CN111171231A - Method for preparing acid liquor system - Google Patents
Method for preparing acid liquor system Download PDFInfo
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- CN111171231A CN111171231A CN201811347907.XA CN201811347907A CN111171231A CN 111171231 A CN111171231 A CN 111171231A CN 201811347907 A CN201811347907 A CN 201811347907A CN 111171231 A CN111171231 A CN 111171231A
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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
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
Abstract
The invention provides a method for preparing an acid liquor system, which comprises the following steps: 1) adding a thickening agent into the hydrochloric acid solution at a first stirring speed, and stirring at a second stirring speed to obtain a first acid solution; 2) sequentially adding an iron ion stabilizer, a corrosion inhibitor and a demulsification cleanup additive into the first acid liquor, stirring uniformly at a third stirring speed, and standing to obtain a base solution; 3) and adding a tackifier into the base solution, and stirring at a fourth stirring speed to obtain the acid liquor system.
Description
Technical Field
The invention provides a method for preparing an acid system.
Background
Ground crosslinked acid and gelled acid are the most common acid systems for acid fracturing modification of high-temperature fracture-cavity carbonate rock. The ground crosslinked acid is crosslinked into a gel structure through organic zirconium or organic titanium to synthesize a polymer, has good retarding and temperature resistance, but has the problems of difficult gel breaking and high damage to a reservoir stratum, and cannot meet the acid fracturing or acidification requirements of compact pore type carbonate rock. The viscosity of the gel acid which is not crosslinked is low at high temperature, so that acidification or short acid pressure etching distance can be caused, and deep penetration cannot be realized. Therefore, it is urgently needed to develop a novel low-damage and low-speed acid solution system.
Disclosure of Invention
The invention provides a method for preparing an acid liquor system, which comprises the following steps:
1) adding a thickening agent into the hydrochloric acid solution at a first stirring speed, and stirring at a second stirring speed to obtain a first acid solution;
2) sequentially adding an iron ion stabilizer, a corrosion inhibitor and a demulsification cleanup additive into the first acid liquor, stirring uniformly at a third stirring speed, and standing to obtain a base solution;
3) and adding a tackifier into the base solution, and stirring at a fourth stirring speed to obtain the acid liquor system.
In one embodiment, the thickener is prepared as follows:
A) dissolving acrylamide, 2-acrylamide-2-methylpropanesulfonic acid and a quaternary ammonium salt type polymerizable surfactant in water to obtain a first solution;
B) adding a cosolvent, a chain transfer agent, a complexing agent and an active agent into the first solution, and uniformly mixing to obtain a second solution;
C) adjusting the pH value of the second solution to 6.5-7.5 to obtain a third solution; then adding the third solution into a polymerization device, and introducing nitrogen;
D) adding a water-soluble azo initiator, a reducing agent and an oxidizing agent into the polymerization device to obtain a fourth solution, and then continuously introducing nitrogen;
E) maintaining the temperature of the fourth solution after the temperature of the fourth solution rises, thereby obtaining a polymer jelly;
F) and (3) granulating, drying, crushing and sieving the polymer jelly to obtain the thickening agent in a dry powder state.
In one embodiment, the quaternary ammonium salt type polymerizable surfactant is at least one selected from the group consisting of tetradecyldimethylammonium chloride, hexadecyldimethylallylammonium chloride, octadecyldimethylammonium chloride, methacryloyloxyethyldimethylhexadecylammonium bromide, and dimethyloctadecylammonium (2-hydroxy-3-acrylamidopropyl) chloride.
In one embodiment, the co-solvent is selected from at least one of urea, thiourea and triethanolamine.
In one embodiment, the chain transfer agent is selected from at least one of sodium formate, potassium formate, and isopropanol.
In one embodiment, the complexing agent is selected from at least one of ethylenediaminetetraacetic acid disalt, ethylenediaminetetraacetic acid tetrasalt, and triethylenetetramine pentaacetate. For example, the salt may be a sodium salt or a potassium salt. For example, the complexing agent is at least one selected from the group consisting of disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, and pentasodium triethylenetetraminepentaacetate.
In one embodiment, the activator is selected from at least one of N, N-tetramethylethylenediamine, ethylenediamine, and triethanolamine.
In one embodiment, the oxidizing agent is selected from at least one of ammonium persulfate, potassium persulfate, and hydrogen peroxide.
In one embodiment, the reducing agent is selected from at least one of sodium bisulfite, sodium sulfite, and ferrous ammonium sulfate.
In one embodiment, the water-soluble azo-type initiator is selected from azobisisobutyramidine hydrochloride and/or azobisisobutyrimidazoline hydrochloride. For example, the salt may be a sodium salt or a potassium salt. For example, the water-soluble azo initiator is selected from the group consisting of azobisisobutyramidine hydrochloride sodium salt and azobisisobutyrimidazoline hydrochloride sodium salt.
In one embodiment, the acrylamide has 20 to 50 parts by mass, the 2-acrylamido-2-methylpropanesulfonic acid has 50 to 80 parts by mass, and the quaternary ammonium salt type polymerizable surfactant has 0.8 to 3.0 parts by mass.
In one embodiment, the acrylamide has 25 to 45 parts by mass, the 2-acrylamido-2-methylpropanesulfonic acid has 53 to 73 parts by mass, and the quaternary ammonium salt type polymerizable surfactant has 1 to 2.5 parts by mass.
In a specific embodiment, the total mass of the acrylamide, the 2-acrylamido-2-methylpropanesulfonic acid, and the quaternary ammonium salt type polymerizable surfactant accounts for 25 wt% to 29 wt% of the total mass of the first solution.
In one embodiment, based on 100% by mass of the total of the acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, and quaternary ammonium salt type polymerizable surfactant (i.e., not based on 100% by mass of the aqueous solution of these three monomers), the cosolvent is used in an amount of 1 wt% to 3 wt%, the chain transfer agent is used in an amount of 0.05 wt% to 0.1 wt%, the complexing agent is used in an amount of 0.03 wt% to 0.08 wt%, the activator is used in an amount of 0.05 wt% to 0.1 wt%, the oxidizing agent is used in an amount of 0.01 wt% to 0.06 wt%, the reducing agent is used in an amount of 0.005 wt% to 0.03 wt%, and the water-soluble azo-type initiator is used in an amount of 0.02 wt% to 0.06 wt%.
In order to facilitate the subsequent acid-base neutralization and prevent the system from imploding, the second solution is preferably cooled. In a specific embodiment, in step B), the second solution obtained by mixing uniformly is cooled to 5 ℃ to 10 ℃. For example, it is cooled in a water bath at 5 ℃ to 10 ℃ for 30 minutes.
Generally, during the adjustment of the pH, an exotherm occurs. Therefore, in order to facilitate the subsequent low-temperature polymerization, it is preferable to cool the third solution. In a particular embodiment, in step C), the third solution obtained after adjusting the pH value is cooled to 5 ℃ to 10 ℃. For example, it is cooled in a water bath at 5 ℃ to 10 ℃ for 30 minutes.
In step D), the azo type initiator, the reducing agent and the oxidizing agent are preferably prepared as aqueous solutions before being added to the polymerization apparatus, respectively, so as to be added to the polymerization apparatus and the aqueous solution of the reactive monomer (i.e., the third solution). The concentration of the preparation is not particularly required, and can be adjusted according to actual needs and the scale of use.
Step E) is mainly a polymerization process, during which a certain amount of heat is released, and the heat is preserved when the heat is released to a certain extent, i.e., 60 ℃ to 80 ℃. In a particular embodiment, in step E), the temperature of the incubation is between 60 ℃ and 80 ℃.
In one embodiment, in step F), the temperature of the drying is 60 ℃ to 80 ℃.
In one embodiment, the nitrogen is introduced independently for a period of 20 to 30 minutes in step C) and step D).
In one embodiment, in step E), the incubation time is from 4 to 5 hours.
In a particular embodiment, in step F), the size of the granules is from 0.3 to 0.5 cm.
In one embodiment, in step F), the temperature of the drying is 60 ℃ to 80 ℃.
