CN111117589A - Thickening agent and preparation method thereof - Google Patents
Thickening agent and preparation method thereof Download PDFInfo
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Abstract
The application provides a thickening agent and a preparation method thereof. The raw materials of the thickening agent comprise an acrylamide monomer, an acid-resistant monomer, a water-soluble monomer containing dimethylamino, a quaternary ammonium salt type polymerizable surfactant, a cosolvent, a chain transfer agent, a complexing agent, an activating agent, an oxidizing agent, a reducing agent, a water-soluble azo initiator and a water-soluble anionic surfactant.
Description
Technical Field
The application provides a thickening agent and a preparation method thereof, and particularly provides an acid-resistant thickening agent which is suitable for both high-temperature cross-linking acid and gelling acid.
Background
In recent years, carbonate reservoirs of deep wells and ultra-deep wells become the key field of oil and gas exploration and development, and medium petrochemicals and medium petroleum have made a certain breakthrough. The temperature of a high-temperature carbonate reservoir which is developed in northwest China at present is generally over 160 ℃, and the aim of economic production is fulfilled by acid fracturing modification. The acid fracturing modification mainly adopts a composite acid fracturing process, and realizes communication between a reservoir body and a crack of the deep fracture-cave carbonate rock reservoir through slickwater cooling, fracturing fluid crack making, gelling acid acidification and crosslinking acid deep acid fracturing. However, the gelling acid and the crosslinking acid system generally use two different thickeners, which have the problems of complex liquid preparation, poor compatibility of the gelling acid and the crosslinking acid system, poor temperature resistance and the like. The gelling acid system thickener is a cationic thickener (synthesis and performance evaluation of high-temperature acid gelling agent [ J ]. the college of high-petrochemical engineering and the like, 2017,30(1):31-35.), the high-temperature crosslinking acid thickener is an anionic thickener (synthesis and performance evaluation of high-temperature crosslinking acid thickener [ J ]. scientific technology and engineering, 2016,16(35): 176-. Meanwhile, the existing field gelled acid and crosslinked acid system has the problem of unstable placement, and due to the limitation of liquid preparation and transportation conditions, the liquid preparation, transportation and acid fracturing of the acid solution can be completed within more than 7 days, and the problems of weak crosslinking or viscosity reduction and the like occur in the placement process of the acid solution system, so that the problems of difficult field pump injection or poor acid fracturing effect and the like are caused.
Disclosure of Invention
One of the applications provides a thickening agent, which comprises raw materials of an acrylamide monomer, an acid-resistant monomer, a water-soluble monomer containing dimethylamino, a quaternary ammonium salt polymerizable surfactant, a cosolvent, a chain transfer agent, a complexing agent, an activating agent, an oxidizing agent, a reducing agent, a water-soluble azo initiator and a water-soluble anionic surfactant.
In one embodiment, the acid resistant monomer is selected from at least one of 2-acrylamido-2-methylpropanesulfonic acid, acryloyloxyethyltrimethylammonium chloride, and methacryloyloxyethyltrimethylammonium chloride.
In one embodiment, the dimethylamino-containing water-soluble monomer is selected from methacryloyloxyethyldimethylamine and/or N, N-dimethylacrylamide.
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, and the like.
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, 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 oxidant 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 water-soluble anionic surfactant is selected from at least one selected from the group consisting of sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, triethanolamine dodecylsulfate, triethanolamine dodecylbenzenesulfonate, and the like.
In one embodiment, the acrylamide monomer has 30 to 50 parts by mass, the acid-resistant monomer has 50 to 70 parts by mass, the dimethylamino group-containing water-soluble monomer has 1.4 to 2 parts by mass, and the quaternary ammonium salt type polymerizable surfactant has 0.2 to 1 part by mass; the total mass of the acrylamide monomer, the acid-resistant monomer, and the water-soluble monomer containing a dimethylamino group and a quaternary ammonium salt type polymerizable surfactant is 100% (note that the total mass of the aqueous solutions of the four monomers is not 100%), 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%, the water-soluble azo initiator is used in an amount of 0.02 wt% to 0.06 wt%, and the water-soluble anionic surfactant is used in an amount of 3 wt% to 5 wt%.
