CN115304707B - Polyacrylamide microsphere emulsion with adjustable particle size, and preparation method and application thereof - Google Patents
Polyacrylamide microsphere emulsion with adjustable particle size, and preparation method and application thereof Download PDFInfo
- Publication number
- CN115304707B CN115304707B CN202110502862.4A CN202110502862A CN115304707B CN 115304707 B CN115304707 B CN 115304707B CN 202110502862 A CN202110502862 A CN 202110502862A CN 115304707 B CN115304707 B CN 115304707B
- Authority
- CN
- China
- Prior art keywords
- weight
- microsphere emulsion
- oil
- microsphere
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
Abstract
The invention relates to polyacrylamide microsphere emulsion with adjustable particle size, and a preparation method and application thereof, and mainly solves the problem that in the prior art, different polymerization methods are generally needed for preparing polyacrylamide microspheres with different particle sizes. The invention prepares the polyacrylamide microsphere emulsion by adopting an inverse microemulsion polymerization method and reacting a mixture composed of oil phase, a composite emulsifier, a polymerization monomer, a cross-linking agent and the like. The preparation method is simple to operate, and the obtained microsphere emulsion can meet the plugging requirements of stratum with different permeability, and can be directly or after being compounded with other oilfield chemicals, used for on-site application of deep profile control, water plugging, oil displacement and the like for tertiary oil recovery of an oilfield, wherein the on-site application is used for improving the recovery ratio.
Description
Technical Field
The invention relates to a polyacrylamide microsphere with adjustable particle size, a preparation method and application thereof.
Background
The polymer microsphere profile control and flooding technology is a novel deep profile control and water shutoff technology developed in recent years, and the design mechanism of the technology is to realize the effect of deep profile control and water shutoff by gradually plugging stratum pore throats with different permeabilities by means of nanometer-to-micrometer-level water-swellable microspheres. The microsphere used in oil field generally refers to polyacrylamide sphere particles containing cross-linking agent, and according to the size of particle diameter, the microsphere is prepared by a reverse microemulsion polymerization method, the microsphere is prepared by a reverse emulsion method, and the microsphere is prepared by a submicron microsphere and a reverse (micro) suspension method. All three contain an oil phase, an aqueous phase and an emulsifier (or stabilizer), but the polymerization mechanism is different.
Microemulsions (microemulsions) are a class of colloidal dispersions which are clear, transparent or translucent, have particle sizes between 10 and 100 nanometers, and are thermodynamically stable. Microemulsions can spontaneously form, an explanation being that in the presence of surfactants, cosurfactants, the oil/water interface creates a so-called negative interfacial tension, and the amount of emulsifier in the system is large, in contrast to inverse emulsions. The inverse microemulsion of the acrylamide is composed of monomers such as the acrylamide, water, oil-soluble solvents, emulsifying agents, auxiliary emulsifying agents, other polymerization auxiliary agents and the like. The usual oil phase is hydrocarbons such as toluene, hexane, kerosene, white oil, isopar M, etc.; the emulsifier is usually Span, tween series, etc., and the amount thereof is 10% by mass or more of the emulsion. The reaction speed is one of the characteristics of the inverse microemulsion polymerization of the acrylamide, and the particle size range of the microsphere product is narrower, generally about 100 nanometers.
The traditional emulsion is an oil-in-water type emulsion system, and the inverse emulsion is an emulsion system which takes liquid of water-soluble monomer dissolved in water as a disperse phase, takes nonpolar hydrocarbon solvent as a continuous phase under the action of an emulsifying agent, and forms water-in-oil type monomer droplets or monomer swelling micelles. The choice of emulsifier is critical to obtain a stable emulsion product. Unlike conventional emulsions, the majority of the inverse emulsions employ nonionic emulsifiers, which are believed to be due to the steric effect of significantly increasing the coalescence of the latex particles after adsorption of such emulsifiers onto the surface of the latex particles. The emulsifier not only reduces the surface tension and interfacial tension between oil and water, but also plays roles in emulsifying, dispersing and solubilising the oil phase and the water phase, so that the polymerization is carried out according to a micelle mechanism or a liquid drop nucleation mechanism. According to the traditional theory, the selection of the emulsifier of the reverse microemulsion polymerization system is generally based on the principle of hydrophilic-lipophilic balance value, and the HLB value of the emulsifier with partial oil solubility is between 3 and 6. It has been found that the composite emulsifier is better than the single emulsifier because the emulsifier has a small affinity for the emulsified substance when the difference between the HLB value of the emulsified substance and the HLB value of the emulsifier is large, and the emulsifying effect is poor; on the contrary, when the HLB value of the emulsifier is small, the affinity to water is small, and the emulsifying effect is also poor. If two or more emulsifiers with different HLB values are mixed to form a composite emulsifier, the emulsifiers with different properties gradually transit from oleophilic to hydrophilic, and the emulsifying effect is greatly improved. Therefore, a nonionic composite emulsifier, such as Span and Tween, is generally used in combination, and a good W/O type emulsifying effect can be obtained. It has also been found that the concentration and HLB value of the emulsifier system can affect the rate of polymerization, the stability of the emulsion system, the viscosity of the emulsion and the size of the latex particles, but little is seen in the report of adjusting the particle size of the microsphere product by adjusting the HLB value of the emulsifier system.
