CN112225667B

CN112225667B - Composite surfactant composition, oil displacement agent, preparation method and application thereof

Info

Publication number: CN112225667B
Application number: CN201910633121.2A
Authority: CN
Inventors: 沈之芹; 李应成; 吴春芳; 虞辰敏
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2019-07-15
Filing date: 2019-07-15
Publication date: 2023-04-07
Anticipated expiration: 2039-07-15
Also published as: CN112225667A

Abstract

The invention relates to a composite surfactant composition, a preparation method and application thereof, and mainly solves the problems that the existing surfactant has low oil displacement efficiency, poor temperature resistance and salt tolerance and large adsorption retention capacity and cannot meet the oil displacement requirement of an oil reservoir. The invention better solves the problem by adopting the technical scheme that the composite surfactant composition comprises the zwitterionic compound shown in the formula (I), the surfactant shown in the formula (II) and containing polyether segments or not containing polyether segments, and at least one of small molecular alcohol or amine, salt and inorganic alkali, and can be used for improving the yield of crude oil in oil fields.

Description

Composite surfactant composition, oil displacement agent, preparation method and application thereof

Technical Field

The invention relates to a composite surfactant composition, an oil displacement agent, a preparation method and application thereof.

Background

The enhanced oil recovery technology, namely the Enhanced Oil Recovery (EOR) and Improved Oil Recovery (IOR) technology generally referred to abroad, can be summarized into six aspects of improving water flooding, chemical flooding, heavy oil thermal recovery, gas flooding, microbial oil recovery, physical oil recovery and the like. Currently, the enhanced oil recovery techniques that enter large-scale applications in mines are concentrated in three major categories, thermal recovery, gas flooding and chemical flooding. Chemical flooding is a strengthening measure for improving the recovery ratio by adding a chemical agent into an aqueous solution and changing the physicochemical property and rheological property of an injected fluid and the interaction characteristic with reservoir rocks, and is rapidly developed in China, mainly because the reservoir deposits in China have strong heterogeneity, the viscosity of the continental-phase crude oil is high, and the method is more suitable for chemical flooding in an EOR method.

Surface activeThe chemical flooding agent is an important component of chemical flooding, and can be divided into two major classes, namely an ionic type and a non-ionic type, according to different chemical components and molecular structures of the chemical flooding agent. The most anionic surfactant types are currently used in tertiary oil recovery studies, followed by nonionic and zwitterionic surfactants, and the least cationic surfactant is used. The results of oil displacement by using alkaline water, surfactant or alkaline water and oil displacement by using zwitterionic surfactant are sequentially reported by US3927716, US4018281 and US4216097 of Mobil Petroleum company, and the zwitterionic surfactant is carboxylic acid or sulfonate type betaine surfactant with different chain lengths, and the interfacial tension on crude oil in Texas south is 10 in simulated saline with total mineralization of 62000-160000 mg/L and calcium and magnesium ions of 1500-18000 mg/L ^-1 ～10 ^-4 mN/m. Cationic surfactants are also reported, for example, chinese patents CN 1528853, CN 1817431 and CN 1066137 sequentially report bisamide cationic, fluorine-containing cationic and pyridyl-containing cationic gemini surfactants, but the use of cationic surfactants in oil field sites is limited due to the defects of large adsorption loss, high cost and the like of cations.

After different types of surfactants are compounded with each other, the defects of a single surfactant can be overcome, and the advantages of all components are exerted, so that the composite surfactant composition has more excellent performance. Chinese patent CN1458219A discloses a surfactant/polymer binary ultra-low interfacial tension composite flooding formulation for tertiary oil recovery, wherein the used surfactant is petroleum sulfonate or a composite surfactant composition compounded by petroleum sulfonate as a main agent, a diluent and other surfactants, the weight percentage of the components is 50-100% of petroleum sulfonate, 0-50% of alkyl sulfonate, 0-50% of carboxylate, 0-35% of alkyl aryl sulfonate and 0-20% of low carbon alcohol, and the surfactant system is too complex. The patent US8211837 of the university of Texas, USA, reports that branched long carbon alcohol is obtained by catalytic dimerization reaction of simple and cheap linear alcohol at high temperature, the branched long carbon alcohol is polymerized with propylene oxide and ethylene oxide and then is subjected to sulfation reaction, compared with expensive sulfonate surfactants, a large hydrophilic group polyether sulfate surfactant is synthesized at low cost, the sulfate surfactant has excellent high-temperature stability under alkaline conditions due to the existence of a large hydrophilic group, 0.3 percent of branched alcohol polyether sulfate (C32-7 PO-6EO sulfate) and 0.3 percent of internal olefin sulfonate (C20-24 IOS) saline solution are mixed with the same amount of crude oil at 85 ℃, and the solubilization parameter is 14. Patent US4370243 of meifu petroleum company reports an oil displacement system composed of oil-soluble alcohol, betaine sulfonate and quaternary ammonium salt, which can function as both surfactant and fluidity control agent, wherein the quaternary ammonium salt is a cationic surfactant with oleophilic carbon chain length of 16-20, and 2% octadecyl dihydroxyethyl propyl betaine sulfonate and 1.0% hexanol are used as oil displacement agent, after 1.9PV is injected, the crude oil can be 100% displaced, but the adsorption loss of the surfactant is as large as 6mg/g, and 2.0% tetraethylammonium bromide with relatively low price is added as sacrificial agent to reduce the adsorption capacity of the surfactant.

Research results at home and abroad show that the surfactant is limited in practical application as an oil displacement agent due to large use amount, high preparation cost and poor use effect of a single surfactant. The invention relates to a composite surfactant composition with stable structure under oil reservoir conditions, an oil displacement agent, a preparation method and application thereof.

Disclosure of Invention

One of the technical problems to be solved by the invention is that the surfactant which is mainly composed of an oil displacement agent system in the prior art has poor crude oil solubilization capacity, low oil displacement efficiency, poor temperature and salt resistance, large adsorption retention and incapability of meeting the oil displacement requirement of a high-temperature and high-salt oil reservoir, and a novel composite surfactant composition is provided. The aqueous solution of the composite surfactant composition can well emulsify crude oil, has strong solubilizing capability and the maximum solubilizing parameter of 17.9-23.7, thereby effectively improving the oil displacement efficiency of the crude oil, having good application prospect of improving the recovery ratio and good performance of reducing the interfacial tension, and the oil-water interfacial tension can reach 10 ^-3 ～10 ^-4 mN/m。

The second technical problem to be solved by the present invention is to provide a method for preparing a composite surfactant composition corresponding to the solution of the first technical problem.

The invention also provides application of the composite surfactant composition corresponding to the solution of one of the technical problems.

The fourth technical problem to be solved by the invention is that the oil displacement agent system containing the surfactant in the prior art has the problems of poor crude oil compatibilization capacity, low oil displacement efficiency, poor temperature resistance and salt resistance, large adsorption retention and incapability of meeting the oil displacement requirement of high-temperature and high-salt oil reservoirs, and the invention provides a novel oil displacement agent, so that the water solution of the oil displacement agent can well emulsify the crude oil, has stronger solubilization capacity, and the maximum solubilization parameter is 17.9-23.7, thereby effectively improving the crude oil displacement efficiency, having good application prospect of improving the recovery ratio, having good performance of reducing the interfacial tension, and the oil-water interfacial tension can reach 10 ^-3 ～10 ^-4 mN/m。

The fifth technical problem to be solved by the present invention is to provide a method for preparing an oil displacement agent corresponding to the fourth technical problem to be solved.

The sixth technical problem to be solved by the present invention is to provide an application of the oil displacement agent corresponding to the fourth technical problem to be solved.

In order to solve one of the technical problems, the technical scheme adopted by the invention is as follows: a composite surfactant composition comprising the following components:

(1) A zwitterionic compound;

(2) A surfactant containing polyether segments or no polyether segments;

wherein the molar ratio of the zwitterionic compound to the polyether-containing or polyether segment-free surfactant is (1; the molecular general formula of the zwitterionic compound is shown as the formula (I):

in the formula (I), R ₁ And R ₄ Is hydrogen, C ₂ ～C ₃₂ Alkyl or substituted alkyl (CH R') _c OH、(CH R') _d CH ₃ One of phenyl, substituted phenyl or benzyl, R ₂ Y ^- Is C ₁ ～C ₅ Alkylene or substituted alkylene carboxylates, C ₁ ～C ₅ Alkyl or substituted alkyl sulfonates, C ₁ ～C ₅ Hydrocarbyl or substituted hydrocarbyl phosphate or C ₁ ～C ₅ At least one of hydrocarbyl or substituted hydrocarbyl sulfate, R ₃ Is hydrogen, C ₂ ～C ₃₂ Alkyl or substituted alkyl (CHR') _e OH, halogen, amino, carboxylic acid group or sulfonic group, R 'and R' are independently selected from H and CH ₃ Or C ₂ H ₅ C is any integer of 1 to 4, d is any integer of 0 to 5, and e is any integer of 0 to 4.

The molecular general formula of the surfactant containing polyether segments or not containing polyether segments is as follows:

in the formula (II), R ₅ Is C ₈ ～C ₃₀ Or one of a substituted hydrocarbon group or C ₄ ～C ₂₀ A phenyl or naphthyl ring substituted by a hydrocarbon or cumyl group, or R ₅ O is abietate; m1 and m2 are the addition number of the ethoxy groups, and m1= 0-50 and m2= 0-50; n is the addition number of the propoxy groups, and n = 0-100; k =0 or 1; when k =1, X is hydrogen or R ₅ Z，R ₅ Is C ₁ ～C ₅ Z is COOM, SO ₃ N or hydrogen, M and N are selected from hydrogen ions, cations or cationic groups; when k =0, X is COOM or SO ₃ And one of N, M and N are selected from hydrogen ions, cations or cationic groups.

