CN116284564B - Emulsion resistance reducing agent and preparation method and application thereof - Google Patents
Emulsion resistance reducing agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an emulsion resistance reducing agent, a preparation method and application thereof, and belongs to the technical field of resistance reducing agents. 1H, 1H-perfluoro propyl methacrylate, 2-acrylamide-2-methylpropanesulfonic acid, N-vinyl pyrrolidone, cationic surfactant monomer, acrylamide and 1-vinyl-3-ethylimidazole bromide are dissolved in water to obtain a water phase; dissolving a surfactant in an organic solvent to obtain an oil phase; adding the water phase into the oil phase, stirring to form reverse emulsion, adding an initiator system under the protection of inert gas, and stirring for reaction to obtain the emulsion resistance reducing agent. According to the invention, the emulsion drag reducer is prepared by adopting an inverse emulsion polymerization method, so that the prepared drag reducer has the advantages of low cost, wide raw material sources, simple preparation method and excellent drag reducing effect, and meanwhile, the solubility of the drag reducer is improved, the dissolution time is shortened, and the preparation method can meet the liquid preparation requirement of continuous mixing in the field construction process and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of resistance reducers, in particular to an emulsion resistance reducer, a preparation method and application thereof.
Background
Shale belongs to an ultralow permeability reservoir, a seepage channel required by economic exploitation cannot be provided, and the purpose of industrial exploitation can be achieved by improving the diversion capacity of the reservoir through fracturing operation. At present, a small amount of friction reducer, propping agent and some additives are mainly added into water to form slick water, and a fracturing process using the slick water as working fluid is used for fracturing a reservoir. Unlike conventional fracturing fluids, the concentration of polymer in slickwater fracturing fluids is lower, and the viscosity of the fracturing fluid is lower than conventional gel-forming fracturing fluids. The main component of the slickwater fracturing fluid is water, and because the water is Newtonian fluid, the turbulence phenomenon of the slickwater fracturing fluid is serious in the flowing process of the slickwater fracturing fluid in a pipeline under the condition of high-speed pumping, and the friction resistance between the fluid and the pipe wall is large. Frictional resistance hinders the flow of slickwater fracturing fluid in the pipeline, resulting in reduced pipeline throughput and increased energy consumption.
The resistance reducing agent is a chemical auxiliary agent for reducing the flow resistance of fluid, is a surfactant, a high molecular polymer, fibers and the like, and has wide application in various fields. During the flow of the fluid in the pipe, certain mechanical energy is consumed due to the viscosity of the fluid and the formation of vortex. The drag reducer is added into the fluid, so that the resistance in the flowing process can be greatly reduced, and the energy consumption of the pump is greatly reduced. A small amount of high polymer resistance reducing agent is added into the fracturing fluid, so that the flow resistance of the fracturing fluid is reduced under a turbulent state. At present, the domestic oil-gas field mainly uses linear glue, guanidine glue or imported resistance reducing agent in the exploitation process, the linear glue and guanidine glue have low resistance reducing efficiency and large stratum injury, and the imported resistance reducing agent has high price. Therefore, the domestic oil and gas field exploitation needs high-quality and low-cost resistance reducing agents.
Chinese patent application CN1487985a, published as 4 th month and 7 th 2004, discloses a surfactant resistance-reducing agent, which relates to the application of a combination of zwitterionic surfactant and ether sulfate or ether carboxylate surfactant as drag reducer in water-based system. But the drag reducer can be used only when reaching the critical micelle concentration of the surfactant, and the use concentration is high, so that the drag reducer is not suitable for the low-cost development requirement of shale gas.
Chinese patent application CN103333672A, publication day is 2013, 10 month and 2 day, discloses an application prepared by polymerizing acrylamide and propenyl trialkyl ammonium chloride or alkyl acrylamide trialkyl ammonium chloride or dialkyl diallyl ammonium chloride aqueous solution and a sodium salt resistance reducing agent of shale gas reservoir, wherein the resistance reducing agent prepared by the method is powder, and the powder is not suitable for large-scale shale gas fracturing construction by adopting a continuous blending construction process.
The Chinese patent CN102977877B is published as 2013 and 20 months, and discloses a drag reducer for shale gas fracturing and a preparation method thereof, wherein the drag reducer is prepared from acrylamide, sodium acrylate and 2-acrylamide-2-methylpropanesulfonic acid sodium, the method needs to prepare a stabilizer through aqueous solution polymerization, then prepares the drag reducer through dispersion polymerization, meanwhile, the preparation process needs to be filled with nitrogen for deoxidization, the preparation time is long (the total reaction time is more than 20 hours), the production process is complex, the industrial production is not facilitated, the solid content of the drag reducer is low, and the addition amount is large during use.