In recent years, better progress and achievement are achieved in the aspects of preparation of polyacrylamide microsphere systems, tertiary oil recovery profile control and oil displacement application in China, polymer microspheres with different sizes are developed by various petroleum institutions, research institutions and the like and used for profile control of stratum with different permeability, but basically, different polymerization methods are adopted for preparation of the polyacrylamide microspheres according to different particle sizes, the nano microspheres are generally subjected to inverse microemulsion polymerization, and due to the fact that the oil phase and emulsifier content are high, the water phase content is low, and the effective solid content is generally about 20%; the submicron microsphere generally adopts inverse emulsion polymerization, and in order to keep the stability of an emulsion system, measures such as strengthening emulsification and homogenization before reaction, precisely controlling the polymerization heating rate and the like are adopted; in order to reduce sedimentation of the microspheres, a certain amount of stabilizing agent is generally added into the system.
Disclosure of Invention
Based on extensive and intensive studies on the synthetic principle, structural characterization and properties of polyacrylamide microsphere systems, the inventors have adopted an inverse microemulsion polymerization method, and can prepare microspheres with different particle diameters in the nanometer, submicron or micrometer level by only adjusting the lipophilic and hydrophilic properties of an emulsifier system, namely the HLB value, respectively, after fixing the HLB value, if a water-soluble azo initiator is added on the basis of a redox initiation system, the particle diameter of the microspheres can be increased, and if an oil-soluble azo initiator is added, the particle diameter of the microspheres can be reduced.
Specifically, the present invention relates to the following:
1. a polyacrylamide microsphere emulsion made by reacting a mixture comprising;
a) 25-55 parts by weight of an oil phase; preferably 30 to 45 parts by weight;
b) 5-25 parts by weight of a compound emulsifier; preferably 8 to15 parts by weight;
c) 20 to 50 parts by weight of a polymeric monomer; preferably 25 to 35 parts by weight;
d) 0.01 to 2.0 parts by weight of a crosslinking agent; preferably 0.1 to 1.0 part by weight;
e) 0.1 to 10 parts by weight of a phase inversion agent; preferably 1 to 3 parts by weight;
f) 0.001 to1 part by weight of an initiator; preferably 0.005 to 0.1 part by weight;
g) 20-50 parts by weight of water; preferably 25 to 40 parts by weight;
wherein the initiator comprises:
1) The weight of the oxidant is 0.002-1.0% of the weight of the polymerized monomer; preferably 0.01 to 0.5%;
2) A reducing agent, the weight of which is 0.02-2.0% of the weight of the polymerized monomer; preferably 0.05 to 1.0%;
3) Azo initiator, its weight is 0-5.0% of the weight of said polymeric monomer; preferably 0 to 2.0%.
2. The polyacrylamide microsphere emulsion of any of the preceding or subsequent aspects, wherein the oil phase is at least one of the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons;
the aliphatic hydrocarbon is at least one selected from industrial white oil and solvent oil; preferably at least one of white oil No. 3, white oil No. 5, solvent oil No. 120 and solvent oil No. 200;
the aromatic hydrocarbon is selected from at least one of benzene, toluene and xylene; preferably xylene;
the halogenated hydrocarbon is selected from at least one of dichloromethane, chloroform and carbon tetrachloride; carbon tetrachloride is preferred.
3. The polyacrylamide microsphere emulsion according to any one of the preceding or subsequent aspects, wherein the composite emulsifier is a nonionic emulsifier, and the HLB is between 4 and 7.
4. The polyacrylamide microsphere emulsion according to any one of the preceding or subsequent aspects, wherein, when HLB is not less than 5.4, the polyacrylamide microsphere emulsion contains nano microspheres; the particle size of the nano microsphere is 50-200 nanometers, preferably 80-150 nanometers;
when HLB is less than or equal to 4.7, the polyacrylamide microsphere emulsion contains microspheres; the particle size of the microsphere is 800-2000 nanometers, preferably 1000-1500 nanometers;
when HLB is 4.7< 5.4, the polyacrylamide microsphere emulsion contains submicron microspheres; the submicron microsphere has a particle size of 200-800 nanometers, preferably 300-600 nanometers.
5. The polyacrylamide microsphere emulsion of any one of the preceding or subsequent aspects, wherein the composite emulsifier comprises a lipophilic surfactant and a hydrophilic surfactant; wherein the lipophilic surfactant is sorbitan fatty acid esters, preferably at least one of Span85, span80, span65 and Span 60; the hydrophilic surfactant is an isomeric alcohol polyoxyethylene ether, and the molecular formula is as follows: RO (CH) 2 CH 2 O) x H，R＝iso-C 13 H 27 X is an integer between 10 and 20, preferably an integer between 12 and 15; the different HLB values of the composite emulsifier are obtained by adjusting the weight ratio of the lipophilic surfactant to the hydrophilic surfactant.
6. The polyacrylamide microsphere emulsion according to any one of the preceding or subsequent aspects, wherein the composite emulsifier further comprises a co-emulsifier, and the content of the co-emulsifier is 0.2-3 parts by weight, preferably 0.5-2 parts by weight; the co-emulsifier is selected from at least one of the group consisting of sodium or potassium salts, preferably sodium and potassium acetates, halides, sulfates and sulfonates.