In the above technical scheme, R ₁ Or R ₄ Preferably hydrogen, C ₈ ～C ₂₄ Alkyl or substituted alkyl, methylEthyl, hydroxyethyl, hydroxypropyl, phenyl, benzyl.

In the above technical scheme, R ₂ Y ^- Preferably C ₁ ～C ₃ Alkylene or substituted alkylene carboxylates, C ₁ ～C ₃ One of alkyl or substituted alkyl sulfonate.

In the above technical scheme, R ₃ Preferably hydrogen, C ₈ ～C ₂₄ Hydrogen, methyl, ethyl, phenyl, hydroxyl, amino, carboxylic acid or sulfonic acid.

In the above technical scheme, R', R ⁰ Preferably H or CH ₃ 。

In the above-described embodiment, c =1 to 2, d =0 to 1, and e =0 to 1 are preferable.

In the above technical scheme, M and N are preferably hydrogen ions, alkali metal cations or compounds represented by the formula NR ₇ (R ₈ )(R ₉ )(R ₁₀ ) At least one of the groups shown.

In the above technical scheme, R ₇ 、R ₈ 、R ₉ 、R ₁₀ Preferably H, (CHR) ⁰ ) _f OH or (CHR) ⁰ ) _g CH ₃ To (3) is provided.

In the above technical scheme, R ⁰ Preferably H, CH ₃ Or C ₂ H ₅ One kind of (1).

In the above-described embodiments, f =1 to 2,g =0 to 1 is preferable.

In the above-mentioned embodiment, j =0 or 1 is preferable

In the above technical scheme, R ₅ Preferably C ₁₂ ～C ₂₄ Or a substituted hydrocarbyl radical of ₄ ～C ₂₀ Saturated and unsaturated hydrocarbon radicals, straight-chain or branched, or cumyl (C) ₆ H ₅ C(CH ₃ ) ₂ ) Substituted benzene or naphthalene rings, or R ₅ O is abietate.

In the above technical scheme, R ₆ Preferably C ₁ ～C ₃ Alkylene or hydrogen.

In the above-described embodiments, m1=0 to 10, m2=0 to 10, and n =0 to 20 are preferable.

In the above technical solution, the composite surfactant composition preferably further comprises the following components:

(3) A small molecule alcohol;

(4) A small molecule amine;

(5) Salt;

(6) An inorganic base;

wherein the molar ratio of the zwitterionic compound, the surfactant containing polyether segments or no polyether segments, the micromolecular alcohol, the micromolecular amine, the salt and the inorganic base is 1 (0.05-20), (0-10) and (0-10); the small molecular alcohol is selected from C ₁ ～C ₈ The fatty alcohol of (a); the small molecule amine is selected from C ₁ ～C ₈ At least one of a primary amine, a secondary amine, or a tertiary amine; the salt is at least one of metal halide and hydroxyl substituted carboxylate; the inorganic base is at least one selected from alkali metal hydroxide, alkali metal carbonate or alkali metal bicarbonate.

In the technical scheme, the mol ratio of the zwitterionic compound, the surfactant containing polyether segments or no polyether segments, the micromolecular alcohol, the micromolecular amine, the salt and the inorganic alkali is 1 (0.2-20) to (0-15) to (0-5).

In the above technical scheme, the preferable small molecular alcohol is C ₁ ～C ₅ The fatty alcohol of (2).

In the above technical scheme, the preferable small molecule amine is C ₁ ～C ₅ The fatty amine of (1).

In the above technical solution, the metal halide is preferably an alkali metal halide, and is further preferably one of sodium chloride, potassium chloride, sodium bromide and potassium bromide; the hydroxyl-substituted carboxylate is preferably one of sodium glycolate and potassium glycolate.

In the above technical solution, the inorganic base is preferably an alkali metal hydroxide, carbonate or bicarbonate.

An N, N-disubstituted aniline compound represented by the formula (I) in the absence of an ionization reaction

Can be obtained from commercial sources or synthesized by conventional techniques in the art.

The composite surfactant composition for oil displacement can also comprise oil displacement components commonly used in the field, such as an oil displacement polymer, an oil displacement foaming agent, oil displacement mineral substances (such as sodium chloride and potassium chloride), alkaline substances (such as sodium hydroxide, sodium carbonate, sodium bicarbonate, diethanolamine, triethanolamine and other micromolecular organic amines), and organic micromolecular auxiliaries comprise short-chain fatty alcohol, low-carbon-chain ketone, DMSO and the like.

The key effective components of the compound oil-displacing surfactant are (1) and (2), and a person skilled in the art knows that the compound oil-displacing surfactant can be supplied in various forms for transportation, storage or field use, such as a non-aqueous solid form, an aqueous paste form or an aqueous solution form; the aqueous solution form comprises a form of preparing a concentrated solution by water and a form of directly preparing a solution with the concentration required by the on-site oil displacement, for example, a solution with the key active ingredient content of 0.005-0.6 wt% by weight is a suitable form for the on-site oil displacement; the water is not particularly required, and can be deionized water or water containing inorganic mineral substances, and the water containing the inorganic mineral substances can be tap water, oil field formation water or oil field injection water.

In order to solve the second technical problem, the technical scheme adopted by the invention is as follows: the preparation method of the composite surfactant composition in one of the technical problems comprises the following steps:

(a) Preparation of zwitterionic compound:

will be provided with

With ionizing agents R ₂ Uniformly mixing Y in water or alcohol water for quaternization reaction to obtain a water solution or an alcohol water solution of the zwitterion compound shown in the formula (I); wherein the concentration of the alcohol aqueous solution is 0-100 wt% (mass percent of alcohol in the alcohol aqueous solution), and the alcohol is selected from C ₁ ～C ₅ The fatty alcohol of (4);

(b) Preparation of the composite surfactant composition:

mixing the aqueous solution or the alcohol aqueous solution of the zwitterionic compound obtained in the step (a) with a surfactant with a structure shown in a formula (II) and optional small molecular alcohol, small molecular amine, salt and inorganic base according to a required molar ratio to obtain the composite surfactant composition;

wherein the surfactant with the structure shown in the formula (II) is prepared by adopting the following method optionally:

(1) in the presence of a basic catalyst, R ₅ OH sequentially reacts with required amount of ethylene oxide, propylene oxide and ethylene oxide to obtain a polyether compound; mixing a required amount of polyether compound with the aqueous solution or the aqueous solution of the compound containing the aniline structure obtained in the step (a) to obtain the surfactant composition for oil displacement; or obtaining the surfactant composition for oil displacement through (2) further reaction:

(2) mixing the polyether compound obtained in the step (1) with an ionizing agent Y ₀ R ₆ Z and alkali metal hydroxide or alkali metal alkoxide are mixed according to the molar ratio of 1 (0.1-20) to 0.1-20, the mixture reacts for 3-15 hours at the reaction temperature of 50-120 ℃ under stirring, the aqueous solution containing the aniline structure compound or the micromolecule alcohol aqueous solution obtained in the step (a) is added according to the required molar ratio, the temperature is raised to 40-100 ℃, and the mixture is stirred for 1-5 hours, so that the required surfactant composition for oil displacement is obtained; wherein, Y ₀ Selected from chlorine, bromine or iodine;

or: (2) mixing the polyether compound obtained in the step (1) with an ionizing agent Y ₀ R ₆ Z ₀ And alkali metal hydroxide or alkali metal alkoxide are mixed according to the molar ratio of 1 (0.1-20) to (0.1-20), the mixture is stirred and reacts for 3-15 hours at the reaction temperature of 50-120 ℃, water is continuously added for saponification reaction, after the mixture is refluxed for 1-10 hours, the aqueous solution containing the aniline structure compound or the small molecular alcohol obtained in the step (a) is added according to the required molar ratio, the temperature is raised to 40-100 ℃, and the mixture is stirred for 1-5 hours, so that the required surfactant composition is obtained; wherein Z is ₀ Is selected from COOR ₀ ,R ₀ Is selected from C ₁ ～C ₈ Alkyl group of (1).

In the above technical scheme, the surfactant having the structure shown in formula (II) is not limited to the above preparation method, and may be commercially available.

In the above technical scheme, the ionizing agent R in the step (a) ₂ Y is preferably at least one of an alkali metal salt of 3-chloro-2-hydroxypropanesulfonic acid, an alkali metal salt of 2-chloroethanesulfonic acid, 1, 3-propanesultone, chloroacetic acid, and an alkali metal salt of chloroacetic acid.

In the above technical scheme, the small molecule alcohol in the step (a) is preferably C ₁ ～C ₄ The fatty alcohol of (1).

In the above technical scheme, in the step (a)

And R ₂ The molar ratio of Y is preferably 1:1 to 3.

In the above technical solution, the reaction temperature in step (b) (1) is preferably 120 to 160 ℃, the basic catalyst is preferably at least one of potassium hydroxide or anhydrous potassium carbonate, and the pressure is preferably 0.30 to 0.60MPa gauge.

In the above technical solution, the alkali metal hydroxide in step (b) (2) is preferably at least one of potassium hydroxide or sodium hydroxide, the molar ratio of the polyether compound to the ionizing agent and the alkali metal hydroxide or the alkali metal alkoxide is preferably 1 (0.3-3) to (0.2-6), and R is ₀ Preferably C ₁ ～C ₄ Alkyl group of (1).

