CN106866881B - hydrophobic association acrylamide polymer emulsion and preparation method thereof - Google Patents
hydrophobic association acrylamide polymer emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a hydrophobic association acrylamide polymer emulsion and a preparation method thereof, and mainly solves the problems that in the prior art, a hydrophobic association polymer is polymerized by a micelle or an aqueous solution mostly, the equipment and the process are long and complex, the energy consumption is high, and the problems of difficulty are brought to oil displacement construction of oilfield field application, particularly offshore oil reservoirs. The invention adopts an inverse emulsion polymerization method, adopts commercial nonionic surfactant as emulsifier in an oil-water system, obtains the hydrophobic association polymer emulsion with higher solid content by controlling the adding speed of initiator, can be rapidly dispersed in water, is convenient for on-site on-line injection to carry out oil displacement operation, adopts the technical scheme that the emulsion comprises 10-50 parts of oil phase, 1-10 parts of emulsifier and co-emulsifier and 40-80 parts of aqueous phase containing comonomer by weight, better solves the problem, and can be used for on-site application for improving recovery ratio such as land phase or offshore oil displacement.
Description
Technical Field
The invention relates to a hydrophobic association acrylamide polymer emulsion and a preparation method thereof.
Background
The hydrophobic association water-soluble polymer refers to a water-soluble polymer with a small amount of hydrophobic groups on a hydrophilic macromolecular chain of the polymer. Due to the unique solution properties of tackifying, salt resistance, shearing resistance and the like, the polymer oil displacement agent has good application prospect when being applied to harsh oil reservoir development.
Because the polarity difference between the hydrophilic monomer and the hydrophobic monomer is large, the hydrophilic monomer and the hydrophobic monomer are difficult to be mixed fully in the synthesis process. Generally, there are two approaches in the synthesis of hydrophobically associating polymers, one is a copolymerization method in which a hydrophobic monomer is directly linked to a water-soluble polymer chain, the product is mainly an acrylamide copolymer, and the other is a macromolecular reaction method in which copolymerization is performed first and then functionalization is performed, and the method is mainly used for hydrophobic modification of macromolecules. With the development of research, new methods such as an emulsion polymerization method, a living ion polymerization method, a radical polymerization method, an ultrasonic method, and a supercritical carbon dioxide medium method have also appeared. The copolymerization method is also a common method for preparing high molecular weight hydrophobic polymers by a micelle polymerization method, and the method is characterized in that a surfactant is added into water to dissolve hydrophobic monomers, so that the hydrophobic monomers enter micelles formed by surfactant molecules to be polymerized. McCormick et al (McCormick C L, Johnson C B.Water-soluble polymers.29.ampholytic polymers of sodium 2-acetylamido-2-methylpropanesulfonate with (2-acetylamido-2-methylpropylpropyl) dimethylammoniumchloride. solution polymers [ J ] Macromolecules,1988,21(3):694 699.) synthesized binary copolymer AM/N-alkylacrylamide using micelle polymerization with N-alkylacrylamide as the hydrophobic monomer. It was found that the longer the carbon chain of the hydrophobic group, the poorer the water solubility of the bipolymer, and that as the proportion of hydrophobic monomers increases, the dependence of the apparent viscosity of the polymer solution on the solution concentration becomes greater. Guruiwei (micelle polymerization preparation and characterization research progress of hydrophobically modified polyacrylamide [ J ] chemical progress 2006,25 (1): 25-30) reviews the research progress of micelle polymerization of hydrophobically associated polymer HMPAM in recent years in detail, introduces the principle and synthesis conditions of micelle polymerization, including monomers, surfactants, initiators, polymerization temperature and polymerization time, and characterization methods of relative molecular mass and composition of HMPAM. Bell-trance (the synthesis and performance of the hydrophobic association acrylamide copolymer and the research on the structural form in the solution [ D ]. Chengdu: Sichuan university, 2004), Jianglinding (the synthesis of a new family of hydrophobic association polyacrylamide and the rheological property of the aqueous solution [ D ]. Taiyuan: Zhongbei university, 2007), Shifeng-Qiang (the research on the hydrophobic association AM/DBA copolymer for tertiary oil recovery [ J ]. applied chemistry 2004, (21)6: 556-560) and the like all adopt a micelle polymerization method to prepare the hydrophobic association polymer. Patents issued on von husson (CN1793189A), tempura (CN101293944A, CN 101148582a), eugonin (CN1317501), poron et al (CN1528734, CN1528797) and BASF corporation (CN 102471415A, CN 103339220A, CN 103328602 a) relate to synthesis of hydrophobic associated polymer micelle method.
