CN113943398A - Preparation method of thickening agent for high-temperature-resistant instant acidizing fracturing fluid - Google Patents
Preparation method of thickening agent for high-temperature-resistant instant acidizing fracturing fluid Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002562 thickening agent Substances 0.000 title claims abstract description 27
- 239000012530 fluid Substances 0.000 title claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 19
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 11
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000084 colloidal system Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 9
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 6
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 6
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 5
- YFVRIXYUQCYRAF-UHFFFAOYSA-N 2-ethenylpiperazine Chemical compound C=CC1CNCCN1 YFVRIXYUQCYRAF-UHFFFAOYSA-N 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 3
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 30
- 125000002091 cationic group Chemical group 0.000 abstract description 20
- 229920002401 polyacrylamide Polymers 0.000 abstract description 12
- 238000000227 grinding Methods 0.000 abstract description 9
- 239000004927 clay Substances 0.000 abstract description 3
- 230000000977 initiatory effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 230000005012 migration Effects 0.000 abstract 1
- 238000013508 migration Methods 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 73
- 229920000642 polymer Polymers 0.000 description 29
- 239000007788 liquid Substances 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 16
- 230000009467 reduction Effects 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000013078 crystal Substances 0.000 description 9
- 238000006392 deoxygenation reaction Methods 0.000 description 9
- -1 AMPS sodium salt Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000012216 screening Methods 0.000 description 8
- 229940010514 ammonium ferrous sulfate Drugs 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- DCRYNQTXGUTACA-UHFFFAOYSA-N 1-ethenylpiperazine Chemical compound C=CN1CCNCC1 DCRYNQTXGUTACA-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- XAUDJQYHKZQPEU-KVQBGUIXSA-N 5-aza-2'-deoxycytidine Chemical compound O=C1N=C(N)N=CN1[C@@H]1O[C@H](CO)[C@@H](O)C1 XAUDJQYHKZQPEU-KVQBGUIXSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003777 experimental drug Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- 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
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- 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
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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)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a preparation method of a thickening agent for high-temperature resistant instant acidizing fracturing fluid, which is prepared by copolymerizing acrylamide monomer, two quaternary ammonium salt cationic monomers, a monomer containing a sulfonic group and a monomer with a heterocyclic structure in an aqueous solution through free radical redox and azosalt composite initiation, granulating, drying and grinding into particles below 40 meshes after polymerization. By introducing the monomer containing sulfonic group and the monomer containing heterocycle, the temperature resistance and the instant solubility of the cation modified polyacrylamide are improved. By introducing two quaternary ammonium salt cationic monomers for copolymerization, the synthesized cationic modified polyacrylamide greatly improves the viscosifying property on acid liquor and the stability of strong acid on clay, and can be used as a viscosifier for strong acid base hydraulic fracturing fluid. Due to the addition of the heterocycle on the chain link, the stability of the acid thickener is enhanced, and the expansion and the migration of the fracturing fluid to the formation clay are inhibited at the later stage.
Description
Technical Field
The invention belongs to the technical field of acid fracturing in petroleum exploitation, and particularly relates to a preparation method of a thickening agent for a high-temperature-resistant instant acid fracturing fluid.
Background
Acid fracturing is a yield increasing technology for oil and gas wells, acid-soluble pollutants and minerals in a stratum are corroded by acid liquor, and the seepage capability of the stratum is recovered or improved in modes of descaling, blockage removal and seam formation, so that the injection increase of a water injection well is realized, and the yield of the oil and gas well is improved. In order to reduce the corrosion of acid liquor to pipelines and equipment on the way, improve the corrosion inhibition performance of the acid liquor, realize uniform acid feeding of a multilayer heterogeneous oil-gas reservoir, control the filtration loss of the acid liquor and the like, the acid liquor needs to be thickened further. The thickener is used as an acid thickener and can reduce H in an acid system+The transmission and diffusion speed of the oil-water separator reduces the fluid filtration loss, and plays a role in delaying acid rock reaction and reducing friction resistance in the acid fracturing process. The introduction of foreign thickening acid solution technology in the last 80 th century of China began, along with deepening of knowledge of the thickening agent, the expansion of field application range of the thickening acid solution technology, and the continuous improvement of requirements on the thickening agent of the acid solution, mainly characterized by strong thickening capability, good stability and compatibility, fast dissolution speed, simple field application, no toxicity and the like. The thickeners commonly used at home and abroad mainly comprise acrylamide copolymers, cellulose and polysaccharide thereof and aliphatic amine polymers. The polymer cannot be applied to a high-temperature well due to poor temperature resistance, and the cationic modified polyacrylamide has a good tackifying effect on acid liquor and can increase acid resistance and temperature resistance. Particularly, monomers such as acrylamide, DAC, DMDAAC, AMPS, N-vinyl pyrrolidone and the like are copolymerized, so that the cation modified polyacrylamide has the characteristics of strong acid liquid stability, viscosity increasing property, strong acid liquid compounding property, high temperature resistance, high dissolution speed and the like, and has the characteristics of wide application rangeAnd (5) landscape.