7. The polyacrylamide microsphere emulsion according to any one of the preceding or subsequent aspects, wherein the polymeric monomer is at least one selected from the group consisting of nonionic water-soluble monomers, anionic monomers, cationic monomers, and hydrophobic monomers;
the nonionic water-soluble monomer is at least one selected from the group consisting of acrylamide, methacrylamide, N-isopropylacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-methylolacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyridine and N-vinylpyrrolidone;
the anionic monomer is selected from at least one of 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, allylphosphonic acid and/or water-soluble alkali metal, alkaline earth metal and ammonium salts thereof;
the cationic monomer is at least one selected from the group consisting of dimethyldiallylammonium chloride, acryloyloxyethyl trimethylammonium chloride, methacryloyloxyethyl trimethylammonium chloride and 2-acrylamido-2-methylpropyl trimethylammonium chloride;
the hydrophobic monomer is selected from monovinyl compounds with 8-22 carbon atoms; the anionic hydrophobic monomer is selected from sodium acrylamide nitrogen alkyl sulfonate with vinyl carbon chain number of 8-18; the cationic hydrophobic monomer is selected from allyl alkyl ammonium chloride with vinyl carbon chain number of 12-22.
8. The polyacrylamide microsphere emulsion according to any one of the preceding or subsequent aspects, wherein the crosslinking agent is at least one selected from the group consisting of methylenebisacrylamide, divinylbenzene, polyethylene glycol diacrylate and pentaerythritol triacrylate;
the phase inversion agent is selected from hydrophilic nonionic surfactant, preferably at least one of isomeric alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether.
9. The polyacrylamide microsphere emulsion of any one of the preceding or subsequent aspects, wherein the oxidizing agent is at least one selected from the group consisting of potassium persulfate, sodium persulfate, ammonium persulfate, and benzoyl peroxide;
the reducing agent is at least one selected from the group consisting of sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium thiosulfate and ferrous chloride;
the azo initiator is at least one selected from the group consisting of 2,2' -azo [2- (2-imidazolin-2-yl) propane ] dihydrochloride, azobisisobutylamidine hydrochloride, azobisisobutyronitrile, and azobisisoheptonitrile.
10. The polyacrylamide microsphere emulsion of any one of the preceding or subsequent aspects, wherein the polyacrylamide microsphere emulsion further comprises h) a complexing agent, the weight of which is 0.01-0.5%, preferably 0.05-0.2% of the weight of the polymerized monomer; the complexing agent is at least one selected from disodium ethylenediamine tetraacetate and sodium diethylenetriamine pentaacetate.
11. The preparation method of the polyacrylamide microsphere emulsion comprises the following steps:
(1) contacting the oil phase with a composite emulsifier to form a continuous phase;
contacting a polymeric monomer, a cross-linking agent, optionally a co-emulsifier, optionally a complexing agent, and water to form an aqueous phase; preparing an initiator solution;
the concentration of the aqueous oxidant solution is preferably 1 to 30wt%, more preferably 5 to 20wt%; the concentration of the aqueous reducing agent solution is preferably 1 to 30wt%, more preferably 5 to 20wt%; the water-soluble azo initiator is directly added into the water phase or is prepared into an aqueous solution, and the concentration of the aqueous solution is preferably 1-30wt%, more preferably 5-20wt%; the oil-soluble azo initiator is directly added into the oil phase or is prepared in an isopropanol solvent, and the concentration is preferably 1-30wt%, more preferably 5-20wt%;
(2) contacting the continuous phase, the aqueous phase and the initiator solution to obtain a mixture a;
(3) and (3) contacting the mixture A with a phase inversion agent to obtain the polyacrylamide microsphere emulsion.
12. The method for preparing a polyacrylamide microsphere emulsion according to any one of the preceding or subsequent aspects, wherein in the step (2), the aqueous phase is divided into m parts and contacted with the continuous phase and the initiator solution to obtain the mixture A; m is an integer greater than or equal to 2, m 1 For the weight of the first part, m 2 M is the weight of the second part m For the weight of the m-th part, m 1 :m 2 :……:m m ＝(1～20):(1～10):……:(1～2)。
13. The preparation method of the polyacrylamide microsphere emulsion according to any one of the previous or subsequent aspects, wherein a first part of aqueous phase is contacted with the continuous phase and the initiator solution to obtain a mixture A1, and the temperature of the mixture A1 is controlled to be 50-90 ℃;
the m-th part of water phase is contacted with the mixture A1 to obtain a mixture A, and the temperature of the mixture A is controlled to be 50-80 ℃;
the increase in reaction temperature is mainly related to the amount of reducing agent added, and the highest temperature is mainly related to the concentration of the monomer.
14. The polyacrylamide microsphere emulsion of any one of the above aspects and the application of the polyacrylamide microsphere emulsion prepared by the preparation method of the polyacrylamide microsphere emulsion of any one of the above aspects in tertiary oil recovery of oil fields. The application can be used alone according to application requirements in the polyacrylamide microsphere emulsion with adjustable particle size, or can be added with surfactant for oil displacement and stirred uniformly, and the system can be used for on-site application of deep profile control, water shutoff, oil displacement and the like for tertiary oil recovery in oil fields to improve recovery efficiency.
