Acid liquid thickener and preparation method thereof

Abstract

The present invention relates to the technical field of oilfields, and discloses a kind of acid liquid thickener and preparation method thereof, 3,4-dihydroxycinnamic acid, acrylamide, sodium olefin sulfonate modified boric acid, quaternized cardanol are added to water, mixed evenly, citric acid is continuously added to adjust pH, nitrogen is continuously introduced, and azobisisobutyronitrile, potassium persulfate, sodium pyrosulfite are added thereto, stirred for reaction, filtered after reaction, washed, and acid liquid thickener is obtained. The acid liquid thickener of the present invention contains adamantane and benzene ring rigid groups, improves the rigidity of the acid liquid thickener, thereby also enhancing its shear resistance and stability; wherein the quaternary ammonium salt group and the sodium sulfonate group improve the temperature resistance and shear resistance of the acid liquid thickener.

Description

Technical Field

[0001] The invention relates to the technical field of oil fields, in particular to an acid liquid thickener and a preparation method thereof. Background Art

[0002] Acid fracturing technology is one of the main measures to increase the production of oil and gas wells. It mainly uses acid to dissolve acid-soluble pollutants and minerals in the formation, and restores the formation seepage capacity by removing scale, unblocking and creating fractures, thereby increasing the production of oil and gas wells. However, during use, if the temperature and shear resistance are poor and the viscosity is not good, it will lead to a decrease in the production of oil and gas wells. Therefore, how to avoid this phenomenon is the key to solving the problem.

[0003] For example, patent CN103525393A discloses a quick-dissolving acid liquid thickener and its preparation method and application. The quick-dissolving acid liquid thickener prepared by the invention has good acid and temperature resistance, and the viscosity loss rate is less than 10% at 90°C, but its heat resistance and salt resistance need to be improved. Summary of the invention

[0004] 1. Technical issues to be resolved

[0005] In view of the deficiencies in the prior art, the present invention provides an acid liquid thickener and a preparation method thereof, which have good shear resistance, temperature resistance and salt resistance.

[0006] (II) Technical solution

[0007] To achieve the above-mentioned object, the present invention provides the following technical scheme: an acid liquid thickener, comprising the following components by weight: 4-6 parts by weight of 3,4-dihydroxycinnamic acid, 70-95 parts by weight of acrylamide, 6-9 parts by weight of sodium olefin sulfonate modified boric acid, 7-10 parts by weight of quaternized cardanol, 0.02-0.023 parts by weight of azobisisobutyronitrile, 0.014-0.026 parts by weight of potassium persulfate, 0.02-0.03 parts by weight of sodium metabisulfite, and 85-150 parts by weight of water.

[0008] Preferably, the preparation method of the sodium olefin sulfonate modified boronic acid is:

[0009] Step 1: Add 1,3,5-trihydroxyadamantane and 4-aminophenylboronic acid to tetrahydrofuran solvent, stir and mix, continue to add anhydrous magnesium sulfate, heat to 45-55°C, stir at 300-400r / min for 4-6h, and vacuum dry to obtain aminoadamantane;

[0010] In the above reaction process, the hydroxyl group in 1,3,5-trihydroxyadamantane and the boric acid group in 4-aminophenylboronic acid undergo esterification reaction, and the amino group and boron element are introduced, thereby obtaining amino adamantane, and at the same time increasing the degree of substitution of the adamantane, further increasing the rigidity of the acid liquid thickener, thereby also enhancing its shear resistance and stability;

[0011] Step 2: adding 5-10 parts by weight of ammonia-ammonium chloride and 8-13 parts by weight of propenyl-1,3-sultone to an acetone solvent for dissolution, then dropping a sodium hydroxide solution with a mass fraction of 2-5%, reacting at 75-92° C., concentrating under reduced pressure after the reaction to remove the solvent, and recrystallizing the crude product in ethanol to obtain sodium olefin sulfonate-modified boronic acid; wherein the amino group in the amonia-ammonium chloride reacts with propenyl-1,3-sultone to generate a sodium sulfonate group, and an olefin group is introduced to obtain sodium olefin sulfonate-modified boronic acid.

[0012] Preferably, in step 1,3,5-trihydroxyadamantane, 4-aminophenylboric acid and anhydrous magnesium sulfate have a mass ratio of 1:0.6-0.82:0.01-0.02.

