CN117567689A - Hyperbranched slow-expansion blocking agent and preparation method thereof - Google Patents
Hyperbranched slow-expansion blocking agent and preparation method thereof Download PDFInfo
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- CN117567689A CN117567689A CN202210942757.7A CN202210942757A CN117567689A CN 117567689 A CN117567689 A CN 117567689A CN 202210942757 A CN202210942757 A CN 202210942757A CN 117567689 A CN117567689 A CN 117567689A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000002981 blocking agent Substances 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims abstract description 62
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 55
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 46
- 239000010936 titanium Substances 0.000 claims abstract description 46
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 24
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010008 shearing Methods 0.000 claims abstract description 15
- 239000008398 formation water Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000004676 glycans Chemical class 0.000 claims abstract description 12
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 12
- 239000005017 polysaccharide Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000012216 screening Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 30
- 229920002472 Starch Polymers 0.000 claims description 24
- 239000008107 starch Substances 0.000 claims description 24
- 235000019698 starch Nutrition 0.000 claims description 24
- 239000000499 gel Substances 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- KPGXRSRHYNQIFN-UHFFFAOYSA-N 2-oxoglutaric acid Chemical compound OC(=O)CCC(=O)C(O)=O KPGXRSRHYNQIFN-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 239000002332 oil field water Substances 0.000 claims description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 3
- 229920001817 Agar Polymers 0.000 claims description 2
- 229920002101 Chitin Polymers 0.000 claims description 2
- 229920002527 Glycogen Polymers 0.000 claims description 2
- 229920001202 Inulin Polymers 0.000 claims description 2
- 239000008272 agar Substances 0.000 claims description 2
- HWXBTNAVRSUOJR-UHFFFAOYSA-N alpha-hydroxyglutaric acid Natural products OC(=O)C(O)CCC(O)=O HWXBTNAVRSUOJR-UHFFFAOYSA-N 0.000 claims description 2
- 229940009533 alpha-ketoglutaric acid Drugs 0.000 claims description 2
- 229940096919 glycogen Drugs 0.000 claims description 2
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 claims description 2
- 229940029339 inulin Drugs 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 4
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 6
- 230000032683 aging Effects 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 24
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 21
- 238000003756 stirring Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000005303 weighing Methods 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 229920000858 Cyclodextrin Polymers 0.000 description 4
- 239000001116 FEMA 4028 Substances 0.000 description 4
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 4
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 4
- 229960004853 betadex Drugs 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000007863 gel particle Substances 0.000 description 4
- 239000003708 ampul Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- -1 propylene sulfonate Chemical compound 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- BFYSJBXFEVRVII-UHFFFAOYSA-N 1-prop-1-enylpyrrolidin-2-one Chemical compound CC=CN1CCCC1=O BFYSJBXFEVRVII-UHFFFAOYSA-N 0.000 description 1
- FKOZPUORKCHONH-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid Chemical compound CC(C)CS(O)(=O)=O FKOZPUORKCHONH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- NOICVUZFTAVDNM-UHFFFAOYSA-N acetamide;pyrrolidin-2-one Chemical compound CC(N)=O.O=C1CCCN1 NOICVUZFTAVDNM-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a hyperbranched slow-expansion plugging agent, and belongs to the technical field of oil and gas field plugging agents. The hyperbranched slow-swelling plugging agent comprises the following components in parts by weight: 1-3 parts of polysaccharide, 2-5 parts of functional monomer, 0.05-0.2 part of cross-linking agent, 0.05-0.5 part of initiator and 91-97 parts of stratum water, wherein the cross-linking agent is an organic titanium cross-linking agent. The invention also provides a preparation method of the hyperbranched slow-swelling plugging agent, which comprises the following steps: s1) preparation of an organic titanium crosslinking agent: is prepared by the reaction of triethanolamine and tetraisopropyl titanate; s2) hyperbranched slow expansion preparation: adding polysaccharide, functional monomer and initiator into formation water, adding organic titanium cross-linking agent, and then introducing inert gas to react to obtain hyperbranched polymer gel; s3) shearing, drying, crushing and screening the prepared hyperbranched polymer gel to obtain the hyperbranched slow-swelling plugging agent. The prepared hyperbranched slow-swelling plugging agent has good temperature resistance, salt resistance, shearing resistance and aging resistance stability.