in micellar copolymerization, it is the water-soluble monomer that is molecularly dissolved in water, and the hydrophobic monomer that is solubilized in micelles or forms mixed micelles with surfactants. The average concentration in the system is much lower than the local concentration of the hydrophobic monomer in the micellar microdomains. Therefore, unlike micellar polymerization and homogeneous polymerization, this microscopic heterogeneity of monomer distribution directly affects the copolymerization behavior between the two types of monomers and the structure of the finally formed hydrophobically associating polymer. Although micellar polymerization is a common polymerization method for preparing hydrophobically associating polymers, the polymerization method needs to add a large amount of surfactant (such as SDS) to solubilize hydrophobic monomers in micelles, but the addition of a large amount of surfactant during the polymerization process has a significant influence on the association behavior of polymers, and the surfactant interacts with hydrophobic segments in the polymerization product to deteriorate the performance of the hydrophobically associating water-soluble polymers. If these surfactants are to be removed, the complexity of the post-treatment processes such as separation and purification is increased. To simplify the work-up and to enhance the solubility of the polymers, hydrophobic monomers which are surface-active per se can be used. The monomer contains hydrophobic groups and hydrophilic groups at the same time, and a surfactant is not required to be added during copolymerization, so that the traditional free radical aqueous solution can be directly adopted for polymerization, and the hydrophobic monomers can be introduced into the copolymer in a highly disordered and irregular manner. Patents of Xiyanmin et al (CN201310435308.4, CN201310435350.6 and CN201310435366.7) relate to a method for preparing a high-temperature and high-salt resistant hydrophobic association polymer by an aqueous solution, and dry powder preparation equipment is still needed in the use process of the product, so that certain difficulty is caused for offshore application.
In view of the above problems, the preparation of hydrophobically associating polymers by emulsion polymerization is receiving more and more attention. Emulsion methods have a mature polymerization mechanism, but for water-soluble monomers, a reverse-phase emulsion method is generally adopted to prepare polymers, the polymerization mechanism is greatly different from that of a normal-phase emulsion, and currently, a micelle nucleation mechanism, a monomer droplet nucleation mechanism and two mechanisms coexist. In foreign countries, water-soluble polymer latex (emulsion) products have been industrially produced and widely used in many fields, and domestic industrial reverse emulsion water-soluble latex products have not become the mainstream. Inverse emulsion polymerization of water soluble monomers provides a polymerization process that can have as high a polymerization rate and a high relative molecular mass product as conventional emulsion polymerization. In addition, the inverse emulsion polymerization enables the water-soluble monomer to be efficiently polymerized into a powdery or milky product, and has the advantages of mild polymerization conditions, less side reactions and convenient use, so that the inverse emulsion polymerization is rapidly developed as a supplement to the emulsion polymerization. Some researchers have been studied in China, for example, Zhaoyong, etc. (the synthesis of hydrophobic association polyacrylamide in reverse microemulsion and its performance research [ J ]. high molecular bulletin, 2000, 1 (5): 550-. The results show that HAPAM synthesized by the reverse microemulsion polymerization method has more excellent salt resistance and shear resistance, which is mainly because the hydrophobic comonomer on the macromolecular chain is distributed randomly rather than in a block way, and the hydrophobic molecular chain is mainly associated with intermolecular rather than intramolecular. Hydrophobic association polymers are prepared by a reverse microemulsion method in Hongjiang et al (chemical engineers, 2009, 10:47-50) and von Yujun et al (CN 101343339 and CN 101372525A) by using a reverse microemulsion method for synthesizing a temperature-resistant and salt-resistant polymer oil-displacing agent [ J ]. chemical engineers, 2009, 10:47-50) and von Yujun et al (CN 101343339 and CN 101372525A), but the emulsifier content in the microemulsion is high, so that some problems can be brought to production cost and later application, Yuanhai (CN 102453191A) obtains the hydrophobic association polymers by using a preparation method of the reverse emulsion polymers for controlling the content of the hydrophobic monomers and increasing the salt resistance, when the content of the hydrophobic monomers is 0.6%, 2000mg/L of polymer solution obtains high viscosity retention rate in NaCl solution with the concentration of 10%, but the test temperature is.
the invention provides a hydrophobic association acrylamide polymer emulsion and a preparation method thereof on the basis of comparing various polymerization methods and carrying out extensive and intensive research on synthesis, structural characterization and properties of an acrylamide hydrophobic association polymer used in an inverse emulsion method, and mainly solves the problems that in the prior art, the hydrophobic association polymer is polymerized by micelle or aqueous solution, and a dry powder preparation is obtained by cutting, crushing, drying, re-crushing and other processes, on one hand, the production process is relatively long and complicated, the energy consumption is relatively high, on the other hand, the preparation of the dry powder of the hydrophobic association polymer needs special equipment, and the processes of high-speed stirring, dissolution, curing and the like are needed, so that the preparation method brings some difficulties for oil field application, especially for oil displacement construction of offshore oil reservoirs. The invention adopts an inverse emulsion polymerization method, adopts commercial nonionic surfactant as emulsifier in an oil-water system, obtains the hydrophobic association polymer emulsion with higher solid content by controlling the adding speed of the initiator, can be quickly dispersed in water, and is convenient for on-site online injection to carry out oil displacement operation. The technical scheme comprises 10-50 parts of oil phase, 1-10 parts of emulsifier and co-emulsifier and 40-80 parts of water phase containing comonomer by weight of emulsion, so that the problem is solved well, and the prepared hydrophobically associating acrylamide polymer emulsion is directly used for road phase or offshore oil displacement and other field chemicals after being compounded, so that the field application of improving the recovery ratio is realized.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the hydrophobically associating polymer in the prior art mostly adopts micelle or aqueous solution polymerization, and a dry powder preparation is obtained through the processes of cutting, crushing, drying, re-crushing and the like of a micelle, so that firstly, the production process is relatively long and complicated, the energy consumption is relatively high, secondly, the preparation of the dry powder of the hydrophobically associating polymer needs special equipment, and the processes of high-speed stirring, dissolving, curing and the like are needed, which brings some difficulties for the oil field application, especially the oil displacement construction of offshore oil reservoirs. Provides a hydrophobic association acrylamide polymer emulsion which has higher solid content of the product and can be dispersed in water rapidly, thus solving the problems.