Disclosure of Invention
The invention aims to provide an emulsion resistance reducing agent, a preparation method and application thereof, wherein the emulsion resistance reducing agent is prepared by adopting an inverse emulsion polymerization method, the prepared resistance reducing agent has low cost, wide raw material sources, simple preparation method and excellent resistance reducing effect, meanwhile, the solubility of the resistance reducing agent is improved, the dissolution time is shortened, and the resistance reducing agent can meet the requirement of continuously mixed liquid in the field construction process and has wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of emulsion resistance-reducing agent, which comprises the steps of dissolving 1H, 1H-perfluoro propyl methacrylate, 2-acrylamide-2-methylpropanesulfonic acid, N-vinyl pyrrolidone, cationic surfactant monomer, acrylamide and 1-vinyl-3-ethylimidazole bromide in water to obtain a water phase; dissolving a surfactant in an organic solvent to obtain an oil phase; adding the water phase into the oil phase, stirring to form reverse emulsion, adding an initiator system under the protection of inert gas, and stirring for reaction to obtain an emulsion resistance reducing agent;
the structural formula of the cationic surfactant monomer is shown in formula I:
a formula I;
wherein r=c n H 2n+1 ；n=8-18。
As a further improvement of the invention, the method comprises the following steps:
s1, reacting methyl benzyl amine with long-chain alkyl chloride to obtain an intermediate, wherein the structure of the intermediate is shown as a formula II:
a formula II;
wherein r=c n H 2n+1 ；n=8-18；
S2, reacting the intermediate with allyl chloride to prepare a cationic surfactant monomer;
s3, dissolving a surfactant in an organic solvent to obtain an oil phase;
s4, dissolving 1H, 1H-perfluoropropyl methacrylate, 2-acrylamide-2-methylpropanesulfonic acid, N-vinyl pyrrolidone and the cationic surfactant monomer prepared in the step S2, acrylamide and 1-vinyl-3-ethylimidazole bromide salt in water, and regulating the pH value to obtain a water phase;
s5, adding the water phase into the oil phase, homogenizing to form reverse emulsion, adding an initiator system under the protection of inert gas, and stirring for reaction to obtain the emulsion resistance reducing agent.
As a further improvement of the present invention, the molar ratio of the methylbenzylamine to the long-chain alkyl chloride in the step S1 is 1:2-2.1, and the long-chain alkyl chloride is at least one of 1-chlorooctane, 1-chlorononane, 1-chlorodecane, 1-chloroundecane, 1-chlorododecane, 1-chlorotridecane, 1-chlorotetradecane, 1-chloropentadecane, 1-chlorohexadecane, 1-chloroheptadecane and 1-chlorooctadecane; the reaction time is 1-2h.
As a further improvement of the invention, the molar ratio of the intermediate to allyl chloride in the step S2 is 1:2.2-2.5, 0.5-1wt% of catalyst is added in the reaction, the catalyst is zinc powder, the temperature of the reaction is 60-70 ℃ and the time is 3-4h.
As a further improvement of the present invention, the surfactant in step S3 is a mixture of a hydrophilic surfactant and a lipophilic surfactant, the hydrophilic surfactant being at least one selected from tween-20, tween-40, tween-60, tween-80; the lipophilic surfactant is at least one selected from span-20, span-40, span-60 and span-80; the organic solvent is at least one of white oil, kerosene, petroleum ether, cyclohexane and n-hexane, and the content of the surfactant in the oil phase is 0.5-1wt%.
As a further improvement of the invention, the hydrophilic surfactant is Tween-80, the lipophilic surfactant is span-80, and the mass ratio of the two is 3-5:7.
As a further improvement of the invention, the mass ratio of the 1H, 1H-perfluoro propyl methacrylate, the 2-acrylamide-2-methylpropanesulfonic acid, the N-vinyl pyrrolidone, the cationic surfactant monomer, the acrylamide and the 1-vinyl-3-ethylimidazole bromide salt in the step S4 is 5-7:3-5:7-10:10-12:15-20:3-5, and the pH value of the solution is adjusted to 6.7-7.
As a further improvement of the invention, the mass ratio of the water phase to the oil phase to the initiator system in the step S5 is 10-15:30-50:0.5-1; homogenizing for 10-15min under 10000-12000 r/min; the initiator system comprises an initiator and a co-initiator, wherein the mass ratio of the initiator to the co-initiator is 3-5:2-3; the initiator is at least one selected from sodium persulfate, potassium persulfate and ammonium persulfate, the auxiliary initiator is sodium sulfite, and the stirring reaction time is 3-4h.