Description
Technical Field
The invention belongs to the technical field of oil and gas field plugging agents, and particularly relates to a hyperbranched slow-expansion plugging agent and a preparation method thereof.
Background
The carbonate reservoir matrix of the Tahe oil field has poor seepage capability, extremely strong reservoir heterogeneity, complex oil-water relationship and the like, so that the development of the reservoir faces a plurality of difficulties. With the continuous deep development of the oil field, the number of high-water-content wells gradually rises, the water injection effect of the well group becomes poor, and the unidirectional effect and the water channeling are increasingly serious. In order to ensure the integral development effect of the oil field, the water content of the oil well is reduced, and the water blocking technology is an effective measure for reducing the water output of the oil well. Compared with linear polymers, the hyperbranched polymer is a novel polymer with special structure and properties, has the properties of highly branched three-dimensional structure, a large number of terminal functional groups, high chemical reactivity, good solubility and the like, and has good application prospect. Under high-speed shearing or high-temperature conditions, the molecular weight of the linear polymer is greatly reduced due to the fracture of the main chain; the hyperbranched polymer is broken into a part of branched structure, and the performance of the main chain is not obviously affected. The hyperbranched polymer will therefore have better resistance to temperature and shear than the linear polymer. The polysaccharide widely exists in the nature, such as common starch, cellulose and the like, is a natural renewable raw material for synthesizing hyperbranched polymer materials, and has good temperature resistance and shearing resistance.
Patent CN 109053959A reports a hyperbranched associative polymer based on polysaccharide modification, which is prepared by polymerization of reactive monomers of acrylamide, acrylic acid, functionalized polyamide-amine hybrid beta-cyclodextrin fβ -CD and N-aryl acrylamide. The preparation method comprises the following steps: step S1: preparing functionalized polyamide-amine hybridized beta-cyclodextrin Fbeta-CD; step S2: adding acrylamide and acrylic acid into distilled water, stirring uniformly, regulating the pH value to 6-8, adding N-aryl acrylamide and sodium dodecyl sulfate, stirring until the solution is clear and transparent, adding functional beta-cyclodextrin Fbeta-CD, and introducing nitrogen to remove dissolved oxygen in the solution; step S3: adding a photoinitiator into the deoxidized solution, and reacting for 4-6 hours at the reaction temperature of 15-30 ℃ to obtain the polysaccharide modified hyperbranched associated polymer. The hyperbranched associative polymer has good solubility, temperature resistance, salt resistance and shearing resistance, is the best choice of oil displacement agents for oil fields, and has wide application prospect. But the polymer is prepared by adopting acrylamide, acrylic acid, functionalized polyamide-amine hybridized beta-cyclodextrin Fbeta-CD and N-aryl acrylamide to carry out polymerization reaction, and has higher cost and poorer expansion multiple stability.
Patent CN109233773a discloses a nonlinear self-degrading temporary plugging agent for multi-cluster fracturing transformation in a section and a preparation method thereof, wherein the temporary plugging agent comprises the following substances in percentage by weight: 80-90% of a body, 2-5% of an initiator, 2-5% of a lubricant, 5-10% of a forming agent, 0.2-0.8% of a reinforcing agent and 1-3% of a degradation promoter, wherein the body is a mixture composed of polyglycolide, polylactide-glycolide and polyvinyl alcohol. The adhesive is not adhered when meeting water at normal temperature, thus being beneficial to pumping; the degradation is slow in a limited time, the dissolution rate and the time show a nonlinear relation at the reservoir temperature, and the technical requirement of multi-cluster fracturing construction in a horizontal well section is met; the micro-expansion capability is achieved, and the strength of the crack in the later plugging stage is improved; can be degraded slowly when the medium environment changes, and has little damage to the reservoir. The intermittent stirring reactor and the double screw extruder are combined, so that the influence of temperature change on the temporary plugging agent product in the production process is improved, and the physical and chemical performance indexes of the product are more stable. However, the self-degrading temporary plugging agent adopts polyglycolide, polylactide-glycolide and polyvinyl alcohol as main plugging agent bodies, and has better micro-expansion capability but poorer temperature resistance and salt resistance.
