CN116716094A - Self-repairing thickening agent and preparation method thereof - Google Patents
Self-repairing thickening agent and preparation method thereof Download PDFInfo
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- CN116716094A CN116716094A CN202310759546.4A CN202310759546A CN116716094A CN 116716094 A CN116716094 A CN 116716094A CN 202310759546 A CN202310759546 A CN 202310759546A CN 116716094 A CN116716094 A CN 116716094A
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- 239000002562 thickening agent Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 60
- 239000000178 monomer Substances 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 24
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000003921 oil Substances 0.000 claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 13
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims description 30
- -1 acyl peroxide Chemical class 0.000 claims description 29
- 229940117986 sulfobetaine Drugs 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 claims description 9
- OYVDXEVJHXWJAE-UHFFFAOYSA-N 5-ethenylpyrrolidin-2-one Chemical compound C=CC1CCC(=O)N1 OYVDXEVJHXWJAE-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 229940048053 acrylate Drugs 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- PCWPQSDFNIFUPO-VDQKLNDWSA-N (1S,3R,5R,6S,8R,10R,11S,13R,15R,16S,18R,20R,21S,23R,25R,26S,28R,30R,31S,33R,35R,36R,37S,38R,39S,40R,41S,42R,43S,44R,45S,46R,47S,48R,49S)-37,39,41,43,45,47,49-heptakis(2-hydroxyethoxy)-5,10,15,20,25,30,35-heptakis(hydroxymethyl)-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontane-36,38,40,42,44,46,48-heptol Chemical compound OCCO[C@H]1[C@H](O)[C@@H]2O[C@H]3O[C@H](CO)[C@@H](O[C@H]4O[C@H](CO)[C@@H](O[C@H]5O[C@H](CO)[C@@H](O[C@H]6O[C@H](CO)[C@@H](O[C@H]7O[C@H](CO)[C@@H](O[C@H]8O[C@H](CO)[C@@H](O[C@H]1O[C@@H]2CO)[C@@H](O)[C@@H]8OCCO)[C@@H](O)[C@@H]7OCCO)[C@@H](O)[C@@H]6OCCO)[C@@H](O)[C@@H]5OCCO)[C@@H](O)[C@@H]4OCCO)[C@@H](O)[C@@H]3OCCO PCWPQSDFNIFUPO-VDQKLNDWSA-N 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical group CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 5
- 229910003321 CoFe Inorganic materials 0.000 claims description 5
- 229920000858 Cyclodextrin Polymers 0.000 claims description 5
- 239000001116 FEMA 4028 Substances 0.000 claims description 5
- 229910001566 austenite Inorganic materials 0.000 claims description 5
- 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 claims description 5
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 5
- 229960004853 betadex Drugs 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229940047670 sodium acrylate Drugs 0.000 claims description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 5
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 4
- CJGJYOBXQLCLRG-UHFFFAOYSA-M sodium;2-hydroxy-3-prop-2-enoxypropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)COCC=C CJGJYOBXQLCLRG-UHFFFAOYSA-M 0.000 claims description 4
- ODLHGICHYURWBS-LKONHMLTSA-N trappsol cyclo Chemical compound CC(O)COC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)COCC(O)C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1COCC(C)O ODLHGICHYURWBS-LKONHMLTSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 150000002978 peroxides Chemical group 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012966 redox initiator Substances 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 3
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000010008 shearing Methods 0.000 abstract description 13
- 150000003839 salts Chemical class 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 7
- 230000033558 biomineral tissue development Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000015784 hyperosmotic salinity response Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/10—Nanoparticle-containing well treatment fluids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a self-repairing thickener and a preparation method thereof, and relates to the technical field of oil fields, wherein the method comprises the following steps: modifying the magnetic nano particles by adopting organosilane to obtain modified magnetic nano particles; carrying out copolymerization reaction on the modified magnetic nano particles, acrylamide, acrylic acid salt, sulfonic acid group-containing monomers, temperature-resistant monomers, water and an initiator to obtain a multi-component copolymer; and uniformly stirring and mixing the multi-component copolymer, the dispersing agent, the white oil, the surfactant and the supporting auxiliary agent to obtain the self-repairing thickening agent. The self-repairing thickener prepared by the invention has excellent shearing resistance, temperature resistance and salt resistance.
Description
Technical Field
The invention relates to the technical field of oil fields, in particular to a self-repairing thickening agent and a preparation method thereof.
Background
The fracturing technology is an important factor influencing the fracturing yield increasing effect, and the fracturing technology which is suitable for the fracturing technology needs to be selected according to the geological conditions, the well depth conditions and other factors of different oil and gas layers so as to smoothly execute fracturing and obtain better yield increasing effect.
With the progress of petroleum exploration technology, the development of oil and gas resources is continuously advanced to depth, well drilling is deeper and deeper, and the temperature of reservoirs to be reformed is also higher and higher. In order to match with the fracturing reformation of a high-temperature oil and gas reservoir, higher requirements are put forward on the temperature resistance and shearing resistance of the fracturing fluid thickener, however, the existing fracturing fluid thickener needs longer dissolution time and is greatly influenced by high temperature, high mineralization degree and shearing, and the problems of poor temperature resistance and salt resistance, poor shearing resistance and the like still exist in practical application.
Disclosure of Invention
The embodiment of the invention provides a self-repairing thickener and a preparation method thereof, wherein the self-repairing thickener has excellent shearing resistance, temperature resistance and salt resistance.