Y ₀ R ₆ Examples of Z include, but are not limited to, chloroacetic acid, sodium chloroacetate, sodium 1-chloro-2-hydroxypropanesulfonate, and the like.

Y ₀ R ₆ Z ₀ Examples of (d) are, but are not limited to, chloroacetates (e.g., ethyl chloroacetate), bromoacetates (e.g., ethyl bromoacetate), and the like.

In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the application of the composite surfactant composition in the technical scheme in oil displacement of oil fields.

In the above technical scheme, the composite surfactant composition can be applied according to the prior artCan be used independently or can be compounded with common oil field additives for use; as a preferable scheme: the total mineralization degree of stratum saline water of the application-preferred oil reservoir is 5000-200000 mg/L, wherein Ca ²⁺ +Mg ²⁺ 10-15000 mg/L of HCO ₃ ^- Is 0 to 2000mg/L; the viscosity of the crude oil is 1.0-200.0 mPa.s; the formation temperature is 50-120 ℃.

The composite surfactant composition prepared by the invention shows synergistic interaction among the components in the aspects of increasing the surface activity, reducing the critical micelle concentration, improving the crude oil solubilizing capability and the like. Especially, the electrostatic effect of the surfactants with opposite electric properties promotes the association between two kinds of surfactant ions with different charges, and the hydrophobic hydrocarbon chains of the two have certain hydrophobic effect to promote different surfactant molecules to adopt a tighter arrangement mode, so that micelles are easily formed in a solution, and higher surface activity and lower critical micelle concentration than a single surfactant are generated. In addition, the preparation method of the composite surfactant composition adopted by the invention has the advantage that the high-purity ionic surfactant is high in price and can be obtained only by complex purification steps such as extraction, column chromatography and the like, so that the preparation cost of the surfactant for oil displacement is greatly increased. Polyether and halogenated carboxylate or halogenated carboxylic ester are adopted to generate polyether carboxylate or polyether carboxylic ester under the catalysis of alkali metal hydroxide or alkali metal alkoxide, separation is not needed or saponification is directly carried out to obtain polyether carboxylate, a required amount of zwitterion compound water or micromolecule alcohol aqueous solution is added for mixing, micromolecule alcohol or amine in a system can form a composite membrane with a surfactant at an interface and is distributed to an oil phase and a water phase, the properties of the oil phase and the water phase are improved, the oil-water interfacial tension is reduced and the formation of microemulsion is facilitated, the generated inorganic salt has a promotion effect on the interfacial performance and does not need to be removed, the excessive alkali metal hydroxide can neutralize acid substances in crude oil to form soap, the solubilizing capacity of the surfactant on the crude oil is further improved, the oil washing efficiency of the composite surfactant composition is improved, and the green production of the surfactant is realized.

The present invention relates to the content or concentration of the surfactant composition, which refers to the total concentration of the components of the molecular formula (I) and the molecular formula (II) in the above technical solution.

In order to solve the fourth technical problem, the invention adopts the technical scheme that: the composite oil displacement agent comprises the following components in parts by weight:

(1) 1 part of the surfactant composition according to any one of claims 1 to 4 or the surfactant composition prepared by the preparation method according to any one of claims 5 to 6;

(2) 0 to 20 parts of polymer and more than 0 part of polymer;

(3) 0 to 30 portions of alkali.

In the above technical solution, the polymer is not strictly limited, and may be various polymers for oil field oil recovery known to those skilled in the art, such as but not limited to at least one selected from xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, anionic polyacrylamide, temperature-resistant and salt-resistant modified polyacrylamide, hydrophobically associating polymer, and polymer microspheres.

In the technical scheme, the preferable molecular chain of the temperature-resistant and salt-resistant modified polyacrylamide comprises an acrylamide structural unit and a temperature-resistant and salt-resistant monomer structural unit, the molar ratio of the acrylamide structural unit to the temperature-resistant and salt-resistant monomer structural unit is (0.1-40) to 1, the viscosity average molecular weight is 800-2500 ten thousand, and further, the preferable temperature-resistant and salt-resistant monomer is 2-acrylamido-2-methylpropanesulfonic acid; the molecular chain of the hydrophobic association polymer comprises an acrylamide structural unit, a temperature-resistant and salt-resistant monomer structural unit and a hydrophobic monomer structural unit, wherein the molar ratio of the acrylamide structural unit to the temperature-resistant and salt-resistant monomer structural unit to the hydrophobic monomer structural unit is 1: (0.1-40): (0.001-0.05) and the viscosity-average molecular weight is 500-2500 ten thousand.

In the technical scheme, the hydrophobic association polymer is preferably copolymerized by acrylamide, a temperature-resistant salt-resistant monomer or a hydrophobic monomer; the temperature-resistant and salt-resistant modified polyacrylamide is preferably copolymerized by acrylamide and a temperature-resistant and salt-resistant monomer; the temperature-resistant salt-resistant monomer or hydrophobic monomer may be at least one of monomers having a large side group or a rigid side group (e.g., styrenesulfonic acid, N-alkylmaleimide, acrylamido long-chain alkylsulfonic acid, long-chain alkylallyl dimethylammonium halide, 3-acrylamido-3-methylbutyric acid, etc.), monomers having a salt-resistant group (e.g., 2-acrylamido-2-methylpropanesulfonic acid), monomers having a hydrolysis-resistant group (e.g., N-alkylacrylamide), monomers having a group that inhibits hydrolysis of an amide group (e.g., N-vinylpyrrolidone), monomers having a hydrophobic group, etc.), which are well known to those skilled in the art, and is preferably 2-acrylamido-2-methylpropanesulfonic acid, and the hydrophobic monomer is preferably 2-acrylamidododecylsulfonic acid.

In the above technical scheme, the mole ratio of acrylamide to the temperature-resistant salt-resistant monomer to the hydrophobic monomer in the hydrophobically associating polymer is preferably 1: (0.1-40): (0.001-0.05) and the viscosity average molecular weight is 500-2500 ten thousand; more preferably, the molar ratio of the acrylamide to the temperature-resistant salt-resistant monomer to the hydrophobic monomer is 1 to (0.1-20) to (0.001-0.01), and the viscosity average molecular weight is 1200-2200 ten thousand.

In the technical scheme, the mol optimal ratio of the acrylamide to the temperature-resistant salt-resistant monomer in the temperature-resistant salt-resistant modified polyacrylamide is (0.1-40) to 1.

In the above technical scheme, the hydrophobic association polymer is preferably formed by copolymerizing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and 2-acrylamidododecyl sulfonic acid, and the molar ratio of acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and 2-acrylamidododecyl sulfonic acid is preferably 1: (0.1-40): (0.001 to 0.05), more preferably 1: 0.1 to 20: 0.001 to 0.01.

In the technical scheme, the temperature-resistant and salt-resistant modified polyacrylamide is preferably prepared by copolymerizing acrylamide and 2-acrylamido-2-methylpropanesulfonic acid, the molar ratio of the acrylamide to the 2-acrylamido-2-methylpropanesulfonic acid is preferably (0.1-40): 1, and the viscosity average molecular weight of the modified polyacrylamide is preferably 800-2500 ten thousand.

In the above technical scheme, the alkali is an inorganic alkaline substance or an organic alkali.

In the above technical solution, the inorganic basic substance is preferably at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide, and an alkali metal carbonate; it is further preferable that the alkali metal hydroxide is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide, the alkaline earth metal hydroxide is at least one selected from the group consisting of magnesium hydroxide and calcium hydroxide, and the alkali metal carbonate is at least one selected from the group consisting of sodium carbonate and sodium bicarbonate.

In the above technical solution, the organic base preferably contains at least one of a primary amine group, a secondary amine group, a tertiary amine group, and a quaternary ammonium base group in a molecule, and more preferably C ₁ ～C ₈ At least one of short carbon chain organic amines, more preferably at least one of ethanolamine, diethanolamine, triethanolamine or triethylamine.

In the technical scheme, the mass ratio of the surfactant composition to the polymer to the alkali in the composite oil displacement agent is preferably 1 to (0.1-2): (0-5).

The key active ingredients of the oil-displacing agent composition of the present invention are the components 1), 2) and 3), and those skilled in the art know that various supply forms, such as a non-aqueous solid form, or an aqueous paste form, or an aqueous solution form, can be adopted for convenience of transportation and storage or field use; the water solution form comprises a form of preparing a concentrated solution by using water and a form of directly preparing an oil displacement agent with the concentration required by on-site oil displacement; the water has no special requirement, and can be deionized water or water containing inorganic mineral, and the water containing inorganic mineral can be tap water, oil field formation water or oil field injection water.

The oil displacement agent composition of the present invention may further contain oil recovery aids such as a foaming agent, small molecular organic substances (e.g., ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, DMSO, etc.) and the like which are commonly used in the art.

