CN114106241A - Preparation method of dication salt-resistant polymer and application of dication salt-resistant polymer in fracturing fluid - Google Patents
Preparation method of dication salt-resistant polymer and application of dication salt-resistant polymer in fracturing fluid Download PDFInfo
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Abstract
The invention discloses a preparation method of a dication salt-resistant polymer and application of the dication salt-resistant polymer in fracturing fluid. The technical scheme is as follows: (1) firstly, carrying out quaternization reaction on octadecyl dimethyl tertiary amine and 1, 3-dibromopropane to obtain quaternary ammonium salt JY, secondly, reacting the quaternary ammonium salt JY with taurine to obtain an intermediate JS, and finally, reacting bromopropylene with the intermediate JS to obtain a hydrophobic monomer YS; (2) and (2) initiating polymerization of the hydrophobic monomer YS, acrylamide, acrylic acid and N, N-dimethyl dodecyl allyl amine for 6 hours at low temperature by adopting a micelle polymerization method to obtain the dicationic salt-resistant polymer. The polymer can be directly prepared from hypersalinity simulated formation water or deionized water to be used as fracturing fluid, and has good temperature resistance, viscoelasticity and shear resistance. The preparation method has the characteristics of low cost and convenient preparation, and the prepared product has good salt thickening property and good application prospect in the development of high-temperature and high-salt oil and gas reservoirs.
Description
Technical Field
The invention relates to a preparation method of a dication salt-resistant polymer and application of the dication salt-resistant polymer in fracturing fluid, belonging to the field of oilfield chemical additives.
Technical Field
The fracturing technology is the most widely applied oil and gas field production increasing and transformation technology and has an important position in the aspect of increasing the oil and gas well production. The fracturing fluid used at home and abroad is water-based fracturing fluid which has huge consumption on fresh water resources. According to statistics, in fracturing construction operation of deep wells and ultra-deep wells, on average, each well needs to consume thousands or even tens of thousands of fresh water resources, so that hydraulic fracturing operation in water-deficient areas such as western parts of China becomes huge in consumption, and the problem needs to be solved urgently.
In the early 90 s of the last century, a hypersalinity water-based fracturing fluid system has been proposed abroad, is mainly applied to a seawater-based fracturing fluid system, and achieves a certain effect. The mineralization degree of the conventional seawater is 30000-80000 mg/L, and the mineralization degree of the formation water of the Tahe oil field in the northwest China of the China petrochemical industry can be up to more than 200000mg/L, so that further challenge is provided for the salt tolerance of a fracturing fluid system. The salt resistance of the water-based fracturing fluid is mainly reflected in the tolerance degree of the thickening agent to mineral components in the fluid. The viscosity of the conventional polymer in a salt solution is greatly reduced due to the curling of molecular chains, so that the performance of the polymer fracturing fluid is greatly reduced, and the use of the fracturing fluid in non-fresh water is limited. Therefore, the research and development of the polymer with the high mineralization degree for the fracturing fluid has an important role in the situations that fresh water resources of oil fields are short and water resources of high-mineralization strata are rich.
Aiming at the problems, the patent designs and adopts a micelle polymerization method to prepare a dicationic salt-resistant polymer to solve the problem of salt resistance of the polymer. The dicationic salt-resistant polymer prepared by the design simultaneously contains a sulfonic acid group and a hydrophobic long chain, and has the following two advantages: (1) the monomer contains sulfonic acid groups, so that the salt resistance of the polymer is improved; (2) the monomer contains two hydrophobic chains with different lengths, has association synergistic effect of reinforcing and inhibiting, and can improve the salt resistance of the polymer. The two monomers are introduced into the main chain of the polymer molecule, and the properties of thickening, temperature resistance, salt resistance, shear resistance and the like of the polymer in saline water are hopefully improved.
Disclosure of Invention
The invention provides a preparation method of a dication salt-resistant polymer aiming at the defects of poor salt-resistant effect and the like of the existing hydrophobic association polymer fracturing fluid. The fracturing fluid densifier can be a fracturing fluid system which has the characteristics of easy dissolution, salt resistance, high viscosity, easy flowback, easy recovery and the like, can adapt to more sources of fracturing water, meets the requirements of good salt resistance, good dispersibility, high sand carrying performance and the like under the condition of high salinity, can be stored for a long time, is convenient to recover and the like, and relieves the pressure of site environmental protection. The fracturing fluid has the advantages of wide raw material source, simple synthesis process and low cost, and can have the effect of remarkable high mineralization resistance under a small using amount.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a dicationic salt-tolerant polymer. The specific structural formula is as follows:
in the formula, x, y, z and w are the molar ratio of acrylamide, acrylic acid, N-dimethyl dodecyl allyl amine and hydrophobic monomer YS, x is 70-90%, y is 8-22%, z is 1-5% and w is 1-3%.
