CN111925477B - Preparation method of fluorine-containing thickening agent capable of thickening hydrochloric acid solution - Google Patents

Preparation method of fluorine-containing thickening agent capable of thickening hydrochloric acid solution Download PDF

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CN111925477B
CN111925477B CN201910393761.0A CN201910393761A CN111925477B CN 111925477 B CN111925477 B CN 111925477B CN 201910393761 A CN201910393761 A CN 201910393761A CN 111925477 B CN111925477 B CN 111925477B
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fluorine
amount
reaction
monomer
solution
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CN111925477A (en
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赵海洋
耿宇迪
王世洁
张�雄
胡文革
罗攀登
焦克波
方裕燕
李永寿
安娜
侯帆
应海玲
房好青
王立静
何晓波
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China Petroleum and Chemical Corp
Sinopec Northwest Oil Field Co
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China Petroleum and Chemical Corp
Sinopec Northwest Oil Field Co
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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
    • C08F220/52—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
    • C09K8/72—Eroding chemicals, e.g. acids
    • C09K8/725—Compositions containing polymers
    • 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
    • C09K8/72—Eroding chemicals, e.g. acids
    • C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
    • 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

Abstract

The invention provides a preparation method of a fluorine-containing thickening agent capable of thickening a hydrochloric acid solution, which comprises the following steps: 1) dissolving acrylamide, a fluorine-containing monomer and a cationic monomer in water to obtain a first solution; 2) adding a complexing agent, an activating agent, an oxidizing agent and an initiator into the first solution, uniformly mixing, and then carrying out a first reaction to obtain a second solution; 3) heating and then carrying out a second reaction to obtain a polymer jelly; 4) and (3) granulating, drying, crushing and sieving the polymer jelly to obtain the thickening agent in a dry powder state. The acid liquor system containing the thickening agent solves the problems of low viscosity, large filtration loss, short action distance, difficult communication with remote reservoirs and the like of the conventional acid liquor at high temperature.

Description

Preparation method of fluorine-containing thickening agent capable of thickening hydrochloric acid solution
Technical Field
The invention provides a preparation method of a fluorine-containing thickening agent capable of thickening a hydrochloric acid solution.
Background
Oil and gas resources are mainly present in sedimentary rock reservoirs. Sedimentary rock reservoirs may in turn be divided into clastic rock reservoirs and carbonate rock reservoirs. From the global perspective, carbonate reservoir reservoirs are widely distributed and have huge reserves. 877 large-scale oil and gas fields of various types are found in the world, and the total oil and gas exploration proves that the recoverable reserves are 2836.6 hundred million tons of oil equivalent. 313 of the carbonate reservoirs are composed of carbonate reservoirs, accounting for about 35.7%; the oil gas has proven that the recoverable reserves of 1434.5 hundred million tons of oil equivalent account for about 50.6 percent. And most of the oil and gas reservoirs with large reserve scale and high yield are carbonate rock oil and gas reservoirs. Carbonate rock oil gas resources in China exceed one third of backup oil gas resources in China, are important strategic replacement resources and occupy important positions. The main component of the carbonate reservoir rock mineral is calcium carbonate. For such reservoirs, when the permeability of the reservoir is low or the wellbore is polluted by drilling mud, the purposes of improving the permeability of the reservoir, removing the wellbore pollution and increasing the productivity of the stratum are generally achieved by adopting an acidification method. The principle of the acidification process is as follows: after the acid liquor enters the stratum, the chemical reaction of the acid and stratum rocks is utilized to enable the acid liquor to erode the rock framework and/or the pollution blocking substances, so that an oil-gas channel is formed, and stratum fluid flows into a shaft through the oil-gas channel and further flows to the ground. Through the process, the acidification reformation of the reservoir is realized.
The acidification measure becomes one of the main measures for improving the recovery ratio of the carbonate reservoir, and the requirement on the acidification effect is continuously improved along with the deep development degree of the oil field. Meanwhile, as the energy of the stratum decreases, the instability factors of the well wall increase, and acid liquor used for conventional acidification is mainly consumed in the near-wellbore area, so that the well wall is easy to collapse repeatedly, and later-period multi-turn operation is brought. The conventional gelled acid has high reaction speed, and the acid liquid is consumed by half when the conventional gelled acid is 30m away from a shaft, and is mainly consumed in a near-wellbore area, so that the near-wellbore flow conductivity is too high, the acid liquid utilization rate is not high, and the far end of a reservoir cannot be effectively reformed.