The second technical problem to be solved by the invention is to provide a method for preparing the hydrophobically associating acrylamide polymer emulsion.
The invention aims to solve the third technical problem and provides the application of the hydrophobically associating acrylamide polymer emulsion in tertiary oil recovery in oil fields.
In order to solve one of the technical problems, the invention adopts the following technical scheme: a hydrophobic association acrylamide polymer emulsion and a preparation method thereof, wherein the emulsion system is prepared by an inverse emulsion polymerization method; the copolymerization component comprises the following components in parts by weight:
a) 10-50 parts of an oil phase;
b) 1-10 parts of an emulsifier and a co-emulsifier;
c) 40-80 parts of a water phase containing a comonomer.
In the technical scheme, the oil-soluble solvent is selected from one or more of aliphatic hydrocarbon, aromatic hydrocarbon, halogenated hydrocarbon and the like, such as toluene, o-xylene, isoparaffin, cyclohexane, heptane, octane, white oil, coal oil and the like, and the dosage of the oil-soluble solvent accounts for 10-50% of the whole system.
In the technical scheme, the emulsifier is formed by compounding an oil-soluble surfactant and a water-soluble surfactant, most of the emulsifier is a nonionic emulsifier, such as fatty acid polyoxyethylene ester, alkyl acid polyoxyethylene ether, fatty alcohol polyoxyethylene ether and the like, and the mass ratio of the two surfactants is 20: 1-2: 1, so that the hydrophilic-lipophilic balance value is 4-7; in order to increase the stability of the system, polymers with lower molecular weight such as polyvinylpyrrolidone, polyvinyl alcohol and the like can be added as co-emulsifiers, and the total amount of the two is 1-10% of the whole system.
in the above technical scheme, the comonomer comprises the following components:
a) 5-99.9 w.t.% of a non-ionic water-soluble monomer;
b) 0-50 w.t.% of an anionic monomer or/and a cationic monomer;
c)0.1 to 10 w.t.% of a hydrophobic monomer.
in the above technical solution, the nonionic water-soluble monomer is selected from water-soluble vinyl monomers, and the vinyl monomer is selected from at least one of monomers represented by formula (1), formula (2), formula (3), or formula (4):
Wherein, R 1, R 4, R 5 and R 6 are all independently selected from hydrogen and C 1 -C 4 alkyl, and R 2 and R 3 are all independently selected from hydrogen, C 1 -C 4 alkyl or hydroxyl substituted alkyl.
In the above technical solution, 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 dimethyl diallyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride and 2-acrylamido-2-methylpropyl trimethyl ammonium chloride.
In the technical scheme, the hydrophobic monomer is one or a mixture of a long carbon chain ionic surface active monomer, an acrylate hydrophobic monomer and a hydrophobic monomer containing a multi-element cyclic compound. Further, the long carbon chain ionic surface active monomer can be cation or cation type, the carbon chain length is 8-22, such as acrylamide nitrogen alkyl sodium sulfonate with 8-18 vinyl carbon chains, allyl alkyl ammonium chloride with 12-22 vinyl carbon chains and the like, the alkyl carbon number of the acrylate can be 4-18, and the polycyclic ring in the multi-element cyclic compound can be five-membered or six-membered.
In the above technical scheme, the initiator may be various initiators well known to those skilled in the art, and those skilled in the art may make routine selections, such as but not limited to a composition of one or more selected from water-soluble oxides, water-soluble oxidation-reduction systems, azo compounds, etc.; wherein the water-soluble oxide is selected from persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, the water-soluble oxidation-reduction system is selected from compounds composed of the above water-soluble persulfates and water-soluble reducing agents such as sulfite or bisulfite, and the azo compounds are selected from azobisisobutylamidine hydrochloride, 2' -azo [2- (2-imidazolin-2-yl) propane ] dihydrochloride, azobisisobutyronitrile and azobisisoheptonitrile.
in order to solve the second technical problem, the invention adopts the following technical scheme: a preparation method of acrylamide hydrophobic association polymer emulsion comprises the following steps:
a) Dissolving a comonomer in water to obtain a water phase I;
b) Adding a co-emulsifier into the water phase I, uniformly mixing, and adjusting the pH value to 5-9 to obtain a water phase II;
c) Stirring the oil phase and the emulsifier uniformly to form a continuous phase;
d) Dissolving a water-soluble initiator in water at a certain concentration to prepare a solution, and dissolving an oil-soluble initiator in a small amount of ethanol or ethyl acetate to prepare a solution at a certain concentration;
e) Putting the continuous phase into a reaction kettle, starting stirring, slowly adding the water phase II into the continuous phase in 2-3 batches, and stirring at a high speed for emulsification until the mixture is uniform; controlling the temperature in the reaction kettle to be 10-30 ℃, then adding an oxidant aqueous solution, or adding an oil-soluble initiator, and then dripping a reducing agent aqueous solution, wherein the dripping speed is controlled to ensure that the heating speed of a polymerization system is 0.5-2.0 ℃/min; controlling the highest temperature to be 40-70 ℃, and stopping dripping the reducing agent;
f) Keeping the temperature of the system at 40-70 ℃ by adjusting the temperature of the water bath, and continuously reacting for 3-8 hours to obtain white opaque hydrophobically associating acrylamide polymer emulsion;
In the above technical scheme, an auxiliary agent, such as a complexing agent, for example, disodium ethylenediamine tetraacetate or sodium diethylenetriamine pentaacetate, may also be added to the aqueous phase system in step (a) to eliminate the influence of metal ions on the reaction, and the amount of the auxiliary agent is 0.01-1% of the copolymerization component.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the application of the acrylamide hydrophobic association polymer emulsion in the technical scheme in tertiary oil recovery in an oil field.