The synthesis reaction formula of the hydrophobic monomer YS is as follows:
(1) the quaternary ammonium salt JY reaction:
(2) synthesizing an intermediate JS:
(3) hydrophobic monomer YS synthesis reaction:
in the formula: r1Is CnH2n+1Wherein n is 12 to 22.
The specific preparation method of the hydrophobic monomer YS comprises the following steps:
(1) dissolving octadecyl dimethyl tertiary amine in a composite solvent (acetone and ether mixed solution), slowly dropwise adding the mixed solution of 1, 3-dibromopropane and the composite solvent by using a constant-pressure funnel according to a molar ratio of 1:1-1.3 under an ice bath condition, transferring to room temperature to continue reacting for 6 hours after the dropwise adding is finished, and after the reaction is finished, filtering, removing impurities, performing low-temperature rotary evaporation, and performing vacuum drying to obtain a white product, namely quaternary ammonium salt JY;
(2) reacting the quaternary ammonium salt JY obtained in the first step with taurine in a molar ratio of 1:1.1-1.4 to obtain an intermediate JS, firstly, dissolving the taurine in a three-neck round-bottom flask by using deionized water, placing the three-neck round-bottom flask in an oil bath kettle at 90 ℃ for condensation and reflux, dissolving the quaternary ammonium salt JY in a composite solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), slowly dropwise adding the quaternary ammonium salt JY solution containing the composite solvent into the three-neck round-bottom flask by using a constant-pressure funnel, and reacting for 24 hours. After the reaction is finished, filtering, removing impurities, performing low-temperature rotary evaporation, and performing vacuum drying to obtain a light yellow product, namely the intermediate JS.
(3) Reacting bromopropene and an intermediate JS in a molar ratio of 1:1 to obtain a hydrophobic monomer YS, firstly, dissolving the intermediate JS in a composite solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), adding a proper amount of polymerization inhibitor, introducing nitrogen for 30min to remove oxygen, placing the mixture in an ice bath, starting stirring, slowly dropwise adding a mixed solution of the bromopropene and the ethanol through a constant-pressure funnel, transferring the mixture into an oil bath kettle at 40 ℃ after complete dropwise adding, fully stirring and reacting for 12-24 hours, filtering, removing impurities, carrying out low-temperature rotary evaporation, and carrying out vacuum drying to obtain a light yellow product, namely the hydrophobic monomer YS.
Further, the octadecyl dimethyl tertiary amine in the step (1) may be any one of dodecyl dimethyl tertiary amine, tetradecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, oleamidopropyl dimethyl tertiary amine, and erucamidopropyl dimethyl tertiary amine.
Further, the 1, 3-dibromopropane in the step (1) may be any one of 1, 2-dibromoethane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, 1, 7-dibromoheptane, 1, 8-dibromooctane, 1, 9-dibromononane and 1, 10-dibromodecane.
Further, taurine in the step (2) may be sulfanilic acid.
Further, the bromopropene in the step (3) may be any one of chloropropene, acryloyl chloride and methacryloyl chloride.
The invention discloses a preparation method of a dicationic salt-resistant polymer, which comprises the following steps:
adding acrylamide, acrylic acid, N-dimethyl dodecyl allyl amine and a hydrophobic monomer YS into deionized water, simultaneously adding betaine surfactant accounting for 2% of the total monomer mass fraction, fully dissolving, adjusting the pH value to 7 by using sodium hydroxide, deoxidizing for 30min, adding a low-temperature initiator accounting for 0.1% -0.4% of the total monomer mass fraction, carrying out polymerization reaction for 6 hours under the low-temperature condition to obtain a transparent colloid, and carrying out granulation, drying and powdering to obtain the dicationic salt-resistant polymer.