In order to solve the fifth technical problem, the invention adopts the technical scheme that: a preparation method of the composite oil displacement agent according to any one of the four technical solutions to solve the technical problems, comprising the following steps:

(a) Preparation of zwitterionic compound:

will be provided with

With ionizing agents R ₂ Uniformly mixing Y in water or alcohol water for quaternization reaction to obtain an aqueous solution or an alcohol aqueous solution of the zwitterionic compound shown in the formula (I); wherein the concentration of the alcohol aqueous solution is 0-100 wt% (mass percent of alcohol in the alcohol aqueous solution), and the alcohol is selected from C ₁ ～C ₅ The fatty alcohol of (4);

(b) Preparation of surfactant composition:

mixing the aqueous solution or the aqueous alcohol solution of the zwitterionic compound obtained in the step (a) with a surfactant with a structure shown in a formula (II) and optional small-molecule alcohol, small-molecule amine, salt and inorganic base according to a required molar ratio to obtain the composite surfactant composition;

(1) in the presence of a basic catalyst, R ₅ OH sequentially reacts with required amount of ethylene oxide, propylene oxide and ethylene oxide to obtain a nonionic polyether compound with a structure shown in a formula (II); (ii) a Or further reacting by an optional step (2) to obtain an ionic polyether compound having a structure represented by formula (II):

(2) mixing the polyether compound obtained in the step (1) with an ionizing agent Y ₀ R ₆ Z and alkali metal hydroxide or alkali metal alkoxide are mixed according to the molar ratio of 1 (0.1-20) to (0.1-20), and the mixture reacts for 3-15 hours at the reaction temperature of 50-120 ℃ under stirring to obtain the ionic polyether compound; wherein, Y ₀ Selected from chlorine, bromine or iodine;

or: (2) mixing the polyether compound obtained in the step (1) with an ionizing agent Y ₀ R ₆ Z ₀ And alkali metal hydroxide or alkali metal alkoxide in molesMixing (0.1-20) and (0.1-20) according to the proportion of 1, reacting for 3-15 hours at the reaction temperature of 50-120 ℃ under stirring, continuously adding water for saponification reaction, and refluxing for 1-10 hours to obtain the ionic polyether compound; wherein, Y ₀ Selected from chlorine, bromine or iodine, Z ₀ Is selected from COOR ₀ ,R ₀ Is selected from C ₁ ～C ₈ Alkyl groups of (a);

(c) And (c) uniformly mixing the required amount of the surfactant composition obtained in the step (b) with a polymer and alkali in parts by mass to obtain the composite oil-displacing agent.

In the above technical solution, the preferable solution is: the ionizing agent R ₂ Y is preferably at least one of an alkali metal salt of 3-chloro-2-hydroxypropanesulfonic acid, an alkali metal salt of 2-chloroethanesulfonic acid, 1, 3-propanesultone, chloroacetic acid, and an alkali metal salt of chloroacetic acid sulfonating agent, and the alcohol is preferably selected from C ₁ ～C ₄ The fatty alcohol of (4); the described

And R ₂ The preferred molar ratio of Y is 1: 1-3; in the step (1): the reaction temperature is preferably 120-160 ℃, the pressure is preferably 0.3-0.6 MPa gauge pressure, and the alkaline catalyst is preferably at least one of potassium hydroxide or anhydrous potassium carbonate; in the step (2): the alkali metal hydroxide is preferably at least one of potassium hydroxide or sodium hydroxide, the molar ratio of the polyether compound to the ionizing agent and the alkali metal hydroxide or the alkali metal alkoxide is preferably 1 (0.3-3) to (0.2-6), and Y is preferably 1 ₀ Preferably one of chlorine or bromine, R ₀ Preferably C ₁ ～C ₄ Alkyl group of (1).

In order to solve the sixth technical problem, the invention adopts the technical scheme that: a method for enhanced oil recovery comprising the steps of:

(1) Mixing the composite oil displacement agent in any one of the four technical schemes for solving the technical problems with water to obtain an oil displacement system;

(2) And contacting the oil displacement system with an oil-bearing stratum under the conditions that the oil displacement temperature is 25-150 ℃ and the total mineralization is more than 500 mg/L of simulated formation water, and displacing the crude oil in the oil-bearing stratum.

In the technical scheme, the compound oil-displacing agent can be obtained by mixing the components according to required amount by adopting various conventional mixing methods, and is dissolved by water according to required concentration when used for displacing oil to obtain the oil-displacing agent for displacing oil; and according to the concentration of the required composite oil-displacing agent, respectively dissolving the components in the composite oil-displacing agent in water to obtain the composite oil-displacing agent for oil displacement. The water used in the preparation can be tap water, river water, seawater and oil field formation water.

In the technical scheme, the composite oil displacement agent can be applied according to the prior art, can be used independently, and can also be compounded with an oil field common auxiliary agent for use; as a preferable scheme: the total mineralization degree of stratum saline water of the application-preferred oil reservoir is 5000-200000 mg/L, wherein Ca ²⁺ +Mg ²⁺ 10-15000 mg/L of HCO ₃ ^- Is 0 to 2000mg/L; the viscosity of the crude oil is 1.0-200.0 mPa.s; the formation temperature is 50-120 ℃.

The composite oil displacement agent disclosed by the invention has various advantages of the composite surfactant, and the modified polyacrylamide or the hydrophobically associating polyacrylamide endows the polymer with better temperature resistance and salt resistance due to the introduction of the temperature resistance and salt resistance segments. Alkali in the oil displacement agent can also form soap with a surfactant in crude oil, so that the interfacial activity of an oil displacement system is further improved, the adsorption of the surfactant on a stratum is reduced, and the oil displacement agent has a good effect of improving the recovery ratio of the crude oil.

The invention adopts a physical simulation displacement evaluation method to evaluate the effect, and the specific evaluation method comprises the following steps: drying the core at constant temperature to constant weight, and measuring the gas logging permeability of the core; calculating the pore volume of the simulated oil field stratum water saturated core, recording the volume of saturated crude oil by using the crude oil saturated core at the oil displacement temperature, pumping stratum water at the speed of 0.2mL/min, driving until the water content reaches 100%, calculating the recovery ratio of the crude oil improved by water drive, then transferring the oil displacement agent obtained in the step (c) at the speed of 0.15mL/min to 0.1-1 PV (core pore volume), driving the water at the speed of 0.2mL/min to the water content of 100%, and calculating the percentage of the recovery ratio of the crude oil improved on the basis of the water drive.

The method for testing the interfacial tension comprises the following steps: (1) Presetting the temperature to the temperature required by the measurement, and waiting for the temperature to be stable; (2) Injecting external phase liquid, filling the centrifuge tube, injecting internal phase liquid, removing bubbles, and tightly covering; (3) The centrifuge tube is arranged in a rotating shaft of the instrument, the rotating speed is set, and a microscope is adjusted to enable inner phase liquid drops or bubbles in the visual field to be very clear; (4) Reading and calculating, and calculating the interfacial tension according to the formula (1):

γ＝0.25ω ² r ³ Δ ρ (L/D ≧ 4) formula (1);

wherein γ is interfacial tension (mN. M) ^-1 ) Δ ρ is the density difference (Kg. M) between two phases ^-3. ) Omega is angular velocity (rad · s) ^-1 ) R is the minor axis radius (m) of the droplet, L is the major axis (centrifuge tube axial) diameter, and D is the minor axis (centrifuge tube radial) diameter.

The method for testing the static adsorption capacity comprises the following steps: fully mixing a simulated saline solution of a surfactant and an adsorbate according to a certain liquid-solid ratio, oscillating for a certain time at a set temperature and frequency, cooling, performing centrifugal separation, taking supernatant, measuring the concentration of effective components of the surfactant, and calculating the adsorption capacity of the surfactant, wherein the formula (2) is shown:

Γ = W (Co × a-Ce)/m formula (2);

wherein gamma is the static adsorption capacity (mg/g), W is the weight (g) of the surfactant solution, co is the initial concentration (mg/g) of the surfactant solution calculated according to the commodity content, A is the effective content (%) of the surfactant product, the effective concentration (mg/g) of the Ce surfactant solution after adsorption is realized, and m is the mass (g) of the adsorbent.

The test method of the solubilization parameter of the invention comprises the following steps: (1) Firstly, sealing the tip of a 5mL temperature-resistant glass pipette, and intercepting the required length for later use; (2) Preparing a surfactant solution with a certain concentration, measuring a certain volume of aqueous solution by using a pipettor, adding the aqueous solution into a glass pipettor with a sealed tip, simultaneously recording the mass of the added solution by using an analytical balance, adding a certain amount of crude oil or simulated oil (the oil-water ratio is determined according to the experimental requirements) according to the same method, and recording the volume and the mass; recording the water phase and oil phase scales; (3) after the sample is added, sealing the upper opening of the glass pipette; (4) adopting vortex oscillation or rotation to mix evenly; (5) Standing for a period of time at a set temperature, continuously shaking to gradually reach equilibrium, photographing to record the change of a phase state along with time, and calculating a solubilization parameter, wherein the formula is shown in (3):

wherein SP is a solubilization parameter, V _S 、V _O 、V _W The volume of surfactant, the volume of crude oil solubilized by the surfactant, and the volume of water solubilized by the surfactant, respectively.

The composite surfactant composition prepared by the invention has the dosage of 0.01-0.15 wt% in percentage by mass, and can be used for the formation with the temperature of 50-120 ℃, the degree of mineralization of 5000-200000 Mg/L and Mg ²⁺ +Ca ²⁺ 20-12000 mg/l, HCO ₃ ^- The dynamic interfacial tension value between the surfactant aqueous solution and the crude oil is measured to be 0-2000 mg/L of oilfield water and crude oil and can reach 10 ^-2 ～10 ^-4 The mN/m low interfacial tension, the static adsorption capacity less than 2mg/g,4wt% of surfactant can well emulsify the crude oil, the maximum solubilization parameter is 23.7, and a better technical effect is achieved.

