Patent US3639853A successfully refreshed from Google Patents.
US5080809A
Expired / Lapsed
US
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Polymers useful in the recovery and processing of natural resources
Assignee: Phillips Petroleum Co
•
Filing: 1985-07-18
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Granted: 1992-01-14
•
Expires: 2005-07-18
Abstract
Abstract Water-soluble polymers comprising an N-vinyl amide such as an N-vinyl lactam are found to be useful in processes wherein the polymer is introduced into a subterranean wellbore. Polymers useful in the recovery of natural resources are prepared by polymerizing an N-vinyl lactam by free radical initiation with polymerization conducted in an aqueous solution polymerization medium preferably containing a mixture of dissolved electrolytes, or in a polymerization medium consisting essentially of a tertiary alkanol. Copolymers of such N-vinyl lactams with unsaturated amides, and terpolymers prepared by polymerizing an N-vinyl lactam and an unsaturated amide with a selected termonomer compound are also useful when prepared by these methods. The invention also broadly encompasses utilizing a water-soluble polymer comprising at least one of a hydrophilic vinyl-containing sulfonate, phosphonate or ester and/or a hydrophilic N-vinyl lactam for applications under hostile conditions.
Inventors
- 👤 G. Allan Stahl
- 👤 I. John Westerman
- 👤 Henry L. Hsieh
- 👤 Ahmad Moradi-Araghi
- 👤 James H. Hedges
- 👤 Geir Bjornson
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 21:58
CPC Classifications
E; E21; E21B; E21B43/00; E21B43/16; E21B43/24; C; C08; C08F; C08F226/00; C08F226/06; C09; C09K; C09K8/00; C09K8/02; C09K8/04; C09K8/14; C09K8/18; C09K8/22; C09K8/24; C09K8/58; C09K8/588; C09K8/592; C09K8/60; C09K8/62; C09K8/66; C09K8/68; Y; Y10; Y10S; Y10S507/00; Y10S507/935; Y10S507/936
Claims Analysis
Total Claims: 80
Claim 1
Independent Claim
185 words
A method comprising: introducing a water-soluble polymer, produced from a monomer composition comprising at least one of a hydrophilic N-vinyl amide or a hydrophilic component of the formula ##STR27## R is methyl, ethyl or H, provided further that at least one of the R groups on the terminal carbon of the vinyl group is H and the other is H or methyl, M is H, Na + , K + , Li + , R"" 4 N + , Ca ++ , Mg ++ , Zn ++ , Sr ++ , Fe ++ , Mn ++ , and + NH 3 R 1 NH 3 + where R 1 is a 1-20 carbon atom divalent hydrocarbon radical, R"" is H, --ROH or a 1-3 carbon atom alkyl group, wherein X is selected from ##STR28## where n is an integer of 1-5 preferably 1-3 and R"' is a 1-3 carbon atom alkyl group or H, into a subterranean formation so that said polymer is exposed to a hostile environment defined as having a temperature and multivalent cation concentration above the infinite days line of FIG. 14.
Claim 2
Independent Claim
185 words
A method comprising: introducing a water-soluble polymer, produced from a monomer composition comprising at least one of a hydrophilic N-vinyl amide or a hydrophilic component of the formula ##STR27## R is methyl, ethyl or H, provided further that at least one of the R groups on the terminal carbon of the vinyl group is H and the other is H or methyl, M is H, Na + , K + , Li + , R"" 4 N + , Ca ++ , Mg ++ , Zn ++ , Sr ++ , Fe ++ , Mn ++ , and + NH 3 R 1 NH 3 + where R 1 is a 1-20 carbon atom divalent hydrocarbon radical, R"" is H, --ROH or a 1-3 carbon atom alkyl group, wherein X is selected from ##STR28## where n is an integer of 1-5 preferably 1-3 and R"' is a 1-3 carbon atom alkyl group or H, into a subterranean formation so that said polymer is exposed to a hostile environment defined as having a temperature and multivalent cation concentration above the infinite days line of FIG. 14.
Claim 3
Dependent Claim
27 words
A method according to claim 1 wherein said N-vinyl amide is an N-vinyl lactam and wherein said component of the formula ##STR29## a sulfonate or sulfonic acid.
