Oil and gas field chemicals

• US 5,836,392 A
• Filed: 08/05/1997
• Issued: 11/17/1998
• Est. Priority Date: 12/22/1994
• Status: Expired due to Term

• Current Assignee: Halliburton Energy Services Incorporated (Halliburton Company)
• Original Assignee: Halliburton Energy Services Incorporated (Halliburton Company)
• Inventors: Urlwin-Smith, Phillip Lance
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): SAROFIM, NABIL F
• Application Number:
  US08/849,904
• Time in Patent Office: 469 Days
• Field of Search: 526/307.7, 166/295, 166/300
• US Class Current: 166/295
• CPC Class Codes: C08F 220/12 of monohydric alcohols or phenols
• CPC Class Codes: C08F 220/56 Acrylamide; Methacrylamide
• CPC Class Codes: C09K 8/512 containing cross-linking agents
• CPC Class Codes: C09K 8/887 containing cross-linking agents

Abstract

A method for conformance control of a reservoir comprising injecting into a zone of the reservoir an aqueous solution of a co-polymer comprising at least one ethylenically unsaturated polar monomer and at least one copolymerizable ethylenically unsaturated ester formed from a hydroxy compound of the formula ROH wherein R is a selected alkyl group, alkenyl group, cycloalkyl group, aryl group or such groups substituted with from 1 to 3 hydroxyl, ether or thio ether groups or a heterocyclic or selected heterocyclic alkylene group and at least one hetereatom selected from oxygen, nitrogen and sulfur and a selected alkenoic or aralkenoic carboxylic acid or sulfonic or phosphoric acid together with a crosslinking agent comprising a multi-valent metal ion capable of crosslinking an acrylic acid polymer to form a viscous gel. The injected fluid is flowed through at least a portion of a high permeability region within said zone wherein it is heated to an elevated temperature whereupon crosslinking of the polymers occurs to form a substantially non-flowable gel within said high permeability region. The crosslinking of the injected fluid to form the non-flowable gel within the formation reduces the permeability of said region in said zone.

Claims

1. A method for conformance control of a reservoir comprising:

injecting into a zone of the reservoir an aqueous solution of a co-polar comprising at least one ethylenically unsaturated polar monomer and at least one copolymerizable ethylenically unsaturated ester formed from a hydroxy compound of the formula ROH wherein R is an alkyl group of 4-30 carbons, alkenyl group of 4-20 carbons, cycloalkyl group of 5-8 carbons, aryl group of 6-20 carbons or such groups, substituted with from 1 to 3 hydroxyl, ether or thio ether groups or a heterocyclic or heterocyclic alkylene group of from 3-8 carbons and at least one heteroatom selected from oxygen, nitrogen and sulfur and an alkenoic or aralkenoic carboxylic acid having from 4-20 carbons or sulfonic or phosphoric acid having from 2-20 carbons together with a crosslinking agent comprising a multi-valent metal ion capable of crosslinking an acrylic acid polymer to form a viscous gel;

allowing the solution to flow through at least a portion of a high permeability region within said zone wherein it is heated to a temperature of at least about 20°

C. while maintained at a pH above about 6.5 whereupon crosslinking occurs to form a substantially non-flowable gel within said high permeability region which reduces the permeability of said region in said zone.

2. The method of claim 1 wherein said solution is heated to a temperature above about 90°

C. in said region of said reservoir.

3. The method of claim 1 wherein R comprises at least one member selected from the groups of N, sec, iso or tertiary butyl, n, sec, iso or tertiary amyl, n, sec, iso or tertiary hexyl, octyl, 2-ethylhexyl, decyl, allyl, cyclohexyl, palmityl, stearyl, phenyl, benzyl, furyl, tetrahydrofuryl, furfuryl, tetrahydrofurfuryl pyranyl and tetrahydropyranyl.

4. The method of claim 1 wherein R comprises at least one member selected from the group of tertiary butyl, trityl, benzyloxymethyl, stearyl and tetrahydropyranyl.

5. The method of claim 1 wherein the multi-valent ion os said crosslinking agent comprises at least one member selected from chromium, iron, aluminum and zirconium.

