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US4606407A Expired / Lapsed US ⏱️ 0.0 years remaining

Programmed gelation of polymers for oil reservoir permeability control

Assignee: Mobil Oil AS
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Filing: 1984-11-29
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Granted: 1986-08-19
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Expires: 2004-11-29
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Abstract

Abstract Polymers used for the control of permeability in stratified subterranean formations are gelled in a controlled manner by the use of rapid and delayed gelling agents. The polymer is first gelled lightly by the use of a rapid gelling agent which partly cross-links the polymer to produce a viscous solution which will selectively enter only the more permeable regions of the formation but can still be readily injected. A delayed cross-linking agent completes the cross-linking process after the polymer has been selectively emplaced to form a firm, full strength gel. Suitable rapid cross-linking agents may be formed by the reaction of alkalies and chromic salts at specified ratios or by the redox reduction of chromium from its higher oxidation states under certain specified conditions. Delayed cross-linking agents are exemplified by chromic salts. Polymers which may be used include polyacrylamides and polysaccharide biopolymers.

Inventors

  • 👤 Paul Shu

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-30 22:04
CPC Classifications
C; C09; C09K; C09K8/00; C09K8/50; C09K8/504; C09K8/506; C09K8/508; C09K8/512

Claims Analysis

Total Claims: 36
Claim 1
Independent Claim 101 words
A method for the programmed gelation of a polymer which is cross-linkable by reaction with a polyvalent metal ion, which comprises: (i) forming a mixture comprising the polymer, a rapid cross-linking agent and a delayed cross-linking agent, (ii) partly gelling the polymer by reacting the polymer with the rapid cross-linking agent which is effective to complete the partial gelation by cross-linking the polymer within four hours, (iii) further gelling the polymer by reacting the polymer with the delayed cross-linking agent which is effective to complete the further gelation by cross-linking the polymer over a period of time longer than four hours.
Claim 2
Independent Claim 101 words
A method for the programmed gelation of a polymer which is cross-linkable by reaction with a polyvalent metal ion, which comprises: (i) forming a mixture comprising the polymer, a rapid cross-linking agent and a delayed cross-linking agent, (ii) partly gelling the polymer by reacting the polymer with the rapid cross-linking agent which is effective to complete the partial gelation by cross-linking the polymer within four hours, (iii) further gelling the polymer by reacting the polymer with the delayed cross-linking agent which is effective to complete the further gelation by cross-linking the polymer over a period of time longer than four hours.
Claim 3
Dependent Claim 21 words
A method according to claim 1 in which the polymer includes functional groups capable of coordinating with the polyvalent metal ions.
Claim 4
Dependent Claim 18 words
A method according to claim 2 in which the polymer comprises a polyacrylamide or a partly hydrolyzed polyacrylamide.
Claim 5
Dependent Claim 13 words
A method according to claim 2 in which the polymer is a polysaccharide.
Claim 6
Dependent Claim 14 words
A method according to claim 1 in which the polyvalent metal is chromium (III).
Claim 7
Independent Claim 78 words
A method for introducing a polymeric gel into a subterranean formation which comprises: (i) reacting a solution of a cross-linkable polymer with a rapid cross-linking agent to cross-link the polymer partly and gel the polymer partly to form a viscous liquid, (ii) injecting the viscous liquid, additionally containing a delayed cross-linking agent, into the formation, (iii) cross-linking the polymer further within the formation by reaction with the delayed cross-linking agent to form a polymer gel within the formation.
Claim 8
Independent Claim 78 words
A method for introducing a polymeric gel into a subterranean formation which comprises: (i) reacting a solution of a cross-linkable polymer with a rapid cross-linking agent to cross-link the polymer partly and gel the polymer partly to form a viscous liquid, (ii) injecting the viscous liquid, additionally containing a delayed cross-linking agent, into the formation, (iii) cross-linking the polymer further within the formation by reaction with the delayed cross-linking agent to form a polymer gel within the formation.
Claim 9
Dependent Claim 23 words
A method according to claim 6 in which the polymer includes functional groups capable of forming cross-linkages by coordination with polyvalent metal ions.
Claim 10
Dependent Claim 18 words
A method according to claim 7 in which the polymer comprises a polyacrylamide or a partly hydrolyzed polyacrylamide.
Claim 11
Dependent Claim 13 words
A method according to claim 7 in which the polymer comprises a polysaccharide.
Claim 12
Dependent Claim 33 words
A method according to claim 7 in which the rapid and cross-linking agent comprises compounds of a polyvalent metal selected from aluminum, zirconium or a metal of the first series of transition metals.
Claim 13
Dependent Claim 37 words
A method according to claim 6 in which the rapid cross-linking agent is produced by the reaction of an alkali with a salt of chromium (III) at an equivalent ratio of up to 3:1 (alkali:Cr (III) salt).
Claim 14
Dependent Claim 27 words
A method according to claim 6 in which the rapid cross-linking agent is produced by the reduction of a chromium compound containing chromium (VI) or chromium (VIII).
Claim 15
Dependent Claim 35 words
A method according to claim 12 in which the rapid cross-linking agent is produced by the reduction of a dichromate salt in acidic solution at a proton:dichromate molar ratio of from 1:1 to 3:1 (proton:dichromate).
Claim 16
Dependent Claim 18 words
A method according to claim 6 in which the delayed cross-linking agent comprises a salt of chromium (III).
Claim 17
Dependent Claim 39 words