Furthermore, in the preparation method of the dicationic salt-tolerant polymer, the betaine surfactant added in the polymer synthesis can be any one of LAB, CAB, LHSB and CHSB.
Further, the chemical reaction process of the dicationic salt-tolerant polymer disclosed by the invention is as follows:
in the formula, x, y, z and w are the molar ratio of acrylamide, acrylic acid, N-dimethyl dodecyl allyl amine and hydrophobic monomer YS, x is 70-90%, y is 8-22%, z is 1-5% and w is 1-3%.
The other technical scheme of the invention is realized as follows: a dication salt-tolerant polymer is fracturing fluid, and comprises 0.3-0.5% of polymer by mass and the balance of hypersalinity simulated formation water or deionized water.
The invention has the beneficial effects that:
(1) the invention provides a preparation method of dication salt-resistant polymer, which has the advantages of relatively easy acquisition of raw materials, simple production flow and lower cost.
(2) The invention provides a preparation method of a hydrophobic monomer YS with a sulfonic acid group and an alkyl long chain.
(3) The dication salt-tolerant polymer provided by the invention contains a sulfonate group and an alkyl hydrophobic long chain, wherein the sulfonate group has good salt resistance, and the alkyl hydrophobic long chain can play a role in tackifying.
(4) The two cationic monomers in the invention have hydrophobic long chains with different lengths, and the association synergistic effect is achieved by adopting a strategy of 'reinforcing and weakening' and 'weakening and weakening', thereby showing better solubility
(5) According to the invention, a micelle polymerization method is adopted, and when the surfactant is dissolved in high-salinity simulated formation water, the surfactant forms micelles to generate a synergistic effect with the hydrophobic long chain, so that the good viscoelasticity and shear resistance are shown.
Drawings
FIG. 1 is a graph showing the viscosity change of the polymer in NaCl solutions of different concentrations in example nine;
FIG. 2 is a plot of the viscous concentration of a fracturing fluid formulated with a polymer in example ten;
FIG. 3 is a shear curve of a fracturing fluid formulated with 0.5% polymer in EXAMPLE eleven;
FIG. 4 is a viscoelasticity curve of a fracturing fluid formulated with 0.5% polymer in example twelve;
figure 5 is a rheological profile of a fracturing fluid formulated with 0.5% polymer in example thirteen.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings.
The first embodiment is as follows:
synthesis of hydrophobic monomer YS
(1) Dissolving dodecyl dimethyl tertiary amine in a composite solvent (acetone and ether mixed solution), slowly dropwise adding the mixed solution of 1, 3-dibromopropane and the composite solvent by using a constant-pressure funnel according to a molar ratio of 1:1 under an ice bath condition, transferring to room temperature to continue reacting for 6 hours after dropwise adding is finished, and after the reaction is finished, filtering, removing impurities, performing low-temperature rotary evaporation, and performing vacuum drying to obtain a white product, namely the quaternary ammonium salt JY with the yield of 78.6%;
(2) firstly, dissolving taurine in a three-neck round-bottom flask by using deionized water, placing the three-neck round-bottom flask in an oil bath kettle at 90 ℃ for condensation reflux, dissolving quaternary ammonium salt JY in a composite solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), slowly dropwise adding a quaternary ammonium salt JY solution containing the composite solvent into the three-neck round-bottom flask by using a constant-pressure funnel, and reacting for 24 hours. After the reaction is finished, filtering, removing impurities, performing low-temperature rotary evaporation, and performing vacuum drying to obtain a light yellow product, namely the intermediate JS, wherein the yield is 81.3%.
(3) Reacting bromopropene and an intermediate JS in a molar ratio of 1:1 to obtain a hydrophobic monomer YS, firstly, dissolving the intermediate JS in a composite solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), adding a proper amount of polymerization inhibitor, introducing nitrogen for 30min to remove oxygen, placing the mixture in an ice bath, starting stirring, slowly dropwise adding a mixed solution of the bromopropene and the ethanol through a constant-pressure funnel, transferring the mixture into an oil bath kettle at 40 ℃ after complete dropwise adding, fully stirring and reacting for 12 hours, filtering, removing impurities, carrying out low-temperature rotary evaporation, and carrying out vacuum drying to obtain a light yellow product, namely the hydrophobic monomer YS, wherein the yield is 80.6%.
