CN109111904B - Profile control agent of isocharged polymer nano-microsphere and preparation method thereof - Google Patents

Profile control agent of isocharged polymer nano-microsphere and preparation method thereof Download PDF

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CN109111904B
CN109111904B CN201810845626.0A CN201810845626A CN109111904B CN 109111904 B CN109111904 B CN 109111904B CN 201810845626 A CN201810845626 A CN 201810845626A CN 109111904 B CN109111904 B CN 109111904B
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李光辉
吴振豪
李晓丹
未九森
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Yanshan University
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Abstract

The invention provides a profile control agent of isocharged polymer nano microspheres, which is easily dispersed in water at normal temperature, when the system is applied to a stratum, the system is contacted with water at the temperature of the stratum, and the microspheres expand, so that surface charges are rearranged on the outer surfaces of the microspheres; after expansion, electrostatic attraction among the heterocharge microspheres is enough to overcome the phenomenon that van der Waals repulsion force is subjected to coagulation sedimentation, and further the dominant water flow channel in the stratum is blocked; the profile control agent can enhance the plugging strength of precipitated particles, and the application permeability range of the nano-microsphere profile control agent is from 0.1 mu m2The left and right are expanded to 3 mu m2。

Description

Profile control agent of isocharged polymer nano-microsphere and preparation method thereof
Technical Field
The invention relates to the technical field of petroleum development, in particular to a profile control agent of a heterocharge polymer nano microsphere and a preparation method thereof.
Background
At present, most of domestic oil fields are in a high-water-content exploitation stage of water injection development, the heterogeneity of an oil deposit is serious, water flow dominant channels are developed, injected water is ineffectively circulated, and the sweep coefficient of the oil layer is low, so that the problems of too low crude oil recovery ratio, flooding of the oil deposit in the later period, equipment corrosion, overlarge sewage treatment load and the like are caused. In addition, with the increasing consumption of crude oil and the high international oil prices, many oil reservoirs under severe conditions such as offshore oil fields, hypotonicity, and hypersalinity are being developed.
Most of the existing profile control agents and related matching technologies are not suitable for such reservoirs because: (1) the inorganic particles are only suitable for plugging large pore passages close to the well and can cause permanent blockage; (2) the polymer jelly and the cross-linking agent (such as chromium ions, zirconium ions and the like) are easy to adsorb, disperse and retain in the stratum, so that the concentration is reduced and the preset cross-linking strength is difficult to achieve; (3) the colloid dispersion gel has small polymer concentration and low strength, and can only be used for oil reservoirs with the formation temperature lower than 90 ℃ and the mineralization degree lower than 5000 mg/L; (4) the preformed gel has complex preparation process, needs drying, grinding and sieving, and is mixed with water and injected into granules which are difficult to control the expansion when in application.
The polyacrylamide microsphere profile control agent can overcome the defects of the profile control agent. The polyacrylamide microsphere is a space net-shaped polyacrylamide particle prepared by taking the microemulsion as a disperse system and acrylamide as a main monomer under the condition of adding a small amount of cross-linking agent. After the polyacrylamide microspheres are injected into the stratum, the polyacrylamide microspheres absorb water to expand, so that the volume of the polyacrylamide microspheres is increased, water flow dominant channels in the stratum can be blocked, and the sweep coefficient of injected water is improved. The prepared polyacrylamide microspheres have small particle size and low aqueous solution viscosity, so that the polyacrylamide nano microspheres can easily enter the deep part of a stratum to realize deep profile control and flooding, and the preparation method has great significance for controlling water and stabilizing oil of old oil reservoirs and improving the water injection development effect of offshore oil fields, low-permeability oil reservoirs and high-salinity oil reservoirs.
Currently, patents CN 101759838A and CN 101805423A related to the synthesis of polyacrylamide microspheres synthesize acrylamide nanoparticles with 35% of solid content and acrylamide nanoparticles with low interfacial tension, respectively. Wherein, the particle size of the nanometer polymer microsphere is tens of nanometers to hundreds of nanometers, and the nanometer polymer microsphere is easy to enter the deep part of the stratum relative to the microsphere of several micrometers to tens of micrometers. However, the strength of the expanded nano-microspheres is inversely related to the expansion multiple, and the plugging strength is sharply reduced along with the increase of the expansion multiple, so that the nano-microspheres are only suitable for medium and low permeability oil reservoirs with strong heterogeneity.
Disclosure of Invention
The invention aims to provide a profile control agent of a heterocharge polymer nano microsphere, which improves the plugging strength and enlarges the application permeability range of the profile control agent.
In order to achieve the above object, the present invention provides the following technical solutions:
the profile control agent for the isocharged polymer nano-microspheres is prepared from the following components in percentage by mass:
20-49% of oil-soluble solvent, 40-71% of water phase and 9-17% of surfactant;
the water phase consists of the following components in percentage by mass:
10 to 70 percent of cationic monomer and anionic monomer, 0.001 to 1.00 percent of cross-linking agent and the balance of water.
Preferably, the cationic monomer is methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride or dimethyl allyl benzyl ammonium chloride.
Preferably, the anionic monomer is one or two of an organic acid, an alkali metal salt of an organic acid, an ammonium salt of an organic acid, and an allyl monomer.
Preferably, the organic acid is acrylic acid, methacrylic acid, vinylsulfonic acid, vinylbenzenesulfonic acid, allylsulfonic acid, allylbenzenesulfonic acid, or 2-acrylamido-2-methylpropanesulfonic acid.
Preferably, the molar ratio of the anionic monomer to the cationic monomer is 1:9 to 9: 1.
The invention provides a preparation method of the isocharged polymer nano-microsphere profile control agent in the technical scheme, which comprises the following steps:
mixing a surfactant with an oil-soluble solvent to obtain an oil phase;
mixing a cross-linking agent, a cationic monomer and water to obtain a cationic monomer water phase;
mixing a cross-linking agent, an anionic monomer and water to obtain an anionic monomer water phase;
mixing the cationic monomer water phase with the oil phase to obtain a microemulsion;
carrying out microemulsion polymerization on the microemulsion to obtain a single-charge polymer nano microsphere system;
mixing the anionic monomer aqueous phase with the single-charge polymer nano microsphere system to obtain an emulsion;
and carrying out emulsion polymerization on the emulsion to obtain the isocharged polymer nano microsphere profile control agent.
Preferably, the mass ratio of the cationic monomer water phase to the oil phase is 1-7: 8.
Preferably, the mass ratio of the anionic monomer aqueous phase to the cationic monomer aqueous phase is 0.3-1: 1.
Preferably, the temperature of the microemulsion polymerization is 10-40 ℃, and the time is 0.5-2 h.
Preferably, the temperature of the emulsion polymerization is 10-40 ℃, and the time is 0.5-2 h.
