CN115304707A - Particle size-adjustable polyacrylamide microsphere emulsion and preparation method and application thereof - Google Patents
Particle size-adjustable polyacrylamide microsphere emulsion and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a particle size-adjustable polyacrylamide microsphere emulsion as well as a preparation method and application thereof, and mainly solves the problem that different polymerization methods are generally adopted for preparing polyacrylamide microspheres with different particle sizes in the prior art. The invention adopts a reverse microemulsion polymerization method, and the polyacrylamide microsphere emulsion is prepared by the reaction of a mixture consisting of oil phase, composite emulsifier, polymerization monomer, cross-linking agent and the like. The preparation method is simple to operate, the obtained microsphere emulsion can meet the plugging requirements of strata with different permeability, and the microsphere emulsion can be directly used for on-site application of deep profile control, water plugging, oil displacement and the like for tertiary oil recovery of an oil field or used for on-site application of improving the recovery ratio after being compounded with other oil field chemicals.
Description
Technical Field
The invention relates to a particle size-adjustable polyacrylamide microsphere and 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 that the nanometer to micron-sized water-swellable microspheres are used for gradually plugging stratum pore throats with different permeabilities to realize the deep profile control and water shutoff effect. The microspheres used in oil fields generally refer to polyacrylamide spherical particles containing a cross-linking agent, and according to the particle size, the nano-scale microspheres are generally prepared by an inverse microemulsion polymerization method, the submicron-scale microspheres are prepared by an inverse emulsion method, and the micron microspheres are prepared by an inverse (micro) suspension method. All three of them contain an oil phase, an aqueous phase and an emulsifier (or stabilizer), but their polymerization mechanisms are different.
The microemulsion (microemulsion) is a colloid dispersion system which is clear, transparent or semitransparent, has a particle size of 10-100 nanometers and is thermodynamically stable. Microemulsions form spontaneously, an explanation is that in the presence of surfactants, co-surfactants, the oil/water interface creates a so-called negative interfacial tension, and the amount of emulsifier used in the system is large, which is quite different from that of inverse emulsions. The reverse microemulsion of acrylamide is composed of monomer such as acrylamide, water, oil-soluble solvent, emulsifier, co-emulsifier and other polymerization assistants. Commonly used oil phases are hydrocarbons such as toluene, hexane, kerosene, white oil, isopar M, etc.; as the emulsifier, span, tween series, etc. are usually used in an amount of 10% by mass or more based on the emulsion. The fast reaction speed is one of the characteristics of acrylamide inverse microemulsion polymerization, and in addition, the particle size range of the microsphere product is also narrow, 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 the liquid of water-soluble monomers dissolved in water as a disperse phase and takes a nonpolar hydrocarbon solvent as a continuous phase under the action of an emulsifier to form 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, nonionic emulsifiers are most often used in inverse emulsions, and it is believed that this is due to steric hindrance that significantly increases the coalescence of latex particles after adsorption of such emulsifiers on the surface of the latex particles. Besides reducing the surface tension and interfacial tension between oil and water, the emulsifier also plays roles in emulsifying, dispersing and solubilizing the oil relative to the water phase, and leads the polymerization to be carried out according to a micelle mechanism or a droplet nucleation mechanism. According to the traditional theory, the emulsifier of the reverse microemulsion polymerization system is selected according to the principle of hydrophilic-lipophilic balance value, and the emulsifier with partial oil solubility is selected, and the HLB value is between 3 and 6. It has been found that the effect of the composite emulsifier is better than that of the single emulsifier, because when the difference between the HLB value of the emulsified substance and the HLB value of the emulsifier is large, the affinity of the emulsifier to the emulsified substance is small, and the emulsifying effect is poor; on the other hand, when the HLB value of the emulsifier is small, the affinity for water is small, and the emulsifying effect is also poor. If two or more kinds of emulsifiers with different HLB values are mixed to form a composite emulsifier, the emulsifying effect of the emulsifier can be greatly improved by gradually changing the emulsifiers with different properties from lipophilic to hydrophilic. Therefore, a good W/O type emulsifying effect can be obtained by using a nonionic complex emulsifier such as a mixture of Span and Tween. It has been found that the concentration and HLB value of the emulsifier system can affect the polymerization rate, the stability of the emulsion system, the viscosity of the emulsion and the size of the emulsion particles, but there is almost no report on 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 made in the preparation of a polyacrylamide microsphere system and the profile control and oil displacement application of tertiary oil recovery in China, polymer microspheres with different sizes are developed by various petroleum colleges, research institutions and the like and are used for profile control of stratums with different permeability, however, different polymerization methods are adopted for preparing the polyacrylamide microspheres basically according to different particle sizes, the nano microspheres are polymerized by using reverse microemulsion, the content of a water phase is low due to the high content of an oil phase and an emulsifier, and the effective solid content is generally about 20%; the submicron microspheres generally adopt inverse emulsion polymerization, and in order to keep the stability of an emulsion system, measures such as strengthening emulsification and homogenization before reaction, accurately controlling the polymerization temperature rise rate and the like are adopted; the micron-sized microspheres generally adopt a reversed-phase (micro) suspension method, and a certain amount of stabilizing agent is generally added into a system in order to reduce the sedimentation of the microspheres.
