymers and polymerizable monomers capable of forming a crosslinkable polymer, (B) a crosslinking agent, (C) hard water, and (D) a buffering agent having a buffering capacity at a pH of at least bout 8 and selected from the group consisting of water-soluble bicarbonate salts, carbonate salts, phosphate salts, and mixtures thereof, wherein the subterranean formation is at a temperature of at least about 175°

F.

20. The method of claim 19 wherein the buffering agent is selected from the group consisting of alkali metal bicarbonates, alkali metal carbonates, dibasic alkali metal phosphates, tribasic alkali metal phosphates, and mixtures thereof.

21. The method of claim 19 wherein the buffering agent is selected from the group consisting of ammonium bicarbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, sodium carbonate, potassium carbonate, and mixtures thereof.

22. The method of claim 19 wherein the composition comprises at least about 0.05 weight percent of the buffering agent based upon the total weight of the composition.

23. The method of claim 19 wherein the composition comprises at least about 1 weight percent of the buffering agent based upon the total weight of the composition.

24. The method of claim 19 wherein the total divalent cation content of the hard water is at least about 10 ppmw.

25. The method of claim 19 wherein the total divalent cation content of the hard water is at least about 1,000 ppmw.

26. The method of claim 19 wherein the water soluble, crosslinkable polymer and the crosslinkable polymer formed from the polymerizable monomers are selected from the group consisting of polymethacrylamides, polyacrylamides, acrylic acid-acrylamide copolymers, and acrylic acid-methacrylamide copolymers.

27. The method of claim 19 wherein the water is sea water.

36. A recovery system comprising:

(a) a subterranean formation;

(b) a well penetrating at least a portion of the subterranean formation; and

(c) a gel located in at least a portion of the subterranean formation, the gel being formed by the method of claim 19.

28. A method for forming a gel in at least a portion of a subterranean formation, the method comprising the step of injecting a composition into at least a portion of a subterranean formation, the composition comprising (A) an ingredient selected from the group consisting of a water soluble, crosslinkable polymer selected from the group consisting of polymethacrylamides, polyacrylamides, acrylic acid acrylamide copolymers, and acrylic acid-methacrylamide copolymers and polymerizable monomers capable of forming a crosslinkable polymer selected from the group consisting of polymethacrylamides, polyacrylamides, acrylic acid-acrylamide copolymers, and acrylic acid-methacrylamide copolymers, (B) a crosslinking agent, (C) hard water, and (D) a chelating agent, wherein the subterranean formation is at a temperature of at least about 175°

F.

29. The method of claim 28 wherein the composition comprises at least about 0.75 mole of the chelating agent per mole of dissolved divalent cations present in the hard water.

30. The method of claim 28 wherein the ratio of the moles of the chelating agent in the composition per mole of dissolved divalent cation present in the hard water used to make the composition is about 0.75:

1 to about 10;

1.

31. The method of claim 28 wherein the water soluble, crosslinkable polymer and the crosslinkable polymer formed from the polymerizable monomers are selected from the group consisting of partially hydrolyzed polymethacrylamides and partially hydrolyzed polyacrylamides.

32. The method of claim 28 wherein the water is sea water.

37. A recovery system comprising;

(a) a subterranean formation;

(b) a well penetrating at least a portion of the subterranean formation; and

(c) a gel located in at least a portion of the subterranean formation, the gel being formed by the method of claim 28.

38. A recovery system comprising:

(a) a subterranean formation at a temperature of at least about 175°

F.;

(b) a well penetrating at least a portion of the subterranean formation; and

(c) a gel located in at least a portion of the subterranean formation, the gel comprising;

(i) a crosslinked polymer;

(ii) hard water; and

(iii) a buffering agent having a buffering capacity at a pH greater than about 8 and selected from the group consisting of water soluble bicarbonte salts, carbonate salts, phosphate salts, and mixtures thereof.

39. A recovery system comprising;

(a) a subterranean formation;

(b) a well penetrating at least a portion of the subterranean formation; and

(c) a gel located in at least a portion of the subterranean formation, the gel comprising;

(i) an organic crosslinking agent corsslinked polymer;

(ii) water; and

(iii) a chelating agent.

40. A recovery system comprising:

(a) a subterranean formation;

(b) a well penetrating at least a portion of the subterranean formation; and

(c) a composition located in at least a portion of the well, the composition comprising;

(i) an ingredient selected from the group consisting of water soluble, crosslinkable polymers and polymerizable monomers capable of forming a crosslinkable polymer;

(ii) hexamethylenetetramine;

(iii) hard water; and

(iv) a stabilizing agent selected from the group consisting of buffering agents having a buffering capacity at a pH greater than about 8, chelating agents, and mixtures thereof.

41. A recovery system comprising;

(a) a subterranean formation;

(b) a well penetrating at least a portion of the subterranean formation; and

(c) a composition located in at least a portion of the well, the composition comprising;

(i) an ingredient selected from the group consisting of water soluble, crosslinkable polymers and polymerizable monomers capable of forming a crosslinkable polymer;

(ii) an organic crosslinking agent;

(iii) water; and

(iv) a chelating agent.