Preferably, in one embodiment, the acrylamide monomer has 30 to 45 parts by mass, the acid-resistant monomer has 50 to 64 parts by mass, the dimethylamino group-containing water-soluble monomer has 1.4 to 1.7 parts by mass, and the quaternary ammonium salt-type polymerizable surfactant has 0.2 to 0.6 parts by mass during the preparation of the second acid with the thickener.
Preferably, in one embodiment, the acrylamide monomer has 35 to 45 parts by mass, the acid-resistant monomer has 53 to 64 parts by mass, the dimethylamino group-containing water-soluble monomer has 1.5 to 1.7 parts by mass, and the quaternary ammonium salt type polymerizable surfactant has 0.3 to 0.6 parts by mass.
The second application provides a preparation method of the thickening agent, which comprises the following steps:
1) dissolving the acrylamide, the acid-resistant monomer, the dimethylamino-containing water-soluble monomer and the quaternary ammonium salt type polymerizable surfactant in water to obtain a first solution;
2) adding the cosolvent, the chain transfer agent, the complexing agent, the activating agent and the water-soluble anionic surfactant into the first solution, and uniformly mixing to obtain a second solution;
3) adjusting the pH value of the second solution to 9-10 to obtain a third solution; then adding the third solution into a polymerization device, and introducing nitrogen;
4) adding the water-soluble azo initiator, the reducing agent and the oxidant 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 a specific embodiment, the total mass of the acrylamide, the acid-resistant monomer, the dimethylamino group-containing water-soluble monomer, and the quaternary ammonium salt-type polymerizable surfactant accounts for 25 wt% to 29 wt% of the total mass of the first solution.
Depending on the type of monomer, some will release heat, and some will not; to facilitate subsequent low temperature polymerization, the second solution is preferably cooled. In a specific embodiment, in step 2), the second solution obtained by uniformly mixing 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 3), 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 one embodiment, the nitrogen is introduced independently for 20 to 30 minutes in step 3) and step 4).
In step 4), the azo 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.
The step 5) is mainly a polymerization process, a certain amount of heat is released in the polymerization process, and when the heat is released to a certain degree, namely 60 ℃ to 80 ℃, the heat preservation is carried out.
In one embodiment, in step 5), the temperature of the incubation is 60 ℃ to 80 ℃.
In one embodiment, in step 5), the incubation time is from 4 to 5 hours.
In a particular embodiment, in step 6), the size of the granules is from 0.3 to 0.5 cm.
In one embodiment, in step 6), the temperature of the drying is 60 ℃ to 80 ℃.
In one embodiment, in step 6), 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 6), the mesh size of the screen is 20 to 40 mesh.
The beneficial effect of this application:
(1) the thickening agent can be used as a general acid thickening agent, can be used for cross-linked acid tackifying and can also be used for gelled acid tackifying, so that the field liquid preparation process is simplified, and the problem of poor compatibility among different acid liquids is solved.
(2) The thickener of the present application is capable of withstanding high temperatures of 200 ℃.
(3) The thickener of the present application can have acid resistance and good solubility.
(4) The thickening agent can improve the elasticity and the shearing recovery performance of the acid liquor, and further improve the retarding and shearing resistance performance of the acid liquor.
(5) The gelled acid or cross-linked acid system prepared by the thickening agent is placed at room temperature (25 +/-5 ℃) for more than 10 days, the viscosity is not increased, the performance is stable, and a great problem in site construction is solved.
(6) The synthesis method of the thickening agent is simple and controllable.
(7) The hydrophobic association polymer dissolution performance is improved by the hydrophobic association polymer synthesis method.