The composite oil displacement agent is used for simulated brine and crude oil with the formation temperature of 50-120 ℃ and the mineralization degree of 5000-200000 mg/L, the oil displacement agent is formed by 0.01-0.15 wt% of surfactant composition, 0-0.3 wt% of polymer and 0-1.2 wt% of alkali according to the mass percentage, the apparent viscosity of the oil displacement agent aqueous solution is measured, and the dynamic interfacial tension value between the oil displacement agent aqueous solution and the oil field dehydrated crude oil can reach 10 ^-2 ～10 ^-4 mN/m. The evaluation in a physical simulation displacement laboratory shows that the oil displacement agent can improve the crude oil recovery rate on the basis of water displacement by up to 26.38 percent, and obtains better technical effect.

Drawings

The zwitterionic compound prepared by the invention and the polyether-containing fragmentThe surfactant can be applied to American Nicolet-5700 spectrometer, and infrared spectrum analysis (scanning range 4000-400 cm) ^-1 ) And determining the chemical structure of the tested sample so as to achieve infrared characterization of the compound.

FIG. 1 is an infrared spectrum of (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt. 2918.4cm of it ^-1 And 2850.4cm ^-1 Is a characteristic peak of C-H expansion of methyl and methylene, 1629.9cm ^-1 C = O absorption peak of stretching vibration, 1546.8cm ^-1 And 1602.8cm ^-1 Is the stretching vibration peak of benzene ring, 1465.1cm ^-1 The C-N flexural vibration absorption peak is 1167.0cm ^-1 And 1239.1cm ^-1 Is the C-N stretching vibration peak, 700.0-800.0 cm ^-1 Is the in-plane rocking absorption peak of CH plane in the benzene ring. FIG. 2 shows the alcohol mixture (C) _14～18 ) Infrared spectrum of polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether acetic acid. Wherein, 2922.0cm ^-1 And 2853.0cm ^-1 Is a characteristic peak of C-H stretching of methyl and methylene, 1757.2cm ^-1 Is the C = O stretching vibration characteristic peak in carboxylic acid, 1457.2cm ^-1 Out-of-plane bending vibration peak of OH, 1248.2cm ^-1 1098.1cm is a C-O stretching vibration peak ^-1 Characteristic absorption peaks of C-O-C ether bonds.

FIG. 3 is a graph of oil-water interfacial tension of 0.15% surfactant after aging for various periods of time.

Fig. 4 is a flow chart of an indoor core displacement experiment.

The invention is further illustrated by the following examples.

Detailed Description

[ example 1 ]

(a) Preparation of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt

359.0 g (1 mol) of N-octadecyl-N-methylaniline are mixed with 174.8 g (1.5 mol) of sodium chloroacetate and 750 g of 50wt% aqueous ethanol solution in a mixer equipped with mechanical stirring and at a temperature ofA2000 ml four-necked flask equipped with a reflux condenser was heated to reflux and reacted for 8 hours, and the reaction was stopped. Taking a small amount of reaction liquid for HPLC analysis, dissolving (the ratio of (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt to N-octadecyl-N-methylaniline is 96.7, 3.3, desalting for multiple times by using ethyl acetate, removing an organic solvent to obtain the zwitterion surfactant, and performing infrared spectrum analysis by using a liquid membrane method (the scanning range is 4000-400 cm) by using an American Nicolet-5700 infrared spectrometer ^-1 ) The infrared spectrum is shown in figure 1. The remaining samples were left untreated and were ready for use.

(b) Preparation of composite surfactant composition S01

RO(CH ₂ CH ₂ O) ₂ (CHCH ₃ CH ₂ O) ₁₂ (CH ₂ CH ₂ O) ₂ CH ₂ COOH.N(C ₂ H ₅ ) ₃

Wherein the carbon chain distribution of R is as follows: c ₁₄ ＝5.53％、C ₁₆ ＝62.93％、C ₁₈ ＝31.54％。

(1) Into a 2L pressure reactor equipped with a stirring device was charged 248 g (1 mol) of a mixed alcohol (C) _14～18 ) 6.5 g of potassium hydroxide, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 90.2 g (2.05 mol) of ethylene oxide, slowly introducing 707.6 g (12.2 mol) of propylene oxide at 150 ℃, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the propylene oxide, slowly introducing 90.2 g (2.05 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out to obtain mixed alcohol (C) _14～18 ) 1080.8 g of polyoxyethylene (2), polyoxypropylene (12) and polyoxyethylene (2) ether, the yield was 96.5%.

(2) Adding the mixed alcohol (C) synthesized in step (b) (1) into a 5000-ml reaction flask equipped with a mechanical stirrer, a thermometer and a reflux condenser while stirring _14～18 ) 560.0 g (0.5 mol) of polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether and 61.6 g (1.1 mol) of potassium hydroxide were added dropwise slowly to 91.9 g (0.55 mol)) Ethyl bromoacetate, controlling the reaction temperature to be 90 ℃, reacting for 5 hours, cooling, adding 1200 g of water and 100 g of 95% ethanol, continuously heating to reflux reaction for 3 hours, cooling to 30 ℃, adding concentrated hydrochloric acid to adjust the pH to be =3, taking a small amount of benzene for extraction, washing, separating an organic layer, decompressing and removing the benzene to obtain a product, applying a Nicolet-5700 infrared spectrometer to perform infrared spectroscopy by a liquid film method (the scanning range is 4000-400 cm) ^-1 ) The infrared spectrum is shown in figure 2.. The remaining reaction solution was neutralized with 55.5 g (0.55 mol) of triethylamine to produce carboxylic acid, and then an aqueous solution of ethanol containing 834.0 g (2.0 mol) of (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt was added to obtain the desired composite surfactant composition S01.

[ example 2 ]

(a) Preparation of (N-carboxymethyl-N-carboxymethyloxyethyl-N-dodecyl) phenylammonium inner salt

359.0 g (1 mol) of N-dodecyl-N-hydroxyethyl aniline, 60.0 g (1.5 mol) of sodium hydroxide and 500 ml of benzene are mixed in a 5000 ml four-neck flask provided with a mechanical stirring device, a thermometer and a reflux condenser tube, the mixture is heated to 50 ℃, 174.8 g (1.5 mol) of sodium chloroacetate is added into a reaction bottle for four times, the mixture is heated to reflux reaction for 6 hours after the addition, the solvent benzene is evaporated under reduced pressure, 1500g of water is added into the mixture after the mixture is cooled to room temperature, the mixture is uniformly stirred, the mixture is heated to 75 ℃, 116.5 g (1.0 mol) of sodium chloroacetate is added into the mixture for three times, the reaction is continued for 5 hours, and the reaction is stopped. A small amount of reaction liquid is taken for HPLC analysis, the ratio of (N-carboxymethyl-N-carboxymethyloxyethyl-N-dodecyl) phenyl ammonium inner salt to N-dodecyl-N-hydroxyethylaniline is 89.6.

(b) Preparation of composite surfactant composition S02

(1) Adding 262 g (1 mol) of dodecylphenol, 4 g of potassium hydroxide and 2.6 g of anhydrous potassium carbonate into a pressure reactor provided with a stirring device, heating to the reaction temperature of 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 701.8 g (12.1 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.50MPa, cooling after the propylene oxide reaction is finished, slowly introducing 88.0 g (2.0 mol) of ethylene oxide at 130 ℃, and controlling the pressure to be less than or equal to 0.60MPa. After the reaction, the same procedure as in example 1 was repeated to give 1015.7 g of dodecylphenol polyoxypropylene (12) polyoxyethylene (2) ether in 97.1% yield.

(2) Adding 52.3 g (0.05 mol) of the dodecylphenol polyoxypropylene (12) polyoxyethylene (2) ether synthesized in the step (b) (1) and 8.0 g (0.2 mol) of sodium hydroxide into a 1000 ml reaction bottle with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, slowly dripping 8.0 g (0.065 mol) of ethyl chloroacetate, controlling the reaction temperature to 90 ℃ for reaction for 4 hours, cooling, adding 80 g of water, and continuously heating until the reflux reaction is carried out for 3 hours. After cooling to 40 ℃, 399.0 g (0.95 mol) of an aqueous solution of the inner salt of (N-carboxymethyl-N-carboxymethyloxyethyl-N-dodecyl) phenylammonium was added and stirring was continued at 40 ℃ for 4 hours to obtain the desired composite surfactant composition S02.

[ example 3 ]

(a) Preparation of (N-carboxymethyl-N-dodecyl-N-methyl) phenyl ammonium inner salt

274.0 g (1 mol) of N-dodecyl-N-methylaniline, 139.8 g (1.2 mol) of sodium chloroacetate and 500g of 5wt% aqueous isopropanol were mixed in a 2000-ml four-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux for 6 hours to stop the reaction. Taking a small amount of reaction liquid for HPLC analysis, wherein the ratio of (N-carboxymethyl-N-dodecyl-N-methyl) phenyl ammonium inner salt to N-dodecyl-N-methylaniline is 94.7, and the rest samples are not processed for later use.

(b) Preparation of anionic and complex surfactant composition S03

(1) Adding 303 g (1 mol) of abietic acid and 5.1 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 145 ℃, slowly introducing 224.4 g (5.1 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.60MPa after the reaction is finished, cooling to 90 ℃, removing low-boiling-point substances in vacuum, cooling, neutralizing and dehydrating to obtain 499.5 g of abietic acid polyoxyethylene (5) ether ester, wherein the yield is 95.5%.