In a particular embodiment, in step F), the water content of the dried product is less than 10 wt%. For example, the water content of the dried product is less than 5 wt%, or the water content of the dried product is less than 3 wt%.
In one embodiment, in step F), the mesh size of the screen is 20 to 40 mesh.
In one embodiment, the tackifier is prepared as follows:
I) mixing polyalcohol and/or polyalcohol amine with water to obtain a first solution;
II) adding an ionic liquid surfactant to the first solution to obtain the viscosifier.
In one specific embodiment, the total content of the polyhydric alcohol and/or the polyalcohol amine is 15-35% by mass percentage, and the ionic liquid surfactant is 30-50%.
In one specific embodiment, the total content of the polyhydric alcohol and/or the polyalcohol amine is 15-30% by mass percentage, and the ionic liquid surfactant is 35-45%.
In one embodiment, the polyol comprises at least one selected from the group consisting of glycerol, ethylene glycol, xylitol, sorbitol, and pentaerythritol.
In one embodiment, the polyalcohol amine comprises at least one selected from the group consisting of ethylene glycol, triethanolamine and diethanolamine.
In one embodiment, the ionic liquid surfactant comprises at least one selected from the group consisting of triethanolamine dodecylbenzene sulfonate, diethanolamine dodecylbenzene sulfonate, ethanolamine dodecylbenzene sulfonate, triethanolamine dodecylsulfate, diethanolamine dodecylsulfate, ethanolamine dodecylsulfate, triethanolamine dodecylsulfate, diethanolamine dodecylsulfonic acid, and ethanolamine dodecylsulfonic acid.
In one embodiment, in step I), the polyol and/or polyalcohol amine is mixed with water homogeneously under stirring at a fifth stirring speed.
In a particular embodiment, the tackifier is obtained after stirring at a sixth stirring speed for 1 to 2 hours at 40 to 60 ℃ in step II).
In a specific embodiment, the first stirring speed, the second stirring speed, the third stirring speed, the fourth stirring speed, the fifth stirring speed, and the sixth stirring speed are independently selected from 300r/min to 1000 r/min.
In one embodiment, the stirring time at the second stirring speed is 30 to 50 minutes.
In one embodiment, the time for standing after stirring uniformly at the third stirring speed is 3 to 6 hours.
In a specific embodiment, stirring is carried out at a fourth stirring speed for 3 to 10 min.
In a specific embodiment, in the step 2), after stirring uniformly at the third stirring speed, the mixture is sealed and kept standing at the natural environment temperature.
In a specific embodiment, 100 parts by mass of the hydrochloric acid solution, 0.5 to 1.2 parts by mass of the thickening agent, 1 to 3.5 parts by mass of the corrosion inhibitor, 0.6 to 1.5 parts by mass of the iron ion stabilizer, 0.6 to 1.2 parts by mass of the demulsification cleanup additive and 1 to 3 parts by mass of the tackifier; wherein the mass concentration of the hydrochloric acid solution is 15 to 30 percent.
In a specific embodiment, 1 to 1.2 parts by mass of the thickening agent, 1 to 1.5 parts by mass of the iron ion stabilizer, 2.5 to 3.5 parts by mass of the corrosion inhibitor, 1 to 1.2 parts by mass of the demulsification cleanup additive and 1.5 to 2.5 parts by mass of the tackifier; the mass concentration of the hydrochloric acid solution is 15-20%.
In one embodiment, the corrosion inhibitor is selected from at least one of imidazolines, quinoline quaternaries, ketone-aldehyde amine condensates, mannich bases; preferably, the corrosion inhibitor is at least one selected from 1-aminoethyl-2-pentadecylimidazoline quaternary ammonium salt, 2-methylquinoline benzyl quaternary ammonium salt and formaldehyde-p-phenylenediamine-acetophenone (obtained by reacting formaldehyde, p-phenylenediamine and acetophenone as reaction raw materials).
In one embodiment, the iron ion stabilizer is an organic acid; more preferably, the iron ion stabilizer is at least one selected from the group consisting of citric acid, lactic acid, acetic acid, ethylenediaminetetraacetic acid and ascorbic acid.
In one embodiment, the demulsifying cleanup additive is prepared as follows:
dissolving 2-20 parts by mass of betaine zwitterionic surfactant and 20-30 parts by mass of polyoxypropylene polyoxyethylene propylene glycol ether in 49-78 parts by mass of water, stirring until the components are fully dissolved, adding 0.05-0.5 part by mass of perfluoro lauryl polyoxyethylene ether, and continuously stirring uniformly to obtain the demulsification cleanup additive for the cross-linked acid.
In a specific embodiment, the betaine zwitterionic surfactant is at least one of lauramidopropyl betaine, cocamidopropyl betaine, and dodecyl dimethyl betaine.
In one embodiment, the pH of the second solution is adjusted with sodium hydroxide and/or sodium carbonate.
The invention has the beneficial effects that:
the thickening agent used in the invention has few monomer types, low price and simple and controllable synthesis method; the thickening agent can improve the temperature resistance of the acid liquor and the tackifying performance of the acid liquor; more importantly, the thickening agent is combined with the tackifier for use, and can be prepared into acid liquor with high viscosity, a reversible cross-linked gel structure and a cantilever hanging property.
The tackifier prepared by the invention has the advantages of simple preparation method and low cost, and can greatly reduce the cost of acid liquor. The viscosity and elasticity of the self-assembled cleaning acid liquor can be greatly increased by using the tackifier, the temperature resistance and shearing resistance of an acid liquor system are improved, and the acid rock reaction rate is reduced; the tackifier forms micelle in acid solution, thereby reducing H+The mass transfer speed of ions slows down the acid rock reaction; the formed clean self-assembly acid liquid system has good temperature resistance, shearing resistance and retarding performance; the self-assembly thickener and the self-assembly cleaning thickener form a physically cross-linked three-dimensional network structure after self-assembly, gel is automatically broken after the acid rock reaction is finished, the gel is broken completely, and the residue content is extremely low, so that the damage to a reservoir stratum is low.
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.
In the following examples, all reagents were commercially available.
Preparation of the thickener for the clean self-assembled acid:
thickener 1 for clean self-assembled acid
1) Preparing a polymerization monomer aqueous solution, adding 35 parts of acrylamide, 64 parts of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) and 0.8 part of hexadecyl dimethyl allyl ammonium chloride in parts by mass into a beaker, and adding distilled water for dissolving to enable the total mass content of the three monomers to be 25 wt%;
2) adding 1.0 wt% of urea, 0.05 wt% of sodium formate, 0.03 wt% of tetrasodium ethylene diamine tetraacetate and 0.05 wt% of ethylenediamine into the monomer aqueous solution (the total mass of the three monomers is 100%), stirring and dissolving uniformly, cooling in a water bath at 5 ℃ for 30min, and cooling to 5 ℃;
3) adding a certain amount of sodium hydroxide into the solution to adjust pH to 6.5, continuously cooling in 5 deg.C water bath for 30min to 5 deg.C, introducing the liquid into heat-insulating polymerization device, and introducing nitrogen for 20 min;
4) adding 0.02 wt% of azodiisobutyl amidine hydrochloride, 0.005 wt% of sodium bisulfite and 0.01 wt% of ammonium persulfate aqueous solution into the mother liquor in sequence, continuously introducing nitrogen for 20min until the mixture becomes viscous, and then stopping introducing nitrogen;
5) observing the temperature change of the system, and keeping the temperature for 5 hours when the temperature of the system rises to 70 ℃;
6) and taking out the gel block obtained by polymerization, granulating, drying at 70 ℃ until the water content is 10 wt%, crushing, and sieving by a 30-mesh sieve to obtain the thickening agent dry powder for the self-assembled cleaning acid liquor.