Polymer gel systems are widely applied to oilfield water shutoff, but at present, the molecular weight of a general linear polymer system is greatly reduced due to easy breakage of a molecular chain under a high temperature condition, and the temperature resistance and salt resistance can not meet the oil reservoir condition, so that a polymer gel system with more excellent performance needs to be developed.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides the hyperbranched slow-swelling plugging agent with good temperature resistance, salt resistance, shearing resistance and aging resistance and good stability and the preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
firstly, a hyperbranched slow-swelling plugging agent is provided, which comprises the following components in parts by weight: 1-3 parts of polysaccharide, 2-5 parts of functional monomer, 0.05-0.2 part of cross-linking agent, 0.05-0.5 part of initiator and 91-97 parts of stratum water.
Further, the polysaccharide is one or more of starch, glycogen, chitin, inulin and agar, and the cross-linking agent is an organic titanium cross-linking agent.
Further, the functional monomer is one or more of an acrylamide monomer, a carboxylic acid monomer, a sulfonic acid monomer and a pyrrolidone monomer.
Further, the acrylamide monomer is one or more of acrylamide, N-dimethylacrylamide and N, N-diethylacrylamide; the carboxylic acid monomer is one or more of an acrylic acid monomer and a methacrylic acid monomer; the sulfonic acid monomer is one or more of 2-methylpropanesulfonic acid, propylene sulfonate and ethylene sulfonate; the pyrrolidone monomer is one or more of vinyl pyrrolidone, methyl pyrrolidone, cyclohexyl pyrrolidone, acetamide pyrrolidone and propenyl pyrrolidone.
Further, the cross-linking agent is an organic titanium cross-linking agent, and the mass fraction of titanium element in the organic titanium cross-linking agent is 5.5-6.5%.
Further, the initiator is one or more of ammonium persulfate, potassium persulfate, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone and alpha-ketoglutaric acid.
Secondly, a preparation method of the hyperbranched slow-swelling plugging agent is provided, which comprises the following steps:
s1) preparation of an organic titanium crosslinking agent: is prepared by the reaction of triethanolamine and tetraisopropyl titanate;
s2) hyperbranched slow expansion preparation: adding polysaccharide, functional monomer and initiator into formation water, adding organic titanium cross-linking agent, and then introducing inert gas to react to obtain hyperbranched polymer gel;
s3) shearing, drying, crushing and screening the prepared hyperbranched polymer gel to obtain the hyperbranched slow-swelling plugging agent.
Further, in the step S1), the molar ratio of the triethanolamine to the tetraisopropyl titanate is 2-2.1:1, and the addition amount of the triethanolamine can be slightly more so as to ensure the complete reaction of the tetraisopropyl titanate.
Further, the reaction in step S1) is performed in an organic solvent, which is one or both of ethanol and isopropanol, and the temperature of the reaction is 50-70 ℃, preferably 55 ℃.
Further, the temperature of the reaction in step S2) is 55-75deg.C, preferably 60deg.C, and the reaction time is 4-8h.
Finally, the application of the hyperbranched slow-swelling plugging agent or the hyperbranched slow-swelling plugging agent obtained by the preparation method in oilfield water shutoff is provided.
