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US4439334A Expired / Lapsed US ⏱️ 0.0 years remaining

Enhanced oil recovery methods and systems

Assignee: Halliburton Co
•
Filing: 1981-07-14
•
Granted: 1984-03-27
•
Expires: 2001-07-14
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Abstract

Abstract Methods of preparing viscous aqueous polymer solutions having improved viscosity and stability properties for use in the treatment of subterranean hydrocarbon-containing formations and in enhanced oil recovery processes are provided. Methods and systems for enhancing the recovery of oil from subterranean oil-containing formations are also provided. The viscous aqueous polymer solutions of the invention are prepared by polymerizing one or more water soluble polymerizable vinyl monomers in a substantially oxygen-free aqueous solvent and then further diluting the resultant concentrated solution in additional solvent. Such viscous aqueous polymer solutions have improved viscosity properties and increased compatibility with oil well treating fluid additives, especially clay stabilizers.

Inventors

  • 👤 John K. Borchardt

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-09 05:08
CPC Classifications
C; C09; C09K; C09K8/00; C09K8/02; C09K8/03; C09K8/035; Y; Y10; Y10S; Y10S507/00; Y10S507/935; Y10S507/936

Claims Analysis

Total Claims: 24
Claim 1
Independent Claim 321 words
A method of enhancing the recovery of oil from a subterranean oil-containing formation wherein a viscous aqueous solution containing one or more water-soluble organic polymers is injected into the formation by way of at least one injection well penetrating the formation and forced through the formation towards at least one production well penetrating the formation, comprising: preparing an aqueous injection solution of desired viscosity and other properties at the site of said injection and production wells by: combining one or more vinyl monomers with a substantially oxygen-free aqueous solvent, said vinyl monomers being selected from the group consisting of monomers and mixtures of monomers having the general formula: ##STR7## wherein: R is hydrogen or --CH 3 ; X is --NH 2 , --NHR 1 , ##STR8## --OR 3 or --OM, with the restriction that X is not --OM when the aqueous polymerization solvent contains divalent metal; R 1 is an alkyl radical having in the range of from 1 to 4 carbon atoms or R 1 is R 4 --Y; R 2 is an alkyl radical having in the range of from 1 to 3 carbon atoms; R 3 is an alkyl radical having in the range of from 1 to 3 carbon atoms; R 4 is an alkyl radical having in the range of from 1 to 4 carbon atoms; Y is --SO 3 H, --CO 2 H, --SO 3 M or --CO 2 M; and M is hydrogen or a metal from Group IA of the Periodic Table of the Elements; and combining a free radical polymerization initiator with the resultant solution to cause the polymerization of said monomers and the formation of a concentrated aqueous viscous polymer solution; and diluting said concentrated viscous aqueous polymer solution with additional amounts of the same substantially oxygen-free aqueous solvent to thereby form said aqueous injection fluid; and injecting said aqueous injection fluid into said formation by way of said injection well.
Claim 2
Independent Claim 321 words
A method of enhancing the recovery of oil from a subterranean oil-containing formation wherein a viscous aqueous solution containing one or more water-soluble organic polymers is injected into the formation by way of at least one injection well penetrating the formation and forced through the formation towards at least one production well penetrating the formation, comprising: preparing an aqueous injection solution of desired viscosity and other properties at the site of said injection and production wells by: combining one or more vinyl monomers with a substantially oxygen-free aqueous solvent, said vinyl monomers being selected from the group consisting of monomers and mixtures of monomers having the general formula: ##STR7## wherein: R is hydrogen or --CH 3 ; X is --NH 2 , --NHR 1 , ##STR8## --OR 3 or --OM, with the restriction that X is not --OM when the aqueous polymerization solvent contains divalent metal; R 1 is an alkyl radical having in the range of from 1 to 4 carbon atoms or R 1 is R 4 --Y; R 2 is an alkyl radical having in the range of from 1 to 3 carbon atoms; R 3 is an alkyl radical having in the range of from 1 to 3 carbon atoms; R 4 is an alkyl radical having in the range of from 1 to 4 carbon atoms; Y is --SO 3 H, --CO 2 H, --SO 3 M or --CO 2 M; and M is hydrogen or a metal from Group IA of the Periodic Table of the Elements; and combining a free radical polymerization initiator with the resultant solution to cause the polymerization of said monomers and the formation of a concentrated aqueous viscous polymer solution; and diluting said concentrated viscous aqueous polymer solution with additional amounts of the same substantially oxygen-free aqueous solvent to thereby form said aqueous injection fluid; and injecting said aqueous injection fluid into said formation by way of said injection well.
