DELAYED GELLING AGENTS

• US 20120037364A1
• Filed: 06/09/2011
• Published: 02/16/2012
• Est. Priority Date: 08/11/2010
• Status: Active Grant

• Current Assignee: Conocophillips Company (ConocoPhillips), University of Kansas
• Original Assignee: ConocoPhillips, University of Kansas
• Inventors: Guan, Huili, Berkland, Cory, Moradi-Araghi, Ahmad, Liang, Jenn-Tai, Zornes, David R., Needham, Riley B., Cheng, Min, Hedges, James H., Scully, Faye L., Johnson, James P.
• Granted Patent: US 9,850,425 B2
• Time in Patent Office: Days
• US Class Current: 166/270
• CPC Class Codes: C09K 8/588 characterised by the use of specific polymers polymeric surfactants C09K8/584
• CPC Class Codes: C09K 8/88 macromolecular compounds
• CPC Class Codes: C09K 8/887 containing cross-linking agents
• CPC Class Codes: C09K 8/92 characterised by their form or by the form of their components, e.g. encapsulated material C09K8/70 takes precedence
• CPC Class Codes: E21B 33/138 Plastering the borehole wall; Injecting into the formation

Abstract

The invention is directed to delayed gelation agents comprising a degradable polymeric cage containing therein one or more gelation agents. The cage degrades in situ, e.g, in an oil reservoir, thus releasing the gelation agent(s), which can then crosslink second polymers in situ to form a gel.

Claims

1. A delayed gelation composition, comprising a degradable polymeric cage, and having within said cage a gelation agent.

2. The composition of claim 1, comprising one or more labile monomers or polymers or crosslinkers that degrade to release said gelation agent.

3. The delayed gelation composition of claim 1, comprising a polymer comprising one or more monomers, said polymer being crosslinked with a labile crosslinker to form said degradable polymeric cage.

4. The composition of claim 3, wherein said monomer is an anionic monomer.

5. The composition of claim 3, wherein said monomer is a sulfonate containing monomer.

6. The composition of claim 3, wherein said monomer is sodium 2-acrylamido-2-methylpropane sulfonate, sodium vinylsulfonate, vinyl sulfate salts, phenyl vinyl sulfonate salts, vinyl phosphate salts or combinations thereof.

7. The composition of claim 3, wherein said monomer is sodium 2-acrylamido-2-methylpropane sulfonate.

8. The composition of claim 3, wherein said gelation agent is a multivalent cation or a cationic polymer or combinations thereof.

9. The composition of claim 3, wherein said gelation agent is a complexed multivalent cation or a cationic polymer or combinations thereof.

10. The composition of claim 3, wherein said gelation agent is at least one selected from the group consisting of a cationic crosslinker, Al³⁺, Fe³⁺, Cr³⁺, Ti⁴⁺, Sn⁴⁺, Zr⁴⁺, poly-ethyleneimine, poly-L-lysine, poly-ε

-lysine, polyallylamine, polyvinylamine and complexes or nanoparticles containing same.

11. The composition of claim 3, comprising an anionic polymer crosslinked with a labile crosslinker and a stable crosslinker to form a partially degradable polymeric cage, and having within said partially degradable cage a cationic gelation agent.

12. The composition of claim 3, wherein the labile crosslinker comprises a diacrylate.

13. The composition of claim 3, wherein the labile crosslinker comprises a polyethylene glycol diacrylate.

14. The composition of claim 3, wherein the monomer comprises sodium AMPS and the labile crosslinker comprises a polyethylene glycol diacrylate and the gelation agent comprises chromium and polyethyleneimine.

15. The composition of claim 3, wherein the labile crosslinker is an acid labile ketal of the formula:

16. The composition of claim 3, wherein the labile crosslinker is 2-bis[2,2′

-di(N-vinylformamido)ethoxy]propane or 2-(N-vinylformamido)ethyl ether.

17. The composition of claim 3, comprising a sulfonate containing polymer crosslinked with a labile diacrylate crosslinker to form a cage, and having within said cage a complexed multivalent cation and a cationic crosslinker, admixed with a second polymer and a fluid comprising water, wherein said gelation agent can crosslink said second polymer to form a gel when said cage is degraded and said gelation agent is released.

18. The composition of claim 3, further comprising a second polymer and a fluid comprising water, and said gelation agent can crosslink said second polymer to form a gel when said cage is degraded and said gelation agent is released.

19. The composition of claim 18, wherein said second polymer contains anionic groups.

20. The composition of claim 18, wherein said second polymer contains carboxylate groups.

21. The composition of claim 18, wherein said second polymer is partially hydrolyzed polyacrylamide.

22. The composition of claim 18, wherein said second polymer comprises acrylamide and sodium acrylate monomers, and the second polymer is crosslinked with methylene bisacrylamide and polyethylene glycol diacrylate.

24. The method of claim 22, wherein injection steps a) and b) are simultaneous.

25. The method of claim 22, wherein injection step b) occurs before injection step a).

26. The method of claim 22, wherein injection step a) occurs before injection step b).

27. The method of claim 22, wherein the second polymer is in the form of an expandable polymeric particle.

28. The method of claim 22, wherein the second polymer is in the form of an expandable polymeric particle that is highly crosslinked with a stable crosslinker and a labile crosslinker.

29. The method of claim 22, wherein the second polymer is part of the degradable polymeric cage.

30. A method of making the composition of claim 3, comprising

a) mixing a monomer and an initiator and a crosslinker and a gelation agent, to form a degradable polymeric cage containing a gelation agent;

or

b) mixing a polymer and a crosslinker and a gelation agent, to form a degradable polymeric cage containing a gelation agent.

23. A method of increasing the recovery of hydrocarbon fluids in a subterranean formation comprising:

a) injecting into a subterranean formation a composition comprising water and a degradable polymeric cage and having within said cage one or more gelation agents,

wherein said degradable polymeric cage degrades on exposure to ambient conditions in said subterranean formation thus releasing said one or more gelation agents,

b) injecting into a subterranean formation a composition comprising a second polymer;

wherein said released gelation agent crosslinks said second polymer to form a gel in said subterranean formation.