As a further improvement of the invention, the method specifically comprises the following steps:
s1, adding 1 molar equivalent of methyl benzyl amine and 2-2.1 molar equivalents of long-chain alkyl chloride into methylene dichloride, stirring and reacting for 1-2 hours, filtering, washing and drying to obtain an intermediate;
s2, mixing 1 molar equivalent of the intermediate with 2.2-2.5 molar equivalents of allyl chloride, adding into water, adding 0.5-1wt% of zinc powder, reacting for 3-4 hours at 60-70 ℃, adding acetonitrile for precipitation, filtering, washing and drying to obtain a cationic surfactant monomer;
s3, dissolving the surfactant in an organic solvent to obtain an oil phase containing 0.5-1wt% of the surfactant;
the surfactant is a mixture of tween-80 and span-80, and the mass ratio is 3-5:7;
s4, dissolving 5-7 parts by weight of 1H, 1H-perfluoropropyl methacrylate, 3-5 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 7-10 parts by weight of N-vinyl pyrrolidone, 10-12 parts by weight of the cationic surfactant monomer prepared in the step S2, 15-20 parts by weight of acrylamide and 3-5 parts by weight of 1-vinyl-3-ethylimidazole bromine salt in 200 parts by weight of water, and regulating the pH value to 6.7-7 to obtain a water phase;
s5, adding 10-15 parts by weight of water phase into 30-50 parts by weight of oil phase, homogenizing for 10-15min at 10000-12000r/min to form reverse emulsion, adding 0.5-1 parts by weight of initiator system under the protection of inert gas, and stirring for reaction for 3-4h to obtain emulsion resistance reducing agent;
the initiator system comprises an initiator and a co-initiator, and the mass ratio is 3-5:2-3.
The invention further protects the emulsion resistance reducing agent prepared by the preparation method.
The invention further protects application of the emulsion resistance reducing agent in preparation of slickwater fracturing fluid.
The invention has the following beneficial effects:
when the Reynolds number is smaller, the shearing rate is lower, the viscous fluid moves in a layered mode, and the resistance reducing agent molecules are arranged in a disordered mode at the moment, and no resistance reducing effect exists. With the increase of the Reynolds number, the solution curve of the emulsion resistance-reducing agent is deviated from the Newton fluid curve, resistance reduction begins to occur, the fluid interface in a unit length in a tube is distorted and deformed under the turbulent state, the curled resistance-reducing agent molecules are fully dispersed, long chains are naturally stretched along the flowing direction and are linearly arranged, and the curve is continuously deviated until the resistance reduction effect reaches the maximum value. At the same time, the friction reducer polymer stretches in the near wall flow region, and the stress generated by stretching is opposite to the eddy acting force, so that eddy suppression is generated. The forward and reverse torque of the friction reducer polymer can inhibit the burst frequency and intensity of vortex, and reduce vortex regeneration, so that turbulent pulsation is reduced, and the flow is in a quasi-laminar state. In addition, the emulsion friction reducing agent can also form an elastic bottom layer in the pipeline, and the elastic bottom layer becomes thicker along with the increase of concentration, so that isolation is generated between the pipe wall and the liquid, the friction resistance of the pipe wall is reduced, and the effect of reducing the friction resistance is achieved.
However, anionic surfactants generally have poor salt resistance and react with calcium and magnesium ions in water easily to form precipitates; the nonionic surfactant has a cloud point, and the surfactant can be changed from full dissolution to partial dissolution at a certain temperature; the price of the amphoteric surfactant is high and the preparation process is complex; the cationic surfactant has good application potential, has a certain sterilization capability, and can also have stable resistance-reducing effect at low concentration.