In the above technical solution, the acrylamide type hydrophobically associating polymer emulsion can be used in tertiary oil recovery in oil field by conventional technical means well known to those skilled in the art, for example, the acrylamide type hydrophobically associating polymer emulsion is directly or uniformly stirred by adding a surfactant into the acrylamide type hydrophobically associating polymer emulsion, and the system can be used in field applications for improving recovery ratio such as land phase or offshore flooding for tertiary oil recovery in oil field.
According to the acrylamide hydrophobic association polymer emulsion and the preparation method thereof, due to the adoption of the inverse emulsion polymerization method, the reaction is easy to control, the product does not need post-treatment, and the acrylamide hydrophobic association polymer emulsion with higher solid content can be obtained. The acrylamide hydrophobic association polymer emulsion prepared by the preparation process provided by the invention can be rapidly dispersed in various water qualities, and can be directly used for field application of improving recovery ratio such as land-based or offshore oil displacement for tertiary oil recovery of an oil field or after being compounded with other oil field chemicals.
the invention is further illustrated by the following specific examples.
Detailed Description
[ example 1 ]
186g of 5 white oil, 30g of Span60 and 4g of Tween60 with the HLB value being 5.9 are added into a reaction kettle, stirred until the mixture is completely and uniformly mixed, the temperature in the kettle is controlled to be 21 ℃, and the stirring speed is 200 rpm. In a separate vessel, 168g of deionized water, 0.12g of disodium Ethylenediaminetetraacetate (EDTA), 38.4g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), 152g of Acrylamide (AM), and 1.5g of sodium 2-acrylamidohexadecylsulfonate were added, and stirred until completely mixed, neutralized with sodium hydroxide (NaOH) in an amount equimolar to AMPS and the pH was adjusted to 7, and 2.18g of polyvinylpyrrolidone (PVP) having a trade name of K30 (molecular weight: about 40000) was added and stirred until completely mixed, to prepare an aqueous solution for later use. Slowly putting the solution into a reaction kettle, stirring and raising the speed to 1000rpm for emulsification for 30min, then lowering the speed to 300rpm, firstly dropping 3.5g of Ammonium Persulfate (APS) aqueous solution with the concentration of 10%, slowly dropping 10.8g of sodium bisulfite (MBS) aqueous solution with the concentration of 1% after 5min, in the process, slowly raising the reaction temperature to 56 ℃, raising the water bath temperature to 50 ℃ for heat preservation reaction, discharging after 4 hours, and obtaining a white opaque emulsion-shaped product which can be stably stored for more than half a year.
Dripping about 10g of polymer emulsion into about 300ml of stirred absolute ethyl alcohol, precipitating a large amount of white solid, standing for several hours, filtering, drying and filtering to obtain filtrate, measuring the content of the precipitated solid by using a weighing method to obtain a solution with the concentration of 32.5%, directly preparing the emulsion into 0.15% solution by using saline water with the total mineralization degree of 180000Mg/L (wherein the concentration of Ca 2+ + Mg 2+ 5000Mg/L), stirring for several minutes to obtain a uniform solution, measuring the apparent viscosity of 39mPa & s at the temperature of 90 ℃ by using a Brookfield viscometer with the shearing rate of 7.34s -1, and measuring the viscosity retention rate of 91.8% after aging for 30 days at the temperature of 90 ℃.
[ example 2 ]
190g of cyclohexane, 28g of Span80, 3.2g of Tween80 and HLB value of 5.4 are added into a reaction kettle, stirred until the materials are completely and uniformly mixed, the temperature in the kettle is controlled to be 21 ℃, and the stirring speed is 200 rpm. In a separate vessel, 162g of deionized water, 0.16g of disodium Ethylenediaminetetraacetate (EDTA), 42g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), 148g of Acrylamide (AM), and 1.2g of cetyldimethylallylammonium chloride were added, and stirred until completely mixed, neutralized with sodium hydroxide (NaOH) in an amount equimolar to AMPS and the pH was adjusted to 7, and 1.26g of polyvinyl alcohol (PVA) having a trade name of 1788 (molecular weight about 80000) was added and stirred until completely mixed, and the mixture was used as an aqueous solution. Slowly putting the solution into a reaction kettle, stirring and raising the rotating speed to 1000rpm for emulsification for 30min, then lowering the rotating speed to 300rpm, firstly dropping 3.2g of Ammonium Persulfate (APS) aqueous solution with the concentration of 10%, slowly dropping 19.8g of sodium bisulfite (MBS) aqueous solution with the concentration of 1% after 5min, in the process, slowly raising the reaction temperature to 52 ℃, raising the water bath temperature to 50 ℃ for heat preservation reaction, discharging after 5 hours, and obtaining a white opaque emulsion-shaped product which can be stably stored for more than half a year.
