CN113563500B - Fracturing fluid thickening agent and preparation method thereof - Google Patents
Fracturing fluid thickening agent and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
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- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
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- C08F228/00—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 bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—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 bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
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- 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
Abstract
The invention relates to the technical field of oil and gas field development, in particular to a fracturing fluid thickening agent and a preparation method thereof. The method comprises the steps of preparing an inner water-based phase and an oil-based phase, carrying out emulsion polymerization, preparing an outer water-based phase, carrying out emulsion polymerization and carrying out post-treatment. The invention adopts the reverse phase polymerization process and the internal and external two-phase polymerization mode, firstly prepares the high salt-resistant self-assembly polymer, then grafts the macromonomer through the chain extender to form a molecular structure with extremely strong rigidity, and reduces the degradation influence of ferrous ions on the thickening agent in use through post treatment, and the prepared supermolecular structure ensures that the polymer not only has high salt resistance, but also has strong free radical resistance, and ensures that the polymer has extremely strong degradation resistance.
Description
Technical Field
The invention relates to the technical field of oil and gas field development, in particular to a fracturing fluid thickening agent and a preparation method thereof.
Background
With the rapid development of the petroleum industry, the petroleum exploitation of most oil fields in China gradually enters the middle and later stages, in order to achieve higher yield increasing effect, a fracturing yield increasing measure is usually adopted, and when the recovery fluid of the oil field progresses to a high water content stage, the clear water is gradually supplied insufficiently along with the great increase of the discharge amount of the oil sewage. In order to save the injection water and reduce the sewage discharge, the fracturing technology of mixed reinjection water is commonly adopted in various large oil fields. The salinity, bacteria content, dissolved oxygen, reducing ions, etc. of the recycled water all cause a reduction in the viscosity of the polymer solution. Wherein, Fe having reducing property2+The ions greatly reduce the viscosity of the polymer solution, especially Fe2+When the ion mass concentration reaches 3mg/L, the viscosity of the fracturing fluid solution is sharply reduced, and the long-term stability of the fracturing fluid is reduced.
It has been proposed to use Fe2+Is a main influencing factor causing poor sewage stability. It has also been experimentally investigated that the order of the effect of cations on the viscosity stability of polymer solutions is Fe2+>Fe3+>Mg2+ (Ca2+) >Na+ (K+). It has also been found that Fe2+Is a main factor causing the viscosity of the solution to be reduced, and suggests to formulate Fe in the sewage2+The concentration is lower than 0.2 mg/L. Although Fe is currently determined in the prior art2+The impact on polymer viscosity, but there is currently no good solution.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides, in a first aspect, a method for preparing a fracturing fluid thickening agent, the method using acrylamide as a raw material, and comprising the steps of:
(1) preparation of the internal aqueous phase
Preparing an internal water-based phase by using acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, a strength monomer, a self-assembly monomer, a stabilizer and water as raw materials;
(2) preparation of oil-based phase
The preparation method comprises the following steps of (1) preparing an oil-based phase by taking white oil, an emulsifier and a film-forming assistant as raw materials:
(3) preparation of internal phase emulsion polymerization products
Sequentially adding the internal water-based phase, the oil-based phase and the oxidant into a mixing kettle, stirring and mixing uniformly, then transferring into a reaction kettle, introducing nitrogen to remove oxygen, and then adding an initiation amount of a first reducing agent to initiate a polymerization reaction to prepare an internal phase emulsion polymerization product;
(4) preparation of the external aqueous phase
Preparing an external water-based phase by using a strength monomer, a macromonomer, a structure regulator, a chain extender and water as raw materials;
5) preparation of external phase polymerization products
Adding the external aqueous phase prepared in the step (4) into the internal phase emulsion polymerization product prepared in the step (3), and then adding an initiating amount of a second reducing agent to initiate polymerization reaction to prepare an external phase polymerization product;
6) post-treatment
And (3) treating the external phase polymerization product prepared in the step (5) by using a free radical consuming agent, a terminating agent and a phase transfer agent to prepare the fracturing fluid thickening agent.
In some preferred embodiments, the raw materials of step (1) are used in the following amounts in parts by weight: acrylamide 10-50, 2-acrylamido-2-methylpropanesulfonic acid 100-200, strength monomer 200-300, self-assembling monomer 0.5-3, stabilizer 5-10, water 170-300; the raw materials of the step (2) are as follows in parts by weight: 200 to 300 parts of white oil, 10 to 20 parts of emulsifier and 3 to 8 parts of film-forming assistant; the amount of the oxidant used in the step (3) is 0.18 to 0.22 part by weight; the raw materials of the step (4) are as follows in parts by weight: 50 to 100 of strength monomer, 20 to 50 of macromonomer, 0.1 to 1 of structure regulator, 1 to 3 of chain extender and 50 to 100 of water; and/or the raw materials in the step (6) are used in the following amounts by weight: 0.5 to 1 of free radical consumption agent, 0.2 to 1 of terminating agent and 25 to 30 of phase inversion agent.
In other preferred embodiments, the strength monomer is selected from one or two of sodium 4-acryloyl benzene sulfonate, methacrylamide ethyl ethylene urea, vinyl benzene sulfonic acid and allyl benzene sulfonic acid; the self-assembly monomer is selected from one or two of perfluorooctyl ethyl methacrylate (cas: 1996-88-9), 2- (perfluorohexyl) ethyl methacrylate (cas: 2144-53-8) and 4- [2- (methacryloyloxy) ethoxy ] benzoic acid (cas: 69260-39-5); and/or the stabilizer is citric acid.
In other preferred embodiments, the emulsifier is selected from one or both of span 60, span 80, and span 83; and/or the film forming auxiliary agent is one or two selected from sodium dodecyl sulfate, propylene glycol methyl ether and ethyl 3-ethoxypropionate.
In other preferred embodiments, the oxidizing agent in step (3) is ammonium persulfate or potassium persulfate; and/or the first reducing agent in step (3) and/or the second reducing agent in step (5) is sodium bisulfite.