Claim 4
Dependent Claim
42 words
A method according to claim 2 wherein said monomer composition contains in addition an unsaturated amide of the formula ##STR30## wherein R" is a 1-alkenyl group and wherein said multivalent cations are present in an amount greater than 1,000 ppm by weight.
Claim 5
Dependent Claim
26 words
A method according to claim 2 wherein said multivalent cations are present in an amount greater than 1,000 ppm by weight and comprise calcium and magnesium.
Claim 6
Dependent Claim
45 words
A method according to claim 2 wherein said polymer in an aqueous surfactant solution, and also steam are injected into said subterranean formation to effect permeability correction by transporting foamed surfactant into high permeability zones to thus divert steam to relatively oil-rich less permeable zones.
Claim 7
Dependent Claim
20 words
A method according to claim 2 wherein said polymer is used as a thickening agent in a hydraulic fracturing process.
Claim 8
Dependent Claim
45 words
A method according to claim 6 wherein said polymer contains carboxylate groups and said polymer composition is crosslinked to give fracture plugging by means of the sequential injection of (1) an oxidant composition containing a reducible polyvalent metal and (2) a water-soluble sulfur-containing reducing agent.
Claim 9
Dependent Claim
32 words
A method according to claim 2 wherein said polymer is crosslinked by the sequential injection of (1) an oxidant composition containing a reducible polyvalent metal and (2) a water-soluble sulfur-containing reducing agent.
Claim 10
Dependent Claim
18 words
A method according to claim 2 wherein said polymer is gelled in-situ for the purpose of permeability correction.
Claim 11
Dependent Claim
18 words
A method according to claim 2 wherein said is consolidated by means of in-situ gelation of said polymer.
Claim 12
Dependent Claim
25 words
A method according to claim 2 wherein said polymer is crosslinked using a sodium dichromate/sodium bisulfite redox system in order to plug high permeability zones.
Claim 13
Dependent Claim
29 words
A method according to claim 2 wherein said polymer is formed by radiation initiation in containers with center holes which are submerged in a cooling bath to facilitate cooling.
Claim 14
Dependent Claim
26 words
A method according to claim 2 wherein said polymer is crosslinked with a crosslinking agent selected from formaldehyde, acetaldehyde, chromium +3 , and aluminum +3 .
Claim 15
Dependent Claim
41 words
A method according to claim 2 wherein said monomer composition contains in addition an unsaturated amide of the formula ##STR31## wherein R" is a 1-alkenyl group and wherein said polymer is gelled with a mixture of a phenolic compound and formaldehyde.
Claim 16
Dependent Claim
39 words
A method according to claim 14 wherein said phenolic compound is phenol and wherein said phenol and phenolic compound are each used in an amount within the range of 1-10 weight percent based on the weight of said polymer.
Claim 17
Dependent Claim
37 words
A method according to claim 14 wherein said polymer is gelled after being introduced into said formation by withholding at least one of the phenolic compound, the formaldehyde, or the polymer, the withheld agent being subsequently injected.
Claim 18
Dependent Claim
12 words
A method according to claim 16 wherein said unsaturated amide is acrylamide.
Claim 19
Dependent Claim
37 words
A method according to claim 2 wherein said monomer composition contains in addition an unsaturated amide of the formula ##STR32## wherein R" is a 1-alkenyl group and wherein said polymer is gelled with a urea-formaldehyde crosslinking system.
Claim 20
Dependent Claim
23 words
A method according to claim 2 wherein said polymer is produced at a polymerization temperature within the range of -10° to 50° C.
Claim 21
Dependent Claim
20 words
A method according to claim 18 wherein said polymerization temperature is within the range of 5° C. to 25° C.
Claim 22
Dependent Claim
14 words
A method according to claim 20 wherein polymerization is initiated with a chemical initiator.
Claim 23
Dependent Claim
11 words
A method according to claim 21 wherein said initiator is 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile).
Claim 24
Dependent Claim
14 words
A method according to claim 20 wherein said polymer is produced by radiation initiation.
Claim 25
Dependent Claim
16 words
A method according to claim 2 wherein said monomer composition consists essentially of said N-vinyl lactam.