[0013] Preferably, the reaction time in step 2 is 6-11 hours.

[0014] Preferably, the preparation method of the quaternized cardanol is:

[0015] S1. Add N,N'-dimethylethylenediamine and cardanol glycidyl ether to tetrahydrofuran, heat to 55-68°C, react for 7-10h, rotary evaporate, wash, and obtain intermediate 1;

[0016] S2. Add acrylic acid and intermediate 1 to N,N-dimethylformamide solvent, stir and dissolve, continue to add p-toluenesulfonic acid catalyst, carry out esterification reaction, react at 90-110° C. for 7-9 hours, and then distill under reduced pressure, wash, and dry to obtain alkenyl cardanol;

[0017] S3. Add 6-8 parts by weight of alkenyl cardanol and 9-14 parts by weight of 3-chlorophenylacetic acid to an acetone solvent, stir to dissolve, react at 80-90° C., cool after the reaction, concentrate under reduced pressure, wash with petroleum ether, and obtain quaternized cardanol.

[0018] In the above reaction process, the secondary amine in N,N'-dimethylethylenediamine reacts with the epoxy group in cardanol glycidyl ether to generate a hydroxyl group, and at the same time a tertiary amine is introduced, thereby obtaining intermediate 1; the hydroxyl group in intermediate 1 reacts with the carboxyl group in acrylic acid to introduce an alkenyl group, thereby obtaining alkenyl cardanol; the tertiary amine in alkenyl cardanol and the chlorine in 3-chlorophenylacetic acid undergo quaternization reaction to generate a quaternary ammonium salt, and at the same time a carboxyl group is introduced, thereby obtaining quaternized cardanol; and the degree of substitution of the quaternary ammonium salt and the benzene ring is also increased, further improving the high temperature resistance and rigidity of the acid liquid thickener.

[0019] Preferably, the mass ratio of N,N'-dimethylethylenediamine to cardanol glycidyl ether in S1 is 0.41-0.57:1.

[0020] Preferably, the mass ratio of acrylic acid, intermediate 1 and p-toluenesulfonic acid catalyst in S2 is 1.45-1.86:1:0.02-0.03.

[0021] Preferably, the reaction time in S3 is 5-6h.

[0022] Preferably, the preparation method of the acid liquid thickener is: adding 3,4-dihydroxycinnamic acid, acrylamide, sodium olefin sulfonate modified boric acid, and quaternized cardanol to water, mixing evenly, continuing to add citric acid to adjust the pH to 3-3.4, continuing to introduce nitrogen, and adding azobisisobutyronitrile, potassium persulfate, and sodium metabisulfite thereto, reacting at 50-70°C for 6-12h, filtering after the reaction, washing, and obtaining the acid liquid thickener.

[0023] 3. Beneficial technical effects

[0024] The present invention adds 3,4-dihydroxycinnamic acid, acrylamide, sodium olefin sulfonate modified boric acid and quaternized cardanol into water, mixes them evenly, continues to add citric acid to adjust the pH, continues to introduce nitrogen, adds azobisisobutyronitrile, potassium persulfate and sodium pyrosulfite, stirs for reaction, filters after the reaction, and washes to obtain an acid liquid thickener.

[0025] The acid liquid thickener of the present invention contains adamantane and benzene ring rigid groups, which improve the rigidity of the acid liquid thickener, thereby enhancing its shear resistance and stability; the quaternary ammonium salt group and the sodium sulfonate group improve the temperature resistance and shear resistance of the acid liquid thickener; the cardanol hydrophobic structure and the carboxyl hydrophilic group are simultaneously introduced into the acid liquid thickener molecular chain to form a good hydrophobic association and amphiphilic interaction, and the alkyl long chains of the cardanol form spatial physical crosslinking, which improves the temperature resistance and viscosity of the acid liquid thickener and has a good thickening effect. DETAILED DESCRIPTION

[0026] The preparation method of cardanol glycidyl ether is prepared according to the method of "Preparation and Properties of Cross-linked Cardanol-based Waterborne Polyurethane" in "Coating Industry", Vol. 47, No. 2, February 2017.