Claim 3
Dependent Claim 28 words
The method of claim 1 wherein said aqueous solvent is selected from the group consisting of fresh water, salt water, oil field brines, sea water and mixtures thereof.
Claim 4
Dependent Claim 25 words
The method of claim 1 wherein said aqueous solvent contains one or more alkali metal or alkaline earth metal salts at concentrations up to saturation.
Claim 5
Dependent Claim 28 words
The method of claim 1 wherein said free radical polymerization initiator is selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, benzoyl peroxide, and 2,2'-azobis(isobutyronitrile).
Claim 6
Dependent Claim 30 words
The method of claim 1 which is further characterized to include the step of combining a chain transfer agent with said aqueous solvent prior to polymerizing said vinyl monomers therein.
Claim 7
Dependent Claim 25 words
The method of claim 5 wherein said chain transfer agent is selected from the group consisting of triethanolamine, butyl alcohol, isopropyl alcohol and mixtures thereof.
Claim 8
Dependent Claim 45 words
The method of claim 1 which is further characterized to include the step of controlling the degree of hydrolysis of the polymers polymerized in said aqueous solvent by adjusting the pH of said aqueous solvent to a selected level prior to polymerizing said monomers therein.
Claim 9
Dependent Claim 50 words
The method of claim 1 which is further characterized to include the step of combining a buffer with said aqueous salt solution in a quantity sufficient to maintain the pH thereof in the range of from about 7 to about 11.5 prior to combining said free radial polymerization initiator therewith.
Claim 10
Dependent Claim 35 words
The method of claim 1 wherein said monomers are combined with said aqueous solvent in an amount in the range of from about 1% to about 10% by weight of the resultant aqueous monomer-salt solution.
Claim 11
Dependent Claim 21 words
The method of claim 5 wherein said free radical polymerization initiator is sodium persulfate and said chain transfer agent is triethanolamine.
Claim 12
Dependent Claim 36 words
The method of claim 1 which is further characterized to include the step of combining one or more organic polymer clay stabilizers which will not function as chain transfer agents with said viscous aqueous treating solution.
Claim 13
Dependent Claim 50 words
The method of claim 1 which is further characterized to include the step of combining one or more organic polymer clay stabilizers which will not function as chain transfer agents with the solution resulting from the combination of the substantially oxygen-free aqueous solvent and the one or more vinyl monomers.
Claim 14
Independent Claim 244 words
A method of enhancing the recovery of oil from a subterranean oil-containing formation wherein a viscous aqueous solution containing one or more water-soluble organic polymers is injected into the formation by way of at least one injection well penetrating the formation and forced through the formation towards at least one production well penetrating the formation, comprising: preparing an aqueous injection solution of desired viscosity and other properties at the site of said injection and production well by: combining one or more vinyl monomers with a substantially oxygen-free aqueous solvent, said vinyl monomers being selected from the group consisting of monomers and mixtures of monomers having the general formula: ##STR9## wherein: R is hydrogen or --CH 3 ; X is --NH 2 , --NHR' ##STR10## --OR' or --OM with the restriction that when divalent metals are present in the aqueous solvent, X is not --OM; R' is an alkyl radical having in the range of from 1 to 4 carbon atoms; and M is hydrogen or a metal from Groups IA of the Periodic Table of the Elements; combining a free radical polymerization initiator with the resultant solution to cause the polymerization of said monomers and the formation of a concentrated viscous aqueous polymer solution; and diluting said concentrated viscous aqueous polymer solution with additional amounts of the same substantially oxygen-free aqueous solvent to thereby form said aqueous injection fluid; and injecting said aqueous injection fluid into said formation by way of said injection well.