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 Monomer (AMPS), 1.4 parts of N, N-dimethylacrylamide and 0.3 part of hexadecyl dimethyl allyl ammonium chloride monomer into a beaker according to parts by mass, and adding distilled water for dissolving to enable the total mass content of the four monomers to be 25 wt%;
2) adding 1.0% of urea, 0.05% of sodium formate, 0.03% of tetrasodium ethylenediamine tetraacetate, 3.0% of sodium dodecyl sulfate and 0.05% of ethylenediamine into the monomer aqueous solution (the total mass of the four 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 9, cooling for 30min, cooling to 5 deg.C in water bath at 5 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.02% azodiisobutyl amidine hydrochloride, 0.005% sodium bisulfite and 0.01% ammonium persulfate water 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 rubber 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 cross-linked acid/gelled acid common acid-resistant thickening agent dry powder.
Example 2
1) Preparing a polymerization monomer aqueous solution, adding 45 parts of acrylamide, 53 parts of acryloyloxyethyl trimethyl ammonium chloride (DAC), 1.7 parts of methacryloyloxyethyl dimethyl amine and 0.6 part of methacryloyloxyethyl dimethyl hexadecyl ammonium bromide monomer into a beaker according to parts by mass, and adding distilled water for dissolving to ensure that the total mass content of the four monomers is 29 wt%;
2) adding 3.0% of thiourea, 0.08% of potassium formate, 0.05% of disodium ethylene diamine tetraacetate, 5.0% of sodium dodecyl sulfate and 0.1% of N, N-tetramethyl ethylenediamine into the monomer aqueous solution (the total mass of the four 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 9.5, 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 0.06% azobisisobutyronitrile hydrochloride, 0.03% sodium sulfite and 0.06% potassium persulfate aqueous solution into the mother liquor in sequence, continuously introducing nitrogen for 20min until the mixture becomes viscous, and 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 rubber 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 cross-linked acid/gelled acid common acid-resistant thickening agent dry powder.
Example 3
1) Preparing a polymerization monomer aqueous solution, adding 40 parts of acrylamide, 58 parts of DAC, 1.5 parts of methacryloxyethyl dimethylamine and 0.5 part of methacryloxyethyl dimethyl hexadecyl ammonium bromide monomer into a beaker according to parts by mass, and adding distilled water for dissolving to ensure that the total mass content of the four monomers is 27 wt%;
2) adding 2.0% of thiourea, 0.04% of potassium formate, 0.03% of disodium ethylene diamine tetraacetate, 4.0% of sodium dodecyl sulfate and 0.08% of N, N-tetramethylethylenediamine into the monomer aqueous solution (the total mass of the four monomers is 100%), stirring and dissolving uniformly, putting into a water bath at 8 ℃ for cooling for 30min, and cooling to 8 ℃;
3) adding a certain amount of sodium carbonate into the above solution to adjust pH to 10, cooling for 30min, cooling to 8 deg.C in water bath at 8 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.04% azobisisobutyronitrile hydrochloride, 0.02% sodium sulfite and 0.04% potassium persulfate aqueous solution into the mother liquor in sequence, continuously introducing nitrogen for 20min until the mixture becomes viscous, and 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 rubber 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 cross-linked acid/gelled acid common acid-resistant thickening agent dry powder.
Example 4
1) Preparing a polymerization monomer aqueous solution, adding 42 parts of acrylamide, 56 parts of methacryloxyethyl trimethyl ammonium chloride (DMC), 1.5 parts of methacryloxyethyl dimethyl amine and 0.5 part of methacryloxyethyl dimethyl hexadecyl ammonium bromide monomer into a beaker according to parts by mass, and adding distilled water for dissolving to enable the total mass content of the four monomers to be 26 wt%;
2) adding 2.0% of thiourea, 0.04% of potassium formate, 0.03% of triethylene tetramine pentaacetic acid pentasodium salt, 3.5% of sodium dodecyl benzene sulfonate and 0.08% of N, N-tetramethyl ethylenediamine into the monomer aqueous solution (the total mass of the four monomers is 100%), stirring and dissolving uniformly, and cooling in a water bath at 10 ℃ for 30min to ensure that the temperature is cooled to 10 ℃;
3) adding a certain amount of sodium carbonate into the above solution to adjust pH to 10, 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 0.05% of azobisisobutyronitrile hydrochloride, 0.015% of sodium sulfite and 0.03% 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 rubber 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 cross-linked acid/gelled acid common acid-resistant thickening agent dry powder.
