Hydrazide-based curing agents for use in subterranean operations

Patent metadata

Field	Value
Publication number	US-10287478-B2
Application number	US-201515535805-A
Country	US
Kind code	B2
Filing date	Jan 16, 2015
Priority date	Jan 16, 2015
Publication date	May 14, 2019
Grant date	May 14, 2019

Abstract

Curable resin compositions comprising an epoxy resin and a hydrazide curing agent and methods for using the curable resin compositions in cementing and/or remedial operations in a subterranean formation are provided. In one embodiment, the method may comprise combining an epoxy resin and a curing agent to form a curable resin composition, wherein the curing agent comprises a hydrazide curing agent; introducing the curable resin composition into a subterranean formation; and allowing the curable resin composition to at least partially cure.

First claim

What is claimed is:

1. A method comprising:
combining an epoxy resin and a curing agent to form a curable resin composition, wherein the curing agent consists of a hydrazide curing agent, and wherein the curable resin composition comprises the curing agent in an amount from about 20% to about 40% by weight of the curable resin composition;
introducing the curable resin composition into an annulus formed between a casing string and a wellbore located within a subterranean formation or a perforation in a cement sheath or the casing string located within the subterranean formation; and
allowing the curable resin composition to at least partially cure within the annulus or the perforation.

2. The method of claim 1 wherein the hydrazide curing agent is a dihydrazide having the following chemical structure:

wherein R comprises (—CH 2 —) n or (—Ar—);
wherein n is a number from 0 to 10; and
wherein Ar is an aromatic ring.

3. The method of claim 1 wherein the hydrazide curing agent comprises at least one compound selected from the group consisting of: an aromatic hydrazide, an aliphatic hydrazide, and any combination thereof.

4. The method of claim 1 wherein the hydrazide curing agent is selected from the group consisting of: adipic acid dihydrazide, 3, 4-diaminobenzhydrazide, succinic dihydrazide, 4-aminobenzoic hydrazide, (+)-biotinamidohexanoic acid hydrazide, oxalyldihydrazide, maleic hydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, 1,4-cyclohexyl dihydrazide, 4,4′-(propane-1,3-diylbisoxy) dibenzoic dihydrazide, terephthalic acid dihydrazide, isophthalic dihydrazide, and any combination thereof.

5. The method of claim 1 wherein the curable resin composition does not cure at room temperature.

6. The method of claim 1 further comprising adding at least one of a diluent, a filler particle, a silane coupling agent, or any combination thereof to the curable resin composition.

7. The method of claim 1 wherein combining the epoxy resin and the curing agent is performed at an off-site location.

8. The method of claim 1 wherein the subterranean formation has a temperature above the activation temperature of the hydrazide curing agent.

9. The method of claim 1 further comprising increasing the temperature of the subterranean formation to above the activation temperature of the hydrazide curing agent before allowing the curable resin composition to cure, wherein the subterranean formation has a temperature below the activation temperature of the hydrazide curing agent when the curable resin composition is introduced into the subterranean formation.

10. The method of claim 1 wherein the curable resin composition is introduced into the subterranean formation using one or more pumps.

11. The method of claim 1 further comprising combining the curable resin composition with a cement slurry before introducing the curable resin composition into a subterranean formation.

12. A method comprising:
combining an epoxy resin and a curing agent to form a curable resin composition, wherein the curable resin composition comprises the curing agent in an amount from about 20% to about 40% by weight of the curable resin composition, and wherein the curing agent consists of a dihydrazide having the following chemical structure:

wherein R comprises (—CH 2 —) n or (—Ar—);
wherein n is a number from 0 to 10; and
wherein Ar is an aromatic ring;

introducing the curable resin composition into a subterranean formation; and
allowing the curable resin composition to at least partially cure.

13. A curable resin composition comprising:
an epoxy resin;
a curing agent consisting of a hydrazide curing agent, wherein the curable resin composition comprises the curing agent in an amount from about 20% to about 40% by weight of the curable resin composition; and
a diluent in an amount from about 0.1% to about 50% by weight of the epoxy resin.

