Radical trap in oil and gas stimulation operations

• US 9,102,866 B2
• Filed: 12/06/2010
• Issued: 08/11/2015
• Est. Priority Date: 12/11/2009
• Status: Active Grant

• Current Assignee: Arkema Incorporated (Arkema)
• Original Assignee: Arkema Incorporated (Arkema)
• Inventors: Seshadri, Sri R., Palys, Leonard H., Feorino, James J. Jr.
• Primary Examiner(s): Bates, Zakiya W
• Application Number:
  US13/514,374
• Publication Number:
  US 20120241158A1
• Time in Patent Office: 1,709 Days
• US Class Current: 1/1
• CPC Class Codes: C09K 2208/26 Gel breakers other than bacteria or enzymes
• CPC Class Codes: C09K 8/68 containing organic compounds
• CPC Class Codes: C09K 8/70 characterised by their form or by the form of their components, e.g. foams
• CPC Class Codes: C09K 8/88 macromolecular compounds
• CPC Class Codes: E21B 43/26 by forming crevices or fractures

Abstract

A method for using a fracture fluid in forming subterranean fractures includes delaying degradation of a polymer in a fracture fluid when the fracture fluid comprises a breaker by combining at least one radical scavenger with the fracture fluid. The mixture for use in a fracture fluid comprises a radical scavenger and a breaker. A method of fracturing a subterranean formation may include providing a fracture fluid comprising a proppant, a polymer, and a breaker and adding a radical scavenger to the fracture fluid. The fracture fluid is supplied to a desired location in the subterranean formation to form at least one fracture where the viscosity of the fracture fluid is maintained. The breaker is then allowed to degrade the polymer and reduce the viscosity of the fracture fluid at a specific time or temperature.

Claims

1. A method for using a fracture fluid in forming subterranean fractures comprising delaying degradation of a polymer or polymeric viscosifying agent in a fracture fluid at a temperature from about 125°

F. to about 450°

F., when the fracture fluid comprises at least one polymer or polymeric viscosifying agent, a breaker and water, by combining at least one radical scavenger with the fracture fluid, wherein the radical scavenger comprises at least one moiety selected from the group consisting of nitroxide radicals, quinones, hindered phenols, hydroxylamines, and slow polymerizing monomers, 2,2,6,6-tetramethylpiperidine-1-oxyl;

4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl;

nitroxide;

1-(diethoxyphosphinyl)-2,2-dimethylpropyl 1,1-dimethylethyl, mono-t-butyl hydroquinone and mixtures thereof; and

wherein the breaker is selected from the group consisting of organic peroxides, inorganic peroxides, azo initiators, bromates, chlorates, persulfates, and mixtures thereof.

2. A method according to claim 1, wherein the radical scavenger comprises a nitroxide radical.

3. A method according to claim 1, wherein the radical scavenger comprises at least one compound selected from the group consisting of quinones, hindered phenols, hydroxylamines, and slow polymerizing monomers.

4. A method according to claim 1, wherein the radical scavenger is selected from the group consisting of 2,2,6,6-tetramethylpiperidine-1-oxyl;

4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl;

nitroxide, 1-(diethoxyphosphinyl)-2,2-dimethylpropyl 1,1-dimethylethyl; and

mixtures thereof.

5. A method according to claim 1, wherein the radical scavenger is mono-t-butyl hydroquinone.

6. A method according to claim 1, wherein the polymer is a water soluble or water swellable polymer.

7. A method according to claim 1, wherein the polymer is selected from the group consisting of polysaccharides, polysaccharide derivatives, polyacrylates, polyacrylamides, acrylamide methyl propane sulfonic acid copolymers, polyvinyl alcohols, polylactic acids, polyvinyl pyrrolidones, maleic anhydride methyl vinyl ether copolymers, polyethylene oxides;

and mixtures thereof.

8. A mixture for use in a fracture fluid at a temperature from about 125°

F. to about 450°

F., said fracture fluid comprising at least one polymer or polymeric viscosifying agent and water, said mixture comprising a radical scavenger and a breaker, wherein the radical scavenger comprises at least one moiety selected from the group consisting of nitroxide radicals, quinones, hindered phenols, hydroxylamines, and slow polymerizing monomers, 2,2,6,6-tetramethylpiperidine-1-oxyl;

4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl;

nitroxide, 1-(diethylphosphinyl)-2,2-dimethylpropyl 1,1-dimethylethyl, mono-t-butyl hydroquinone, and mixtures thereof; and

wherein the breaker is selected from the group consisting of organic peroxides, inorganic peroxides, azo initiators, bromates, chlorates, persulfates, and mixtures thereof.

9. A mixture according to claim 8, wherein the radical scavenger is selected from the group consisting of 2,2,6,6-tetramethylpiperidine-1-oxyl;

4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl;

nitroxide, 1-(diethoxyphosphinyl)-2,2-dimethylpropyl 1,1-dimethylethyl; and

mixtures thereof; and

the breaker is selected from the group consisting of organic peroxides;

inorganic peroxides;

azo initiators;

oxidizing agents; and

mixtures thereof.

10. A mixture according to claim 8, wherein the breaker is an organic peroxide selected from the group consisting of solid peroxydicarbonates, diacyl peroxides, peroxyesters, monoperoxycarbonates, dialkyl peroxides, peroxyketals, hydroperoxides, ketone peroxides, endoperoxides, and mixtures thereof.

11. A mixture according to claim 8, wherein the mixture is in the form of a homogenous liquid, a free-flowing solid powder, a compressed powder, an encapsulated solid, an encapsulated liquid, or an emulsion.

12. A mixture according to claim 8, wherein the mixture comprises an aqueous liquid.

13. A mixture according to claim 8, wherein the mixture is coated onto or absorbed into a filler material.

14. A fracture fluid mixture comprising:

a proppant;

a water soluble or water swellable polymer selected from the group consisting of polysaccharides, polysaccharide derivatives, polyacrylates, polyacrylamides, acrylamide methyl propane sulfonic acid copolymers, polyvinyl alcohols, polylactic acids, polyvinyl pyrrolidones, maleic anhydride, methyl vinyl ether copolymers, polyethylene oxides; and

mixtures thereof;

a radical scavenger comprising at least one moiety selected from the group consisting of nitroxide radicals, quinones, hindered phenols, hydroxylamines, and slow polymerizing monomers, 2,2,6,6-tetramethylpiperidine-1-oxyl;

4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl;

nitroxide, 1-(diethoxyphosphinyl)-2,2-dimethylpropyl 1,1-dimethylethyl, mono-t-butyl hydroquinone, and mixtures thereof;

a breaker; and

an aqueous fluid.

15. A fracture fluid according to claim 14, further comprising an accelerator.

16. A fracture fluid according to claim 14, wherein the radical scavenger is present in an amount of about 0.01 to 100 parts by weight of the radical scavenger relative to 100 parts by weight of the breaker.

17. A fracture fluid according to claim 14, wherein the breaker is present in amount of about 1 ppm to about 100,000 ppm by weight based on the fracturing fluid.

18. A fracture fluid according to claim 14, additionally comprising at least one surfactant.