Disclosure of Invention
The invention aims to provide a preparation method of a thickening agent for a high-temperature-resistant instant-dissolving type acidizing fracturing fluid, which has good temperature resistance and instant solubility and strong stability.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a thickening agent for high-temperature-resistant instant acidizing fracturing fluid comprises the following steps:
1) adding 150 parts by weight of refined acrylamide monomer 100 parts by weight, 250 parts by weight of quaternary ammonium salt cationic monomer 100 parts by weight, 50-200 parts by weight of monomer containing sulfonic acid group and 5-10 parts by weight of monomer with heterocyclic structure into 610 parts by weight of pure water 290-610 parts by weight, stirring until the monomers are completely dissolved, adjusting the pH value of the solution to 4-7 by using phosphoric acid or hydrochloric acid, adding 0.001-0.002 part by weight of azodiisobutyronitrile after deoxidizing nitrogen gas at the temperature of 0-2 ℃ for 20min, continuing deoxidizing for 10min, adding 0.00002-0.00005 part by weight of azosalt-V500.00001-0.00003 part by weight, continuing deoxidizing for 20min, adding 0.00002-0.00006-0.0001 part by weight of tert-butyl hydroperoxide, adding 2min, then adding 0.00006-0.0001 part by weight of ferrous ammonium sulfate, introducing nitrogen gas until the solution is viscous, and sealing.
2) After the solution is sealed, the temperature of the solution is raised to the maximum value and naturally cooled for 2 hours, the colloid is taken out and granulated into particles of 2-3mm, the particles are dried at 65 ℃, and after the drying is finished, the particles are ground and sieved into particles below 40 meshes, thus obtaining the finished product.
Further, the quaternary ammonium salt cationic monomers in the step 1) are two of acryloyloxyethyltrimethyl ammonium chloride (DAC), dimethyldiallylammonium chloride (DMDAAC), and methacryloyloxyethyltrimethylammonium chloride (DMC).
Further, the sulfonic acid group-containing monomer in step 1) is one of 2-acrylamido-2-methyl sodium sulfonate (AMPS sodium salt) or sodium allyl sulfonate.
Further, the monomer with a heterocyclic structure in the step 1) is one of vinyl pyrrolidone or 2-vinyl piperazine.
The structural formula of the thickening agent is as follows:
wherein m is 15-25, n is 12-38, p is 18-49, x is 47-16, and y is 2-8.
The invention has the following beneficial effects:
(1) the invention is prepared by copolymerization of a plurality of monomers, because the reactivity ratios of the monomers are different, if the conventional potassium persulfate and ammonium persulfate initiator are adopted to react slowly and the high molecular product cannot be obtained by adding, the invention adopts a strong redox and azo compound initiation system, the initiation is fast at low temperature, the later polymerization is stable, and the molecular weight of the polymer is improved.
(2) According to the invention, the viscosifier has improved viscosifier viscosity to acid liquor and strong acid stability to clay by introducing two quaternary ammonium salt cationic monomers insensitive to acid liquor, and side group steric hindrance of molecular chains of the viscosifier is increased, thereby increasing resistance of molecular thermal motion, and greatly improving temperature resistance of the viscosifier in strong acid base liquid. A rigid chain structure is added in the molecular chain link of the thickening agent polymer by introducing a small amount of monomers with ring-shaped structures, so that the thermal stability of a main chain is improved; the hydration group-sulfonic group with good chemical stability is introduced to improve the hydrophilicity of polymer chain links, accelerate the water dissolution speed, greatly improve the temperature resistance and the dissolution speed of the fracturing fluid densifier taking strong acid as base fluid, resist the temperature of more than 140 ℃, and control the dissolution speed within 20 min.