Disclosure of Invention
Based on the extensive and intensive research on the synthesis principle, the structural representation and the property of a polyacrylamide microsphere system, the inventor can respectively prepare microspheres with different particle sizes of nanometer, submicron or micron by adopting a reverse microemulsion polymerization method and only adjusting the oleophilic property and the hydrophilic property, namely the HLB value, of an emulsifier system, after the HLB value is fixed, if a water-soluble azo initiator is added on the basis of a redox initiation system, the particle size of the microspheres can be increased, and if the oil-soluble azo initiator is added, the particle size of the microspheres can be reduced.
Specifically, the present invention relates to the following aspects:
1. a polyacrylamide microsphere emulsion is prepared by reacting a mixture containing the following components;
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 composite emulsifier; preferably 8 to15 parts by weight;
c) 20 to 50 parts by weight of a polymerized 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 transfer 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 to 50 parts by weight of water; preferably 25 to 40 parts by weight;
wherein the initiator comprises:
1) An oxidizing agent, the weight of which is 0.002-1.0% of the weight of the polymerization monomer; preferably 0.01 to 0.5%;
2) A reducing agent, the weight of which is 0.02 to 2.0 percent 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 polymerization monomer; preferably 0 to 2.0%.
2. The polyacrylamide microsphere emulsion according to any one of the preceding or subsequent aspects, 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 of industrial white oil and solvent oil; preferably at least one of No. 3 white oil, no. 5 white oil, no. 120 mineral spirits, and No. 200 mineral spirits;
the aromatic hydrocarbon is selected from at least one of benzene, toluene and xylene; preferably xylene;
the halogenated hydrocarbon is 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 hydrophilic-lipophilic balance value 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 greater than or equal to 5.4, the polyacrylamide microsphere emulsion contains nano microspheres; the particle size of the nano microsphere is 50-200 nm, preferably 80-150 nm;
when the HLB is less than or equal to 4.7, the polyacrylamide microsphere emulsion contains microspheres; the particle size of the micro-microspheres is 800-2000 nm, preferably 1000-1500 nm;
when 4.7 yarn-woven HLB yarn-woven fabric is 5.4, the polyacrylamide microsphere emulsion contains submicron microspheres; the particle size of the submicron microsphere is 200-800 nm, preferably 300-600 nm.
5. The polyacrylamide microsphere emulsion according to 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 ester, preferably at least one of Span85, span80, span65 and Span 60; the hydrophilic surfactant is 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 to 3 parts by weight, preferably 0.5 to 2 parts by weight; the coemulsifier is selected from sodium or potassium salts, preferably at least one of sodium, potassium acetate, halide, sulfate and sulfonate.
7. The polyacrylamide microsphere emulsion according to any one of the preceding or subsequent aspects, wherein the polymerized 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 the group consisting 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, acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride and 2-acrylamido-2-methylpropyltrimethylammonium chloride;
the hydrophobic monomer is selected from a monovinyl compound with 8-22 carbon atoms; the anionic hydrophobic monomer is selected from acrylamide nitrogen alkyl sodium sulfonate with a vinyl carbon chain number of 8-18; the cationic hydrophobic monomer is selected from allyl alkyl ammonium chloride with a 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 surfactants, preferably at least one of isomeric alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether.
