CN117143283B - Salt-resistant fracturing fluid thickening agent and preparation method thereof - Google Patents
Salt-resistant fracturing fluid thickening agent and preparation method thereof Download PDFInfo
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- 239000012530 fluid Substances 0.000 title claims abstract description 62
- 239000002562 thickening agent Substances 0.000 title claims abstract description 54
- 150000003839 salts Chemical class 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 86
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 acrylic ester Chemical class 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 230000000977 initiatory effect Effects 0.000 claims description 17
- 239000006184 cosolvent Substances 0.000 claims description 14
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 10
- JVVRCYWZTJLJSG-UHFFFAOYSA-N 4-dimethylaminophenol Chemical compound CN(C)C1=CC=C(O)C=C1 JVVRCYWZTJLJSG-UHFFFAOYSA-N 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- ZLYYJUJDFKGVKB-OWOJBTEDSA-N (e)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C\C(Cl)=O ZLYYJUJDFKGVKB-OWOJBTEDSA-N 0.000 claims description 5
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 5
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims description 4
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- MXXDSLLVYZMTFA-UHFFFAOYSA-N octadecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 MXXDSLLVYZMTFA-UHFFFAOYSA-N 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 229960000776 sodium tetradecyl sulfate Drugs 0.000 claims description 2
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 claims description 2
- UPUIQOIQVMNQAP-UHFFFAOYSA-M sodium;tetradecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCOS([O-])(=O)=O UPUIQOIQVMNQAP-UHFFFAOYSA-M 0.000 claims description 2
- 239000012267 brine Substances 0.000 claims 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims 1
- 238000010008 shearing Methods 0.000 abstract description 9
- 150000001768 cations Chemical class 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 230000009878 intermolecular interaction Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920002401 polyacrylamide Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000015784 hyperosmotic salinity response Effects 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003140 primary amides Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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- 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
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/24—Esters containing sulfur
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- 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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- 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)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a salt-resistant fracturing fluid thickener and a preparation method thereof, and belongs to the technical field of fracturing fluid thickeners. The salt-resistant fracturing fluid thickener comprises the raw materials of monomer A, monomer B, acrylamide, 1H, 2H-heptadecafluorodecane acrylic ester, and the mass ratio of the monomer A to the monomer B to the acrylamide to the 1H, 2H-heptadecafluorodecane acrylic ester is 59-120:33-56:28-36:62-89. The salt-resistant fracturing fluid thickener prepared by the invention has the advantages that all monomer molecules are mutually inserted, anions and cations are mutually attracted, the network structure of the fracturing fluid is more complicated to realize adhesion enhancement through intermolecular hydrogen bonds and intermolecular interaction force, and meanwhile, the salt-resistant fracturing fluid thickener also has excellent salt resistance, better temperature resistance and shearing resistance and wide application prospect.
Description
Technical Field
The invention relates to the technical field of fracturing fluid thickeners, in particular to a salt-resistant fracturing fluid thickener and a preparation method thereof.
Background
Fracturing is one of the most important production increasing measures for oil and gas field exploitation in China, and the performance of the fracturing fluid is directly related to the construction effect. The fracturing fluid adopted in fracturing must have the characteristics of high viscosity, good shearing resistance and the like. The fracturing fluid thickener is used as a main agent of the fracturing fluid and is used for improving the viscosity of the fracturing fluid.
The commonly used natural polymer thickener can not completely meet the requirements of high-temperature fracturing on the performance of fracturing fluid due to the reasons of chain scission of high polymers, degradation of functional groups, weakening or fracture of crosslinking bonds and the like at high temperature. Compared with natural polymer fracturing fluid, the synthetic polymer-based fracturing fluid has the characteristics of strong thickening capability, insensitivity to bacteria, good gel stability, strong sand suspending capability, no residue and low damage to stratum. The synthetic polymer fracturing fluid usually uses anionic polyacrylamide as a thickening agent, and the anionic polyacrylamide has a certain tackifying effect, but has poor salt resistance. The cationic polyacrylamide greatly improves the salt tolerance of the polyacrylamide, but the problems of water solubility, low viscosity and the like still exist.