Example 5
1) Preparing a polymerization monomer aqueous solution, adding 43 parts of acrylamide, 55 parts of DMC, 1.5 parts of methacryloyloxyethyl dimethylamine and 0.5 part of tetradecyl dimethyl allyl ammonium chloride monomer into a beaker according to parts by mass, and adding distilled water for dissolving to ensure that the total mass content of the four monomers is 26 wt%;
2) adding 2.5% of thiourea, 0.04% of potassium formate, 0.03% of triethylene tetramine pentaacetic acid pentasodium, 3.5% of sodium dodecyl benzene sulfonate triethanolamine and 0.08% of N, N-tetramethyl ethylenediamine into the monomer aqueous solution (the total mass of the four monomers is 100%), stirring and dissolving uniformly, cooling in a water bath at the temperature of 8 ℃ for 30min, and cooling to the temperature of 8 ℃;
3) adding a certain amount of sodium carbonate into the above solution to adjust pH to 10, cooling for 30min, cooling to 8 deg.C in water bath at 8 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.05% of azobisisobutyric imidazoline hydrochloride, 0.015% of ammonium ferrous sulfate and 0.03% 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 rubber 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 cross-linked acid/gelled acid common acid-resistant thickening agent dry powder.
Example 6
1) Preparing a polymerization monomer aqueous solution, adding 30 parts of acrylamide, 50 parts of DMC, 1.5 parts of methacryloyloxyethyl dimethylamine and 0.2 part of dimethyl octadecyl (2-hydroxy-3-acrylamide propyl) ammonium chloride monomer into a beaker according to the mass parts, and adding distilled water for dissolving to ensure that the total mass content of the four monomers is 25 wt%;
2) adding 1 wt% of thiourea, 0.05% of potassium formate, 0.03% of triethylene pentaacetic acid pentasodium salt, 3% of sodium dodecyl benzene sulfonate triethanolamine and 0.05% of N, N-tetramethyl ethylenediamine into the monomer aqueous solution (the total mass of the four monomers is 100%), stirring and dissolving uniformly, and cooling in a water bath at 10 ℃ for 30min to ensure that the temperature is cooled to 10 ℃;
3) adding a certain amount of sodium carbonate into the above solution to adjust pH to 10, 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 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 rubber 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 cross-linked acid/gelled acid common acid-resistant thickening agent dry powder.
Example 7
1) Preparing a polymerization monomer aqueous solution, adding 30 parts of acrylamide, 50 parts of DMC, 1.5 parts of methacryloyloxyethyl dimethylamine and 0.2 part of tetradecyl dimethyl allyl ammonium chloride monomer into a beaker according to parts by mass, and adding distilled water for dissolving to enable the total mass content of the four monomers to be 25 wt%;
2) adding 3 wt% of thiourea, 0.1 wt% of potassium formate, 0.08 wt% of triethylene tetramine pentaacetic acid pentasodium, 5 wt% of sodium dodecyl benzene sulfonate triethanolamine and 0.1 wt% of N, N-tetramethyl ethylenediamine into the monomer aqueous solution (the total mass of the four monomers is 100%), stirring and dissolving uniformly, cooling in a water bath at 10 ℃ for 30min, and cooling to 10 ℃;
3) adding a certain amount of sodium carbonate into the above solution to adjust pH to 10, 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 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 rubber 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 cross-linked acid/gelled acid common acid-resistant thickening agent dry powder.