Clean thickener for self-assembled acid 2
1) Preparing a polymerization monomer aqueous solution, adding 45 parts of acrylamide, 53 parts of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) and 1.0 part of methacryloyloxyethyl dimethyl hexadecyl ammonium bromide into a beaker according to parts by mass, and adding distilled water for dissolving to ensure that the total mass content of the three monomers is 29 wt%;
2) adding 3.0 wt% of thiourea, 0.08 wt% of potassium formate, 0.05 wt% of disodium ethylene diamine tetraacetic acid and 0.1 wt% of N, N-tetramethyl ethylenediamine into the monomer aqueous solution (the total mass of the three monomers is 100%), stirring and dissolving uniformly, putting into a water bath at 10 ℃ for cooling for 30min, and cooling to 10 ℃;
3) adding a certain amount of sodium hydroxide into the solution to adjust pH to 7.0, continuously cooling in 10 deg.C water bath for 30min to 10 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding aqueous solutions of 0.06 wt% of azobisisobutyrimidazoline hydrochloride, 0.03 wt% of sodium sulfite and 0.06 wt% of potassium persulfate into the mother liquor in sequence, continuously introducing nitrogen for 20min until the mixture becomes viscous, and stopping introducing the nitrogen;
5) observing the temperature change of the system, and keeping the temperature for 5 hours when the temperature of the system rises to 70 ℃;
6) and taking out the gel block obtained by polymerization, granulating, drying at 70 ℃ until the water content is 5 wt%, crushing, and sieving by a 30-mesh sieve to obtain the thickening agent dry powder for the self-assembled cleaning acid liquor.
Thickener 3 for clean self-assembled acid
1) Preparing a polymerization monomer aqueous solution, adding 25 parts of acrylamide, 58 parts of AMPS and 1.5 parts of methacryloyloxyethyl dimethyl hexadecyl ammonium bromide into a beaker according to parts by mass, and adding distilled water for dissolving to ensure that the total mass content of the three monomers is 27 wt%;
2) adding 2.0 wt% of thiourea, 0.04 wt% of potassium formate, 0.03 wt% of disodium ethylene diamine tetraacetate and 0.08 wt% of N, N-tetramethylethylenediamine into the monomer aqueous solution (the total mass of the three monomers is 100%), stirring and dissolving uniformly, cooling in a water bath at 8 ℃ for 30min, and cooling to 8 ℃;
3) adding a certain amount of sodium hydroxide into the solution to adjust pH to 7.5, continuously cooling in 8 deg.C water bath for 30min to 8 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding aqueous solutions of 0.04 wt% of azobisisobutyrimidazoline hydrochloride, 0.02 wt% of sodium sulfite and 0.04 wt% of potassium persulfate into the mother liquor in sequence, continuously introducing nitrogen for 20min until the mixture becomes viscous, and stopping introducing the nitrogen;
5) observing the temperature change of the system, and keeping the temperature for 5 hours when the temperature of the system rises to 70 ℃;
6) and taking out the gel block obtained by polymerization, granulating, drying at 70 ℃ until the water content is 3 wt%, crushing, and sieving by a 30-mesh sieve to obtain the thickening agent dry powder for the self-assembled cleaning acid liquor.
Clean thickener for self-assembled acid 4
1) Preparing a polymerization monomer aqueous solution, adding 42 parts of acrylamide, 56 parts of AMPS and 2.0 parts of methacryloyloxyethyl dimethyl hexadecyl ammonium bromide into a beaker according to parts by mass, and adding distilled water for dissolving to ensure that the total mass content of the three monomers is 26 wt%;
2) adding 2.0 wt% of thiourea, 0.04 wt% of potassium formate, 0.03 wt% of triethylene pentaacetic acid pentasodium and 0.08 wt% of N, N-tetramethyl ethylenediamine into the monomer aqueous solution (the total mass of the three monomers is 100%), stirring and dissolving uniformly, putting into a water bath at 10 ℃ for cooling for 30min, and cooling to 10 ℃;
3) adding a certain amount of sodium hydroxide into the solution to adjust pH to 7.0, continuously cooling in 10 deg.C water bath for 30min to 10 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.05 wt% of azobisisobutyronitrile hydrochloride, 0.015 wt% of sodium sulfite and 0.03 wt% of potassium persulfate aqueous solution into the mother liquor in sequence, continuously introducing nitrogen for 20min until the mixture becomes viscous, and stopping introducing the nitrogen;
5) observing the temperature change of the system, and keeping the temperature for 5 hours when the temperature of the system rises to 70 ℃;
6) and taking out the gel block obtained by polymerization, granulating, drying at 70 ℃ until the water content is 5 wt%, crushing, and sieving by a 30-mesh sieve to obtain the thickening agent dry powder for the self-assembled cleaning acid liquor.
Thickener 5 for clean self-assembly acid
1) Preparing a polymerization monomer aqueous solution, adding 50 parts of acrylamide, 55 parts of AMPS and 2.5 parts of tetradecyl dimethyl allyl ammonium chloride into a beaker according to parts by mass, and adding distilled water to dissolve so that the total mass content of the three monomers is 26 wt%;
2) adding 2.5 wt% of thiourea, 0.04 wt% of potassium formate, 0.03 wt% of triethylene pentaacetic acid pentasodium and 0.08 wt% of N, N-tetramethyl ethylene diamine into the monomer aqueous solution (based on the total mass of the three monomers as 100%), stirring and dissolving uniformly, cooling in a water bath at 8 ℃ for 30min, and cooling to 8 ℃;
3) adding a certain amount of sodium hydroxide into the solution to adjust pH to 7.0, continuously cooling in 8 deg.C water bath for 30min to 8 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.05 wt% of azobisisobutyric imidazoline hydrochloride, 0.015 wt% of ammonium ferrous sulfate and 0.03 wt% of hydrogen peroxide aqueous solution into the mother solution in sequence, continuously introducing nitrogen for 20min until the mixture becomes viscous, and then stopping introducing the nitrogen;
5) observing the temperature change of the system, and keeping the temperature for 5 hours when the temperature of the system rises to 70 ℃;
6) and taking out the gel block obtained by polymerization, granulating, drying at 70 ℃ until the water content is 3 wt%, crushing, and sieving by a 30-mesh sieve to obtain the thickening agent dry powder for the self-assembled cleaning acid liquor.
Thickener 6 for clean self-assembly acid
1) Preparing a polymerization monomer aqueous solution, adding 30 parts of acrylamide, 50 parts of AMPS and 2.0 parts of dimethyl octadecyl (2-hydroxy-3-acrylamide propyl) ammonium chloride into a beaker according to parts by mass, and adding distilled water for dissolving to enable the total mass content of the three monomers to be 25 wt%;
2) adding 1 wt% of thiourea, 0.05 wt% of potassium formate, 0.03 wt% of triethylene pentaacetic acid pentasodium and 0.05 wt% of N, N-tetramethyl ethylenediamine into the monomer aqueous solution (the total mass of the three monomers is 100%), stirring and dissolving uniformly, putting into a water bath at 10 ℃ for cooling for 30min, and cooling to 10 ℃;
3) adding a certain amount of sodium hydroxide into the solution to adjust pH to 7.0, continuously cooling in 10 deg.C water bath for 30min to 10 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding aqueous solution of 0.02 wt% of azobisisobutyric imidazoline hydrochloride, 0.005 wt% of ammonium ferrous sulfate and 0.01 wt% of hydrogen peroxide into the mother liquor in sequence, continuously introducing nitrogen for 20min until the mixture becomes viscous, and stopping introducing the nitrogen;
5) observing the temperature change of the system, and keeping the temperature for 4 hours when the temperature of the system rises to 60 ℃;
6) and taking out the gel block obtained by polymerization, granulating, drying at 60 ℃ until the water content is 3 wt%, crushing, and sieving by a 20-mesh sieve to obtain the thickening agent dry powder for the self-assembled cleaning acid liquor.