(2) Adding 261.5 g (0.5 mol) of rosin acid polyoxyethylene (5) ether ester synthesized in the step (b) (1) and 60.0 g (1.5 mol) of sodium hydroxide into a 2000 ml reaction bottle with a mechanical stirring, a thermometer and a reflux condenser pipe, slowly dropping 135.8 g (0.75 mol) of n-propyl bromoacetate, controlling the reaction temperature to be 95 ℃ for reaction for 5 hours, cooling, adding 400 g of water and 75 g of 95% isopropanol, and continuously heating until reflux reaction is carried out for 3 hours. After cooling to 40 deg.C, an aqueous isopropanol solution containing 249.1 g (0.75 mole) of the inner salt of (N-carboxymethyl-N-dodecyl-N-methyl) phenylammonium was added and stirring was continued at 45 deg.C for 3 hours to obtain the desired composite surfactant composition S03.

[ example 4 ]

(a) Preparation of (N-carboxymethyl-N, N-dimethyl) -4-hexadecyl phenyl ammonium inner salt

345.0 g (1 mol) of N, N-dimethyl- (4-hexadecyl) aniline, 128.2 g (1.1 mol) of sodium chloroacetate and 600 g of a 15wt% aqueous isopropanol solution were mixed in a 2000-ml four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux for 9 hours to stop the reaction. A small amount of the reaction solution was taken for HPLC analysis, the ratio of (N-carboxymethyl-N, N-dimethyl) -4-hexadecylphenylammonium inner salt to N, N-dimethyl- (4-hexadecyl) aniline was 91.2, and the rest samples were left untreated and used.

(b) Preparation of composite surfactant composition S04

RO(CHCH ₃ CH ₂ O) ₁₂ (CH ₂ CH ₂ O) ₂ CH ₂ COONa

Wherein R = iso-C ₁₃ H ₂₇ 。

(1) Adding 200 g (1 mol) of isomeric tridecanol, 4 g of potassium hydroxide and 2.6 g of anhydrous potassium carbonate into a pressure reactor provided with a stirring device, heating to the reaction temperature of 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 701.8 g (12.1 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.50MPa, cooling after the propylene oxide reaction is finished, slowly introducing 88.0 g (2.0 mol) of ethylene oxide at 130 ℃, and controlling the pressure to be less than or equal to 0.60MPa. After the reaction, the temperature was lowered to 90 ℃ and the low boiling point substance was removed in vacuo, followed by cooling, neutralization and dehydration to give 955.5 g of isotridecanol polyoxypropylene (12) polyoxyethylene (2) ether in a yield of 97.1%.

(2) Adding 492 g (0.5 mol) of isomeric tridecanol polyoxypropylene (12) polyoxyethylene (2) ether synthesized in the step (b) (1) and 60.0 g (1.5 mol) of sodium hydroxide into a 5000 ml reaction bottle provided with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, slowly dripping 79.6 g (0.65 mol) of ethyl chloroacetate, controlling the reaction temperature to be 90 ℃ for reaction for 4 hours, cooling, adding 700 g of water and 50 g of 95% ethanol, and continuously heating until reflux reaction is carried out for 5 hours. After cooling to 40 deg.C, an aqueous isopropanol solution containing 80.6 g (0.2 mole) of the inner salt of (N-carboxymethyl-N, N-dimethyl) -4-hexadecylphenylammonium was added and stirring was continued at 40 deg.C for 4 hours to obtain the desired composite surfactant composition S04.

[ example 5 ]

(a) Preparation of (N- (2-hydroxy-3-propanesulfonic acid) -N-methyl-N-hexadecyl) -4-methylphenyl ammonium inner salt

345.0 g (1 mol) of N-hexadecyl-N-methyl-4-methylaniline, 357.3 g (1.8 mol) of sodium 3-chloro-2-hydroxypropanesulfonate and 800 g of a 25wt% aqueous ethanol solution were mixed in a 2000-ml four-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux reaction for 12 hours to stop the reaction. A small amount of the reaction solution was taken for HPLC analysis, the ratio of (N- (2-hydroxy-3-propanesulfonic acid) -N-methyl-N-hexadecyl) -4-methylphenylammonium inner salt to N-hexadecyl-N-methyl-4-methylaniline was 87.5, and the rest samples were left untreated and used.

(b) Preparation of composite surfactant composition S05

(1) 276 g (1 mol) of dodecyl benzyl alcohol and 4.6 g of potassium hydroxide are added into a 2L pressure reactor provided with a stirring device, when the temperature is heated to 80-90 ℃, a vacuum system is started, dehydration is carried out for 1 hour under high vacuum, then nitrogen is used for replacing for 3-4 times, the reaction temperature of the system is adjusted to 140 ℃, 178.2 g (4.05 mol) of ethylene oxide is slowly introduced, 469.8 g (8.1 mol) of propylene oxide is slowly introduced at 150 ℃, the pressure is controlled to be less than or equal to 0.60MPa, after the reaction of the propylene oxide is finished, the temperature is adjusted to 140 ℃, 44.0 g (1.0 mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.40MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, thus obtaining 925.4 g of dodecyl benzyl alcohol polyoxyethylene (4), polyoxypropylene (8) and polyoxyethylene (1) ether, and the yield is 96.4%.

(2) And (b) adding 96.0 g (0.1 mol) of the dodecyl benzyl alcohol polyoxyethylene (4) polyoxypropylene (8) polyoxyethylene (1) ether synthesized in the step (b) (1) and 9.6 g (0.25 mol) of sodium hydroxide into a 5000-ml reaction bottle with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, slowly dripping 21.7 g (0.12 mol) of isopropyl bromoacetate, controlling the reaction temperature to be 90 ℃ for reaction for 4 hours, cooling, adding 160 g of water, and continuously heating until the reflux reaction is carried out for 3 hours. After cooling to 40 ℃, an aqueous ethanol solution containing 434.7 g (0.9 mol) of (N- (2-hydroxy-3-propanesulfonic acid) -N-methyl-N-hexadecyl) -4-methylphenylammonium inner salt was added, and stirring was continued at 45 ℃ for 3 hours to obtain the desired composite surfactant composition S05.

[ example 6 ]

(a) Preparation of (N-carboxymethyl-N, N-dimethyl) phenyl ammonium inner salt

121.0 g (1 mol) of N, N-dimethylaniline, 139.8 g (1.2 mol) of sodium chloroacetate and 500g of a 5wt% aqueous solution of isopropanol were mixed in a 2000 ml four-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux for 8 hours to stop the reaction. And (3) taking a small amount of reaction liquid for HPLC analysis, wherein the ratio of (N-carboxymethyl-N, N-dimethyl) phenyl ammonium inner salt to N, N-dimethylaniline is 95.1.

(b) Preparation of composite surfactant composition S06

(1) Adding 242 g (1 mol) of isomeric hexadecanol, 8 g of potassium hydroxide and 5.5 g of anhydrous potassium carbonate into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 178.2 g (4.05 mol) of ethylene oxide, slowly introducing 350.9 g (6.05 mol) of propylene oxide at 150 ℃, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the propylene oxide, slowly introducing 88.0 g (2.0 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa. After the reaction, the temperature was reduced to 90 ℃, the low boiling point material was removed in vacuum, and after cooling, neutralization and dehydration were carried out, so that 894.9 g of isomeric hexadecanol polyoxyethylene (4) polyoxypropylene (6) polyoxyethylene (2) ether was obtained, with a yield of 94.2%.

(2) Adding 475.0 g (0.5 mol) of isomeric hexadecyl alcohol polyoxyethylene (4) polyoxypropylene (6) polyoxyethylene (2) ether synthesized in the step (b) (1) and 87.0 g (1.5 mol) of potassium hydroxide into a 2000 ml reaction bottle provided with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, slowly dropping 102.4 g (0.75 mol) of isopropyl chloroacetate, controlling the reaction temperature to be 100 ℃, reacting for 3 hours, cooling, adding 600 g of water, and continuously heating until the reflux reaction is carried out for 3 hours. After cooling to 40 deg.C, an aqueous isopropanol solution containing 9.0 g (0.05 mole) of the inner salt of (N-carboxymethyl-N, N-dimethyl) phenylammonium was added and stirring was continued at 40 deg.C for 5 hours to obtain the desired composite surfactant composition S06.

[ example 7 ]

(a) Preparation of (N-carboxymethyl-N, N-diethyl) phenyl ammonium inner salt

144.0 g (1 mol) of N, N-diethylaniline, 151.5 g (1.3 mol) of sodium chloroacetate, and 500g of a 15wt% aqueous solution of isopropanol were mixed in a 2000 ml four-necked flask equipped with a mechanical stirrer, a thermometer, and a reflux condenser, and the mixture was heated to reflux reaction for 8 hours to stop the reaction. And (3) taking a small amount of reaction liquid for HPLC analysis, wherein the ratio of the (N-carboxymethyl-N, N-diethyl) phenyl ammonium inner salt to the N, N-diethylaniline is 92.5, and the rest samples are not processed and are reserved.

(b) Preparation of composite surfactant composition S07

RO(CHCH ₃ CH ₂ O) ₁₂ (CH ₂ CH ₂ O) ₂ CH ₂ COOH.N(C ₂ H ₅ ) ₃

Wherein, the carbon chain distribution of R is as follows: c ₁₄ ＝5.53％、C ₁₆ ＝62.93％、C ₁₈ ＝31.54％。

(1) Into a 2L pressure reactor equipped with a stirring device was charged 248 g (1 mol) of a mixed alcohol (C) _14～18 ) 6.5 g of potassium hydroxide, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, and adjusting the reaction temperature of the system707.6 g (12.2 mol) of propylene oxide is slowly introduced at the temperature of 150 ℃, the pressure is controlled to be less than or equal to 0.60MPa, the temperature is adjusted to 140 ℃ after the propylene oxide reaction is finished, and 90.2 g (2.05 mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.40MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out to obtain mixed alcohol (C) _14～18 ) 995.9 g of polyoxypropylene (12) polyoxyethylene (2) ether, and the yield is 96.5%.