The invention provides a profile control agent for isocharged polymer nano microspheres, which utilizes the strong hydrophilicity of anionic monomers and cationic monomers, ionic monomers are distributed in the microspheres in the prepared inverse emulsion, and no copolymerization and sedimentation can occur among particles;
the profile control agent for the isocharged polymer nano-microspheres is easily dispersed in water at normal temperature, and when the profile control agent is applied to a stratum, the profile control agent is contacted with water at the temperature of 50-90 ℃, and the microspheres expand, so that surface charges are rearranged on the outer surfaces of the microspheres; after expansion, electrostatic attraction among the heterocharge microspheres is enough to overcome the phenomenon that van der Waals repulsion force is subjected to coagulation sedimentation, and further the dominant water flow channel in the stratum is blocked;
when the profile control agent is used for the stratum, the rotation speed of emulsification and dispersion equipment is used for adjusting and controlling the size of emulsion droplets, and the emulsion droplets are aggregated and precipitated in the target stratum to form nanoparticle aggregates, so that the profile control agent can meet the requirements of stratum profile control with different permeabilities and wide pore throat scales;
when the method is applied, firstly, a slug of low molecular alcohol is injected into the stratum, then, a buffer slug is injected, then, a microsphere slug is injected, and the depth of the stratum, in which the microsphere slug meets the alcohol to form a coagulation, is adjusted through the size of the buffer slug, so that the stratum position on which the microsphere acts is controlled;
the profile control agent can solve the problem that the strength and the expansion multiple of the traditional nano microsphere are difficult to be considered, the diameter of the traditional nano microsphere is about 50-200 nm before expansion, the particle size is hundreds of nanometers to several micrometers after expansion, the strength of the expanded microsphere is sharply reduced along with the increase of the expansion multiple, and the profile control agent is mainly applied to permeability of less than 0.1 mu m2Of (4 μm average pore diameter). The strength of the expanded nano microspheres is controlled by controlling the amount of the cross-linking agent, and the expansion capacity of the obtained nano microspheres is not good when the amount of the cross-linking agent is differentMeanwhile, the strength of the nano-microsphere with small expansion factor is relatively large. The invention ensures the strength of the expanded microspheres by adding a proper amount of cross-linking agent, forms microsphere aggregates by coagulation generated by electrostatic attraction between the heterocharge microspheres, improves the range of the size of the blocked pores, expands the application permeability range of the nano-microsphere profile control agent, and can change the application permeability range of the nano-microspheres from 0.1 mu m2The left and right are expanded to 3 mu m2. The invention obtains the isocharged polymer nano microsphere dispersion system through microemulsion polymerization and emulsion polymerization, and the method is simple and easy to implement.
Detailed Description
The invention provides a profile control agent for a polymer nano microsphere with different charges, which is prepared from the following components in percentage by mass:
20-49% of oil-soluble solvent, 40-71% of water phase and 9-17% of surfactant;
the water phase consists of the following components in percentage by mass:
10 to 70 percent of cationic monomer and anionic monomer, 0.001 to 1.00 percent of cross-linking agent and the balance of water.
In the invention, the raw materials for preparing the profile control agent of the isocharged polymer nano-microsphere comprise 20-49% of oil-soluble solvent by mass fraction, preferably 35-45%. In the present invention, the oil-soluble solvent is preferably gasoline, kerosene, diesel oil, white oil, paraffin, vegetable oil, toluene, cyclohexane or isooctane.
In the invention, the raw material for preparing the profile control agent of the isocharged polymer nano-microsphere comprises 40-71% of water phase by mass fraction, and preferably 55-65%. In the invention, the water phase consists of the following components in percentage by mass: 10 to 70 percent of cationic monomer and anionic monomer, 0.001 to 1.00 percent of cross-linking agent and the balance of water.
In the invention, the water phase comprises 10-70% of cationic monomer and anionic monomer by mass, preferably 20-50%, and more preferably 30-40%. In the present invention, the cationic monomer is preferably methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, dimethyldiallylammonium chloride or dimethylallylbenzyl ammonium chloride; the anionic monomer is preferably one or two of organic acid, alkali metal salt of organic acid, ammonium salt of organic acid and allyl monomer; the organic acid is preferably acrylic acid, methacrylic acid, vinylsulfonic acid, vinylbenzenesulfonic acid, allylsulfonic acid, allylbenzenesulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid. In the present invention, the molar ratio of the anionic monomer to the cationic monomer is preferably 1:9 to 9:1, and more preferably 1:3 to 6: 1. According to the invention, the strong hydrophilicity of the cationic monomer and the anionic monomer is utilized, so that different charges are arranged on the inner surface of the microsphere, and no coagulation and sedimentation can occur among particles, thereby obtaining the profile control agent for the isocharged polymer nano microsphere.
In the invention, the water phase comprises 0.001-1.00% of cross-linking agent by mass fraction, preferably 0.01-0.5%, and more preferably 0.1-0.3%. In the invention, the crosslinking agent is preferably one or two of Methylene Bisacrylamide (MBA), Divinylbenzene (DVB) and polyethylene glycol diacrylate (PEGDA), and when the crosslinking agent is MBA and PEGDA, the mass ratio of the two crosslinking agents is preferably 1: 1-50, and more preferably 1: 10-30. The invention utilizes the cross-linking agent to adjust the strength of the expanded microspheres.
In the invention, the water phase preferably further comprises an oxidant with the mass fraction of less than or equal to 2.30%, more preferably 1.0-1.5%, and the oxidant is preferably sodium persulfate, ammonium persulfate, potassium persulfate, peroxyacetic acid, sodium percarbonate or peroxyisobutanol.
In the invention, the raw materials for preparing the profile control agent for the nano-microspheres of the isocharged polymer comprise 9-17% by mass of surfactant, preferably 12-15% by mass of surfactant, and the surfactant is preferably two of sorbitan fatty acid ester (SPAN), polyoxyethylene sorbitan fatty acid ester (TWEEN), alkylphenol polyoxyethylene ether (OP) and α olefin sulfonate (AOS), wherein when the two surfactants are any one of SPAN and TWEEN, SPAN and OP and SPAN and AOS, the mass ratio of the two surfactants is preferably 0.25-4: 1, more preferably 0.5-3: 1.
In the invention, the raw materials for preparing the profile control agent of the isocharged polymer nano-microsphere preferably also comprise a reducing agent with the mass fraction of less than or equal to 1.0%, and more preferably 0.2-0.6%. In the present invention, the reducing agent is preferably sodium metabisulfite, sodium sulfite, sodium thiosulfate or sodium bisulfite.
The invention provides a preparation method of the isocharged polymer nano-microsphere profile control agent in the technical scheme, which comprises the following steps:
mixing a surfactant with an oil-soluble solvent to obtain an oil phase;
mixing a cross-linking agent, a cationic monomer and water to obtain a cationic monomer water phase;
mixing a cross-linking agent, an anionic monomer and water to obtain an anionic monomer water phase;
mixing the cationic monomer water phase with the oil phase to obtain a microemulsion;
carrying out microemulsion polymerization on the microemulsion to obtain a single-charge polymer nano microsphere system;
mixing the anionic monomer aqueous phase with the single-charge polymer nano microsphere system to obtain an emulsion;
and carrying out emulsion polymerization on the emulsion to obtain the isocharged polymer nano microsphere profile control agent.