Thickener 7 for clean self-assembly acid
1) Preparing a polymerization monomer aqueous solution, adding 30 parts of acrylamide, 50 parts of AMPS and 1.5 parts of tetradecyl dimethyl allyl ammonium chloride into a beaker according to parts by mass, and adding distilled water to dissolve so that the total mass content of the three monomers is 25 wt%;
2) adding 3 wt% of thiourea, 0.1 wt% of potassium formate, 0.08 wt% of triethylene pentaacetic acid pentasodium and 0.1 wt% of N, N-tetramethyl ethylenediamine into the monomer aqueous solution (the total mass of the three monomers is 100%), stirring and dissolving uniformly, putting into a water bath at 10 ℃ for cooling for 30min, and cooling to 10 ℃;
3) adding a certain amount of sodium carbonate into the solution to adjust pH to 7.0, continuously cooling in 10 deg.C water bath for 30min to 10 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 30 min;
4) adding 0.06 wt% of azodiisobutyl imidazoline hydrochloride, 0.03 wt% of ammonium ferrous sulfate and 0.06 wt% of hydrogen peroxide aqueous solution into the mother solution in sequence, continuously introducing nitrogen for 30min until the mixture becomes viscous, and then stopping introducing the nitrogen;
5) observing the temperature change of the system, and keeping the temperature for 4 hours when the temperature of the system rises to 80 ℃;
6) and taking out the gel block obtained by polymerization, granulating, drying at 80 ℃ until the water content is 5 wt%, crushing, and sieving by a 30-mesh sieve to obtain the thickening agent dry powder for the self-assembled cleaning acid liquor.
Thickener 8 for clean self-assembly acid
1) Preparing a polymerization monomer aqueous solution, adding 35 parts of acrylamide, 64 parts of AMPS and 2.3 parts of octadecyl dimethyl allyl ammonium chloride into a beaker according to parts by mass, and adding distilled water for dissolving to enable the total mass content of the three monomers to be 25 wt%;
2) adding 1.0 wt% of urea, 0.05 wt% of sodium formate, 0.03 wt% of tetrasodium ethylene diamine tetraacetate and 0.05 wt% of ethylenediamine into the monomer aqueous solution (the total mass of the three monomers is 100%), stirring and dissolving uniformly, cooling in a water bath at 5 ℃ for 30min, and cooling to 5 ℃;
3) adding a certain amount of sodium carbonate into the above solution to adjust pH to 6.5, further cooling in 5 deg.C water bath for 30min to 5 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.02 wt% of azodiisobutyl amidine hydrochloride, 0.005 wt% of sodium bisulfite and 0.01 wt% of ammonium persulfate aqueous solution into the mother liquor in sequence, continuously introducing nitrogen for 20min until the mixture becomes viscous, and then stopping introducing nitrogen;
5) observing the temperature change of the system, and keeping the temperature for 5 hours when the temperature of the system rises to 70 ℃;
6) and taking out the gel block obtained by polymerization, granulating, drying at 70 ℃ until the water content is 5 wt%, crushing, and sieving by a 30-mesh sieve to obtain the thickening agent dry powder for the self-assembled cleaning acid liquor.
Clean thickener for self-assembled acid 9
1) Preparing a polymerization monomer aqueous solution, adding 35 parts of acrylamide, 64 parts of 2-acrylamide-2-methylpropyl AMPS and 1.0 part of tetradecyl dimethyl allyl ammonium chloride into a beaker according to parts by mass, and adding distilled water for dissolving to enable the total mass content of the three monomers to be 25 wt%;
2) adding 1.0 wt% of urea, 0.05 wt% of sodium formate, 0.03 wt% of tetrasodium ethylene diamine tetraacetate and 0.05 wt% of ethylenediamine into the monomer aqueous solution (the total mass of the three monomers is 100%), stirring and dissolving uniformly, cooling in a water bath at 5 ℃ for 30min, and cooling to 5 ℃;
3) adding a certain amount of sodium carbonate into the above solution to adjust pH to 7.5, further cooling in 5 deg.C water bath for 30min to 5 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.02 wt% of azodiisobutyl amidine hydrochloride, 0.005 wt% of sodium bisulfite and 0.01 wt% of ammonium persulfate aqueous solution into the mother liquor in sequence, continuously introducing nitrogen for 20min until the mixture becomes viscous, and then stopping introducing nitrogen;
5) observing the temperature change of the system, and keeping the temperature for 5 hours when the temperature of the system rises to 70 ℃;
6) and taking out the gel block obtained by polymerization, granulating, drying at 70 ℃ until the water content is 5 wt%, crushing, and sieving by a 30-mesh sieve to obtain the thickening agent dry powder for the self-assembled cleaning acid liquor.
Clean thickener for self-assembled acid 10
1) Preparing a polymerization monomer aqueous solution, adding 35 parts of acrylamide, 64 parts of AMPS and 1.5 parts of hexadecyl dimethyl allyl ammonium chloride into a beaker according to parts by mass, and adding distilled water to dissolve so that the total mass content of the three monomers is 25 wt%;
2) adding 1.0 wt% of triethanolamine, 0.05 wt% of sodium formate, 0.03 wt% of tetrasodium ethylene diamine tetraacetate and 0.05 wt% of ethylenediamine into the monomer aqueous solution (the total mass of the three monomers is 100%), stirring and dissolving uniformly, cooling in a water bath at 5 ℃ for 30min, and cooling to 5 ℃;
3) adding a certain amount of sodium hydroxide into the above solution to adjust pH to 7.0, further cooling in 5 deg.C water bath for 30min to 5 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.02 wt% of azodiisobutyl amidine hydrochloride, 0.005 wt% of sodium bisulfite and 0.01 wt% of ammonium persulfate aqueous solution into the mother liquor in sequence, continuously introducing nitrogen for 20min until the mixture becomes viscous, and then stopping introducing nitrogen;
5) observing the temperature change of the system, and keeping the temperature for 5 hours when the temperature of the system rises to 70 ℃;
6) and taking out the gel block obtained by polymerization, granulating, drying at 70 ℃ until the water content is 5 wt%, crushing, and sieving by a 30-mesh sieve to obtain the thickening agent dry powder for the self-assembled cleaning acid liquor.
Clean thickener 11 for self-assembled acid
1) Preparing a polymerization monomer aqueous solution, adding 35 parts of acrylamide, 73 parts of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) and 3.0 parts of hexadecyl dimethyl allyl ammonium chloride in parts by mass into a beaker, and adding distilled water for dissolving to enable the total mass content of the three monomers to be 25 wt%;
2) adding 1.0 wt% of urea, 0.05 wt% of isopropanol, 0.03 wt% of tetrasodium ethylene diamine tetraacetate and 0.05 wt% of ethylenediamine into the monomer aqueous solution (the total mass of the three monomers is 100%), stirring and dissolving uniformly, cooling in a water bath at 5 ℃ for 30min, and cooling to 5 ℃;
3) adding a certain amount of sodium hydroxide into the solution to adjust the pH value of the solution to 7.0, continuously placing the solution into a water bath at 5 ℃ for cooling for 30min to cool the solution to 5 ℃, introducing the liquid into a heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.02 wt% of azodiisobutyl amidine hydrochloride, 0.005 wt% of sodium bisulfite and 0.01 wt% of ammonium persulfate aqueous solution into the mother liquor in sequence, continuously introducing nitrogen for 20min until the mixture becomes viscous, and then stopping introducing nitrogen;
5) observing the temperature change of the system, and keeping the temperature for 5 hours when the temperature of the system rises to 70 ℃;
6) and taking out the gel block obtained by polymerization, granulating, drying at 70 ℃ until the water content is 5 wt%, crushing, and sieving by a 30-mesh sieve to obtain the thickening agent dry powder for the self-assembled cleaning acid liquor.
Clean thickener 12 for self-assembling acid
1) Preparing a polymerization monomer aqueous solution, adding 20 parts of acrylamide, 80 parts of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) and 1.8 parts of hexadecyl dimethyl allyl ammonium chloride in parts by mass into a beaker, and adding distilled water for dissolving to enable the total mass content of the three monomers to be 25 wt%;
2) adding 1.0 wt% of urea, 0.05 wt% of sodium formate, 0.03 wt% of tetrasodium ethylene diamine tetraacetate and 0.05 wt% of ethylenediamine into the monomer aqueous solution (the total mass of the three monomers is 100%), stirring and dissolving uniformly, cooling in a water bath at 5 ℃ for 30min, and cooling to 5 ℃;
3) adding a certain amount of sodium carbonate into the above solution to adjust pH to 6.5, further cooling in 5 deg.C water bath for 30min to 5 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.02 wt% of azodiisobutyl amidine hydrochloride, 0.005 wt% of sodium bisulfite and 0.01 wt% of ammonium persulfate aqueous solution into the mother liquor in sequence, continuously introducing nitrogen for 20min until the mixture becomes viscous, and then stopping introducing nitrogen;
5) observing the temperature change of the system, and keeping the temperature for 5 hours when the temperature of the system rises to 70 ℃;
6) and taking out the gel block obtained by polymerization, granulating, drying at 70 ℃ until the water content is 5 wt%, crushing, and sieving by a 30-mesh sieve to obtain the thickening agent dry powder for the self-assembled cleaning acid liquor.