9. The polyacrylamide microsphere emulsion according to 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 bisulfite, potassium bisulfite, 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 according to any one of the preceding or subsequent aspects, wherein the polyacrylamide microsphere emulsion further comprises h) a complexing agent, and the weight of the complexing agent is 0.01 to 0.5 percent, preferably 0.05 to 0.2 percent of the weight of the polymerized monomer; the complexing agent is at least one selected from disodium ethylene diamine tetraacetate and sodium diethylenetriamine pentaacetate.
11. A preparation method of polyacrylamide microsphere emulsion comprises the following steps:
(1) contacting the oil phase with a complex emulsifier to form a continuous phase;
contacting a polymerized monomer, a crosslinking agent, an optional co-emulsifier, an optional 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 prepared into water solution, and the concentration of the water solution is preferably 1 to 30 weight percent, more preferably 5 to 20 weight percent; the oil-soluble azo initiator is directly added into an oil phase or is prepared in an isopropanol solvent, and the concentration is preferably 1 to 30 weight percent, more preferably 5 to 20 weight percent;
(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 preparation method of the polyacrylamide microsphere emulsion according to any one of the preceding or subsequent aspects, wherein in the step (2), m parts of the aqueous phase are contacted with the continuous phase and the initiator solution to obtain the mixture A; m is an integer of 2 or more, m 1 Is the weight of the first part, m 2 Is the weight of the second part, m m Is 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 preceding or subsequent aspects, wherein a first partial 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 ℃;
contacting the m-th partial aqueous phase with the mixture A1 to obtain a mixture A, and controlling the temperature of the mixture A to be 50-80 ℃;
the increase in reaction temperature is primarily a function of the amount of reducing agent added, and the maximum temperature is primarily a function of the monomer concentration.
14. The polyacrylamide microsphere emulsion of any one of the preceding aspects and the application of the polyacrylamide microsphere emulsion prepared by the preparation method of the polyacrylamide microsphere emulsion of any one of the preceding aspects in tertiary oil recovery in oil fields. The polyacrylamide microsphere emulsion with adjustable particle size can be used independently according to application requirements, and can also be added with a surfactant for oil displacement and stirred uniformly, so that the system can be used for the field application of improving the recovery ratio for deep profile control, water shutoff, oil displacement and the like for tertiary oil recovery in an oil field.
Technical effects
According to the particle size-adjustable polyacrylamide microsphere emulsion and the preparation method thereof, microspheres with different particle sizes of nanometer, submicron or micron can be prepared only by adjusting the lipophilic and hydrophilic properties (namely HLB) value) of an emulsifier system, and after the HLB value is fixed, if a water-soluble azo initiator is added on the basis of a redox initiation system, the particle size of the microspheres can be increased; 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 strata with different permeability, and can be directly used for on-site application of improving the recovery ratio for deep profile control, water plugging, oil displacement and the like for tertiary oil recovery of an oil field or after being compounded with other oil field chemicals.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the 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 same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with the claims defining the existence of materials, methods, procedures, means, or components, or the like, that are regarded as being "known to one of ordinary skill in the art", "prior art", or the like, it is intended that the subject matter so derived encompass those materials, methods, procedures, means, or components which have been conventionally used in the art at the time of filing this application, but which may not be so commonly used at the present time, but will become known in the art as being suitable for a similar purpose.
In the context of the specification, the content of precipitable solid matters, the initial particle size and the plugging rate of the polyacrylamide microsphere emulsion are tested according to a method for determining the temperature-resistant salt-resistant polymer microsphere profile control and flooding agent of the enterprise standard Shanghai petrochemical industry institute of Q/SH 3375-2019, china petrochemical industry, inc.