Dripping about 10g of polymer emulsion into about 300ml of stirred absolute ethyl alcohol, precipitating a large amount of white solid, standing for several hours, filtering, drying and filtering to obtain filtrate, measuring the content of the precipitated solid by using a weighing method to obtain 31.8%, directly preparing the emulsion into 0.15% solution by using saline water with the total mineralization degree of 180000Mg/L (wherein the content of the precipitated solid is Ca 2+ + Mg 2+ 5000Mg/L), stirring for several minutes to obtain uniform solution, measuring the apparent viscosity at 90 ℃ by using a Brookfield viscometer at the shearing rate of 7.34s -1 to be 36 mPas, and measuring the viscosity retention rate at 90 ℃ after aging for 30 days to be 93.2%.
[ example 3 ]
Adding 180g of No. 120 solvent oil, 26g of Span85, 4.2g of Tween80 and HLB value of 5.8 into a reaction kettle, stirring until the mixture is completely and uniformly mixed, controlling the temperature in the kettle to be 21 ℃ and the stirring speed to be 200 rpm. In a separate vessel, 172g of deionized water, 0.16g of disodium Ethylenediaminetetraacetate (EDTA), 52g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), 178g of Acrylamide (AM), and 1.6g of sodium 2-acrylamidotetradecylsulfonate were added, and stirred until completely mixed, neutralized with sodium hydroxide (NaOH) in an amount equimolar to AMPS and the pH was adjusted to 7, and 1.1g of polyvinylpyrrolidone (PVP) having a molecular weight of K60 (molecular weight of about 200000) was added and stirred until completely mixed to prepare an aqueous solution for later use. Slowly putting the solution into a reaction kettle, stirring and raising the rotating speed to 1000rpm for emulsification for 30min, then lowering the rotating speed to 300rpm, firstly dropping 4.7g of Ammonium Persulfate (APS) aqueous solution with the concentration of 10%, slowly dropping 13.5g of sodium bisulfite (MBS) aqueous solution with the concentration of 1% after 5min, in the process, slowly raising the reaction temperature to 62 ℃, raising the water bath temperature to 60 ℃ for heat preservation reaction, discharging after 5 hours, and obtaining a white opaque emulsion-shaped product which can be stably stored for more than half a year.
Dripping about 10g of polymer emulsion into about 300ml of stirred absolute ethyl alcohol, precipitating a large amount of white solid, standing for several hours, filtering, drying and filtering to obtain filtrate, measuring the content of the precipitated solid by using a weighing method to obtain a solution with the content of 43.2 percent, directly preparing the emulsion into 0.15 percent solution by using brine with the total mineralization of 180000Mg/L (wherein the content of Ca 2+ + Mg 2+ 5000Mg/L), stirring for several minutes to obtain a uniform solution, measuring the apparent viscosity of 45mPa & s at the shearing rate of 7.34s -1 by using a Brookfield viscometer at 90 ℃, and measuring the viscosity retention rate of 92.3 percent after aging for 30 days at 90 ℃.
[ example 4 ]
180g of 7 white oil, 30g of Span80, 3.8g of OP10, HLB value of 5.4 and 3.8g of tert-butyl styrene are added into a reaction kettle, stirred until the mixture is completely and uniformly mixed, the temperature in the kettle is controlled to be 21 ℃, and the stirring speed is 200 rpm. In a separate vessel 163g of deionized water, 0.15g of disodium Ethylenediaminetetraacetate (EDTA), 38.4g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), and 152g of Acrylamide (AM) were added, stirred until completely mixed, neutralized with sodium hydroxide (NaOH) in an amount equimolar to AMPS and the pH was adjusted to 7, and then 2.8g of Hydroxyethylcellulose (HEC) was added and stirred until completely mixed to prepare an aqueous solution for later use. Slowly putting the solution into a reaction kettle, stirring and raising the speed to 1000rpm for emulsification for 30min, then lowering the speed to 300rpm, firstly dropping 4.5g of Ammonium Persulfate (APS) aqueous solution with the concentration of 10%, and after 5min, slowly dropping 12.8g of sodium bisulfite (MBS) aqueous solution with the concentration of 1%, wherein the reaction temperature is slowly raised to 71 ℃, the water bath temperature is raised to 60 ℃ for heat preservation reaction, discharging is carried out after 4 hours, and the product is a white opaque emulsion-shaped system and can be stably stored for more than half a year.
Dripping about 10g of polymer emulsion into about 300ml of stirred absolute ethyl alcohol, precipitating a large amount of white solid, standing for several hours, filtering, drying and filtering to obtain filtrate, measuring the content of the precipitated solid by using a weighing method to obtain a solution with the content of 33.9 percent, directly preparing the emulsion into 0.15 percent solution by using brine with the total mineralization of 180000Mg/L (wherein the content of Ca 2+ + Mg 2+ 5000Mg/L), stirring for several minutes to obtain a uniform solution, measuring the apparent viscosity of 41mPa & s at the shearing rate of 7.34s -1 by using a Brookfield viscometer at 90 ℃, and measuring the viscosity retention rate of 89.6 percent after aging for 30 days at 90 ℃.
[ example 5 ]
172g of No. 200 solvent oil, 30g of Span80, 6.2g of AEO9 and HLB value of 5.9 are added into a reaction kettle, and the mixture is stirred until the mixture is completely and uniformly mixed, the temperature in the reaction kettle is controlled to be 21 ℃, and the stirring speed is 200 rpm. In a separate vessel, 168g of deionized water, 0.15g of disodium Ethylenediaminetetraacetate (EDTA), 38.4g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), 152g of Acrylamide (AM), and 1.5g of octadecyl dimethyl allyl ammonium chloride were added, and stirred until completely mixed, neutralized with sodium hydroxide (NaOH) in an amount equimolar to AMPS and the pH was adjusted to 7, and 2.9g of carboxymethylcellulose (CMC) was added and stirred until completely mixed, and the mixture was used as an aqueous solution for future use. Slowly putting the solution into a reaction kettle, stirring and raising the speed to 1000rpm for emulsification for 30min, then lowering the speed to 300rpm, firstly dropping 3.6g of Ammonium Persulfate (APS) aqueous solution with the concentration of 10%, slowly dropping 11.2g of sodium bisulfite (MBS) aqueous solution with the concentration of 1% after 5min, slowly raising the reaction temperature to 54 ℃ in the process, raising the water bath temperature to 50 ℃ for heat preservation reaction, discharging after 7 hours, and obtaining a white opaque emulsion-shaped product which can be stably stored for more than half a year.
Dripping about 10g of polymer emulsion into about 300ml of stirred absolute ethyl alcohol, precipitating a large amount of white solid, standing for several hours, filtering, drying and filtering to obtain filtrate, measuring the content of the precipitated solid by using a weighing method to obtain a solution with the content of 34.6 percent, directly preparing the emulsion into 0.15 percent solution by using brine with the total mineralization of 180000Mg/L (wherein the content of Ca 2+ + Mg 2+ 5000Mg/L), stirring for several minutes to obtain a uniform solution, measuring the apparent viscosity of 41mPa & s at the shearing rate of 7.34s -1 by using a Brookfield viscometer at 90 ℃, and measuring the viscosity retention rate of 90.3 percent after aging for 30 days at 90 ℃.
[ example 6 ]
192g of kerosene, 32g of Span80, 4.2g of Tween80, 5.5 of HLB value, 2.6g of octadecyl acrylate and 0.5g of AIBNB are added into a reaction kettle, stirred until the mixture is completely and uniformly mixed, the temperature in the kettle is controlled to be 21 ℃, and the stirring speed is 200 rpm. In a separate vessel, 168g of deionized water, 0.1g of disodium Ethylenediaminetetraacetate (EDTA), 29.3g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), 152g of Acrylamide (AM), and 12g of acryloyloxyethyltrimethyl ammonium chloride were added, stirred until completely mixed, neutralized with sodium hydroxide (NaOH) in an amount equimolar to AMPS and the pH was adjusted to 7, and 1.92g of polyvinylpyrrolidone (PVP) having a molecular weight of K30 (molecular weight: about 40000) was added and stirred until completely mixed to prepare an aqueous solution for later use. Slowly putting the solution into a reaction kettle, stirring and raising the speed to 1000rpm for emulsification for 30min, then lowering the speed to 300rpm, firstly dropping 4.1g of Ammonium Persulfate (APS) aqueous solution with the concentration of 10%, and after 5min, slowly dropping 12.3g of sodium bisulfite (MBS) aqueous solution with the concentration of 1%, wherein the reaction temperature is slowly raised to 56 ℃, the water bath temperature is raised to 50 ℃ for heat preservation reaction, discharging after 4 hours, and the product is a white opaque emulsion-shaped system and can be stably stored for more than half a year.
Dripping about 10g of polymer emulsion into about 300ml of stirred absolute ethyl alcohol, precipitating a large amount of white solid, standing for several hours, filtering, drying and filtering to obtain filtrate, measuring the content of the precipitated solid by using a weighing method to obtain a solution with the content of 34.6 percent, directly preparing the emulsion into 0.15 percent solution by using brine with the total mineralization of 180000Mg/L (wherein the content of Ca 2+ + Mg 2+ 5000Mg/L), stirring for several minutes to obtain a uniform solution, measuring the apparent viscosity of 43mPa & s at the shearing rate of 7.34s -1 by using a Brookfield viscometer at 90 ℃, and measuring the viscosity retention rate of 93.2 percent after aging for 30 days at 90 ℃.
[ example 7 ]
190g of cyclohexane, 24.14g of Span80, 7.06g of Tween60 and HLB value of 6.7 are added into a reaction kettle, stirred until the materials are completely and uniformly mixed, the temperature in the kettle is controlled to be 21 ℃, and the stirring speed is 200 rpm. In a separate vessel, 162g of deionized water, 0.16g of disodium Ethylenediaminetetraacetate (EDTA), 42g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), 148g of Acrylamide (AM), and 1.2g of cetyldimethylallylammonium chloride were added, and stirred until completely mixed, neutralized with sodium hydroxide (NaOH) in an amount equimolar to AMPS and the pH was adjusted to 7, and 1.26g of polyvinyl alcohol (PVA) having a trade name of 1788 (molecular weight about 80000) was added and stirred until completely mixed, and the mixture was used as an aqueous solution. Slowly putting the solution into a reaction kettle, stirring and raising the speed to 1000rpm for emulsification for 30min, then lowering the speed to 300rpm, firstly dropping 3.2g of Ammonium Persulfate (APS) aqueous solution with the concentration of 10%, and after 5min, slowly dropping 19.8g of sodium bisulfite (MBS) aqueous solution with the concentration of 1%, wherein the reaction temperature is slowly raised to 54 ℃, the water bath temperature is raised to 55 ℃ for heat preservation reaction, discharging is carried out after 5 hours, and the product is a white opaque emulsion-shaped system and can be stably stored for more than half a year.
Dripping about 10g of polymer emulsion into about 300ml of stirred absolute ethyl alcohol, precipitating a large amount of white solid, standing for several hours, filtering, drying and filtering to obtain filtrate, measuring the content of the precipitated solid by using a weighing method to obtain 29.6%, directly preparing the emulsion into 0.15% solution by using saline water with the total mineralization degree of 180000Mg/L (wherein the content of the precipitated solid is Ca 2+ + Mg 2+ 5000Mg/L), stirring for several minutes to obtain uniform solution, measuring the apparent viscosity of 39mPa & s at the shearing rate of 7.34s -1 by using a Brookfield viscometer at 90 ℃, and measuring the viscosity retention rate of 95.2% after aging for 30 days at 90 ℃.
[ COMPARATIVE EXAMPLE 1 ]
190g of cyclohexane and 31.2g of Span40 were added into a reaction kettle, and the mixture was stirred until the mixture was completely mixed with the HLB value of 6.7, the temperature in the kettle was controlled at 21 ℃ and the stirring speed was 200 rpm. In a separate vessel, 162g of deionized water, 0.16g of disodium Ethylenediaminetetraacetate (EDTA), 42g of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), 148g of Acrylamide (AM), and 1.2g of cetyldimethylallylammonium chloride were added, and stirred until completely mixed, neutralized with sodium hydroxide (NaOH) in an amount equimolar to AMPS and the pH was adjusted to 7, and 1.26g of polyvinyl alcohol (PVA) having a trade name of 1788 (molecular weight about 80000) was added and stirred until completely mixed, and the mixture was used as an aqueous solution. Slowly putting the solution into a reaction kettle, stirring and increasing the rotation speed to 1000rpm for emulsification for 30min, then reducing the rotation speed to 300rpm, firstly dripping 3.2g of Ammonium Persulfate (APS) aqueous solution with the concentration of 10%, slowly dripping 19.8g of sodium bisulfite (MBS) aqueous solution with the concentration of 1% after 5min, slowly increasing the reaction temperature to 52 ℃ in the process, increasing the water bath temperature to 50 ℃ for heat preservation reaction, discharging after 5 hours, wherein the product is a white opaque emulsion system, but obvious layering appears after the solution is placed on the next day.
the polymer emulsion is uniformly stirred, about 10g of the polymer emulsion is dripped into about 300ml of stirred absolute ethyl alcohol, a large amount of white solid is separated out, the polymer emulsion is placed for several hours, then is filtered and dried, the content of the separated solid is measured by a weighing method, the emulsion is directly prepared into 0.15 percent solution by using saline water with the total mineralization degree of 180000Mg/L (wherein, Ca 2+ + Mg 2+ 5000Mg/L), the solution is stirred for several minutes to obtain uniform solution, a Brookfield viscometer is adopted at 90 ℃, the apparent viscosity measured at the shearing rate of 7.34s -1 is 17 mPas, and the viscosity retention rate after aging for 30 days at 90 ℃ is 75.6 percent respectively.
The difference between the comparative example 1 and the example 7 is that the emulsifier, the example 7 is a compound type, and the comparative example 1 is a single type, from the appearance and performance evaluation of the polymer emulsion product, the single type emulsifier prepared product has poor stability, and the solution viscosity and the aging retention rate are lower than those of the compound type emulsifier.
Claims (8)
1. A hydrophobic association acrylamide polymer emulsion is prepared by an inverse emulsion polymerization method; the copolymerization component comprises the following components in parts by weight:
a) 10-50 parts of an oil phase;
b) 1-10 parts of an emulsifier and a co-emulsifier;
c) 40-80 parts of a water phase containing a comonomer;
the emulsifier is a nonionic emulsifier, the hydrophilic-lipophilic balance value is 4-7, and the emulsifier is prepared by compounding an oil-soluble surfactant and a water-soluble surfactant, wherein the mass ratio of the oil-soluble surfactant to the water-soluble surfactant is 20: 1-2: 1;
The coemulsifier is selected from low molecular weight polymers selected from at least one of polyvinylpyrrolidone and polyvinyl alcohol;
The hydrophobic association acrylamide polymer emulsion is prepared by a method comprising the following steps:
a) Dissolving a comonomer in water to obtain a water phase I;
b) Adding a co-emulsifier into the water phase, uniformly mixing, and adjusting the pH value to 5-9 to obtain a water phase II;
c) stirring the oil phase and the emulsifier uniformly to form a continuous phase;
d) Dissolving a water-soluble initiator in water at a certain concentration to prepare a solution, and dissolving an oil-soluble initiator in a small amount of ethanol or ethyl acetate to prepare a solution at a certain concentration;
e) Putting the continuous phase into a reaction kettle, starting stirring, slowly adding the water phase II into the continuous phase in 2-3 batches, and stirring at a high speed for emulsification until the mixture is uniform; controlling the temperature in the reaction kettle to be 10-30 ℃, then adding an oxidant aqueous solution, or adding an oil-soluble initiator, and then dripping a reducing agent aqueous solution, wherein the dripping speed is controlled to ensure that the heating speed of a polymerization system is 0.5-2.0 ℃/min; controlling the highest temperature to be 40-70 ℃, and stopping dripping the reducing agent;
f) and (3) keeping the temperature of the system at 40-70 ℃ by adjusting the temperature of the water bath, and continuing to react for 3-8 hours to obtain white opaque hydrophobically associating acrylamide polymer emulsion.