Preparation of tackifier for cleaning self-assembly acid:
tackifier 1 for cleaning self-assembly acid
1) Adding 15 parts by mass of ethylene glycol into 55 parts by mass of water, and uniformly stirring at 500 r/min;
2) heating the solution in the step 1) to 40 ℃, then gradually adding 30 parts by mass of triethanolamine dodecylbenzene sulfonate into the solution in the step 1), and stirring for 1 hour at 500 r/min;
3) cooling to 25 ℃ to obtain the tackifier for the self-assembly cleaning acid liquor.
Tackifier 2 for cleaning self-assembly acid
1) Adding 30 parts by mass of glycerol into 25 parts by mass of water, and uniformly stirring at 800 r/min;
2) heating the solution in the step 1) to 50 ℃, then gradually adding 45 parts by mass of lauryl sulfuric acid triethanolamine salt into the solution in the step 1), and stirring for 1.5 hours at the speed of 800 r/min;
3) cooling to 25 ℃ to obtain the tackifier for the self-assembly cleaning acid liquor.
Tackifier 3 for cleaning self-assembly acid
1) Adding 35 parts by mass of triethanolamine into 15 parts by mass of water, and uniformly stirring at 1000 r/min;
2) heating the solution in the step 1) to 60 ℃, then gradually adding 50 parts by mass of lauryl sulfuric acid triethanolamine salt into the solution in the step 1), and stirring for 2 hours at 1000 r/min;
3) cooling to 25 ℃ to obtain the tackifier for the self-assembly cleaning acid liquor.
Tackifier 4 for cleaning self-assembly acid
1) Adding 25 parts by mass of sorbitol into 35 parts by mass of water, and uniformly stirring at 800 r/min;
2) heating the solution in the step 1) to 50 ℃, then gradually adding 40 parts by mass of triethanolamine dodecylbenzene sulfonate into the solution in the step 1), and stirring for 1.5 hours at 800 r/min;
3) cooling to 25 ℃ to obtain the tackifier for the self-assembly cleaning acid liquor.
Tackifier 5 for cleaning self-assembly acid
1) Adding 25 parts by mass of xylitol into 35 parts by mass of water, and uniformly stirring at 800 r/min;
2) heating the solution in the step 1) to 50 ℃, then gradually adding 40 parts by mass of dodecylbenzene sulfonic acid diethanol amine salt into the solution in the step 1), and stirring for 1.5 hours at 800 r/min;
3) cooling to 25 ℃ to obtain the tackifier for the self-assembly cleaning acid liquor.
Tackifier 6 for cleaning self-assembly acid
1) Adding 25 parts by mass of pentaerythritol into 35 parts by mass of water, and uniformly stirring at 800 r/min;
2) heating the solution in the step 1) to 50 ℃, then gradually adding 40 parts by mass of dodecylbenzene sulfonic acid ethanolamine salt into the solution in the step 1), and stirring for 1.5 hours at 800 r/min;
3) cooling to 25 ℃ to obtain the tackifier for the self-assembly cleaning acid liquor.
Tackifier 7 for cleaning self-assembly acid
1) Adding 25 parts by mass of glycol into 35 parts by mass of water, and uniformly stirring at 800 r/min;
2) heating the solution in the step 1) to 50 ℃, then gradually adding 40 parts by mass of lauryl sulfuric acid triethanolamine salt into the solution in the step 1), and stirring for 1.5 hours at the speed of 800 r/min;
3) cooling to 25 ℃ to obtain the tackifier for the self-assembly cleaning acid liquor.
Tackifier 8 for cleaning self-assembly acid
1) Adding 25 parts by mass of glycol into 35 parts by mass of water, and uniformly stirring at 600 r/min;
2) heating the solution in the step 1) to 50 ℃, then gradually adding 40 parts by mass of dodecyl sulfate diethanolamine salt into the solution in the step 1), and stirring for 1.5 hours at 800 r/min;
3) cooling to 25 ℃ to obtain the tackifier for the self-assembly cleaning acid liquor.
Tackifier 9 for cleaning self-assembly acid
1) Adding 25 parts by mass of glycol into 35 parts by mass of water, and uniformly stirring at 800 r/min;
2) heating the solution in the step 1) to 50 ℃, then gradually adding 40 parts by mass of lauryl sulfuric acid ethanolamine salt into the solution in the step 1), and stirring for 1.5 hours at the speed of 800 r/min;
3) cooling to 25 ℃ to obtain the tackifier for the self-assembly cleaning acid liquor.
Tackifier 10 for cleaning self-assembling acid
1) Adding 25 parts by mass of glycol into 35 parts by mass of water, and uniformly stirring at 800 r/min;
2) heating the solution in the step 1) to 50 ℃, then gradually adding 40 parts by mass of triethanolamine dodecylsulfonate into the solution in the step 1), and stirring for 1.5 hours at 800 r/min;
3) cooling to 25 ℃ to obtain the tackifier for the self-assembly cleaning acid liquor.
Tackifier 11 for cleaning self-assembly acid
1) Adding 25 parts by mass of glycol into 35 parts by mass of water, and uniformly stirring at 800 r/min;
2) heating the solution in the step 1) to 50 ℃, then gradually adding 40 parts by mass of dodecyl sulfonic acid diethanolamine salt into the solution in the step 1), and stirring for 1.5 hours at 800 r/min;
3) cooling to 25 ℃ to obtain the tackifier for the self-assembly cleaning acid liquor.
Tackifier 12 for cleaning self-assembly acid
1) Adding 25 parts by mass of glycol into 35 parts by mass of water, and uniformly stirring at 800 r/min;
2) heating the solution in the step 1) to 50 ℃, then gradually adding 40 parts by mass of dodecyl sulfonic acid ethanolamine salt into the solution in the step 1), and stirring for 1.5 hours at the speed of 800 r/min;
3) cooling to 25 ℃ to obtain the tackifier for the self-assembly cleaning acid liquor.
Tackifier 13 for cleaning self-assembly acid
1) Adding 25 parts by mass of triethanolamine into 35 parts by mass of water, and uniformly stirring at 800 r/min;
2) heating the solution in the step 1) to 50 ℃, then gradually adding 40 parts by mass of dodecyl sulfonic acid ethanolamine salt into the solution in the step 1), and stirring for 1.5 hours at the speed of 800 r/min;
3) cooling to 25 ℃ to obtain the tackifier for the self-assembly cleaning acid liquor.
Tackifier 14 for cleaning self-assembling acid
1) Adding 25 parts by mass of diethanolamine into 35 parts by mass of water, and uniformly stirring at 800 r/min;
2) heating the solution in the step 1) to 50 ℃, then gradually adding 40 parts by mass of dodecyl sulfonic acid ethanolamine salt into the solution in the step 1), and stirring for 1.5 hours at the speed of 800 r/min;
3) cooling to 25 ℃ to obtain the tackifier for the self-assembly cleaning acid liquor.
Preparing a demulsifying and cleanup additive:
demulsifying and cleanup additive 1
20 parts by mass of polyoxypropylene polyoxyethylene propylene glycol ether and 2 parts by mass of lauramidopropyl betaine are dissolved in 77.95 parts by mass of water, the mixture is fully stirred and dissolved, and then 0.05 part by mass of perfluoro lauryl polyoxyethylene ether is added to be continuously stirred uniformly to prepare the demulsification cleanup additive.