In a first aspect, the present invention provides a method for preparing a self-healing thickener, the method comprising:
(1) Modifying the magnetic nano particles by adopting organosilane to obtain modified magnetic nano particles;
(2) Carrying out copolymerization reaction on the modified magnetic nano particles, acrylamide, acrylate, sulfonic acid group-containing monomer, temperature-resistant monomer, water and initiator to obtain a multi-component copolymer;
(3) And uniformly stirring and mixing the multi-component copolymer, the dispersing agent, the white oil, the surfactant and the supporting auxiliary agent to obtain the self-repairing thickening agent.
Preferably, in step (1), the organosilane is 3-aminopropyl triethoxysilane and/or N-aminoethyl-3-aminopropyl triethoxysilane.
Preferably, in step (1), the magnetic nanoparticle is at least one of Fe3O4, γ -Fe2O3, coFe2O 4.
Preferably, in step (1), the volume ratio of the organosilane to the magnetic nanoparticles is (1.2-2): 1.
Preferably, in the step (1), the temperature of the modification is 25-30 ℃ and the reaction time is 5-8 h.
Preferably, in step (1), the magnetic nanoparticles have a particle size of 1 to 1000nm.
Preferably, in the step (2), the multi-component copolymer is a powder having a particle size of 100 to 120 mesh.
Preferably, in step (2):
the components for preparing the multi-component copolymer are as follows: 3-8 parts of modified magnetic nano particles, 150-220 parts of acrylamide, 50-70 parts of acrylate, 20-80 parts of sulfonic acid group-containing monomer, 5-10 parts of temperature-resistant monomer, 610-772 parts of water and 0.1-0.5 part of initiator.
Preferably, in step (2): the acrylic acid salt is sodium acrylate and/or potassium acrylate;
the sulfonic acid group-containing monomer is at least one of sodium 3-allyloxy-2-hydroxy-1-propane sulfonate, sodium p-styrene sulfonate and sodium 2-acrylamide-2-methylpropanesulfonate;
the temperature resistant monomer is N-vinyl pyrrolidone and/or 5-vinyl-2-pyrrolidone.
Preferably, in step (2):
uniformly mixing the modified magnetic nano particles, acrylamide, acrylate, sulfonic acid group-containing monomers, temperature-resistant monomers and water to obtain a mixed solution; regulating the pH of the mixed solution to 6.5-8.0, and adding the initiator into the mixed solution after introducing nitrogen to initiate copolymerization reaction to obtain a reaction product; and (3) drying and grinding the reaction product to obtain the multi-component copolymer.
More preferably, in step (2), the pH of the mixed solution is 7.2 to 7.8.
Preferably, in the step (2), nitrogen is introduced for 30 to 70 minutes.
More preferably, in the step (2), the nitrogen gas is introduced for 50 to 60 minutes.
Preferably, in step (2), the initiator is a redox initiator comprising an oxidizing agent and a reducing agent.
Preferably, the oxidant is at least one of acyl peroxide, tert-butyl hydroperoxide and hydrogen peroxide;
the reducing agent is at least one of ethylenediamine, sodium bisulphite and sodium metabisulfite.
More preferably, the initiator is a peroxide acyl group or ethylenediamine.
Preferably, in step (3), the dispersant is silica and/or titania.
More preferably, the particle size of the dispersant is 1 to 1000nm;
the surfactant comprises a monomer containing sulfobetaine and an emulsifier.
More preferably, the monomer containing the sulfobetaine is at least one of decane hydroxypropyl sulfobetaine, dodecyl hydroxypropyl sulfobetaine, tetradecyl hydroxypropyl sulfobetaine, hexadecyl hydroxypropyl sulfobetaine and octadecyl hydroxypropyl sulfobetaine;
the emulsifier is at least one of op-10, op-13 and op-15.
Preferably, the supporting auxiliary agent is at least one of beta-cyclodextrin, hydroxyethyl-beta-cyclodextrin and hydroxypropyl-beta-cyclodextrin.
Preferably, in step (3):
the self-repairing thickener is prepared from the following components in parts by weight: 500-550 parts of the multipolymer, 1.5-3.5 parts of dispersing agent, 439-495 parts of white oil, 0.5-1.5 parts of surfactant and 3-6 parts of supporting auxiliary agent.
Preferably, in step (3), the stirring speed is 1000 to 3000rpm.
More preferably, in step (3), the stirring speed is 2000 to 2500rpm.
In a second aspect, the invention provides a self-repairing thickener prepared by the preparation method of any one of the first aspects.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the invention, the modified magnetic nanoparticles are modified, so that the modified magnetic nanoparticles are provided with double bonds, can be subjected to copolymerization reaction with acrylamide and acrylic acid salt, meanwhile, a sulfonic acid group-containing monomer and a temperature-resistant monomer are added in the copolymerization reaction, so that the multipolymer has excellent temperature resistance and salt resistance, then, the multipolymer is dispersed in a dispersion system which takes white oil as a dispersion main body and contains a surfactant, a dispersing agent and a supporting auxiliary agent, so that a suspension emulsion is formed, and the suspension emulsion is used as a self-repairing thickening agent. Because of adding the sulfonic acid group-containing monomer and the temperature-resistant monomer, the self-repairing thickener has excellent temperature resistance and salt resistance.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by persons of ordinary skill in the art without making creative efforts based on the embodiments of the present invention are all within the scope of protection of the present invention.