Therefore, the invention synthesizes the gemini cationic surfactant monomer with long chain alkyl chain, the monomer has simple preparation method, mild synthesis condition, high yield and high resistance reducing efficiency, can efficiently form micelle, ensures that the solution has viscoelasticity to reduce resistance, and the prepared monomer has double bonds and can be polymerized and fixed on a polymer chain. In addition, the 1-vinyl-3-ethylimidazole bromine salt is added into the resistance reducing agent polymer, which is an ionic liquid compound with double bonds, and improves the high temperature stability, shearing resistance and salt resistance of the emulsion adhesion promoter, because the ionic group of the emulsion adhesion promoter is not shielded by the added salt, thereby avoiding salt ions from weakening electrostatic repulsion between ions and showing good salt resistance effect. N-methyl pyrrolidone is introduced into the polymer chain, and because the pyrrole ring structure has a certain three-dimensional effect, the N-methyl pyrrolidone is used as a rigid molecule to move to generate larger steric hindrance, and the N-methyl pyrrolidone has good shearing strength, so that the rigidity of the polymer is increased, and the thermal stability of the resistance reducing agent is increased. The 2-acrylamide-2-methylpropanesulfonic acid is introduced into the polymer chain, and the monomer contains sulfonate, so that a stronger hydrogen bond can be formed with water, and the resistance reducing agent has stronger stability; the 1H, 1H-perfluoropropyl methacrylate is introduced into the polymer chain, so that the shearing resistance of the polymer chain in the construction injection process is improved. The polyacrylamide main chain of the invention contains a large amount of amide groups, and has strong water solubility, higher activity, controllable performance and strong operability.
According to the invention, the emulsion drag reducer is prepared by adopting an inverse emulsion polymerization method, so that the prepared drag reducer has the advantages of low cost, wide raw material sources, simple preparation method and excellent drag reducing effect, and meanwhile, the solubility of the drag reducer is improved, the dissolution time is shortened, and the preparation method can meet the liquid preparation requirement of continuous mixing in the field construction process and has a wide application prospect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of an emulsion resistance reducing agent, which specifically comprises the following steps:
s1, adding 0.1mol of methylbenzylamine and 0.2mol of 1-chlorooctadecane into 100mL of dichloromethane, stirring and reacting for 1h, filtering, washing with deionized water, and drying to obtain an intermediate; ESI-MS calculated: c (C) 44 H 85 N 2 (m+h) + 641.66, found: 641.7, yield 85.2%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ6.41（d，J=6.5Hz，4H），3.32（t，4H），2.85（s，6H），1.52（m，4H），1.28-1.33（m，60H），0.95（t，6H）。
s2, mixing 0.1mol of intermediate and 0.22mol of allyl chloride, adding into 50mL of water, adding zinc powder accounting for 0.wt% of the total mass of the system, reacting for 3 hours at 60 ℃, adding an equal volume of acetonitrile for precipitation, filtering, washing with deionized water, and drying to obtain a cationic surfactant monomer; the yield thereof was found to be 91.0%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ8.32（d，J=6.2Hz，4H），5.70（m，2H），4.98-5.02（m，4H），3.92（m，4H），3.72（s，6H），3.24（t，4H），1.72（m，4H），1.29-1.33（m，60H），0.95（t，6H）。
s3, dissolving a surfactant in kerosene to obtain an oil phase containing 0.5wt% of the surfactant;
the surfactant is a mixture of tween-80 and span-80, and the mass ratio is 3:7;
s4, dissolving 5 parts by weight of 1H, 1H-perfluoropropyl methacrylate, 3 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 7 parts by weight of N-vinyl pyrrolidone, 10 parts by weight of the cationic surfactant monomer prepared in the step S2, 15 parts by weight of acrylamide and 3 parts by weight of 1-vinyl-3-ethylimidazole bromide in 200 parts by weight of water, and regulating the pH value to 6.7 to obtain a water phase;
s5, adding 10 parts by weight of water phase into 30 parts by weight of oil phase, homogenizing for 10min at 10000r/min to form reverse emulsion, adding 0.5 part by weight of initiator system under the protection of nitrogen, and stirring for reaction for 3h to obtain emulsion resistance reducing agent;
the initiator system comprises sodium persulfate and sodium sulfite in a mass ratio of 3:2.
The infrared spectrum analysis is as follows: 3440. 3207cm -1 The stretching vibration peak of the N-H bond in the amido and the O-H bond in the carboxyl; 2917cm -1 Is C-H telescopic vibration peak on imidazole ring substituent, 1205cm -1 The stretching vibration peak of the C-N bond proves that the polyacrylamide is successfully introduced into the molecular main chain; 1047cm -1 Characteristic peaks at sulfonate s=o; 1692cm -1 Characteristic peaks of lactam groups; 1677cm -1 A stretching vibration peak of c=o, 1330cm -1 The place is the telescopic vibration absorption peak of-CF, 1407cm -1 Is provided with a stretching vibration peak of pyrrole ring, 957cm -1 In-plane rocking bending vibration peak of C-H on imidazole ring, 845cm -1 Is characterized by that the benzene ring is characterized by absorption peak,771cm -1 out-of-plane rocking bending vibration peak of C-H on imidazole ring, 715cm -1 Is a hydrophobic chain- (CH) 2 ) Absorption peak of n. At 995-985cm -1 With 915-905cm -1 The C-H out-of-plane bending vibration absorption peak without olefin indicates that all the double bonds of C=C are reacted. In summary, it can be demonstrated that each functional monomer is successfully polymerized onto the drag reducer molecular chain, and the obtained product is the designed product.