The old well acidification measure also brings a problem that the well repair cost is high due to frequent replacement of the operation pipe column, so that the problem of high well repair cost is solved by exploring the immobile pipe column acidification technology and researching and developing an acid liquid system matched with the immobile pipe column acidification technology.
Disclosure of Invention
Aiming at the difficult problems of large filtration loss, short action distance, difficult communication with a remote reservoir body and the like caused by low viscosity of conventional acid liquor at high temperature, the invention provides a novel thickening agent for gelled acid, namely a fluorine-containing thickening agent capable of thickening a hydrochloric acid solution.
Specifically, the invention provides a preparation method of a fluorine-containing thickening agent, which comprises the following steps:
1) dissolving acrylamide, a fluorine-containing monomer and a cationic monomer in water (such as deionized water) to obtain a first solution;
2) adding a complexing agent, an activating agent, an oxidizing agent and an initiator into the first solution, uniformly mixing, and then carrying out a first reaction to obtain a second solution;
3) heating and then carrying out a second reaction to obtain a polymer jelly;
4) and (3) granulating, drying, crushing and sieving the polymer jelly to obtain the thickening agent in a dry powder state.
In one embodiment, the mass ratio of the acrylamide, the fluorine-containing monomer, the cationic monomer and the water is 1 (0.01-0.5): 0.01-0.1): 0.1-1.
In a specific embodiment, the complexing agent is used in an amount of 0.001 wt% to 0.01 wt%, the activator is used in an amount of 0.01 wt% to 0.05 wt%, the oxidizing agent is used in an amount of 0.01 wt% to 0.05 wt%, and the initiator is used in an amount of 0.05 wt% to 0.2 wt%, based on 100% by mass of the acrylamide monomer, the fluorine-containing monomer, and the cationic monomer.
In a specific embodiment, the complexing agent is used in an amount of 0.0035 wt% to 0.006 wt%, the activator is used in an amount of 0.01 wt% to 0.02 wt%, the oxidizing agent is used in an amount of 0.02 wt% to 0.035 wt%, and the initiator is used in an amount of 0.1 wt% to 0.2 wt%, based on 100% by mass of the total of the acrylamide monomer, the fluorine-containing monomer, and the cationic monomer.
In one embodiment, it is a matter of routine choice in the art to first pass nitrogen through the first solution prior to adding the complexing agent, activator, oxidant, and initiator to the first solution, and those skilled in the art will readily appreciate that the time for passing nitrogen may typically be from 20 to 60 minutes.
In one embodiment, nitrogen is passed through the first solution for 30 minutes before the complexing agent, activator, oxidant, and initiator are added to the first solution.
In one embodiment, the time of the first reaction is 2 to 12 hours.
In one embodiment, the time of the first reaction is 3 to 6 hours.
In one embodiment, the time for the first reaction is 4 hours.
In one embodiment, the temperature of the first reaction is from 5 to 15 ℃.
In one embodiment, the temperature of the first reaction is from 8 to 12 ℃.
In one embodiment, the temperature of the first reaction is 10 ℃.
In one embodiment, the second reaction is for a time of 1 to 5 hours.
In one embodiment, the time of the second reaction is 2 to 3 hours.
In one embodiment, the temperature of the second reaction is from 40 to 50 ℃.
In one embodiment, the temperature of the second reaction is from 44 to 46 ℃.
In one embodiment, the temperature of the second reaction is 45 deg.C
In one embodiment, the fluoromonomer comprises a fluoroacrylate. For example, the fluoromonomer may be a fluoroacrylate.
In a specific embodiment, the fluoromonomer comprises at least one of perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate, hexafluorobutyl acrylate, perfluorocyclohexylmethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, and dodecafluoroheptyl methacrylate. Specifically, the fluorine-containing monomer may be at least one of perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate, hexafluorobutyl acrylate, perfluorocyclohexylmethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, and dodecafluoroheptyl methacrylate.