In other preferred embodiments, the strength monomer is selected from one or two of sodium 4-acryloyl benzene sulfonate, methacrylamide ethyl ethylene urea, vinyl benzene sulfonic acid and allyl benzene sulfonic acid; the macromolecular monomer is selected from one or two of (methacryloxymethyl) triethoxysilane (cas:5577-72-0) and vinyl tris (trimethylsiloxy) silane (cas: 5356-84-3); the structure regulator is one or two of polyethylene glycol 400 diacrylate (cas:26570-48-9), divinylbenzene and pentaerythritol triacrylate; and/or the chain extender is selected from one or two of 1, 4-butanediol, diethylene glycol and diethylaminoethanol.
In other preferred embodiments, the free radical consuming agent is selected from one or two of reduced glutathione, vitamin C and vitamin E; the terminator is p-hydroxyanisole; and/or the phase transfer agent is selected from one or two of isomeric tridecanol polyoxyethylene ether 1310 (such as 1310 manufactured by Shandong Kepler Biotech Co., Ltd., cas: 9043-30-5) and fatty alcohol ethoxylate 23E7 (such as 23E7 manufactured by Saxol chemical Co., Ltd., cas: 160901-19-9).
In other preferred embodiments, in step (1), the pH of the internal aqueous-based phase is adjusted to 6.0 to 7.0 by a pH adjuster; and/or in step (4), the pH of the external aqueous phase is adjusted to 6.0 to 7.0 by a pH adjuster.
In other preferred embodiments, step (1) is performed as follows: sequentially adding acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, a strength monomer, a self-assembly monomer, a stabilizer and water into a mixing kettle, uniformly mixing, and adjusting the pH value to 6.0-7.0 to obtain the internal water-based phase; the step (2) is carried out in the following way: adding white oil, an emulsifier and a film-forming assistant into the mixing kettle in sequence and mixing uniformly to prepare the oil-based phase; the step (3) is carried out in the following way: sequentially adding the internal water-based phase, the oil-based phase and an oxidant into a mixing kettle, stirring at a high speed of 3000-6000 rpm for 0.5-1.5 hours, then transferring into a reaction kettle, introducing nitrogen to remove oxygen for 25-35 minutes, pumping a first reducing agent to initiate polymerization reaction while stirring at a low speed of 100-200 rpm, and preparing the internal phase emulsion polymerization product; wherein, in the process of the polymerization reaction, the reaction temperature of the polymerization reaction is controlled to be 28 to 32 ℃, and the reaction time of the polymerization reaction is 2.5 to 3.5 hours; the step (4) is carried out in the following way: sequentially adding a strength monomer, a macromonomer, a structure regulator, a chain extender and water into a mixing kettle, uniformly mixing, and regulating the pH value to 6.0-7.0 to prepare the external water-based phase; the step (5) is carried out in the following way: dropwise adding the outer water-based phase prepared in the step (4) into the inner phase emulsion polymerization product prepared in the step (3) to initiate polymerization while pumping a second reducing agent to prepare an outer phase polymerization product; wherein the dripping of the external water-based phase and the pumping of the second reducing agent are finished within 1.5 to 2.5 hours, and the reaction is continued for 1.5 to 2.5 hours after the dripping is finished; and wherein during the dropwise addition and during the continued reaction after the dropwise addition, stirring is carried out at a stirring rotational speed of from 200 to 400 revolutions per minute; the step (6) is carried out in the following way: and (4) sequentially adding a free radical consuming agent, a terminating agent and a phase transfer agent into the external-phase polymerization product prepared in the step (5), and uniformly mixing to prepare the fracturing fluid thickening agent.
In a second aspect, the present invention provides a fracturing fluid thickening agent obtained by the production method according to the first aspect of the present invention.
Compared with the prior art, the invention has the following technical advantages:
the fracturing fluid thickening agent is a polymer emulsion consisting of an inner layer and an outer layer, wherein the inner layer is a high-salt-resistance self-assembly polymer, and a macromolecular structure is grafted on the basis of the polymer of the inner layer through a chain extender. The degree of freedom of the inner phase polymer is extremely low, the rotation potential barrier in the molecular chain is high, the molecular chain has extremely high rigidity and salt resistance, the molecular chain has extremely high stability, the hydrolysis is not easy to occur under the conditions of high temperature and high salt, and the influence of the mineralization degree on the polymer is low; the grafted outer phase polymer has supermolecular structure and micro cross-linked network structure, and the special structure of the polymer makes the polymer possess high salt tolerance, powerful free radical resisting capacity and powerful degradation resistance.
In addition, the polymer is added with the free radical consuming agent and the terminating agent through the post-treatment process, so that free radicals generated in the oxidation process of ferrous ions can be consumed or eliminated, and the degradation influence of the ferrous ions on the thickening agent is further reduced.
Drawings
FIG. 1 shows the viscosity retention versus curve for the thickeners prepared in examples 1 to 4.
Figure 2 shows the viscosity retention versus curve for the thickener prepared in example 1 and each comparative example.
Detailed Description
Fe resistance of the polymers of the invention2+The research is carried out, and a fracturing fluid thickening agent and a preparation method thereof are provided through molecular design of a polymer. The polymer emulsion prepared by the invention has salt resistance and degradation resistance, and the tolerance to ferrous ions is obviously improved, so that the requirement of oil field reinjection water fracturing construction on water sources is reduced.