The invention mixes the surface active agent and the oil-soluble solvent to obtain the oil phase. The surfactant and the oil-soluble solvent are preferably mixed, and N is introduced at the temperature of 10-40 DEG C2Deoxidizing and stirring uniformly to obtain the oil phase.
The invention mixes the cross-linking agent, the cationic monomer and water to obtain the cationic monomer water phase. In the invention, in the cationic monomer aqueous phase, the mass fraction of the cross-linking agent is preferably 0.001-1.00%, more preferably 0.01-0.5%, and most preferably 0.1-0.3%; the mass fraction of the cationic monomer is preferably 10% to 70%, more preferably 30% to 50%.
In the invention, when the raw materials for preparing the heterocharge polymer nano microsphere profile control agent also comprise an oxidant, the invention preferably mixes the cross-linking agent, the cationic monomer, water and the oxidant to obtain the cationic monomer water phase. In the invention, the mass fraction of the oxidant in the cationic monomer aqueous phase is preferably less than or equal to 2.3%, and more preferably 0.8-1.5%.
The invention mixes the cross-linking agent, the anionic monomer and water to obtain the anionic monomer water phase. In the invention, in the anionic monomer aqueous phase, the mass fraction of the cross-linking agent is preferably 0.001-1.00%, more preferably 0.01-0.5%, and most preferably 0.1-0.3%; the mass fraction of the anionic monomer is preferably 10% to 70%, more preferably 30% to 50%.
In the invention, when the raw materials for preparing the heterocharge polymer nano microsphere profile control agent also comprise an oxidant, the invention preferably mixes the cross-linking agent, the anionic monomer, water and the oxidant to obtain the anionic monomer aqueous phase. In the invention, the mass fraction of the oxidant in the anionic monomer aqueous phase is preferably less than or equal to 2.3%, and more preferably 0.8-1.5%.
After the cationic monomer water phase and the oil phase are obtained, the cationic monomer water phase and the oil phase are mixed to obtain the microemulsion. In the invention, the mass ratio of the cationic monomer aqueous phase to the oil phase is preferably 1-7: 8. The invention preferably mixes and stirs the cationic monomer water phase and the oil phase at 20-40 ℃ to form microemulsion; the stirring speed is preferably 200-600 rpm/min.
After the microemulsion is obtained, the microemulsion is subjected to microemulsion polymerization to obtain a single-charge polymer nano microsphere system. In the invention, the temperature of the microemulsion polymerization is preferably 10-40 ℃, and the time is preferably 0.5-2 h. According to the invention, preferably, the microemulsion is firstly subjected to nitrogen introduction and oxygen removal at the temperature of 10-40 ℃, then polymerization is initiated, microemulsion polymerization is carried out, the reaction is continued after the heat release peak, the total reaction time is controlled to be 0.5-2 h, and the temperature is controlled before the liquid recovery reducing agent is added, so that the single-charge polymer nano microsphere system is obtained.
In the invention, when the raw materials for preparing the profile control agent of the polymer nano-microspheres with different charges also comprise a reducing agent, the microemulsion is preferably mixed with the reducing agent and then subjected to microemulsion polymerization to obtain a polymer nano-microsphere system with single charge.
After the single-charge polymer nano microsphere system is obtained, the anionic monomer aqueous phase and the single-charge polymer nano microsphere system are mixed to obtain the emulsion. In the present invention, the mass ratio of the anionic monomer aqueous phase to the cationic monomer aqueous phase is preferably 0.3 to 1: 1. The anionic monomer aqueous phase and the single charge polymer nano microsphere system are preferably mixed and stirred at 10-40 ℃ to form emulsion; the stirring speed is preferably 200-600 rpm/min.
After the emulsion is obtained, the emulsion is subjected to emulsion polymerization to obtain the isocharged polymer composite nano microsphere system. In the invention, the temperature of the emulsion polymerization is preferably 10-40 ℃, and the time is preferably 0.5-2 h. Preferably, the emulsion is firstly subjected to nitrogen introduction and oxygen removal at the temperature of 10-40 ℃, then polymerization is initiated, emulsion polymerization is carried out, the reaction is continued after the heat release peak, the total reaction time is controlled to be 0.5-2 h, and the temperature is controlled to be before the liquid recovery reducing agent is added, so that the isocharged polymer nano microsphere profile control agent is obtained.
In the invention, when the raw materials for preparing the profile control agent of the polymer nano-microspheres with different charges also comprise a reducing agent, the invention preferably mixes the emulsion and the reducing agent and then carries out emulsion polymerization to obtain the profile control agent of the polymer nano-microspheres with different charges.
In the invention, at least one of an oxidizing agent and a reducing agent is preferably used in the raw materials for preparing the isocharged polymer nano microsphere profile control agent; when a reducing agent is not used, it is preferred in the present invention that an oxidizing agent is used to initiate the polymerization; when the oxidant is not used, the invention utilizes the residual peroxide groups in the preparation process of the reducing agent and the composite surfactant to form a redox system to play the role of the oxidant.
The following examples are provided to illustrate the preparation method of the isocharged polymer composite nano microsphere system of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing 33g of gasoline, adding into a three-neck flask, adding a surfactant prepared from 16g of sorbitan fatty acid ester (Span80) and 4g of polyoxyethylene sorbitan fatty acid ester (Tween60), and introducing N at 30 ℃2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; mixing 22.69g of Acrylamide (AM), 2.56g of acryloyloxyethyltrimethylammonium chloride (AETMA), 0.02g of Methylenebisacrylamide (MBA), 0.32g of potassium persulfate (APK) and 12.8g of distilled water to obtain a cationic monomer aqueous phase; adding the cationic monomer water phase into the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxidizing for 10min, adding 0.64g of sodium pyrosulfate (SMS) water solution with the mass concentration of 10% as a reducing agent while stirring to initiate polymerization reaction, continuing to react for 0.5h after the heat release peak, and obtaining a single-charge polyacrylamide nano microsphere system after the temperature of the liquid is recovered to the temperature before the reducing agent is added;
mixing 16.64g of Acrylamide (AM), 2.56g of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), 0.01g of Methylene Bisacrylamide (MBA), 0.32g of potassium persulfate (APK) and 12.8g of distilled water to obtain an anionic monomer aqueous phase, adding the anionic monomer aqueous phase into the single-charge polyacrylamide nano microsphere system, uniformly stirring and mixing to obtain an emulsion, introducing N into the emulsion2Deoxidizing for 10min, adding 0.64g of SMS aqueous solution with the mass concentration of 10% to initiate polymerization reaction again, continuing to react for 1.5h after the heat release peak, and obtaining the isocharged polyacrylamide nano-microsphere profile control agent at the temperature before the liquid recovery reducing agent is added.
Specific data for example 1 are shown in table 1.
TABLE 1 raw material ratios of profile control agents in example 1
Figure BDA0001746552520000081
According to the analysis and calculation of the synthesized product shown in the table 1, the oil phase accounts for 42.4% of the total mass of the system, the mass ratio of the surfactant Span80 to the Tween60 is 4:1, and the total using amount accounts for 16% of the total mass of the system; the water phase accounts for 55.01% of the total mass of the system, the dosage of the cross-linking agent accounts for 0.05% of the mass of the water phase system, and the proportion of the anionic monomer to the cationic monomer is 1: 1; the dosage of the oxidant accounts for 0.92 percent of the total mass of the system, and the dosage of the reducing agent accounts for 1.0 percent of the total mass of the system.
