Hydrazide crosslinked polymer emulsions for use in crude oil recovery
View Patent ↗Emulsions of mobility control polymers can be used to increase recovery of crude oil from a subterranean hydrocarbon-containing formation. A flooding fluid comprising the polymer emulsions are injected into a well that is in contact with the subterranean hydrocarbon-containing formation. The polymers can be temporarily cross-linked via hydrolyzable crosslinking moieties derived from a multifunctional hydrazide, a multifunctional amine, a multifunctional hydroxylamine, or a combination thereof and have improved injectivity into the well; the improved injectivity can be measured in terms of the flooding fluid's filter ratio, flow rate, and viscosity.
1. A method for increasing recovery of crude oil from a subterranean hydrocarbon-containing formation, the method comprising injecting an aqueous flooding fluid into a well that is in contact with the subterranean hydrocarbon-containing formation, the aqueous flooding fluid comprising injection water and a mobility control agent, the mobility control agent comprising a crosslinked water-soluble polymer,
wherein the crosslinking units are derived from a multifunctional hydrazide, a multifunctional amine, a multifunctional hydroxylamine, or a combination thereof and degrade to form a water-soluble polymer having fewer crosslinks and
wherein the mobility control agent does not block the pores of the subterranean hydrocarbon-containing formation and an aqueous flooding fluid comprising the water-soluble polymer with fewer crosslinks has a higher viscosity than the aqueous flooding fluid comprising the crosslinked water-soluble polymer.
2. The method of claim 1 , wherein the crosslinking units are derived from the multifunctional hydrazide.
3. The method of claim 1 , wherein the water-soluble polymer comprises a carbonyl group, and the crosslinks within the crosslinked water-soluble polymer are derived from reaction of the multifunctional hydrazide with the carbonyl group of the water-soluble polymer, wherein the crosslinks are degraded after the aqueous flooding fluid comprising the crosslinked water-soluble polymer is contacted with the hydrocarbon-containing formation to form the aqueous flooding fluid comprising the water-soluble polymer having fewer crosslinks.
4. The method of claim 1 , wherein the water-soluble polymer comprising a carbonyl group is an uncrosslinked water-soluble polymer.
5. The method of claim 1 , wherein the crosslinked water-soluble polymer comprises crosslinking units derived from a hydrazide corresponding to Formulae I or II:
wherein
Y is a bond, C 2 -C 18 alkylene, C 2 -C 18 alkenylene, arylene, or alkarylene.
6. The method of claim 5 , wherein Y is a bond, ethylene, or butylene.
7. The method of claim 5 , wherein the water-soluble polymer comprises a repeat unit derived from acrylic acid, an acrylic acid salt, a methacrylic acid salt, methacrylic acid, diacetone acrylamide, acrylamide, a 2-acrylamido-2-methylpropane sulfonic acid salt, or a combination thereof.
8. The method of claim 5 , wherein the crosslinks within the crosslinked water-soluble polymer are formed (a) prior to polymerization, (b) during polymerization, or (c) after polymerization.
9. The method of claim 8 , wherein the crosslinked water-soluble polymer comprises about 0.1 ppm to about 2000 ppm covalently bonded crosslinking units based on the total weight of the water-soluble polymer.
10. The method of claim 9 , wherein the weight average molecular weight of the uncrosslinked water-soluble polymer is from about 4 MDa to about 20 MDa.
11. The method of claim 1 , wherein the aqueous flooding fluid as injected into the well has a filter ratio of from 1 to about 1.5 at 1000 ppm polymer concentration when the membrane filter size is less than 5.0 microns.
12. The method of claim 11 , wherein the membrane filter size is 1.2 microns.
13. The method of claim 1 , wherein the aqueous flooding fluid comprises about 100 ppm to about 10000 ppm of the water-soluble polymer.
14. The method of claim 1 , wherein prior to injection, the aqueous flooding fluid has a viscosity of about 0 cPs to about 100 cPs.
15. The method of claim 1 , wherein after injection, the aqueous flooding fluid has a viscosity of about 1 cPs to about 5000 cPs.
16. A composition comprising water and a crosslinked water-soluble polymer, wherein the crosslinked water-soluble polymer is derived from a multifunctional hydrazide and a carbonyl functionality present in an uncrosslinked water-soluble polymer, and the weight number average molecular weight of the uncrosslinked water-soluble polymer is from about 5 MDa to about 20 MDa as determined by multi-angle light scattering (MALS).
17. The composition of claim 16 , wherein the uncrosslinked water-soluble polymer comprises a repeat unit derived from acrylic acid, an acrylic acid salt, a (meth)acrylic acid salt, (meth)acrylic acid, diacetone acrylamide, acrylamide, a 2-acrylamido-2-methylpropane sulfonic acid salt, or a combination thereof.
18. A crosslinked polymer wherein the polymer is derived from a 2-acrylamido-2-methylpropane sulfonic acid salt, a styrene sulfonic acid salt, 2-(acryloyloxy)-N,N,N-trimethylethanaminium salt, N,N-dimethylaminoethyl acrylate methyl chloride quaternary salt, N,N-dimethylaminoethyl methacrylate methyl chloride quaternary salt, N,N-dimethylaminopropyl acrylamide methyl chloride quaternary salt, N,N-dimethylaminopropyl methacrylamide methyl chloride quaternary salt, N-vinylformamide, N-vinylpyrrolidinone, diallyldimethyl ammonium chloride, or a combination thereof; and the crosslinking units are derived from a hydrazide corresponding to Formulae I or II:
wherein Y is a bond, C 2 -C 18 alkylene, or C 2 -C 18 alkenylene, arylene, or alkarylene.
19. The crosslinked polymer of claim 18 , wherein the polymer is derived from a 2-acrylamido-2-methylpropane sulfonic acid salt, a styrene sulfonic acid salt, or a combination thereof.