Example 2
The embodiment provides a preparation method of an emulsion resistance reducing agent, which specifically comprises the following steps:
s1, adding 0.1mol of methyl benzyl amine and 0.21mol of 1-chlorohexadecane into 100mL of dichloromethane, stirring and reacting for 2 hours, filtering, washing with deionized water, and drying to obtain an intermediate; ESI-MS calculated: c (C) 40 H 77 N 2 (m+h) + 585.60, found: 585.6, yield 88.1%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ6.42（d，J=6.4Hz，4H），3.34（t，4H），2.86（s，6H），1.52（m，4H），1.29-1.32（m，52H），0.94（t，6H）。
s2, mixing 0.1mol of intermediate and 0.25mol of allyl chloride, adding into 50mL of water, adding zinc powder accounting for 1wt% of the total mass of the system, reacting for 4 hours at 70 ℃, adding an equal volume of acetonitrile for precipitation, filtering, washing with deionized water, and drying to obtain a cationic surfactant monomer;
nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ8.33（d，J=6.0Hz，4H），5.72（m，2H），4.98-5.03（m，4H），3.91（m，4H），3.73（s，6H），3.24（t，4H），1.72（m，4H），1.29-1.32（m，52H），0.95（t，6H）。
s3, dissolving a surfactant in kerosene to obtain an oil phase containing 1wt% of the surfactant;
the surfactant is a mixture of tween-80 and span-80, and the mass ratio is 5:7;
s4, dissolving 7 parts by weight of 1H, 1H-perfluoropropyl methacrylate, 5 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 10 parts by weight of N-vinyl pyrrolidone, 12 parts by weight of the cationic surfactant monomer prepared in the step S2, 20 parts by weight of acrylamide and 5 parts by weight of 1-vinyl-3-ethylimidazole bromide in 200 parts by weight of water, and regulating the pH value to 7 to obtain a water phase;
s5, adding 15 parts by weight of water phase into 50 parts by weight of oil phase, homogenizing for 15min at 12000r/min to form reverse emulsion, adding 1 part by weight of initiator system under the protection of nitrogen, and stirring for reaction for 4 hours to obtain emulsion resistance reducing agent;
the initiator system comprises potassium persulfate and sodium sulfite in a mass ratio of 5:3.
Example 3
The embodiment provides a preparation method of an emulsion resistance reducing agent, which specifically comprises the following steps:
s1, adding 0.1mol of methyl benzyl amine and 0.205mol of 1-chlorododecane into 100mL of dichloromethane, stirring and reacting for 1.5h, filtering, washing with deionized water, and drying to obtain an intermediate; ESI-MS calculated: c (C) 32 H 61 N 2 (m+h) + 473.48, found: 473.5, yield 88.1%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ6.43（d，J=6.4Hz，4H），3.33（t，4H），2.85（s，6H），1.51（m，4H），1.27-1.31（m，36H），0.92（t，6H）。
s2, mixing 0.1mol of intermediate and 0.235mol of allyl chloride, adding into 50mL of water, adding zinc powder accounting for 0.7wt% of the total mass of the system, reacting for 3.5 hours at 65 ℃, adding into an equal volume of acetonitrile for precipitation, filtering, washing with deionized water, and drying to obtain a cationic surfactant monomer;
nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ8.31（d，J=6.0Hz，4H），5.71（m，2H），4.99-5.02（m，4H），3.91（m，4H），3.72（s，6H），3.25（t，4H），1.72（m，4H），1.27-1.32（m，36H），0.95（t，6H）。
s3, dissolving a surfactant in the white oil to obtain an oil phase containing 0.7wt% of the surfactant;
the surfactant is a mixture of tween-80 and span-80, and the mass ratio is 4:7;
s4, 6 parts by weight of 1H, 1H-perfluoropropyl methacrylate, 4 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 8.5 parts by weight of N-vinyl pyrrolidone, 11 parts by weight of the cationic surfactant monomer prepared in the step S2, 17 parts by weight of acrylamide and 4 parts by weight of 1-vinyl-3-ethylimidazole bromine salt are dissolved in 200 parts by weight of water, and the pH value is regulated to 6.8 to obtain a water phase;
s5, adding 12 parts by weight of water phase into 40 parts by weight of oil phase, homogenizing for 10-15min at 11000r/min to form reverse emulsion, adding 0.7 part by weight of initiator system under the protection of nitrogen, and stirring for reaction for 3.5h to obtain emulsion resistance reducing agent;
the initiator system comprises ammonium persulfate and sodium sulfite in a mass ratio of 4:2.5.
