CN111171230A - Self-assembled thickening agent for cleaning acid liquor - Google Patents
Self-assembled thickening agent for cleaning acid liquor Download PDFInfo
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Abstract
The invention provides a self-assembly thickening agent for cleaning acid liquor. The preparation method comprises the following steps: 1) dissolving acrylamide, 2-acrylamide-2-methylpropanesulfonic acid and a quaternary ammonium salt type polymerizable surfactant in water to obtain a first solution; 2) adding a cosolvent, a chain transfer agent, a complexing agent and an activating agent into the first solution, and uniformly mixing to obtain a second solution; 3) 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; 4) 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; 5) maintaining the temperature of the fourth solution after the temperature of the fourth solution rises, thereby obtaining a polymer jelly; 6) and (3) granulating, drying, crushing and sieving the polymer jelly to obtain the thickening agent in a dry powder state.
Description
Technical Field
The invention provides a self-assembly thickening agent for cleaning acid liquor and a preparation method thereof.
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 preparation method of a thickening agent, which comprises the following steps:
1) dissolving acrylamide, 2-acrylamide-2-methylpropanesulfonic acid and a quaternary ammonium salt type polymerizable surfactant in water to obtain a first solution;
2) adding a cosolvent, a chain transfer agent, a complexing agent and an activating agent into the first solution, and uniformly mixing to obtain a second solution;
3) 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;
4) 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;
5) maintaining the temperature of the fourth solution after the temperature of the fourth solution rises, thereby obtaining a polymer jelly;
6) 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.
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.
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, it is preferable that 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 a specific embodiment, in step 2), the second solution obtained by uniformly mixing is cooled to 5 ℃ to 10 ℃.
In a particular embodiment, in step 3), the third solution obtained after adjusting the pH value is cooled to 5 ℃ to 10 ℃.
In one embodiment, in step 5), the temperature of the incubation is 60 ℃ to 80 ℃.
In one embodiment, in step 6), the temperature of the drying is 60 ℃ to 80 ℃.
In one embodiment, in step 3), the nitrogen is introduced for a period of 20 to 30 minutes.
In one embodiment, in step 4), the nitrogen is introduced for a period of 20 to 30 minutes.
In one embodiment, in step 5), the incubation time is from 4 to 5 hours.
In one embodiment, in step 6), the mesh size of the screen is 20 to 40 mesh.
The second invention provides a thickening agent prepared by the preparation method of any one of the first invention.
The invention has the beneficial effects that:
(1) the thickening agent prepared by the method has the advantages of few monomer types, low price and simple and controllable synthesis method;
(2) the thickening agent prepared by the invention contains more hydrophobic monomers, so that the temperature resistance of the acid liquor and the tackifying performance of the acid liquor can be improved;
(3) the thickening agent for the self-assembly acid and the thickening agent can form a reversible cross-linked gel acid solution which has high viscosity and can be selected and hung through self-assembly.
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 the drugs were commercially available products.
Example 1
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.
Example 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.
Example 3
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.
Example 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.
Example 5
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, 0.0 wt% of 3 wt% of triethylene pentaacetic acid pentasodium and 0.08 wt% of N, N-tetramethyl ethylene diamine 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 7.0, 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.
Example 6
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.
Example 7
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.
Example 8
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.
Example 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.
Example 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.
Example 11
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.
Example 12
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.
Comparative example 1
1) Preparing a polymerization monomer aqueous solution, adding 15.0 parts of acrylamide, 83 parts of AMPS and 4.0 parts of tridecyl 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 wt% of thiourea, 0.1 wt% of potassium formate, 0.08 wt% of triethylene tetramine 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 value to 5, 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 0.1 wt% of azodiisobutyl imidazoline hydrochloride, 0.1 wt% of ammonium ferrous sulfate and 0.1 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 4 hours when the temperature of the system rises to 80 ℃;
6) and taking out the polymerized rubber blocks, granulating, drying at 80 ℃ until the water content is within 5 wt%, crushing, and sieving by a 30-mesh sieve to obtain the thickening agent dry powder for the self-assembled cleaning acid liquor.
