Crosslinked alginate-based gels for matrix conformance

• US 5,563,186 A
• Filed: 11/21/1994
• Issued: 10/08/1996
• Est. Priority Date: 11/21/1994
• Status: Expired due to Fees

• Current Assignee: Marathon Oil Company (Marathon Oil Corporation)
• Original Assignee: Marathon Oil Company (Marathon Oil Corporation)
• Inventors: Thompson, Ronald G.
• Primary Examiner(s): Nutter, Nathan M.
• Application Number:
  US08/342,945
• Time in Patent Office: 687 Days
• Field of Search: 523/130, 523/131, 523/132, 507/110, 507/209, 507/211, 507/219, 507/221, 507/224, 507/225, 507/230, 507/269, 507/270, 507/271, 507/272, 507/277, 507/922
• US Class Current: 523/130
• CPC Class Codes: C08B 37/0084 Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 5/04 Alginic acid; Derivatives thereof
• CPC Class Codes: C09K 8/887 containing cross-linking agents
• CPC Class Codes: Y10S 507/922 Fracture fluid

Abstract

A composition of matter for matrix conformance formed from an aqueous solution of an alginate polysaccharide and a method of forming an alginate polysaccharide gel. A Group IIA cation, Fe²⁺, Fe³⁺, Al³⁺, Mn² +, Zn²⁺, a dialdehyde, or a diamine may be used to crosslink the resulting alginate gel. The gel may also comprise a modifier, such as a polyvinyl alcohol, a polycarboxylic acid, or a polyacrylamide. The rate and extent of crosslinking are controlled by varying the alginate molecular weight, the alginate concentration, or the type and concentration of crosslinker, or by adding a sequestering agent such as EDTA or citrate.

Claims

1. A method for modifying the fluid flow profile in a subterranean formation having a heterogeneous permeability distribution, the method comprising:

a) forming a composition comprising an aqueous solution of an alginate polysaccharide having a molecular weight between about 80,000 Daltons and about 200,000 Daltons, the polysaccharide being present in an amount up to about 10 percent by weight, a crosslinking agent selected from the group consisting of Group IIA cations, Fe²⁺, Fe³⁺, Al³⁺, Mn²⁺, Zn²⁺, dialdehydes, diamines, and mixtures thereof, the crosslinking agent being present in an amount ranging from about 0.0001M to about 0.05M, and a modifier present in an amount up to about 5 percent by weight and selected from the group consisting of synthetic polymers consisting of polyvinyl alcohols, neutral polycarboxylic acids, polyacrylamides, and mixtures thereof, the solution capable of forming a gel;

b) injecting the composition into a subterranean formation; and

c) allowing the composition to form a gel.

2. The method of claim 1 wherein said alginate polysaccharide is present in an amount between about 0.5 percent and about 2 percent by weight.

3. The method of claim 1 wherein said alginate polysaccharide has a molecular weight between about 120,000 and about 190,000 Daltons.

4. The method of claim 1 wherein said alginate polysaccharide is derived from algae of the species Macrocystis pyrifera.

5. The method of claim 1 wherein said crosslinking agent is present at a concentration between about 0.0001M and about 0.001M.

6. The method of claim 1 wherein said modifier is 87-89 percent hydrolyzed polyvinyl alcohol with a molecular weight between about 13 and about 186 Daltons.

7. The method of claim 1 wherein said composition further comprises a sequestering agent selected from citrate, phosphate, pyrophosphate, EDTA, adipic acid, salts of D-gluconic acid, and mixtures thereof, at a concentration up to about 5 percent by weight.

8. The method of claim 7 wherein said sequestering agent is present at a concentration up to about 0.005M.

9. The method of claim 1 wherein said gel has a strength which is controlled by varying the molecular weight of said polysaccharide between about 80,000 and about 200,000 Daltons.

10. The method of claim 1 wherein said gel has a strength which is controlled by varying the concentration of said polysaccharide between about 0 percent and about 10 percent by weight.

11. The method of claim 1 wherein said gel has a strength which is controlled by varying the concentration of said crosslinking agent between about 0.0001M and about 0.05M.

12. The method of claim 1 wherein said gel has a strength which is controlled by varying said crosslinking agent selected from the group of Group IIA cations, Fe²⁺, Fe³⁺, Al³⁺, Mn²⁺, Zn²⁺, dialdehydes, diamines, and mixtures thereof.

13. The method of claim 1 wherein said gel has a strength which is controlled by varying the modifier selected from the group of polyvinyl alcohols, polycarboxylic acids, polyacrylamides, and mixtures thereof.

14. The method of claim 1 wherein said gel has a strength which is controlled by varying the concentration of said modifier between about 0 percent and about 5 percent by weight.

15. The method of claim 1 wherein said gel has a strength which is controlled by varying the concentration of said polysaccharide between about 0 percent and about 10 percent by weight.

16. The method of claim 1 wherein said solution has a gelation rate which is controlled by varying said crosslinking agent selected from the group of Group IIA cations, Fe²⁺, Fe³⁺, Al³⁺, Mn²⁺, Zn²⁺, dialdehydes, diamines, and mixtures thereof.

17. The method of claim 1 wherein said solution has a gelation rate which is controlled by varying the concentration of said crosslinking agent between about 0.0001M and about 0.05M.

18. The method of claim 1 wherein said solution has a gelation rate which is controlled by varying the type of modifier selected from the group of synthetic polymers consisting of polyvinyl alcohols, neutral polycarboxylic acids, polyacrylamides, and mixtures thereof.

19. The method of claim 1 wherein said solution has a gelation rate which is controlled by varying the concentration of said modifier between about 0 percent and about 5 percent by weight.

20. The method of claim 1 wherein said solution has a gelation rate which is controlled by adding a sequestering agent to delay gelation, the sequestering agent selected from citrate, phosphate, pyrophosphate, EDTA, adipic acid, and mixtures thereof.

21. The method of claim 1 wherein syneresis of said gel is controlled by varying said concentration of said modifier in said solution between zero percent and about 5 percent by weight.

22. The method of claim 1 wherein syneresis of said gel is controlled by varying said modifier selected from the group of polyvinyl alcohols, neutral polycarboxylic acids, polyacrylamides, and mixtures thereof.

23. The method of claim 1 further comprising:

d) injecting a reservoir flooding fluid into said formation, said gel diverting said fluid into a portion of said formation not occupied by said gel.