(3) The thickening agent prepared by the invention has better thickening effect in the fracturing fluid taking strong acid as base fluid, can reduce the using amount and reduce the use cost of the fracturing fluid.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the scope of the present invention is not limited to these examples. All changes, modifications and equivalents that do not depart from the spirit of the invention are intended to be included within the scope thereof.
Experimental drugs used in the present invention: acrylamide crystals (refined), AMPS sodium salt (high purity) 50% liquid, sodium allylsulfonate (high purity), acryloyloxyethyl trimethyl ammonium chloride (produced in Shandong), dimethyldiallyl ammonium chloride (produced in Shandong, Jinan) 70% liquid, methacryloyloxyethyl trimethyl ammonium chloride (produced in Shandong), vinylpyrrolidone (produced in Jiangsu), 2-vinylpiperazine (produced in Hubei), sodium formate (analytically pure), azodiacetonitrile (analytically pure), azoate V50 (analytically pure), tert-butyl hydroperoxide (analytically pure), ferrous ammonium sulfate (analytically pure), phosphoric acid (analytically pure), hydrochloric acid (analytically pure). The parts of the medicines in the following examples are parts by weight, and the percentage concentration is mass percentage concentration.
Example 1: preparation of thickener A
(1) Preparation method
Firstly, adding 397 parts of pure water into a 1000mL beaker, adding 100 parts of acrylamide crystals, stirring to completely dissolve, adding 150 parts of DAC cationic monomers (liquid is broken into hundred), stirring to completely dissolve, adding 80 parts of DMDAAC cationic monomers (liquid is broken into hundred), stirring to completely dissolve, adding 50 parts of AMPS sodium salt monomer again, stirring to completely dissolve, finally adding 5 parts of vinyl pyrrolidone, stirring to completely dissolve, adjusting the pH value of the solution to 4-7 by using phosphoric acid or hydrochloric acid, adding 0.002 part of azodiisobutyronitrile after carrying out nitrogen blowing deoxidization for 20min at the temperature of 0-2 ℃, continuing deoxidization for 10min, adding 500.00001 parts of azoate, continuing deoxidization for 20min, adding 0.00004 part of tert-butyl hydroperoxide, adding 0.00005 part of ammonium ferrous sulfate after 2min, introducing nitrogen until the solution becomes viscous, and sealing.
And step two, after the solution is sealed, after the temperature of the solution is raised to the maximum value and naturally cooled for 2 hours, taking out the colloid, granulating into 2-3mm particles, drying at 65 ℃, grinding and screening into particles below 40 meshes after drying, and obtaining the finished product.
(2) Evaluation of cationic modified Polyacrylamide Properties
The relative molecular mass, cationic degree and water-insoluble matter were evaluated according to GB/T31246-.
The viscosity was evaluated according to the method in GB/T2794-. Wherein the preparation method of 0.6% viscosity comprises the following steps: preparing a polymer solution with the concentration of 0.6% by using a 20% hydrochloric acid solution, and detecting at 30 ℃; evaluation method of high temperature stability: putting the detected 0.6% polymer solution at 120 DEGAfter standing for 4 hours, the appearance is observed to be unchanged; method for evaluating viscosity reduction ratio: detecting the initial viscosity T of the prepared 0.6 percent polymer solution at normal temperature0And the viscosity T is measured again after the mixture is placed at 120 ℃ for 2h1Using the formula (T)1-T0)/T0X 100% calculate the rate of viscosity reduction. The results are shown in the following table:
example 2: preparation of thickener B
(1) Preparation method
Firstly, adding 445 parts of pure water into a 1000mL beaker, adding 110 parts of acrylamide crystals, stirring and completely dissolving, adding 150 parts of DAC cationic monomer (liquid is broken), stirring and completely dissolving, adding 50 parts of DMDAAC cationic monomer (liquid is broken), stirring and completely dissolving, adding 80 parts of monomer AMPS sodium salt, stirring and completely dissolving, finally adding 10 parts of vinyl pyrrolidone, stirring and completely dissolving, adjusting the pH value of the solution to 4-7 by using phosphoric acid or hydrochloric acid, adding 0.001 part of azodiisobutyronitrile after blowing nitrogen for deoxygenation for 20min at the temperature of 0-2 ℃, continuing to deoxygenate for 10min, adding 0.00003 part of azosalt-V500.00002 part, continuing to deoxygenate for 20min, adding 0.00003 part of tert-butyl hydroperoxide, adding 0.00006 part of ferrous ammonium sulfate after 2min, introducing nitrogen until the solution becomes viscous, and sealing.