The invention provides a preparation method of a self-repairing thickener, which comprises the following steps:
(1) Modifying the magnetic nano particles by adopting organosilane to obtain modified magnetic nano particles;
(2) Carrying out copolymerization reaction on the modified magnetic nano particles, acrylamide, acrylic acid salt, sulfonic acid group-containing monomers, temperature-resistant monomers, water and an initiator to obtain a multi-component copolymer;
(3) And uniformly stirring and mixing the multi-component copolymer, the dispersing agent, the white oil, the surfactant and the supporting auxiliary agent to obtain the self-repairing thickening agent.
According to the invention, the modified magnetic nanoparticles are modified to have double bonds, so that the modified magnetic nanoparticles can be subjected to copolymerization reaction with acrylamide and acrylic acid salt, then the multipolymer is dispersed in a dispersion system which takes white oil as a dispersion main body and contains a surfactant, a dispersing agent and a supporting auxiliary agent to form suspension emulsion, and the suspension emulsion is used as a self-repairing thickening agent. Because of adding the sulfonic acid group-containing monomer and the temperature-resistant monomer, the self-repairing thickener has excellent temperature resistance and salt resistance.
According to some preferred embodiments, in step (1), the organosilane is 3-aminopropyl triethoxysilane and/or N-aminoethyl-3-aminopropyl triethoxysilane.
According to some preferred embodiments, in step (1), the magnetic nanoparticle is Fe 3 O 4 、γ-Fe 2 O 3 、CoFe 2 O 4 At least one of them.
At least one kind is a mixture of any one or any plurality of kinds mixed in any proportion.
According to some preferred embodiments, in step (1), the volume ratio of organosilane to magnetic nanoparticle is (1.2-2): 1 (e.g., may be 1.2:1, 1.3:1, 1.5:1, 1.6:1, 1.8:1, 1.9:1, or 2:1).
In the invention, the volume of the organosilane is excessive so as to ensure that the magnetic nano particles can be fully immersed, so that the magnetic nano particles can be subjected to surface treatment, and the modified magnetic nano particles with double bonds are obtained.
According to some preferred embodiments, in step (1), the temperature of modification is 25-30 ℃ (e.g. may be 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃), and the reaction time is 5-8 hours (e.g. may be 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours or 8 hours).
According to some preferred embodiments, in step (1), the magnetic nanoparticles have a particle size of 1 to 1000nm (e.g., may be 1nm, 10nm, 20nm, 50nm, 100nm, 200nm, 500nm, 600nm, 800nm or 1000 nm).
Specifically, step (1) includes: repeatedly washing magnetic nano particles with deionized water, dispersing in a mixed solution of ethanol/water (volume ratio is 1:1), stirring until the magnetic nano particles are uniformly dispersed, transferring into a three-necked flask, magnetically stirring under the protection of argon or nitrogen atmosphere, adding organosilane to carry out surface treatment (namely modification) on the magnetic nano particles, stirring for 5-8 h at 25-30 ℃, repeatedly washing with absolute ethyl alcohol, washing with pure water for a plurality of times, and then drying and grinding in a vacuum drier at 65 ℃ to obtain the multipolymer. The magnetic nanoparticles are dispersed in an ethanol aqueous solution with a volume ratio of 1:1, so that hydroxyl groups are carried on the surfaces of the magnetic nanoparticles, and the magnetic nanoparticles can react with organosilane to carry out modification.
According to some preferred embodiments, in step (2), the parts by weight of the components of the preparation of the multipolymer are as follows:
3 to 8 parts (for example, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, or 8 parts) of modified magnetic nanoparticles, 150 to 220 parts (for example, 150 parts, 155 parts, 160 parts, 165 parts, 170 parts, 175 parts, 180 parts, 185 parts, 190 parts, 195 parts, 200 parts, 205 parts, 210 parts, 215 parts, or 220 parts) of acrylamide, 50 to 70 parts (for example, 50 parts, 55 parts, 60 parts, 65 parts, or 70 parts) of sulfonic acid group-containing monomers (for example, may be 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts or 80 parts), 5 to 10 parts of a temperature resistant monomer (for example, may be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts or 10 parts), 610 to 772 parts of water (for example, may be 610 parts, 620 parts, 630 parts, 640 parts, 650 parts, 660 parts, 670 parts, 680 parts, 700 parts, 720 parts, 750 parts, 760 parts, 770 parts or 772 parts), and 0.1 to 0.5 parts of an initiator (for example, may be 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts or 0.5 parts).
The viscosity average molecular weight of the multi-element copolymer prepared by the above proportion is 800-1500.
In the invention, experiments prove that when the dosage of other components is unchanged, 3-8 parts of modified magnetic nano particles are limited, and if the dosage of the modified magnetic nano particles is too small, the self-repairing performance of the prepared self-repairing thickening agent under the shearing action can be influenced; if the dosage of the modified magnetic nano particles is too large, double bonds provided by the modified magnetic nano particles are too large, so that the prepared self-repairing thickener has poor solubility in practical application, and further the performance of the self-repairing thickener is affected. When the dosage of other components is unchanged, limiting 20-80 parts of sulfonic acid group-containing monomers, and if the dosage of the sulfonic acid group-containing monomers is too small, the salt tolerance of the multi-component copolymer is poor, so that the salt tolerance of the self-repairing thickener is poor; if the amount of the sulfonic acid group-containing monomer is too large, the molecular weight of the multi-component copolymer is low, and the performance of the self-repairing thickener is affected. When the dosage of other components is unchanged, 5-10 parts of temperature-resistant monomer is limited, if the dosage of the temperature-resistant monomer is too small, the temperature resistance of the multi-component copolymer is poor, and then the temperature resistance of the self-repairing thickener is poor; if the amount of the temperature-resistant monomer is too large, the copolymerization reaction rate is slow, and the performance of the multi-component copolymer is affected, so that the performance of the self-repairing thickener is affected.