In some specific embodiments, the preparation method of the hyperbranched slow-swelling plugging agent comprises the following steps:
s1) preparation of an organic titanium crosslinking agent:
and weighing triethanolamine and tetraisopropyl titanate according to a molar ratio of 2-2.1:1, adding the triethanolamine into isopropanol, adding the tetraisopropyl titanate under stirring to uniformly mix, heating to 50-70 ℃, reacting for 3-5h, taking a small amount of system, dripping into water, completely dissolving, and stopping reacting to obtain the organic titanium crosslinking agent.
S2) hyperbranched slow expansion preparation:
weighing starch, an Acrylamide Monomer (AM), an acrylic acid monomer (AA), a vinyl pyrrolidone monomer and an initiator according to a formula, adding the starch, the Acrylamide Monomer (AM), the acrylic acid monomer (AA), the vinyl pyrrolidone monomer and the initiator into formation water, adding the organic titanium crosslinking agent prepared in the step S1), stirring and mixing uniformly, introducing nitrogen to deoxidize, and reacting for 4-8 hours at 55-75 ℃ to obtain hyperbranched polymer gel;
s3) shearing, drying, crushing and screening the prepared hyperbranched polymer gel to obtain the product.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts starch polysaccharide as a core material, selects a proper initiator, carries out graft copolymerization with hydrophilic monomers AM, AA and other functional monomers to form hyperbranched polymers, and finally adds a high-temperature crosslinking agent to prepare hyperbranched slow-swelling bodies with better temperature resistance and salt resistance;
(2) The system has excellent aging stability at 140 ℃, and can maintain expansion multiple of more than 5 times within 150 days under the condition of a Tahe oil reservoir.
Detailed Description
It is to be noted that the raw materials used in the present invention are all common commercial products, and the sources thereof are not particularly limited.
Example 1
The hyperbranched slow-swelling plugging agent is prepared by adopting the following formula: 1.5 parts of starch, 1.5 parts of acrylamide monomer, 0.85 part of acrylic acid monomer, 0.4 part of vinyl pyrrolidone monomer, 0.15 part of organic titanium cross-linking agent, 0.15 part of ammonium persulfate and 95.45 parts of stratum water, wherein the mass fraction of titanium element in the organic titanium cross-linking agent is 6%.
The preparation method comprises the following steps:
s1) preparation of an organic titanium crosslinking agent:
according to 2.05:1, weighing triethanolamine and tetraisopropyl titanate according to a molar ratio, adding the triethanolamine into isopropanol, adding the tetraisopropyl titanate under the stirring condition, uniformly mixing, heating to 55 ℃, reacting for 5 hours, taking a small amount of system, dripping into water, completely dissolving, and stopping reacting to obtain the organic titanium crosslinking agent.
S2) hyperbranched slow expansion preparation:
weighing starch, an acrylamide monomer, an acrylic acid monomer, a vinyl pyrrolidone monomer and an initiator according to a formula, adding the starch, the acrylamide monomer, the acrylic acid monomer, the vinyl pyrrolidone monomer and the initiator into formation water, adding the organic titanium crosslinking agent prepared in the step S1), stirring and mixing uniformly, introducing nitrogen to deoxidize, and reacting for 5 hours at 60 ℃ to obtain hyperbranched polymer gel;
s3) shearing, drying, crushing and screening the prepared hyperbranched polymer gel to obtain the product A.
Example 2
The hyperbranched slow-swelling plugging agent is prepared by adopting the following formula: 2 parts of starch, 0.5 part of acrylamide monomer, 1.5 parts of acrylic acid monomer, 2 parts of vinyl pyrrolidone monomer, 0.2 part of organic titanium cross-linking agent, 0.45 part of potassium persulfate and 93.35 parts of formation water, wherein the mass fraction of titanium element in the organic titanium cross-linking agent is 6.5%.