In the context of the present specification, the names and abbreviations of the compounds mentioned are as shown in the following table:
| name of the Compound | 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 |
| Azobisisobutylamidine hydrochloride | V50 |
| Azobisisobutyronitrile | AIBN |
| Azobisisoheptonitrile | ABVN |
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
[ example 1 ] A method for producing a polycarbonate
Firstly, 1000g of No. 5 white oil, 300g of span80 (HLB = 4.3), 36g of TO12 (HLB = 14.5) and a composite emulsifier HLB value =5.4 are added into a reaction kettle; stirring until the mixture is completely and uniformly mixed, controlling the temperature in the kettle to be 22 ℃ and the stirring speed to be 200rpm. Adding 725g of water, 850g of acrylamide, 80g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 30g of sodium acetate, 1.0g of ethylene diamine tetraacetic acid, 130g of 60% dimethyl diallyl ammonium chloride and 1.5g of methylene bisacrylamide into another container, stirring and dissolving uniformly to obtain a water phase, and uniformly dividing the water phase into two parts, namely I and II; 30g of 20% ammonium persulfate and 30g of sodium bisulfite aqueous solution are respectively prepared for standby. Adding the water phase I into the oil phase in the reaction kettle, stirring for several minutes until the emulsion is uniform, introducing nitrogen for 30 minutes, then dripping 3g of ammonium persulfate aqueous solution, dripping 3g of sodium bisulfite aqueous solution after 5 minutes, quickly raising the temperature to 76 ℃, keeping the temperature for reaction for 1.5 hours, and then reducing the temperature 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 bisulfite aqueous solution after 5 min, heating to 58 ℃, reacting for 1.5 h under heat preservation, finally cooling to about 30 ℃, slowly dripping 30g of OP10, uniformly stirring, discharging, sampling and analyzing.
The content of the precipitated solid matter is 31.6 percent and the initial particle size is 98nm according to the test method of the temperature-resistant salt-resistant polymer microsphere profile control and flooding agent of the enterprise standard of Shanghai petrochemical industry institute of Q/SH 3375-2019, china petrochemical industry, inc. Aging at 95 deg.C and total mineralization of 20000mg/L saline for 30 days, injecting aged 0.2% polymer microsphere emulsion 0.5PV with 200mD sand filling pipe, and measuring the plugging rate to 89%.
[ example 2 ] A method for producing a polycarbonate
Firstly, 1000g of No. 5 white oil, 300g of span80 (HLB = 4.3), 36g of TO12 (HLB = 14.5) and a composite emulsifier HLB value =5.4 are added into a reaction kettle; stirring until the mixture is completely and uniformly mixed, controlling the temperature in the kettle to be 22 ℃ and the stirring speed to be 200rpm. Adding 725g of water, 850g of acrylamide, 80g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 30g of sodium acetate, 1.0g of ethylene diamine tetraacetic acid disodium, 130g of 60% dimethyldiallylammonium chloride, 1.5g of methylene bisacrylamide and 1.5g of V044 into another container, stirring to dissolve uniformly to obtain a water phase, and uniformly dividing the water phase into two parts, namely I and II; 30g of 20% ammonium persulfate and 30g of sodium bisulfite aqueous solution are prepared respectively for standby. Adding the water phase I into the oil phase in the reaction kettle, stirring for several minutes until the mixture is emulsified uniformly, introducing nitrogen for 30 minutes, then dropwise adding 3g of ammonium persulfate aqueous solution, dropwise adding 3g of sodium bisulfite aqueous solution after 5 minutes, raising the temperature to 78 ℃ quickly, keeping the temperature for reaction for 1.5 hours, and then reducing the temperature to 22 ℃; and adding the water phase II again, uniformly mixing, introducing nitrogen for 30min, then dripping 5g of ammonium persulfate aqueous solution, dripping 5g of sodium bisulfite aqueous solution after 5 min, heating to 60 ℃, keeping the temperature for reaction for 1.5 h, finally cooling to about 30 ℃, slowly dripping 30g of OP10, uniformly stirring, discharging, sampling and analyzing.
According to a test method of a measuring method of 'temperature-resistant salt-resistant polymer microsphere profile control and flooding agent' of Shanghai petrochemical industry research institute enterprise standard of Q/SH 3375-2019, china petrochemical industry, inc., the content of the precipitable solid is 33.2%, and the initial particle size is 145nm. Aging at 95 deg.C under saline water with total mineralization of 20000mg/L for 30 days, injecting aged 0.2% polymer microsphere emulsion 0.5PV with 300mD sand filling pipe, and measuring the plugging rate to 85%.