According to some preferred embodiments, in step (2), the acrylate is sodium acrylate and/or potassium acrylate;
the sulfonic acid group-containing monomer is at least one of sodium 3-allyloxy-2-hydroxy-1-propane sulfonate, sodium p-styrene sulfonate and sodium 2-acrylamide-2-methylpropanesulfonate;
the temperature resistant monomer is N-vinyl pyrrolidone and/or 5-vinyl-2-pyrrolidone.
According to some preferred embodiments, in step (2), the multipolymer is a powder having a particle size of 100 to 120 mesh (for example, may be 100 mesh, 105 mesh, 110 mesh, 115 mesh or 120 mesh).
In the invention, the particle size of the multi-component copolymer is limited, so that the prepared self-repairing thickener has excellent suspension performance.
According to some preferred embodiments, in step (2), the modified magnetic nanoparticles, acrylamide, acrylate, sulfonic acid group-containing monomer, temperature-resistant monomer and water are mixed uniformly to obtain a mixed solution; the pH of the mixed solution is adjusted to 6.5 to 8.0 (for example, the pH can be 6.5, 6.6, 6.8, 7.0, 7.5 or 8.0), and an initiator is added into the mixed solution after nitrogen is introduced to initiate the copolymerization reaction, so that a reaction product is obtained; and (3) drying and grinding the reaction product to obtain the multi-element copolymer.
According to some preferred embodiments, in step (2), the pH of the mixed solution is between 7.2 and 7.8 (e.g. may be 7.2, 7.3, 7.4, 7.5, 7.6, 7.7 or 7.8).
In the invention, experiments prove that the pH of the mixed solution is regulated to 6.5-8.0, so that the influence of the acid-base property of the reaction medium on the decomposition rate of the initiator can be avoided, and the polymerization degree of the multipolymer is ensured.
According to some preferred embodiments, in step (2), the nitrogen is introduced for a period of time ranging from 30 to 70min (for example, it may be 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min or 70 min).
According to some more preferred embodiments, in step (2), the nitrogen is introduced for a period of 50 to 60 minutes (for example, 50 minutes, 52 minutes, 55 minutes, 56 minutes, 58 minutes or 60 minutes may be allowed).
According to some preferred embodiments, in step (2), the initiator is a redox initiator comprising an oxidizing agent and a reducing agent.
According to some preferred embodiments, the oxidizing agent is at least one of acyl peroxide, t-butyl hydroperoxide, hydrogen peroxide;
the reducing agent is at least one of ethylenediamine, sodium bisulphite and sodium metabisulfite.
According to some more preferred embodiments, the initiator is a peroxide and ethylenediamine.
Specifically, in step (2): uniformly mixing modified magnetic nano particles, acrylamide, acrylic acid salt, a sulfonic acid group-containing monomer, a temperature-resistant monomer and water to obtain a mixed solution; the pH of the mixed solution is regulated to 6.5-8.0, and after the mixed solution is deoxygenated for 30-70 min by introducing nitrogen, an initiator is added to the mixed solution to initiate copolymerization reaction, the temperature is raised to the highest temperature as the end of the reaction, then the temperature is kept at the highest temperature for 2-6 h (for example, 2h, 3h, 4h, 5h or 6 h) so as to fully react the residual acrylamide monomer, and then the obtained mixture is dried and ground at 50-90 ℃ (for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃) to obtain the 100-120-mesh multipolymer.
In the invention, water is used as a reaction medium for the polymerization reaction, so that the cost is low, the influence of an organic solvent on environmental pollution can be eliminated, the preparation process is simple, and the reaction heat release is not needed to be heated. The reaction medium is neutral in environment, the preparation process is environment-friendly, pollution-free, low in energy consumption, and the product is nontoxic and noncorrosive, does not produce secondary pollution, and accords with the development direction of the green environment-friendly chemical auxiliary agent.
According to some preferred embodiments, in step (3), the dispersant is silica and/or titania.
According to some preferred embodiments, the particle size of the dispersant is from 1 to 1000nm (e.g., may be 1nm, 10nm, 20nm, 50nm, 100nm, 200nm, 500nm, 600nm, 800nm, or 1000 nm);
the surfactant includes a monomer containing sulfobetaine and an emulsifier.
According to some more preferred embodiments, the sulfobetaine-containing monomer is at least one of decane hydroxypropyl sulfobetaine, dodecyl hydroxypropyl sulfobetaine, tetradecyl hydroxypropyl sulfobetaine, hexadecyl hydroxypropyl sulfobetaine, octadecyl hydroxypropyl sulfobetaine;
the emulsifier is at least one of op-10, op-13 and op-15.
According to some preferred embodiments, the support aid is at least one of beta-cyclodextrin, hydroxyethyl-beta-cyclodextrin, hydroxypropyl-beta-cyclodextrin.