CN113621106B discloses a multi-effect emulsion type thickener which is prepared from the following components, by weight, 20-40 parts of polymerized monomers, 20-40 parts of solvent oil, 20-40 parts of deionized water, 3-6 parts of an emulsifier, 2-4 parts of a redox initiator, 1-2 parts of a complexing agent, 1-3 parts of a phase inversion agent and sodium hydroxide solution. However, the thickener has poor salt resistance.
Disclosure of Invention
The invention aims to provide a salt-resistant fracturing fluid thickening agent and a preparation method thereof, wherein monomer molecules are mutually inserted, anions and cations are mutually attracted, and the network structure of the fracturing fluid is more complicated to realize thickening through intermolecular hydrogen bonds and intermolecular interaction force, and meanwhile, the salt-resistant fracturing fluid thickening agent also has excellent salt resistance, better temperature resistance and shearing resistance and wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a salt-resistant fracturing fluid thickener, which has a structure shown in a formula I:
a formula I;
wherein, a is b and c is d=10-20:15-25:40-50:12-17.
As a further improvement of the invention, the raw materials of the salt-resistant fracturing fluid thickener comprise monomer A, monomer B, acrylamide, 1H, 2H-heptadecafluorodecane acrylic ester, and the mass ratio is 59-120:33-56:28-36:62-89; wherein, the structural formula of the monomer A is shown as a formula II:
a formula II;
the structural formula of the monomer B is shown in a formula III:
formula III.
As a further improvement of the present invention, the synthesis method of the monomer a is as follows:
s1, reacting fumaryl chloride with 4-dimethylaminophenol to prepare an intermediate A, wherein the structure of the intermediate A is as follows:
；
s2, reacting the intermediate A with propane sultone to obtain the monomer A.
As a further improvement of the invention, the molar ratio of the fumaryl chloride to the 4-dimethylaminophenol in the step S1 is 1:2-2.1, the reaction temperature is 0-4 ℃, and a base is also added, wherein the base is at least one of triethylamine, diethylamine, naOH and KOH, and the reaction time is 1-2 hours; the molar ratio of the intermediate A to the propane sultone in the step S2 is 1:2-2.1, the reaction temperature is 30-35 ℃, and the reaction time is 20-24h.
As a further improvement of the present invention, the synthesis method of the monomer B is as follows: n, N-dimethylacrylamide and propane sultone are reacted to prepare the monomer B.
As a further improvement of the invention, the molar ratio of the N, N-dimethylacrylamide to the propane sultone is 1:1-1.05, the reaction temperature is 30-35 ℃, and the reaction time is 18-20h.
As a further improvement of the invention, the raw materials of the salt-resistant fracturing fluid thickener also comprise a cosolvent, a chain transfer agent and an initiating system, wherein the mass of the cosolvent is 0.2-0.4wt% of the total mass of the monomers, the mass of the chain transfer agent is 0.02-0.05wt% of the total mass of the monomers, and the mass of the initiating system is 0.01-0.03wt% of the total mass of the monomers; the cosolvent is at least one selected from sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium tetradecyl sulfate, sodium hexadecyl sulfonate, sodium hexadecyl benzene sulfonate, sodium octadecyl sulfate and sodium octadecyl benzene sulfonate; the chain transfer agent is polyethylene glycol dimethacrylate; the initiating system is a mixture of an initiator and sodium sulfite, the mass ratio is 1:0.9-1.2, and the initiator is at least one selected from sodium persulfate, ammonium persulfate and potassium persulfate.
The invention further provides a preparation method of the salt-resistant fracturing fluid thickener, which comprises the following steps:
(1) Adding the monomer A, the monomer B, the acrylamide, the 1H, 2H-heptadecafluorodecane acrylic ester and the cosolvent into water, and stirring and mixing uniformly to prepare a water mixed solution with the total mass concentration of the monomers of 32-37 wt%;
(2) Under the protection of inert gas, adding chain transfer agent, initiating system and water to prepare aqueous solution with the total mass concentration of monomers of 27-32wt%, stirring and reacting for 2-4h at 55-60 ℃, filtering, washing, drying and crushing the product to obtain the salt-resistant fracturing fluid thickening agent.
The invention further protects a monomer A, which has a structural formula shown in a formula II:
formula II.
