Methods and compositions for reducing subterranean formation permeabilities

• US 7,091,160 B2
• Filed: 06/24/2004
• Issued: 08/15/2006
• Est. Priority Date: 06/24/2004
• Status: Expired due to Fees

• Current Assignee: Halliburton Energy Services Incorporated (Halliburton Company)
• Original Assignee: Halliburton Energy Services Incorporated (Halliburton Company)
• Inventors: Bouwmeester, Ron, Verlaan, Marco, Reddy, B. Raghava, Dao, Bach, Biezen, Ewout
• Primary Examiner(s): Tucker, Philip C.
• Application Number:
  US10/875,649
• Publication Number:
  US 20050288190A1
• Time in Patent Office: 782 Days
• Field of Search: 507/224, 507/221, 507/211, 507/239, 507/269, 507/271, 507/272, 507/903, 166/285, 166/293, 166/300
• US Class Current: 507/224
• CPC Class Codes: C09K 8/5083 obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09K 8/512 containing cross-linking agents
• CPC Class Codes: C09K 8/5753 obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09K 8/5756 containing cross-linking agents
• CPC Class Codes: Y10S 507/903 Crosslinked resin or polymer

Abstract

Methods and compositions for reducing the permeabilities of subterranean formations or zones are provided. The methods of the invention are basically comprised of introducing an aqueous composition into the formation or zone comprised of water, a water soluble organic polymer, an organic gelling agent for cross-linking the organic polymer and a gel retarder comprised of a chemical compound that hydrolyzes or thermolyzes to produce one or more acids in the composition and then allowing the aqueous composition to form a cross-linked gel in the formation or zone.

Claims

1. A method of reducing the permeability of a subterranean formation or zone having a temperature above about 200°

F. comprising the steps of;

(a) introducing an aqueous composition into said formation or zone comprised of water, a water soluble organic polymer, an organic gelling agent comprising an amino group for cross-linking said organic polymer wherein said gelling agent is selected from the group consisting of a polyalkyleneimine, a polyfunctional aliphatic amine, an aralkylamine, and a heteroaralkylamine; and

a gel retarder comprised of a chemical compound that is capable of acetylating an organic amine and/or hydrolyzing or thermolyzing to produce one or more acids in said composition; and

(b) allowing said aqueous composition to form a cross-linked gel in said formation or zone.

2. The method of claim 1 wherein said chemical compound of said gel retarder comprises at least one member selected from the group consisting of anhydrides, esters, amides and polyamides, imides, polyacids and their salts.

3. The method of claim 1 wherein said water soluble organic polymer is comprised of a copolymer of an ethylenically unsaturated polar monomer and an ethylenically unsaturated ester.

4. The method of claim 3 wherein said ethylenically unsaturated polar monomer in said copolymer is an amide of an unsaturated carboxylic acid.

5. The method of claim 3 wherein said ethylenically unsaturated polar monomer in said copolymer is acrylamide.

6. The method of claim 3 wherein said ethylenically unsaturated ester in said copolymer is formed of a hydroxyl compound and an ethylenically unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid and cinnamic acid.

7. The method of claim 6 wherein said hydroxyl compound is an alcohol having the formula ROH wherein R is a group selected from alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, a heterocyclic group substituted with one or more groups selected from hydroxyl, ether and thioether, and an aromatic group substituted with one or more groups selected from hydroxyl, ether and thioether.

8. The method of claim 3 wherein said ethylenically unsaturated ester is t-butyl acrylate.

9. The method of claim 1 wherein said organic gelling agent is selected from the group consisting of polyethylene imine, polypropylene imine, polyethylene polyamine, polypropylene polyamine, polyvinylamine, polyallylamine, poly(vinylalcohol/vinylamine), chitosan, a derivative of chitosan, polylysine, polymyxin and combinations there of.

10. The method of claim 1 wherein said water soluble organic polymer is a terpolymer of an ethylenically unsaturated polar monomer, an ethylenically unsaturated ester and a bulky monomer selected from the group consisting of 2-acrylamido-2-methylpropane sulfonic acid, N-vinylpyrrolidone, and N,N-dimethylacrylamide or said water soluble polymer is a tetrapolymer of an ethylenically unsaturated polar monomer, an ethylenically unsaturated ester, 2-acrylamido-2-methylpropane sulfonic acid and a monomer selected from the group consisting of N-vinylpyrrolidone and N,N-dimethylacrylamide.

11. The method of claim 10 wherein said ethylenically unsaturated polar monomer in said terpolymer or tetrapolymer is an amide of an unsaturated carboxylic acid.

12. The method of claim 10 wherein said ethylenically unsaturated polar monomer in said terpolymer or tetrapolymer is acrylamide.

13. The method of claim 10 wherein said ethylenically unsaturated ester in said terpolymer or tetrapolymer is formed of a hydroxyl compound and an ethylenically unsaturated carboxylic acid selected from the group of acrylic acid, methacrylic acid, crotonic acid and cinnamic acid.

14. The method of claim 13 wherein said hydroxyl compound is an alcohol having the formula ROH wherein R is a group selected from alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, a heterocyclic group substituted with one or more groups selected from hydroxyl, ether and thioether, and an aromatic group substituted with one or more groups selected from hydroxyl, ether and thioether.