Demulsifying and cleanup additive 2
Dissolving 25 parts by mass of polyoxypropylene polyoxyethylene propylene glycol ether and 10 parts by mass of lauramidopropyl betaine in 64.75 parts by mass of water, stirring to fully dissolve, adding 0.25 part by mass of perfluoro lauryl polyoxyethylene ether, and continuously stirring uniformly to obtain the demulsification cleanup additive.
Demulsifying and cleanup additive 3
30 parts by mass of polyoxypropylene polyoxyethylene propylene glycol ether and 20 parts by mass of lauramidopropyl betaine are dissolved in 49.5 parts by mass of water, the mixture is fully dissolved by stirring, and then 0.5 part by mass of perfluoro lauryl polyoxyethylene ether is added to be continuously stirred uniformly to prepare the demulsification cleanup additive.
Preparing acid liquor:
example 1
1) The self-assembly cleaning acid base solution is prepared from the following components in parts by mass: taking 100 parts of 15 wt% hydrochloric acid solution, slowly adding 0.5 part of thickening agent 1 for self-assembled cleaning acid at the rotating speed of 500r/min, continuously stirring at the rotating speed of 500r/min for half an hour to form uniform solution, then adding 0.6 part of iron ion stabilizer citric acid (sold in the market), 1.0 part of 2-methylquinoline benzyl quaternary ammonium salt corrosion inhibitor (sold in the market) and 0.6 part of demulsification cleanup additive 1, stirring uniformly at the rotating speed of 500r/min, sealing, standing at room temperature for 3 hours;
2) adding 1 part of the self-assembly cleaning acid tackifier 1 into the self-assembly cleaning acid base solution, and stirring for 8min at the rotating speed of 500r/min to form the self-assembly cleaning acid.
Example 2
1) The self-assembly cleaning acid base solution is prepared from the following components in parts by mass: taking 100 parts of 20 wt% hydrochloric acid solution, slowly adding 0.8 part of thickener 2 for self-assembled cleaning acid at the rotating speed of 500r/min, continuously stirring at the rotating speed of 600r/min for half an hour to form a uniform solution, then adding 1.0 part of iron ion stabilizer lactic acid (sold in the market), 2.5 parts of 1-aminoethyl-2-pentadecylimidazoline quaternary ammonium salt (sold in the market) and 0.8 part of demulsification discharge assistant 3, stirring uniformly at the rotating speed of 550r/min, sealing, standing at room temperature for 5 hours;
2) and adding 1.5 parts of self-assembly cleaning acid tackifier 2 into the self-assembly cleaning acid base solution, and stirring for 8min at the rotating speed of 1000r/min to form the self-assembly cleaning acid.
Example 3
1) The self-assembly cleaning acid base solution is prepared from the following components in parts by mass: taking 100 parts of hydrochloric acid solution with the concentration of 25 wt%, slowly adding 1.2 parts of thickening agent 3 for self-assembled cleaning acid at the rotating speed of 500r/min, continuously stirring for half an hour at the rotating speed of 500r/min to form uniform solution, then adding 1.5 parts of iron ion stabilizer acetic acid (sold in the market), 3.5 parts of formaldehyde-p-phenylenediamine-acetophenone corrosion inhibitor (sold in the market) and 1.2 parts of demulsification cleanup additive 3, stirring uniformly at the rotating speed of 500r/min, and standing at sealed room temperature for 6 hours;
2) adding 3.0 parts of the self-assembly cleaning acid tackifier 3 into the self-assembly cleaning acid base solution, and continuously stirring at the rotating speed of 500r/min for 8min to form the self-assembly cleaning acid.
Example 4
1) The self-assembly cleaning acid base solution is prepared from the following components in parts by mass: taking 100 parts of 20 wt% hydrochloric acid solution, slowly adding 1.0 part of thickener 4 for self-assembled cleaning acid at the rotating speed of 500r/min, continuously stirring for half an hour at the rotating speed of 500r/min to form a uniform solution, then adding 1.0 part of iron ion stabilizer lactic acid (sold in the market), 2.5 parts of 1-aminoethyl-2-pentadecylimidazoline quaternary ammonium salt (sold in the market) and 0.8 part of demulsification discharge assistant 3, stirring uniformly at the rotating speed of 500r/min, sealing, standing at room temperature for 3 hours;
2) and adding 1.0 part of self-assembly cleaning acid tackifier 8 into the self-assembly cleaning acid base solution, and stirring for 8min at the rotating speed of 500r/min to form the self-assembly cleaning acid.
Example 5
1) The self-assembly cleaning acid base solution is prepared from the following components in parts by mass: taking 100 parts of 20 wt% hydrochloric acid solution, slowly adding 1.0 part of thickener 5 for self-assembled cleaning acid at the rotating speed of 500r/min, continuously stirring for half an hour at the rotating speed of 500r/min to form a uniform solution, then adding 1.0 part of iron ion stabilizer ethylenediamine tetraacetic acid (commercially available), 2.5 parts of 1-aminoethyl-2-pentadecylimidazoline quaternary ammonium salt (commercially available) and 0.8 part of demulsification discharge assistant 3, stirring uniformly at the rotating speed of 500r/min, sealing, standing at room temperature for 3 hours;
2) and adding 1.5 parts of self-assembly cleaning acid tackifier 7 into the self-assembly cleaning acid base solution, and stirring at the rotating speed of 500r/min for 8min to form the self-assembly cleaning acid.
Example 6
1) The self-assembly cleaning acid base solution is prepared from the following components in parts by mass: taking 100 parts of 20 wt% hydrochloric acid solution, slowly adding 1.2 parts of thickening agent 6 for self-assembled cleaning acid at the rotating speed of 500r/min, continuously stirring at the rotating speed of 500r/min for half an hour to form a uniform solution, then adding 1.5 parts of iron ion stabilizer ethylenediamine tetraacetic acid (commercially available), 3.5 parts of formaldehyde-p-phenylenediamine-acetophenone corrosion inhibitor (commercially available) and 0.8 part of demulsification cleanup additive 3, stirring uniformly at the rotating speed of 500r/min, sealing, standing at room temperature for 5 hours;
2) and adding 1.5 parts of self-assembly cleaning acid tackifier 6 into the self-assembly cleaning acid base solution, and stirring for 3min at the rotating speed of 500r/min to form the self-assembly cleaning acid.
Example 7
1) The self-assembly cleaning acid base solution is prepared from the following components in parts by mass: taking 100 parts of 20 wt% hydrochloric acid solution, slowly adding 1.2 parts of thickening agent 7 for self-assembled cleaning acid at the rotation speed of 1000r/min, continuously stirring at the rotation speed of 1000r/min for half an hour to form a uniform solution, then adding 1.5 parts of iron ion stabilizer ascorbic acid (sold in the market), 3.5 parts of formaldehyde-p-phenylenediamine-acetophenone corrosion inhibitor (sold in the market) and 1.2 parts of demulsification cleanup additive 3, stirring uniformly at the rotation speed of 1000r/min, sealing, standing at room temperature for 5 hours;
2) and adding 1.5 parts of self-assembled cleaning acid tackifier 8 into the self-assembled cleaning acid base solution, and stirring for 3min at the rotating speed of 1000r/min to form the ground crosslinked underground steering temporary plugging crosslinked acid.
Example 8
1) The self-assembly cleaning acid base solution is prepared from the following components in parts by mass: taking 100 parts of 20 wt% hydrochloric acid solution, slowly adding 1.2 parts of thickening agent 8 for self-assembled cleaning acid at the rotating speed of 800r/min, continuously stirring at the rotating speed of 800r/min for half an hour to form a uniform solution, then adding 1.5 parts of iron ion stabilizer ascorbic acid (sold in the market), 3.5 parts of formaldehyde-p-phenylenediamine-acetophenone corrosion inhibitor (sold in the market) and 1.2 parts of demulsification cleanup additive 3, stirring uniformly at the rotating speed of 800r/min, sealing, standing at room temperature for 5 hours;
2) and adding 1.5 parts of self-assembly cleaning acid tackifier 9 into the self-assembly cleaning acid base solution, and stirring at the rotating speed of 800r/min for 8min to form the self-assembly cleaning acid.