The invention provides a preparation method of a fracturing fluid thickening agent, which takes acrylamide as a raw material and comprises the following steps:
(1) preparation of the internal aqueous phase
Preparing an internal water-based phase by using acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, a strength monomer, a self-assembly monomer, a stabilizer and water as raw materials;
(2) preparation of oil-based phase
The preparation method comprises the following steps of (1) preparing an oil-based phase by taking white oil, an emulsifier and a film-forming assistant as raw materials:
(3) preparation of internal phase emulsion polymerization products
Sequentially adding the internal water-based phase, the oil-based phase and the oxidant into a mixing kettle, stirring and mixing uniformly, then transferring into a reaction kettle, introducing nitrogen to remove oxygen, and then adding an initiation amount of a first reducing agent to initiate a polymerization reaction to prepare an internal phase emulsion polymerization product;
(4) preparation of the external aqueous phase
Preparing an external water-based phase by using a strength monomer, a macromonomer, a structure regulator, a chain extender and water as raw materials;
5) preparation of external phase polymerization products
Adding the external aqueous phase prepared in the step (4) into the internal phase emulsion polymerization product prepared in the step (3), and then adding an initiating amount of a second reducing agent to initiate polymerization reaction to prepare an external phase polymerization product;
6) post-treatment
And (3) treating the external phase polymerization product prepared in the step (5) by using a free radical consuming agent, a terminating agent and a phase transfer agent to prepare the fracturing fluid thickening agent.
The fracturing fluid thickening agent prepared by the method is a polymer emulsion consisting of an inner phase layer and an outer phase layer. Wherein the inner phase layer is formed by a high salt-resistant self-assembly polymer, and a macromolecular structure is grafted on the basis of the polymer of the inner phase layer through a chain extender. The degree of freedom of the inner phase polymer is extremely low, the rotation potential barrier in the molecular chain is high, the molecular chain has extremely high rigidity and salt resistance, the molecular chain has extremely high stability, the hydrolysis is not easy to occur under the conditions of high temperature and high salt, and the influence of the mineralization degree on the polymer is low; the grafted outer phase polymer has supermolecular structure and micro cross-linked network structure, and the special structure of the polymer makes the polymer possess high salt tolerance, powerful free radical resisting capacity and powerful degradation resistance.
In addition, the polymer is added with the free radical consuming agent and the terminating agent through the post-treatment process, so that free radicals generated in the oxidation process of ferrous ions can be consumed or eliminated, and the degradation influence of the ferrous ions on the thickening agent is further reduced.
In some preferred embodiments, the raw materials of step (1) are used in the following amounts in parts by weight: acrylamide 10 to 50 (e.g., 20, 30, or 40), 2-acrylamido-2-methylpropanesulfonic acid 100 to 200 (e.g., 120, 140, 160, or 180), strength monomers 200 to 300 (e.g., 250), self-assembling monomers 0.5 to 3 (e.g., 1 or 2), stabilizers 5 to 10 (e.g., 6 or 8), water 170 to 300 (e.g., 200 or 250). Additionally preferably or further preferably, the raw materials of the step (2) are used in the following amounts in parts by weight, relative to the amount of the raw materials of the step (1): white oil 200 to 300 (e.g., 250), emulsifier 10 to 20 (e.g., 15), coalescent 3 to 8 (e.g., 4, 5, 6, or 7); the oxidizing agent of step (3) is used in an amount of 0.18 to 0.22 parts by weight (e.g., 0.19, 0.20, or 0.21). The raw materials of the step (4) are as follows in parts by weight: strength monomers 50 to 100 (e.g., 60, 70, 80, or 90), macromers 20 to 50 (e.g., 30 or 40), structure modifiers 0.1 to 1 (e.g., 0.5 or 0.8), chain extenders 1 to 3 (e.g., 2), water 50 to 100 (e.g., 60, 70, 80, or 90). In addition, preferably or further preferably, the raw materials in the step (6) are used in the following amounts in parts by weight: a radical consuming agent 0.5 to 1 (e.g., 0.6 or 0.8), a terminating agent 0.2 to 1 (e.g., 0.4, 0.6 or 0.8), and a phase inversion agent 25 to 30 (e.g., 28).
In other preferred embodiments, the strength monomer is selected from one or two of sodium 4-acryloyl benzene sulfonate, methacrylamide ethyl ethylene urea, vinyl benzene sulfonic acid and allyl benzene sulfonic acid; the self-assembly monomer is selected from one or two of perfluorooctyl ethyl methacrylate (cas: 1996-88-9), 2- (perfluorohexyl) ethyl methacrylate (cas: 2144-53-8) and 4- [2- (methacryloyloxy) ethoxy ] benzoic acid (cas: 69260-39-5). Additionally preferably or further preferably, the stabilizer is citric acid.
In other preferred embodiments, the emulsifier is selected from one or both of span 60, span 80, and span 83. Additionally or further preferably, the film forming aid is selected from one or two of sodium lauryl sulfate, propylene glycol methyl ether and ethyl 3-ethoxypropionate.
In other preferred embodiments, the oxidizing agent in step (3) is ammonium persulfate or potassium persulfate. It is further preferred or further preferred that the first reducing agent described in step (3) is further preferred or further preferred that the second reducing agent described in step (5) is sodium bisulfite.
In other preferred embodiments, the strength monomer is selected from one or two of sodium 4-acryloyl benzene sulfonate, methacrylamide ethyl ethylene urea, vinyl benzene sulfonic acid and allyl benzene sulfonic acid; the macromonomer is selected from one or two of (methacryloxymethyl) triethoxysilane and vinyltris (trimethylsiloxy) silane; the structure regulator is selected from one or two of polyethylene glycol 400 diacrylate (e.g., polyethylene glycol 400 diacrylate with CAS number 26570-48-9), divinylbenzene and pentaerythritol triacrylate. Additionally preferably or further preferably, the chain extender is selected from one or two of 1, 4-butanediol, diethylene glycol and diethylaminoethanol.
In other preferred embodiments, the free radical consuming agent is selected from one or two of reduced glutathione, vitamin C and vitamin E; the terminator is p-hydroxyanisole; it is also preferred or further preferred that the phase transfer agent is selected from one or both of isomeric tridecanol polyoxyethylene ether 1310 (e.g., 1310 manufactured by Shandong Kepler Biotech Co., Ltd., cas: 9043-30-5) and fatty alcohol ethoxylate 23E7 (e.g., 23E7 manufactured by Saxol chemical Co., Ltd., cas: 160901-19-9).