And step two, after the solution is sealed, after the temperature of the solution is raised to the maximum value and naturally cooled for 2 hours, taking out the colloid, granulating into 2-3mm particles, drying at 65 ℃, grinding and screening into particles below 40 meshes after drying, and obtaining the finished product.
(2) Evaluation of cationic modified Polyacrylamide Properties
The relative molecular mass, cationic degree and water-insoluble matter were evaluated according to GB/T31246-.
The viscosity was evaluated according to the method in GB/T2794-. Wherein the preparation method of 0.6% viscosity comprises the following steps: preparing a polymer solution with the concentration of 0.6% by using a 20% hydrochloric acid solution, and detecting at 30 ℃; evaluation method of high temperature stability: placing the detected 0.6% polymer solution at 120 ℃ for 4No change in appearance was observed after hours; method for evaluating viscosity reduction ratio: detecting the initial viscosity T of the prepared 0.6 percent polymer solution at normal temperature0And the viscosity T is measured again after the mixture is placed at 120 ℃ for 2h1Using the formula (T)1-T0)/T0X 100% calculate the rate of viscosity reduction. The results are shown in the following table:
example 3: preparation of thickener C
(1) Preparation method
Firstly, adding 529 parts of pure water into a 1000mL beaker, adding 150 parts of acrylamide crystals, stirring and completely dissolving, adding 100 parts of DAC cationic monomer (liquid is broken), stirring and completely dissolving, adding 80 parts of DMDAAC cationic monomer (liquid is broken), stirring and completely dissolving, adding 100 parts of monomer sodium allylsulfonate, stirring and completely dissolving, finally adding 5 parts of vinyl pyrrolidone, stirring and completely dissolving, adjusting the pH value of the solution to 4-7 by using phosphoric acid or hydrochloric acid, adding 0.002 part of azodiisobutyronitrile after blowing nitrogen for deoxygenation for 20min at the temperature of 0-2 ℃, continuing to deoxygenate for 10min, adding 0.00004 part of azosalt-V500.00001 part of tert-butyl hydroperoxide, adding 0.00005 part of ammonium ferrous sulfate after 2min, introducing nitrogen until the solution becomes viscous, and sealing.
And step two, after the solution is sealed, after the temperature of the solution is raised to the maximum value and naturally cooled for 2 hours, taking out the colloid, granulating into 2-3mm particles, drying at 65 ℃, grinding and screening into particles below 40 meshes after drying, and obtaining the finished product.
(2) Evaluation of cationic modified Polyacrylamide Properties
The relative molecular mass, cationic degree and water-insoluble matter were evaluated according to GB/T31246-.
The viscosity was evaluated according to the method in GB/T2794-. Wherein the preparation method of 0.6% viscosity comprises the following steps: preparing a polymer solution with the concentration of 0.6% by using a 20% hydrochloric acid solution, and detecting at 30 ℃; evaluation method of high temperature stability: putting the detected 0.6% polymer solution at 120 DEGAfter standing for 4 hours, the appearance is observed to be unchanged; method for evaluating viscosity reduction ratio: detecting the initial viscosity T of the prepared 0.6 percent polymer solution at normal temperature0And the viscosity T is measured again after the mixture is placed at 120 ℃ for 2h1Using the formula (T)1-T0)/T0X 100% calculate the rate of viscosity reduction. The results are shown in the following table:
example 4: preparation of thickener D
(1) Preparation method
Firstly, adding 515 parts of pure water into a 1000mL beaker, adding 120 parts of acrylamide crystals, stirring and completely dissolving, adding 150 parts of DAC cationic monomer (liquid is folded in hundred), stirring and completely dissolving, adding 50 parts of DMDAAC cationic monomer (liquid is folded in hundred), stirring and completely dissolving, adding 200 parts of monomer sodium allylsulfonate again, stirring and completely dissolving, finally adding 10 parts of vinyl piperazine, stirring and completely dissolving, adjusting the pH value of the solution to 4-7 by using phosphoric acid or hydrochloric acid, adding 0.001 part of azodiisobutyronitrile after carrying out nitrogen scavenging for 20min at the temperature of 0-2 ℃, continuing to carry out oxygen scavenging for 10min, adding 0.00003 part of azosalt-V500.00002 part, continuing to carry out oxygen scavenging for 20min, adding 0.00006 part of ammonium ferrous sulfate after 2min, introducing nitrogen until the solution is viscous and sealing.