Claim 26
Dependent Claim
12 words
A method according to claim 24 wherein said N-vinyl lactam is N-vinyl-2-pyrrolidone.
Claim 27
Dependent Claim
17 words
A method according to claim 2 wherein said monomer composition consists essentially of said hydrophilic vinyl-containing sulfonate.
Claim 28
Dependent Claim
18 words
A method according to claim 26 wherein said polymer is formed at a pH of greater than 7.
Claim 29
Dependent Claim
28 words
A method according to claim 26 wherein said vinyl-containing sulfonate is selected from sodium vinyl sulfonate, sodium 2-acrylamido-2methyl-propanesulfonate, sodium styrene sulfonate, sodium p-vinylbenzenyl sulfonate and sodium vinyltoluene sulfonate.
Claim 30
Dependent Claim
13 words
A method according to claim 28 wherein said vinyl-containing sulfonate is sodium 2-acrylamido-2-methylpropanesulfonate.
Claim 31
Dependent Claim
21 words
A method according to claim 2 wherein said monomer composition comprises a mixture of said N-vinyl lactam and said vinyl-containing sulfonate.
Claim 32
Dependent Claim
18 words
A method according to claim 30 wherein said polymer is produced at a pH of greater than 7.
Claim 33
Dependent Claim
29 words
A method according to claim 30 wherein said vinyl-containing sulfonate is selected from sodium vinyl sulfonate, sodium 2-acrylamido-2-methylpropane sulfonate, sodium styrene sulfonate, sodium p-vinylbenzenyl sulfonate and sodium vinyltoluene sulfonate.
Claim 34
Dependent Claim
19 words
A method according to claim 32 wherein said vinyl-containing sulfonate is sodium 2-acrylamido-2-methylpropanesulfonate and said N-vinyl lactam is N-vinyl-2-pyrrolidone.
Claim 35
Dependent Claim
21 words
A method according to claim 33 wherein said polymer is produced at a pH within the range of 7 to 10.5.
Claim 36
Dependent Claim
23 words
A method according to claim 2 wherein said monomer composition comprises a mixture of said N-vinyl lactam and in addition an unsaturated amide.
Claim 37
Dependent Claim
31 words
A method according to claim 35 wherein said polymer is produced at a pH within the range of 5 to 10.5 and said monomer composition consists essentially of N-vinyl-2-pyrrolidone and acrylamide.
Claim 38
Dependent Claim
15 words
A method according to claim 35 wherein said polymer is produced utilizing a chemical initiator.
Claim 39
Dependent Claim
14 words
A method according to claim 34 wherein said polymer is produced by radiation initiation.
Claim 40
Dependent Claim
19 words
A method according to claim 35 wherein said polymer is produced utilizing a combination of chemical initiator and radiation.
Claim 41
Dependent Claim
24 words
A method according to claim 35 wherein said polymer is produced at a polymerization temperature within the range of minus 10° to 50° C.
Claim 42
Dependent Claim
22 words
A method according to claim 2 wherein said polymer has a composition within the area represented by area B of FIG. 15.
Claim 43
Dependent Claim
51 words
A method according to claim 2 wherein said monomer composition comprises said hydrophilic N-vinyl lactam, said hydrophilic vinyl-containing sulfonate salt and in addition a hydrophilic unsaturated amide, said polymer being further characterized as being stable for 7 days at a 0.25 wt. % concentration in synthetic sea water at 300° F.
Claim 44
Dependent Claim
25 words
A method according to claim 42 wherein said N-vinyl lactam is N-vinyl-2-pyrrolidone, said such unsaturated amide is acrylamide and said vinyl-containing sulfonate is sodium 2-acryl-amido-2-methylpropanesulfonate.
Claim 45
Dependent Claim
14 words
A method according to claim 42 wherein said unsaturated amide is an N-substituted acrylamide.
Claim 46
Dependent Claim
12 words
A method according to claim 42 wherein said N-substituted acrylamide is N,N-dimethylacrylamide.
Claim 47
Dependent Claim
17 words
A method according to claim 45 wherein said polymer is produced at a pH greater than 7.