Comparative example 1
In comparison with example 3, 1H-perfluoropropyl methacrylate was not added.
The method comprises the following steps:
s4, dissolving 4 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 8.5 parts by weight of N-vinyl pyrrolidone, 11 parts by weight of the cationic surfactant monomer prepared in the step S2, 17 parts by weight of acrylamide and 10 parts by weight of 1-vinyl-3-ethylimidazole bromine salt in 200 parts by weight of water, and regulating the pH value to 6.8 to obtain a water phase.
Comparative example 2
In comparison with example 3, the difference is that no 1-vinyl-3-ethylimidazole bromide was added.
The method comprises the following steps:
s4, dissolving 10 parts by weight of 1H, 1H-perfluoropropyl methacrylate, 4 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 8.5 parts by weight of N-vinyl pyrrolidone, 11 parts by weight of the cationic surfactant monomer prepared in the step S2 and 17 parts by weight of acrylamide in 200 parts by weight of water, and regulating the pH value to 6.8 to obtain a water phase.
Comparative example 3
In comparison with example 3, 1H-perfluoropropyl methacrylate and 1-vinyl-3-ethylimidazole bromide were not added.
The method comprises the following steps:
s4, dissolving 4 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 8.5 parts by weight of N-vinyl pyrrolidone, 11 parts by weight of the cationic surfactant monomer prepared in the step S2 and 27 parts by weight of acrylamide in 200 parts by weight of water, and regulating the pH value to 6.8 to obtain a water phase.
Comparative example 4
In comparison with example 3, the difference is that no N-vinylpyrrolidone was added.
The method comprises the following steps:
s4, 6 parts by weight of 1H, 1H-perfluoropropyl methacrylate, 12.5 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 11 parts by weight of the cationic surfactant monomer prepared in the step S2, 17 parts by weight of acrylamide and 4 parts by weight of 1-vinyl-3-ethylimidazole bromide are dissolved in 200 parts by weight of water, and the pH value is regulated to 6.8, so that a water phase is obtained.
Comparative example 5
In comparison with example 3, the difference is that 2-acrylamido-2-methylpropanesulfonic acid was not added.
The method comprises the following steps:
s4, 6 parts by weight of 1H, 1H-perfluoropropyl methacrylate, 12.5 parts by weight of N-vinyl pyrrolidone, 11 parts by weight of the cationic surfactant monomer prepared in the step S2, 17 parts by weight of acrylamide and 4 parts by weight of 1-vinyl-3-ethylimidazole bromine salt are dissolved in 200 parts by weight of water, and the pH value is regulated to 6.8, so that a water phase is obtained.
Comparative example 6
In comparison with example 3, the difference is that N-vinylpyrrolidone and 2-acrylamido-2-methylpropanesulfonic acid are not added.
The method comprises the following steps:
s4, 6 parts by weight of 1H, 1H-perfluoropropyl methacrylate, 11 parts by weight of the cationic surfactant monomer prepared in the step S2, 29.5 parts by weight of acrylamide and 4 parts by weight of 1-vinyl-3-ethylimidazole bromine salt are dissolved in 200 parts by weight of water, and the pH value is regulated to 6.8, so that a water phase is obtained.
Comparative example 7
The difference compared to example 3 is that no cationic surfactant monomer was added.
The method comprises the following steps:
s4, 6 parts by weight of 1H, 1H-perfluoropropyl methacrylate, 4 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 8.5 parts by weight of N-vinyl pyrrolidone, 28 parts by weight of acrylamide and 4 parts by weight of 1-vinyl-3-ethylimidazole bromide are dissolved in 200 parts by weight of water, and the pH value is regulated to 6.8, so that a water phase is obtained.
Test example 1 stability test
The emulsion resistance reducers prepared in examples 1 to 3 and comparative examples 1 to 7 of the present invention were left to stand at normal temperature for 48 hours and 72 hours, respectively, and then left to stand at a high temperature of 90℃for 24 hours and 36 hours, and the states thereof were observed, and the results are shown in Table 1.
TABLE 1
As shown in the table above, the emulsion resistance reducers prepared in examples 1-3 of the present invention have good stability.