According to some preferred embodiments, in step (3), the weight parts of the components of the self-healing thickener are prepared as follows:
500 to 550 parts (for example, 500 parts, 505 parts, 510 parts, 515 parts, 520 parts, 525 parts, 530 parts, 535 parts, 540 parts, 545 parts, or 550 parts), 1.5 to 3.5 parts (for example, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, or 3.5 parts) of a dispersant, 439 to 495 parts (for example, 439 parts, 440 parts, 445 parts, 450 parts, 455 parts, 460 parts, 465 parts, 470 parts, 475 parts, 480 parts, 485 parts, 490 parts, or 495 parts), 0.5 to 1.5 parts (for example, 0.5 parts, 0.55 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, or 1.5 parts), and 3 to 6 parts (for example, 3.5, 4 parts, 4, 5, or 5 parts) of a supporting aid.
According to some preferred embodiments, in step (3), the stirring speed is 1000 to 3000rpm (for example, it may be 1000rpm, 1500rpm, 1800rpm, 2000rpm, 2500rpm or 3000 rpm).
According to some more preferred embodiments, in step (3), the stirring speed is between 2000 and 2500rpm (for example, it may be 2000rpm, 2100rpm, 2200rpm, 2300rpm, 2400rpm or 2500 rpm).
Specifically, step (3) includes: uniformly mixing the multipolymer with a dispersing agent to obtain a mixture; and adding the mixture into a dispersion system comprising white oil, a surfactant and a supporting auxiliary agent, and stirring and uniformly mixing to obtain the self-repairing thickening agent.
In the invention, in order to avoid aggregation or agglomeration of the multipolymer, the multipolymer and the dispersing agent are uniformly mixed firstly, so that the dispersing agent is attached to the surface of the multipolymer, and the multipolymer is stirred at a high speed at a rotating speed of 2000-2500 rpm, so that the multipolymer can be uniformly dispersed in a dispersion system taking white oil as a dispersion main body; meanwhile, the dispersing agent also has an antioxidation function.
According to the invention, the dissolution time of the prepared self-repairing thickener in water or brine is less than 2min by limiting the parts of the components used by the self-repairing thickener, so that the time utilization rate is improved and the production cost is reduced in the actual field application process. Meanwhile, the self-repairing thickener has excellent temperature resistance, salt resistance and shearing resistance, and has a magnetic self-repairing function after shearing.
In the present invention, when the amounts of the other components are not changed, 500 to 550 parts of the multi-component copolymer used for preparing the self-repairing thickener is defined. Therefore, poor dispersibility caused by excessive dosage of the multi-component copolymer can be avoided, and the performance of the self-repairing thickener is influenced; meanwhile, when the dosage is too low, the solid content of the multipolymer in the self-repairing thickener is low, and the temperature resistance, the salt resistance and the shearing resistance of the self-repairing thickener are further influenced. The surfactant is used for enhancing the solubility of the self-repairing thickener; the supporting auxiliary agent is used for providing stable suspension performance for the self-repairing thickening agent.
The invention also provides a self-repairing thickener, which is prepared by adopting the preparation method provided by the invention.
In order to more clearly illustrate the technical scheme and advantages of the invention, a self-repairing thickener and a preparation method thereof are described in detail through a plurality of examples.
In the following examples, magnetic nanoparticles Fe 3 O 4 、γ-Fe 2 O 3 、CoFe 2 O 4 The grain diameter of the polymer is 1-1000 nm;
and the mass of the modified magnetic nano particles, the acrylamide, the acrylic acid salt, the monomer containing sulfonic acid groups, the temperature-resistant monomer, the deionized water, the initiator, the multipolymer, the dispersing agent, the white oil, the surfactant and the supporting auxiliary agent are all expressed in parts by weight.
Preparation of modified magnetic nanoparticles:
10g of Fe 3 O 4 The particles were repeatedly washed with deionized water and then dissolved in 200mL of aqueous ethanol at a volume ratio of 1:1Stirring to disperse uniformly, transferring into a three-necked flask, magnetically stirring under the protection of argon, and adding 50g of 3-aminopropyl triethoxysilane to perform magnetic stirring on nano-scale Fe 3 O 4 The particles are subjected to surface treatment and stirred for 6 hours at 25 ℃, then repeatedly washed by absolute ethyl alcohol, washed by pure water for a plurality of times, and finally dried in a vacuum drier at 65 ℃ to obtain the modified magnetic nano particles A.
10g of gamma-Fe 2 O 3 Repeatedly washing the particles with deionized water, dissolving in 200mL of ethanol water solution with volume ratio of 1:1, stirring until the particles are uniformly dispersed, transferring into a three-necked flask, magnetically stirring under the protection of argon, and adding 50g of 3-aminopropyl triethoxysilane to perform nano-scale gamma-Fe 2 O 3 The particles are subjected to surface treatment and stirred for 6 hours at 25 ℃, then repeatedly washed by absolute ethyl alcohol, washed by pure water for a plurality of times, and finally dried in a vacuum drier at 65 ℃ to obtain the modified magnetic nano particles B.
10g of CoFe 2 O 4 Repeatedly washing the particles with deionized water, dissolving in 200mL of ethanol water solution with volume ratio of 1:1, stirring to disperse uniformly, transferring into a three-necked flask, magnetically stirring under the protection of argon, and adding 50g of N-aminoethyl-3-aminopropyl triethoxysilane to CoFe 2 O 4 The particles are subjected to surface treatment and stirred for 6 hours at 25 ℃, then repeatedly washed by absolute ethyl alcohol, washed by pure water for a plurality of times, and finally dried in a vacuum drier at 65 ℃ to obtain the modified magnetic nano particles C.