[ example 3 ] A method for producing a polycarbonate
880g No. 200 solvent oil, 240g Span65 (HLB = 2.1), 66g TO15 (HLB = 15.5) and composite emulsifier HLB =5.0 are added into a reaction kettle, stirred until the mixture is completely mixed evenly, the temperature in the kettle is controlled to be 25 ℃, and the stirring speed is 200rpm. Adding 720g of water, 850g of acrylamide, 80g of sodium acrylate, 130g of 80% acryloyloxyethyl trimethyl ammonium chloride, 15g of hexadecyl dimethyl allyl ammonium chloride, 5g of maleic acid, 30g of sodium acetate, 1.2g of ethylene diamine tetraacetic acid and 3.5g of polyethylene glycol diacrylate into another container, and uniformly stirring and dissolving to obtain 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; 30g of 10% ammonium persulfate, a sodium bisulfite aqueous solution and 2,2' -azo (2-methylpropylamidine) dihydrochloride (V50) were prepared separately. Adding the water phase I into the oil phase in the reaction kettle, stirring for several minutes until the emulsion is uniform, introducing nitrogen for 30 minutes, then dropwise adding 5g of ammonium persulfate aqueous solution and 0.5g of V50, dropwise adding 5g of sodium bisulfite aqueous solution after 5 minutes, quickly raising the temperature to 86 ℃, keeping the temperature for reaction for 1.5 hours, and then reducing the temperature to 50 ℃; and adding the water phase II again, uniformly mixing, introducing nitrogen for 30min, then dropwise adding 5g of V50, heating to 72 ℃, keeping the temperature for reaction for 1.5 hours, finally cooling to about 30 ℃, slowly dropwise adding 32g of AEO9, uniformly stirring, discharging, sampling and analyzing.
The content of the precipitable solid is 34.2 percent and the initial particle size is 423nm according to the test method of the temperature-resistant and salt-resistant polymer microsphere profile control and flooding agent of the enterprise standard of Shanghai petrochemical industry research institute of Q/SH 3375-2019, china petrochemical industry Limited company. Aging at 95 deg.C and total mineralization of 20000mg/L saline for 30 days, injecting aged 0.2% polymer microsphere emulsion 0.5PV with 500mD sand filling pipe, and measuring the plugging rate to 86%.
[ example 4 ]
The aqueous phase, oil phase and initiator system of example 3 were held constant and Span65 was adjusted to 220g and TO15 to 55.5g so that the complex emulsifier HLB value =4.8.
The content of the precipitated solid is 33.5 percent and the initial particle size is 639nm according to the test method of the temperature-resistant salt-resistant polymer microsphere profile control and flooding agent of the enterprise standard of Shanghai petrochemical industry institute of Q/SH 3375-2019, china petrochemical industry, inc. Aging at 95 deg.C and total mineralization of 20000mg/L saline for 30 days, injecting aged 0.2% polymer microsphere emulsion 0.5PV with 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 constant.
The content of the precipitated solid matter is 32.6 percent and the initial particle size is 326nm according to the test method of the temperature-resistant salt-resistant polymer microsphere profile control and flooding agent of the enterprise standard of Shanghai petrochemical industry institute of Q/SH 3375-2019, china petrochemical industry, inc. Aging at 95 deg.C and total mineralization of 20000mg/L saline for 30 days, injecting aged 0.2% polymer microsphere emulsion 0.5PV with 500mD sand filling pipe, and measuring the plugging rate to 90%.
[ example 6 ] A method for producing a polycarbonate
Firstly, 830g of white oil No. 3, 215g of Span85 (HLB = 1.8), 58g of TO15 (HLB = 15.5) and a composite emulsifier HLB value =4.7 are added into a reaction kettle; stirring until the mixture is completely and uniformly mixed, controlling the temperature in the kettle to be 22 ℃ and the stirring speed to be 200rpm. Adding 620g of water, 770g of acrylamide, 80g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 120g of 60% dimethyldiallylammonium chloride, 1lg of 2-acrylamidotetradecylsulfonate, 3g of maleic acid, 28g of sodium acetate, 0.9g of ethylene diamine tetraacetic acid and 3.0g of methylenebisacrylamide into a separate container, and uniformly stirring and dissolving to obtain a water phase; the mixture is divided into three parts, namely I, II and III according to the weight of 3; 20% ammonium persulfate aqueous solution and 30g sodium bisulfite aqueous solution are respectively prepared for standby. Adding the water phase I into the oil phase in the reaction kettle, stirring for several minutes until the emulsion is uniform, introducing nitrogen for 30 minutes, then dripping 2g of ammonium persulfate aqueous solution, dripping 2g of sodium bisulfite aqueous solution after 5 minutes, quickly raising the temperature to 76 ℃, keeping the temperature for reaction for 1.5 hours, and then reducing the temperature 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 bisulfite aqueous solution after 5 min, heating to 82 ℃, keeping the temperature, reacting for 1.5 h, and then cooling to 30 ℃; and adding the water phase III again, uniformly mixing, introducing nitrogen for 30min, then dripping 5g of ammonium persulfate aqueous solution, dripping 5g of sodium bisulfite aqueous solution after 5 min, heating to 52 ℃, keeping the temperature, reacting 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 size is 1426nm according to the test method of the temperature-resistant and salt-resistant polymer microsphere profile control and flooding agent of the enterprise standard of Shanghai petrochemical industry research institute of Q/SH 3375-2019, china petrochemical industry, inc. Aging at 95 deg.C and total mineralization of 20000mg/L saline for 30 days, injecting aged 0.2% polymer microsphere emulsion 0.5PV with 2000mD sand filling pipe, and measuring the plugging rate to 93%.