Test example 2 salt and shear resistance test
The emulsion resistance-reducing agents prepared in examples 1 to 3 and comparative examples 1 to 7 of the present invention were formulated into an aqueous solution having a content of 0.2% by weight, and performance test was conducted.
Salt tolerance test
NaCl was added to the solution so that the concentration of NaCl in the solution was 0.25% by weight, and the mixture was stirred at room temperature (25 ℃) for 170 seconds by means of a six-speed rotational viscometer -1 Apparent viscosity was measured at a shear rate, and a viscosity retention (%) was calculated.
Shear resistance test
Measuring with rheometer, measuring rotor with PZ38 and rotor diameter 38mm with high temperature closed test system at 65deg.C and 170s -1 The solution was continuously sheared for 2 hours, the apparent viscosity was measured by a six-speed rotational viscometer, and the viscosity retention (%) was calculated.
Viscosity retention (%) = (apparent viscosity η at the time of measurement) 1 Apparent viscosity eta of initial state 0 ) Apparent viscosity eta of initial state 0 ×100%
The results are shown in Table 2.
TABLE 2
As shown in the table above, the emulsion resistance reducing agents prepared in examples 1-3 of the present invention have good salt resistance and shear resistance.
Test example 3
The emulsion resistance-reducing agents prepared in examples 1 to 3 and comparative examples 1 to 7 of the present invention were formulated into an aqueous solution having a content of 0.2% by weight, and performance test was conducted.
And adopting a flow loop friction resistance testing system to perform resistance reduction testing on the drag reducer, comparing the drag reducer with clear water, and adding the drag reducer with a certain concentration into the clear water. And (3) testing by using a pipeline with the diameter of 8mm, recording friction pressure drop of the fluid after the fluid passes through the pipeline, and calculating the drag reduction rate.
Wherein, eta is the resistivity of the solution,%; ΔP Water and its preparation method -pressure drop in clear water through the test line, MPa; ΔP-the pressure drop of the aqueous drag reducer solution through the test line at the same flow rate, MPa.
The resistivity was measured at flow rates of 20L/min, 40L/min, and 60L/min.
The results are shown in Table 3.
TABLE 3 Table 3
As shown in the table above, the emulsion resistance reducers prepared in examples 1-3 of the present invention have good resistance reducing performance.
Comparative examples 1 and 2 compared with example 3, 1H-perfluoropropyl methacrylate or 1-vinyl-3-ethylimidazole bromide was not added. Comparative example 3 in comparison with example 3, 1H-perfluoropropyl methacrylate and 1-vinyl-3-ethylimidazole bromide were not added. The salt resistance and the shearing resistance are reduced, and the drag reduction rate is reduced. The invention adds 1-vinyl-3-ethylimidazole bromine salt into the polymer, which is an ionic liquid compound with double bonds, improves the high temperature stability, shearing resistance and salt resistance of the emulsion tackifier, because the ionic group is not shielded by the added salt, thereby avoiding salt ions weakening electrostatic repulsion between ions and showing good salt resistance effect. The 1H, 1H-perfluoropropyl methacrylate is introduced into the polymer chain, so that the shearing resistance of the polymer chain in the construction injection process is improved.
Comparative examples 4 and 5 were compared with example 3, in which no N-vinylpyrrolidone or 2-acrylamido-2-methylpropanesulfonic acid was added. Comparative example 6 in comparison with example 3, no N-vinylpyrrolidone and 2-acrylamido-2-methylpropanesulfonic acid were added. The thermal stability is reduced and the drag reduction rate is reduced. N-methyl pyrrolidone is introduced into the polymer chain, and because the pyrrole ring structure has a certain three-dimensional effect, the N-methyl pyrrolidone is used as a rigid molecule to move to generate larger steric hindrance, and the N-methyl pyrrolidone has good shearing strength, so that the rigidity of the polymer is increased, and the thermal stability of the resistance reducing agent is increased. The polymer chain of the invention is introduced with 2-acrylamide-2-methylpropanesulfonic acid, and the monomer contains sulfonate, which can form stronger hydrogen bond with water, so that the resistance reducing agent has stronger stability.