Claim 15
Independent Claim 244 words
A method of enhancing the recovery of oil from a subterranean oil-containing formation wherein a viscous aqueous solution containing one or more water-soluble organic polymers is injected into the formation by way of at least one injection well penetrating the formation and forced through the formation towards at least one production well penetrating the formation, comprising: preparing an aqueous injection solution of desired viscosity and other properties at the site of said injection and production well by: combining one or more vinyl monomers with a substantially oxygen-free aqueous solvent, said vinyl monomers being selected from the group consisting of monomers and mixtures of monomers having the general formula: ##STR9## wherein: R is hydrogen or --CH 3 ; X is --NH 2 , --NHR' ##STR10## --OR' or --OM with the restriction that when divalent metals are present in the aqueous solvent, X is not --OM; R' is an alkyl radical having in the range of from 1 to 4 carbon atoms; and M is hydrogen or a metal from Groups IA of the Periodic Table of the Elements; combining a free radical polymerization initiator with the resultant solution to cause the polymerization of said monomers and the formation of a concentrated viscous aqueous polymer solution; and diluting said concentrated viscous aqueous polymer solution with additional amounts of the same substantially oxygen-free aqueous solvent to thereby form said aqueous injection fluid; and injecting said aqueous injection fluid into said formation by way of said injection well.
Claim 16
Dependent Claim 25 words
The method of claim 13 wherein said aqueous solvent contains one or more alkali metal or alkaline earth metal salts at concentrations up to saturation.
Claim 17
Dependent Claim 30 words
The method of claim 13 which is further characterized to include the step of combining a chain transfer agent with said aqueous solvent prior to polymerizing said vinyl monomers therein.
Claim 18
Dependent Claim 25 words
The method of claim 15 wherein said chain transfer agent is selected from the group consisting of triethanolamine, butyl alcohol, isopropyl alcohol and mixtures thereof.
Claim 19
Dependent Claim 45 words
The method of claim 13 which is further characterized to include the step of controlling the degree of hydrolysis of the polymers polymerized in said aqueous solvent by adjusting the pH of said aqueous solvent to a selected level prior to polymerizing said monomers therein.
Claim 20
Dependent Claim 36 words
The method of claim 13 which is further characterized to include the step of combining one or more organic polymer clay stabilizers which will not function as chain transfer agents with said viscous aqueous treating solution.
Claim 21
Dependent Claim 28 words
The method of claim 14 wherein said free radial polymerization initiator is selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, benzoyl peroxide and 2,2'-azobis(isobutyronitrile).
Claim 22
Dependent Claim 49 words
The method of claim 14 which is further characterized to include the step of combining a buffer with said aqueous solvent in a quantity sufficient to maintain the pH thereof in the range of from about 7 to about 11.5 prior to combining said free radical polymerization initiator therewith.
Claim 23
Dependent Claim 35 words
The method of claim 14 wherein said vinyl monomers are combined with said aqueous solvent in an amount in the range of from about 1% to about 10% by weight of the resultant aqueous solution.
Claim 24
Dependent Claim 50 words
The method of claim 13 which is further characterized to include the step of combining one or more organic polymer clay stabilizers which will not function as chain transfer agents with the solution resulting from the combination of the substantially oxygen-free aqueous solvent and the one or more vinyl monomers.

References Cited (Backward Citations)

US3405106A Cited
US3509114A Cited
US4137969A Cited
US4297226A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1987-03-27 1987-09-26 1988-03-27 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1991-03-27 1991-09-26 1992-03-27 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1995-03-27 1995-09-26 1996-03-27 $7700.00 Window Closed / Lapsed

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