Preparation of a multipolymer:
the parts by weight of the components for preparing the multipolymer I are as follows: 3 parts of modified magnetic nano particles A, 150 parts of acrylamide, 50 parts of sodium acrylate, 20 parts of sulfonic acid group-containing monomer (3-allyloxy-2-hydroxy-1-propane sodium sulfonate), 5 parts of temperature-resistant monomer (N-vinyl pyrrolidone), 771.9 parts of water and 0.1 part of initiator (0.05 part of acyl peroxide and 0.05 part of ethylenediamine);
the preparation method comprises the following steps: adding modified magnetic nano particles A, acrylamide, sodium acrylate, 3-allyloxy-2-hydroxy-1-propane sodium sulfonate and N-vinyl pyrrolidone into deionized water, and fully mixing to obtain a mixed solution; and regulating the pH value of the mixed solution to 7.2, introducing nitrogen to deoxidize for 50min, adding an oxidant and a reducing agent into the mixed solution to initiate polymerization, heating to the highest temperature to be regarded as the end of the reaction, preserving the heat for 2h, drying at 70 ℃, and grinding for 100-120 meshes to obtain the multi-component copolymer I.
The parts by weight of the components for preparing the multipolymer II are as follows: 8 parts of modified magnetic nano particles B, 220 parts of acrylamide, 70 parts of potassium acrylate, 80 parts of sulfonic acid group-containing monomer (sodium p-styrenesulfonate), 10 parts of temperature-resistant monomer (5-vinyl-2-pyrrolidone), 611.5 parts of water and 0.5 part of initiator (0.3 part of acyl peroxide and 0.2 part of ethylenediamine);
the preparation method comprises the following steps: adding the modified magnetic nano particles B, acrylamide, potassium acrylate, sodium p-styrenesulfonate and 5-vinyl-2-pyrrolidone into deionized water, and fully mixing to obtain a mixed solution; and regulating the pH value of the mixed solution to 7.4, introducing nitrogen to deoxidize for 60min, adding an oxidant and a reducing agent into the mixed solution to initiate polymerization, heating to the highest temperature to be regarded as the end of the reaction, preserving the heat for 3h, drying at 75 ℃, and grinding for 100-120 meshes to obtain the multipolymer II.
The parts by weight of the components for preparing the multipolymer III are as follows: 5.5 parts of modified magnetic nano particles C, 185 parts of acrylamide, 60 parts of potassium acrylate, 50 parts of sulfonic acid group-containing monomer (sodium p-styrenesulfonate), 7.5 parts of temperature-resistant monomer (5-vinyl-2-pyrrolidone), 691.7 parts of water and 0.3 part of initiator (0.15 part of acyl peroxide and 0.15 part of ethylenediamine);
the preparation method comprises the following steps: adding modified magnetic nano particles C, acrylamide, potassium acrylate, sodium p-styrenesulfonate and 5-vinyl-2-pyrrolidone into deionized water, and fully mixing to obtain a mixed solution; and regulating the pH value of the mixed solution to 7.4, introducing nitrogen to deoxidize for 60min, adding an oxidant and a reducing agent into the mixed solution to initiate polymerization, heating to the highest temperature to be regarded as the end of the reaction, preserving the heat for 3h, drying at 75 ℃, and grinding for 100-120 meshes to obtain the multi-element copolymer III.
The parts by weight of the components for preparing the multipolymer IV are as follows: 5.5 parts of modified magnetic nano particles C, 185 parts of acrylamide, 60 parts of potassium acrylate, 50 parts of sulfonic acid group-containing monomer (2-acrylamide-2-methylpropanesulfonic acid sodium salt), 7.5 parts of temperature-resistant monomer (5-vinyl-2-pyrrolidone), 691.7 parts of water and 0.3 part of initiator (0.15 part of acyl peroxide and 0.15 part of ethylenediamine);
the preparation method comprises the following steps: adding modified magnetic nano particles C, acrylamide, potassium acrylate, 2-acrylamide-2-methylpropanesulfonic acid sodium and 5-vinyl-2-pyrrolidone into deionized water, and fully mixing to obtain a mixed solution; and regulating the pH value of the mixed solution to 7.4, adding an oxidant and a reducing agent into the mixed solution after introducing nitrogen to deoxidize for 60min to initiate polymerization, heating to the highest temperature as the end of the reaction, preserving the heat for 3h, and then drying and grinding at 75 ℃ for 100-120 meshes to obtain the multipolymer IV.
Example 1
The self-repairing thickener is prepared from the following components in parts by weight: 500 parts of a multipolymer I, 1.5 parts of silicon dioxide, 495 parts of white oil, 0.5 part of a surfactant (0.3 part of decane-hydroxypropyl sulfobetaine, 0.2 part of op-10), and 3 parts of a supporting auxiliary agent (beta-cyclodextrin);
preparation of self-repairing thickener:
uniformly mixing the multipolymer I with silicon dioxide to obtain a mixture; adding decyl hydroxypropyl sulfobetaine, op-10 and beta-cyclodextrin into white oil, fully mixing uniformly, and then adding the mixture, fully mixing at 2000rpm to uniformly disperse the system, thereby obtaining the self-repairing thickener with the magnetic self-repairing function.