Claim 48
Dependent Claim
22 words
A method according to claim 46 wherein said polymer has a composition within the area represented by area B of FIG. 16.
Claim 49
Dependent Claim
31 words
A method according to claim 2 wherein said monomer composition comprises a mixture of a major portion of said hydrophilic vinyl-containing sulfonate and a minor amount of a hydrophilic unsaturated amide.
Claim 50
Dependent Claim
34 words
A method according to claim 48 wherein said unsaturated amide is acrylamide and said vinyl-containing sulfonate is selected from sodium vinyl sulfonate, sodium 2-acrylamido-2-methylpropanesulfonate, sodium styrene sulfonate, sodium vinylbenzenyl sulfonate and sodium vinyltoluene sulfonate.
Claim 51
Dependent Claim
14 words
A method according to claim 49 wherein said vinyl-containing sulfonate monomer is sodium 2-acrylamido-2-methylpropanesulfonate.
Claim 52
Dependent Claim
21 words
A method according to claim 50 wherein said unsaturated amide is present in an amount up to about 10 weight percent.
Claim 53
Dependent Claim
14 words
A method according to claim 50 wherein said unsaturated amide is an N-substituted acrylamide.
Claim 54
Dependent Claim
57 words
A method according to claim 47 wherein said monomer composition comprises sodium 2-acrylamido-2-methylpropanesulfonate, N-vinyl-2-pyrrolidone and acrylamide, said acrylamide being present in an amount within the range of 10 to 90 wt. % based on the total weight of the monomers incorporated in said polymer, and wherein M is + NH 3 R 1 NH 3 + .
Claim 55
Dependent Claim
18 words
A method according to claim 53 wherein said polymer is produced at a pH of greater than 7.
Claim 56
Dependent Claim
16 words
A method according to claim 2 wherein said polymer is produced by an inverse emulsion process.
Claim 57
Dependent Claim
13 words
A method according to claim 1 wherein said N-vinyl amide is N-methyl-N-vinyl acetamide.
Claim 58
Dependent Claim
13 words
A method according to claim 1 wherein said component of the formula ##STR33##
Claim 59
Dependent Claim
13 words
A method according to claim 57 wherein said ester is (3-sulfopropyl)methacrylic ester salt.
Claim 60
Dependent Claim
16 words
A method according to claim 58 wherein said salt is a salt of K or Na.
Claim 61
Dependent Claim
13 words
A method according to claim 1 wherein said component of the formula ##STR34##
Claim 62
Dependent Claim
16 words
A method according to claim 60 wherein said phosphonate is a salt of 2-acrylamido-2-methylpropane phosphonic acid.
Claim 63
Dependent Claim
13 words
A method according to claim 61 wherein said salt is a sodium salt.
Claim 64
Dependent Claim
21 words
A method according to claim 1 wherein said monomer composition contains in addition a carboxylic acid or a carboxylic acid salt.
Claim 65
Dependent Claim
22 words
A method according to claim 63 wherein said composition contains a carboxylic acid and wherein said polymer is produced by emulsion polymerization.
Claim 66
Dependent Claim
14 words
A method according to claim 63 wherein said composition contains a carboxylic acid salt.
Claim 67
Dependent Claim
16 words
A method according to claim 65 wherein said carboxylic acid salt is an acrylic acid salt.
Claim 68
Dependent Claim
12 words
A method according to claim 66 wherein said salt is sodium acrylate.
Claim 69
Dependent Claim
33 words
A method according to claim 66 wherein said polymer is a polymer of N-vinyl pyrrolidone/acrylamide/2-acrylamido-2-methylpropane sulfonate/sodium acrylate in a weight ratio of about 30/10/55/5 and is used in conjunction with a gelling agent.
Claim 70
Dependent Claim
24 words
A method according to claim 2 wherein said composition contains in addition a carboxylic acid salt and is gelled with a polyvalent metal composition.
Claim 71
Dependent Claim
14 words
A method according to claim 2 wherein said sulfonate is a purified 2-acrylamido-2-methylpropane sulfonate.