15. The method of claim 10 wherein said ethylenically unsaturated ester is t-butyl acrylate.

16. The method of claim 1 wherein said organic gelling agent is a chelated organic gelling agent.

17. The method of claim 16 wherein said chelated organic gelling agent is comprised of a metal ion chelated water soluble polyalkyleneimine.

18. The method of claim 17 wherein said polyalkyleneimine is selected from the group consisting of polyethyleneimine and polypropyleneimine.

19. The method of claim 17 wherein said polyalkyleneimine is polyethyleneimine.

20. The method of claim 17 wherein said metal ion is selected from the group consisting of zirconium(IV) ion, cobalt (II or III) ion, nickel (II) ion, ferric ion, titanium (IV ion) and copper (II) ion.

21. The method of claim 17 wherein said metal ion is zirconium ion.

43. The method of claim 1 wherein said chemical compound of said gel retarder comprises at least one member selected from the group consisting of polysuccinimide, polyaspartic acid, polyglutamic acid and their salts.

22. A composition for reducing the permeability of a subterranean formation or zone comprising:

water;

a water soluble organic polymer;

an organic gelling agent comprising an amino group for cross-linking said organic polymer wherein said gelling agent is selected from the group consisting of a polyalkyleneimine, a polyfunctional aliphatic amine, an aralkylamine, and a heteroaralkylamine; and

a gel retarder comprising at least one member selected from the group consisting of polysuccinimide, polyaspartic acid, polyglutamic acid and their salts.

23. The composition of claim 22 wherein said gel retarder is comprised of polysuccinimide or polyaspartic acid.

24. The composition of claim 22 wherein said water soluble organic polymer is comprised of a copolymer of an ethylenically unsaturated polar monomer and an ethylenically unsaturated ester.

25. The composition of claim 24 wherein said ethylenically unsaturated polar monomer in said copolymer is an amide of an unsaturated carboxylic acid.

26. The composition of claim 24 wherein said ethylenically unsaturated polar monomer in said copolymer is acrylamide.

27. The composition of claim 24 wherein said ethylenically unsaturated ester in said copolymer is formed of a hydroxyl compound and an ethylenically unsaturated carboxylic acid selected from the group of acrylic acid, methacrylic acid, crotonic acid and cinnamic acid.

28. The composition of claim 27 wherein said hydroxyl compound is an alcohol having the formula ROH wherein R is a group selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, a heterocyclic group substituted with one or more groups selected from hydroxyl, ether and thioether, and an aromatic group substituted with one or more groups selected from hydroxyl, ether and thioether.

29. The composition of claim 24 wherein said ethylenically unsaturated ester is t-butyl acrylate.

30. The composition of claim 22 wherein said organic gelling agent is selected from the group consisting of polyethylene imine, polypropylene imine, polyethylene polyamine, polypropylene polyamine, polyvinylamine, polyallylamine, poly(vinylalcohol/vinylamine), chitosan, a derivative of chitosan, polylysine, polymyxin and combinations there of.

31. The composition of claim 22 wherein said water soluble organic polymer is a terpolymer of an ethylenically unsaturated polar monomer, an ethylenically unsaturated ester and a bulky monomer selected from the group consisting of 2-acrylamido-2-methylpropane sulfonic acid, N-vinylpyrrolidone, and N,N-dimethylacrylamide or said water soluble polymer is a tetrapolymer of an ethylenically unsaturated polar monomer, an ethylenically unsaturated ester, 2-acrylamido-2-methylpropane sulfonic acid and a monomer selected from the group consisting of N-vinylpyrrolidone and N,N-dimethylacrylamide.

32. The composition of claim 31 wherein said ethylenically unsaturated polar monomer in said terpolymer or tetrapolymer is an amide of an unsaturated carboxylic acid.

33. The composition of claim 31 wherein said ethylenically unsaturated polar monomer in said terpolymer or tetrapolymer is acrylamide.

34. The composition of claim 31 wherein said ethylenically unsaturated ester in said terpolymer or tetrapolymer is formed of a hydroxyl compound and an ethylenically unsaturated carboxylic acid selected from the group of acrylic acid, methacrylic acid, crotonic acid and cinnamic acid.

35. The composition of claim 34 wherein said hydroxyl compound is an alcohol having the formula ROH wherein R is a group selected from alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, a heterocyclic group substituted with one or more groups selected from hydroxyl, ether and thioether, and an aromatic group substituted with one or more groups selected from hydroxyl, ether and thioether.

36. The composition of claim 31 wherein said ethylenically unsaturated ester is t-butyl acrylate.

37. The composition of claim 22 wherein said organic gelling agent is a chelated organic gelling agent.

38. The composition of claim 37 wherein said chelated organic gelling agent is comprised of a metal ion chelated water soluble polyalkyleneimine.

39. The composition of claim 38 wherein said polyalkyleneimine is selected from the group consisting of polyethyleneimine and polypropyleneimine.

40. The composition of claim 38 wherein said polyalkyleneimine is polyethyleneimine.

41. The composition of claim 38 wherein said metal ion is selected from the group of zirconium ion, cobalt ion, nickel ion, ferric ion, titanium IV ion and copper ion.

42. The composition of claim 38 wherein said metal ion is zirconium ion.