And (2) under the action of a homogenizing emulsifying machine, controlling the rotating speed to be 1000r/min, stirring for 10 minutes, and carrying out homogenizing dispersion on the microspheres obtained in the example 1 to ensure that the particle size of the isocharged polyacrylamide nano microspheres is 90-150 mu m.
The application of the heterocharge nano-microsphere in the permeability of 3.06 mu m2The sand-filled pipe has the plugging strength of 12.3 and the residual resistance coefficient of 6.2.
Wherein, the plugging strength and the applicable permeability range of the microsphere are measured according to the following experimental methods:
(1) simulating formation rock by using a sand filling pipe with the diameter of 2.5cm and the length of 30cm, filling sand by adopting a wet method, and weighing and calculating the pore volume in the sand filling process;
(2) measuring the water permeability at room temperature at an injection rate of 1 mL/min;
(3) injecting 1 Pore Volume (PV) of ethanol at an injection rate of 1 mL/min;
(4) injecting a 1PV profile control agent at an injection rate of 1 mL/min;
(5) the sand-filled pipe is sealed and then placed in an oven at 80 ℃ for 2 days, and after being taken out and placed to room temperature, the permeability is measured by water again at the injection speed of 1 mL/min. When the first drop of water flows out of the sand filling pipe, the first drop of water is breakthrough pressure, and the pressure ratio value of the pressure and the primary water permeability is used for expressing the plugging strength. And when the pressure of the water permeability reaches the balance, the pressure ratio of the pressure to the initial water permeability is the residual resistance coefficient, and when the residual resistance coefficient is more than 5, the stratum with the permeability can be effectively plugged.
Example 2
39.88g of kerosene is weighed and added into a three-neck flask, then 4.57g of surfactant compounded by Span20 and 9.14g of Tween80 are added, and N is introduced at the temperature of 40 DEG C2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; 18.61g of 10 percent by massAcrylamide (AM), 3.67g methacryloyloxyethyl trimethyl ammonium chloride (DMC), 0.01g divinylbenzene (TVB), 0.04g Ammonium Persulfate (APS) and 13.79g distilled water were mixed to obtain a cationic monomer aqueous phase; adding the cationic monomer water phase into the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxidizing for 10min, adding 0.10g of Benzoyl Peroxide (BP) aqueous solution with the mass concentration of 10% while stirring to initiate polymerization reaction, continuing to react for 1.5h after the heat release peak, and obtaining a single-charge polyacrylamide nano microsphere system until the temperature of the liquid is recovered to the temperature before adding the reducing agent;
mixing 11.29g of Acrylamide (AM) with the mass fraction of 10%, 2.87g of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), 0.02g of divinylbenzene (TVB), 0.04g of Ammonium Persulfate (APS) and 15g of distilled water to obtain an anionic monomer water phase, adding the anionic monomer water phase into the single-charge polyacrylamide nano microsphere system, and uniformly stirring and mixing to obtain an emulsion; introducing the emulsion into N2Deoxidizing for 10min, adding 0.10g of 10% Benzoyl Peroxide (BP) aqueous solution to initiate polymerization reaction again, continuing the reaction for 1h after the heat release peak, and obtaining the isocharged polyacrylamide nano-microsphere profile control agent after the temperature is reached before the liquid recovers the reducing agent is added.
Specific data for example 2 are shown in table 2.
Table 2 raw material ratio of profile control agent in example 2
Figure BDA0001746552520000091
Figure BDA0001746552520000101
According to the analysis and calculation of a synthesized product in the table 2, the oil phase accounts for 44.99% of the total mass of the system, the mass ratio of the surfactant Span20 to the Tween80 is 1:2, and the total using amount accounts for 11.51% of the total mass of the system; the water phase accounts for 54.84 percent of the total mass of the system, the dosage of the cross-linking agent accounts for 0.05 percent of the mass of the water phase system, and the proportion of the anionic monomer to the cationic monomer is 2: 3; the dosage of the oxidant accounts for 0.12 percent of the mass of the water phase system, and the dosage of the reducing agent accounts for 0.17 percent of the total mass of the system.
And (3) under the action of a homogenizing emulsifying machine, controlling the rotating speed to be 2000r/min, stirring for 10 minutes, and homogenizing and dispersing the microspheres obtained in the embodiment 2 to ensure that the particle size of the isocharged polyacrylamide nano microspheres is 80-120 microns. The application of the heterocharge nano-microsphere in the permeability of 2.52 mu m2The sand-filled pipe has the plugging strength of 20.3 and the residual resistance coefficient of 9.2.
Example 3
Weighing 12.6g of diesel oil, adding the diesel oil into a three-neck flask, adding a surfactant prepared by compounding 9.25g of span80 and 7.55g of Tween80, and introducing N at the temperature of 20 DEG C2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; mixing 16.44g of Acrylamide (AM) with the mass fraction of 30%, 7.3g of methacryloyloxyethyl trimethyl ammonium chloride (DMC), 0.005g of Methylene Bisacrylamide (MBA), 0.21g of Ammonium Persulfate (APS) and 14.85g of distilled water to obtain a cationic monomer water phase, adding the cationic monomer water phase into the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxygenation for 10min, 0.30g of sodium bisulfite (NaHSO) was added with stirring3) Initiating a polymerization reaction, continuing the reaction for 1h after the heat release peak, and obtaining a single-charge polyacrylamide nano microsphere system at the temperature before the liquid recovers the reducing agent and is added;
mixing 16.68g of Acrylamide (AM) with the mass fraction of 30%, 8.16g of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), 0.005g of Methylene Bisacrylamide (MBA), 0.21g of Ammonium Persulfate (APS) and 10.6g of distilled water to obtain an anionic monomer aqueous phase; adding the anionic monomer aqueous phase into the single-charge polyacrylamide nano microsphere system, and uniformly stirring and mixing to obtain an emulsion; introducing the emulsion into N2Deoxygenation was carried out for 10min, followed by addition of 1.05g of 10% strength by mass sodium bisulfite (NaHSO)3) And (3) initiating the polymerization reaction again by the aqueous solution, continuing the reaction for 2h after the heat release peak till the temperature before the addition of the liquid recovery reducing agent is reached, and obtaining the isocharged polyacrylamide nano microsphere profile control agent.
Specific data for example 3 are shown in table 3.
Table 3 raw material ratio of profile control agent in example 3
Figure BDA0001746552520000111
According to analysis and calculation of a synthesized product in the table 3, the oil phase accounts for 28% of the total mass of the system, the mass ratio of the surfactant Span80 to the Tween80 is 1.22: 1, and the total using amount accounts for 16% of the total mass of the system; the water phase accounts for 71 percent of the total mass of the system, the dosage of the cross-linking agent accounts for 0.001 percent of the mass of the water phase system, and the proportion of the anionic monomer to the cationic monomer is 1.12: 1; the dosage of the oxidant accounts for 0.56 percent of the mass of the water phase system, and the dosage of the reducing agent accounts for 1.0 percent of the total mass of the system.