The invention further protects a monomer B, which has a structural formula shown in a formula III:
formula III.
The invention has the following beneficial effects: according to the salt-resistant fracturing fluid thickener disclosed by the invention, two zwitterionic monomers are adopted, wherein the amphoteric monomer comprises a monomer A and a monomer B, the monomer A is a Gemini type amphoteric ionic monomer and the monomer B is a zwitterionic monomer, and meanwhile, the salt-resistant fracturing fluid thickener has good solubility and salt resistance, and as the monomer is connected with a rigid benzene ring group, the phenomenon of molecular chain curling caused by attraction between a positively charged quaternary ammonium salt decomposition structure and a negatively charged sulfonic group structure can be effectively inhibited, the viscosity retention rate is prolonged, and the temperature resistance and the shearing resistance of a polymer are greatly improved. Meanwhile, because the monomer has huge side groups,the steric hindrance is increased, the hydrolysis resistance is stronger, the sulfonic acid group is a strong polar group, the copolymer has good water solubility due to strong hydrophilic effect and electrostatic repulsive force, the hydrodynamic volume of a molecular chain is greatly increased, and meanwhile, the copolymer has excellent temperature resistance and salt resistance and divalent cation Ca 2+ 、Mg 2+ No precipitate is generated; the amphoteric ion monomer satisfies the condition that the number of positive and negative charge groups on a molecular chain is equal, so that the molecular stretching condition of the polymer in saline water with different mineralization degrees is little in change, the viscosity is little in change, and the excellent salt resistance is shown. The Gemini type monomer also obviously improves the salt resistance, shearing resistance and temperature resistance.
In addition, the invention also adopts a hydrophobic association monomer 1H, 2H-heptadecafluorodecane acrylic ester, and a small amount of fluorine-containing hydrophobic monomer is introduced into the main chain, so that the formed polymer can generate intermolecular association in the aqueous solution thereof, and has good tackifying effect on the solution, thereby further enhancing the thickening effect of the thickener. In addition, the selected polyacrylamide monomer also greatly improves the solubility of the polymer.
The salt-resistant fracturing fluid thickener prepared by the invention has the advantages that all monomer molecules are mutually inserted, anions and cations are mutually attracted, the network structure of the fracturing fluid is more complicated to realize adhesion enhancement through intermolecular hydrogen bonds and intermolecular interaction force, and meanwhile, the salt-resistant fracturing fluid thickener also has excellent salt resistance, better temperature resistance and shearing resistance and wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a synthetic route for the salt-tolerant fracturing fluid thickener of this invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Preparation example 1 Synthesis of monomer A
The synthetic route is as follows:
the method comprises the following steps:
s1, dissolving 0.1mol of fumaryl chloride, 0.205mol of 4-dimethylaminophenol and 0.5mol of triethylamine in 200mL of dichloromethane, reacting for 2 hours at the temperature of 0 ℃, removing the solvent under reduced pressure, and separating by column chromatography (the volume ratio of ethyl acetate to petroleum ether is 1:10) of a product to prepare an intermediate A; ESI-MS calculated: c (C) 22 H 23 N 2 O 4 (m+h) + 355.16, found: 355.2, the yield thereof was found to be 92.4%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ7.02（s，2H），6.85（d，J=7.2Hz，4H），6.52（d，J=7.1Hz，4H），2.83（s，12H）。
s2, adding 0.1mol of the intermediate A and 0.205mol of propane sultone into 200mL of acetone, reacting for 24h at 32 ℃, filtering, washing with ethanol, and drying to obtain a monomer A. ESI-MS calculated: c (C) 26 H 35 N 2 O 10 S 2 (m+h) + 599.17, found: 599.2, the yield was 89.5%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ7.90（d，J=6.8Hz，4H），7.41（d，J=6.7Hz，4H），7.05（s，2H），3.72（s，12H），3.25（t，4H），1.82（m，4H），1.31（t，4H）。