And step two, after the solution is sealed, after the temperature of the solution is raised to the maximum value and naturally cooled for 2 hours, taking out the colloid, granulating into 2-3mm particles, drying at 65 ℃, grinding and screening into particles below 40 meshes after drying, and obtaining the finished product.
(2) Evaluation of cationic modified Polyacrylamide Properties
The relative molecular mass, cationic degree and water-insoluble matter were evaluated according to GB/T31246-.
The viscosity was evaluated according to the method in GB/T2794-. Wherein the preparation method of 0.6% viscosity comprises the following steps: preparing a polymer solution with the concentration of 0.6% by using a 20% hydrochloric acid solution, and detecting at 30 ℃; evaluation method of high temperature stability: placing the detected 0.6% polymer solution at 120 DEGNo change in appearance was observed after 4 hours; method for evaluating viscosity reduction ratio: detecting the initial viscosity T of the prepared 0.6 percent polymer solution at normal temperature0And the viscosity T is measured again after the mixture is placed at 120 ℃ for 2h1Using the formula (T)1-T0)/T0X 100% calculate the rate of viscosity reduction. The results are shown in the following table:
example 5: preparation of thickener E
(1) Preparation method
Firstly, adding 610 parts of pure water into a 1000mL beaker, adding 150 parts of acrylamide crystals, stirring and completely dissolving, adding 100 parts of DAC cationic monomer (liquid is broken into one hundred), stirring and completely dissolving, adding 80 parts of DMDAAC cationic monomer (liquid is broken into one hundred), stirring and completely dissolving, adding 90 parts of monomer AMPS sodium salt (liquid is broken into one hundred), stirring and completely dissolving, finally adding 5 parts of 2-vinylpiperazine, stirring and completely dissolving, adjusting the pH value of the solution to 4-7 by using phosphoric acid or hydrochloric acid, adding 0.002 part of azodiisobutyronitrile after carrying out nitrogen blowing deoxidization for 20min at the temperature of 0-2 ℃, continuing deoxidization for 10min, adding 0.00004 part of tert-butyl hydroperoxide, adding 0.00005 part of ammonium ferrous sulfate after 2min, introducing nitrogen until the solution becomes viscous, and sealing.
And step two, after the solution is sealed, after the temperature of the solution is raised to the maximum value and naturally cooled for 2 hours, taking out the colloid, granulating into 2-3mm particles, drying at 65 ℃, grinding and screening into particles below 40 meshes after drying, and obtaining the finished product.
(2) Evaluation of cationic modified Polyacrylamide Properties
The relative molecular mass, cationic degree and water-insoluble matter were evaluated according to GB/T31246-.
The viscosity was evaluated according to the method in GB/T2794-. Wherein the preparation method of 0.6% viscosity comprises the following steps: preparing a polymer solution with the concentration of 0.6% by using a 20% hydrochloric acid solution, and detecting at 30 ℃; evaluation method of high temperature stability: placing the detected 0.6% polymer solution at 120 ℃ for 4No change in appearance was observed after hours; method for evaluating viscosity reduction ratio: detecting the initial viscosity T of the prepared 0.6 percent polymer solution at normal temperature0And the viscosity T is measured again after the mixture is placed at 120 ℃ for 2h1Using the formula (T)1-T0)/T0X 100% calculate the rate of viscosity reduction. The results are shown in the following table:
example 6: preparation of thickener F
(1) Preparation method
Firstly, 385 parts of pure water is added into a 1000mL beaker, 120 parts of acrylamide crystals are added, stirred and dissolved completely, 100 parts of DAC cationic monomers (liquid is broken) are added, stirred and dissolved completely, 50 parts of DMDAAC cationic monomers (liquid is broken) are added, stirred and dissolved completely, 100 parts of AMPS sodium salt is added again, stirred and dissolved completely, finally 6 parts of vinyl pyrrolidone is added, stirred and dissolved completely, the pH value of the solution is adjusted to be 4-7 by phosphoric acid or hydrochloric acid, 0.001 part of azobisisobutyronitrile is added after nitrogen is blown for deoxygenation for 20min at the temperature of 0-2 ℃, then azosalt-V500.00002 parts are added after the deoxygenation is continued for 10min, 0.00005 part of tert-butyl hydroperoxide is added after the deoxygenation is continued for 20min, 0.00006 part of ammonium ferrous sulfate is added after the deoxygenation is continued for 2min, then nitrogen is introduced until the solution becomes viscous, and then the opening is carried out.