Comparative example 7 compared to example 3, no cationic surfactant monomer was added. The thermal stability and the resistivity decrease. The invention synthesizes a Gemini type cationic surfactant monomer with long chain alkyl chain, the monomer has simple preparation method, mild synthesis condition, high yield and high resistance reducing efficiency, can efficiently form micelle, ensures that solution has viscoelasticity to reduce resistance, and the prepared monomer has double bonds and can be fixed on a polymer chain through polymerization reaction. Meanwhile, the rigid structure of the benzene ring also improves the thermal stability of the resistance reducing agent.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The preparation method of the emulsion resistance-reducing agent is characterized in that 1H, 1H-perfluoro propyl methacrylate, 2-acrylamide-2-methylpropanesulfonic acid, N-vinyl pyrrolidone, cationic surfactant monomer, acrylamide and 1-vinyl-3-ethylimidazole bromine salt are dissolved in water to obtain a water phase; dissolving a surfactant in an organic solvent to obtain an oil phase; adding the water phase into the oil phase, stirring to form inverse emulsion, adding an initiator system under the protection of inert gas, and stirring for reaction to obtain an emulsion resistance reducing agent;
the mass ratio of the 1H, 1H-perfluoropropyl methacrylate to the 2-acrylamide-2-methylpropanesulfonic acid to the N-vinyl pyrrolidone to the cationic surfactant monomer to the acrylamide to the 1-vinyl-3-ethylimidazole bromide salt is 5-7:3-5:7-10:10-12:15-20:3-5;
the mass ratio of the water phase to the oil phase to the initiator system is 10-15:30-50:0.5-1;
the structural formula of the cationic surfactant monomer is shown in formula I:
a formula I;
wherein r=c n H 2n+1 ；n=8-18。
2. The preparation method according to claim 1, comprising the steps of:
s1, reacting methyl benzyl amine with long-chain alkyl chloride to obtain an intermediate, wherein the structure of the intermediate is shown as a formula II:
a formula II;
wherein r=c n H 2n+1 ；n=8-18；
S2, reacting the intermediate with allyl chloride to prepare a cationic surfactant monomer;
s3, dissolving a surfactant in an organic solvent to obtain an oil phase;
s4, dissolving 1H, 1H-perfluoropropyl methacrylate, 2-acrylamide-2-methylpropanesulfonic acid, N-vinyl pyrrolidone and the cationic surfactant monomer prepared in the step S2, acrylamide and 1-vinyl-3-ethylimidazole bromide salt in water, and regulating the pH value to obtain a water phase;
s5, adding the water phase into the oil phase, homogenizing to form inverse emulsion, adding an initiator system under the protection of inert gas, and stirring for reaction to obtain the emulsion resistance reducing agent.
3. The preparation method according to claim 2, wherein the molar ratio of the methylbenzylamine to the long-chain alkyl chloride in the step S1 is 1:2-2.1, and the long-chain alkyl chloride is at least one of 1-chlorooctane, 1-chlorononane, 1-chlorodecane, 1-chloroundecane, 1-chlorododecane, 1-chlorotridecane, 1-chlorotetradecane, 1-chloropentadecane, 1-chlorohexadecane, 1-chloroheptadecane, and 1-chlorooctadecane; the reaction time is 1-2h.
4. The preparation method according to claim 2, wherein the molar ratio of the intermediate to allyl chloride in the step S2 is 1:2.2-2.5, 0.5-1wt% of catalyst is added in the reaction, the catalyst is zinc powder, the reaction temperature is 60-70 ℃ and the reaction time is 3-4h.
5. The preparation method according to claim 2, wherein the surfactant in step S3 is a mixture of a hydrophilic surfactant and a lipophilic surfactant, and the hydrophilic surfactant is at least one selected from tween-20, tween-40, tween-60, and tween-80; the lipophilic surfactant is at least one selected from span-20, span-40, span-60 and span-80, the organic solvent is at least one selected from white oil, kerosene, petroleum ether, cyclohexane and n-hexane, and the content of the surfactant in the oil phase is 0.5-1wt%.
6. The preparation method according to claim 5, wherein the hydrophilic surfactant is tween-80, and the lipophilic surfactant is span-80, and the mass ratio of the tween-80 to span-80 is 3-5:7.
7. The method according to claim 2, wherein the pH of the solution is adjusted to 6.7-7 in step S4.
8. The method according to claim 2, wherein the homogenization conditions in step S5 are 10000-12000r/min for 10-15min; the initiator system comprises an initiator and a co-initiator, wherein the mass ratio of the initiator to the co-initiator is 3-5:2-3; the initiator is at least one selected from sodium persulfate, potassium persulfate and ammonium persulfate, the auxiliary initiator is sodium sulfite, and the stirring reaction time is 3-4h.
9. An emulsion drag reducer made by the method of any one of claims 1-8.
10. Use of the emulsion drag reducer of claim 9 in the preparation of slickwater fracturing fluids.
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