Example 9
1) The self-assembly cleaning acid base solution is prepared from the following components in parts by mass: taking 100 parts of 20 wt% hydrochloric acid solution, slowly adding 1.2 parts of thickening agent 9 for self-assembled cleaning acid at the rotating speed of 500r/min, continuously stirring at the rotating speed of 500r/min for half an hour to form a uniform solution, then adding 1.5 parts of iron ion stabilizer ascorbic acid (sold on the market), 3.5 parts of formaldehyde-p-phenylenediamine-acetophenone corrosion inhibitor (sold on the market) and 1.2 parts of demulsification cleanup additive 3, stirring uniformly at the rotating speed of 500r/min, sealing, standing at room temperature for 5 hours;
2) and adding 1.5 parts of self-assembly cleaning acid tackifier 10 into the self-assembly cleaning acid base solution, and stirring at the rotating speed of 500r/min for 8min to form the self-assembly cleaning acid.
Example 10
1) The self-assembly cleaning acid base solution is prepared from the following components in parts by mass: taking 100 parts of 20 wt% hydrochloric acid solution, slowly adding 1.2 parts of thickening agent 10 for self-assembled cleaning acid at the rotating speed of 300r/min, continuously stirring at the rotating speed of 300r/min for 50min to form a uniform solution, then adding 1.5 parts of iron ion stabilizer ascorbic acid (sold in the market), 3.5 parts of formaldehyde-p-phenylenediamine-acetophenone corrosion inhibitor (sold in the market) and 1.2 parts of demulsification cleanup additive 3, stirring uniformly at the rotating speed of 300r/min, and standing at sealed room temperature for 5 hours;
2) and adding 1.5 parts of the self-assembly cleaning acid tackifier 12 into the self-assembly cleaning acid base solution, and stirring at the rotating speed of 300r/min for 8min to form the self-assembly cleaning acid.
Example 11
1) The self-assembly cleaning acid base solution is prepared from the following components in parts by mass: taking 100 parts of 20 wt% hydrochloric acid solution, slowly adding 1.0 part of thickening agent 11 for self-assembled cleaning acid at the rotating speed of 500r/min, continuously stirring at the rotating speed of 500r/min for half an hour to form a uniform solution, then adding 1.0 part of iron ion stabilizer ascorbic acid (sold in the market), 2.0 parts of 2-methylquinoline benzyl quaternary ammonium salt (sold in the market) and 1.0 part of demulsification cleanup additive 3, stirring uniformly at the rotating speed of 500r/min, sealing, standing at room temperature for 5 hours;
2) and adding 1.2 parts of self-assembly cleaning acid tackifier 13 into the self-assembly cleaning acid base solution, and stirring at the rotating speed of 500r/min for 8min to form the self-assembly cleaning acid.
Example 12
1) The self-assembly cleaning acid base solution is prepared from the following components in parts by mass: taking 100 parts of 20 wt% hydrochloric acid solution, slowly adding 1.0 part of thickening agent 12 for self-assembled cleaning acid at the rotating speed of 500r/min, continuously stirring at the rotating speed of 500r/min for half an hour to form a uniform solution, then adding 1.1 parts of iron ion stabilizer ascorbic acid (sold in the market), 3.0 parts of 2-methylquinoline benzyl quaternary ammonium salt (sold in the market) and 1.0 part of demulsification cleanup additive 3, stirring uniformly at the rotating speed of 500r/min, sealing, standing at room temperature for 5 hours;
2) and adding 1.2 parts of the self-assembly cleaning acid tackifier 14 into the self-assembly cleaning acid base solution, and stirring at the rotating speed of 500r/min for 8min to form the self-assembly cleaning acid.
Example 13
1) The self-assembly cleaning acid base solution is prepared from the following components in parts by mass: taking 100 parts of 20 wt% hydrochloric acid solution, slowly adding 1.0 part of thickening agent 12 for self-assembled cleaning acid at the rotating speed of 500r/min, continuously stirring at the rotating speed of 500r/min for half an hour to form a uniform solution, then adding 1.1 parts of iron ion stabilizer ascorbic acid (sold in the market), 3.0 parts of 2-methylquinoline benzyl quaternary ammonium salt (sold in the market) and 1.0 part of demulsification cleanup additive 3, stirring uniformly at the rotating speed of 500r/min, sealing, standing at room temperature for 5 hours;
2) adding 2.5 parts of the self-assembly cleaning acid tackifier 14 into the self-assembly cleaning acid base solution, and stirring for 8min at the rotating speed of 500r/min to form the self-assembly cleaning acid.
Example 14
1) The self-assembly cleaning acid base solution is prepared from the following components in parts by mass: taking 100 parts of 20 wt% hydrochloric acid solution, slowly adding 1.2 parts of thickening agent 12 for self-assembled cleaning acid at the rotating speed of 500r/min, continuously stirring at the rotating speed of 500r/min for half an hour to form a uniform solution, then adding 1.1 parts of iron ion stabilizer ascorbic acid (sold in the market), 3.0 parts of 2-methylquinoline benzyl quaternary ammonium salt (sold in the market) and 1.0 part of demulsification cleanup additive 3, stirring uniformly at the rotating speed of 500r/min, sealing, standing at room temperature for 5 hours;
2) and adding 2.0 parts of self-assembly cleaning acid tackifier 5 into the self-assembly cleaning acid base solution, and stirring at the rotating speed of 500r/min for 8min to form the self-assembly cleaning acid.
Example 15
To further demonstrate the technical effect of the present invention, the performance of the self-assembled cleaning acids prepared in examples 1 to 14 was tested.
1) Evaluating the temperature resistance and shear resistance of the self-assembled cleaning acid solution prepared in the step 2) according to the industrial standard SY/T5107-2005, namely, the temperature resistance and shear resistance are evaluated at 160 ℃ for 170s-1And shearing for 1h to measure the temperature resistance and shearing resistance of the self-assembled cleaning acid solution.
2) And (3) evaluating the gel breaking performance of the self-assembled cleaning acid liquid prepared in the step 2) according to an industrial standard SY/T5107-2005. To 100ml of the above acid solution, 0.5% sodium bromate was added, gel breaking time was observed at 90 ℃ and the gel breaking residue was measured at room temperature.
The results are shown in Table 1.
TABLE 1 tackifying performance and temperature and shear resistance
The performance test results show that the self-assembly cleaning acid solution has good delayed tackifying performance, tackifying performance and temperature and shear resistance. The self-assembled cleaning acid system can thoroughly break the gel, has low content of gel breaking liquid residues and has wide application prospect.
While the present application 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 present application. In addition, many modifications may be made to adapt a particular situation, material, composition of matter, and method to the objective, spirit and scope of the present application. All such modifications are intended to be included within the scope of the claims of this application.
Claims (16)
1. A method of preparing an acid system comprising the steps of:
1) adding a thickening agent into the hydrochloric acid solution at a first stirring speed, and stirring at a second stirring speed to obtain a first acid solution;
2) sequentially adding an iron ion stabilizer, a corrosion inhibitor and a demulsification cleanup additive into the first acid liquor, stirring uniformly at a third stirring speed, and standing to obtain a base solution;
3) and adding a tackifier into the base solution, and stirring at a fourth stirring speed to obtain the acid liquor system.
2. The method according to claim 1, characterized in that the thickener is prepared as follows:
A) dissolving acrylamide, 2-acrylamide-2-methylpropanesulfonic acid and a quaternary ammonium salt type polymerizable surfactant in water to obtain a first solution;
B) adding a cosolvent, a chain transfer agent, a complexing agent and an active agent into the first solution, and uniformly mixing to obtain a second solution;
C) adjusting the pH value of the second solution to 6.5-7.5 to obtain a third solution; then adding the third solution into a polymerization device, and introducing nitrogen;
D) adding a water-soluble azo initiator, a reducing agent and an oxidizing agent into the polymerization device to obtain a fourth solution, and then continuously introducing nitrogen;
E) maintaining the temperature of the fourth solution after the temperature of the fourth solution rises, thereby obtaining a polymer jelly;
F) and (3) granulating, drying, crushing and sieving the polymer jelly to obtain the thickening agent in a dry powder state.