Example 8
1) Preparing a polymerization monomer aqueous solution, adding 35 parts of acrylamide, 64 parts of 2-acrylamide-2-methylpropanesulfonic Acid Monomer (AMPS), 1.4 parts of N, N-dimethylacrylamide and 0.3 part of octadecyl dimethyl allyl ammonium chloride monomer into a beaker according to parts by mass, and adding distilled water for dissolving to enable the total mass content of the four monomers to be 25 wt%;
2) adding 1.0% of urea, 0.05% of sodium formate, 0.03% of tetrasodium ethylenediamine tetraacetate, 3.0% of sodium dodecyl sulfate and 0.05% of ethylenediamine into the monomer aqueous solution (the total mass of the four 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 9, cooling for 30min, cooling to 5 deg.C in water bath at 5 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.02% azodiisobutyl amidine hydrochloride, 0.005% sodium bisulfite and 0.01% ammonium persulfate water 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 rubber 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 cross-linked acid/gelled acid common acid-resistant thickening agent dry powder.
Example 9
1) Preparing a polymerization monomer aqueous solution, adding 35 parts of acrylamide, 64 parts of 2-acrylamide-2-methylpropanesulfonic Acid Monomer (AMPS), 1.4 parts of N, N-dimethylacrylamide and 0.3 part of tetradecyl dimethyl allyl ammonium chloride monomer into a beaker according to parts by mass, and adding distilled water for dissolving to enable the total mass content of the four monomers to be 25 wt%;
2) adding 1.0% of urea, 0.05% of sodium formate, 0.03% of tetrasodium ethylenediamine tetraacetate, 3.0% of sodium dodecyl sulfate and 0.05% of ethylenediamine into the monomer aqueous solution (the total mass of the four 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 9, cooling for 30min, cooling to 5 deg.C in water bath at 5 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.02% azodiisobutyl amidine hydrochloride, 0.005% sodium bisulfite and 0.01% ammonium persulfate water 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 rubber 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 cross-linked acid/gelled acid common acid-resistant thickening agent dry powder.
Example 10
1) Preparing a polymerization monomer aqueous solution, adding 35 parts of acrylamide, 64 parts of 2-acrylamide-2-methylpropanesulfonic Acid Monomer (AMPS), 1.4 parts of N, N-dimethylacrylamide and 0.3 part of hexadecyl dimethyl allyl ammonium chloride monomer into a beaker according to parts by mass, and adding distilled water for dissolving to enable the total mass content of the four monomers to be 25 wt%;
2) adding 1.0% triethanolamine, 0.05% sodium formate, 0.03% tetrasodium ethylenediamine tetraacetate, 3.0% sodium lauryl sulfate and 0.05% ethylenediamine into the monomer aqueous solution (based on the total mass of the four monomers being 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 9, cooling for 30min, cooling to 5 deg.C in water bath at 5 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.02% azodiisobutyl amidine hydrochloride, 0.005% sodium bisulfite and 0.01% ammonium persulfate water 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 rubber 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 cross-linked acid/gelled acid common acid-resistant thickening agent dry powder.
Example 11
1) Preparing a polymerization monomer aqueous solution, adding 35 parts of acrylamide, 64 parts of 2-acrylamide-2-methylpropanesulfonic Acid Monomer (AMPS), 1.4 parts of N, N-dimethylacrylamide and 0.3 part of hexadecyl dimethyl allyl ammonium chloride monomer into a beaker according to parts by mass, and adding distilled water for dissolving to enable the total mass content of the four monomers to be 25 wt%;
2) adding 1.0% of urea, 0.05% of isopropanol, 0.03% of tetrasodium ethylenediamine tetraacetate, 3.0% of sodium dodecyl sulfate and 0.05% of ethylenediamine into the monomer aqueous solution (the total mass of the four 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 9, cooling for 30min, cooling to 5 deg.C in water bath at 5 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.02% azodiisobutyl amidine hydrochloride, 0.005% sodium bisulfite and 0.01% ammonium persulfate water 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 rubber 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 cross-linked acid/gelled acid common acid-resistant thickening agent dry powder.