In other preferred embodiments, in step (1), the pH of the internal aqueous-based phase is adjusted to 6.0 to 7.0 by a pH adjuster. It is also preferred or further preferred that in step (4), the pH of the external aqueous phase is adjusted to 6.0 to 7.0 by a pH adjuster. Preferably, the pH adjusting agent used for pH adjustment is sodium hydroxide. The amount of the pH adjustor used in the present invention is not particularly limited as long as the pH can be adjusted to a target range. For example, the sodium hydroxide may be used in an amount of 19 to 38 (e.g., 20, 25, 30 or 35) parts by weight relative to the above-mentioned preferred amount in step (1). For another example, the amount of sodium hydroxide used in step (4) to adjust the pH may be 0.1 to 1 (e.g., 0.5 or 0.8) parts by weight relative to the above-mentioned preferred amount of step (1).
In other preferred embodiments, step (1) is performed as follows: sequentially adding acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, a strength monomer, a self-assembly monomer, a stabilizer and water into a mixing kettle, uniformly mixing, and adjusting the pH value to 6.0-7.0 (such as 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8 or 6.9) to prepare the internal water-based phase.
In some further preferred or further preferred embodiments, step (2) is performed in the following manner: and (3) sequentially adding white oil, an emulsifier and a film-forming auxiliary agent into the mixing kettle, and uniformly mixing to obtain the oil-based phase.
In some further preferred or further preferred embodiments, step (3) is performed in the following manner: the internal aqueous phase, the oil-based phase and the oxidizing agent are sequentially added to a mixing kettle, stirred at a high speed of 3000 to 6000 (e.g., 4000 or 5000) revolutions per minute for 0.5 to 1.5 hours (e.g., 1.0 hour), then transferred to a reaction kettle, deoxygenated by introducing nitrogen for 25 to 35 minutes (e.g., 30 minutes), and a first reducing agent is pumped in while stirring at a low speed of 100 to 200 revolutions per minute to initiate polymerization, thereby producing the internal phase emulsion polymerization product. Wherein, in the course of the polymerization reaction, the reaction temperature of the polymerization reaction is controlled to be 28 to 32 ℃ (e.g., 30 ℃), and the reaction time of the polymerization reaction is 2.5 to 3.5 hours (e.g., 3.0 hours). More specifically, the temperature is adjusted to 28 to 32 ℃ before the first reducing agent is initially pumped in, and the first reducing agent is then pumped in to initiate the polymerization.
In some further preferred or further preferred embodiments, step (4) is performed in the following manner: adding a strength monomer, a macromonomer, a structure regulator, a chain extender and water into a mixing kettle in sequence, uniformly mixing, and regulating the pH value to 6.0-7.0 (such as 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8 or 6.9) to prepare the external water-based phase.
In some further preferred or further preferred embodiments, step (5) is performed in the following manner: and (3) dropwise adding the outer water-based phase prepared in the step (4) into the inner phase emulsion polymerization product prepared in the step (3), and pumping a second reducing agent simultaneously with the dropwise adding to initiate polymerization reaction to prepare the outer phase polymerization product. Wherein the external aqueous phase addition and the second reducing agent pumping is completed within 1.5 to 2.5 hours (e.g., 2.0 hours), and the reaction is continued for 1.5 to 2.5 hours (e.g., 2.0 hours) after the addition is completed; and wherein during the dropwise addition and during the continued reaction after the dropwise addition, stirring is carried out at a stirring speed of 200 to 400 (e.g., 300) revolutions per minute.
In some further preferred or further preferred embodiments, step (6) is performed in the following manner: and (4) sequentially adding a free radical consuming agent, a terminating agent and a phase transfer agent into the external-phase polymerization product prepared in the step (5), and uniformly mixing to prepare the fracturing fluid thickening agent.
In some more specific embodiments, the preparation method comprises the steps of:
(1) preparation of an internal aqueous phase:
the internal water-based phase is prepared from the following raw materials in parts by weight: acrylamide 10-50, 2-acrylamido-2-methylpropanesulfonic acid 100-200, strength monomer 200-300, self-assembling monomer 0.5-3, stabilizer 5-10, sodium hydroxide 19-38, and water 170-300. The preparation process comprises the following steps: sequentially adding acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, a strength monomer, a self-assembly monomer, a stabilizer and water into a mixing kettle, uniformly mixing, and adjusting the pH value to 6.0-7.0 by using sodium hydroxide.
(2) Preparation of oil-based phase:
the oil-based phase is prepared from the following raw materials in parts by weight: 200 to 300 portions of white oil, 10 to 20 portions of emulsifier and 3 to 8 portions of film-forming assistant. The preparation process comprises the following steps: and (3) adding the white oil, the emulsifier and the film-forming auxiliary agent into the mixing kettle in sequence and mixing uniformly.
3) Preparation of internal phase emulsion polymerization product:
adding the water-based phase, the oil-based phase and 0.2 part by weight of oxidant into a mixing kettle in sequence, stirring at a high speed of 3000-6000 rpm for 1.0 hour, then transferring the materials into a reaction kettle, introducing nitrogen to remove oxygen for 30 minutes, controlling the temperature to be 30 ℃, pumping 0.2 part by weight of first reducing agent to initiate polymerization reaction while stirring at a low speed of 100-200 rpm, wherein the reaction temperature of the polymerization reaction is 30 ℃, the reaction time of the polymerization reaction is 4 hours, and finishing the reaction after the reaction time is up.
4) Preparation of external aqueous phase:
the external water-based phase is prepared from the following raw materials in parts by weight: 50 to 100 of strength monomer, 20 to 50 of macromonomer, 0.1 to 1 of structure regulator, 1 to 3 of chain extender and 50 to 100 of water. The preparation process comprises the following steps: and (3) sequentially adding a strength monomer, a macromonomer, a structure regulator, a chain extender and water into a mixing kettle, uniformly mixing, and then adjusting the pH value to 6.0-7.0 by using sodium hydroxide to obtain the external water-based phase.