[0027] Add 119.4 g of cardanol to a three-necked flask, heat to 95°C, add 0.12 g of ZnCl2, then drop 50 mL of epichlorohydrin, react for 3 hours, then drop a 193 g / L sodium hydroxide aqueous solution, heat to 100°C, react for 3 hours, transfer the solution product to a separatory funnel, heat deionized water for extraction and washing, add anhydrous sodium sulfate to the organic layer after separation, dry and remove water, filter, and distill the filtrate under reduced pressure to remove excess epichlorohydrin to obtain cardanol glycidyl ether. Example 1

[0028] (1) Add 1,3,5-trihydroxyadamantane and 4-aminophenylboronic acid to tetrahydrofuran solvent, stir and mix, continue to add anhydrous magnesium sulfate, wherein the mass ratio of 1,3,5-trihydroxyadamantane, 4-aminophenylboronic acid and anhydrous magnesium sulfate is 1:0.6:0.01, heat to 45°C, stir at 300 r / min for 4 hours, and vacuum dry to obtain aminoadamantane;

[0029] (2) adding 5 parts by weight of amino adamantane and 8 parts by weight of propenyl-1,3-sultone to an acetone solvent for dissolution, then dropping a 2% by weight sodium hydroxide solution, reacting at 75° C. for 6 h, concentrating under reduced pressure to remove the solvent after the reaction, and recrystallizing the crude product in ethanol to obtain sodium olefin sulfonate modified boronic acid;

[0030] (3) Add N,N'-dimethylethylenediamine and cardanol glycidyl ether to tetrahydrofuran, wherein the mass ratio of N,N'-dimethylethylenediamine to cardanol glycidyl ether is 0.41:1, heat to 55°C, react for 7 hours, rotary evaporate, and wash to obtain intermediate 1;

[0031] (4) Adding acrylic acid and intermediate 1 to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of acrylic acid, intermediate 1, and p-toluenesulfonic acid catalyst is 1.45:1:0.02, to carry out esterification reaction, reacting at 90° C. for 7 hours, and then distilling under reduced pressure, washing, and drying to obtain alkenyl cardanol;

[0032] (5) Add 6 parts by weight of alkenyl cardanol and 9 parts by weight of 3-chlorophenylacetic acid into acetone solvent, stir to dissolve, react at 80° C. for 5 h, cool after the reaction, concentrate under reduced pressure, and wash with petroleum ether to obtain quaternized cardanol;

[0033] (6) Add 4 parts by weight of 3,4-dihydroxycinnamic acid, 70 parts by weight of acrylamide, 6 parts by weight of sodium olefin sulfonate modified boric acid, and 7 parts by weight of quaternized cardanol to 85 parts by weight of water, mix well, continue to add citric acid to adjust the pH to 3, continue to introduce nitrogen, and add 0.02 parts by weight of azobisisobutyronitrile, 0.014 parts by weight of potassium persulfate, and 0.02 parts by weight of sodium metabisulfite, and react at 50°C for 6 hours. After the reaction, filter and wash to obtain an acid thickener. Example 2

[0034] (1) Add 1,3,5-trihydroxyadamantane and 4-aminophenylboronic acid to tetrahydrofuran solvent, stir and mix, continue to add anhydrous magnesium sulfate, wherein the mass ratio of 1,3,5-trihydroxyadamantane, 4-aminophenylboronic acid and anhydrous magnesium sulfate is 1:0.82:0.02, heat to 55°C, stir at 400 r / min for 6 hours, and vacuum dry to obtain aminoadamantane;

[0035] (2) adding 10 parts by weight of amino adamantane and 13 parts by weight of propenyl-1,3-sultone to an acetone solvent for dissolution, then dropping a 5% by weight sodium hydroxide solution, reacting at 92° C. for 11 hours, concentrating under reduced pressure to remove the solvent after the reaction, and recrystallizing the crude product in ethanol to obtain sodium olefin sulfonate modified boronic acid;

[0036] (3) Add N,N'-dimethylethylenediamine and cardanol glycidyl ether to tetrahydrofuran, wherein the mass ratio of N,N'-dimethylethylenediamine to cardanol glycidyl ether is 0.57:1, heat to 68°C, react for 10 hours, rotary evaporate, and wash to obtain intermediate 1;