(2) Adding the mixed alcohol (C) synthesized in the step (b) (1) into a 5000 ml reaction bottle provided with a mechanical stirring device, a thermometer and a reflux condenser pipe under stirring _14～18 ) Polyoxypropylene (12) polyoxyethylene (2) ether 516.0 g (0.5 mol) and 61.6 g (1.1 mol) of potassium hydroxide were added dropwise slowly 91.9 g (0.55 mol) of ethyl bromoacetate, the reaction temperature was controlled at 90 ℃ to react for 5 hours, 600 g of water and 100 g of 95% ethanol were added after cooling, the mixture was further heated to reflux reaction for 3 hours, cooled to 30 ℃, concentrated hydrochloric acid was added to adjust pH =3, 55.5 g (0.55 mol) of triethylamine was added to neutralize the produced carboxylic acid, and an aqueous isopropanol solution containing 24.8 g (0.12 mol) of (N-carboxymethyl-N, N-diethyl) phenylammonium inner salt was added to obtain the desired composite surfactant composition S07.

[ example 8 ]

(a) Preparation of (N-carboxymethyl-N-methyl-N-ethyl) phenylammonium inner salt

130.0 g (1 mol) of N-methyl-N-ethylaniline, 151.5 g (1.3 mol) of sodium chloroacetate, and 500g of a 15wt% aqueous solution of isopropanol were mixed in a 2000-ml four-necked flask equipped with a mechanical stirrer, a thermometer, and a reflux condenser, and the mixture was heated to reflux reaction for 6.5 hours, and the reaction was stopped. And (3) taking a small amount of reaction liquid for HPLC analysis, wherein the ratio of (N-methyl-N-ethyl) phenyl ammonium inner salt to N-methyl-N-ethyl aniline is 93.7.

(b) Preparation of composite surfactant composition S08

(1) Adding 262 g (1 mol) of dodecylphenol, 4 g of potassium hydroxide and 2.6 g of anhydrous potassium carbonate into a pressure reactor provided with a stirring device, heating to the reaction temperature of 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 121.8 g (2.1 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.50MPa, cooling after the propylene oxide reaction is finished, slowly introducing 312.4 g (7.1 mol) of ethylene oxide at 130 ℃, and controlling the pressure to be less than or equal to 0.60MPa. After the reaction, the reaction mixture was worked up in the same manner as in example 1 to obtain 665.8 g of dodecylphenol polyoxypropylene (2) polyoxyethylene (7) ether, the yield was 97.2%.

(2) 342.5 g (0.5 mol) of the dodecylphenol polyoxypropylene (2) polyoxyethylene (7) ether synthesized in the step (b) (1) and 80.0 g (2.0 mol) of sodium hydroxide are added into a 5000 ml reaction bottle provided with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, 79.6 g (0.65 mol) of ethyl chloroacetate is slowly dropped into the reaction bottle, the reaction temperature is controlled to be 90 ℃ for reaction for 4 hours, 600 g of water and 100 g of 50% isopropanol are added after cooling, and the reaction bottle is continuously heated until reflux reaction is carried out for 3 hours. Cooled to 40 deg.C, an aqueous isopropanol solution containing 56.4 g (0.3 mole) of the (N-methyl-N-ethyl) phenylammonium inner salt was added and stirring continued at 40 deg.C for 4 hours to give the desired composite surfactant composition S08.

[ example 9 ] A method for producing a polycarbonate

(a) The same as [ example 1 ] a.

(b) Preparation of composite surfactant composition S09

Preparation of Mixed alcohol (C) in the same manner as in [ example 1 ] _14～18 ) Polyoxyethylene (2) polyoxypropylene (1)2) Polyoxyethylene (2) ether.

Adding the mixed alcohol (C) synthesized in step (b) (1) into a 5000-ml reaction flask equipped with a mechanical stirrer, a thermometer and a reflux condenser while stirring _14～18 ) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether 560.0 g (0.5 mol), 56.0 g (1.0 mol) potassium hydroxide and 1000 ml benzene were reacted at 70 ℃ for 4 hours, then cooled to 87.4 g (0.75 mol) sodium chloroacetate was slowly added, refluxed for 8 hours, cooled to 30 ℃, concentrated hydrochloric acid was added to adjust pH =3, benzene was evaporated under reduced pressure, 55.5 g (0.55 mol) triethylamine was added to neutralize the resulting carboxylic acid, and an aqueous ethanol solution containing 834.0 g (2.0 mol) (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt was added to obtain the desired composite surfactant composition S09.

[ example 10 ] A method for producing a polycarbonate

The same as [ example 1 ] except that 560.0 g (0.5 mol) of the mixed alcohol (C) was used _14～18 ) The polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether was added to 600 g of water, 73.0 g (1.0 mol) of N-butylamine and an aqueous ethanol solution containing 166.8 g (0.4 mol) of (N-carboxymethyl-N-octadecyl-N-methyl) anilinium inner salt without further reaction to obtain the desired complex surfactant composition S10.

[ example 11 ]

The same as in example 1, except that the alcohol solvent was distilled off under reduced pressure at the end of the reaction in the steps (a) and (b), to obtain the desired surfactant composition S11.

[ example 12 ]

The same as [ example 1 ] except that the mixed alcohol (C) was replaced with 0.5 mol of coconut oil acid triethylamine salt _14～18 ) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether acetic acid triethylamine salt, and an aqueous ethanol solution containing 834.0 g (2.0 mol) of (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt was added to obtain the desired complex surfactant composition S12.

[ example 13 ]

The same as [ example 1 ] except that the mixed alcohol (C) was replaced with 0.5 mol of triethylamine dodecylsulfonate _14～18 ) Polyethylene oxide(2) Polyoxypropylene (12) polyoxyethylene (2) ether acetic acid triethylamine salt was added to the solution, and an aqueous solution of ethanol containing 417.0 g (1.0 mol) of (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt was added to obtain the desired complex surfactant composition S13.

[ example 14 ]

(a) The same as [ example 6 ] a.

(b) Preparation of composite surfactant composition S14

(1) 242 g (1 mol) of isomeric hexadecanol, 8 g of potassium hydroxide and 5.5 g of anhydrous potassium carbonate are added into a 2L pressure reactor provided with a stirring device, a vacuum system is started when the temperature is heated to 80-90 ℃, the dehydration is carried out for 1 hour under high vacuum, then nitrogen is used for replacing for 3-4 times, the reaction temperature of the system is adjusted to 140 ℃, 178.2 g (4.05 mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.40MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, so that 397.9 g of isomeric hexadecanol polyoxyethylene (4) ether is obtained, and the yield is 95.2%.

(2) In a 2000 ml reaction flask equipped with a mechanical stirrer, thermometer and reflux condenser, the isomeric hexadecyl polyoxyethylene (4) ether 4209.0 g (0.5 mol), 87.0 g (1.5 mol) potassium hydroxide and 500 ml toluene synthesized in step (b) (1) were added under stirring, heated to 75 ℃ and reacted for 4 hours, cooled to 60 ℃, 299.2 g (1.5 mol) sodium 3-chloro-2-hydroxypropanesulfonate was slowly added, the reaction temperature was controlled to 90 ℃ and reacted for 8 hours, after cooling, 600 g water was added, an aqueous isopropanol solution containing 36.0 g (0.2 mol) of an aqueous isopropanol solution of (N-carboxymethyl-N, N-dimethyl) phenylammonium inner salt was added, and stirring was continued at 40 ℃ for 5 hours to obtain the desired composite surfactant composition S14.

[ example 15 ]

And (3) performance experiments of the composite surfactant composition as an oil displacement agent.

Simulated water with different salt contents is prepared, and the composition is shown in table 1. The crude oil used in the experiment was used in the oil field, and the properties of the crude oil are shown in Table 2, after dehydration.

The phase state experiment can well reflect the solubilizing capability of the surfactant to the crude oil, and the solubilizing parameters of the surfactant to the crude oil and the optimal salt content of the surfactant are obtained. The experimental process is as follows: first, 4.0 wt.% aqueous solutions of different salt contents (1) were prepared ^# ～9 ^# Simulated water), adding 2.5mL of the solution into a 5mL pipette with one end sealed, adding 2.5mL of dehydrated crude oil (oil-water volume ratio = 1.

The static adsorption test is mainly based on the research of adsorption loss amount of the surfactant on the formation rock core, and the economy and the formability of the surfactant synthesized in the embodiment in the field application of improving the crude oil recovery rate are explored. The experimental process is as follows: mixing 3g of simulated saline solution of the surfactant and 1g of clay-containing quartz sand, oscillating for 24h at a set temperature, cooling, performing centrifugal separation, taking supernatant, measuring the concentration of effective components of the surfactant by using High Performance Liquid Chromatography (HPLC), and calculating the adsorption amount of the surfactant in mg/g, wherein the result is shown in Table 3. Wherein, the clay-containing quartz sand comprises the following components: 10wt% of kaolin and 90wt% of quartz sand with 100-200 meshes.

The composite surfactant composition was dissolved in corresponding simulated water, and the oil-water interfacial tension of the surfactant solution on crude oil was measured, and the results are shown in table 4. Filling 0.15wt% of composite surfactant composition simulated saline solution into a 20 ml anbei bottle, sealing and placing into an oven, measuring the oil-water interfacial tension after different aging times, and finding that the oil-water interfacial tension can still maintain 10 after aging ^-3 ～10 ^-4 Ultra low values of mN/m are shown in FIG. 3. The oil-water interfacial tension (IFT) was measured by a model TX500 rotary droplet interfacial tensiometer manufactured by Texas university, USA and a SVT 20 high temperature rotary droplet interfacial tensiometer manufactured by Dataphysics.