Technical effects
According to the polyacrylamide microsphere emulsion with adjustable particle size and the preparation method thereof, microspheres with different particle sizes of nanometer, submicron or micron can be prepared by only adjusting the lipophilic and hydrophilic properties of an emulsifier system, namely the HLB value, and after the HLB value is fixed, the particle size of the microspheres can be increased if a water-soluble azo initiator is added on the basis of a redox initiation system; if an oil-soluble azo initiator is added, the particle size of the microspheres can be reduced.
The preparation method is simple to operate, and the prepared polyacrylamide microsphere emulsion with different particle sizes can meet the plugging requirements of stratum with different permeability, and can be directly or after being compounded with other oilfield chemicals, used for on-site application of deep profile control, water plugging, oil displacement and the like for tertiary oil recovery of an oilfield, wherein the recovery rate is improved.
Detailed Description
The following detailed description of embodiments of the invention is provided, but it should be noted that the scope of the invention is not limited by these embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, definitions, will control.
When the specification derives materials, substances, methods, steps, devices, or elements and the like in the word "known to those skilled in the art", "prior art", or the like, such derived objects encompass those conventionally used in the art at the time of the application, but also include those which are not currently commonly used but which would become known in the art to be suitable for similar purposes.
In the context of the present specification, the precipitable solids content, primary particle size and plugging rate of the polyacrylamide microsphere emulsion were tested according to the determination method of the Q/SH3375 134-2019 Shanghai petrochemical institute of England-Shanghai petrochemical industry, inc. Standard of Heat-resistant salt-resistant Polymer microsphere Conditioning agent.
In the context of the present specification, the names and abbreviations of the compounds mentioned are shown in the following table:
| names of Compounds | Short for short |
| Sorbitan monostearate | Span60 |
| Sorbitan tristearate | Span65 |
| Sorbitan monooleate | Span80 |
| Sorbitan trioleate | Span85 |
| C 13 Isomeric alcohol polyoxyethylene ether (eo=12) | TO12 |
| C 13 Isomeric alcohol polyoxyethylene ether (eo=15) | TO15 |
| C 13 Isomeric alcohol polyoxyethylene ether (eo=20) | TO20 |
| Alkylphenol ethoxylates (eo=10) | OP10 |
| Fatty alcohol polyoxyethylene ether (eo=9) | AEO9 |
| Fatty alcohol polyoxyethylene ether (eo=15) | AEO15 |
| 2,2' -azo [2- (2-imidazolin-2-yl) propane]Dihydrochloride salt | V044 |
| Azo diisobutyl amidine hydrochloride | V50 |
| Azobisisobutyronitrile | AIBN |
| Azo diisoheptonitrile | ABVN |
Unless explicitly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise clear to the routine knowledge of a person skilled in the art.
[ example 1 ]
1000g white oil No. 5, 300g span80 (HLB=4.3), 36g TO12 (HLB=14.5) and the HLB value of the composite emulsifier=5.4 are added into a reaction kettle; stirring until the materials are completely and uniformly mixed, controlling the temperature in the kettle to be 22 ℃ and the stirring speed to be 200rpm. 725g of water, 850g of acrylamide, 80g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 30g of sodium acetate, 1.0g of disodium ethylenediamine tetraacetate, 130g of 60% dimethyldiallylammonium chloride and 1.5g of methylenebisacrylamide are added into a different container, stirred and dissolved uniformly to serve as a water phase, and uniformly divided into two parts of I and II; 30g of 20% ammonium persulfate and sodium bisulphite aqueous solution are prepared for later use respectively. Adding the water phase I into an oil phase in a reaction kettle, stirring for a plurality of minutes until emulsification is uniform, introducing nitrogen for 30 minutes, then dripping 3g of ammonium persulfate aqueous solution, dripping 3g of sodium bisulfate aqueous solution after 5 minutes, quickly raising the temperature to 76 ℃, preserving heat for reaction for 1.5 hours, and then cooling to 22 ℃; adding the water phase II again, uniformly mixing, introducing nitrogen for 30min, then dripping 5g of ammonium persulfate aqueous solution, dripping 5g of sodium bisulphite aqueous solution after 5 min, heating to 58 ℃, carrying out heat preservation reaction for 1.5 h, finally cooling to about 30 ℃, slowly dripping 30g of OP10, uniformly stirring, discharging, sampling and analyzing.
The content of the precipitable solid is 31.6% according to the measurement method of Q/SH3375 134-2019 China petrochemical industry Co-Ltd Shanghai petrochemical industry institute enterprise standard heat-resistant salt-resistant polymer microsphere profile control agent, and the initial particle size is 98nm. Aging at 95deg.C under 20000mg/L saline for 30 days, injecting 0.5PV of 0.2% concentration polymer microsphere emulsion after aging into 200mD sand filling pipe, and measuring to obtain the plugging rate of 89%.