[ example 7 ] A method for producing a polycarbonate
On the basis of example 6, 5% azobisisoheptonitrile isopropanol solution was prepared, and before the three steps of reaction, 3g,4g of the solution was added into the oil phase, and then the water phase was added for reaction, and other conditions were kept unchanged.
The content of the precipitated solid matter is 35.2 percent and the initial particle size is 263nm according to the measurement method of the temperature-resistant salt-resistant polymer microsphere profile control and flooding agent of the enterprise standard of Shanghai petrochemical industry institute of Q/SH 3375-2019, china petrochemical industry, inc. Aging at 95 deg.C under saline water with total mineralization of 20000mg/L for 30 days, injecting aged 0.2% polymer microsphere emulsion 0.5PV with 300mD sand filling pipe, and measuring the plugging rate to 93%.
[ example 8 ]
Based on example 1, only the composite emulsifier is changed to 300gSpan60 and 52gTO15, the HLB value of the composite emulsifier is =6.3, and other conditions are kept unchanged.
The initial particle size is 86nm according to the measurement method of the temperature-resistant salt-resistant polymer microsphere profile control and flooding agent of the enterprise standard of Shanghai petrochemical industry research institute of Q/SH 3375-2019, china petrochemical industry, inc.
[ example 9 ] A method for producing a polycarbonate
Based on example 6, only the composite emulsifier is changed to 300gSpan85 and 70gTO12, the HLB value of the composite emulsifier is =4.2, and other conditions are kept unchanged.
The initial particle size is 1856nm according to the measurement method of the standard 'temperature-resistant salt-resistant polymer microsphere profile control and flooding agent' of Shanghai petrochemical industry research institute enterprise standard of Q/SH 3375-2019, china petrochemical industry, inc.
Claims (14)
1. A polyacrylamide microsphere emulsion is prepared by reacting a mixture containing the following components;
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 composite emulsifier; preferably 8 to15 parts by weight;
c) 20 to 50 parts by weight of a polymerization 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 transfer 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 to 50 parts by weight of water; preferably 25 to 40 parts by weight;
wherein the initiator comprises:
1) An oxidizing agent, the weight of which is 0.002-1.0% of the weight of the polymerization monomer; preferably 0.01 to 0.5%;
2) A reducing agent, the weight of which is 0.02 to 2.0 percent 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 polymerization monomer; preferably 0 to 2.0%.
2. The polyacrylamide microsphere emulsion according to claim 1, wherein said 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 of industrial white oil and solvent oil; preferably at least one of No. 3 white oil, no. 5 white oil, no. 120 mineral spirits, and No. 200 mineral spirits;
the aromatic hydrocarbon is selected from at least one of benzene, toluene and xylene; preferably xylene;
the halogenated hydrocarbon is at least one of dichloromethane, chloroform and carbon tetrachloride; carbon tetrachloride is preferred.
3. The polyacrylamide microsphere emulsion according to claim 1, wherein the composite emulsifier is a nonionic emulsifier, and the hydrophilic-lipophilic balance value HLB is between 4 and 7.
4. The polyacrylamide microsphere emulsion according to claim 1 or 3, 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 nm, preferably 80-150 nm;
when the HLB is less than or equal to 4.7, the polyacrylamide microsphere emulsion contains microspheres; the particle size of the micro-microspheres is 800-2000 nm, preferably 1000-1500 nm;
when 4.7 yarn-woven HLB yarn-woven fabric is 5.4, the polyacrylamide microsphere emulsion contains submicron microspheres; the particle size of the submicron microsphere is 200-800 nm, preferably 300-600 nm.