Example two:
synthesis of hydrophobic monomer YS
(1) Dissolving octadecyl dimethyl tertiary amine in a composite solvent (acetone and ether mixed solution), slowly dropwise adding the mixed solution of 1, 3-dibromopropane and the composite solvent by using a constant-pressure funnel according to a molar ratio of 1:1.1 under an ice bath condition, transferring to room temperature to continue reacting for 6 hours after the dropwise adding is finished, and after the reaction is finished, filtering, removing impurities, performing low-temperature rotary evaporation, and performing vacuum drying to obtain a white product, namely the quaternary ammonium salt JY with the yield of 84.8%;
(2) firstly, dissolving taurine in a three-neck round-bottom flask by using deionized water, placing the three-neck round-bottom flask in an oil bath kettle at 90 ℃ for condensation reflux, dissolving quaternary ammonium salt JY in a composite solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), slowly dropwise adding a quaternary ammonium salt JY solution containing the composite solvent into the three-neck round-bottom flask by using a constant-pressure funnel, and reacting for 24 hours. After the reaction is finished, filtering, removing impurities, performing low-temperature rotary evaporation, and performing vacuum drying to obtain a light yellow product, namely the intermediate JS, wherein the yield is 88.3%.
(3) Reacting bromopropene and an intermediate JS in a molar ratio of 1:1 to obtain a hydrophobic monomer YS, firstly, dissolving the intermediate JS in a composite solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), adding a proper amount of polymerization inhibitor, introducing nitrogen for 30min to remove oxygen, placing the mixture in an ice bath, starting stirring, slowly dropwise adding a mixed solution of the bromopropene and the ethanol through a constant-pressure funnel, transferring the mixture into an oil bath kettle at 40 ℃ after complete dropwise adding, fully stirring and reacting for 16 hours, filtering, removing impurities, carrying out low-temperature rotary evaporation, and carrying out vacuum drying to obtain a light yellow product, namely the hydrophobic monomer YS, wherein the yield is 90.3%.
Example three:
synthesis of hydrophobic monomer YS
(1) Dissolving octadecyl dimethyl tertiary amine in a composite solvent (acetone and ether mixed solution), slowly dropwise adding the mixed solution of 1, 3-dibromopropane and the composite solvent by using a constant-pressure funnel according to a molar ratio of 1:1.2 under an ice bath condition, transferring to room temperature to continue reacting for 6 hours after the dropwise adding is finished, and after the reaction is finished, filtering, removing impurities, performing low-temperature rotary evaporation, and performing vacuum drying to obtain a white product, namely the quaternary ammonium salt JY with the yield of 89.5%;
(2) firstly, dissolving taurine in a three-neck round-bottom flask by using deionized water, placing the three-neck round-bottom flask in an oil bath kettle at 90 ℃ for condensation reflux, dissolving quaternary ammonium salt JY in a composite solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), slowly dropwise adding a quaternary ammonium salt JY solution containing the composite solvent into the three-neck round-bottom flask by using a constant-pressure funnel, and reacting for 24 hours. After the reaction is finished, filtering, removing impurities, performing low-temperature rotary evaporation, and performing vacuum drying to obtain a light yellow product, namely the intermediate JS, wherein the yield is 91.3%.
(3) Reacting bromopropene and an intermediate JS in a molar ratio of 1:1 to obtain a hydrophobic monomer YS, firstly, dissolving the intermediate JS in a composite solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), adding a proper amount of polymerization inhibitor, introducing nitrogen for 30min to remove oxygen, placing the mixture in an ice bath, starting stirring, slowly dropwise adding a mixed solution of the bromopropene and the ethanol through a constant-pressure funnel, transferring the mixture into an oil bath kettle at 40 ℃ after complete dropwise adding, fully stirring and reacting for 20 hours, filtering, removing impurities, carrying out low-temperature rotary evaporation, and carrying out vacuum drying to obtain a light yellow product, namely the hydrophobic monomer YS, wherein the yield is 94.3%.