And (3) under the action of a homogenizing emulsifying machine, controlling the rotating speed to be 3000r/min, stirring for 10 minutes, and carrying out homogenizing dispersion on the microspheres obtained in the example 3 to ensure that the particle size of the isocharged polyacrylamide nano microspheres is 40-80 μm. The application of the nano-microsphere with the abnormal charge in the permeability of 2.18 mu m2The sand-filled pipe has the plugging strength of 21.4 and the residual resistance coefficient of 8.6.
Example 4
Weighing 27.63g of liquid paraffin, adding into a three-neck flask, adding a surfactant prepared by compounding 2.94g of span80 and 11.76g of Tween60, and introducing N at 30 DEG C2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; mixing 8.36g of 30 mass percent Acrylamide (AM), 3.16g of methacryloyloxyethyltrimethylammonium chloride (DMC), 0.01g of a crosslinking agent (0.005g of divinylbenzene, 0.005g of methylenebisacrylamide) (TM), 0.2g of Ammonium Persulfate (APS), and 10.6g of distilled water to obtain a cationic monomer aqueous phase; adding the cationic monomer water phase into the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxidizing for 10min, adding 0.43g of Benzoyl Peroxide (BP) aqueous solution with the mass concentration of 10% while stirring to initiate polymerization reaction, and continuing to react for 1h after the heat release peak till the temperature before adding the liquid recovery reducing agent, thus obtaining the single-charge polyacrylamide nano microsphere system;
7.88g of 30% by mass Acrylamide (AM) and 2.18g of 2-acryloylAmine-2-methylpropanesulfonic Acid (AMPS), 0.01g of a crosslinking agent (0.005g of divinylbenzene, 0.005g of methylenebisacrylamide) (TM), 0.2g of Ammonium Persulfate (APS) and 10.6g of distilled water to give an anionic monomer aqueous phase; adding the anionic monomer aqueous phase into the single-charge polyacrylamide nano microsphere system, and uniformly stirring and mixing to obtain an emulsion; introducing the emulsion into N2Deoxidizing for 10min, adding 0.43g of 10% Benzoyl Peroxide (BP) aqueous solution to initiate polymerization reaction again, continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, and obtaining the isocharged polyacrylamide nano-microsphere profile control agent.
Specific data for example 4 are shown in table 4.
Table 4 raw material ratio of profile control agent in example 4
Figure BDA0001746552520000121
According to the analysis and calculation of the synthesized product in the table 4, the oil phase accounts for 32.25 percent of the total mass of the system, the mass ratio of the surfactant Span80 to the Tween60 is 1: 4, and the total dosage accounts for 17 percent of the total mass of the system; the water phase accounts for 50% of the total mass of the system, the amount of the cross-linking agent (0.005g of divinylbenzene and 0.005g of methylenebisacrylamide) accounts for 0.05% of the mass of the water phase system, and the proportion of the anionic monomer to the anionic monomer is 0.69: 1; the dosage of the oxidant accounts for 0.93 percent of the mass of the water phase system, and the dosage of the reducing agent accounts for 0.75 percent of the total mass of the system.
And (3) under the action of a homogenizing emulsifying machine, controlling the rotating speed to 4000r/min, stirring for 10 minutes, and homogenizing and dispersing the microspheres obtained in the embodiment 4 to ensure that the particle size of the isocharged polyacrylamide nano microspheres is 30-50 microns. The application of the heterocharge nano-microsphere in the permeability of 1.84 mu m2The plugging strength of the sand-filled pipe is 18.7, and the residual resistance coefficient is 7.9.
Example 5
Weighing 44.32g vegetable oil, adding into a three-neck flask, adding surfactant prepared from 4g Span20 and 12g Tween60, introducing N at 30 deg.C2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; 28.31g of acrylamide with the mass fraction of 50 percent(AM), 21.24g of dimethylallyl benzyl ammonium chloride (TMABC), 0.07g of divinylbenzene (TVB), 0.22g of Ammonium Persulfate (APS) and 19.19g of distilled water are mixed to obtain a cationic monomer aqueous phase, the cationic monomer aqueous phase is added into the oil phase, and the mixture is stirred to form a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxidizing for 10min, adding 0.48g of Sodium Thiosulfate (ST) with the mass concentration of 10% while stirring to initiate polymerization reaction, and continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, thus obtaining the single-charge polyacrylamide nano microsphere system;
mixing 7.86g of Acrylamide (AM) with a mass fraction of 50%, 2.36g of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), 0.02g of divinylbenzene (TVB), 0.10g of Ammonium Persulfate (APS) and 9.67g of distilled water to obtain an anionic monomer aqueous phase; adding the anionic monomer aqueous phase into the single-charge polyacrylamide nano microsphere system, and uniformly stirring and mixing to obtain an emulsion; introducing the emulsion into N2Deoxidizing for 10min, then adding 0.16g of Sodium Thiosulfate (ST) aqueous solution with the mass concentration of 10% to initiate polymerization reaction again, continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, and obtaining the isocharged polyacrylamide nano-microsphere profile control agent.
Specific data for example 5 are shown in table 5.
TABLE 5 raw material ratios of profile control agents in example 5
Figure BDA0001746552520000131
According to analysis and calculation of a synthesized product in the table 5, the oil phase accounts for 40.22% of the total mass of the system, the mass ratio of the surfactant Span20 to the Tween60 is 1:3, and the total using amount accounts for 10.67% of the total mass of the system; the water phase accounts for 59.35% of the total mass of the system, the dosage of the cross-linking agent accounts for 0.1% of the mass of the water phase system, and the proportion of the anionic monomer to the cationic monomer is 1: 9; the dosage of the oxidant accounts for 0.36 percent of the mass of the water phase system, and the dosage of the reducing agent accounts for 0.43 percent of the total mass of the system.
Stirring the mixture for 10 minutes at a controlled rotation speed of 5000r/min under the action of a homogenizing emulsifying machine, and performing the stirring treatment on the mixture obtained in the step 5And (3) carrying out homogeneous dispersion on the obtained microspheres to ensure that the particle size of the isocharged polyacrylamide nano microspheres is 20-40 μm. The application of the heterocharge nano-microsphere in the permeability of 1.32 mu m2The plugging strength of the sand-filled pipe is 16.7, and the residual resistance coefficient is 7.2.