The preparation method comprises the following steps:
s1) preparation of an organic titanium crosslinking agent:
according to 2.1:1, weighing triethanolamine and tetraisopropyl titanate according to a molar ratio, adding the triethanolamine into isopropanol, adding the tetraisopropyl titanate under the stirring condition, uniformly mixing, heating to 70 ℃, reacting for 3 hours, taking a small amount of system, dripping into water, completely dissolving, and stopping reacting to obtain the organic titanium crosslinking agent.
S2) hyperbranched slow expansion preparation:
weighing starch, an acrylamide monomer, an acrylic acid monomer, a vinyl pyrrolidone monomer and an initiator according to a formula, adding the starch, the acrylamide monomer, the acrylic acid monomer, the vinyl pyrrolidone monomer and the initiator into formation water, adding the organic titanium crosslinking agent prepared in the step S1), stirring and mixing uniformly, introducing nitrogen to deoxidize, and reacting for 4 hours at 75 ℃ to obtain hyperbranched polymer gel;
s3) shearing, drying, crushing and screening the prepared hyperbranched polymer gel to obtain a product B.
Example 3
The hyperbranched slow-swelling plugging agent is prepared by adopting the following formula: 1 part of starch, 1 part of acrylamide monomer, 0.8 part of acrylic acid monomer, 0.2 part of vinyl pyrrolidone monomer, 0.1 part of organic titanium cross-linking agent, 0.1 part of potassium persulfate and 96.8 parts of stratum water, wherein the mass fraction of titanium element in the organic titanium cross-linking agent is 6%.
The preparation method comprises the following steps:
s1) preparation of an organic titanium crosslinking agent:
according to 2:1, weighing triethanolamine and tetraisopropyl titanate according to a molar ratio, adding the triethanolamine into isopropanol, adding the tetraisopropyl titanate under the stirring condition, uniformly mixing, heating to 55 ℃, reacting for 5 hours, taking a small amount of system, dripping into water, completely dissolving, and stopping reacting to obtain the organic titanium crosslinking agent.
S2) hyperbranched slow expansion preparation:
weighing starch, an acrylamide monomer, an acrylic acid monomer, a vinyl pyrrolidone monomer and an initiator according to a formula, adding the starch, the acrylamide monomer, the acrylic acid monomer, the vinyl pyrrolidone monomer and the initiator into formation water, adding the organic titanium crosslinking agent prepared in the step S1), stirring and mixing uniformly, introducing nitrogen to deoxidize, and reacting for 5 hours at 60 ℃ to obtain hyperbranched polymer gel;
s3) shearing, drying, crushing and screening the prepared hyperbranched polymer gel to obtain a product C.
Example 4
The hyperbranched slow-swelling plugging agent is prepared by adopting the following formula: 3 parts of starch, 2 parts of acrylamide monomer, 1.5 parts of acrylic acid monomer, 1.5 parts of vinyl pyrrolidone monomer, 0.2 part of organic titanium cross-linking agent, 0.5 part of potassium persulfate and 91.3 parts of formation water, wherein the mass fraction of titanium element in the organic titanium cross-linking agent is 5.5%.
The preparation method comprises the following steps:
s1) preparation of an organic titanium crosslinking agent:
according to 2.05:1, weighing triethanolamine and tetraisopropyl titanate according to a molar ratio, adding the triethanolamine into isopropanol, adding the tetraisopropyl titanate under the stirring condition, uniformly mixing, heating to 55 ℃, reacting for 5 hours, taking a small amount of system, dripping into water, completely dissolving, and stopping reacting to obtain the organic titanium crosslinking agent.
S2) hyperbranched slow expansion preparation:
weighing starch, an acrylamide monomer, an acrylic acid monomer, a vinyl pyrrolidone monomer and an initiator according to a formula, adding the starch, the acrylamide monomer, the acrylic acid monomer, the vinyl pyrrolidone monomer and the initiator into formation water, adding the organic titanium crosslinking agent prepared in the step S1), stirring and mixing uniformly, introducing nitrogen to deoxidize, and reacting for 5 hours at 60 ℃ to obtain hyperbranched polymer gel;
s3) shearing, drying, crushing and screening the prepared hyperbranched polymer gel to obtain a product D.
