Delayed gelation of polymers

Patent metadata

Field	Value
Publication number	US-2016137906-A1
Application number	US-201514847734-A
Country	US
Kind code	A1
Filing date	Sep 8, 2015
Priority date	Nov 19, 2014
Publication date	May 19, 2016
Grant date	—

Abstract

The disclosure is directed to methods and compositions delaying the gelation of polymers in water flooding by sequentially or co-injecting a carboxylate-containing polymer solution, a gel-delaying polymer, and gelation agent into a hydrocarbon reservoir. Delays of weeks are observed.

First claim

1 ) A method of increasing the recovery of hydrocarbon fluids in a subterranean formation comprising:
a) sequentially injecting a carboxylate-containing polymer, at least one gel-delaying polymer, and a crosslinker into an in-line mixer to form a gelling solution; b) mixing said gelling solution in said in-line mixer; and, c) injecting said gelling solution into said subterranean formation; wherein said gel-delaying polymer delays the gelation of said carboxylate-containing polymer by said crosslinker in said subterranean formation.

2 ) The method of claim 1 ), further comprising step d) injecting fluid into said subterranean formation to displace said gelling solution deeper into said subterranean formation.

3 ) The method of claim 1 ), wherein said carboxylate-containing polymer is partially hydrolyzed polyacrylamide (HPAM), a polymeric microparticle containing acrylamide and sodium acrylate, copolymers of N-vinyl-2-pyrrolidone and sodium acrylate, tetrapolymers of sodium-2-acrylamido-2-methylpropanesulfonate, acrylamide and N-vinyl-2-pyrrolidone and sodium acrylate; and copolymers of sodium-2-acrylamido-2-methylpropanesulfonate and sodium acrylate; carboxylated polysaccharide; carboxymethylcellulose; carboxylated guar; and combinations thereof.

4 ) The method of claim 1 ), wherein said gel-delaying polymer is made from monomers selected from the group of vinyl, allyl, styrene, and acrylamide monomers and their derivatives, conjugated with a dicarboxylate or tricarboxylate.

5 ) The method of claim 4 ), wherein said dicarboxylate or tricarboxylate is citrate, succinate, aspartate, glutamate, malate, oxalate, malonate, glutarate, adipate, or pimelate, or a derivative thereof.

6 ) The method of claim 1 ), wherein said gel-delaying polymer is polyvinyl alcohol succinate (PVAS), N-hydroxylmethyl acrylamide (NHMA) succinate, allyl alcohol succinate and allylamine succinate, PVA malate, NHMA malate, allyl alcohol malate or allylamine malate.

7 ) The method of claim 1 ), wherein said gel-delaying polymer polyaspartate (PAsp), polymalate, polyoxalate, polymalonate, polyglutarate, polyadipate, or polypimelate.

8 ) The method of claim 1 ), wherein said crosslinker is a multivalent metal ion.

9 ) The method of claim 8 ), wherein said multivalent metal ion is chromium, zirconium, iron, aluminum, and titanium.

10 ) The method of claim 1 ), wherein said crosslinker is polyethylenimine (“PEI”).

11 ) The method of claim 1 ), wherein said gel-delaying polymer is PAsp, said crosslinker is Cr(III) and said carboxylate-containing polymer is HPAM.

12 ) The method of claim 1 ), wherein said gel-delaying polymer is PVAS, said crosslinker is Cr(III) and said carboxylate-containing polymer is HPAM.

13 ) The method of claim 1 ), wherein said gel-delaying polymer is PAsp, said crosslinker is Cr(III) and said carboxylate-containing polymer is a microparticle containing HPAM.

14 ) The method of claim 1 ), wherein said gel-delaying polymer is PVAS, said crosslinker is Cr(III) and said carboxylate-containing polymer is a microparticle containing HPAM.

15 ) An improved method of sweeping for oil or gas, said method requiring blocking thief zones with a polymer, and sweeping a reservoir for oil or gas, the improvement comprising:
a) injecting into a reservoir, in order:
i) a carboxylate-containing polymer,
ii) at least one gel-delaying polymer, and
iii) a crosslinker,
to form a gelling composition;
b) aging said composition until the viscosity increases; and, c) sweeping the reservoir for oil or gas.