[0037] (4) Adding acrylic acid and intermediate 1 to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of acrylic acid, intermediate 1, and p-toluenesulfonic acid catalyst is 1.86:1:0.03, to carry out esterification reaction, reacting at 110° C. for 9 hours, and then distilling under reduced pressure, washing, and drying to obtain alkenyl cardanol;

[0038] (5) adding 8 parts by weight of alkenyl cardanol and 14 parts by weight of 3-chlorophenylacetic acid to an acetone solvent, stirring to dissolve, reacting at 90° C. for 6 h, cooling after the reaction, concentrating under reduced pressure, and washing with petroleum ether to obtain quaternized cardanol;

[0039] (6) Add 6 parts by weight of 3,4-dihydroxycinnamic acid, 95 parts by weight of acrylamide, 9 parts by weight of sodium olefin sulfonate modified boric acid, and 10 parts by weight of quaternized cardanol to 150 parts by weight of water, mix well, continue to add citric acid to adjust the pH to 3.4, continue to introduce nitrogen, and add 0.023 parts by weight of azobisisobutyronitrile, 0.026 parts by weight of potassium persulfate, and 0.03 parts by weight of sodium metabisulfite, and react at 70°C for 12 hours. After the reaction, filter and wash to obtain an acid thickener. Example 3

[0040] (1) Add 1,3,5-trihydroxyadamantane and 4-aminophenylboronic acid to tetrahydrofuran solvent, stir and mix, continue to add anhydrous magnesium sulfate, wherein the mass ratio of 1,3,5-trihydroxyadamantane, 4-aminophenylboronic acid and anhydrous magnesium sulfate is 1:0.74:0.01, heat to 50°C, stir at 350r / min for 56h, and vacuum dry to obtain aminoadamantane;

[0041] (2) adding 6 parts by weight of amino adamantane and 10 parts by weight of propenyl-1,3-sultone to an acetone solvent for dissolution, then dropping a 4% by weight sodium hydroxide solution, reacting at 85° C. for 8 h, concentrating under reduced pressure to remove the solvent after the reaction, and recrystallizing the crude product in ethanol to obtain sodium olefin sulfonate modified boronic acid;

[0042] (3) Add N,N'-dimethylethylenediamine and cardanol glycidyl ether to tetrahydrofuran, wherein the mass ratio of N,N'-dimethylethylenediamine to cardanol glycidyl ether is 0.46:1, heat to 62°C, react for 8 hours, rotary evaporate, and wash to obtain intermediate 1;

[0043] (4) Adding acrylic acid and intermediate 1 to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of acrylic acid, intermediate 1, and p-toluenesulfonic acid catalyst is 1.67:1:0.02, to carry out esterification reaction, reacting at 100° C. for 8 hours, and then distilling under reduced pressure, washing, and drying to obtain alkenyl cardanol;

[0044] (5) adding 7 parts by weight of alkenyl cardanol and 12 parts by weight of 3-chlorophenylacetic acid to an acetone solvent, stirring to dissolve, reacting at 85° C. for 6 h, cooling after the reaction, concentrating under reduced pressure, and washing with petroleum ether to obtain quaternized cardanol;

[0045] (6) Add 5 parts by weight of 3,4-dihydroxycinnamic acid, 85 parts by weight of acrylamide, 8 parts by weight of sodium olefin sulfonate modified boric acid, and 9 parts by weight of quaternized cardanol to 130 parts by weight of water, mix well, continue to add citric acid to adjust the pH to 3.2, continue to introduce nitrogen, and add 0.021 parts by weight of azobisisobutyronitrile, 0.024 parts by weight of potassium persulfate, and 0.02 parts by weight of sodium metabisulfite, and react at 60°C for 9 hours. After the reaction, filter and wash to obtain an acid thickener. Example 4

[0046] (1) Add 1,3,5-trihydroxyadamantane and 4-aminophenylboronic acid to tetrahydrofuran solvent, stir and mix, continue to add anhydrous magnesium sulfate, wherein the mass ratio of 1,3,5-trihydroxyadamantane, 4-aminophenylboronic acid and anhydrous magnesium sulfate is 1:0.6:0.01, heat to 45°C, stir at 300 r / min for 4 hours, and vacuum dry to obtain aminoadamantane;