And step two, after the solution is sealed, after the temperature of the solution is raised to the maximum value and naturally cooled for 2 hours, taking out the colloid, granulating into 2-3mm particles, drying at 65 ℃, grinding and screening into particles below 40 meshes after drying, and obtaining the finished product.
(2) Evaluation of cationic modified Polyacrylamide Properties
The relative molecular mass, cationic degree and water-insoluble matter were evaluated according to GB/T31246-.
The viscosity was evaluated according to the method in GB/T2794-. Wherein 0.6 percentThe viscosity preparation method comprises the following steps: preparing a polymer solution with the concentration of 0.6% by using a 20% hydrochloric acid solution, and detecting at 30 ℃; evaluation method of high temperature stability: placing the detected 0.6% polymer solution at 120 ℃ for 4 hours, and observing that the appearance is not changed; method for evaluating viscosity reduction ratio: detecting the initial viscosity T of the prepared 0.6 percent polymer solution at normal temperature0And the viscosity T is measured again after the mixture is placed at 120 ℃ for 2h1Using the formula (T)1-T0)/T0X 100% calculate the rate of viscosity reduction. The results are shown in the following table:
example 7: preparation of thickener G
(1) Preparation method
Firstly, adding 430 parts of pure water into a 1000mL beaker, adding 150 parts of acrylamide crystals, stirring and completely dissolving, adding 100 parts of DMC cationic monomer (liquid is broken into one hundred), stirring and completely dissolving, adding 150 parts of DMDAAC cationic monomer (liquid is broken into one hundred), stirring and completely dissolving, adding 60 parts of broken hundred monomer AMPS sodium salt again, stirring and completely dissolving, finally adding 5 parts of vinyl pyrrolidone, stirring and completely dissolving, adjusting the pH value of the solution to 4-7 by using phosphoric acid or hydrochloric acid, adding 0.002 part of azobisisobutyronitrile after blowing nitrogen gas for deoxygenation for 20min at the temperature of 0-2 ℃, adding 0.00004 part of azosalt after continuing deoxygenation for 10min, adding 0.00004 part of tert-butyl hydroperoxide after continuing deoxygenation for 20min, adding 0.00001 part of ammonium ferrous sulfate after 2min, introducing nitrogen gas until the solution becomes viscous, and sealing.
And step two, after the solution is sealed, after the temperature of the solution is raised to the maximum value and naturally cooled for 2 hours, taking out the colloid, granulating into 2-3mm particles, drying at 65 ℃, grinding and screening into particles below 40 meshes after drying, and obtaining the finished product.
(2) Evaluation of cationic modified Polyacrylamide Properties
The relative molecular mass, cationic degree and water-insoluble matter were evaluated according to GB/T31246-.
The viscosity was evaluated according to the method in GB/T2794-. Wherein 0.6 percentThe viscosity preparation method comprises the following steps: preparing a polymer solution with the concentration of 0.6% by using a 20% hydrochloric acid solution, and detecting at 30 ℃; evaluation method of high temperature stability: placing the detected 0.6% polymer solution at 120 ℃ for 4 hours, and observing that the appearance is not changed; method for evaluating viscosity reduction ratio: detecting the initial viscosity T of the prepared 0.6 percent polymer solution at normal temperature0And the viscosity T is measured again after the mixture is placed at 120 ℃ for 2h1Using the formula (T)1-T0)/T0X 100% calculate the rate of viscosity reduction. The results are shown in the following table:
example 8: preparation of thickener H
(1) Preparation method
Firstly, adding 290 parts of pure water into a 1000mL beaker, adding 120 parts of acrylamide crystals, stirring and completely dissolving, adding 50 parts of DMC cationic monomer (liquid is broken), stirring and completely dissolving, adding 50 parts of DMDAAC cationic monomer (liquid is broken), stirring and completely dissolving, adding 200 parts of monomer sodium allylsulfonate again, stirring and completely dissolving, finally adding 10 parts of vinyl pyrrolidone, stirring and completely dissolving, adjusting the pH value of the solution to 4-7 by using phosphoric acid or hydrochloric acid, adding 0.001 part of azodiisobutyronitrile after carrying out nitrogen blowing deoxidization for 20min at the temperature of 0-2 ℃, continuing deoxidization for 10min, adding 500.00002 parts of azosalt, continuing deoxidization for 20min, adding 0.00003 part of tert-butyl hydroperoxide, adding 0.00006 part of ferrous ammonium sulfate after 2min, introducing nitrogen until the solution becomes viscous, and sealing.