16 ) An improved method of producing oil or gas, said method requiring injecting a polymer into a reservoir and producing an oil or gas, the improvement comprising:
a) injecting into a reservoir, in order,
i) a carboxylate-containing polymer,
ii) at least one gel-delaying polymer, and
iii) a crosslinker into a reservoir,
to form a gelling composition;
b) aging said composition for at least 35 days at 85° C. until the viscosity increases; and c) producing said oil or gas.

17 ) The method of claim 15 ), wherein said carboxylate-containing polymer is partially hydrolyzed polyacrylamide (HPAM), a polymeric microparticle containing acrylamide and sodium acrylate, copolymers of N-vinyl-2-pyrrolidone and sodium acrylate, tetrapolymers of sodium-2-acrylamido-2-methylpropanesulfonate, acrylamide and N-vinyl-2-pyrrolidone and sodium acrylate; and copolymers of sodium-2-acrylamido-2-methylpropanesulfonate and sodium acrylate; carboxylated polysaccharide; carboxymethylcellulose; carboxylated guar; and combinations thereof.

18 ) The method of claim 15 ), wherein said gel-delaying polymer is polyvinyl alcohol succinate (PVAS), N-hydroxylmethyl acrylamide (NHMA) succinate, allyl alcohol succinate and allylamine succinate, PVA malate, NHMA malate, allyl alcohol malate or allylamine malate.

19 ) The method of claim 15 ), wherein said gel-delaying polymer wherein said carboxylated polymer polyaspartate (PAsp), polymalate, polyoxalate, polymalonate, polyglutarate, polyadipate, or polypimelate.

20 ) The method of claim 15 ), wherein said crosslinker is a multivalent metal ion selected from chromium, zirconium, iron, aluminum, and titanium.

21 ) The method of claim 15 ), wherein said crosslinker is PEI.

22 ) The method of claim 15 ), wherein said gel-delaying polymer is PAsp, said crosslinker is Cr(III) and said carboxylate-containing polymer is HPAM.

23 ) The method of claim 15 ), wherein said gel-delaying polymer is PVAS, said crosslinker is Cr(III) and said carboxylate-containing polymer is HPAM.

24 ) The method of claim 15 ), wherein said gel-delaying polymer is PAsp, said crosslinker is Cr(III) and said carboxylate-containing polymer is a microparticle containing HPAM.

25 ) The method of claim 15 ), wherein said gel-delaying polymer is PVAS, said crosslinker is Cr(III) and said carboxylate-containing polymer is a microparticle containing HPAM.

26 ) A product produced by the methods in claim 1 .

27 ) A delayed gelling composition comprising a carboxylate-containing polymer, at least one gel-delaying polymer, and a crosslinker admixed with an injection fluid.

28 ) The delayed gelling composition of claim 27 ), wherein said crosslinker is a multivalent metal ion selected from chromium, zirconium, iron, aluminum, and titanium.

29 ) The delayed gelling composition of claim 27 ), wherein said crosslinker is PEI.

30 ) The delayed gelling composition of claim 27 ), wherein said carboxylate-containing polymer is partially hydrolyzed polyacrylamide (HPAM), copolymers of N-vinyl-2-pyrrolidone and sodium acrylate, tetrapolymers of sodium-2-acrylamido-2-methylpropanesulfonate, acrylamide, N-vinyl-2-pyrrolidone and sodium acrylate; and copolymers of sodium-2-acrylamido-2-methylpropanesulfonate and sodium acrylate; carboxylated polysaccharide; carboxymethylcellulose; carboxylated guar; and combinations thereof.

31 ) The delayed gelling composition of claim 27 ), wherein said carboxylate-containing polymer is a microparticle containing HPAM.

32 ) The delayed gelling composition of claim 27 ), wherein said gel-delaying polymer is made from monomers selected from the group of vinyl, allyl, styrene, and acrylamide monomers and their derivatives, conjugated with a dicarboxylate or t

Assignees

• Conocophillips Co
• Univ Kansas

Inventors

• Guan Huili
• Berkland Cory
• Moradi-Araghi Ahmad
• Liang Jenn-Tai
• Christian Terry M
• Needham Riley B
• Cheng Min

Classifications

• C09K8/512

  containing cross-linking agents · CPC title

• C09K8/50

  Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls (compositions for consolidating loose sand or the like around wells C09K8/56) · CPC title

• C09K8/588 Primary

  characterised by the use of specific polymers {(polymeric surfactants C09K8/584)} · CPC title

• E21B43/16

  Enhanced recovery methods for obtaining hydrocarbons · CPC title