Example 5
The hyperbranched slow-swelling plugging agent is prepared by adopting the following formula: 1 part of starch, 1 part of acrylamide monomer, 0.8 part of acrylic acid monomer, 0.2 part of vinyl pyrrolidone monomer, 0.05 part of organic titanium cross-linking agent, 0.05 part of potassium persulfate and 96.9 parts of stratum water, wherein the mass fraction of titanium element in the organic titanium cross-linking agent is 6%.
The preparation method comprises the following steps:
s1) preparation of an organic titanium crosslinking agent:
according to 2:1, weighing triethanolamine and tetraisopropyl titanate according to a molar ratio, adding the triethanolamine into isopropanol, adding the tetraisopropyl titanate under the stirring condition, uniformly mixing, heating to 55 ℃, reacting for 5 hours, taking a small amount of system, dripping into water, completely dissolving, and stopping reacting to obtain the organic titanium crosslinking agent.
S2) hyperbranched slow expansion preparation:
weighing starch, an acrylamide monomer, an acrylic acid monomer, a vinyl pyrrolidone monomer and an initiator according to a formula, adding the starch, the acrylamide monomer, the acrylic acid monomer, the vinyl pyrrolidone monomer and the initiator into formation water, adding the organic titanium crosslinking agent prepared in the step S1), stirring and mixing uniformly, introducing nitrogen to deoxidize, and reacting for 5 hours at 60 ℃ to obtain hyperbranched polymer gel;
s3) shearing, drying, crushing and screening the prepared hyperbranched polymer gel to obtain a product E.
Comparative example 1
The hyperbranched slow-swelling plugging agent is prepared by adopting the following formula: 3.5 parts of starch, 2.5 parts of acrylamide monomer, 2 parts of acrylic acid monomer, 1 part of vinyl pyrrolidone monomer, 0.25 part of organic titanium cross-linking agent, 0.55 part of potassium persulfate and 90.2 parts of formation water, wherein the mass fraction of titanium element in the organic titanium cross-linking agent is 6%.
The preparation method comprises the following steps:
s1) preparation of an organic titanium crosslinking agent:
according to 2.05:1, weighing triethanolamine and tetraisopropyl titanate according to a molar ratio, adding the triethanolamine into isopropanol, adding the tetraisopropyl titanate under the stirring condition, uniformly mixing, heating to 55 ℃, reacting for 5 hours, taking a small amount of system, dripping into water, completely dissolving, and stopping reacting to obtain the organic titanium crosslinking agent.
S2) hyperbranched slow expansion preparation:
weighing starch, an acrylamide monomer, an acrylic acid monomer, a vinyl pyrrolidone monomer and an initiator according to a formula, adding the starch, the acrylamide monomer, the acrylic acid monomer, the vinyl pyrrolidone monomer and the initiator into formation water, adding the organic titanium crosslinking agent prepared in the step S1), stirring and mixing uniformly, introducing nitrogen to deoxidize, and reacting for 5 hours at 60 ℃ to obtain hyperbranched polymer gel;
s3) shearing, drying, crushing and screening the prepared hyperbranched polymer gel to obtain a product F.
Experimental example
The expansion performance of the products A-F prepared above is evaluated by the following evaluation method: weigh m 0 The samples (products A-F) were placed in ampoules and the total weight m of the sample and ampoule was weighed 1 Then adding a proper amount of simulated water for sealing, finally putting the mixture into an oven for expansion, and recording the expansion temperature and the swelling time. After swelling for a period of time, filtering free water with a screen, weighing the total weight of the filtered sample and ampoule bottle to obtain mass m 2 . And after weighing, adding the simulated water again to continue soaking, and repeating the experimental operation in the previous step until the experimental design time is up. The water absorption expansion coefficient of the sample is calculated as follows:
wherein: m is m n -the total mass of the sample and ampoule after soaking for a certain time.