(5) Preparation of external phase polymerization product:
the external phase polymerization product is prepared by adopting a dropping reaction process. Specifically, the external aqueous phase prepared in the step (4) is dripped into the internal phase emulsion polymerization product prepared in the step (3), the dripping is completed in 1 hour, and the reaction is continued for 2 hours after the dripping is completed; 0.2 part by weight of a second reducing agent was pumped in simultaneously with the dropwise addition to initiate the polymerization. During the dropwise addition and during the continued reaction after completion of the dropwise addition, stirring was carried out by a stirrer at a stirring speed of 200 to 400 revolutions per minute.
(6) Post-treatment
The post-treatment comprises the following raw materials in parts by weight: 0.5 to 1 of free radical consumption agent, 0.2 to 1 of terminating agent and 25 to 30 of phase inversion agent. The operation process is as follows: and (4) sequentially adding a free radical consuming agent, a terminating agent and a phase transfer agent into the material obtained after the polymerization reaction in the step (5), and uniformly mixing to obtain the fracturing fluid thickening agent.
In a second aspect, the present invention provides a fracturing fluid thickening agent obtained by the production method according to the first aspect of the present invention.
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be described more clearly and more completely with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
In this embodiment, the preparation method of the fracturing fluid densifier includes the following steps:
(1) preparation of an internal aqueous phase:
the internal water-based phase is prepared from the following raw materials in parts by weight: 10 parts by weight of acrylamide, 100 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 200 parts by weight of sodium 4-acryloylbenzenesulfonate as a strength monomer, 1 part by weight of perfluorooctylethyl methacrylate (available from Korea technology, the same applies hereinafter) as a self-assembling monomer, 5 parts by weight of citric acid as a stabilizer, 19 parts by weight of sodium hydroxide for adjusting the pH value, and 200 parts by weight of water. The preparation process comprises the following steps: acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, 4-acryloyl sodium benzenesulfonate, perfluorooctyl ethyl methacrylate, citric acid and water are sequentially added into a mixing kettle, and after the materials are fully mixed uniformly, the pH value is adjusted to 6.2 by using sodium hydroxide.
(2) Preparation of oil-based phase:
the oil-based phase is prepared from the following raw materials in parts by weight: 200 parts by weight of white oil, 60 parts by weight of span 60(10 parts by weight) as an emulsifier, and 3 parts by weight of sodium lauryl sulfate as a film-forming aid. The preparation process comprises the following steps: adding white oil, span 60 and sodium dodecyl sulfate into the mixing kettle in sequence, and fully and uniformly mixing.
(3) Preparation of internal phase emulsion polymerization product:
and sequentially adding the inner water-based phase, the oil-based phase and ammonium persulfate serving as an oxidant into a mixing kettle, stirring for 1h under the stirring condition of the rotating speed of 3000/min, then transferring the materials into a reaction kettle, introducing nitrogen to remove oxygen for 30min, controlling the temperature to be 30 ℃, pumping 0.2 part by weight of sodium bisulfite under the stirring condition of the rotating speed of 150/min to initiate polymerization reaction, reacting for 4h, and then finishing the reaction.
(4) Preparation of external aqueous phase:
the external water-based phase is prepared from the following raw materials in parts by weight: 50 parts by weight of 4-acryloylbenzenesulfonate as a strength monomer, 20 parts by weight of (methacryloyloxymethyl) triethoxysilane as a macromonomer, 0.1 part by weight of polyethylene glycol 400 diacrylate (available from Jiangsu Runfeng synthetic science and technology Co., Ltd., CAS number 26570-48-9, the same applies hereinafter) as a structure regulator, 1 part by weight of 1, 4-butanediol as a chain extender, and 60 parts by weight of water. The preparation process comprises the following steps: 4-acryloyl sodium benzenesulfonate, (methacryloxymethyl) triethoxysilane, polyethylene glycol 400 diacrylate, 1, 4-butanediol and water are added into a mixing kettle in sequence, and after the materials are fully and uniformly mixed, the pH value is adjusted to 6.2 by using sodium hydroxide.
(5) Preparation of external phase polymerization product:
the external phase polymerization is carried out by adopting a dropping reaction process, the external water-based phase prepared by mixing in the step (4) is slowly dropped into the internal phase emulsion polymerization product prepared in the step (3), the dropping is completed in 1h, 0.2 weight part of sodium bisulfite is pumped in to initiate polymerization reaction while the dropping is completed, and the reaction is continued for 2h after the dropping is completed; wherein, in the processes of dripping and pumping and the process of continuing the reaction after finishing dripping, the stirrer is used for stirring at the rotating speed of 200 r/min.
(6) And (3) post-treatment:
the post-treatment dosage is as follows: 0.5 part by weight of reducing glutathione as a radical consuming agent, 0.2 part by weight of p-hydroxyanisole as a terminating agent, and isomeric tridecanol polyoxyethylene ether 1310 (available from Kepler Biotech Co., Ltd., Shandong, the same; 25 parts by weight) as a phase transfer agent. The operation process is as follows: and (3) sequentially adding reductive glutathione, p-hydroxyanisole and isomeric tridecanol polyoxyethylene ether 1310 into the material obtained after the reaction in the step (5), and fully and uniformly mixing to obtain the fracturing fluid thickening agent.
Example 2
In this embodiment, the preparation method of the fracturing fluid densifier includes the following steps:
(1) preparation of an internal aqueous phase:
the internal water-based phase is prepared from the following raw materials in parts by weight: 25 parts by weight of acrylamide, 150 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 250 parts by weight of methacrylamidoethylethylene urea as a strength monomer, 2 parts by weight of 2- (perfluorohexyl) ethyl methacrylate as a self-assembly monomer, 7 parts by weight of citric acid as a stabilizer, 28 parts by weight of sodium hydroxide for adjusting the pH value, and 250 parts by weight of water. The preparation process comprises the following steps: acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, methacrylamide ethyl ethylene urea, 2- (perfluorohexyl) ethyl methacrylate, citric acid and water are sequentially added into a mixing kettle, and after the materials are fully mixed uniformly, the pH value is adjusted to 6.5 by using sodium hydroxide.