Example 2
The self-repairing thickener is prepared from the following components in parts by weight: 550 parts of multipolymer II, 3.5 parts of silicon dioxide, 439 parts of white oil, 1.5 parts of surfactant (0.6 part of octadecyl hydroxypropyl sulfobetaine, 0.9 part of op-15) and 6 parts of supporting auxiliary agent (hydroxyethyl-beta-cyclodextrin);
preparation of self-repairing thickener:
uniformly mixing the multipolymer II with silicon dioxide to obtain a mixture; adding octadecyl hydroxypropyl sulfobetaine, op-15 and hydroxyethyl-beta-cyclodextrin into white oil, fully and uniformly mixing, then adding the mixture, fully mixing at 2500rpm, and uniformly dispersing the system to obtain the self-repairing thickening agent with the magnetic self-repairing function.
Example 3
The self-repairing thickener is prepared from the following components in parts by weight: 525 parts of a multipolymer III, 2.5 parts of titanium dioxide, 467 parts of white oil, 1 part of a surfactant (0.5 part of octadecyl hydroxypropyl sulfobetaine, 0.5 part of op-15), and 4.5 parts of a supporting auxiliary agent (hydroxyethyl-beta-cyclodextrin);
preparation of self-repairing thickener:
uniformly mixing the multipolymer III with titanium dioxide to obtain a mixture; adding octadecyl hydroxypropyl sulfobetaine, op-15 and hydroxyethyl-beta-cyclodextrin into white oil, fully and uniformly mixing, then adding the mixture, fully mixing at 2200rpm, and uniformly dispersing the system to obtain the self-repairing thickening agent with the magnetic self-repairing function.
Example 4
Example 4 is substantially the same as example 3 except that: the multipolymer III was replaced with multipolymer IV.
Example 5
Example 5 is substantially the same as example 3 except that: the octadecyl hydroxypropyl sulfobetaine was replaced with tetradecyl hydroxypropyl sulfobetaine.
Example 6
Example 6 is substantially the same as example 3 except that: op-15 is replaced with op-13.
Example 7
Example 7 is substantially the same as example 3 except that: the supporting auxiliary agent is hydroxypropyl-beta-cyclodextrin.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that: the modified magnetic nanoparticles A were not added in the preparation of the multipolymer I.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that: sodium 3-allyloxy-2-hydroxy-1-propanesulfonate was not added to prepare the multipolymer I.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that: n-vinylpyrrolidone was not added to prepare the multipolymer I.
The self-healing thickeners obtained in examples 1 to 7 and the self-healing thickeners obtained in comparative examples 1 to 3 were used as samples, and the apparent viscosity, the shear resistance, the apparent viscosity after shearing, and the temperature resistance were measured, respectively, and the measurement results are shown in table 1.
Determination of apparent viscosity: placing a beaker containing 400mL of mineralized water with the mineralization degree of 32000mg/L on a stirrer, regulating the rotating speed to 400r/min, weighing 2.0g of sample, adding the sample into the mineralized water, stirring for 1min to obtain a solution to be tested, and testing the apparent viscosity eta of the solution to be tested at the rotating speed of 100r/min by using a Fann-35 six-speed rotary viscometer 0 。
Test of shear resistance: placing a beaker containing 400mL of mineralized water with the mineralization degree of 32000mg/L on a stirrer, regulating the rotating speed to 400r/min, weighing 2.0g of sample, adding the sample into the mineralized water, stirring for 1min to obtain a solution to be tested, placing the solution to be tested on a variable-frequency high-speed stirrer, stirring for 60min at 10000r/min, using a Fann-35 six-speed rotary viscometer after high-speed stirring is completed, and testing the apparent viscosity eta of the solution to be tested at the rotating speed of 100r/min 1 。
Test of apparent viscosity after shear: after the solution to be tested after finishing the shear resistance test is placed for 2min, using a Fann-35 six-speed rotary viscometer to test the apparent viscosity eta of the solution to be tested at the rotating speed of 100r/min 2 。
Testing of temperature resistance: (1) Placing 400mL of mineralized water with the mineralization degree of 32000mg/L on a stirrer, weighing 2.0g of sample, adding the sample into the mineralized water, stirring for 1min to obtain a solution to be tested, placing the solution to be tested in a constant temperature heater at 80 ℃, placing the solution to be tested for 20 days, and testing the apparent viscosity eta of the solution to be tested at the rotating speed of 100r/min by using a Fann-35 six-speed rotary viscometer 3 。
(2) Will contain 400mL of mineralization degreePlacing a beaker of 32000mg/L mineralized water on a stirrer, weighing 2.0g of sample, adding the sample into the mineralized water, stirring for 1min to obtain a solution to be tested, placing the solution to be tested in a constant temperature heater at 100 ℃, placing the solution to be tested in the constant temperature heater for 20 days, and measuring apparent viscosity eta of the solution to be tested at 100r/min by using a Fann-35 six-speed rotary viscometer 4 。
The mineralized water with the mineralization degree of 32000mg/L is configured by the following steps: 1932.72g of distilled water is accurately weighed into a beaker with a measuring range of 2L, 60.476g of sodium chloride, 3.8864g of anhydrous calcium chloride and 2.9376g of magnesium chloride hexahydrate are sequentially added, in the preparation process, after one reagent is added and dissolved completely, the other reagent is added, and mineralized water with the mineralization degree of 32000mg/L is prepared after uniform stirring, wherein the total amount of calcium ions and magnesium ions is 874mg/L.