Claim 72
Dependent Claim
48 words
A method according to claim 2 wherein said monomer composition contains in addition an unsaturated amide of the formula ##STR35## wherein R" is a 1-alkenyl group and wherein said polymer is injected under steam flood conditions and wherein said polymer is used in conjunction with a gelling agent.
Claim 73
Dependent Claim
14 words
A method according to claim 2 wherein said polymer is injected with carbon dioxide.
Claim 74
Independent Claim
206 words
A method comprising introducing a water-soluble polymer, produced from a monomer composition comprising at least one of a hydrophilic N-vinyl amide or a hydrophilic component of the formula ##STR36## R is methyl, ethyl or H, provided further that at least one of the R groups on the terminal carbon of the vinyl group is H and the other is H or methyl, M is H, Na + , K + , Li + , R"" 4 N + , Ca ++ , Mg ++ , Zn ++ , Sr++, Fe ++ , Mn ++ , and + NH 3 R 1 NH 3 + where R 1 is a 1-20 carbon atom divalent hydrocarbon radical, R"" is H, --ROH or a 1-3 carbon atom alkyl group, wherein X is selected from ##STR37## where n is an integer of 1-5 preferably 1-3 and R"' is a 1-3 carbon atom alkyl group, or H, R"" is H, --ROH or a 1-3 carbon atom alkyl group, into a subterranean formation where said polymer is exposed to a hostile environment defined as including a temperature within the range of 170° to 300° F. and a multivalent cation concentration within the range of 500 to 220,000 parts per million by weight.
Claim 75
Independent Claim
206 words
A method comprising introducing a water-soluble polymer, produced from a monomer composition comprising at least one of a hydrophilic N-vinyl amide or a hydrophilic component of the formula ##STR36## R is methyl, ethyl or H, provided further that at least one of the R groups on the terminal carbon of the vinyl group is H and the other is H or methyl, M is H, Na + , K + , Li + , R"" 4 N + , Ca ++ , Mg ++ , Zn ++ , Sr++, Fe ++ , Mn ++ , and + NH 3 R 1 NH 3 + where R 1 is a 1-20 carbon atom divalent hydrocarbon radical, R"" is H, --ROH or a 1-3 carbon atom alkyl group, wherein X is selected from ##STR37## where n is an integer of 1-5 preferably 1-3 and R"' is a 1-3 carbon atom alkyl group, or H, R"" is H, --ROH or a 1-3 carbon atom alkyl group, into a subterranean formation where said polymer is exposed to a hostile environment defined as including a temperature within the range of 170° to 300° F. and a multivalent cation concentration within the range of 500 to 220,000 parts per million by weight.
Claim 76
Independent Claim
73 words
A method comprising introducing a polymer produced from a monomer composition comprising at least one of a hydrophilic N-vinyl lactam and a hydrophilic vinyl-containing sulfonate salt or the corresponding acid, into a subterranean formation where said polymer is exposed to a hostile environment defined as including a temperature within the range of 170° to 300° F. and a multivalent cation concentration within the range of 500 to 220,000 parts per million by weight.
Claim 77
Independent Claim
73 words
A method comprising introducing a polymer produced from a monomer composition comprising at least one of a hydrophilic N-vinyl lactam and a hydrophilic vinyl-containing sulfonate salt or the corresponding acid, into a subterranean formation where said polymer is exposed to a hostile environment defined as including a temperature within the range of 170° to 300° F. and a multivalent cation concentration within the range of 500 to 220,000 parts per million by weight.
Claim 78
Dependent Claim
43 words
A process according to claim 2 wherein an aqueous solution of said water soluble polymer is injected into said subterranean formation through at least one injection well to displace oil through said formation to at least one production well where it is recovered.
Claim 79
Dependent Claim
19 words
A process according to claim 75 wherein said monomer composition comprises at least one of N-vinyl-2-pyrrolidone and sodium 2-acrylamido-2-methyl-propanesulfonate.
Claim 80
Dependent Claim
14 words
A process according to claim 76 wherein said monomer composition contains in addition acrylamide.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1995-01-13 | 1995-07-15 | 1996-01-14 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1999-01-13 | 1999-07-15 | 2000-01-14 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2003-01-13 | 2003-07-15 | 2004-01-14 | $7700.00 | Window Closed / Lapsed |