In one embodiment, the cationic monomer comprises methacryloyloxyethyl trimethyl ammonium chloride and/or dimethyl diallyl ammonium chloride.
In one embodiment, the complexing agent comprises at least one selected from the group consisting of ethylenediaminetetraacetic acid disalt, ethylenediaminetetraacetic acid tetraacetate tetrasalt, and triethylenetetramine pentaacetate. Specifically, the complexing agent may be at least one of ethylenediaminetetraacetic acid dihydrochloride, ethylenediaminetetraacetic acid tetraacetate, and triethylene tetraamine pentaacetate.
In one embodiment, the complexing agent comprises at least one member selected from the group consisting of disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, and sodium triethylenetetramine pentaacetate.
In one embodiment, the activator comprises at least one selected from the group consisting of tetramethylethylenediamine, ethylenediamine, and triethanolamine.
In a specific embodiment, the oxidizing agent comprises at least one selected from the group consisting of ammonium persulfate, sodium persulfate, and potassium persulfate.
In one embodiment, the initiator comprises an azo-type initiator. For example, the initiator is an azo-type initiator.
In one embodiment, the initiator comprises one of azobisisobutyrimidazoline hydrochloride, azobisisobutylamidine hydrochloride, azobiscyanovaleric acid, and azobisisopropylimidazoline.
The invention also provides gelled acid which comprises the thickening agent prepared by the preparation method.
The invention further provides the use of a thickener prepared by the process of the invention as defined above in gelled acids and/or acid liquors.
In one embodiment, the viscosifying agents of the present invention are particularly useful in high-retardance and/or deep-penetrating acid fluids.
In one embodiment, the thickeners of the present invention are particularly useful in hydrochloric acid solutions.
The invention has the beneficial effects that:
the method aims to solve the problems that the conventional acid liquor has low viscosity, large filtration loss, short action distance, difficulty in communicating with remote reservoirs and the like at high temperature. The invention develops the thickening agent suitable for a high-retarding and deep-penetrating acid liquid system. The acid liquor system prepared by the method has the characteristics of temperature resistance of 120 ℃ and good corrosion inhibition effect. Can meet the requirements of long open hole section acidification and immobile string acidification. The deep penetration reconstruction is realized by the different components in the acid solution containing the thickening agent of the invention acting on different parts of the crack. So that the near-well diversion is increased by the reaction of hydrogen ions in hydrochloric acid and a reservoir in the near-well cylinder; at the far end of the crack, the etching on the far end of the reservoir is continuously expanded through the slow release of hydrogen ions in the organic acid, the far-end flow conductivity is improved, and the method is one of the main directions of future acidification. The acid liquor system containing the thickening agent can replace the existing gelled acid to carry out deep penetration acidification field tests in Tahe oil fields, and has wider application range. The deep penetration retarded acid is applied for 30 wells per year, the annual average dosage of the deep penetration retarded acid is estimated to reach 0.6 ten thousand by calculation of a single well with the scale of 200, and the method has a good popularization prospect.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary of the invention and are not to be construed as limiting the invention in any way.
Unless otherwise specified, the reagents used in the following examples are commercially available.
Example 1
The preparation of the thickening agent comprises the following steps:
10g of trifluoroethyl methacrylate, 6g of methacryloyloxyethyl trimethyl ammonium chloride, 100g of acrylamide and 30g of deionized water (acrylamide: trifluoroethyl methacrylate: methacryloyloxyethyl trimethyl ammonium chloride: water ═ 1:0.1:0.06:0.3) were added to a three-necked glass bottle equipped with a stirrer, a nitrogen-introducing tube and a thermometer, the temperature was controlled at about 10 ℃ and after 30 minutes of oxygen removal by introducing nitrogen, 0.0058g of disodium ethylenediaminetetraacetate (0.0050 wt% based on 100% by mass of the total of the acrylamide monomer, the fluorine-containing monomer and the cationic monomer), 0.0232g of tetramethylethylenediamine (0.020 wt% based on 100% by mass of the total of the acrylamide monomer, the fluorine-containing monomer and the cationic monomer), 0.0348g of ammonium persulfate (100% by mass of the total of the acrylamide monomer, the fluorine-containing monomer and the cationic monomer), 0.030 wt%), 0.1624g of azodicyano valeric acid (0.140 wt% based on 100% of the total mass of acrylamide monomer, fluorine-containing monomer and cationic monomer), reacting for 4h, raising the temperature to 45 ℃, reacting for 2h, drying and crushing the product to obtain the polymer product.