Example four:
synthesis of hydrophobic monomer YS
(1) Dissolving octadecyl dimethyl tertiary amine in a composite solvent (acetone and ether mixed solution), slowly dropwise adding the mixed solution of 1, 3-dibromopropane and the composite solvent by using a constant-pressure funnel according to a molar ratio of 1:1.3 under an ice bath condition, transferring to room temperature to continue reacting for 6 hours after the dropwise adding is finished, and after the reaction is finished, filtering, removing impurities, performing low-temperature rotary evaporation, and performing vacuum drying to obtain a white product, namely the quaternary ammonium salt JY with the yield of 92.9%;
(2) firstly, dissolving taurine in a three-neck round-bottom flask by using deionized water, placing the three-neck round-bottom flask in an oil bath kettle at 90 ℃ for condensation reflux, dissolving quaternary ammonium salt JY in a composite solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), slowly dropwise adding a quaternary ammonium salt JY solution containing the composite solvent into the three-neck round-bottom flask by using a constant-pressure funnel, and reacting for 24 hours. After the reaction is finished, filtering, removing impurities, performing low-temperature rotary evaporation, and performing vacuum drying to obtain a light yellow product, namely the intermediate JS, wherein the yield is 94.6%.
(3) Firstly, dissolving the intermediate JS in a composite solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), adding a proper amount of polymerization inhibitor, introducing nitrogen for 30min to remove oxygen, placing the mixture in an ice bath, starting stirring, slowly dropwise adding a mixed solution of the bromopropene and the ethanol through a constant-pressure funnel, transferring the mixture to an oil bath kettle at 40 ℃ after complete dropwise addition, fully stirring and reacting for 24 hours, filtering, removing impurities, carrying out low-temperature rotary evaporation, and carrying out vacuum drying to obtain a light yellow product, namely the hydrophobic monomer YS, wherein the yield is 96.8%.
Example five:
synthesis of dication salt-resistant polymer
Adding 70 mol percent of acrylamide, 22 mol percent of acrylic acid, 5 mol percent of N, N-dimethyl dodecyl allyl amine and 3 mol percent of hydrophobic monomer YS into deionized water, simultaneously adding betaine surfactant LAB accounting for 2 mass percent of the total monomers, fully dissolving, adjusting the pH value to 7 by using sodium hydroxide, deoxidizing for 30min, adding a low-temperature initiator accounting for 0.1 mass percent of the total monomers, carrying out polymerization reaction for 6 hours under the low-temperature condition to obtain a transparent colloid, and carrying out granulation, drying and powdering to obtain the dicationic salt-resistant polymer.
Further, 0.5% of polymer powder was dissolved in deionized water and hypersalinity-stimulated formation water at 25 ℃ respectively, and after complete dissolution, apparent viscosities thereof were 79mpa.s and 98mpa.s, respectively, as measured by a six-speed viscometer.
Example six:
synthesis of dication salt-resistant polymer
Adding 76 mol percent of acrylamide, 18 mol percent of acrylic acid, 4 mol percent of N, N-dimethyl dodecyl allyl amine and 2 mol percent of hydrophobic monomer YS into deionized water, simultaneously adding betaine surfactant CAB accounting for 2 mass percent of the total monomers, fully dissolving, adjusting the pH value to 7 by using sodium hydroxide, deoxidizing for 30min, adding a low-temperature initiator accounting for 0.2 mass percent of the total monomers, carrying out polymerization reaction for 6 hours under the low-temperature condition to obtain a transparent colloid, and carrying out granulation, drying and powdering to obtain the dicationic salt-resistant polymer.
Further, 0.5% of polymer powder was dissolved in deionized water and hypersalinity-stimulated formation water at 25 ℃ respectively, and after complete dissolution, the apparent viscosities thereof were 64mpa.s and 102mpa.s, respectively, as measured by a six-speed viscometer.
Example seven:
synthesis of dication salt-resistant polymer
Adding 82 mol percent of acrylamide, 14 mol percent of acrylic acid, 3 mol percent of N, N-dimethyl dodecyl allyl amine and 1 mol percent of hydrophobic monomer YS into deionized water, simultaneously adding betaine surfactant LHSB accounting for 2 mass percent of the total monomers, fully dissolving, adjusting the pH value to 7 by using sodium hydroxide, deoxidizing for 30min, adding low-temperature initiator accounting for 0.3 mass percent of the total monomers, carrying out polymerization reaction for 6 hours under the low-temperature condition to obtain transparent colloid, and carrying out granulation, drying and powdering to obtain the dicationic salt-resistant polymer.
Further, 0.5% of polymer powder was dissolved in deionized water and hypersalinity-stimulated formation water at 25 ℃ respectively, and after complete dissolution, apparent viscosities thereof were 130mpa.s and 289mpa.s, respectively, using a six-speed viscometer.