TABLE 1
From the data in Table 1, it can be seen that the self-repairing thickener prepared by the invention has higher apparent viscosity in high-mineralization brine, and the apparent viscosity is more than 120 mPa.s; the apparent viscosity is slightly reduced after the high shearing action, but the apparent viscosity can be recovered to be normal after the shearing action is eliminated for 2 minutes, and the apparent viscosity retention rate is extremely high; and the apparent viscosity retention rate is still high after aging for 20 days at the high temperature of 80 ℃, so that the self-repairing thickener prepared by the invention has excellent salt resistance, temperature resistance and shearing resistance.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention. The invention is not described in detail in a manner known to those skilled in the art.
Claims (10)
1. The preparation method of the self-repairing thickener is characterized by comprising the following steps:
(1) Modifying the magnetic nano particles by adopting organosilane to obtain modified magnetic nano particles;
(2) Carrying out copolymerization reaction on the modified magnetic nano particles, acrylamide, acrylate, sulfonic acid group-containing monomer, temperature-resistant monomer, water and initiator to obtain a multi-component copolymer;
(3) And uniformly stirring and mixing the multi-component copolymer, the dispersing agent, the white oil, the surfactant and the supporting auxiliary agent to obtain the self-repairing thickening agent.
2. The method of claim 1, wherein in step (1):
the organosilane is 3-aminopropyl triethoxysilane and/or N-aminoethyl-3-aminopropyl triethoxysilane; and/or
The magnetic nano particles are Fe 3 O 4 、γ-Fe 2 O 3 、CoFe 2 O 4 At least one of them.
3. The method of claim 1, wherein in step (1):
the volume ratio of the organosilane to the magnetic nanoparticles is (1.2-2): 1; and/or
The temperature of the modification is 25-30 ℃, and the reaction time is 5-8 h.
4. The method of manufacturing according to claim 1, characterized in that:
the particle size of the magnetic nano particles is 1-1000 nm; and/or
The multi-element copolymer is powder with the grain diameter of 100-120 meshes.
5. The method of claim 1, wherein in step (2):
the components for preparing the multi-component copolymer are as follows: 3-8 parts of modified magnetic nano particles, 150-220 parts of acrylamide, 50-70 parts of acrylate, 20-80 parts of sulfonic acid group-containing monomer, 5-10 parts of temperature-resistant monomer, 610-772 parts of water and 0.1-0.5 part of initiator; and/or
The acrylic acid salt is sodium acrylate and/or potassium acrylate;
the sulfonic acid group-containing monomer is at least one of sodium 3-allyloxy-2-hydroxy-1-propane sulfonate, sodium p-styrene sulfonate and sodium 2-acrylamide-2-methylpropanesulfonate;
the temperature resistant monomer is N-vinyl pyrrolidone and/or 5-vinyl-2-pyrrolidone.
6. The method of claim 1, wherein in step (2):
uniformly mixing the modified magnetic nano particles, acrylamide, acrylate, sulfonic acid group-containing monomers, temperature-resistant monomers and water to obtain a mixed solution; regulating the pH of the mixed solution to 6.5-8.0, and adding the initiator into the mixed solution after introducing nitrogen to initiate copolymerization reaction to obtain a reaction product; drying and grinding the reaction product to obtain the multi-element copolymer;
preferably, the pH of the mixed solution is 7.2-7.8;
preferably, the nitrogen is introduced for a period of 30 to 70 minutes, more preferably 50 to 60 minutes.
7. The method of claim 1, wherein in step (2):
the initiator is a redox initiator comprising an oxidant and a reducing agent;
preferably, the oxidant is at least one of acyl peroxide, tert-butyl hydroperoxide and hydrogen peroxide;
the reducing agent is at least one of ethylenediamine, sodium bisulphite and sodium metabisulfite;
more preferably, the initiator is a peroxide acyl group or ethylenediamine.
8. The method of claim 1, wherein in step (3):
the dispersing agent is silicon dioxide and/or titanium dioxide; preferably, the particle size of the dispersing agent is 1-1000 nm;
the surfactant comprises a monomer containing sulfobetaine and an emulsifier;
preferably, the monomer containing the sulfobetaine is at least one of decane hydroxypropyl sulfobetaine, dodecyl hydroxypropyl sulfobetaine, tetradecyl hydroxypropyl sulfobetaine, hexadecyl hydroxypropyl sulfobetaine and octadecyl hydroxypropyl sulfobetaine;
the emulsifier is at least one of op-10, op-13 and op-15;
and/or the number of the groups of groups,
the supporting auxiliary agent is at least one of beta-cyclodextrin, hydroxyethyl-beta-cyclodextrin and hydroxypropyl-beta-cyclodextrin.
9. The method according to any one of claims 1 to 8, wherein in step (3):
the self-repairing thickener is prepared from the following components in parts by weight: 500-550 parts of the multipolymer, 1.5-3.5 parts of dispersing agent, 439-495 parts of white oil, 0.5-1.5 parts of surfactant and 3-6 parts of supporting auxiliary agent;
preferably, the rotational speed of the stirring is 1000 to 3000rpm, more preferably 2000 to 2500rpm.
10. A self-healing thickener prepared by the method of any one of claims 1 to 9.
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