Example 2
The same procedure as in example 1 was repeated except that the amount of trifluoroethyl methacrylate added was 6g and the amount of disodium ethylenediaminetetraacetate added was 0.00112 g. Then the ratio of acrylamide: trifluoroethyl methacrylate: methacryloyloxyethyl trimethyl ammonium chloride: water 1:0.06:0.06: 0.3; the total mass of the acrylamide monomer, the fluorine-containing monomer and the cationic monomer is 100%, the amount of the ethylene diamine tetraacetic acid is 0.001 wt%, and the amount of the tetramethylethylenediamine is 0.021 wt%; the amount of ammonium persulfate is 0.031 wt%; the amount of azobiscyanovaleric acid was 0.145 wt%.
Example 3
The fluorine-containing monomer is perfluorooctyl ethyl methacrylate, the addition amount is 1g, and the deionized water is 10 g; the amount of azobiscyanovaleric acid was 0.0535g, otherwise as in example 1. Then the ratio of acrylamide: perfluorooctyl ethyl methacrylate: methacryloyloxyethyl trimethyl ammonium chloride: water 1:0.01:0.06: 0.1; the total mass of the acrylamide monomer, the fluorine-containing monomer and the cationic monomer is 100%, the amount of the ethylene diamine tetraacetic acid is 0.0054 wt%, and the amount of the tetramethylethylenediamine is 0.022 wt%; the amount of ammonium persulfate is 0.033 wt%; the amount of azobiscyanovaleric acid was 0.05 wt%.
Example 4
The fluorine-containing monomer is perfluorooctyl ethyl acrylate, the addition amount is 50g, and the deionized water is 100 g; 0.00546g of ethylene diamine tetraacetic acid disodium salt; the amount of tetramethylethylenediamine was 0.0156 g; ammonium persulfate 0.0312 g. Adding complexing agent, activating agent, oxidant and initiator, mixing, reacting at 5 deg.C for 12 hr, and heating to 50 deg.C for 1 hr. The rest is the same as example 1. Then the ratio of acrylamide: octyl ethyl perfluoroacrylate: methacryloyloxyethyl trimethyl ammonium chloride: water 1:0.5:0.06: 1; the total mass of the acrylamide monomer, the fluorine-containing monomer and the cationic monomer is 100%, the content of the ethylene diamine tetraacetic acid is 0.0035 wt%, and the content of the tetramethylethylenediamine is 0.01 wt%; the amount of ammonium persulfate is 0.020 wt%; the amount of azobiscyanovaleric acid was 0.104 wt%.
Example 5
The fluorine-containing monomer is dodecafluoroheptyl methacrylate, the addition amount is 20g, the deionized water is 50g, and the amount of ammonium persulfate is 0.0126 g. Adding complexing agent, activating agent, oxidant and initiator, mixing, reacting at 15 deg.C for 2 hr, and heating to 40 deg.C for 5 hr. The rest is the same as example 1. Then the ratio of acrylamide: dodecafluoroheptyl methacrylate: methacryloyloxyethyl trimethyl ammonium chloride: water 1:0.2:0.06: 0.5; the total mass of the acrylamide monomer, the fluorine-containing monomer and the cationic monomer is 100%, the amount of the ethylene diamine tetraacetic acid is 0.0046 wt%, and the amount of the tetramethylethylenediamine is 0.018 wt%; the amount of ammonium persulfate was 0.01 wt%; the amount of azobiscyanovaleric acid was 0.129 wt%.