Example eight:
synthesis of dication salt-resistant polymer
Adding 90 mol percent of acrylamide, 8 mol percent of acrylic acid, 1 mol percent of N, N-dimethyl dodecyl allyl amine and 1 mol percent of hydrophobic monomer YS into deionized water, simultaneously adding betaine surfactant CHSB accounting for 2 mass percent of the total monomers, fully dissolving, adjusting the pH value to 7 by using sodium hydroxide, deoxidizing for 30min, adding low-temperature initiator accounting for 0.4 mass percent of the total monomers, carrying out polymerization reaction for 6 hours under the low-temperature condition to obtain a transparent colloid, and carrying out granulation, drying and powdering to obtain the dicationic salt-resistant polymer.
Further, 0.5% of polymer powder was dissolved in deionized water and hypersalinity-stimulated formation water at 25 ℃ respectively, and after complete dissolution, apparent viscosities thereof were measured as 128mpa.s and 168mpa.s respectively using a six-speed rotational viscometer.
Example nine:
taking the dicationic salt-resistant polymer in the seventh embodiment, 0.3%, 0.4% and 0.5% of polymer powder is dissolved in NaCl solutions with different concentrations at 25 ℃, after the polymer powder is completely dissolved, the change of the viscosity of the polymer powder is measured by a six-speed rotational viscometer, and the apparent viscosity of the polymer solution with different concentrations is firstly reduced and then increased along with the increase of the NaCl concentration, and the salt thickening phenomenon is more obvious along with the increase of the polymer concentration.
Example ten:
taking the dicationic salt-tolerant polymer in the seventh embodiment, preparing the fracturing fluid by respectively mixing polymer powder with different concentrations with deionized water and hypersalinity simulation formation water at 25 ℃, measuring the apparent viscosity of the fracturing fluid by using an HAAKE MARS III high-temperature and high-pressure rheometer, and finding that when the concentration is more than 0.1%, the viscosity of the fracturing fluid in the hypersalinity simulation formation water is more than that of the deionized water, so that the fracturing fluid shows obvious salt resistance
Example eleven:
taking the dicationic salt-tolerant polymer in the seventh embodiment, preparing a fracturing fluid by respectively mixing 0.5% of polymer powder with deionized water and hypersalinity simulated formation water at 25 ℃, and measuring the change condition of the apparent viscosity of the fracturing fluid along with the shear rate by using an HAAKE MARS III high-temperature and high-pressure rheometer, so that the viscosity of the fracturing fluid in the hypersalinity simulated formation water is always greater than that of the deionized water in the whole shearing process, which indicates that the dicationic salt-tolerant polymer has good shear resistance as the fracturing fluid.
Example twelve:
taking the dicationic salt-tolerant polymer in the seventh embodiment, preparing a fracturing fluid by respectively mixing 0.5% of polymer powder with deionized water and hypersalinity simulation formation water at 25 ℃, setting the temperature of a rheometer to be 25 ℃ in an Anton Paar MCR301 type rheometer, and carrying out frequency scanning within the range of 0.1-10 Hz to test the viscoelasticity of the fracturing fluid.
Example thirteen:
taking the dicationic salt-resistant polymer in the seventh embodiment, 0.5 percent of polymer powder and hypersalinity simulation formation water are prepared into fracturing fluid at 25 ℃, and the fracturing fluid is prepared at 140 ℃ and 170s-1And the apparent viscosity is still maintained above 60mPa.s after shearing for about 2 hours, and the requirement of an industrial standard SY/T6376-2008 is met.
While the present invention has been described in detail with reference to the specific embodiments thereof, it should not be construed as limited by the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
TABLE 1 mineralogical composition of hypersalinity simulated formation water
| Composition (I) | Na+/K+ | Mg2+ | Ca2+ | Cl- | HCO3- | SO4 2- | TDS |
| mg/L | 71890.72 | 1161.84 | 11272.50 | 133658.00 | 33.84 | 150.00 | 218166.90 |
Claims (9)
1. A dicationic salt-tolerant polymer characterized by the structural formula:
in the formula, x, y, z and w are the molar ratio of acrylamide, acrylic acid, N-dimethyl dodecyl allyl amine and hydrophobic monomer YS, x is 70-90%, y is 8-22%, z is 1-5% and w is 1-3%.