Comparative example 2
1) Preparing a polymerization monomer aqueous solution, adding 65.0 parts of acrylamide, 32 parts of AMPS and 0.5 part of octadecyl 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 wt% of thiourea, 0.1 wt% of potassium formate, 0.08 wt% of triethylene tetramine 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 above solution to adjust pH to 12, cooling for 30min, cooling to 10 deg.C in 10 deg.C water bath, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.1 wt% of azodiisobutyl imidazoline hydrochloride, 0.2 wt% of ammonium ferrous sulfate and 0.1 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 4 hours when the temperature of the system rises to 80 ℃;
6) and taking out the polymerized rubber blocks, granulating, drying at 80 ℃ until the water content is within 5 wt%, crushing, and sieving by a 30-mesh sieve to obtain the thickening agent dry powder for the self-assembled cleaning acid liquor.
Example 13
The preparation method of the self-assembled cleaning acid viscosifier comprises the following steps:
to further demonstrate the technical effect of the present invention, the performance of the thickeners prepared in examples 1 to 12 and comparative examples 1 and 2 were tested.
The thickening agent synthesized in the above embodiments is dissolved in hydrochloric acid at 500r/min, and then corrosion inhibitor 2-methylquinoline benzyl quaternary ammonium salt (commercially available) is added at 500r/min to make the final contents of thickening agent, hydrochloric acid and corrosion inhibitor 1 wt%, 20 wt% and 3 wt%, respectivelyAnd percent, stirring uniformly to obtain gelled acid, measuring the apparent viscosity of the gelled acid by using a six-speed viscometer, and measuring the viscosity every 3 minutes until the viscosity is stable. Then adding 1.5 parts by mass of tackifier into every 100 parts by mass of gelled acid, and stirring for 8min at the rotating speed of 500r/min to form the self-assembled cleaning acid liquid. According to the industrial standard SY/T5107-2005, the temperature is 160 ℃ and the time is 170s-1And shearing for 1h, and measuring the temperature resistance and shearing resistance of the self-assembled cleaning acid solution.
The tackifier is prepared as follows:
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.
The test results are shown in Table 1. As can be seen from Table 1, the dissolution time of the polymer thickener synthesized by the invention in acid is less than 20min, the apparent viscosity of the base solution is about 70mPa.s, the tail viscosity of the self-assembled cleaning acid solution is more than 70mPa.s after the self-assembled cleaning acid solution is sheared at a high temperature of 160 ℃, and the performance requirement of the acid solution system is met. While the dissolution time of comparative example 1 is more than 120min, and the tail viscosity of comparative example 2 is 15mPa.s, which can not meet the field requirement.
TABLE 1
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 (10)
1. A method for preparing a thickener, comprising the steps of:
1) dissolving acrylamide, 2-acrylamide-2-methylpropanesulfonic acid and a quaternary ammonium salt type polymerizable surfactant in water to obtain a first solution;
2) adding a cosolvent, a chain transfer agent, a complexing agent and an activating agent into the first solution, and uniformly mixing to obtain a second solution;
3) 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;
4) 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;
5) maintaining the temperature of the fourth solution after the temperature of the fourth solution rises, thereby obtaining a polymer jelly;
6) and (3) granulating, drying, crushing and sieving the polymer jelly to obtain the thickening agent in a dry powder state.
2. The production method according to claim 1, 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 dimethyloctadecyl (2-hydroxy-3-acrylamidopropyl) ammonium chloride.
3. The method according to claim 1 or 2, wherein the co-solvent is at least one selected from 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.