Example 6
The fluorine-containing monomer is hexafluorobutyl acrylate, the addition amount is 40g, and the deionized water is 70 g. Adding complexing agent, activating agent, oxidant and initiator, mixing, reacting at 8 deg.C for 6 hr, and heating to 44 deg.C for 3 hr. The rest is the same as example 1. Then the ratio of acrylamide: hexafluorobutyl acrylate: methacryloyloxyethyl trimethyl ammonium chloride: water 1:0.4:0.06: 0.7; the total mass of the acrylamide monomer, the fluorine-containing monomer and the cationic monomer is 100%, the amount of the ethylene diamine tetraacetic acid is 0.0040 wt%, and the amount of the tetramethylethylenediamine is 0.016 wt%; the amount of ammonium persulfate was 0.024 wt%; the amount of azobiscyanovaleric acid was 0.111 wt%.
Example 7
The fluorine-containing monomer is perfluorocyclohexyl methyl acrylate, the adding amount is 30g, deionized water is 50g, a complexing agent, an activating agent, an oxidizing agent and an initiator are added, after uniform mixing, the mixture reacts at 12 ℃ for 3 hours, and then the temperature is raised to 46 ℃ for 2 hours, and the rest is the same as that of the example 1. Then the ratio of acrylamide: methyl perfluorocyclohexyl acrylate: methacryloyloxyethyl trimethyl ammonium chloride: water 1:0.3:0.06: 0.5; the total mass of the acrylamide monomer, the fluorine-containing monomer and the cationic monomer is 100%, the content of the ethylene diamine tetraacetic acid is 0.0043 wt%, and the content of the tetramethylethylenediamine is 0.017 wt%; the amount of ammonium persulfate is 0.026 wt%; the amount of azobiscyanovaleric acid was 0.119 wt%.
Example 8
The fluorine-containing monomer is hexafluorobutyl methacrylate, the addition amount is 10g, deionized water is 30g, and the other steps are the same as those of example 1. Then the ratio of acrylamide: hexafluorobutyl methacrylate: methacryloyloxyethyl trimethyl ammonium chloride: water 1:0.1:0.06: 0.3; the total mass of the acrylamide monomer, the fluorine-containing monomer and the cationic monomer is 100%, the amount of the ethylene diamine tetraacetic acid is 0.0050 wt%, and the amount of the tetramethylethylenediamine is 0.020 wt%; the amount of ammonium persulfate was 0.030 wt%; the amount of azobiscyanovaleric acid was 0.140 wt%.
Example 9
The amount of methacryloyloxyethyltrimethyl ammonium chloride added was 1 g; 0.00666g of ethylene diamine tetraacetic acid disodium salt; 0.03885g of ammonium persulfate; the rest is the same as example 1. Then the ratio of acrylamide: hexafluorobutyl methacrylate: methacryloyloxyethyl trimethyl ammonium chloride: water 1:0.1:0.01: 0.3; the total mass of the acrylamide monomer, the fluorine-containing monomer and the cationic monomer is 100%, the content of the ethylene diamine tetraacetic acid is 0.0060 wt%, and the content of the tetramethylethylenediamine is 0.021 wt%; the amount of ammonium persulfate was 0.035 wt%; the amount of azobiscyanovaleric acid was 0.146 wt%.
Example 10
The amount of methacryloyloxyethyltrimethyl ammonium chloride added was 10g, as in example 1. Then the ratio of acrylamide: hexafluorobutyl methacrylate: methacryloyloxyethyl trimethyl ammonium chloride: water 1:0.1:0.1: 0.3; the total mass of the acrylamide monomer, the fluorine-containing monomer and the cationic monomer is 100%, the amount of the ethylene diamine tetraacetic acid is 0.0048 wt%, and the amount of the tetramethylethylenediamine is 0.019 wt%; the amount of ammonium persulfate was 0.029 wt%; the amount of azobiscyanovaleric acid was 0.135 wt%.
Example 11
The cationic monomer was dimethyldiallylammonium chloride in an amount of 10g, as in example 1. Then the ratio of acrylamide: hexafluorobutyl methacrylate: dimethyldiallylammonium chloride: water 1:0.1:0.1: 0.3; the total mass of the acrylamide monomer, the fluorine-containing monomer and the cationic monomer is 100%, the amount of the ethylene diamine tetraacetic acid is 0.0048 wt%, and the amount of the tetramethylethylenediamine is 0.019 wt%; the amount of ammonium persulfate was 0.029 wt%; the amount of azobiscyanovaleric acid was 0.135 wt%.