Example 12
1) Preparing a polymerization monomer aqueous solution, adding 35 parts of acrylamide, 64 parts of 2-acrylamide-2-methylpropanesulfonic Acid Monomer (AMPS), 1.4 parts of N, N-dimethylacrylamide and 0.3 part of hexadecyl dimethyl allyl ammonium chloride monomer into a beaker according to parts by mass, and adding distilled water for dissolving to enable the total mass content of the four monomers to be 25 wt%;
2) adding 1.0% of urea, 0.05% of sodium formate, 0.03% of tetrasodium ethylenediamine tetraacetate, 3.0% of triethanolamine lauryl sulfate and 0.05% of ethylenediamine into the monomer aqueous solution (the total mass of the four 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 9, cooling for 30min, cooling to 5 deg.C in water bath at 5 deg.C, introducing the liquid into heat insulation polymerization device, and introducing nitrogen for 20 min;
4) adding 0.02% azodiisobutyl amidine hydrochloride, 0.005% sodium bisulfite and 0.01% ammonium persulfate water 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 rubber 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 cross-linked acid/gelled acid common acid-resistant thickening agent dry powder.
Comparative example 1
1) Preparing a polymerization monomer aqueous solution, adding 26.0 parts of acrylamide, 50 parts of DMC, 5 parts of methacryloyloxyethyl dimethylamine and 0.7 part of tetradecyl dimethyl allyl ammonium chloride monomer into a beaker according to parts by mass, and adding distilled water for dissolving to enable the total mass content of the four 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, 7 wt% of sodium dodecyl benzene sulfonate triethanolamine and 0.1 wt% of N, N-tetramethyl ethylenediamine into the monomer aqueous solution (the total mass of the four monomers is 100%), stirring and dissolving uniformly, cooling in a water bath at 10 ℃ for 30min, and cooling to 10 ℃.
3) Adding a certain amount of sodium carbonate into the above solution to adjust pH to 6, 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, 0.1 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 cross-linked acid/gelled acid general acid-resistant thickening agent dry powder.
Comparative example 2
1) Preparing a polymerization monomer aqueous solution, adding 58.0 parts of acrylamide, 50 parts of DMC, 5 parts of methacryloyloxyethyl dimethylamine and 1.7 parts of octadecyl dimethyl allyl ammonium chloride monomers into a beaker according to parts by mass, and adding distilled water for dissolving to enable the total mass content of the four 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, 7 wt% of sodium dodecyl benzene sulfonate triethanolamine and 0.1 wt% of N, N-tetramethyl ethylenediamine into the monomer aqueous solution (the total mass of the four monomers is 100%), stirring and dissolving uniformly, cooling in a water bath at 10 ℃ 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 cross-linked acid/gelled acid general acid-resistant thickening agent dry powder.
Example 13
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.
Wherein, the cross-linking agent SRAC-2 is prepared as follows:
1) adding 15 parts by mass of zirconium oxychloride into 24 parts by mass of water, and fully stirring and dissolving at 60 ℃;
2) sequentially adding 23 parts by mass of xylitol and 23 parts by mass of oxalic acid into the solution in the step 1), and reacting at a constant temperature of 60 ℃ for 3 hours;
3) adjusting pH to 5 with sodium hydroxide, and cooling to 25 deg.C;
4) adding 15 parts by mass of sodium dodecyl sulfate into the solution obtained in the step 3), and uniformly stirring and mixing to obtain the cross-linking agent.
The thickening agent synthesized in each example above was dissolved in hydrochloric acid, then a corrosion inhibitor (SRAI-1, available from the institute of petroleum and petroleum engineering technology, petrochemical) was added to make the final contents of the thickening agent, hydrochloric acid and corrosion inhibitor 1 wt%, 20 wt% and 3 wt%, respectively, and stirred uniformly to obtain gelled acid, and the apparent viscosity of the base liquid (gelled acid) was measured using a six-speed viscometer. The crosslinking acid is then formed by adding a crosslinking agent for the crosslinking acid (SRAC-2 organic zirconium crosslinker, available from the petrochemical Petroleum engineering research institute). According to the industrial standard SY/T5107-2005, at 180 deg.C for 170s-1Shearing for 1h, and measuring the temperature resistance and the shearing resistance of the gelling acid and the crosslinking acid.