The evaluation results are shown in table 1:
TABLE 1
From Table 1, it can be seen that the expansion times of the hyperbranched polymer gel particles prepared by the invention can reach more than 5 times at different temperatures. As the temperature rises, the thermal motion of the polymer chain segment of the slow expansion particles is aggravated, and the water absorption speed is increased, so that the expansion speed is increased, and the maximum expansion multiple is increased; when the temperature is higher, the crosslinking reaction of the polymer and divalent ions is accelerated, the crosslinking degree between polymer chain segments of the slow-expansion particles is increased, so that the expansion multiple is reduced due to the occurrence of partial dehydration, and when the crosslinking reaction reaches a certain degree, the crosslinking degree is basically stable, so that the expansion multiple is basically stable.
The invention also adopts the formation water of the Tahe oil reservoir to evaluate the expansion performance and the aging performance of the hyperbranched polymer gel particles prepared by the invention, and the evaluation results are shown in tables 2 and 3:
TABLE 2
As can be seen from Table 2, the initial expansion multiple of the hyperbranched polymer gel particles can reach 8-12 times under the condition of a Tahe oil reservoir, and the hyperbranched polymer gel particles can be stabilized at about 6 times after 72 hours.
TABLE 3 Table 3
From Table 3, it can be seen that the system has excellent aging stability, and can maintain expansion multiple of more than 5 times in 150 days under the condition of a Tahe oil reservoir.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The hyperbranched slow-swelling plugging agent is characterized by comprising the following components in parts by weight: 1-3 parts of polysaccharide, 2-5 parts of functional monomer, 0.05-0.2 part of cross-linking agent, 0.05-0.5 part of initiator and 91-97 parts of stratum water.
2. The hyperbranched slow-swelling plugging agent according to claim 1, wherein the polysaccharide is one or more of starch, glycogen, chitin, inulin and agar, and the cross-linking agent is an organic titanium cross-linking agent.
3. The hyperbranched slow-swelling plugging agent according to claim 1, wherein the functional monomer is one or more of an acrylamide monomer, a carboxylic acid monomer, a sulfonic acid monomer and a pyrrolidone monomer.
4. The hyperbranched slow-swelling plugging agent according to claim 1, wherein the cross-linking agent is an organic titanium cross-linking agent, and the mass fraction of titanium element in the organic titanium cross-linking agent is 5.5-6.5%.
5. The hyperbranched slow-swelling plugging agent according to claim 1, wherein the initiator is one or more of ammonium persulfate, potassium persulfate, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and alpha-ketoglutaric acid.
6. The method for preparing the hyperbranched slow-swelling plugging agent according to any one of claims 1 to 5, which is characterized by comprising the following steps:
s1) preparation of an organic titanium crosslinking agent: is prepared by the reaction of triethanolamine and tetraisopropyl titanate;
s2) hyperbranched slow expansion preparation: adding polysaccharide, functional monomer and initiator into formation water, adding organic titanium cross-linking agent, and then introducing inert gas to react to obtain hyperbranched polymer gel;
s3) shearing, drying, crushing and screening the prepared hyperbranched polymer gel to obtain the hyperbranched slow-swelling plugging agent.
7. The method according to claim 6, wherein the molar ratio of triethanolamine to tetraisopropyl titanate in step S1) is 2-2.1:1.
8. The process according to claim 6, wherein the reaction in step S1) is carried out in an organic solvent which is one or both of ethanol and isopropanol, and the temperature of the reaction is 50 to 70 ℃.
9. The process according to claim 6, wherein the reaction in step S2) is carried out at a temperature of 55 to 75℃for a period of 4 to 8 hours.
10. Use of the hyperbranched slow-swelling plugging agent according to any one of claims 1-5 or the hyperbranched slow-swelling plugging agent obtained by the preparation method according to any one of claims 6-9 in oilfield water shutoff.
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