Example 12
The amount of disodium edetate was 0.0116g, and the rest was the same as in example 1. The amount of disodium ethylenediaminetetraacetate was 0.01 wt% based on 100% by mass of the total of the acrylamide monomer, the fluorine-containing monomer, and the cationic monomer.
Example 13
The complexing agent was tetrasodium ethylenediamine tetraacetate, 0.0058g, and the procedure was otherwise the same as in example 1.
Example 14
The complexing agent was triethylene tetramine pentaacetate (0.0058 g), and the procedure was otherwise the same as in example 1.
Example 15
Tetramethylethylenediamine (0.0580 g), the same as in example 1. The amount of tetramethylethylenediamine was 0.050% by weight based on 100% by mass of the total of the acrylamide monomer, the fluorine-containing monomer, and the cationic monomer.
Example 16
The activator was ethylenediamine added in an amount of 0.0232g, otherwise as in example 1.
Example 17
The activator was triethanolamine, added in an amount of 0.0232g, otherwise as in example 1.
Example 18
The oxidant was sodium persulfate in an amount of 0.058g, otherwise as in example 1.
Example 19
The oxidizing agent potassium persulfate was added in an amount of 0.0348g, as in example 1.
Example 20
The azo initiator was azobisisobutyrimidazoline hydrochloride in an amount of 0.232g, as in example 1. The amount of azobisisobutyrimidazoline hydrochloride was 0.2 wt% based on 100% by mass of the total of the acrylamide monomer, the fluorine-containing monomer, and the cationic monomer.
Example 21
The azo initiator was azodiisopropylimidazoline, added in an amount of 0.116g, and the same as in example 1. The amount of azodiisopropylimidazoline was 0.100 wt% based on 100% by mass of the total of the acrylamide monomer, the fluorine-containing monomer, and the cationic monomer.
Example 22
The azo initiator was azobisisobutylamidine hydrochloride in an amount of 0.1624g, as in example 1.
Comparative example 1
The reaction was otherwise the same as in example 1, except that no fluoromonomer was added. Then the ratio of acrylamide: dimethyldiallylammonium chloride: water 1:0.06: 0.3.
The performance of the products of the examples and the comparative examples is evaluated:
preparing polymer solution with polymer concentration of 0.5% with 20% hydrochloric acid solution, shearing at 120 deg.C for 120min at shearing speed of 170s-1The viscosity of the samples after shearing was measured and the data are shown in table 1.
TABLE 1 evaluation results of shear resistance
Figure BDA0002057478950000071
Figure BDA0002057478950000081
While the invention has been described with reference to specific embodiments, those skilled in the art will appreciate that various changes can be made without departing from the true spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation, material, composition of matter, and method to the essential scope and spirit of the present invention. All such modifications are intended to be included within the scope of the present invention as defined in the appended claims.

Claims (29)

1. A preparation method of a fluorine-containing thickening agent comprises the following steps:
1) dissolving acrylamide, a fluorine-containing monomer and a cationic monomer in water to obtain a first solution;
2) adding a complexing agent, an activating agent, an oxidizing agent and an initiator into the first solution, uniformly mixing, and then carrying out a first reaction to obtain a second solution;
3) heating and then carrying out a second reaction to obtain a polymer jelly;
4) and (3) granulating, drying, crushing and sieving the polymer jelly to obtain the thickening agent in a dry powder state.
2. The method according to claim 1, wherein the mass ratio of the acrylamide, the fluorine-containing monomer, the cationic monomer and the water is 1 (0.01-0.5): 0.01-0.1): 0.1-1.
3. The method according to claim 1, wherein the complexing agent is used in an amount of 0.001 to 0.01 wt%, the activator is used in an amount of 0.01 to 0.05 wt%, the oxidizing agent is used in an amount of 0.01 to 0.05 wt%, and the initiator is used in an amount of 0.05 to 0.2 wt%, based on 100% by mass of the acrylamide monomer, the fluorine-containing monomer, and the cationic monomer.