[ example 2 ]
1000g white oil No. 5, 300g span80 (HLB=4.3), 36g TO12 (HLB=14.5) and the HLB value of the composite emulsifier=5.4 are added into a reaction kettle; stirring until the materials are completely and uniformly mixed, controlling the temperature in the kettle to be 22 ℃ and the stirring speed to be 200rpm. 725g of water, 850g of acrylamide, 80g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 30g of sodium acetate, 1.0g of disodium ethylenediamine tetraacetate, 130g of 60% dimethyldiallylammonium chloride, 1.5g of methylenebisacrylamide and 1.5g of V044 are added into a different container, stirred and dissolved uniformly to be used as a water phase, and uniformly divided into two parts of I and II; 30g of 20% ammonium persulfate and sodium bisulphite aqueous solution are prepared for later use respectively. Adding the water phase I into an oil phase in a reaction kettle, stirring for a plurality of minutes until emulsification is uniform, introducing nitrogen for 30 minutes, then dripping 3g of ammonium persulfate aqueous solution, dripping 3g of sodium bisulfate aqueous solution after 5 minutes, quickly raising the temperature to 78 ℃, preserving heat for reaction for 1.5 hours, and then cooling to 22 ℃; adding the water phase II again, uniformly mixing, introducing nitrogen for 30min, then dripping 5g of ammonium persulfate aqueous solution, dripping 5g of sodium bisulphite aqueous solution after 5 min, heating to 60 ℃, carrying out heat preservation reaction for 1.5 h, finally cooling to about 30 ℃, slowly dripping 30g of OP10, uniformly stirring, discharging, sampling and analyzing.
The content of the precipitated solid is 33.2% and the initial particle diameter is 145nm according to the measurement method of Q/SH3375 134-2019 China petrochemical industry Co-Ltd Shanghai petrochemical industry institute enterprise standard, namely the heat-resistant salt-resistant polymer microsphere profile control agent. Aging at 95deg.C under 20000mg/L saline water for 30 days, injecting 0.5PV of 0.2% concentration polymer microsphere emulsion after aging into 300mD sand filling pipe, and measuring plugging rate to 85%.
[ example 3 ]
Firstly, adding 200 g of No. 200 solvent naphtha 240g of span65 (HLB=2.1), 66g of TO15 (HLB=15.5) into a reaction kettle, stirring the mixture until the mixture is completely and uniformly mixed, controlling the temperature in the kettle to be 25 ℃, and stirring the mixture at 200rpm. 720g of water, 850g of acrylamide, 80g of sodium acrylate, 130g of 80% acryloyloxyethyl trimethyl ammonium chloride, 15g of hexadecyldimethylallyl ammonium chloride, 5g of maleic acid, 30g of sodium acetate, 1.2g of disodium edetate and 3.5g of polyethylene glycol diacrylate are added into another container, and stirred and dissolved uniformly to be used as a water phase; stirring and dissolving uniformly to obtain a water phase, and uniformly dividing the water phase into two parts, namely I and II; 10% ammonium persulfate, sodium bisulphite aqueous solution and 30g of 2,2' -azo (2-methylpropionamidine) dihydrochloride (V50) were prepared separately for use. Adding the water phase I into an oil phase in a reaction kettle, stirring for a plurality of minutes until emulsification is uniform, introducing nitrogen for 30 minutes, then dripping 5g of ammonium persulfate aqueous solution and 0.5g of V50, dripping 5g of sodium bisulfite aqueous solution after 5 minutes, quickly raising the temperature to 86 ℃, preserving heat for 1.5 hours, and then cooling to 50 ℃; adding the water phase II again, uniformly mixing, introducing nitrogen for 30min, then dripping 5g of V50, heating to 72 ℃, reacting for 1.5 hours at a temperature of heat preservation, finally cooling to about 30 ℃, slowly dripping 32g of AEO9, uniformly stirring, discharging, sampling and analyzing.
The content of the precipitated solid is 34.2% and the initial particle diameter is 423nm according to the measurement method of Q/SH3375 134-2019 China petrochemical industry Co-Ltd Shanghai petrochemical industry institute enterprise standard heat-resistant salt-resistant polymer microsphere profile control agent. Aging at 95deg.C under 20000mg/L saline water for 30 days, injecting 0.5PV of 0.2% concentration polymer microsphere emulsion after aging into 500mD sand filling pipe, and measuring plugging rate to 86%.
[ example 4 ]
The aqueous phase, oil phase and initiator system of example 3 were kept unchanged, span65 was adjusted to 220g and TO15 was adjusted to 55.5g such that the composite emulsifier HLB value = 4.8.
The content of the precipitated solid is 33.5 percent according to the measurement method of Q/SH3375 134-2019 China petrochemical industry Co-Ltd Shanghai petrochemical industry institute enterprise standard heat-resistant salt-resistant polymer microsphere profile control agent, and the initial particle size is 639nm. Aging at 95deg.C under 20000mg/L saline water for 30 days, injecting 0.5PV of 0.2% concentration polymer microsphere emulsion after aging into 1000mD sand filling pipe, and measuring the plugging rate to 91%.
[ example 5 ]
On the basis of example 4, the water-soluble azo initiator (V50) was removed and the other conditions were kept unchanged.
The content of the precipitated solid is 32.6 percent and the initial particle diameter is 326nm according to the measurement method of Q/SH3375 134-2019 China petrochemical industry Co-Ltd Shanghai petrochemical industry institute enterprise standard of heat-resistant salt-resistant polymer microsphere profile control agent. Aging at 95deg.C under 20000mg/L saline for 30 days, injecting 0.5PV of 0.2% concentration polymer microsphere emulsion after aging into 500mD sand filling pipe, and measuring to obtain plugging rate of 90%.