(2) Preparation of oil-based phase:
the oil-based phase is prepared from the following raw materials in parts by weight: 240 parts of white oil, 80 parts of span (15 parts by weight) as an emulsifier, and 5 parts of propylene glycol methyl ether as a film-forming aid. The preparation process comprises the following steps: adding white oil, span 80 and propylene glycol monomethyl ether into the mixing kettle in sequence, and fully and uniformly mixing.
(3) Preparation of internal phase emulsion polymerization product:
sequentially adding the prepared water-based phase, oil-based phase and 0.2 part by weight of ammonium persulfate serving as an oxidant into a mixing kettle, stirring for 1h under the condition of high-speed (rotating speed of 5000 r/min), transferring into a reaction kettle, introducing nitrogen to remove oxygen for 30min, controlling the temperature to be 30 ℃, pumping 0.2 part by weight of sodium bisulfite serving as a first initiator under the stirring condition of rotating speed of 150 r/min to initiate polymerization reaction for 4h, and then finishing the reaction.
(4) Preparation of external aqueous phase:
the external water-based phase is prepared from the following raw materials in parts by weight: 75 parts by weight of methacrylamidoethylethylene urea as a strength monomer, 35 parts by weight of vinyltris (trimethylsiloxy) silane as a macromonomer, 0.5 part by weight of divinylbenzene as a structure modifier, 2 parts by weight of diethylene glycol as a chain extender, and 75 parts by weight of water. The preparation process comprises the following steps: sequentially adding methacrylamide ethyl ethylene urea, vinyl tri (trimethylsiloxy) silane, divinyl benzene, diethylene glycol and water into a mixing kettle, fully and uniformly mixing, and adjusting the pH value to 6.5 by using sodium hydroxide.
(5) Preparation of external phase polymerization product:
and (3) adopting a dropping reaction process for external phase polymerization, slowly dropping the mixed water-based phase in the step 4) into the internal phase emulsion polymerization product obtained in the step (3), completing dropping in 1 hour, pumping 0.2 weight part of sodium bisulfite while dropping to initiate polymerization reaction, and continuing to react for 2 hours after dropping. Wherein, in the processes of dripping and pumping and the process of continuing the reaction after finishing dripping, the stirrer is used for stirring at the rotating speed of 300 r/min.
(6) And (3) post-treatment:
the post-treatment is carried out by the following raw materials in parts by weight: 0.7 parts by weight of vitamin C, 0.5 parts by weight of p-hydroxyanisole, and 29 parts by weight of fatty alcohol ethoxylate 23E7 (available from Sasol chemical Co., Ltd., the same below). The preparation process comprises the following steps: and sequentially adding vitamin C, p-hydroxyanisole and fatty alcohol ethoxylate 23E7 into the reacted material, and fully and uniformly mixing to obtain the fracturing fluid thickening agent.
Example 3
In this embodiment, the preparation method of the fracturing fluid densifier includes the following steps:
(1) preparation of an internal aqueous phase:
the internal water-based phase is prepared from the following raw materials in parts by weight: 50 parts by weight of acrylamide, 200 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 280 parts by weight of allylbenzenesulfonic acid as a strength monomer, 3 parts by weight of 4- [2- (methacryloyloxy) ethoxy ] benzoic acid as a self-assembling monomer, 10 parts by weight of citric acid as a stabilizer, 38 parts by weight of sodium hydroxide for adjusting the pH value, and 300 parts by weight of water. The preparation process comprises the following steps: acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, allylbenzenesulfonic acid, 4- [2- (methacryloyloxy) ethoxy ] benzoic acid, citric acid and water are sequentially added into a mixing kettle, and after the materials are fully mixed uniformly, the pH value is adjusted to 7.0 by using sodium hydroxide.
(2) Preparation of oil-based phase:
the oil-based phase is prepared from the following raw materials in parts by weight: 300 parts of white oil, span 83(20 parts by weight) as an emulsifier, and 8 parts of ethyl 3-ethoxypropionate as a film-forming aid. The preparation process comprises the following steps: adding white oil, span 83 and 3-ethoxy ethyl propionate into the mixing kettle in sequence, and fully and uniformly mixing.
(3) Preparation of internal phase emulsion polymerization product:
and (2) sequentially adding the prepared water-based phase, oil-based phase and 0.2 part by weight of ammonium persulfate into a mixing kettle, stirring for 1h under the condition of high-speed (4000 revolutions per minute) stirring, transferring into a reaction kettle, introducing nitrogen to remove oxygen for 30min, controlling the temperature to be 30 ℃, pumping 0.2 part by weight of sodium bisulfite under the stirring condition of 150 revolutions per minute to initiate polymerization reaction for 4h, and then finishing the reaction.
(4) Preparation of external aqueous phase:
the external water-based phase is prepared from the following raw materials in parts by weight: 75 parts by weight of allylbenzenesulfonic acid as a strength monomer, 35 parts by weight of vinyltris (trimethylsiloxy) silane as a macromonomer, 0.5 parts by weight of pentaerythritol triacrylate as a structure modifier, 3 parts by weight of diethylaminoethanol as a chain extender, and 100 parts by weight of water. The preparation process comprises the following steps: allyl benzene sulfonic acid, vinyl tri (trimethylsiloxy) silane, pentaerythritol triacrylate, diethylaminoethanol and water are sequentially added into a mixing kettle, and after fully and uniformly mixing, the pH value is adjusted to 7.0 by using sodium hydroxide.
(5) Preparation of external phase polymerization product:
and (3) adopting a dropping reaction process for external phase polymerization, slowly dropping the water-based phase prepared in the step (4) into the polymer obtained in the step (3), completing the dropping in 1 hour, pumping 0.2 weight part of sodium bisulfite while dropping to initiate polymerization, wherein in the dropping and pumping processes and the continuous reaction process after the dropping is finished, stirring at the rotating speed of 400 r/min by using a stirrer.