Example 6
42.36g of isooctane is weighed and added into a three-neck flask, then 12g of surfactant compounded by Span20 and 4g of Tween80 are added, and N is introduced at the temperature of 10 DEG C2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; mixing 7.86g of Acrylamide (AM) with the mass fraction of 50%, 2.35g of dimethyl allyl benzyl ammonium chloride (TMABC), 0.02g of divinylbenzene (TVB), 0.32g of Ammonium Persulfate (APS) and 12.36g of distilled water to obtain a cationic monomer water phase, adding the cationic monomer water phase into the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxidizing for 10min, adding 0.16g of Sodium Thiosulfate (ST) aqueous solution with the mass concentration of 10% while stirring to initiate polymerization reaction, and continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, so as to obtain a single-charge polyacrylamide nano microsphere system;
mixing 30.47g of Acrylamide (AM) with a mass fraction of 50%, 21.15g of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), 0.02g of divinylbenzene (TVB), 1.28g of Ammonium Persulfate (APS) and 18.9g of distilled water to obtain an anionic monomer aqueous phase; adding the anionic monomer aqueous phase into the single-charge polyacrylamide nano microsphere system, and uniformly stirring and mixing to obtain an emulsion; introducing the emulsion into N2Deoxidizing for 10min, then adding 0.16g of Sodium Thiosulfate (ST) aqueous solution with the mass concentration of 10% to initiate polymerization reaction again, continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, and obtaining the isocharged polyacrylamide nano-microsphere profile control agent.
Specific data for example 6 are shown in table 6.
TABLE 6 raw material ratios of profile control agents in example 6
Figure BDA0001746552520000141
Figure BDA0001746552520000151
According to analysis and calculation of a synthesized product in the table 6, the oil phase accounts for 38.03% of the total mass of the system, the mass ratio range of the surfactant Span20 and the Tween80 is 3:1, and the total using amount accounts for 10.42% of the total mass of the system; the water phase accounts for 61.76 percent of the total mass of the system, the dosage of the cross-linking agent accounts for 0.04 percent of the mass of the water phase system, and the proportion of the anionic monomer to the cationic monomer is 9: 1; the dosage of the oxidant accounts for 1.7 percent of the mass of the water phase system, and the dosage of the reducing agent accounts for 0.21 percent of the total mass of the system.
And (3) under the action of a homogenizing emulsifying machine, controlling the rotating speed of 6000r/min, stirring for 10 minutes, and carrying out homogenizing dispersion on the microspheres obtained in the embodiment 6 to ensure that the particle size of the isocharged polyacrylamide nano microspheres is 10-30 microns. The isocharge nano-microsphere is applied to the permeability of 0.93 mu m2The sand-filled pipe has the plugging strength of 17.4 and the residual resistance coefficient of 8.9.
Example 7
Weighing 21.16g of white oil, adding into a three-neck flask, adding a surfactant prepared from 6g of span20 and 4g of Tween80, and introducing N at 30 DEG C2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; mixing 14.25g of Acrylamide (AM), 5.35g of methacryloyloxyethyl trimethyl ammonium chloride (DMC), 0.045g of a cross-linking agent (0.0009g of polyethylene glycol diacrylate, 0.0441g of methylene bisacrylamide) (PM), 0.16g of Ammonium Persulfate (APS) and 10.16g of distilled water to obtain a cationic monomer aqueous phase, adding the cationic monomer aqueous phase to the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxygenation for 10min, 0.16g of sodium bisulfite (NaHSO) was added with stirring3) Initiating a polymerization reaction, continuing the reaction for 0.5h after the heat release peak till the temperature before the liquid recovers the reducing agent is added, and obtaining a single-charge polyacrylamide nano microsphere system;
9.43g of Acrylamide (AM), 4.28g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), 0.045g of a crosslinking agent (0.009g of polyethylene glycol diacrylate, 0.0441g of methylenebisacrylamide) ((AM))PM), 0.16g Ammonium Persulfate (APS) and 10.24g distilled water to obtain an anionic monomer aqueous phase; adding the anionic monomer aqueous phase into the single-charge polyacrylamide nano microsphere system, and uniformly stirring and mixing to obtain an emulsion; introducing the emulsion into N2Deoxygenation was carried out for 10min, followed by addition of 0.16g of 10% strength by mass sodium bisulfite (NaHSO)3) And (3) initiating the polymerization reaction again by the aqueous solution, continuing the reaction for 0.5h after the heat release peak till the temperature before the addition of the liquid recovery reducing agent is reached, and obtaining the isocharged polyacrylamide nano microsphere profile control agent.
Specific data for example 7 are shown in table 7.
TABLE 7 raw material ratios of profile control agents in example 7
Figure BDA0001746552520000161
According to analysis and calculation of a synthesized product in the table 7, the oil phase accounts for 35.98% of the total mass of the system, the mass ratio of the surfactant Span20 to the Tween80 is 3: 2, and the total using amount accounts for 11.55% of the total mass of the system; the water phase accounts for 63.65% of the total mass of the system, the cross-linking agent (0.0018g of polyethylene glycol diacrylate, 0.0882g of methylene bisacrylamide) accounts for 0.1% of the mass of the water phase system, and the proportion of the anionic monomer to the cationic monomer is 4: 5; the dosage of the oxidant accounts for 0.58 percent of the mass of the water phase system, and the dosage of the reducing agent accounts for 0.37 percent of the total mass of the system.
And (3) under the action of a homogenizing emulsifying machine, controlling the rotating speed to 7000r/min, stirring for 10 minutes, and carrying out homogenizing dispersion on the microspheres obtained in the example 7 to enable the particle size of the isocharged polyacrylamide nano microspheres to be 10-20 microns. The isocharge nano-microsphere is applied to the permeability of 0.56 mu m2The sand-filled pipe has the plugging strength of 14.3 and the residual resistance coefficient of 7.2.
Example 8
35.16g of toluene is weighed and added into a three-neck flask, then a surfactant prepared by compounding 2.11g of span80 and 8.44g of Tween60 is added, and N is introduced at the temperature of 30 DEG C2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; 19.22g of 30% by mass Acrylamide (AM), 8.52g of dimethylallylbenzylammonium chloride (TMABC) and 0.02g of methylene chlorideBisacrylamide (MBA), 1.06g Ammonium Persulfate (APS) and 11.8g distilled water were mixed to obtain a cationic monomer aqueous phase; adding the cationic monomer water phase into the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxidizing for 10min, adding 0.16g of Benzoyl Peroxide (BP) aqueous solution with the mass concentration of 10% while stirring to initiate polymerization reaction, continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, and obtaining the single-charge polyacrylamide nano microsphere system;
13.44g of 30 mass percent Acrylamide (AM), 4.26g of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), 0.01g of Methylene Bisacrylamide (MBA), 0.54g of Ammonium Persulfate (APS) and 11.8g of distilled water are mixed to obtain an anionic monomer aqueous phase; adding the anionic monomer aqueous phase into the single-charge polyacrylamide nano microsphere system, and uniformly stirring and mixing to obtain an emulsion; introducing the emulsion into N2Deoxidizing for 10min, adding 0.16g of 10% Benzoyl Peroxide (BP) aqueous solution to initiate polymerization reaction again, continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, and obtaining the isocharged polyacrylamide nano-microsphere profile control agent.
Specific data for example 8 are shown in Table 8.
TABLE 8 raw material ratios of profile control agents in example 8
Figure BDA0001746552520000171
According to the analysis and calculation of the synthesized product in the table 8, the oil phase accounts for 40.31% of the total mass of the system, and the mass ratio of the surfactants Span80 and Tween60 is 1: 4, the total amount accounts for 10.75 percent of the total mass of the system; the water phase accounts for 59.42 percent of the total mass of the system, the dosage of the cross-linking agent accounts for 0.05 percent of the mass of the water phase system, and the proportion of the anionic monomer to the cationic monomer is 1: 2; the dosage of the oxidant accounts for 2.3 percent of the mass of the water phase system, and the dosage of the reducing agent accounts for 0.27 percent of the total mass of the system.