3. The method according to claim 2, wherein the quaternary ammonium salt type polymerizable surfactant is at least one selected from the group consisting of tetradecyldimethylammonium chloride, hexadecyldimethylallylammonium chloride, octadecyldimethylammonium chloride, methacryloyloxyethyldimethylhexadecylammonium bromide, and dimethyloctadecylammonium (2-hydroxy-3-acrylamidopropyl) chloride.
4. The method according to claim 2 or 3, wherein the co-solvent is selected from at least one of urea, thiourea and triethanolamine; and/or
The chain transfer agent is selected from at least one of sodium formate, potassium formate and isopropanol; and/or
The complexing agent is at least one of ethylene diamine tetraacetic acid disalt, ethylene diamine tetraacetic acid tetrasalt and triethylene tetramine pentaacetate; and/or
The activator is selected from at least one of N, N-tetramethyl ethylene diamine, ethylene diamine and triethanolamine; and/or
The oxidant is selected from at least one of ammonium persulfate, potassium persulfate and hydrogen peroxide; and/or
The reducing agent is selected from at least one of sodium bisulfite, sodium sulfite and ferrous ammonium sulfate; and/or
The water-soluble azo initiator is selected from azobisisobutylamidine hydrochloride and/or azobisisobutylimidazoline hydrochloride.
5. The method according to any one of claims 2 to 4, characterized in that the acrylamide has 20 to 50 parts by mass, the 2-acrylamido-2-methylpropanesulfonic acid has 50 to 80 parts by mass, and the quaternary ammonium salt type polymerizable surfactant has 0.8 to 3.0 parts by mass;
preferably, the acrylamide has 25 to 45 parts by mass, the 2-acrylamido-2-methylpropanesulfonic acid has 53 to 73 parts by mass, and the quaternary ammonium salt type polymerizable surfactant has 1 to 2.5 parts by mass;
preferably, the total mass of the acrylamide, the 2-acrylamido-2-methylpropanesulfonic acid, and the quaternary ammonium salt type polymerizable surfactant accounts for 25 wt% to 29 wt% of the total mass of the first solution;
preferably, the cosolvent is used in an amount of 1 wt% to 3 wt%, the chain transfer agent is used in an amount of 0.05 wt% to 0.1 wt%, the complexing agent is used in an amount of 0.03 wt% to 0.08 wt%, the activator is used in an amount of 0.05 wt% to 0.1 wt%, the oxidizing agent is used in an amount of 0.01 wt% to 0.06 wt%, the reducing agent is used in an amount of 0.005 wt% to 0.03 wt%, and the water-soluble azo initiator is used in an amount of 0.02 wt% to 0.06 wt%, based on 100% by mass of the total of the acrylamide, the 2-acrylamide-2 methylpropanesulfonic acid, and the quaternary ammonium salt type polymerizable surfactant.
6. The method according to any one of claims 2 to 5, wherein in step B), the second solution obtained by uniformly mixing is cooled to 5 ℃ to 10 ℃; and/or in step C), the third solution obtained after pH value adjustment is cooled to 5 ℃ to 10 ℃; and/or in step E), the temperature of the heat preservation is 60 ℃ to 80 ℃; and/or in step F), the temperature for drying is 60 ℃ to 80 ℃;
preferably, in step C) and step D), the nitrogen is introduced independently for a period of 20 to 30 minutes; and/or in step E), the incubation time is between 4 and 5 hours.
7. A process according to any one of claims 1 to 6, characterized in that the tackifier is prepared as follows:
I) mixing polyalcohol and/or polyalcohol amine with water to obtain a first solution;
II) adding an ionic liquid surfactant to the first solution to obtain the viscosifier.
8. The method according to claim 7, characterized in that the total content of the polyhydric alcohol and/or the polyhydric alcohol amine is 15-35% by mass, and the ionic liquid surfactant is 30-50%;
preferably, the total content of the polyhydric alcohol and/or the polyalcohol amine is 15-30% by mass percentage, and the ionic liquid surfactant is 35-45%.
9. The method according to claim 7 or 8, wherein the polyol comprises at least one selected from the group consisting of glycerol, ethylene glycol, xylitol, sorbitol, and pentaerythritol; and/or
The polyalcohol amine comprises at least one selected from ethylene glycol, triethanolamine and diethanolamine; and/or
The ionic liquid surfactant comprises at least one selected from the group consisting of triethanolamine dodecylbenzene sulfonate, diethanolamine dodecylbenzene sulfonate, ethanolamine dodecylbenzene sulfonate, triethanolamine dodecylsulfate, diethanolamine dodecylsulfate, ethanolamine dodecylsulfate, triethanolamine dodecylsulfonate, diethanolamine dodecylsulfonic acid, and ethanolamine dodecylsulfonic acid.
10. The method according to any one of claims 7 to 9, wherein in step I), the polyol and/or the polyalcohol amine is mixed with water uniformly under stirring at a fifth stirring speed; and/or in step II) the tackifier is obtained after stirring at a sixth stirring speed for 1 to 2 hours at 40 to 60 ℃.
11. The method of any one of claims 1 to 10, wherein the first stirring speed, the second stirring speed, the third stirring speed, the fourth stirring speed, the fifth stirring speed, and the sixth stirring speed are independently selected from 300r/min to 1000 r/min.
12. The method according to any one of claims 1 to 11, wherein the stirring time at the second stirring speed is 30 to 50 minutes; and/or
Standing for 3 to 6 hours after uniformly stirring at a third stirring speed; and/or
Stirring at a fourth stirring speed for 3 to 10 min.
13. The method according to any one of claims 1 to 12, wherein in step 2), after stirring uniformly at the third stirring speed, the mixture is left standing in a sealed state at a natural ambient temperature.
14. The method according to any one of claims 1 to 13, wherein 100 parts by mass of the hydrochloric acid solution, 0.5 to 1.2 parts by mass of the thickener, 1 to 3.5 parts by mass of the corrosion inhibitor, 0.6 to 1.5 parts by mass of the iron ion stabilizer, 0.6 to 1.2 parts by mass of the demulsification cleanup additive, and 1 to 3 parts by mass of the tackifier; wherein the mass concentration of the hydrochloric acid solution is 15 to 30 percent;
preferably, the thickening agent is 1 to 1.2 parts by mass, the iron ion stabilizer is 1 to 1.5 parts by mass, the corrosion inhibitor is 2.5 to 3.5 parts by mass, the demulsification cleanup additive is 1 to 1.2 parts by mass, and the tackifier is 1.5 to 2.5 parts by mass; the mass concentration of the hydrochloric acid solution is 15-20%.
15. The method according to any one of claims 1 to 14, wherein the corrosion inhibitor is selected from at least one of imidazolines, quinoline quaternaries, ketoaldehyde amine condensates, mannich bases; preferably, the corrosion inhibitor is selected from at least one of 1-aminoethyl-2-pentadecylimidazoline quaternary ammonium salt, 2-methylquinoline benzyl quaternary ammonium salt and formaldehyde-p-phenylenediamine-acetophenone;
preferably, the iron ion stabilizer is an organic acid; more preferably, the iron ion stabilizer is at least one selected from the group consisting of citric acid, lactic acid, acetic acid, ethylenediaminetetraacetic acid and ascorbic acid.
16. The method of any one of claims 1 to 15, wherein the demulsifying cleanup additive is prepared by:
dissolving 2-20 parts by mass of betaine zwitterionic surfactant and 20-30 parts by mass of polyoxypropylene polyoxyethylene propylene glycol ether in 49-78 parts by mass of water, stirring until the components are fully dissolved, adding 0.05-0.5 part by mass of perfluoro lauryl polyoxyethylene ether, and continuously stirring uniformly to obtain the demulsification cleanup additive for the cross-linking acid;
preferably, the betaine zwitterionic surfactant is at least one of lauramidopropyl betaine, cocamidopropyl betaine, and dodecyl dimethyl betaine.
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