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 50mPa.s, the viscosity of the base solution is stable after the base solution is placed at room temperature for 10 days, the viscosity of the cross-linking acid tail and the viscosity of the gelled acid are respectively more than 70mPa.s and 20mPa.s after the cross-linking acid and the cross-linking acid are sheared at high temperature of 180 ℃, and the performance requirement of an acid solution system is met. The dissolution time of the comparative example is more than 30min, and the viscosity of the cross-linking acid tail and the viscosity of the gelled acid after high-temperature shearing at 180 ℃ are about 40mPa.s and 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 (11)
1. A thickening agent comprises raw materials of an acrylamide monomer, an acid-resistant monomer, a water-soluble monomer containing dimethylamino, a quaternary ammonium salt polymerizable surfactant, a cosolvent, a chain transfer agent, a complexing agent, an activating agent, an oxidizing agent, a reducing agent, a water-soluble azo initiator and a water-soluble anionic surfactant.
2. The thickener of claim 1, wherein the acid resistant monomer is selected from at least one of 2-acrylamido-2-methylpropanesulfonic acid, acryloyloxyethyltrimethylammonium chloride, and methacryloyloxyethyltrimethylammonium chloride.
3. Thickener according to claim 1 or 2, wherein the water-soluble monomer comprising a dimethylamino group is selected from methacryloyloxyethyldimethylamine and/or N, N-dimethylacrylamide.
4. The thickener according to any one of claims 1 to 3, wherein the quaternary ammonium salt type polymerizable surfactant is selected from at least one of tetradecyldimethylammonium chloride, hexadecyldimethylallylammonium chloride, octadecyldimethylammonium chloride, methacryloyloxyethyldimethylhexadecylammonium bromide, and dimethyloctadecyl (2-hydroxy-3-acrylamidopropyl) ammonium chloride.
5. The thickener according to any one of claims 1 to 4, 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; and/or
The water-soluble anionic surfactant is selected from at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, triethanolamine dodecyl sulfate and triethanolamine dodecyl benzene sulfonate.
6. The thickener according to any one of claims 1 to 5, wherein the acrylamide monomer has 30 to 50 parts by mass, the acid-resistant monomer has 50 to 70 parts by mass, the dimethylamino group-containing water-soluble monomer has 1.4 to 1.7 parts by mass, and the quaternary ammonium salt type polymerizable surfactant has 0.2 to 1 part by mass;
the total mass of the acrylamide monomer, the acid-resistant monomer and the water-soluble monomer containing the dimethylamino group and the quaternary ammonium salt type polymerizable surfactant is 100%, 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%, the water-soluble azo initiator is used in an amount of 0.02 wt% to 0.06 wt%, and the water-soluble anionic surfactant is used in an amount of 3 wt% to 5 wt%.
7. A method of producing a thickener according to any of claims 1 to 6 comprising the steps of:
1) dissolving the acrylamide, the acid-resistant monomer, the dimethylamino-containing water-soluble monomer and the quaternary ammonium salt type polymerizable surfactant in water to obtain a first solution;
2) adding the cosolvent, the chain transfer agent, the complexing agent, the activating agent and the water-soluble anionic surfactant into the first solution, and uniformly mixing to obtain a second solution;
3) adjusting the pH value of the second solution to 9-10 to obtain a third solution; then adding the third solution into a polymerization device, and introducing nitrogen;
4) adding the water-soluble azo initiator, the reducing agent and the oxidant 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.
8. The production method according to claim 7, wherein the total mass of the acrylamide, the acid-resistant monomer, the dimethylamino group-containing water-soluble monomer, and the quaternary ammonium salt-type polymerizable surfactant accounts for 25 to 29 wt% of the total mass of the first solution.
9. The method according to claim 7 or 8, wherein in the step 2), the second solution obtained by uniformly mixing 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 ℃;
in step 6), the temperature of the drying is 60 ℃ to 80 ℃.
10. The production method according to any one of claims 7 to 9, wherein in step 3) and step 4), the time for introducing nitrogen gas is independently 20 to 30 minutes; and/or
In step 5), the incubation time is 4 to 5 hours.
11. The production method according to any one of claims 7 to 10, wherein the number of meshes of the sieve in step 6) is 20 to 40 meshes.
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