The microspheres obtained in the example 8 are homogenized and dispersed under the action of a homogenizing and emulsifying machine with the rotation speed of 8000r/min for 10 minutes to ensure that the electricity is differentThe particle size of the polyacrylamide-loaded nano-microspheres is 3-20 μm. The isocharge nano-microsphere is applied to the permeability of 0.2 mu m2The sand-filled pipe has the plugging strength of 27.6 and the residual resistance coefficient of 14.5.
According to the embodiments, the profile control agent provided by the invention is used for the stratum, and the size of formed coagulation particles can be controlled by emulsification and dispersion equipment, so that the profile control agent can meet the requirements of different permeability stratums with wide pore throat scales; the profile control agent can enhance the plugging strength of precipitated particles, and the application permeability range of the nano-microsphere profile control agent is from 0.1 mu m2Expanding to 3 μm2。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (8)

1. A profile control agent for polymer nano-microspheres with different charges is prepared by the following steps: weighing 33g of gasoline, adding the gasoline into a three-neck flask, adding a surfactant prepared by compounding 16g of Span80 and 4g of Tween60, and introducing N at the temperature of 30 DEG C2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; mixing 22.69g of acrylamide, 2.56g of acryloyloxyethyltrimethyl ammonium chloride, 0.02g of methylenebisacrylamide, 0.32g of potassium persulfate and 12.8g of distilled water to obtain a cationic monomer aqueous phase; adding the cationic monomer water phase into the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxidizing for 10min, adding 0.64g of sodium pyrosulfate aqueous solution with the mass concentration of 10% as a reducing agent while stirring to initiate polymerization reaction, continuing to react for 0.5h after the heat release peak, and obtaining a single-charge polyacrylamide nano microsphere system after the temperature of the liquid is recovered to the temperature before the reducing agent is added;
16.64g of acrylamide, 2.56g of 2-acrylamido-2-methylpropanesulfonic acid, 0.01g of methylenebisacrylamide,Mixing 0.32g of potassium persulfate and 12.8g of distilled water to obtain an anionic monomer water phase, adding the anionic monomer water phase into the single-charge polyacrylamide nano microsphere system, uniformly stirring and mixing to obtain an emulsion, and introducing N into the emulsion2Deoxidizing for 10min, adding 0.64g of sodium pyrosulfate aqueous solution with the mass concentration of 10% to initiate polymerization reaction again, continuing to react for 1.5h after the heat release peak, and obtaining the isocharged polyacrylamide nano-microsphere profile control agent at the temperature before the liquid recovery reducing agent is added.
2. The profile control agent for the heterocharge polymer nano microspheres is characterized by comprising the following steps: 39.88g of kerosene is weighed and added into a three-neck flask, then 4.57g of surfactant compounded by Span20 and 9.14g of Tween80 are added, and N is introduced at the temperature of 40 DEG C2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; 18.61g of acrylamide with a mass fraction of 10%, 3.67g of methacryloyloxyethyltrimethylammonium chloride, 0.01g of divinylbenzene, 0.04g of ammonium persulfate and 13.79g of distilled water were mixed to obtain a cationic monomer aqueous phase; adding the cationic monomer water phase into the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxidizing for 10min, adding 0.10g of 10% by mass benzoyl peroxide aqueous solution while stirring to initiate polymerization reaction, continuing to react for 1.5h after the heat release peak, and obtaining a single-charge polyacrylamide nano microsphere system after the temperature is reached before the liquid recovers the reducing agent is added;
mixing 11.29g of acrylamide with the mass fraction of 10%, 2.87g of 2-acrylamide-2-methylpropanesulfonic acid, 0.02g of divinylbenzene, 0.04g of ammonium persulfate and 15g of distilled water to obtain an anionic monomer water phase, adding the anionic monomer water phase into the single-charge polyacrylamide nano microsphere system, and stirring and uniformly mixing to obtain an emulsion; introducing the emulsion into N2Deoxidizing for 10min, adding 0.10g of 10% benzoyl peroxide aqueous solution to initiate polymerization reaction again, continuing reaction for 1h after the heat release peak, and obtaining the product after the liquid recovers the temperature before the reducing agent is addedTo obtain the isocharged polyacrylamide nano microsphere profile control agent.
3. The profile control agent for the heterocharge polymer nano microspheres is characterized by comprising the following steps: weighing 12.6g of diesel oil, adding the diesel oil into a three-neck flask, adding a surfactant prepared by compounding 9.25g of span80 and 7.55g of Tween80, and introducing N at the temperature of 20 DEG C2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; mixing 16.44g of acrylamide with the mass fraction of 30%, 7.3g of methacryloyloxyethyl trimethyl ammonium chloride, 0.005g of methylene bisacrylamide, 0.21g of ammonium persulfate and 14.85g of distilled water to obtain a cationic monomer water phase, adding the cationic monomer water phase into the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxidizing for 10min, adding 0.30g of sodium bisulfite while stirring to initiate polymerization reaction, continuing to react for 1h after the heat release peak, and obtaining a single-charge polyacrylamide nano microsphere system after the temperature of the liquid is recovered and before the reducing agent is added;
mixing 16.68g of acrylamide with the mass fraction of 30%, 8.16g of 2-acrylamide-2-methylpropanesulfonic acid, 0.005g of methylenebisacrylamide, 0.21g of ammonium persulfate and 10.6g of distilled water to obtain an anionic monomer aqueous phase; adding the anionic monomer aqueous phase into the single-charge polyacrylamide nano microsphere system, and uniformly stirring and mixing to obtain an emulsion; introducing the emulsion into N2Deoxidizing for 10min, adding 1.05g of sodium bisulfite aqueous solution with the mass concentration of 10% to initiate polymerization reaction again, continuing to react for 2h after the heat release peak till the temperature before adding the liquid recovery reducing agent, and obtaining the isocharged polyacrylamide nano microsphere profile control agent.
4. The profile control agent for the heterocharge polymer nano microspheres is characterized by comprising the following steps: weighing 27.63g of liquid paraffin, adding into a three-neck flask, adding a surfactant prepared by compounding 2.94g of Span80 and 11.76g of Tween60, and introducing N at 30 DEG C2Removing oxygen, stirring thoroughly to mixHomogenizing to obtain an oil phase; mixing 8.36g of 30 mass percent acrylamide, 3.16g of methacryloyloxyethyltrimethylammonium chloride, 0.005g of divinylbenzene, 0.005g of methylenebisacrylamide, 0.2g of ammonium persulfate and 10.6g of distilled water to obtain a cationic monomer aqueous phase; adding the cationic monomer water phase into the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxidizing for 10min, adding 0.43g of 10% by mass benzoyl peroxide aqueous solution while stirring to initiate polymerization reaction, continuing to react for 1h after the heat release peak till the temperature before adding the liquid recovery reducing agent, and obtaining the single-charge polyacrylamide nano microsphere system;
mixing 7.88g of acrylamide with a mass fraction of 30%, 2.18g of 2-acrylamide-2-methylpropanesulfonic acid, 0.005g of divinylbenzene, 0.005g of methylenebisacrylamide, 0.2g of ammonium persulfate and 10.6g of distilled water to obtain an anionic monomer aqueous phase; adding the anionic monomer aqueous phase into the single-charge polyacrylamide nano microsphere system, and stirring and mixing uniformly to obtain an emulsion; introducing the emulsion into N2Deoxidizing for 10min, adding 0.43g of 10% by mass benzoyl peroxide aqueous solution to initiate polymerization reaction again, continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, and obtaining the isocharged polyacrylamide nano microsphere profile control agent.