6. The method of claim 1 wherein said solution is heated to a temperature in the range of from about 90°

-150°

C. in said high permeability region.

7. A method of blocking a high permeability region in a zone of a subterranean formation penetrated by a wellbore comprising:

injecting into a zone of a subterranean formation having a temperature of from about 60°

-150°

C. an aqueous solution of a copolymer comprising at least one ethylenically unsaturated polar monomer and at least one copolymerizable ethylenically unsaturated ester formed from a hydroxy compound of the formula ROH wherein R is an alkyl group of 4-30 carbons, alkenyl group of 4-20 carbons, cycloalkyl group of 5-8 carbons, aryl group of 6-20 carbons or such groups, substituted with from 1 to 3 hydroxyl, ether or thio ether groups or a heterocyclic or heterocyclic alkylene group of from 3-8 carbons and at least one heteroatom selected from oxygen, nitrogen and sulfur and an alkenoic or aralkenoic carboxylic acid having from 4-20 carbons or sulfonic or phosphoric acid having from 2-20 carbons together with a crosslinking agent comprising a multi-valent metal ion capable of crosslinking an acrylic acid polymer to form a viscous gel;

shutting-in said wellbore for from about 1 to about 70 hours.

8. The method of claim 7 wherein said formation is sandstone having a formation water pH of from about 3-6.5.

9. The method of claim 7 wherein said formation is limestone having a formation water pH of from about 6.5-8.

10. The method of claim 7 wherein R comprises at least one member selected from the groups of N, sec, iso or tertiary butyl, n, sec, iso or tertiary amyl, n, sec, iso or tertiary hexyl, octyl, 2-ethylhexyl, decyl, allyl, cyclohexyl, palmityl, stearyl, phenyl, benzyl, furyl, tetrahydrofuryl, furfuryl, tetrahydrofurfuryl pyranyl and tetrahydropyranyl.

11. The method of claim 7 wherein R comprises at least one member selected from the group of tertiary butyl, trityl, benzyloxymethyl, stearyl and tetrahydropyranyl.

12. The method of claim 7 wherein the multi-valent ion os said crosslinking agent comprises at least one member selected from chromium, iron, aluminum and zirconium.

13. A method for reducing the permeability of a relatively higher permeability zone of a subterranean sandstone formation penetrated by a wellbore comprising

introducing into the relatively higher permeability zone of said formation through said wellbore a quantity of an aqueous solution of a copolymer comprising at least one copolymerizable ethylenically unsaturated ester formed from a hydroxy compound of the formula ROH wherein R is an alkyl group of 4-30 carbons, alkenyl group of 4-20 carbons, cycloalkyl group of 5-8 carbons, aryl group of 6-20 carbons or such groups, substituted with from 1 to 3 hydroxyl, ether or thio ether groups or a heterocyclic or heterocyclic alkylene group of from 3-8 carbons and at least one heteroatom selected from oxygen, nitrogen and sulfur and an alkenoic or aralkenoic carboxylic acid having from 4-20 carbons or sulfonic or phosphoric acid having from 2-20 carbons together with a crosslinking agent comprising a multi-valent metal ion capable of crosslinking an acrylic acid polymer to form a viscous gel;

and

heating said aqueous solution to a temperature in excess of about 90°

C. within said formation while subjecting said solution to an acidic pH of below about 6.5 whereupon a crosslinking reaction occurs to form a substantially non-flowable gel in said formation to substantially non-flowable gel in said formation to substantially decrease the permeability of the portion of said formation occupied by said gel.

14. The method of claim 13 wherein said solution is heated to a temperature above about 90°

C. in said region of said reservoir.

15. The method of claim 13 wherein R comprises at least one member selected from the groups of N, sec, iso or tertiary butyl, n, sec, iso or tertiary amyl, n, sec, iso or tertiary hexyl, octyl, 2-ethylhexyl, decyl, allyl, cyclohexyl, palmityl, stearyl, phenyl, benzyl, furyl, tetrahydrofuryl, furfuryl, tetrahydrofurfuryl pyranyl and tetrahydropyranyl.

16. The method of claim 13 wherein R comprises at least one member selected from the group of tertiary butyl, trityl, benzyloxymethyl, stearyl and tetrahydropyranyl.

17. The method of claim 13 wherein the multivalent ion os said crosslinking agent comprises at least one member selected from chromium, iron, aluminum and zirconium.

18. The method of claim 13 wherein said solution is heated to a temperature in the range of from about 90°

-150°

C. in said high permeability region.