A method according to claim 6 in which the delayed cross-linking agent is produced by the reduction of a dichromate salt in an acidic solution at a proton:dichromate molar ratio of less than 1:1 or greater than 3:1 (proton:dichromate).
Claim 18
Dependent Claim 27 words
A method according to claim 6 in which the delayed cross-linking agent is produced by the reduction of a dichromate salt in a neutral or basic solution.
Claim 19
Dependent Claim 37 words
A method according to claim 6 in which the delayed cross-linking agent is produced by the reaction of an alkali with a salt of chromium (III) at an equivalent ratio of at least 3:1 (alkali:Cr (III) salt).
Claim 20
Dependent Claim 17 words
A method according to claim 6 in which the delayed cross-linking agent comprises a chromium (III) hydrosol.
Claim 21
Dependent Claim 31 words
A method according to claim 18 in which the chromium (III) hydrosol is prepared by heating a solution of a Cr (III) salt in the presence of SO 4 2- .
Claim 22
Dependent Claim 169 words
In a method for the enhanced recovery of oil by a flooding technique in which a fluid is injected into a stratified subterranean, oil bearing formation through an injection well extending from the surface of the earth to the formation to displace oil from the formation towards a production well situated at a horizontal distance from the injection well and extending from the surface of the earth into the formation, the improvement comprising controlling the movement of the flooding fluid through the formation by the selective injection of a cross-linkable polymer into the more highly permeable regions of the formation by the steps of: (i) reacting a solution of a cross-linkable polymer with a rapid cross-linking agent to cross-link the polymer partly and gel the polymer partly to form a viscous liquid, (ii) injecting the viscous liquid, additionally containing a delayed cross-linking agent, into the formation, (iii) cross-linking the polymer further within the formation by reaction with the delayed cross-linking agent to form a polymer gel within the formation.
Claim 23
Dependent Claim 169 words
In a method for the enhanced recovery of oil by a flooding technique in which a fluid is injected into a stratified subterranean, oil bearing formation through an injection well extending from the surface of the earth to the formation to displace oil from the formation towards a production well situated at a horizontal distance from the injection well and extending from the surface of the earth into the formation, the improvement comprising controlling the movement of the flooding fluid through the formation by the selective injection of a cross-linkable polymer into the more highly permeable regions of the formation by the steps of: (i) reacting a solution of a cross-linkable polymer with a rapid cross-linking agent to cross-link the polymer partly and gel the polymer partly to form a viscous liquid, (ii) injecting the viscous liquid, additionally containing a delayed cross-linking agent, into the formation, (iii) cross-linking the polymer further within the formation by reaction with the delayed cross-linking agent to form a polymer gel within the formation.
Claim 24
Dependent Claim 27 words
A method according to claim 20 in which the polymer comprises a cross-linkable polymer including functional groups capable of forming cross-linkages by coordination with polyvalent metal ions.
Claim 25
Dependent Claim 18 words
A method according to claim 21 in which the polymer comprises a polyacrylamide or a partly hydrolyzed polyacrylamide.
Claim 26
Dependent Claim 13 words
A method according to claim 21 in which the polymer comprises a polysaccharide.
Claim 27
Dependent Claim 34 words
A method according to claim 20 in which the rapid and delayed cross-linking agents comprise compounds of a polyvalent metal selected from aluminum, zirconium or a metal of the first series of transition metals.
Claim 28
Dependent Claim 19 words
A method according to claim 24 in which the rapid and delayed cross-linking agents comprise compounds of Cr (III).
Claim 29
Dependent Claim 37 words
A method according to claim 25 in which the rapid cross-linking agent is produced by the reaction of an alkali with a salt of chromium (III) at an equivalent ratio of up to 3:1 (alkali:Cr (III) salt).
Claim 30
Dependent Claim 27 words
A method according to claim 25 in which the rapid cross-linking agent is produced by the reduction of a chromium compound containing chromium (VI) or chromium (VII).
Claim 31
Dependent Claim 35 words
A method according to claim 27 in which the rapid cross-linking agent is produced by the reduction of a dichromate salt in acidic solution at a proton:dichromate molar ratio of from 1:1 to 3:1 (proton:dichromate).
Claim 32
Dependent Claim 18 words
A method according to claim 25 in which the delayed cross-linking agent comprises a salt of chromium (III).
Claim 33
Dependent Claim 39 words
A method according to claim 25 in which the delayed cross-linking agent is produced by the reduction of a dichromate salt in an acidic solution at a proton:dichromate molar ratio of less than 1:1 or greater than 3:1 (proton:dichromate).
Claim 34
Dependent Claim 27 words
A method according to claim 25 in which the delayed cross-linking agent is produced by the reduction of a dichromate salt in a neutral or basic solution.
Claim 35
Dependent Claim 37 words
A method according to claim 25 in which the delayed cross-linking agent is produced by the reaction of an alkali with a salt of chromium (III) at an equivalent ratio of at least 3:1 (alkali:Cr (III) salt).
Claim 36
Dependent Claim 17 words
A method according to claim 25 in which the delayed cross-linking agent comprises a chromium (III) hydrosol.

References Cited (Backward Citations)

US3208518A Cited
US3749172A Cited
US4574887A Cited
US3981363A Cited
US4040484A Cited
US4488601A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1989-08-18 1990-02-17 1990-08-19 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1993-08-18 1994-02-17 1994-08-19 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1997-08-18 1998-02-17 1998-08-19 $7700.00 Window Closed / Lapsed

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