14. The curable resin composition of claim 13 wherein the epoxy resin is selected from the group consisting of: bisphenol A diglycidyl ether resins, bisphenol F diglycidyl ether resins, bisphenol AF diglycidyl ether resins, bisphenol S diglycidyl ether resins, novolac epoxy resins, cyclohexanedimethanol diglycidyl ether, tetraphenylolethane glycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propyleneglycol) diglycidyl ether, hexanediol diglycidyl ether, epoxy cresol novolacs, butanediol diglycidyl ether, N,N-diglycidyl-4-glycidyloxyaniline, resorcinol diglycidyl ether, tris(4-hydroxyphenyl) methane triglycidyl ether, and tetraglycidyl-4,4′-methylenedianiline, neopentyl glycol diglycidyl ether, and any combination thereof.

15. The curable resin composition of claim 13 wherein the hydrazide curing agent is selected from the group consisting of: adipic acid dihydrazide, 3, 4-diaminobenzhydrazide, succinic dihydrazide, 4-aminobenzoic hydrazide, (+)-biotinamidohexanoic acid hydrazide, oxalyldihydrazide, maleic hydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, 1,4-cyclohexyl dihydrazide, 4,4′-(propane-1,3-diylbisoxy) dibenzoic dihydrazide, terephthalic acid dihydrazide, isophthalic dihydrazide, and any combination thereof.

16. The curable resin composition of claim 13 wherein the diluent is selected from the group consisting of: polyethylene glycol, butyl lactate, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dimethyl formamide, diethylene glycol methyl ether, ethyleneglycol butyl ether, diethyleneglycol butyl ether, propylene carbonate, d-limonene, fatty acid methyl esters, xylenes, solvent naphthas, butyl glycidyl ether, ethylhexyl glycidyl ether, C 12 -C 14 alcohol glycidyl ether, cresol glycidyl ether, tert-butyl glycidyl ether, tert-butyl phenol glycidyl ether, cashew nut shell liquid glycidyl ether, and any combination thereof.

17. The curable resin composition of claim 13 further comprising a plurality of filler particles selected from the group consisting of: aluminum oxide, awaruite, barium carbonate, barium oxide, barite, calcium carbonate, calcium oxide, chromite, chromium oxide, copper, copper oxide, dolomite, galena, gold, hematite, a hollow glass microsphere, ilmenite, iron oxide, kaolinite, siderite, magnetite, magnesium oxide, manganese carbonate, manganese dioxide, manganese (IV) oxide, manganese oxide, manganese tetraoxide, manganese (II) oxide, manganese (III) oxide, molybdenum (IV) oxide, molybdenum oxide, molybdenum trioxide, Portland cement, pumice, pyrite, spherelite, silica, silver, tenorite, titania, titanium (II) oxide, titanium (III) oxide, titanium (IV) dioxide, zirconium oxide, zirconium silicate, zinc oxide, cement-kiln dust, unexpanded and expanded perlite, attapulgite, bentonite, zeolite, an elastomer, sand, and any combination thereof.

18. The curable resin composition of claim 13 further comprising a silane coupling agent selected from the group consisting of: N-2-(aminoyl)-3-aminopropyl triethoxy silane, 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxy silane, and any combination thereof.

Assignees

• Halliburton Energy Services Inc

Inventors

• Kellum Matthew Grady
• Hundt Gregory Robert
• Jones Paul Joseph
• Karcher Jeffery Dwane

Classifications

• C04B26/14

  Polyepoxides · CPC title

• C09K8/42 Primary

  Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells (compositions for plastering C09K8/50) · CPC title

• C04B28/02

  containing hydraulic cements other than calcium sulfates · CPC title

• C09K8/44 Primary

  containing organic binders only · CPC title

• E21B33/13

  Methods or devices for cementing, for plugging holes, crevices or the like · CPC title