And step two, after the solution is sealed, after the temperature of the solution is raised to the maximum value and naturally cooled for 2 hours, taking out the colloid, granulating into 2-3mm particles, drying at 65 ℃, grinding and screening into particles below 40 meshes after drying, and obtaining the finished product.
(2) Evaluation of cationic modified Polyacrylamide Properties
The relative molecular mass, cationic degree and water-insoluble matter were evaluated according to GB/T31246-.
The viscosity was evaluated according to the method in GB/T2794-. It is composed ofThe preparation method of medium 0.6% viscosity comprises the following steps: preparing a polymer solution with the concentration of 0.6% by using a 20% hydrochloric acid solution, and detecting at 30 ℃; evaluation method of high temperature stability: placing the detected 0.6% polymer solution at 120 ℃ for 4 hours, and observing that the appearance is not changed; method for evaluating viscosity reduction ratio: detecting the initial viscosity T of the prepared 0.6 percent polymer solution at normal temperature0And the viscosity T is measured again after the mixture is placed at 120 ℃ for 2h1Using the formula (T)1-T0)/T0X 100% calculate the rate of viscosity reduction. The results are shown in the following table:
the present invention is not limited to the above embodiments, and any structural changes made under the teaching of the present invention shall fall within the scope of the present invention, which is similar or similar to the technical solutions of the present invention.
The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (4)
1. A preparation method of a thickening agent for a high-temperature-resistant instant acidizing fracturing fluid is characterized by comprising the following steps:
1) sequentially adding 150 parts by weight of 100-610 parts by weight of refined acrylamide monomer, 250 parts by weight of quaternary ammonium salt cationic monomer, 50-200 parts by weight of monomer containing sulfonic acid group and 5-10 parts by weight of monomer with heterocyclic structure into 610 parts by weight of 290-610 parts by weight of pure water, stirring until the monomers are completely dissolved, adjusting the pH value of the solution to 4-7 by using phosphoric acid or hydrochloric acid, adding 0.001-0.002 part by weight of azodiisobutyronitrile after deoxidizing 20min by using nitrogen gas at the temperature of 0-2 ℃, continuing deoxidizing for 10min, adding 0.00002-0.00005 part by weight of azosalt-V500.00001-0.00003 part by weight of azosalt, continuing deoxidizing for 20min, adding 0.00006-0.0001 part by weight of tert-butyl hydroperoxide, adding 2min later, adding 0.00006-0.0001 part by weight of ferrous ammonium sulfate, introducing nitrogen gas until the solution becomes viscous, and sealing;
2) after the solution is sealed, the temperature of the solution is raised to the maximum value and naturally cooled for 2 hours, the colloid is taken out and granulated into particles of 2-3mm, the particles are dried at 65 ℃, and after the drying is finished, the particles are ground and sieved into particles below 40 meshes, thus obtaining the finished product.
2. The method for preparing the thickening agent for the high-temperature resistant quick-dissolving acidified fracturing fluid of claim 1, wherein the quaternary ammonium salt cationic monomers in the step 1) are two of acryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride and methacryloyloxyethyl trimethyl ammonium chloride.
3. The method for preparing the thickening agent for the high-temperature resistant instant-dissolving acidified fracturing fluid according to claim 1, wherein the sulfonic acid group-containing monomer in the step 1) is one of 2-acrylamido-2-methyl sodium sulfonate or sodium allyl sulfonate.
4. The method for preparing the thickening agent for the high-temperature resistant quick-dissolving acidified fracturing fluid according to claim 1, wherein the monomer with the heterocyclic structure in the step 1) is one of vinyl pyrrolidone or 2-vinyl piperazine.
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| CN116535566A (en) * | 2023-06-21 | 2023-08-04 | 中石化西南石油工程有限公司 | High-temperature-resistant gelling agent for acidizing and fracturing and preparation method thereof |
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