5. The profile control agent for the heterocharge polymer nano microspheres is characterized by comprising the following steps: weighing 44.32g vegetable oil, adding into a three-neck flask, adding surfactant prepared from 4g Span20 and 12g Tween60, introducing N at 30 deg.C2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; mixing 28.31g of acrylamide with the mass fraction of 50%, 21.24g of dimethyl allyl benzyl ammonium chloride, 0.07g of divinylbenzene, 0.22g of ammonium persulfate and 19.19g of distilled water to obtain a cationic monomer water phase, adding the cationic monomer water phase into the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxidizing for 10min, stirringThen 0.48g of sodium thiosulfate with the mass concentration of 10% is added to initiate polymerization reaction, the reaction is continued for 0.5h after the heat release peak till the temperature before the liquid recovery reducing agent is added, and then the single-charge polyacrylamide nano microsphere system can be obtained;
mixing 7.86g of acrylamide with a mass fraction of 50%, 2.36g of 2-acrylamido-2-methylpropanesulfonic acid, 0.02g of divinylbenzene, 0.10g of ammonium persulfate and 9.67g of distilled water to obtain an anionic monomer aqueous phase; adding the anionic monomer aqueous phase into the single-charge polyacrylamide nano microsphere system, and stirring and mixing uniformly to obtain an emulsion; introducing the emulsion into N2Deoxidizing for 10min, then adding 0.16g of sodium thiosulfate aqueous solution with the mass concentration of 10% to initiate polymerization reaction again, continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, and obtaining the isocharged polyacrylamide nano microsphere profile control agent.
6. The profile control agent for the heterocharge polymer nano microspheres is characterized by comprising the following steps: 42.36g of isooctane is weighed and added into a three-neck flask, then 12g of surfactant compounded by Span20 and 4g of Tween80 are added, and N is introduced at the temperature of 10 DEG C2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; mixing 7.86g of acrylamide with the mass fraction of 50%, 2.35g of dimethyl allyl benzyl ammonium chloride, 0.02g of divinylbenzene, 0.32g of ammonium persulfate and 12.36g of distilled water to obtain a cationic monomer water phase, adding the cationic monomer water phase into the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxidizing for 10min, adding 0.16g of sodium thiosulfate aqueous solution with the mass concentration of 10% while stirring to initiate polymerization reaction, continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, and obtaining the single-charge polyacrylamide nano microsphere system;
mixing 30.47g of acrylamide with a mass fraction of 50%, 21.15g of 2-acrylamide-2-methylpropanesulfonic acid, 0.02g of divinylbenzene, 1.28g of ammonium persulfate and 18.9g of distilled water to obtain an anionic monomer aqueous phase; the anionic monomer water is addedAdding the mixture into the single-charge polyacrylamide nano microsphere system, and stirring and mixing the mixture uniformly to obtain emulsion; introducing the emulsion into N2Deoxidizing for 10min, then adding 0.16g of sodium thiosulfate aqueous solution with the mass concentration of 10% to initiate polymerization reaction again, continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, and obtaining the isocharged polyacrylamide nano microsphere profile control agent.
7. The profile control agent for the heterocharge polymer nano microspheres is characterized by comprising the following steps: weighing 21.16g of white oil, adding into a three-neck flask, adding a surfactant prepared from 6g of Span20 and 4g of Tween80, and introducing N at 30 DEG C2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; mixing 14.25g of acrylamide, 5.35g of methacryloxyethyl trimethyl ammonium chloride, 0.0009g of polyethylene glycol diacrylate, 0.0441g of methylene bisacrylamide, 0.16g of ammonium persulfate and 10.16g of distilled water to obtain a cationic monomer water phase, adding the cationic monomer water phase into the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxidizing for 10min, adding 0.16g of sodium bisulfite while stirring to initiate polymerization reaction, and continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, thus obtaining the polyacrylamide nano microsphere system with single charge;
mixing 9.43g of acrylamide, 4.28g of 2-acrylamido-2-methylpropanesulfonic acid, 0.009g of polyethylene glycol diacrylate, 0.0441g of methylenebisacrylamide, 0.16g of ammonium persulfate and 10.24g of distilled water to obtain an anionic monomer aqueous phase; adding the anionic monomer aqueous phase into the single-charge polyacrylamide nano microsphere system, and stirring and mixing uniformly to obtain an emulsion; introducing the emulsion into N2Deoxidizing for 10min, adding 0.16g of 10% sodium bisulfite aqueous solution to initiate polymerization reaction again, continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, and obtaining the isocharged polyacrylamide nano microsphere profile control agent.
8. The profile control agent for the heterocharge polymer nano microspheres is characterized by comprising the following steps: 35.16g of toluene is weighed and added into a three-neck flask, then a surfactant compounded by 2.11g of Span80 and 8.44g of Tween60 is added, and N is introduced at the temperature of 30 DEG C2Deoxidizing, and fully stirring to uniformly mix the components to obtain an oil phase; mixing 19.22g of acrylamide with the mass fraction of 30%, 8.52g of dimethyl allyl benzyl ammonium chloride, 0.02g of methylene bisacrylamide, 1.06g of ammonium persulfate and 11.8g of distilled water to obtain a cationic monomer water phase; adding the cationic monomer water phase into the oil phase, and stirring to obtain a uniform transparent emulsion to obtain a microemulsion; introducing the microemulsion into N2After deoxidizing for 10min, adding 0.16g of 10% by mass benzoyl peroxide aqueous solution while stirring to initiate polymerization reaction, continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, and obtaining the single-charge polyacrylamide nano microsphere system;
mixing 13.44g of acrylamide with the mass fraction of 30%, 4.26g of 2-acrylamide-2-methylpropanesulfonic acid, 0.01g of methylenebisacrylamide, 0.54g of ammonium persulfate and 11.8g of distilled water to obtain an anionic monomer aqueous phase; adding the anionic monomer aqueous phase into the single-charge polyacrylamide nano microsphere system, and stirring and mixing uniformly to obtain an emulsion; introducing the emulsion into N2Deoxidizing for 10min, adding 0.16g of 10% by mass benzoyl peroxide aqueous solution to initiate polymerization reaction again, continuing to react for 0.5h after the heat release peak till the temperature before adding the liquid recovery reducing agent, and obtaining the isocharged polyacrylamide nano microsphere profile control agent.
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