(6) And (3) post-treatment:
the post-treatment is carried out by the following raw materials in parts by weight: vitamin E1 parts by weight as a radical consuming agent, p-hydroxyanisole 1 part by weight as a terminating agent, and isotridecanol polyoxyethylene ether 1310(30 parts by weight) as a phase transfer agent. The preparation process comprises the following steps: and (3) sequentially adding vitamin E, p-hydroxyanisole and isomeric tridecanol polyoxyethylene ether 1310 into the reacted materials, and fully and uniformly mixing to obtain the fracturing fluid thickening agent.
Example 4
The procedure was carried out in substantially the same manner as in example 1 except that vinylbenzenesulfonic acid was used instead of sodium 4-acryloylbenzenesulfonate in step (1) and step (4) as the strength unit, and potassium persulfate was used instead of ammonium persulfate as the oxidizing agent used in step (3).
Comparative example 1
The procedure was carried out in substantially the same manner as in example 1 except that sodium 4-acryloylbenzenesulfonate was not added as a strength monomer in steps (1) and (4), and the amount thereof was replaced with acrylamide.
Comparative example 2
The procedure was carried out in substantially the same manner as in example 1 except that (methacryloxymethyl) triethoxysilane as a macromonomer was not added in step (4) and the amount thereof was replaced with acrylamide.
Comparative example 3
The procedure was carried out in substantially the same manner as in example 1, except that polyethylene glycol 400 diacrylate as a structure regulator and 1, 4-butanediol as a chain extender were not added in step (4).
Comparative example 4
The procedure was carried out in substantially the same manner as in example 1 except that in step (6), reducing glutathione as a radical consuming agent and p-hydroxyanisole as a terminator were not added.
Comparative example 5
In substantially the same manner as in example 1 except that the inner aqueous-based phase (instead of the outer aqueous-based phase) was prepared in step (4), and the inner aqueous-based phase prepared in step (1) was substituted for the outer aqueous-based phase prepared in step (4) in example 1 in step (5) in the same parts by weight as the outer aqueous-based phase.
Comparative example 6
In substantially the same manner as in example 1, except that the external aqueous-based phase (instead of the internal aqueous-based phase) was prepared in step (1), and the internal aqueous-based phase prepared in step (1) of example 1 was replaced in step (4) with the same weight of the external aqueous-based phase as the internal aqueous-based phase prepared in example 1.
Test example
The effect of the fracturing fluid thickening agents prepared in the examples and the comparative examples is compared and evaluated.
The apparent viscosity of the polymer solution is measured according to the method of 7.4 in the standard SY/T5107-2016 water-based fracturing fluid performance evaluation method in the China oil and gas industry. The polymer solution adopts simulated produced water liquid preparation, and the formula is shown in the following chart:
the content of ferrous ions was adjusted to 0, 0.5, 1, 5, 10, 20ppm based on the composition of the simulated produced water, 1% of the polymer solutions (i.e., fracturing fluid thickeners) prepared in the examples and comparative examples were prepared with the simulated produced water having different ferrous ion content, respectively, and the change in viscosity of the fracturing fluid thickener was measured.
As can be seen from the experimental data, the fracturing fluid densifier synthesized in the example has Fe content of 10ppm2+The viscosity retention rate in the solution reaches more than 80 percent and is 20ppm of Fe2+The viscosity retention rate in the solution reaches more than 50 percent. It can be seen that the fracturing fluid densifier synthesized by the invention has excellent ferrous ion resistance.
By comparing example 1 with comparative example 1It is seen that without the addition of the strength monomer sodium 4-acryloyl benzenesulfonate, the thickener base viscosity is reduced, the thickener is at a low Fe2+Viscosity retention under conditions of little effect, but at high Fe2+The viscosity retention rate is greatly reduced under the condition.
As can be seen by comparing example 1 with comparative example 2, the base viscosity of the thickener is reduced without the addition of macromer (methacryloxymethyl) triethoxysilane, the thickener is low in Fe2+Less influence under conditions, but in Fe2+The viscosity is greatly reduced after the content exceeds 10 ppm.
As can be seen by comparing example 1 with comparative example 3, without the addition of the structure regulator polyethylene glycol 400 diacrylate and the chain extender 1, 4-butanediol, the base viscosity of the thickener is reduced and the thickener is low in Fe2+Less influence under conditions, but in Fe2+After the content exceeds 5ppm, the viscosity is greatly reduced, which shows that the micro-crosslinking structure of the molecular chain of the outer polymer resists high content Fe2+Has obvious effect, and the micro-cross-linked structure has stronger salt resistance and free radical resistance.
As can be seen by comparing example 1 with comparative example 4, the thickener has a higher base viscosity without the addition of the free radical consuming agent reducing glutathione and the terminating agent p-hydroxyanisole, but at low Fe2+The viscosity of the thickening agent is greatly reduced under the condition.
As can be seen by comparing example 1 with comparative example 5, when monomers of the internal aqueous phase are used in the polymerization of both the inner and outer layers, the thickener has a higher base viscosity, but at high Fe2+The viscosity of the thickening agent is greatly reduced under the condition.