5. The polyacrylamide microsphere emulsion according to claim 1 or 3, wherein the composite emulsifier comprises a lipophilic surfactant and a hydrophilic surfactant; wherein the lipophilic surfactant is sorbitan fatty acid ester, preferably at least one of Span85, span80, span65 and Span 60; the hydrophilic surfactant is 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 And x is an integer of 10 to 20, preferably 12 to 15.
6. The polyacrylamide microsphere emulsion according to claim 1 or 3, wherein the composite emulsifier further comprises a co-emulsifier in an amount of 0.2 to 3 parts by weight, preferably 0.5 to 2 parts by weight; the coemulsifier is selected from sodium or potassium salts, preferably at least one of sodium, potassium acetate, halide, sulfate and sulfonate.
7. The polyacrylamide microsphere emulsion according to claim 1, wherein said polymeric monomer is at least one selected from the group consisting of nonionic water-soluble monomers, anionic monomers, cationic monomers, 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 the group consisting 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, acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride and 2-acrylamido-2-methylpropyltrimethylammonium chloride;
the hydrophobic monomer is selected from a monovinyl compound with 8-22 carbon atoms; the anionic hydrophobic monomer is selected from acrylamide nitrogen alkyl sodium sulfonate with a vinyl carbon chain number of 8-18; the cationic hydrophobic monomer is selected from allyl alkyl ammonium chloride with a vinyl carbon chain number of 12-22.
8. The polyacrylamide microsphere emulsion of claim 1 wherein said crosslinking agent is selected from at least one member of the group consisting of methylenebisacrylamide, divinylbenzene, polyethyleneglycol diacrylate and pentaerythritol triacrylate;
the phase inversion agent is selected from hydrophilic nonionic surfactants, preferably at least one of isomeric alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether.
9. The polyacrylamide microsphere emulsion according to claim 1, wherein said 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 bisulfite, potassium bisulfite, 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 according to claim 1, wherein said polyacrylamide microsphere emulsion further comprises h) a complexing agent in an amount of 0.01 to 0.5%, preferably 0.05 to 0.2% by weight based on the weight of said polymerized monomers; the complexing agent is at least one selected from disodium ethylene diamine tetraacetate and sodium diethylenetriamine pentaacetate.
11. A preparation method of polyacrylamide microsphere emulsion comprises the following steps:
(1) contacting the oil phase with a complex emulsifier to form a continuous phase;
contacting a polymerized monomer, a crosslinking agent, an optional co-emulsifier, an optional complexing agent, and water to form an aqueous phase;
preparing an initiator solution;
(2) contacting the continuous phase, the aqueous phase and the initiator solution to obtain a mixture A;
(3) and contacting the mixture A with a phase transfer agent to obtain the polyacrylamide microsphere emulsion.
12. The method for preparing polyacrylamide microsphere emulsion according to claim 11, wherein in the step (2), m portions of the aqueous phase are contacted with the continuous phase and the initiator solution to obtain the mixture a; m is an integer of 2 or more, m 1 Is the weight of the first part, m 2 Is the weight of the second part, m m Is the weight of the m-th part, m 1 :m 2 :……:m m ＝(1～20):(1～10):……:(1～2)。
13. The method for preparing the polyacrylamide microsphere emulsion according to claim 12, wherein a first portion of the 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 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 ℃.
14. Use of the polyacrylamide microsphere emulsion according to any one of claims 1 to 10 and the polyacrylamide microsphere emulsion prepared by the method according to any one of claims 11 to 13 in tertiary oil recovery in oil fields.
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| 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 |
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| 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 |
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| CN117886993A (en) * | 2024-03-12 | 2024-04-16 | 四川省威沃敦石油科技股份有限公司成都分公司 | Supermolecule microsphere profile control agent convenient for deep profile control of oil field and preparation method thereof |
| CN117886993B (en) * | 2024-03-12 | 2024-05-31 | 四川省威沃敦石油科技股份有限公司成都分公司 | Supermolecule microsphere profile control agent convenient for deep profile control of oil field and preparation method thereof |
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