42. A method for forming a gel in at least a portion of a subterranean formation, the method comprising the steps of:

(A) injecting a composition into at least a portion of a subterranean formation, the composition comprising (i) an ingredient selected from the group consisting of polymethacrylamides, polyacrylamides, acrylic acid-acrylamide copolymers, and acrylic acid methacrylamide copolymers and polymerizable monomers capable of forming a crosslinkable polymer selected from the group consisting of polymethacrylamides, polyacrylamides, acrylic acid-acrylamide copolymers, and acrylic acid-methacrylamide copolymers and (ii) water;

(B) injecting a crosslinking agent into at least a portion of the subterranean formation; and

(C) injecting a stabilizing amount of a stabilizing agent into at least a portion of the subterranean formation, the stabilizing agent being selected from the group consisting of buffering agents having a buffering capacity at a pH greater than about 8, chelating agents, and mixtures thereof, wherein the subterranean formation is at a temperature of at least about 175°

F.

43. The method of claim 42 wherein the water comprises a hard water.

44. The method of claim 42 wherein the water in hard water.

45. The method of claim 42 wherein the water is sea water.

46. A method for forming a gel in at least a portion of a subterranean formation, the method comprising the steps of:

(A) injecting a composition into at least a portion of a subterranean formation, the composition comprising (i) an ingredient selected from the group consisting of water soluble, crosslinkable polymers and polymerizable monomers capable of forming a crosslinkable polymer and (ii) water;

(B) injecting an organic crosslinking agent into at least a portion of the subterranean formation; and

(C) injecting a stabilizing amount of stabilizing agent into at least a portion of the subterranean formation, the stabilizing agent being selected from the group consisting of buffering agents having a buffering capacity at a pH greater than about 8, chelating agents, and mixtures thereof, wherein the subterranean formation is at a temperature of at least about 175°

F.

47. The method of claim 46 wherein the water soluble, crosslinkable polymer and the crosslinkable polymer formed from the polymerizable monomers are selected from the group consisting of polymethacrylamides, polyacrylamides, acrylic acid acrylamide copolymers, and acrylic acid-methacrylamide copolymers.

48. The method of claim 46 wherein the stabilizing agent comprises a buffering agent selected from the group consisting of water soluble bicarboante salts, carbonate salts, phosphate salts, and mixtures thereof.

49. The method of claim 46 wherein the stabilizing agent comprises a chelating agent.

50. The method of claim 46 wherein the water soluble, crosslinkable polymer and the crosslinkable polymer formed from the polymerizable monomers are selected from the group consisting of polymethacrylamides, polyacrylamides, acrylic acid-acrylamide copolymers, and acrylic acid-methacrylamide copolymers;

and the stabilizing agent comprises a buffering agent having a buffering capacity at a pH greater than about 8 and selected from the group consisting of water soluble bicarbonate salts, carbonate salts, phosphate salts, and mixtures thereof.

51. The method of claim 46 wherein the organic crosslinking agent comprises hexamethylenetetramine.

52. The method of claim 46 wherein the organic crosslinking agent comprises hexamethylenetetramine and the stabilizing agent comprises a buffering agent selected from the group consisting of water soluble bicarbonate salts, carbonate salts, phosphate salts, and mixtures thereof.

53. The method of claim 46 wherein the organic crosslinking agent comprises hexamethylenetetramine and the water soluble, crosslinkable polymer and the crosslinkable polymer formed from the polymerizable monomers are selected from the group consisting of polymethacrylamides, polyacrylamides, acrylic acid acrylamide copolymers, and acrylic acid-methacrylamide copolymers.

54. The method of claim 46 wherein the organic crosslinking agent comprises hexamethylenetetramine;

the water soluble, crosslinkable polymer and the crosslinkable polymer formed from the polymerizable monomers are selected from the group consisting of polymethacrylamides, polyacrylamides, acrylic acid-acrylamide copolymers, and acrylic acid-methacrylamide copolymers; and

the stabilizing agent comprises a buffering agent having a buffering capacity at a pH greater than about 8 and selected from the group consisting of water soluble bicarbonate salts, carbonate salts, phosphate salts, and mixtures thereof.

55. The method of claim 46 wherein the water is hard water.

56. The method of claim 46 wherein the water in sea water.

57. A method for forming a gel in at least a portion of a subterranean formation, the method comprising the steps of:

(A) injecting a composition into at least a portion of a subterranean formation, the composition comprising (i) an ingredient selected from the group consisting of water soluble, crosslinkable polymers and polymerizable momoner capable of forming a crosslinkable polymer and (ii) water;

(B) injecting an inorganic crosslinking agent into at least a portion of the subterranean formation, the inorganic crosslinking agent being selected from the group consisting of polyvalent metals, chelated polyvalent metals, and compounds capable of yielding polyvalent metals; and

(C) injecting a stabilizing amount of a stabilizing agent into at least a portion of the subterranean formation, the stabilizing agent being selected from the group consisting of buffering agents having a buffering capacity at a pH greater than about 8, chelating agents, and mixtures thereof, wherein the subterranean formation is at a temperature of at least about 175°

F.

58. The method of claim 57 wherein the inorganic crosslinking agent is selected from the group consisting of chromium salts, aluminates, gallates, titanium chelates, titanium complexes, aluminum citrate, zirconium chelates, zirconium complexes, and mixtures thereof.

59. The method of claim 57 wherein the water is hard water.

60. The method of claim 57 wherein the water is sea water.