As can be seen by comparing example 1 with comparative example 6, the thickener has better Fe resistance when monomers in the outer aqueous phase are used in the polymerization of both the inner and outer layers2+Capability, but lower base viscosity, in Fe2+At a content of 20ppm, the thickener viscosity was only 33mPa · s.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. The preparation method of the fracturing fluid thickening agent is characterized by comprising the following steps of:
(1) preparation of the internal aqueous phase
Preparing an internal water-based phase by using acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, a strength monomer, a self-assembly monomer, a stabilizer and water as raw materials;
(2) preparation of oil-based phase
The preparation method comprises the following steps of (1) preparing an oil-based phase by taking white oil, an emulsifier and a film-forming assistant as raw materials:
(3) preparation of internal phase emulsion polymerization products
Sequentially adding the internal water-based phase, the oil-based phase and the oxidant into a mixing kettle, stirring and mixing uniformly, then transferring into a reaction kettle, introducing nitrogen to remove oxygen, and then adding an initiation amount of a first reducing agent to initiate a polymerization reaction to prepare an internal phase emulsion polymerization product;
(4) preparation of the external aqueous phase
Preparing an external water-based phase by using a strength monomer, a macromonomer, a structure regulator, a chain extender and water as raw materials;
(5) preparation of external phase polymerization products
Adding the external aqueous phase prepared in the step (4) into the internal phase emulsion polymerization product prepared in the step (3), and then adding an initiating amount of a second reducing agent to initiate polymerization reaction to prepare an external phase polymerization product;
(6) post-treatment
Treating the external phase polymerization product prepared in the step (5) by using a free radical consuming agent, a terminating agent and a phase transfer agent to prepare the fracturing fluid thickening agent;
wherein the raw materials in the step (1) are as follows in parts by weight: acrylamide 10-50, 2-acrylamido-2-methylpropanesulfonic acid 100-200, strength monomer 200-300, self-assembling monomer 0.5-3, stabilizer 5-10, water 170-300;
the raw materials of the step (2) are as follows in parts by weight: 200 to 300 parts of white oil, 10 to 20 parts of emulsifier and 3 to 8 parts of film-forming assistant; the amount of the oxidant used in the step (3) is 0.18 to 0.22 part by weight; the raw materials of the step (4) are as follows in parts by weight: 50 to 100 of strength monomer, 20 to 50 of macromonomer, 0.1 to 1 of structure regulator, 1 to 3 of chain extender and 50 to 100 of water; the raw materials in the step (6) are as follows in parts by weight: a radical consuming agent 0.5 to 1, a terminating agent 0.2 to 1, a phase inversion agent 25 to 30;
wherein, in step (1): the strength monomer is selected from one or two of 4-acryloyl sodium benzenesulfonate, methacrylamide ethyl ethylene urea, vinyl benzene sulfonic acid and allyl benzene sulfonic acid; the self-assembly monomer is selected from one or two of perfluorooctyl ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate and 4- [2- (methacryloyloxy) ethoxy ] benzoic acid;
wherein, in step (4): the strength monomer is selected from one or two of 4-acryloyl sodium benzenesulfonate, methacrylamide ethyl ethylene urea, vinyl benzene sulfonic acid and allyl benzene sulfonic acid; the macromonomer is selected from one or two of (methacryloxymethyl) triethoxysilane and vinyltris (trimethylsiloxy) silane; the structure regulator is selected from one or two of polyethylene glycol 400 diacrylate, divinyl benzene and pentaerythritol triacrylate; the chain extender is one or two selected from 1, 4-butanediol, diethylene glycol and diethylaminoethanol;
wherein, in step (6): the free radical consuming agent is one or two selected from reducing glutathione, vitamin C and vitamin E.
2. The method of claim 1, wherein the stabilizer is citric acid.
3. The production method according to claim 1, wherein in step (2):
the emulsifier is selected from one or two of span 60, span 80 and span 83; and/or
The film-forming assistant is one or two of sodium dodecyl sulfate, propylene glycol methyl ether and ethyl 3-ethoxypropionate.
4. The method of claim 1, wherein:
the oxidant in the step (3) is ammonium persulfate or potassium persulfate; and/or
The first reducing agent in the step (3) and/or the second reducing agent in the step (5) is sodium bisulfite.
5. The production method according to claim 1, wherein in step (6):
the phase inversion agent is selected from one or two of isomeric tridecanol polyoxyethylene ether 1310 and fatty alcohol ethoxylate 23E 7.
6. The method of claim 1, wherein:
in step (1), the pH of the internal aqueous phase is adjusted to 6.0 to 7.0 by a pH adjuster; and/or
In step (4), the pH of the external aqueous phase is adjusted to 6.0 to 7.0 by a pH adjuster.
7. The production method according to any one of claims 1 to 6, characterized in that:
the step (1) is carried out in the following way: sequentially adding acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, a strength monomer, a self-assembly monomer, a stabilizer and water into a mixing kettle, uniformly mixing, and adjusting the pH value to 6.0-7.0 to obtain the internal water-based phase;
the step (2) is carried out in the following way: adding white oil, an emulsifier and a film-forming assistant into the mixing kettle in sequence and mixing uniformly to prepare the oil-based phase;
the step (3) is carried out in the following way: sequentially adding the internal water-based phase, the oil-based phase and an oxidant into a mixing kettle, stirring at a high speed of 3000-6000 rpm for 0.5-1.5 hours, then transferring into a reaction kettle, introducing nitrogen to remove oxygen for 25-35 minutes, pumping a first reducing agent to initiate polymerization reaction while stirring at a low speed of 100-200 rpm, and preparing the internal phase emulsion polymerization product; wherein, in the process of the polymerization reaction, the reaction temperature of the polymerization reaction is controlled to be 28 to 32 ℃, and the reaction time of the polymerization reaction is 2.5 to 3.5 hours;
the step (4) is carried out in the following way: sequentially adding a strength monomer, a macromonomer, a structure regulator, a chain extender and water into a mixing kettle, uniformly mixing, and regulating the pH value to 6.0-7.0 to prepare the external water-based phase;
the step (5) is carried out in the following way: dropwise adding the outer water-based phase prepared in the step (4) into the inner phase emulsion polymerization product prepared in the step (3) to initiate polymerization while pumping a second reducing agent to prepare an outer phase polymerization product; wherein the dripping of the external water-based phase and the pumping of the second reducing agent are finished within 1.5 to 2.5 hours, and the reaction is continued for 1.5 to 2.5 hours after the dripping is finished; and wherein during the dropwise addition and during the continued reaction after the dropwise addition, stirring is carried out at a stirring rotational speed of from 200 to 400 revolutions per minute;
the step (6) is carried out in the following way: and (4) sequentially adding a free radical consuming agent, a terminating agent and a phase transfer agent into the external-phase polymerization product prepared in the step (5), and uniformly mixing to prepare the fracturing fluid thickening agent.
8. A fracturing fluid thickening agent produced by the production method according to any one of claims 1 to 7.
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