[ example 6 ]
830g white oil No. 3, 215g span85 (HLB=1.8), 58g TO15 (HLB=15.5) and the HLB value of the composite emulsifier=4.7 are added into a reaction kettle; stirring until the materials are completely and uniformly mixed, controlling the temperature in the kettle to be 22 ℃ and the stirring speed to be 200rpm. 620g of water, 770g of acrylamide, 80g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 120g of 60% dimethyldiallylammonium chloride, 16g of 2-acrylamido sodium tetradecyl sulfonate, 3g of maleic acid, 28g of sodium acetate, 0.9g of disodium ethylenediamine tetraacetate and 3.0g of methylenebisacrylamide are added into another container, and the mixture is stirred and dissolved uniformly to obtain a water phase; dividing the mixture into three parts of I, II and III according to the weight ratio of 3:2:1; respectively preparing 20% ammonium persulfate aqueous solution and 30g sodium bisulphite aqueous solution for later use. Adding the water phase I into an oil phase in a reaction kettle, stirring for a plurality of minutes until emulsification is uniform, introducing nitrogen for 30 minutes, then dripping 2g of ammonium persulfate aqueous solution, dripping 2g of sodium bisulfate aqueous solution after 5 minutes, quickly raising the temperature to 76 ℃, preserving heat for reaction for 1.5 hours, and then cooling to 26 ℃; adding the water phase II again, uniformly mixing, introducing nitrogen for 30min, then dripping 5g of ammonium persulfate aqueous solution, dripping 5g of sodium bisulphite aqueous solution after 5 min, heating to 82 ℃, preserving heat for 1.5 h, and then cooling to 30 ℃; adding the water phase III again, uniformly mixing, introducing nitrogen for 30min, then dripping 5g of ammonium persulfate aqueous solution, dripping 5g of sodium bisulphite aqueous solution after 5 min, heating to 52 ℃, carrying out heat preservation reaction for 1.5 h, finally cooling to about 30 ℃, slowly dripping 35g of AEO15, uniformly stirring, discharging, sampling and analyzing.
The content of the precipitated solid is 34.5 percent and the initial particle diameter is 1426nm according to the measurement method of Q/SH3375 134-2019 China petrochemical industry Co-Ltd Shanghai petrochemical industry institute enterprise standard heat-resistant salt-resistant polymer microsphere profile control agent. Aging at 95deg.C under 20000mg/L saline water for 30 days, injecting 0.5PV of 0.2% concentration polymer microsphere emulsion after aging into 2000mD sand filling pipe, and measuring to obtain the plugging rate of 93%.
[ example 7 ]
Based on example 6, an isopropanol solution of 5% azodiisoheptonitrile was additionally prepared, 3g and 4g were added to the oil phase before the three-step reaction, respectively, and the aqueous phase was added to carry out the reaction under the other conditions.
The content of the precipitated solid is 35.2% and the initial particle diameter is 263nm according to the measurement method of Q/SH3375 134-2019 China petrochemical industry Co-Ltd Shanghai petrochemical industry institute enterprise standard heat-resistant salt-resistant polymer microsphere profile control agent. Aging at 95deg.C under 20000mg/L saline water for 30 days, injecting 0.5PV of 0.2% concentration polymer microsphere emulsion after aging into 300mD sand filling pipe, and measuring the plugging rate to 93%.
[ example 8 ]
On the basis of example 1, the complex emulsifier was changed to 300g span60 and 52gTO, the complex emulsifier HLB value=6.3, and the other conditions remained unchanged.
The initial particle size is 86nm according to the measurement method of Q/SH3375 134-2019 China petrochemical industry Co-Ltd Shanghai petrochemical industry institute enterprise standard heat-resistant salt-resistant polymer microsphere profile control agent.
[ example 9 ]
On the basis of example 6, the complex emulsifier was changed to 300g span85 and 70gTO12 alone, the complex emulsifier HLB value=4.2, and the other conditions remained unchanged.
The initial particle size is 1856nm according to the measurement method of Q/SH3375 134-2019 China petrochemical industry Co-Ltd Shanghai petrochemical industry institute enterprise standard heat-resistant salt-resistant polymer microsphere profile control agent.