4. The production method according to claim 1, wherein the complexing agent is used in an amount of 0.0035 to 0.006 wt%, the activator is used in an amount of 0.01 to 0.02 wt%, the oxidizing agent is used in an amount of 0.02 to 0.035 wt%, and the initiator is used in an amount of 0.1 to 0.2 wt%, based on 100% by mass of the total of the acrylamide monomer, the fluorine-containing monomer, and the cationic monomer.
5. The method according to claim 1, wherein nitrogen gas is introduced into the first solution for 20 to 60 minutes before the complexing agent, the activator, the oxidizing agent and the initiator are added to the first solution.
6. The method according to claim 1, wherein nitrogen gas is introduced into the first solution for 30 minutes before the complexing agent, the activator, the oxidizing agent and the initiator are added to the first solution.
7. The production method according to claim 1, wherein the time of the first reaction is 2 to 12 hours.
8. The production method according to claim 1, wherein the time of the first reaction is 3 to 6 hours.
9. The production method according to claim 1, wherein the temperature of the first reaction is 5 to 15 ℃.
10. The production method according to claim 1, wherein the temperature of the first reaction is 8 to 12 ℃.
11. The production method according to claim 1, wherein the temperature of the first reaction is 10 ℃.
12. The method of claim 1, wherein the second reaction is carried out for 1 to 5 hours.
13. The method of claim 1, wherein the second reaction time is 2 to 3 hours.
14. The method of claim 1, wherein the temperature of the second reaction is 40 to 50 ℃.
15. The method of claim 1, wherein the temperature of the second reaction is 44 to 46 ℃.
16. The method according to claim 1, wherein the temperature of the second reaction is 45 ℃.
17. The method of claim 1, wherein the fluorine-containing monomer comprises a fluorine-containing acrylate.
18. The method according to claim 1, wherein the fluorine-containing monomer comprises at least one of perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate, hexafluorobutyl acrylate, perfluorocyclohexylmethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, and dodecafluoroheptyl methacrylate.
19. The method of claim 1, wherein the cationic monomer comprises methacryloyloxyethyl trimethyl ammonium chloride and/or dimethyldiallyl ammonium chloride.
20. The production method according to any one of claims 1 to 19, wherein the complexing agent includes at least one selected from the group consisting of ethylenediaminetetraacetic acid disalt, ethylenediaminetetraacetic acid tetraacetate tetrasalt, and triethylenetetramine pentaacetate.
21. The production method according to any one of claims 1 to 19, wherein the complexing agent includes at least one selected from the group consisting of disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, and sodium triethylenetetraminepentaacetate.
22. The production method according to any one of claims 1 to 19, wherein the activator comprises at least one selected from the group consisting of tetramethylethylenediamine, ethylenediamine, and triethanolamine.
23. The production method according to any one of claims 1 to 19, wherein the oxidizing agent includes at least one selected from the group consisting of ammonium persulfate, sodium persulfate, and potassium persulfate.
24. The production method according to any one of claims 1 to 19, wherein the initiator includes an azo-based initiator.
25. The method of any one of claims 1 to 19, wherein the initiator comprises one of azobisisobutylimidazoline hydrochloride, azobisisobutylamidine hydrochloride, azobiscyanovaleric acid, and azobisisopropylimidazoline.
26. A gelled acid comprising the thickener obtained by the production method according to any one of claims 1 to 25.
27. Use of a thickener obtained by the process according to any of claims 1 to 25 in gelled acids and/or acid liquors.
28. Use according to claim 27, wherein the viscosifying agent is used in high retardation and/or deep penetration acid.
29. Use according to claim 27, wherein the thickener is used in a hydrochloric acid solution.
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CN102675534A (en) * 2012-05-17 2012-09-19 陕西科技大学 Cationic fluorocarbon modified polyacrylamide prepared by ultrasonic auxiliary method
CN105062455A (en) * 2015-07-21 2015-11-18 烟台润星环保科技发展有限公司 Water-based fracturing fluid thickening agent and synthetic method thereof
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US4426296A (en) * 1981-10-13 1984-01-17 The Dow Chemical Company Method of acidizing wells using gelled acids
CN102675534A (en) * 2012-05-17 2012-09-19 陕西科技大学 Cationic fluorocarbon modified polyacrylamide prepared by ultrasonic auxiliary method
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