preparation example 2 Synthesis of monomer B
The synthetic route is as follows:
the method comprises the following steps: 0.1mol of N, N-dimethylacrylamide and 0.102mol of propane sultone are added into 200mL of acetone, reacted for 20h at 32 ℃, filtered, washed with ethanol and dried to prepare a monomer B. ESI-MS calculated: c (C) 8 H 16 NO 4 S (m+h) + 222.07, found: 222.1 in 91.2% yield.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ6.35（m，2H），6.12（m，1H），3.42（t，2H），3.24（t，2H），2.91（s，6H），2.27（m，2H）。
example 1
As shown in fig. 1, the embodiment provides a salt-resistant fracturing fluid thickener, and the preparation method comprises the following steps:
(1) 59 parts by weight of the monomer A prepared in preparation example 1, 33 parts by weight of the monomer B prepared in preparation example 2, 28 parts by weight of acrylamide, 62 parts by weight of 1H, 2H-heptadecafluorodecane acrylic acid ester and cosolvent sodium hexadecylsulfonate are added into water, and uniformly stirred and mixed to prepare a water mixed solution with the total mass concentration of the monomers of 32 wt%;
(2) Under the protection of nitrogen, adding polyethylene glycol dimethacrylate, an initiating system and water to prepare an aqueous solution with the total mass concentration of the monomers of 27wt%, stirring and reacting for 2 hours at 55 ℃, filtering, washing, drying and crushing the product to prepare the salt-resistant fracturing fluid thickener; infrared spectrogram identification of 1620-1680cm -1 No absorption peak is found, which indicates that the carbon-carbon double bond is completely consumed to participate in the polymerization reaction; 3020cm -1 Is Ar-H telescopic vibration peak of 2885cm -1 Is a medium pressure methyl (-CH) group in the main chain and side chain of the polymer 2 A stretching vibration peak of (-); 3425cm -1 The absorption peak at the position is the telescopic vibration of primary amide N-H; 1657cm -1 C=o stretching vibration with absorption peak of carboxyl; at 1502cm -1 Is characterized by the characteristic absorption peak of C-N in quaternary ammonium salt; 1120cm -1 Characteristic absorption peak of C-F, 1172cm -1 And 1059cm -1 The absorption peak at the position is sulfonic group-SO 3 Characteristic absorption peak, 910cm -1 、782cm -1 、665cm -1 Is the vibration peak of the internal frame structure of the benzene ring.
The initiating system is a mixture of potassium persulfate and sodium sulfite, the mass ratio is 1:0.9, and the mass of the initiating system is 0.01wt% of the total mass of the monomers.
The mass of the polyethylene glycol dimethacrylate is 0.02wt% of the total mass of the monomers;
the mass of the cosolvent sodium hexadecyl sulfonate is 0.2 weight percent of the total mass of the monomer.
Example 2
As shown in fig. 1, the embodiment provides a salt-resistant fracturing fluid thickener, and the preparation method comprises the following steps:
(1) 120 parts by weight of the monomer A prepared in preparation example 1, 56 parts by weight of the monomer B prepared in preparation example 2, 36 parts by weight of acrylamide, 89 parts by weight of 1H, 2H-heptadecafluorodecane acrylic acid ester and cosolvent sodium dodecyl sulfate are added into water, and uniformly stirred and mixed to prepare a water mixed solution with the total mass concentration of the monomers of 37 wt%;
(2) Under the protection of nitrogen, adding polyethylene glycol dimethacrylate, an initiating system and water to prepare an aqueous solution with the total mass concentration of the monomers of 32wt%, stirring and reacting for 4 hours at 60 ℃, filtering, washing, drying and crushing the product to prepare the salt-resistant fracturing fluid thickener;
the initiating system is a mixture of ammonium persulfate and sodium sulfite, the mass ratio is 1.2, and the mass of the initiating system is 0.03 weight percent of the total mass of the monomers.
The mass of the polyethylene glycol dimethacrylate is 0.05wt% of the total mass of the monomers;
the mass of the cosolvent sodium dodecyl sulfate is 0.4wt% of the total mass of the monomer.