4. The production method according to any one of claims 1 to 3, 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.
5. The production method according to any one of claims 1 to 4, characterized in that the total mass of the acrylamide, the 2-acrylamido-2-methylpropanesulfonic acid, and the quaternary ammonium salt type polymerizable surfactant accounts for 25 to 29 wt% of the total mass of the first solution.
6. The production method according to any one of claims 1 to 5, wherein 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-based 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, 2-acrylamido-2-methylpropanesulfonic acid, and the quaternary ammonium salt-based polymerizable surfactant.
7. The method according to any one of claims 1 to 6, wherein in step 2), the second solution obtained by mixing uniformly is cooled to 5 ℃ to 10 ℃; and/or
In the step 3), the third solution obtained after the pH value is adjusted is cooled to 5-10 ℃; and/or
In the step 5), the temperature for heat preservation is 60-80 ℃; and/or
In step 6), the temperature of the drying is 60 ℃ to 80 ℃.
8. The production method according to any one of claims 1 to 7, wherein in step 3), the nitrogen gas is introduced for 20 to 30 minutes; and/or
In the step 4), introducing nitrogen for 20 to 30 minutes; and/or
In step 5), the incubation time is 4 to 5 hours.
9. The production method according to any one of claims 1 to 8, wherein the number of meshes of the sieve in step 6) is 20 to 40 meshes.
10. A thickener obtained by the production method according to any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979870A (en) * | 2021-03-08 | 2021-06-18 | 西南石油大学 | Instant drag reducer and preparation method thereof |
| CN116262801A (en) * | 2021-12-15 | 2023-06-16 | 中国石油天然气股份有限公司 | High-salt-resistance shearing-resistance profile control agent and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4762862A (en) * | 1986-04-04 | 1988-08-09 | Dai-Ichi Kogyo Seiyaku Co. Ltd. | Process for preparing high molecular weight acrylic polymers |
| CN101412906A (en) * | 2008-12-05 | 2009-04-22 | 河南省科学院高新技术研究中心 | Acid fracturing thickening agent and preparation thereof |
| CN106008803A (en) * | 2016-05-26 | 2016-10-12 | 中国石油集团渤海钻探工程有限公司 | High temperature resistant cross-linked acid thickening agent and preparation method thereof |
| CN108715757A (en) * | 2018-07-03 | 2018-10-30 | 成都劳恩普斯科技有限公司 | A kind of preparation method of acidproof thickening agent and its application in multifunctional acid and acid-resistant pressing crack liquid |
-
2018
- 2018-11-13 CN CN201811346413.XA patent/CN111171230B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4762862A (en) * | 1986-04-04 | 1988-08-09 | Dai-Ichi Kogyo Seiyaku Co. Ltd. | Process for preparing high molecular weight acrylic polymers |
| CN101412906A (en) * | 2008-12-05 | 2009-04-22 | 河南省科学院高新技术研究中心 | Acid fracturing thickening agent and preparation thereof |
| CN106008803A (en) * | 2016-05-26 | 2016-10-12 | 中国石油集团渤海钻探工程有限公司 | High temperature resistant cross-linked acid thickening agent and preparation method thereof |
| CN108715757A (en) * | 2018-07-03 | 2018-10-30 | 成都劳恩普斯科技有限公司 | A kind of preparation method of acidproof thickening agent and its application in multifunctional acid and acid-resistant pressing crack liquid |
Non-Patent Citations (1)
| Title |
|---|
| 贾文峰等: "高温携砂酸液体系及其性能评价", 《钻井液与完井液》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979870A (en) * | 2021-03-08 | 2021-06-18 | 西南石油大学 | Instant drag reducer and preparation method thereof |
| CN112979870B (en) * | 2021-03-08 | 2022-04-19 | 西南石油大学 | Instant drag reducer and preparation method thereof |
| CN116262801A (en) * | 2021-12-15 | 2023-06-16 | 中国石油天然气股份有限公司 | High-salt-resistance shearing-resistance profile control agent and preparation method and application thereof |
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