Claims (7)
1. The preparation method of the polyacrylamide microsphere emulsion with adjustable particle size comprises the following steps of reacting a mixture containing the following components;
a) 30-45 parts by weight of an oil phase;
b) 8-15 parts by weight of a composite emulsifier;
c) 25-35 parts by weight of a polymeric monomer;
d) 0.1-1.0 parts by weight of a crosslinking agent;
e) 1-3 parts by weight of a phase inversion agent;
f) 0.005-0.1 parts by weight of an initiator;
g) 25-40 parts by weight of water;
wherein the initiator consists of the following components:
1) The weight of the oxidant is 0.01-0.5% of the weight of the polymerized monomer;
2) The weight of the reducing agent is 0.05-1.0% of the weight of the polymerized monomer;
3) An azo initiator, wherein the weight of the azo initiator is 0-2.0% of the weight of the polymerization monomer;
the composite emulsifier is a nonionic emulsifier, and the HLB (hydrophilic-lipophilic balance) value is between 4 and 7;
the composite emulsifier comprises a lipophilic surfactant and a hydrophilic surfactant; wherein the lipophilic surfactant is Span85, span80. At least one of Span65 and Span 60; the hydrophilic surfactant is an isomeric alcohol polyoxyethylene ether, and the molecular formula is as follows: RO (CH) 2 CH 2 O) x H，R=iso-C 13 H 27 X is an integer of 12-15;
the composite emulsifier also comprises an auxiliary emulsifier, and the content of the auxiliary emulsifier is 0.5-2 parts by weight;
the polymerization monomer is at least one selected from the group consisting of nonionic water-soluble monomers, anionic monomers, cationic monomers and hydrophobic monomers;
the nonionic water-soluble monomer is at least one selected from the group consisting of acrylamide, methacrylamide, N-isopropylacrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-methylolacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyridine and N-vinylpyrrolidone;
the anionic monomer is selected from at least one of 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, allylphosphonic acid and/or water-soluble alkali metal, alkaline earth metal and ammonium salts thereof;
the cationic monomer is at least one selected from the group consisting of dimethyldiallylammonium chloride, acryloyloxyethyl trimethylammonium chloride, methacryloyloxyethyl trimethylammonium chloride and 2-acrylamido-2-methylpropyl trimethylammonium chloride;
the hydrophobic monomer is selected from monovinyl compounds with 8-22 carbon atoms; the anionic hydrophobic monomer is selected from sodium acrylamide nitrogen alkyl sulfonate with vinyl carbon chain number of 8-18; the cationic hydrophobic monomer is selected from allyl alkyl ammonium chloride with vinyl carbon chain number of 12-22;
the azo initiator is at least one selected from the group consisting of 2,2' -azo [2- (2-imidazolin-2-yl) propane ] dihydrochloride, azobisisobutylamidine hydrochloride, azobisisobutyronitrile and azobisisoheptonitrile;
the microsphere emulsion further comprises h) a complexing agent, wherein the weight of the complexing agent is 0.05-0.2% of the weight of the polymerized monomer;
the preparation method of the microsphere emulsion comprises the following steps:
contacting the oil phase with a composite emulsifier to form a continuous phase;
contacting a polymeric monomer, a cross-linking agent, optionally a co-emulsifier, optionally a complexing agent, and water to form an aqueous phase;
preparing an initiator solution;
the water-soluble azo initiator is directly added into the water phase or is prepared into water solution; the oil-soluble azo initiator is directly added into an oil phase or is prepared into an isopropanol solvent;
(2) contacting the continuous phase, the aqueous phase and the initiator solution to obtain a mixture a;
(3) contacting the mixture A with a phase inversion agent to obtain the polyacrylamide microsphere emulsion;
according to the preparation method of the microsphere emulsion, microspheres with different particle sizes can be prepared by adjusting the lipophilic and hydrophilic properties of the composite emulsifier, namely the HLB value;
according to the preparation method of the microsphere emulsion, the particle size of the microsphere can be increased by adding the water-soluble azo initiator, and the particle size of the microsphere can be reduced by adding the oil-soluble azo initiator;
when HLB of the composite emulsifier is more than or equal to 5.4, the polyacrylamide microsphere emulsion prepared by the preparation method of the microsphere emulsion contains nano microspheres; the particle size of the nano microsphere is 80-150 nanometers;
when HLB of the composite emulsifier is less than or equal to 4.7, the polyacrylamide microsphere emulsion prepared by the preparation method of the microsphere emulsion contains microspheres; the particle size of the microsphere is 1000-1500 nanometers;
when the HLB of the composite emulsifier is 4.7< 5.4, the polyacrylamide microsphere emulsion prepared by the preparation method of the microsphere emulsion contains submicron microspheres; the particle size of the submicron microsphere is 300-600 nanometers.
2. The method for producing a microsphere emulsion according to claim 1, wherein the oil phase is at least one selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons;
the aliphatic hydrocarbon is at least one selected from white oil No. 3, white oil No. 5, solvent oil No. 120 and solvent oil No. 200; the aromatic hydrocarbon is dimethylbenzene; the halogenated hydrocarbon is carbon tetrachloride.
3. The method for preparing a microsphere emulsion according to claim 1, wherein the crosslinking agent is at least one selected from the group consisting of methylenebisacrylamide, divinylbenzene, polyethylene glycol diacrylate and pentaerythritol triacrylate;
the phase inversion agent is at least one selected from the group consisting of isomeric alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether.
4. The method for producing a microsphere emulsion according to claim 1, wherein the oxidizing agent is at least one selected from the group consisting of potassium persulfate, sodium persulfate, ammonium persulfate and benzoyl peroxide;
the reducing agent is at least one selected from the group consisting of sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium thiosulfate and ferrous chloride.