[0047] (2) adding 5 parts by weight of amino adamantane and 8 parts by weight of propenyl-1,3-sultone to an acetone solvent for dissolution, then dropping a 2% by weight sodium hydroxide solution, reacting at 75° C. for 6 h, concentrating under reduced pressure to remove the solvent after the reaction, and recrystallizing the crude product in ethanol to obtain sodium olefin sulfonate modified boronic acid;

[0048] (3) Add N,N'-dimethylethylenediamine and cardanol glycidyl ether to tetrahydrofuran, wherein the mass ratio of N,N'-dimethylethylenediamine to cardanol glycidyl ether is 0.57:1, heat to 68°C, react for 10 hours, rotary evaporate, and wash to obtain intermediate 1;

[0049] (4) Adding acrylic acid and intermediate 1 to N,N-dimethylformamide solvent, stirring to dissolve, and continuing to add p-toluenesulfonic acid catalyst, wherein the mass ratio of acrylic acid, intermediate 1, and p-toluenesulfonic acid catalyst is 1.86:1:0.03, to carry out esterification reaction, reacting at 110° C. for 9 hours, and then distilling under reduced pressure, washing, and drying to obtain alkenyl cardanol;

[0050] (5) adding 7 parts by weight of alkenyl cardanol and 12 parts by weight of 3-chlorophenylacetic acid to an acetone solvent, stirring to dissolve, reacting at 85° C. for 6 h, cooling after the reaction, concentrating under reduced pressure, and washing with petroleum ether to obtain quaternized cardanol;

[0051] (6) Add 5 parts by weight of 3,4-dihydroxycinnamic acid, 85 parts by weight of acrylamide, 8 parts by weight of sodium olefin sulfonate modified boric acid, and 9 parts by weight of quaternized cardanol to 130 parts by weight of water, mix well, continue to add citric acid to adjust the pH to 3.2, continue to introduce nitrogen, and add 0.021 parts by weight of azobisisobutyronitrile, 0.024 parts by weight of potassium persulfate, and 0.02 parts by weight of sodium metabisulfite, and react at 60°C for 9 hours. After the reaction, filter and wash to obtain an acid thickener.

[0052] Comparative Example 1

[0053] The difference between this comparative example and Example 5 is that no sodium olefin sulfonate is added to modify the boric acid.

[0054] Comparative Example 2

[0055] Compared with Example 5, this comparative example is different in that quaternized cardanol is not added.

[0056] The acid liquid thickener obtained in Examples 1-4 and Comparative Examples 1-2 was granulated, dried, ground, and sieved (the mesh size was 250 μm) to obtain acid liquid thickener particles. The acid liquid thickener particles were used as samples to test the apparent viscosity, shear resistance, apparent viscosity after shearing, and temperature resistance. The test results are shown in Table 1.

[0057] Preparation of thickening acid: prepare a hydrochloric acid solution containing 20% ​​by mass with saline having a mineralization degree of 100,000 mg / L and a calcium and magnesium ion content of 2000 mg / L; weigh 3.00 g of the sample, slowly add it to 497.00 g of the above hydrochloric acid solution while stirring with a magnetic stirrer (the adding time is less than 10 s), stir until there is no insoluble matter and the mixture is homogeneous, then stop stirring and cover the mixture, and place it in a constant temperature water bath at 25°C for 30 min to allow it to fully swell to prepare the thickening acid; the mass fraction of the sample in the thickening acid is 6%.

[0058] Determination of apparent viscosity: The thickened acid was transferred to the sample cup of a six-speed rotary viscometer and -1 Test the apparent viscosity η0 at 25°C under shear rate, mPa·s; Test the apparent viscosity under shear and temperature resistance: transfer the thickened acid to the rheometer sample tank and set the shear rate of the rheometer to 170s -1 , the temperature is 120℃, and the apparent viscosity η1, mPa·s after shearing for 2h is tested. Viscosity retention rate K: K=η1 / η0×100%, %.

[0059] Table 1: Acid thickener performance test.