Example 3
As shown in fig. 1, the embodiment provides a salt-resistant fracturing fluid thickener, and the preparation method comprises the following steps:
(1) 102 parts by weight of a monomer A prepared in preparation example 1, 45 parts by weight of a monomer B prepared in preparation example 2, 30 parts by weight of acrylamide, 75 parts by weight of 1H, 2H-heptadecafluorodecane acrylic acid ester and cosolvent sodium stearyl sulfate are added into water, and uniformly stirred and mixed to prepare a water mixed solution with the total mass concentration of the monomers of 35 wt%;
(2) Under the protection of nitrogen, adding polyethylene glycol dimethacrylate, an initiating system and water to prepare an aqueous solution with the total mass concentration of monomers of 30wt%, stirring and reacting for 3 hours at 57 ℃, filtering, washing, drying and crushing the product to prepare the salt-resistant fracturing fluid thickener;
the initiating system is a mixture of sodium persulfate and sodium sulfite, the mass ratio is 1:1, and the mass of the initiating system is 0.02wt% of the total mass of the monomers.
The mass of the polyethylene glycol dimethacrylate is 0.04 weight percent of the total mass of the monomers;
the mass of the cosolvent sodium octadecyl sulfate is 0.3 weight percent of the total mass of the monomer.
Comparative example 1
The difference compared to example 3 is that no monomer A is added.
Comparative example 2
The difference compared to example 3 is that no monomer B was added.
Comparative example 3
The difference compared to example 3 is that monomer A and monomer B are not added.
Comparative example 4
The difference compared to example 3 is that monomer A and monomer B consist of equal amounts; 2-acrylamido-2-methylpropanesulfonic acid.
Comparative example 5
In comparison with example 3, 1H, 2H-heptadecafluorodecane acrylate was not added.
Test example 1
The salt-resistant fracturing fluid thickeners prepared in examples 1-3 and comparative examples 1-5 were formulated as 0.3wt% solutions at 25℃for 170s -1 The apparent viscosity was measured as follows. The results are shown in Table 1.
TABLE 1
As shown in the table above, the salt-resistant fracturing fluid thickening agents prepared in the embodiments 1-3 have good tackifying effect.
Test example 2
The salt-resistant fracturing fluid thickeners prepared in examples 1-3 and comparative examples 1-5 were formulated into 0.3wt% solutions at 160℃180℃200℃170s, respectively -1 The apparent viscosity was measured as follows. The results are shown in Table 2.
TABLE 2
As shown in the table above, the salt-resistant fracturing fluid thickening agent prepared in the embodiments 1-3 still has good viscosity at a high temperature and good temperature resistance.
Test example 3
The salt-resistant fracturing fluid thickeners prepared in examples 1-3 and comparative examples 1-5 were formulated as 0.3wt% solutions at 25℃for 170s, respectively -1 Shearing for 2 hours, and testing the apparent viscosity. The results are shown in Table 3.
TABLE 3 Table 3
As can be seen from the above table, the salt-resistant fracturing fluid thickeners prepared in examples 1 to 3 of the present invention were used for 170 seconds -1 The lower shearing time is 2 hours, the apparent viscosity is still kept very good, and the shearing resistance is good.
Test example 4
The salt-resistant fracturing fluid thickeners prepared in examples 1-3 and comparative examples 1-5 were formulated as 0.3wt% solutions, and NaCl was added to the system at a NaCl concentration of 0.5g/L or CaCl was added, respectively 2 CaCl in the system 2 The concentration is 0.5g/L, and the temperature is 25 ℃ and 170s -1 The apparent viscosity was measured as follows. The results are shown in Table 4.
TABLE 4 Table 4
As can be seen from the above table, the salt-resistant fracturing fluid thickeners prepared in examples 1 to 3 of the present invention are used in NaCl solution or CaCl 2 The solution still has good apparent viscosity, which indicates that the solution has excellent salt tolerance.
Test example 5
The salt-resistant fracturing fluid thickeners prepared in examples 1 to 3 and comparative examples 1 to 5 were prepared into 0.3wt% solutions, hexamethylenetetramine was added to a final concentration of 0.3wt%, and the resultant gel was subjected to crosslinking reaction at a room temperature of 25℃for 120 seconds, and the apparent viscosity of the resulting gel was measured. Ammonium persulfate was then added to the formed gel to a final concentration of 0.1wt%, stirred for 10 seconds, and the apparent viscosity of the gel was measured.