5. The method of preparing a microsphere emulsion according to claim 1, wherein in step (2), the aqueous phase is divided into m parts and contacted with the continuous phase and the initiator solution to obtain the mixture a; m is an integer greater than or equal to 2, m 1 For the weight of the first part, m 2 M is the weight of the second part m For the weight of the m-th part, m 1 :m 2 :……:m m =（1~20）:（1~10）:……:（1~2）。
6. The method for preparing the microsphere emulsion according to claim 1, wherein the first part of aqueous phase is contacted with the continuous phase and the initiator solution to obtain a mixture A1, and the temperature of the mixture A1 is controlled to be 50-90 ℃;
and (3) contacting the m-th part of water phase with the mixture A1 to obtain a mixture A, and controlling the temperature of the mixture A to be 50-80 ℃.
7. The use of the polyacrylamide microsphere emulsion prepared by the preparation method of the polyacrylamide microsphere emulsion according to any one of claims 1-6 in tertiary oil recovery in oil fields.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110502862.4A CN115304707B (en) | 2021-05-08 | 2021-05-08 | Polyacrylamide microsphere emulsion with adjustable particle size, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110502862.4A CN115304707B (en) | 2021-05-08 | 2021-05-08 | Polyacrylamide microsphere emulsion with adjustable particle size, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115304707A CN115304707A (en) | 2022-11-08 |
| CN115304707B true CN115304707B (en) | 2023-08-04 |
Family
ID=83853525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110502862.4A Active CN115304707B (en) | 2021-05-08 | 2021-05-08 | Polyacrylamide microsphere emulsion with adjustable particle size, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115304707B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1653152A (en) * | 2002-05-14 | 2005-08-10 | 株式会社资生堂 | Tickener, cosmetic preparation containing the same, and process for producing the same |
| CN104448126A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Harsh oil deposit reversed-phase microemulsion profile-control flooding system and preparation method thereof |
| CN108314758A (en) * | 2017-01-17 | 2018-07-24 | 中国石油化工股份有限公司 | Polyacrylamide microsphere lotion and preparation method thereof |
| CN109666475A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Temperature-resistant anti-salt low-tension nanosphere profile control agent and preparation method thereof |
-
2021
- 2021-05-08 CN CN202110502862.4A patent/CN115304707B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1653152A (en) * | 2002-05-14 | 2005-08-10 | 株式会社资生堂 | Tickener, cosmetic preparation containing the same, and process for producing the same |
| CN104448126A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Harsh oil deposit reversed-phase microemulsion profile-control flooding system and preparation method thereof |
| CN108314758A (en) * | 2017-01-17 | 2018-07-24 | 中国石油化工股份有限公司 | Polyacrylamide microsphere lotion and preparation method thereof |
| CN109666475A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Temperature-resistant anti-salt low-tension nanosphere profile control agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115304707A (en) | 2022-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4681912A (en) | Process for manufacturing inverse microlatices of watersoluble copolymers, the resultant inverse microlatices and their use for improving the production of hydrocarbons | |
| CN109666475B (en) | Temperature-resistant salt-resistant low-tension nano-microsphere profile control and flooding agent and preparation method thereof | |
| CN108315003B (en) | Polyacrylamide microsphere deep profile control and flooding agent and preparation method and application thereof | |
| CN105586025B (en) | High-temperature high-salinity reservoir polymer microsphere disperse system profile control and flooding agent and preparation method and application thereof | |
| CN108329420B (en) | Low-tension polymer microsphere profile control and flooding agent and preparation method and application thereof | |
| US11795376B2 (en) | Viscosifying friction reducers | |
| CN106866881B (en) | hydrophobic association acrylamide polymer emulsion and preparation method thereof | |
| US4975482A (en) | Viscoelastic fluids formed through the interaction of polymerizable vesicles and alkyl-containing polymers (C-2381) | |
| CN109666099B (en) | Core-shell polymer microsphere and preparation method thereof | |
| US4831092A (en) | Micellar process for preparing hydrophobically functionalized cationic polymers (C-2114) | |
| CN106867496B (en) | Online injection type oil displacement agent containing hydrophobically associating polymer emulsion and preparation method thereof | |
| CN108314758B (en) | Polyacrylamide microsphere emulsion and preparation method thereof | |
| CN110698580B (en) | Nano latex strong plugging agent for drilling fluid and preparation method thereof | |
| US4764574A (en) | Inverse emulsion polymerization with sorbitan fatty acid esters and ethoxylated alcohol | |
| US11773199B2 (en) | Auto-invertible inverse polymer emulsion | |
| JPH11116762A (en) | New associated polymer and production thereof by reversed phase emulsion polymerization | |
| KR0184519B1 (en) | Water-in-oil emulsion of cationic polymer | |
| CN115304707B (en) | Polyacrylamide microsphere emulsion with adjustable particle size, and preparation method and application thereof | |
| CN111087553B (en) | Multilayer core-shell structure polymer microsphere, profile control agent, preparation method and application thereof | |
| JPH10306123A (en) | New association polymer, and its production by reverse-phase micro-emulsion polymerization | |
| CA3129662A1 (en) | Friction reducers | |
| CN113652220A (en) | Resistance reducing agent, water-based fracturing fluid containing resistance reducing agent and application of water-based fracturing fluid | |
| CN115707722A (en) | Self-assembled emulsified core-shell polymer microsphere and preparation method and application thereof | |
| JP4753401B2 (en) | How to use water-in-oil water-soluble polymer emulsion | |
| CN114085661B (en) | Gel particle emulsion liquid system and method for improving recovery ratio thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |