CN114507164B - Gemini surfactant, preparation method, composition and application thereof - Google Patents

Gemini surfactant, preparation method, composition and application thereof Download PDF

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CN114507164B
CN114507164B CN202111668291.8A CN202111668291A CN114507164B CN 114507164 B CN114507164 B CN 114507164B CN 202111668291 A CN202111668291 A CN 202111668291A CN 114507164 B CN114507164 B CN 114507164B
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gemini surfactant
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oil
water
sodium
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CN114507164A (en
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田茂章
吕伟峰
胡景宏
周新宇
周炜
宋文枫
胡伟伟
王璐
廉黎明
黄佳
杨胜建
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Petrochina Co Ltd
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Abstract

The invention provides a Gemini surfactant, a preparation method, a composition and application thereof, wherein the preparation method comprises the following steps: adding halogenated compound, anhydride or lactone with hydrophilic group into monosubstituted aliphatic diamine, and reacting to obtain an intermediate; the intermediate is further reacted with halohydrocarbon to obtain the Gemini surfactant. The nano-particle and surfactant composition obtained by the invention can exert the synergistic effect of the surfactant and the nano-particle, has low interfacial tension, strong oil washing capacity and emulsification wave expansion and effect, and improves the microscopic wave efficiency of a low permeability reservoir, thereby improving the recovery ratio; the nanoparticle and surfactant composition has simple preparation method, can be produced in a large scale and has wide application prospect in low permeability reservoirs; the composite flooding composition containing the two-dimensional nano particles can effectively block a hypertonic channel, reduce sewage discharge, reduce invalid circulation and invalid energy consumption, and has wide application prospect.

Description

Gemini surfactant, preparation method, composition and application thereof
Technical Field
The invention belongs to the technical field of petroleum development, and particularly relates to a Gemini surfactant, a preparation method, a composition and application thereof.
Background
Compared with a medium-high permeability reservoir, the low permeability reservoir has more complex reservoir physical properties, more outstanding development contradiction and higher development difficulty. When water injection development is carried out, the water absorption capacity of the water injection well is low; the water lock, water sensitivity, speed sensitivity and other problems can be more serious in the water injection process, and the stratum is injured; the rock physical properties are poor, the pore throat is small, the serious Jack effect is achieved, the water injection recovery ratio of the low permeability oil field is low, the initial productivity of the oil reservoir is low, the yield is fast in decline, a large amount of crude oil still remains underground after water flooding and cannot be effectively developed, and therefore the overall development level is low.
At present, a considerable part of low-permeability oil reservoirs enter a high-water-content or even ultra-high-water-content stage, invalid circulation is serious, and development of a succession technology for greatly improving recovery efficiency is urgently needed. At present, the tertiary oil recovery mainly develops and takes over technologies such as chemical compound flooding, and a plurality of technologies have already passed the pilot test and enter the industrialized popularization stage, but the enhanced oil recovery technologies mainly aim at medium-high permeability reservoirs. The enhanced recovery ratio of the low permeability reservoir is still in the research stage, a feasible enhanced recovery ratio technology is developed, and the realization of effective development of the low permeability reservoir is particularly important.
Low permeability reservoirs typically have strong microscopic heterogeneity and heterogeneous pore distribution, affecting sweep efficiency of the flooding system. The traditional compound flooding mainly improves the sweep efficiency through the polymer, but the pore throat of the low-permeability oil reservoir is small, a high-molecular-weight high-viscosity system such as the polymer is difficult to inject, and the viscosity loss is serious after the polymer is sheared by a gap after being injected, so that the sweep cannot be deeply expanded. Therefore, conventional high viscosity polymer flooding systems cannot meet the needs of low permeability reservoirs to expand and increase recovery.
The prior art scheme is that a nano oil displacement technology is developed on the basis of chemical flooding. CN 110484229A discloses a compound oil displacement system for low permeability reservoir, and preparation and application methods thereof, the system comprises the following components in percentage by mass: 0.05 to 0.35 percent of nano graphite; 0.05 to 0.15 percent of dispersing agent; 0.15 to 0.35 percent of zwitterionic surfactant; the balance being water. The system has the capability of obviously reducing the oil-water interfacial tension and improving the oil washing efficiency, and the particle aggregation effect of the modified nano-graphite emulsion can realize the dual functions of deep regulation and control of stratum and expansion of swept volume. The oil layer is injected in a mode of slug injection, so that the oil displacement effect of the heterogeneous composite oil displacement system can be improved to the greatest extent. CN 111394076A discloses a preparation method of a profile control agent for a hypotonic oil reservoir with an efficient plugging effect. By adding the nano calcium carbonate, the surface density of the profile control agent is increased, and when water contacts with the profile control agent, the water slides off the surface of the profile control agent and cannot be fused with the profile control agent, so that the plugging performance of the profile control agent is improved.
The nanoparticles can also form stable emulsions in addition to increasing the viscoelasticity and stability of the flooding system. The nanoparticles produce irreversible adsorption at the oil-water interface, forming a stable emulsion. After the nano particles are compounded with the surfactant, the emulsifying capacity can be further improved through the synergistic effect of the nano particles and the surfactant, so that the microscopic wave efficiency is improved. Therefore, it is very necessary to develop a high-efficiency nanoparticle/surfactant complex flooding system with strong emulsifying properties.
Disclosure of Invention
Aiming at the problems, the invention provides a Gemini surfactant, a preparation method, a composition and application thereof, which can exert the synergistic effect of the surfactant and nano particles to the greatest extent, expand microscopic wave and volume through emulsification and greatly improve the recovery ratio of a low permeability reservoir. In order to achieve the above purpose, the following technical scheme is adopted:
a Gemini surfactant has a molecular structural formula as follows:
wherein R is 1 Is C 2 ～C 6 Alkane, alkene or arene;
R 2 is-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 or-C 6 H 5 ；
R 3 is-CH 2 CO 2 - Na + 、-CH 2 CH 2 CO 2 - Na + 、-COCH＝CHCO 2 - Na + -CH 2 CH 2 SO 3 - Na + 、-CH 2 CH 2 CH 2 SO 3 - Na + 、-CH 2 CH(OH)CH 2 SO 3 - Na + or-CH 2 CH 2 CH 2 CH 2 SO 3 - Na + ；
R 4 Is alkane-C n H 2n+1 olefin-C n H 2n-1 Or alkylaromatics-C n H 2n-7 ，n＝6～18。
The preparation method of the Gemini surfactant comprises the following steps:
adding halogeno, anhydride or lactone with hydrophilic group into monosubstituted aliphatic diamine to react to obtain intermediate
The intermediate is further reacted with halohydrocarbon to obtain the Gemini surfactant
Preferably, R 1 Is C 2 ～C 6 Alkane, alkene or arene;
R 2 is-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 or-C 6 H 5 ；
R 3 is-CH 2 CO 2 - Na + 、-CH 2 CH 2 CO 2 - Na + 、-COCH＝CHCO 2 - Na + -CH 2 CH 2 SO 3 - Na + 、-CH 2 CH 2 CH 2 SO 3 - Na + 、-CH 2 CH(OH)CH 2 SO 3 - Na + or-CH 2 CH 2 CH 2 CH 2 SO 3 - Na + ；
R 4 Is alkane-C n H 2n+1 olefin-C n H 2n-1 Or alkylaromatics-C n H 2n-7 ，n＝6～18；
R 3 X is any one or more of the halogenide, anhydride or lactone with hydrophilic groups;
R 4 y is the halogenated hydrocarbon.
Preferably, the adding of the halogeno compound, anhydride or lactone with hydrophilic group into the mono-substituted aliphatic diamine, and the reaction to obtain the intermediate is specifically as follows:
and dissolving the monosubstituted aliphatic diamine in an organic solvent, adding a halogenide, an anhydride or a lactone with a hydrophilic group, heating and refluxing for reaction, monitoring the reaction of the aliphatic diamine as a raw material by TLC until the reaction of the aliphatic diamine is complete, and then washing, filtering and purifying the product to obtain an intermediate.
Preferably, the monosubstituted aliphatic diamine is reacted with R 3 The ratio of the amount of X is 1:2.0-5.0.
Preferably, the halide is selected from any one or more of sodium 2-chloroacetate, sodium 2-bromoacetate, sodium 3-chloropropionate, sodium 3-bromopropionate, sodium 4-chlorobutyrate, sodium 4-bromobutyrate, sodium 2-chloroethyl sulfonate, sodium 2-bromoethyl sulfonate, sodium 3-chloropropyl sulfonate, sodium 3-bromopropyl sulfonate or sodium 3-chloro-2-hydroxy propyl sulfonate; the anhydride is selected from maleic anhydride and/or succinic anhydride; the lactone is selected from propane sultone or/and butane sultone.
Preferably, the temperature of the heated reflux is 70-150 ℃.
Preferably, the intermediate is further reacted with halogenated hydrocarbon to obtain the Gemini surfactant specifically comprises:
dissolving the intermediate in an organic solvent, and then adding R 4 And Y, heating and refluxing, and washing, filtering and purifying the product after TLC monitors complete conversion of the intermediate to obtain the Gemini surfactant.
Preferably, the intermediateBody and R 4 The ratio of the amount of Y is 1:2.0-3.0.
Preferably, the temperature of the heating reflux is 60-120 ℃.
Preferably, the organic solvent is any one or more of methanol, ethanol, isopropanol, propylene glycol, butanol, ethyl acetate and acetone.
Preferably, the aliphatic diamine is N-methyl ethylenediamine, N-ethyl ethylenediamine, N-phenyl ethylenediamine, N-methylpropanediamine, N-ethylpropanediamine, N-phenylpropane diamine, N-methylbutanediamine, N-ethylbutanediamine, N-phenylbutanediamine, N-methylpentanediamine, N-ethylpentanediamine, N-phenylpentanediamine, N-methylhexanediamine, N-ethylhexyl diamine, N-phenylhexanediamine or N-methylparaben diamine.
A composition comprising two-dimensional nanoparticles and a Gemini surfactant prepared as described above.
Preferably, the weight ratio of the two-dimensional nano particles to the Gemini surfactant is 0.1-90:10-99.9.
Preferably, the two-dimensional nanoparticle is an amphiphilic two-dimensional nanoparticle.
Preferably, the two-dimensional nano particles are graphene oxide, montmorillonite, silicon dioxide, cellulose, metal oxide or organic-inorganic composite nano materials.
A composition comprising water, two-dimensional nanoparticles and a Gemini surfactant prepared as described above; wherein the mass concentration of the two-dimensional nano particles is 0.0005wt% to 0.05wt%, the mass concentration of the Gemini surfactant is 0.05wt% to 0.5wt%, and the balance is water.
Use of said composition in tertiary oil recovery.
Preferably, the composition is injected into a medium or low permeability reservoir or a tight reservoir for huff-puff or displacement.
A composition comprising water, crude oil, two-dimensional nanoparticles and a Gemini surfactant prepared by the preparation method as defined in claim 2; the mass concentration of the two-dimensional nano particles is 0.0005wt% to 0.01wt%, the mass concentration of the Gemini surfactant is 0.001wt% to 0.01wt%, the mass fraction of the crude oil is 10wt% to 90wt%, and the balance is water.
Use as a particle stabilized emulsion flooding system in accordance with the use of the composition.
Preferably, the particle stabilized emulsion flooding system is applied in tertiary oil recovery.
Preferably, the particle stable emulsion oil displacement system is injected after water displacement or polymer displacement of the low permeability reservoir for huff and puff or oil displacement.
A tertiary oil recovery method comprising the steps of: and taking the composition as an oil displacement slug to carry out throughput or oil displacement.
The invention has the following beneficial effects: the nano-particle and surfactant composition obtained by the invention can exert the synergistic effect of the surfactant and the nano-particle, has low interfacial tension, strong oil washing capacity and emulsification wave expansion and effect, and improves the microscopic wave efficiency of a low permeability reservoir, thereby improving the recovery ratio; the nanoparticle and surfactant composition has simple preparation method, can be produced in a large scale and has wide application prospect in low permeability reservoirs; the composite flooding composition containing the two-dimensional nano particles can effectively block a hypertonic channel, reduce sewage discharge, reduce invalid circulation and invalid energy consumption, and has wide application prospect.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of modified graphene oxide nanoparticles of example 1;
FIG. 2 is a scanning electron microscope image of the organic-inorganic composite nanoparticle of example 2;
FIG. 3 is an atomic force microscope image of cellulose nanoparticles of example 3;
FIG. 4 is a nuclear magnetic resonance spectrum of the sulfoGemini surfactant prepared in example 4;
FIG. 5 is a nuclear magnetic resonance spectrum of the sulfoGemini surfactant prepared in example 5;
FIG. 6 is a nuclear magnetic resonance spectrum of the carboxyGemini surfactant prepared in example 6;
FIG. 7 is a microscopic state diagram of emulsion formed by the compound flooding system at a water-to-oil volume ratio of 8:2 in example 7;
FIG. 8 is a microscopic state diagram of the emulsion formed by the compound flooding system at a water-to-oil volume ratio of 8:2 in example 8;
FIG. 9 is a microscopic state diagram of the emulsion formed by the complex flooding system at a water to oil volume ratio of 7:3 in example 9;
FIG. 10 is a graph of the pressure change in the core flow produced by the particle stabilized emulsion system of example 10;
FIG. 11 is a dynamic interface Zhang Litu of the complex flooding system of example 11;
FIG. 12 is a graph showing interfacial tension of the complex flooding system of example 11 as a function of adsorption times;
FIG. 13 is a dynamic interface Zhang Litu of the complex flooding system of example 12.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A Gemini surfactant has a molecular structural formula as follows:
wherein R is 1 Is C 2 ～C 6 Alkane, alkene or arene;
R 2 is-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 or-C 6 H 5 ；
R 3 is-CH 2 CO 2 - Na + 、-CH 2 CH 2 CO 2 - Na + 、-COCH＝CHCO 2 - Na + -CH 2 CH 2 SO 3 - Na + 、-CH 2 CH 2 CH 2 SO 3 - Na + 、-CH 2 CH(OH)CH 2 SO 3 - Na + or-CH 2 CH 2 CH 2 CH 2 SO 3 - Na + ；
R 4 Is alkane-C n H 2n+1 olefin-C n H 2n-1 Or alkylaromatics-C n H 2n-7 ，n＝6～18。
The preparation method of the Gemini surfactant comprises the following steps:
adding halogeno, anhydride or lactone with hydrophilic group into monosubstituted aliphatic diamine to react to obtain intermediate
The intermediate is further reacted with halohydrocarbon to obtain the Gemini surfactant
Wherein R is 1 Is C 2 ～C 6 Alkane, alkene or arene;
R 2 is-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 or-C 6 H 5 ；
R 3 is-CH 2 CO 2 - Na + 、-CH 2 CH 2 CO 2 - Na + 、-COCH＝CHCO 2 - Na + -CH 2 CH 2 SO 3 - Na + 、-CH 2 CH 2 CH 2 SO 3 - Na + 、-CH 2 CH(OH)CH 2 SO 3 - Na + or-CH 2 CH 2 CH 2 CH 2 SO 3 - Na + ；
R 4 Is alkane-C n H 2n+1 olefin-C n H 2n-1 Or alkylaromatics-C n H 2n-7 ，n＝6～18；
R 3 X is any one or more of the halogenide, anhydride or lactone with hydrophilic groups;
R 4 y is the halogenated hydrocarbon.
Further, the step of adding a halogenated compound, anhydride or lactone with a hydrophilic group into the mono-substituted aliphatic diamine to react to obtain an intermediate comprises the following specific steps:
and dissolving the monosubstituted aliphatic diamine in an organic solvent, adding a halogenide, an anhydride or a lactone with a hydrophilic group, heating and refluxing for reaction, monitoring the reaction of the aliphatic diamine as a raw material by TLC until the reaction of the aliphatic diamine is complete, and then washing, filtering and purifying the product to obtain an intermediate.
Further, the monosubstituted aliphatic diamine is mixed with R 3 The ratio of the amounts of X is 1:2.0 to 5.0, preferably 1:2.2 to 4.0.
Further, the halide is selected from any one or more of sodium 2-chloroacetate, sodium 2-bromoacetate, sodium 3-chloropropionate, sodium 3-bromopropionate, sodium 4-chlorobutyrate, sodium 4-bromobutyrate, sodium 2-chloroethyl sulfonate, sodium 2-bromoethyl sulfonate, sodium 3-chloropropylsulfonate, sodium 3-bromopropyl sulfonate or sodium 3-chloro-2-hydroxy propyl sulfonate; the anhydride is selected from maleic anhydride and/or succinic anhydride; the lactone is selected from propane sultone or/and butane sultone.
Further, the temperature of the heating reflux is 70-150 ℃. The temperature rise in the reaction process can improve the substitution reaction rate, but the reaction temperature is not too high, and the side reaction is aggravated by the too high temperature, so that the yield is affected.
Further, the intermediate is further reacted with halogenated hydrocarbon to obtain the Gemini surfactant, which is specifically:
dissolving the intermediate in an organic solvent, and then adding R 4 And Y, heating and refluxing, and washing, filtering and purifying the product after TLC monitors complete conversion of the intermediate to obtain the Gemini surfactant.
Further, the intermediate and R 4 The ratio of the amount of Y is 1:2.0-3.0.
Further, the temperature of the heating reflux is 60-120 ℃. In the reaction process, the temperature is not too high, and polysubstituted reaction can be generated due to the too high temperature.
Further, the organic solvent is any one or more of methanol, ethanol, isopropanol, propylene glycol, butanol, ethyl acetate and acetone. Alcohols are used as reaction solvents to obtain better effects.
Further, the aliphatic diamine is N-methyl ethylenediamine, N-ethyl ethylenediamine, N-phenyl ethylenediamine, N-methyl propylenediamine, N-ethyl propylenediamine, N-phenyl propylenediamine, N-methyl butylenediamine, N-ethyl butylenediamine, N-phenyl butylenediamine, N-methyl pentylene diamine, N-ethyl pentylene diamine, N-phenyl pentylene diamine, N-methyl hexylenediamine, N-ethyl hexylenediamine, N-phenyl hexylenediamine or N-methyl p-phenylenediamine.
The preparation method provided by the invention takes common synthetic raw materials of halogenated alkane and aliphatic diamine as raw materials, and prepares the target product of the Gemini surfactant by adopting only 2 steps of reactions. The preparation process of the surfactant is simple, easy to realize and easy to popularize in actual industrial production.
The first composition comprises two-dimensional nano particles and the Gemini surfactant prepared by the preparation method. The two-dimensional nano-particles are single-layer or multi-layer nano-particles, the smaller the thickness of the nano-particles is, the more obvious the implementation effect is, but the single-layer nano-particles are often difficult to obtain, and the nano-particles are usually multi-layer. The two-dimensional nanoparticles used can be synthesized or modified, and the nanoparticles are kept to be proper in hydrophilicity and lipophilicity in the synthesis or modification process, and neither the nanoparticles are too hydrophilic nor too lipophilic. The nanoparticles have aryl structures with strong interactions with crude oil, which will result in better performance. Compared with the conventional nanoparticles, the nanoparticles with the two-dimensional structure have larger specific surface area and higher efficiency in oil-water interface action. Therefore, the amount of the additive used is lower to achieve the same effect.
Further, the weight ratio of the two-dimensional nano particles to the Gemini surfactant is 0.1-90:10-99.9, preferably 0.1-50:50-99.9.
Further, the two-dimensional nanoparticles are amphiphilic two-dimensional nanoparticles. The two-dimensional nano particles with double-sided anisotropy have better implementation effect.
Further, the two-dimensional nano particles are graphene oxide, montmorillonite, silicon dioxide, cellulose, metal oxide or organic-inorganic composite nano materials.
The second composition can be used as a composite nano oil displacement system and comprises water, two-dimensional nano particles and the Gemini surfactant prepared by the preparation method; wherein the mass concentration of the two-dimensional nano particles is 0.0005wt% to 0.05wt%, the mass concentration of the Gemini surfactant is 0.05wt% to 0.5wt%, and the balance is water. The water is oilfield injection water.
Use of a second composition in tertiary oil recovery.
Further, the composition is injected into a medium-low permeability reservoir or a tight reservoir for huff-puff or oil displacement.
The first composition or/and the second composition are injected into the medium-low permeability oil reservoir and the dense oil reservoir for huff-puff or oil displacement, the synergistic effect of the nano particles and the surfactant can be exerted, the oil displacement efficiency and sweep efficiency of an oil displacement system are further improved, and the recovery ratio of the medium-low permeability oil reservoir and the dense oil reservoir can be greatly improved.
A third composition comprising water, crude oil, two-dimensional nanoparticles and a Gemini surfactant prepared by the preparation method as defined in claim 2; the mass concentration of the two-dimensional nano particles is 0.0005wt% to 0.01wt%, the mass concentration of the Gemini surfactant is 0.001wt% to 0.01wt%, the mass fraction of the crude oil is 10wt% to 90wt%, and the balance is water.
The third composition is used as a particle stabilized emulsion displacement system.
Further, the particle stabilized emulsion displacement system is applied to tertiary oil recovery.
Further, after water flooding or polymer flooding of the low-permeability reservoir, the particle stable emulsion oil displacement system is injected for huff and puff or oil displacement, the swept volume of the oil displacement system can be remarkably improved, and the recovery ratio of the heterogeneous reservoir is greatly improved.
A tertiary oil recovery method comprising the steps of: the second composition or/and the third composition is used as an oil displacement slug to carry out huff and puff or displace oil, so that the requirements of tertiary oil recovery of low permeability and dense oil reservoirs of different types can be met, and the recovery ratio is greatly improved.
The following examples are given by way of illustration only:
example 1
Preparation of amphiphilic graphene oxide nano particles
3g of graphite powder and 1.5g of sodium nitrate are weighed, poured into a beaker, the temperature of the beaker is controlled by a water bath, 100ml of 95% concentrated sulfuric acid is poured, stirring is carried out at 450rpm for 15 minutes, 8g of potassium permanganate is slowly added into the solution, ice is removed after the solution turns green, and 200ml of cold water is added to stir for 30 minutes by a dropper after stirring for 12 hours. Then 30ml of 30% hydrogen peroxide is added by a dropper, the mixture is stirred for 2 hours to turn golden yellow, the supernatant is poured off after standing, ammonia water is added for powerful ultrasonic washing until the pH value is=10, and black graphene oxide powder is obtained after freeze drying. And (3) alternately centrifugally washing the graphene oxide nanoparticles by deionized water and ethanol for 3 times, and vacuum drying the graphene oxide nanoparticles at 40 ℃. The microscopic morphology of the nanoparticles was observed by transmission electron microscopy, as shown in fig. 1. From the figure, the nano particles are nano particles with a two-dimensional structure, which shows that the method can prepare graphene oxide particles with a two-dimensional structure.
Example 2
Preparation of amphiphilic organic-inorganic composite nano particles
1.89g of manganese chloride and 2.1g of tribenzoic acid were added to a 100mL flask, 50mL of an ethanol solution was poured into the beaker, magnetons were added, and the mixture was vigorously stirred at room temperature for 2 minutes with a magnetic stirrer, then 2mL of triethylamine was dropwise added to the system, and the reaction was stopped by continuing to vigorously stir at room temperature for 6 hours with a magnetic stirrer. Filtering and washing to obtain organic-inorganic composite nano particles, wherein the micro morphology of the nano particles is shown in figure 2. The nano-particles are shown as nano-particles with a two-dimensional structure in the figure, which shows that the method can prepare the amphiphilic organic-inorganic composite nano-particles with the two-dimensional structure.
Example 3
Preparation of amphiphilic flaky cellulose nano-particles
5g of paper pulp is dispersed into 50mL of silicone oil, 0.8g of acetyl chloride is added, then the dispersion is added into a ball milling system for milling, the rotation speed of the ball mill is 200rpm, the intermittent time is 2min, after ball milling is carried out for 20min, DMF and deionized water are sequentially added into the ball milled product, and then the product is centrifuged and washed to remove the silicone oil, so that the flaky amphiphilic nano-cellulose is obtained, the microscopic morphology of the nano-particles is observed through atomic force, as shown in figure 3 (Height in the figure represents "Height", width represents "Width", and High represents "High"). From the figure, it is seen that the nanoparticle is a nanoparticle having a two-dimensional structure, illustrating that the method is capable of preparing a two-dimensional structured sheet-like cellulose nanoparticle.
Example 4
Preparation of sulfo Gemini surfactant
Dissolving 0.88g of N-methyl propane diamine into a three-mouth bottle containing ethyl acetate, dropwise adding 3.67g of 1, 3-propane sultone, heating and refluxing for reaction for 24 hours, filtering, washing the obtained solid with diethyl ether for multiple times, recrystallizing the ethanol and the ethyl acetate for multiple times, and neutralizing the product with NaOH to obtain an intermediate; adding the 3.76 intermediate into a three-mouth bottle containing isopropanol, heating and refluxing, dropwise adding 6.23g bromododecane, reacting for 24 hours, filtering to obtain a white solid, and recrystallizing methanol and ethyl acetate for multiple times to obtain the sulfo Gemini surfactant, wherein the nuclear magnetic spectrum is shown in figure 4. The nuclear magnetic spectrum diagram shows that the Gemini surfactant synthesized by the method is prepared into a target product.
Example 5
Preparation of sulfo Gemini surfactant
Dissolving 0.88g of N-methyl propane diamine into a three-mouth bottle containing ethyl acetate, dropwise adding 3.67g of 1, 3-propane sultone, heating and refluxing for reaction for 24 hours, filtering, washing the obtained solid with diethyl ether for multiple times, recrystallizing the ethanol and the ethyl acetate for multiple times, and neutralizing the product with NaOH to obtain an intermediate; adding the 3.76 intermediate into a three-mouth bottle containing isopropanol, heating and refluxing, dropwise adding 6.71g of bromohexadecane, reacting for 24 hours, filtering to obtain a white solid, and recrystallizing methanol and ethyl acetate for multiple times to obtain the sulfo Gemini surfactant, wherein the nuclear magnetic spectrum is shown in figure 5. The nuclear magnetic spectrum diagram shows that the Gemini surfactant synthesized by the method is prepared into a target product.
Example 6
Preparation of carboxyl Gemini surfactant
Dissolving 0.76g of N-methyl ethylenediamine into a three-mouth bottle containing isopropanol, adding 3.50g of sodium chloroacetate, heating and refluxing for reaction for 24 hours, filtering, washing the obtained solid with diethyl ether for multiple times, recrystallizing the ethanol and ethyl acetate for multiple times, and neutralizing the product with NaOH to obtain an intermediate; adding the 2.34 intermediate into a three-mouth bottle containing isopropanol, heating and refluxing, dropwise adding 5.3g bromododecane, reacting for 48 hours, filtering to obtain a white solid, and recrystallizing methanol and ethyl acetate for multiple times to obtain the carboxyl Gemini surfactant, wherein the nuclear magnetic spectrum is shown in figure 6. The nuclear magnetic spectrum diagram shows that the Gemini surfactant synthesized by the method is prepared into a target product.
Example 7
Emulsifying Properties of nanoparticle and surfactant compositions
The modified graphene oxide nanoparticles prepared in example 1, the Gemini surfactant prepared in example 4 and crude oil were formulated into an emulsion, and the viscosity and stability of the emulsion were tested. In the composition, the concentration of the modified graphene oxide nano particles is 0.002wt%, the concentration of the surfactant is 0.01wt%, the oil water is Jidong oil field oil water, and the testing temperature is 90 ℃. Crude oil, dispersion was placed in a beaker at a water to oil volume ratio of 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2 or 9:1 (10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90% in order by volume of water), kept at 90 ℃ for 1 hour, dispersed for 1 minute with an IKA homogenizer, and the emulsion was observed for apparent viscosity, emulsion state and viscosity were tested by a rheometer as shown in table 1. Test temperature 90℃and shear rate 10s -1 . Under the volume ratio of water to oil below 8:2, the oil and water can be emulsified to form stable water-in-oil emulsion, and the highest water content can reach 80%. The viscosity of the emulsion increases gradually with the increase of the oil-water ratio, and is up to 70 times that of crude oil. At a water to oil volume ratio of 7:3, the emulsion state is shown in FIG. 7. The emulsion is seen to be a water-in-oil emulsion with water as the internal phase and the emulsion droplets are closely packed, demonstrating the strong ability of the composition to emulsify crude oil.
TABLE 1 emulsion formation and viscosity of modified graphene oxide and Gemini surfactant in example 7
Example 8
Emulsifying Properties of nanoparticle and surfactant compositions
The organic-inorganic composite nano-particles prepared in example 2, the Gemini surfactant prepared in example 5 and crude oil were formulated into an emulsion, and the viscosity and stability of the emulsion were tested. The combination isIn the material, the concentration of the inorganic composite nano particles is 0.006wt%, the concentration of the surfactant is 0.024wt%, the oil water is Jilin oil field oil water, and the test temperature is 66 ℃. Crude oil and dispersion were placed in beakers at water-to-oil volume ratios of 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2 or 9:1 (10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90% in order by volume of water), kept at 66 ℃ for 1 hour, dispersed for 1 minute with an IKA homogenizer, and the emulsification was observed and the apparent viscosity of the emulsion was tested by a rheometer. Test temperature 66℃and shear rate 10s -1 The emulsion state and viscosity are shown in table 2. Under the volume ratio of water to oil below 8:2, the oil and water can be emulsified to form stable water-in-oil emulsion, and the highest water content can reach 80%. The viscosity of the emulsion gradually increases with the increase of the oil-water ratio, and the viscosity of the emulsion is up to 100 times that of crude oil. At a water to oil volume ratio of 7:3, the emulsion state is shown in FIG. 8. The emulsion is seen to be a water-in-oil emulsion with water as the internal phase and the emulsion droplets are closely packed, demonstrating the strong ability of the composition to emulsify crude oil.
TABLE 2 emulsion states and viscosities of organic-inorganic nanoparticles and Gemini surfactants in example 8
Example 9
Emulsifying Properties of nanoparticle and surfactant compositions
The flaky cellulose nanoparticles prepared in example 3, the Gemini surfactant prepared in example 6 and crude oil were formulated into an emulsion, and the viscosity and stability of the emulsion were tested. In the composition, the concentration of the flaky cellulose nano particles is 0.1wt% and the concentration of the active agent is 0.05wt%, the oil-water is Xinjiang oil-water, the testing temperature is 72 ℃, and the water-oil volume ratio is 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2 or 9:1 (the water-containing volume fractions are sequentially10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%) of the crude oil, the dispersion was placed in a beaker, kept at 72 ℃ for 1 hour, dispersed with an IKA homogenizer for 1 minute, the emulsification was observed, and the apparent viscosity of the emulsion was measured by a rheometer. Test temperature 72℃and shear rate 10s -1 The emulsion state and viscosity are shown in table 3. Under the volume ratio of water to oil of 7:3, the oil and water can be emulsified to form stable water-in-oil emulsion, and the highest water content can reach 70%. The emulsion viscosity increases gradually with increasing oil-water ratio, and is up to 50 times higher than the viscosity of crude oil. At a water to oil volume ratio of 7:3, the emulsion state is shown in FIG. 9. The emulsion is seen to be a water-in-oil emulsion with water as the internal phase and the emulsion droplets are closely packed, demonstrating the strong ability of the composition to emulsify crude oil.
TABLE 3 emulsion state and viscosity of the sheeted cellulose and Gemini surfactant of example 9
Water-oil volume ratio Emulsion state Viscosity (mPas)
Crude oil / 1.1
1:9 Phase separation-free 1.4
2:8 Phase separation-free 1.8
3:7 Phase separation-free 2.6
4:6 Phase separation-free 4.4
5:5 Phase separation-free 12.8
6:4 Phase separation-free 30.3
7:3 Phase separation-free 71.9
8:2 Phase separation /
9:1 Phase separation /
The emulsion water content of the particle stabilized emulsion system is compared with that of the emulsion formed by the conventional oil displacement surfactant. The emulsion pairs of the highest water content of the emulsions formed in examples 7, 8, 9 with conventional oil displacing surfactants are shown in table 4. As can be seen from the table, the oil displacing surfactant, petroleum sulfonate, and heavy alkylbenzene system alone form emulsion with water content up to 30%. The highest water content of the emulsion formed by the nano particles and the Gemini surfactant composition provided by the invention is more than 70%, even 80%, which shows that the particle stable emulsion system provided by the invention has very strong crude oil emulsifying capability.
Table 4 comparison of emulsion formation Capacity of nanoparticles and surfactant compositions
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Example 10
Seepage capability of particle stabilized emulsion flooding system in core
The profile control capability of the particle stabilized emulsion displacement system prepared in example 7 was tested by core flowability experiments. Preparing the crude oil and the dispersion liquid into a 70% water-containing particle stable emulsion oil displacement system, sequentially injecting stratum water and the particle stable emulsion oil displacement system into a saturated water core, injecting a subsequent water slug after pressure balance, and recording pressure change in the process. The permeability of the core is 2129mD, the oil-water used is Jidong oil-water in oil field, and the test temperature is 90 ℃. From fig. 10, after 70% water-containing particles are injected into the core to stabilize the emulsion displacement system, the pressure is 20 times of the water injection pressure, which shows that the system has great potential in expanding the swept volume of the heterogeneous oil reservoir.
Example 11
Low-permeability recovery effect of nano composite oil displacement system
The organic-inorganic nano particles prepared in the example 2 and the Gemini surfactant prepared in the example 5 are prepared into a nano composite oil displacement system. In the nano composite oil displacement system, the mass percent of the Gemini surfactant is 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt% and the mass percent of the organic-inorganic composite nano particles is 0.08wt%. The oil-water used was Xinjiang oil-water, and the test temperature was 72 ℃. The interfacial tension of the organic-inorganic composite nanoparticle/Gemini surfactant nanocomposite displacement system and Xinjiang crude oil was tested by a TX500C interfacial tensiometer, and the results are shown in FIG. 11. As shown in the figure, the evaluated organic-inorganic composite nano-particle/Gemini surfactant nano-composite oil displacement system can reach ultra-low interfacial tension with Xinjiang crude oil, and has excellent interfacial properties.
The adsorption resistance of the compound oil displacement system prepared in the example was evaluated by interfacial tension. Adding 100-200 meshes of Xinjiang oil sand and a compound oil displacement system into a grinding conical flask with a plug according to a solid-liquid ratio of 1:9, sealing, placing into a constant-temperature oscillating water bath with a temperature of 72 ℃ for oscillating for 24 hours, taking out the conical flask, measuring the interfacial tension of an upper solution, continuing to adsorb with the new oil sand, and repeating the steps until the interfacial tension cannot reach ultralow, wherein the result is shown in figure 12. It can be seen that the interfacial tension of the compound oil displacement system still reaches ultra-low after the oil-water adsorption of Xinjiang is performed four times, and the anti-adsorption performance is excellent.
The core oil displacement experiment is used for evaluating the oil displacement efficiency of the organic-inorganic composite nano particle/Gemini surfactant nano composite oil displacement system prepared in the embodiment. Table 5 shows the results of the oil displacement experiment of the nanocomposite oil displacement system prepared in this example. The mass percentage of the Gemini surfactant in the nano composite oil displacement system is 0.4wt%, the mass percentage of the organic-inorganic composite nano particles is 0.08wt%, the permeability of the used core is 17.2Md, the used oil-water is Xinjiang oil-water, the test temperature is 72 ℃, and the slug of the oil displacement system is 0.7PV. Experimental results show that the recovery ratio of the nanocomposite flooding system is improved by 15.2%.
TABLE 5 Low permeability displacement efficiencies for different displacement systems
Example 12
Low-permeability recovery effect of nano composite oil displacement system
The modified graphene oxide nano particles prepared in the example 1 and the Gemini surfactant prepared in the example 5 are prepared into a nano composite oil displacement system. In the nanocomposite oil displacement system, the mass percent of the Gemini surfactant is 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt% or 0.5wt%, and the mass percent of the modified graphene oxide nanoparticles is 0.05wt%. The oil-water used was Jilin oil-water, and the test temperature was 66 ℃. The interfacial tension of the graphene oxide nanoparticle/Gemini surfactant nanocomposite flooding system and Jilin crude oil was tested by a TX500C interfacial tensiometer, and the results are shown in fig. 13. The graph shows that the evaluated modified graphene oxide nanoparticle/Gemini surfactant nanocomposite oil displacement system can reach ultralow interfacial tension with Jilin crude oil, and has excellent interfacial performance.
The oil displacement efficiency of the graphene oxide nanoparticle/Gemini surfactant nanocomposite oil displacement system prepared in the embodiment is evaluated through a core oil displacement experiment. Table 5 shows the results of the oil displacement experiment of the nanocomposite oil displacement system prepared in this example. The mass percentage of the Gemini surfactant in the nano composite oil displacement system is 0.4wt%, the mass percentage of the graphene oxide nano particles is 0.05wt%, the permeability of the used core is 45.3mD, the oil-water is Jilin oil-water, the test temperature is 66 ℃, and the slug of the oil displacement system is 0.7PV. Experimental results show that the recovery ratio of the nanocomposite flooding system is improved by 18.3%.
Example 13
Low permeability recovery effect of petroleum sulfonate system
Oil displacement efficiency of petroleum sulfonate with interfacial tension reaching ultra-low was evaluated by core oil displacement experiments, as shown in table 5. The mass percent of petroleum sulfonate is 0.5wt%, the core permeability is 15.5mD, and other test conditions are the same as those of test example 11. From the experimental results, the recovery ratio of the nonionic surfactant system is improved by 10.1% on the basis of water flooding.
The comparison shows that the low-permeability oil displacement efficiency of the oil displacement system of the nano composite oil displacement system is about 5 percent higher than that of the surfactant. The effect of emulsifying and expanding the microscopic wave and volume of the nano particles is a main reason for improving the oil displacement efficiency.
Example 14
Low permeability and high recovery efficiency of nonionic surfactant system
The oil displacement efficiency of the alkylphenol polyoxyethylene nonionic surfactant system with the interfacial tension reaching the ultra-low level was evaluated by a core oil displacement experiment, as shown in table 5. The mass percent of the nonionic surfactant system was 0.5wt%, the core permeability was 49.1mD, and the other test conditions were the same as in test example 12. From the experimental results, the recovery ratio of the nonionic surfactant system is improved by 11.6% on the basis of water flooding.
The comparison shows that the low-permeability oil displacement efficiency of the oil displacement system of the nano composite oil displacement system is about 7 percent higher than that of the surfactant under the same permeability condition.
The result shows that the effect of the emulsification of the nano particles to enlarge the microscopic wave and volume can improve the recovery ratio of the hypotonic oil reservoir. The nano composite oil displacement system provided by the invention has great advantages in the field of hypotonic chemical displacement.
In conclusion, the nano-particle and surfactant composition obtained by the invention can exert the synergistic effect of the surfactant and the nano-particle, has low interfacial tension, strong oil washing capacity and emulsification and wave expansion effects, and improves the microscopic wave efficiency of the low permeability reservoir, thereby improving the recovery ratio; the nanoparticle and surfactant composition has simple preparation method, can be produced in a large scale and has wide application prospect in low permeability reservoirs; the composite flooding composition containing the two-dimensional nano particles can effectively block a hypertonic channel, reduce sewage discharge, reduce invalid circulation and invalid energy consumption, and has wide application prospect.
Although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (23)

1. A Gemini surfactant is characterized by having the following molecular structural formula:
wherein R is 1 Is C 2 ～C 6 Is an alkane of (a);
R 2 is-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 or-C 6 H 5 ；
R 3 is-CH 2 CO 2 - Na + 、-CH 2 CH 2 CO 2 - Na + 、-COCH＝CHCO 2 - Na +
-CH 2 CH 2 SO 3 - Na + 、-CH 2 CH 2 CH 2 SO 3 - Na + 、-CH 2 CH(OH)CH 2 SO 3 - Na + Or (b)
-CH 2 CH 2 CH 2 CH 2 SO 3 - Na + ；
R 4 Is alkane-C n H 2n+1 ，n＝6～18。
2. The preparation method of the Gemini surfactant based on claim 1 is characterized by comprising the following steps:
adding halogeno, anhydride or lactone with hydrophilic group into monosubstituted aliphatic diamine to react to obtain intermediate
The intermediate reacts with halohydrocarbon to obtain the Gemini surfactant
Wherein R is 1 Is C 2 ～C 6 Is an alkane of (a); r is R 2 is-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 or-C 6 H 5 ；R 3 is-CH 2 CO 2 - Na + 、-CH 2 CH 2 CO 2 - Na + 、-COCH＝CHCO 2 - Na + 、-CH 2 CH 2 SO 3 - Na + 、-CH 2 CH 2 CH 2 SO 3 - Na + 、-CH 2 CH(OH)CH 2 SO 3 - Na + or-CH 2 CH 2 CH 2 CH 2 SO 3 - Na + ；R 4 Is alkane-C n H 2n+1 ，n＝6～18；R 3 X is any one or more of the halogenide, anhydride or lactone with hydrophilic groups; r is R 4 Y is the halogenated hydrocarbon.
3. The preparation method of the Gemini surfactant according to claim 2, wherein the step of adding a halogenated compound, anhydride or lactone with a hydrophilic group into the mono-substituted aliphatic diamine, and reacting to obtain an intermediate is specifically:
and dissolving the monosubstituted aliphatic diamine in an organic solvent, adding a halogenide, an anhydride or a lactone with a hydrophilic group, heating and refluxing for reaction, monitoring the reaction of the aliphatic diamine as a raw material by TLC until the reaction of the aliphatic diamine is complete, and then washing, filtering and purifying the product to obtain an intermediate.
4. The method for preparing Gemini surfactant according to claim 2, wherein the mono-substituted aliphatic diamine is mixed with R 3 The ratio of the amount of X is 1:2.0-5.0.
5. The preparation method of the Gemini surfactant according to claim 2, wherein the halide is selected from any one or more of sodium 2-chloroacetate, sodium 2-bromoacetate, sodium 3-chloropropionate, sodium 3-bromopropionate, sodium 4-chlorobutyrate, sodium 4-bromobutyrate, sodium 2-chloroethyl sulfonate, sodium 2-bromoethyl sulfonate, sodium 3-chloropropylsulfonate, sodium 3-bromopropyl sulfonate and sodium 3-chloro-2-hydroxypropyl sulfonate; the anhydride is selected from maleic anhydride and/or succinic anhydride; the lactone is selected from propane sultone or/and butane sultone.
6. The method for preparing a Gemini surfactant according to claim 3, wherein the temperature of the heated reflux is 70-150 ℃.
7. The preparation method of the Gemini surfactant according to claim 2, wherein the reaction of the intermediate and halogenated hydrocarbon to obtain the Gemini surfactant is specifically:
dissolving the intermediate in an organic solvent, and then adding R 4 And Y, heating and refluxing, and washing, filtering and purifying the product after TLC monitors complete conversion of the intermediate to obtain the Gemini surfactant.
8. The method for preparing Gemini surfactant according to claim 2, wherein the intermediate and R 4 The ratio of the amount of Y is 1:2.0-3.0.
9. The method for preparing the Gemini surfactant according to claim 7, wherein the temperature of the heating reflux is 60-120 ℃.
10. The method for preparing the Gemini surfactant according to claim 3 or 7, wherein the organic solvent is any one or more of methanol, ethanol, isopropanol, propylene glycol, butanol, ethyl acetate and acetone.
11. The method for preparing a Gemini surfactant according to any one of claims 2 to 9, wherein the aliphatic diamine is N-methylethylenediamine, N-ethylethylenediamine, N-phenylethanylenediamine, N-methylpropylenediamine, N-ethylpropylenediamine, N-phenylpropylenediamine, N-methylbutylenediamine, N-ethylbutanediamine, N-phenylbutanediamine, N-methylpentanediamine, N-ethylpentanediamine, N-phenylpentanediamine, N-methylhexanediamine, N-ethylhexyl diamine, N-phenylhexanediamine or N-methylparaben.
12. A composition comprising two-dimensional nanoparticles and a Gemini surfactant prepared according to claim 2.
13. The composition of claim 12, wherein the weight ratio of the two-dimensional nanoparticles to the Gemini surfactant is from 0.1 to 90:10 to 99.9.
14. The composition of claim 12, wherein the two-dimensional nanoparticle is an amphiphilic two-dimensional nanoparticle.
15. The composition of claim 14, wherein the two-dimensional nanoparticle is graphene oxide, montmorillonite, silica, cellulose, metal oxide, or organic-inorganic composite nanomaterial.
16. The composition of any one of claims 12-15, wherein the composition further comprises water; wherein the mass concentration of the two-dimensional nano particles is 0.0005wt% to 0.05wt%, the mass concentration of the Gemini surfactant is 0.05wt% to 0.5wt%, and the balance is water.
17. The composition of any one of claims 12-15, wherein the composition further comprises water and crude oil; the mass concentration of the two-dimensional nano particles is 0.0005wt% to 0.01wt%, the mass concentration of the Gemini surfactant is 0.001wt% to 0.01wt%, the mass fraction of the crude oil is 10wt% to 90wt%, and the balance is water.
18. Use of the composition according to claim 16 in tertiary oil recovery.
19. The use of claim 18, wherein the composition is injected into a medium or low permeability reservoir or a tight reservoir for huff-puff or oil displacement.
20. Use of a composition according to claim 17 as a particle stabilized emulsion displacement system.
21. The use of the composition of claim 20, wherein the particle stabilized emulsion displacement system is used in tertiary oil recovery.
22. Use of a composition according to claim 21, wherein the particle stabilized emulsion flooding system is injected for throughput or flooding after a hypotonic reservoir water flood or polymer flood.
23. The tertiary oil recovery method is characterized by comprising the following steps of: handling or displacing the composition of claim 16 or 17 as a displacement slug.
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CN114907224B (en) * 2022-07-19 2022-09-23 华巍博大(北京)科技有限公司 Acid-resistant NEDTA complexing agent and synthesis method and application thereof
CN116622359A (en) * 2023-04-28 2023-08-22 成都赛璐石油科技有限公司 Self-assembled gel foam oil displacement agent suitable for high-temperature high-salt fracture-cavity oil reservoir and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101856600A (en) * 2010-06-25 2010-10-13 西北大学 Amphoteric ionic Gemini surfactant and synthetic method thereof
CN103374341A (en) * 2012-04-13 2013-10-30 中国石油天然气股份有限公司 Preparation method and application of gemini amphiphilic surfactant
CN104263341A (en) * 2014-08-08 2015-01-07 中国石油天然气股份有限公司 Anionic and cationic surfactant compound mixture and preparation method thereof
CN104945562A (en) * 2015-07-22 2015-09-30 陕西延长石油(集团)有限责任公司研究院 Novel thickener and preparation method thereof
CN105439909A (en) * 2015-11-19 2016-03-30 中国石油天然气股份有限公司 Glycine betaine sulfonate and glycine betaine sulfonate type hydrophobic polymer as well as production method and application thereof
CN110872505A (en) * 2019-12-03 2020-03-10 成都理工大学 Organic porous nano-particle/surfactant composite oil displacement system and preparation method thereof
CN112457834A (en) * 2019-09-06 2021-03-09 中国石油天然气股份有限公司 Gemini cationic surfactant and preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI290561B (en) * 2005-08-16 2007-12-01 National Taiwan Normal Univers Amphoteric copolymer

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101856600A (en) * 2010-06-25 2010-10-13 西北大学 Amphoteric ionic Gemini surfactant and synthetic method thereof
CN103374341A (en) * 2012-04-13 2013-10-30 中国石油天然气股份有限公司 Preparation method and application of gemini amphiphilic surfactant
CN104263341A (en) * 2014-08-08 2015-01-07 中国石油天然气股份有限公司 Anionic and cationic surfactant compound mixture and preparation method thereof
CN104945562A (en) * 2015-07-22 2015-09-30 陕西延长石油(集团)有限责任公司研究院 Novel thickener and preparation method thereof
CN105439909A (en) * 2015-11-19 2016-03-30 中国石油天然气股份有限公司 Glycine betaine sulfonate and glycine betaine sulfonate type hydrophobic polymer as well as production method and application thereof
CN112457834A (en) * 2019-09-06 2021-03-09 中国石油天然气股份有限公司 Gemini cationic surfactant and preparation method and application thereof
CN110872505A (en) * 2019-12-03 2020-03-10 成都理工大学 Organic porous nano-particle/surfactant composite oil displacement system and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Amphoteric Water-Soluble Copolymer for Barium Titanate Slurries. I. Synthesis and Dispersing Ability;Lung-Pin Chen等;《Journal of Applied Polymer Science》;第95卷(第4期);1443-1450页 *
一种非对称双尾阳离子表面活性剂的合成及表面活性;姜小明等;《精细化工》;第28卷(第12期);1159-1163页 *
一类反应型两性表面活性剂的合成及性能研究;李苛等;《日用化学工业》;第48卷(第4期);183-187页 *

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