And (3) centrifuging 50 mL gel breaking liquid for 30min at 3000r/min, pouring supernatant, washing a gel breaking container with water, pouring into a centrifuge tube again, centrifuging at 3000r/min for 30min, pouring supernatant, placing the centrifuge tube into a baking oven, baking until the weight of the centrifuge tube is constant, and dividing the residue mass by the using amount of fracturing fluid to obtain the residue content of the fracturing fluid.
The results are shown in Table 5.
TABLE 5
As can be seen from the above table, the salt-resistant fracturing fluid thickening agents prepared in the embodiments 1 to 3 can well form cross-linking, and meanwhile, can rapidly break gel, and meanwhile, the content of residues after breaking gel is extremely low, and almost no residues exist, so that the damage to stratum is extremely small.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. The salt-resistant fracturing fluid thickener is characterized by having a structure shown in a formula I:
a formula I;
wherein, a is b and c is d=10-20:15-25:40-50:12-17.
2. The salt-resistant fracturing fluid thickener according to claim 1, wherein the raw materials of the salt-resistant fracturing fluid thickener comprise monomer A, monomer B, acrylamide, 1H, 2H-heptadecafluorodecane acrylic ester, and the mass ratio is 59-120:33-56:28-36:62-89; wherein, the structural formula of the monomer A is shown as a formula II:
a formula II;
the structural formula of the monomer B is shown in a formula III:
formula III.
3. The salt-resistant fracturing fluid thickener according to claim 2, wherein the synthesis method of the monomer A is as follows:
s1, reacting fumaryl chloride with 4-dimethylaminophenol to prepare an intermediate A, wherein the structure of the intermediate A is as follows:
；
s2, reacting the intermediate A with propane sultone to obtain the monomer A.
4. The salt-resistant fracturing fluid thickener according to claim 3, wherein the molar ratio of the fumaryl chloride to the 4-dimethylaminophenol in the step S1 is 1:2-2.1, the reaction temperature is 0-4 ℃, and a base is further added, wherein the base is at least one selected from triethylamine, diethylamine, naOH and KOH, and the reaction time is 1-2h; the molar ratio of the intermediate A to the propane sultone in the step S2 is 1:2-2.1, the reaction temperature is 30-35 ℃, and the reaction time is 20-24h.
5. The salt-resistant fracturing fluid thickener according to claim 2, wherein the synthesis method of the monomer B is as follows: n, N-dimethylacrylamide and propane sultone are reacted to prepare the monomer B.
6. The brine resistant fracturing fluid thickener of claim 5 wherein the molar ratio of N, N-dimethylacrylamide to propane sultone is 1:1-1.05, the reaction temperature is 30-35 ℃ and the reaction time is 18-20 hours.
7. The salt-resistant fracturing fluid thickener according to claim 1, wherein the raw materials of the salt-resistant fracturing fluid thickener further comprise a cosolvent, a chain transfer agent and an initiating system, wherein the mass of the cosolvent is 0.2-0.4wt% of the total mass of monomers, the mass of the chain transfer agent is 0.02-0.05wt% of the total mass of monomers, and the mass of the initiating system is 0.01-0.03wt% of the total mass of monomers; the cosolvent is at least one selected from sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium tetradecyl sulfate, sodium hexadecyl sulfonate, sodium hexadecyl benzene sulfonate, sodium octadecyl sulfate and sodium octadecyl benzene sulfonate; the chain transfer agent is polyethylene glycol dimethacrylate; the initiating system is a mixture of an initiator and sodium sulfite, the mass ratio is 1:0.9-1.2, and the initiator is at least one selected from sodium persulfate, ammonium persulfate and potassium persulfate.
8. A method of preparing a salt-resistant fracturing fluid thickener according to any of claims 1 to 7, comprising the steps of:
(1) Adding the monomer A, the monomer B, the acrylamide, the 1H, 2H-heptadecafluorodecane acrylic ester and the cosolvent into water, and stirring and mixing uniformly to prepare a water mixed solution with the total mass concentration of the monomers of 32-37 wt%;
(2) Under the protection of inert gas, adding chain transfer agent, initiating system and water to prepare aqueous solution with the total mass concentration of monomers of 27-32wt%, stirring and reacting for 2-4h at 55-60 ℃, filtering, washing, drying and crushing the product to obtain the salt-resistant fracturing fluid thickening agent.
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