2. The biscationic salt-tolerant polymer of claim 1 wherein the chemical equation for the hydrophobic monomer YS comprises the steps of:
(1) the quaternary ammonium salt JY reaction:
(2) synthesizing an intermediate JS:
(3) hydrophobic monomer YS synthesis reaction:
in the formula: r1Is CnH2n+1Wherein n is 12 to 22.
3. The method for synthesizing the hydrophobic monomer YS according to claim 2, comprising the steps of:
(1) dissolving octadecyl dimethyl tertiary amine in a composite solvent (acetone and ether mixed solution), slowly dropwise adding the mixed solution of 1, 3-dibromopropane and the composite solvent by using a constant-pressure funnel according to a molar ratio of 1:1-1.3 under an ice bath condition, transferring to room temperature to continue reacting for 6 hours after the dropwise adding is finished, and after the reaction is finished, filtering, removing impurities, performing low-temperature rotary evaporation, and performing vacuum drying to obtain a white product, namely quaternary ammonium salt JY;
(2) reacting the quaternary ammonium salt JY obtained in the first step with taurine in a molar ratio of 1:1.1-1.4 to obtain an intermediate JS, firstly, dissolving the taurine in a three-neck round-bottom flask by using deionized water, placing the three-neck round-bottom flask in an oil bath kettle at 90 ℃ for condensation and reflux, dissolving the quaternary ammonium salt JY in a composite solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), slowly dropwise adding the quaternary ammonium salt JY solution containing the composite solvent into the three-neck round-bottom flask by using a constant-pressure funnel, and reacting for 24 hours. After the reaction is finished, filtering, removing impurities, performing low-temperature rotary evaporation, and performing vacuum drying to obtain a light yellow product, namely an intermediate JS;
(3) reacting bromopropene and an intermediate JS in a molar ratio of 1:1 to obtain a hydrophobic monomer YS, firstly, dissolving the intermediate JS in a composite solvent of ethanol and water (the volume ratio of the ethanol to the water is 1:1), adding a proper amount of polymerization inhibitor, introducing nitrogen for 30min to remove oxygen, placing the mixture in an ice bath, starting stirring, slowly dropwise adding a mixed solution of the bromopropene and the ethanol through a constant-pressure funnel, transferring the mixture into an oil bath kettle at 40 ℃ after complete dropwise adding, fully stirring and reacting for 12-24 hours, filtering, removing impurities, carrying out low-temperature rotary evaporation, and carrying out vacuum drying to obtain a light yellow product, namely the hydrophobic monomer YS.
4. The method for synthesizing hydrophobic monomer YS as claimed in claim 3, wherein the octadecyl dimethyl tertiary amine in step (1) can be any one of dodecyl dimethyl tertiary amine, tetradecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, oleic acid amidopropyl dimethyl tertiary amine, erucic acid amidopropyl dimethyl tertiary amine.
5. The method for synthesizing the hydrophobic monomer YS as claimed in claim 3, wherein the 1, 3-dibromopropane in the step (1) is any one of 1, 2-dibromoethane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, 1, 7-dibromoheptane, 1, 8-dibromooctane, 1, 9-dibromononane and 1, 10-dibromodecane.
6. The method for synthesizing hydrophobic monomer YS according to claim 3, wherein the taurine obtained in step (2) is sulfanilic acid.
7. The method for synthesizing the hydrophobic monomer YS as claimed in claim 3, wherein the bromopropene in the step (3) can be any one of chloropropene, acryloyl chloride and methacryloyl chloride.
8. The method of claim 1, comprising the steps of:
adding acrylamide, acrylic acid, N-dimethyl dodecyl allyl amine and a hydrophobic monomer YS into deionized water, simultaneously adding betaine surfactant accounting for 2% of the total monomer mass fraction, fully dissolving, adjusting the pH value to 7 by using sodium hydroxide, deoxidizing for 30min, adding a low-temperature initiator accounting for 0.1% -0.4% of the total monomer mass fraction, carrying out polymerization reaction for 6 hours under the low-temperature condition to obtain a transparent colloid, and carrying out granulation, drying and powdering to obtain the dicationic salt-resistant polymer.
9. The method according to claim 8, wherein the betaine surfactant is selected from LAB, CAB, LHSB, and CHSB.
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