2. The hydrophobically associating acrylamide polymer emulsion according to claim 1, wherein the oil phase is selected from one or a mixture of more than two of aliphatic hydrocarbon, aromatic hydrocarbon, halogenated hydrocarbon, etc., and the amount of the oil phase is 10-50% of the total copolymerization components.
3. The hydrophobically associating acrylamide-based polymer emulsion according to claim 1, wherein the total amount of the emulsifier is 1-10% of the total amount of the copolymerization components.
4. The hydrophobically associative acrylamide-based polymer emulsion according to claim 1, wherein the comonomers comprise:
a) 5-99.9 w.t.% of a non-ionic water-soluble monomer;
b) 0-50 w.t.% of an anionic monomer or/and a cationic monomer;
c)0.1 to 10 w.t.% of a hydrophobic monomer.
5. the hydrophobically associative acrylamide-based polymer emulsion according to claim 4, wherein the nonionic water-soluble monomer is selected from water-soluble vinyl monomers, and the vinyl monomer is selected from at least one of the monomers represented by formula (1), formula (2) or formula (4):
wherein, R 1, R 4 and R 5 are all independently selected from hydrogen and C 1 -C 4 alkyl, and R 2 and R 3 are all independently selected from hydrogen, C 1 -C 4 alkyl or hydroxyl substituted alkyl.
6. the hydrophobically associative acrylamide-based polymer emulsion according to claim 4, wherein 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 dimethyl diallyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride and 2-acrylamido-2-methylpropyl trimethyl ammonium chloride; the hydrophobic monomer is one or a mixture of more than two of a long carbon chain ionic surface active monomer, an acrylate hydrophobic monomer and a hydrophobic monomer containing a multi-element cyclic compound, wherein the length of a carbon chain of the long carbon chain ionic surface active monomer is 8-16, the number of alkyl carbon atoms of the acrylate can be 4-18, and a multi-element ring in the multi-element cyclic compound can be five-element or six-element.
7. The method for preparing the hydrophobically associating acrylamide polymer emulsion as claimed in any one of claims 1 to 6, comprising the following steps:
Dissolving a comonomer in water to obtain a water phase I;
adding a co-emulsifier into the water phase, uniformly mixing, and adjusting the pH value to 5-9 to obtain a water phase II;
stirring the oil phase and the emulsifier uniformly to form a continuous phase;
Dissolving a water-soluble initiator in water at a certain concentration to prepare a solution, and dissolving an oil-soluble initiator in a small amount of ethanol or ethyl acetate to prepare a solution at a certain concentration;
Putting the continuous phase into a reaction kettle, starting stirring, slowly adding the water phase II into the continuous phase in 2-3 batches, and stirring at a high speed for emulsification until the mixture is uniform; controlling the temperature in the reaction kettle to be 10-30 ℃, then adding an oxidant aqueous solution, or adding an oil-soluble initiator, and then dripping a reducing agent aqueous solution, wherein the dripping speed is controlled to ensure that the heating speed of a polymerization system is 0.5-2.0 ℃/min; controlling the highest temperature to be 40-70 ℃, and stopping dripping the reducing agent;
and (3) keeping the temperature of the system at 40-70 ℃ by adjusting the temperature of the water bath, and continuing to react for 3-8 hours to obtain white opaque hydrophobically associating acrylamide polymer emulsion.
8. use of the hydrophobically associating acrylamide-based polymer emulsion according to any one of claims 1 to 6 in tertiary oil recovery in oil fields.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304201A (en) * | 2011-05-27 | 2012-01-04 | 中国海洋石油总公司 | Hydrophobic association crosslinked polymer coil and preparation method thereof |
| CN102453191A (en) * | 2010-10-18 | 2012-05-16 | 袁俊海 | Method for preparing salt resistance enhanced inverse emulsion polymer by controlling hydrophobic monomer content |
| CN102796222A (en) * | 2012-08-28 | 2012-11-28 | 山东大学 | Synthesis method of hydrophobically associated polyacrylamide |
| CN104292384A (en) * | 2014-09-19 | 2015-01-21 | 中国海洋石油总公司 | Preparation method of cationic polyacrylamide reverse-phase microemulsion |
| CN104448125A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Amphoteric hydrophobically-associating polymer and preparation method thereof |
| 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 |
| CN104448128A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Polymer mobility control agent suitable for high-temperature and high-salinity harsh reservoir and preparation method of polymer mobility control agent |
-
2015
- 2015-12-14 CN CN201510923095.9A patent/CN106866881B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453191A (en) * | 2010-10-18 | 2012-05-16 | 袁俊海 | Method for preparing salt resistance enhanced inverse emulsion polymer by controlling hydrophobic monomer content |
| CN102304201A (en) * | 2011-05-27 | 2012-01-04 | 中国海洋石油总公司 | Hydrophobic association crosslinked polymer coil and preparation method thereof |
| CN102796222A (en) * | 2012-08-28 | 2012-11-28 | 山东大学 | Synthesis method of hydrophobically associated polyacrylamide |
| CN104448125A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Amphoteric hydrophobically-associating polymer and preparation method thereof |
| 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 |
| CN104448128A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Polymer mobility control agent suitable for high-temperature and high-salinity harsh reservoir and preparation method of polymer mobility control agent |
| CN104292384A (en) * | 2014-09-19 | 2015-01-21 | 中国海洋石油总公司 | Preparation method of cationic polyacrylamide reverse-phase microemulsion |
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