[0060] project <![CDATA[η0(mPa·s)]]> <![CDATA[η1(mPa·s)]]> K（%） stability Example 1 63.7 58.4 94.5 No stratification, no precipitation Example 2 65.7 61.9 95.8 No stratification, no precipitation Example 3 64.3 59.1 95.1 No stratification, no precipitation Example 4 64.8 59.6 94.9 No stratification, no precipitation Comparative Example 1 42.6 40.3 80.1 Layering, flocculent precipitation Comparative Example 2 41.8 41.5 79.7 Layering, flocculent precipitation

[0061] As can be seen from Table 1, the acid liquid thickener of the present invention, Examples 1-4, have better heat resistance, shear resistance and salt resistance than Comparative Examples 1-2; meanwhile, they have good acid resistance and viscosity increasing ability; and they also have better stability at 120°C.

[0062] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An acid liquid thickener, characterized in that: The invention comprises the following components by weight: 4-6 parts by weight of 3,4-dihydroxycinnamic acid, 70-95 parts by weight of acrylamide, 6-9 parts by weight of sodium olefin sulfonate modified boric acid, 7-10 parts by weight of quaternized cardanol, 0.02-0.023 parts by weight of azobisisobutyronitrile, 0.014-0.026 parts by weight of potassium persulfate, 0.02-0.03 parts by weight of sodium pyrosulfite, and 85-150 parts by weight of water; The preparation method of the sodium olefin sulfonate modified boric acid is as follows: Step 1: Add 1,3,5-trihydroxyadamantane and 4-aminophenylboronic acid to tetrahydrofuran solvent, stir and mix, continue to add anhydrous magnesium sulfate, heat to 45-55°C, stir at 300-400r / min for 4-6h, and vacuum dry to obtain aminoadamantane; Step 2: adding 5-10 parts by weight of amino adamantane and 8-13 parts by weight of propenyl-1,3-sultone to an acetone solvent for dissolution, then dropping a sodium hydroxide solution with a mass fraction of 2-5%, reacting at 75-92° C., concentrating under reduced pressure to remove the solvent after the reaction, and recrystallizing the crude product in ethanol to obtain sodium olefin sulfonate modified boronic acid; The preparation method of the quaternized cardanol is: S1. Add N,N'-dimethylethylenediamine and cardanol glycidyl ether to tetrahydrofuran, heat to 55-68°C, react for 7-10h, rotary evaporate, wash, and obtain intermediate 1; S2. Add acrylic acid and intermediate 1 to N,N-dimethylformamide solvent, stir and dissolve, continue to add p-toluenesulfonic acid catalyst, carry out esterification reaction, react at 90-110° C. for 7-9 hours, and then distill under reduced pressure, wash, and dry to obtain alkenyl cardanol; S3. Add 6-8 parts by weight of alkenyl cardanol and 9-14 parts by weight of 3-chlorophenylacetic acid to an acetone solvent, stir to dissolve, react at 80-90° C., cool after the reaction, concentrate under reduced pressure, wash with petroleum ether, and obtain quaternized cardanol.

2. The acid liquid thickener according to claim 1, characterized in that: In the step 1, the mass ratio of 1,3,5-trihydroxyadamantane, 4-aminophenylboric acid and anhydrous magnesium sulfate is 1:0.6-0.82:0.01-0.

02.

3. The acid liquid thickener according to claim 1, characterized in that: The reaction time in step 2 is 6-11 hours.

4. The acid liquid thickener according to claim 1, characterized in that: The mass ratio of N,N'-dimethylethylenediamine to cardanol glycidyl ether in S1 is 0.41-0.57:

1.

5. The acid liquid thickener according to claim 1, characterized in that: The mass ratio of acrylic acid, intermediate 1 and p-toluenesulfonic acid catalyst in S2 is 1.45-1.86:1:0.02-0.

03.

6. The acid liquid thickener according to claim 1, characterized in that: The reaction time in S3 is 5-6h.

7. A method for preparing an acid liquid thickener according to any one of claims 1 to 6, characterized in that: The preparation method of the acid liquid thickener is as follows: 3,4-dihydroxycinnamic acid, acrylamide, sodium olefin sulfonate modified boric acid, and quaternized cardanol are added to water, mixed evenly, citric acid is added to adjust the pH to 3-3.4, nitrogen is introduced, and azobisisobutyronitrile, potassium persulfate, and sodium pyrosulfite are added thereto, reacting at 50-70° C. for 6-12 hours, filtering after the reaction, and washing to obtain the acid liquid thickener.