[ COMPARATIVE EXAMPLE 1 ]

Octadecyl benzyl methyl betaine

Octadecyl dimethyl betaine

The same as in example 1 except that (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt was replaced with commercially available octadecyl benzyl methyl betaine or octadecyl dimethyl betaine, and the rest was the same, surfactant compositions S15 and S16 were obtained. The performance test was carried out as in example 15, and the results are shown in Table 5.

[ COMPARATIVE EXAMPLE 2 ]

RO(CH ₂ CH ₂ O) ₄ (CHCH ₃ CH ₂ O) ₁₂ CH ₂ COOH.N(C ₂ H ₅ ) ₃

The same as in example 1 except that in step (b) (1), 180.4 g (4.1 mol) of ethylene oxide was introduced followed by 707.6 g (12.2 mol) of propylene oxide to give the isomeric tridecanol polyoxyethylene (4) polyoxypropylene (12) ether, and the same applies to give surfactant composition S17. The performance test was carried out as in example 15, and the results are shown in Table 5.

[ COMPARATIVE EXAMPLE 3 ]

The same as example 1, except that the reaction with propylene oxide and ethylene oxide was not carried out successively in steps, but carried out in one step after mixing, i.e., a mixture of 707.6 g (12.2 mol) of propylene oxide and 180.4 g (4.1 mol) of ethylene oxide was slowly introduced at 110 to 150 ℃ under a controlled pressure of not more than 0.60MPa, and the rest was the same, S18 was obtained, and the results of the performance test were as shown in Table 5 in example 15.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

[ example 16 ]

359.0 g (1 mol) of N-octadecyl-N-methylaniline, 174.8 g (1.5 mol) of sodium chloroacetate and 750 g of 50wt% aqueous ethanol were mixed in a 2000 ml four-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux for 8 hours to stop the reaction. Taking a small amount of reaction liquid for HPLC analysis, dissolving and desalting (the ratio of (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt to N-octadecyl-N-methylaniline is 96.7: 3.3) with ethyl acetate for multiple times, removing the organic solvent to obtain the zwitterionic surfactant, and performing infrared spectrum analysis (the scanning range is 4000-400 cm) by a liquid film method by using an American Nicolet-5700 infrared spectrometer (the scanning range is 4000-400 cm) ^-1 ) The infrared spectrum is shown in figure 1. The remaining samples were left untreated and were ready for use.

(b) Preparation of composite surfactant composition S01

(1) Into a 2L pressure reactor equipped with a stirring device was charged 248 g (1 mol) of a mixed alcohol (C) _14～18 ) 6.5 g of potassium hydroxide, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 90.2 g (2.05 mol) of ethylene oxide, slowly introducing 707.6 g (12.2 mol) of propylene oxide at 150 ℃, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the propylene oxide, slowly introducing 90.2 g (2.05 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out to obtain mixed alcohol (C) _14～18 ) 1080.8 g of polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether, the yield was 96.5%.

(2) Adding the mixed alcohol (C) synthesized in step (b) (1) into a 5000-ml reaction flask equipped with a mechanical stirrer, a thermometer and a reflux condenser while stirring _14～18 ) 560.0 g (0.5 mol) of polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether and 61.6 g (1.1 mol) of potassium hydroxide are slowly dropped into 91.9 g (0.55 mol) of ethyl bromoacetate, the reaction temperature is controlled to be 90 ℃ for reaction for 5 hours, 1200 g of water and 100 g of 95% ethanol are added after cooling, the mixture is continuously heated to reflux reaction for 3 hours, the mixture is cooled to 30 ℃, concentrated hydrochloric acid is added to adjust the pH to =3, a small amount of benzene is taken for extraction, an organic layer is separated after water washing, benzene is removed under reduced pressure to obtain a product, an American Nicolet-5700 infrared spectrometer is used for infrared spectrum analysis by a liquid-film method (the scanning range is 4000-400 cm) ^-1 ) The infrared spectrum is shown in figure 2.. The remaining reaction solution was neutralized with 55.5 g (0.55 mol) of triethylamine, and 834.0 g (2.0 mol) of a solution containing acetic acid was added) (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt ethanol aqueous solution to obtain the required composite surfactant composition S01.

Simulated water with different salt contents is prepared, and the composition is shown in table 1. Crude oil was used for the experiments in the oil field, the properties of which are shown in table 2, after dehydration.

The phase state experiment can well reflect the solubilizing capability of the surfactant to the crude oil, and the solubilizing parameters of the surfactant to the crude oil and the optimal salt content of the surfactant are obtained. The experimental process is as follows: first, 4.0wt% aqueous surfactant solutions (1) of different salt contents were prepared ^# ～9 ^# Simulated water), adding 2.5mL of the solution into a 5mL pipette with one end sealed, adding 2.5mL of dehydrated crude oil (oil-water volume ratio = 1.

Mixing 3g of surfactant simulated aqueous solution and 1g of clay-containing quartz sand, oscillating for 24h, cooling, centrifuging, taking supernatant to measure the adsorption capacity in mg/g, and obtaining the result shown in Table 3. Wherein, the adsorption capacity is determined by a TOC method, and the clay-containing quartz sand comprises the following components: 10wt% of kaolin and 90wt% of quartz sand with 100-200 meshes.

(c) Performance test of oil-displacing agent

(1) Preparation of oil-displacing agent aqueous solution

Preparing an S01 surfactant composition, a modified polyacrylamide polymer (P1, the molar ratio of the copolymer AM/AMPS =1/0.05, and the viscosity average molecular weight of 2500 ten thousand) and a diethanol amine aqueous solution by using simulated water, and mixing and diluting according to a required proportion to obtain a uniform oil displacement agent.

(2) The viscosity and the oil-water interfacial tension of the oil-displacing agent were measured and compared with those of S01 and P1, as shown in Table 6. Wherein the apparent viscosity is measured by a HAAKE MARS type III rotational rheometer, and the interfacial tension is measured by a TX500 type rotational droplet interfacial tension meter manufactured by Texas university, USA, and a SVT 20 high temperature rotational droplet interfacial tension meter manufactured by Datophysics.

(3) And drying the artificial core at constant temperature to constant weight, measuring the average diameter and the length of the core, weighing the dry weight of the core, and measuring the gas logging permeability of the core. The pore volume was tested with the above simulated brine saturated core. And (4) recording the volume of the saturated crude oil by using the oil field dehydrated crude oil saturated core. At the temperature of 75 ℃,11# simulation water is used for driving until the water content of produced liquid reaches 100%, the recovery ratio of the crude oil improved by water driving is calculated, after 0.3PV (core pore volume) oil displacement agent is injected, the water is driven until the water content reaches 100%, the percentage of the crude oil improved on the basis of water driving is calculated, and meanwhile, the comparison with the injection of the same PV surfactant and polymer is shown in the table 6. The flow of the simulated core displacement test used is shown in fig. 4. The viscosity of the dehydrated crude oil is 2.5mPa.s.

[ example 17 ]

(b) Preparation of composite surfactant composition S02

(1) Adding 262 g (1 mol) of dodecylphenol, 4 g of potassium hydroxide and 2.6 g of anhydrous potassium carbonate into a pressure reactor provided with a stirring device, heating to the reaction temperature of 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 701.8 g (12.1 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.50MPa, cooling after the propylene oxide reaction is finished, slowly introducing 88.0 g (2.0 mol) of ethylene oxide at 130 ℃, and controlling the pressure to be less than or equal to 0.60MPa. After the reaction, the same procedure as in example 16 was repeated to give 1015.7 g of dodecylphenol polyoxypropylene (12) polyoxyethylene (2) ether in 97.1% yield.

(2) Adding 52.3 g (0.05 mol) of the dodecylphenol polyoxypropylene (12) polyoxyethylene (2) ether synthesized in the step (b) (1) and 8.0 g (0.2 mol) of sodium hydroxide into a 1000 ml reaction bottle with a mechanical stirrer, a thermometer and a reflux condenser pipe under stirring, slowly dripping 8.0 g (0.065 mol) of ethyl chloroacetate, controlling the reaction temperature to 90 ℃ for reacting for 4 hours, cooling, adding 80 g of water, and continuously heating until reflux reaction is carried out for 3 hours. After cooling to 40 ℃, 399.0 g (0.95 mol) of an aqueous solution of the inner salt of (N-carboxymethyl-N-carboxymethyloxyethyl-N-dodecyl) phenylammonium was added and stirring was continued at 40 ℃ for 4 hours to obtain the desired composite surfactant composition S02. Phase and static adsorption experiments were carried out as in [ example 16 ], with the results shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 16 ] except that S02 was used instead of S01, a hydrophobically associating polymer P2 (AM/AMPS/2-acrylamidododecylsulfonic acid copolymer molar ratio =1/0.45/0.002, viscosity average molecular weight 1750 ten thousand) was used instead of the modified polyacrylamide polymer (P1, AM/AMPS copolymer molar ratio =1/0.05, viscosity average molecular weight 2500 ten thousand), diethanolamine was used instead of sodium carbonate, 9# simulated water was used to prepare an oil displacement agent aqueous solution, the temperature was 110 ℃, the viscosity of crude oil was 1.9mpa.s, and the results are shown in table 7.

[ example 18 ]

(b) Preparation of anionic and complex surfactant composition S03

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(2) Adding 261.5 g (0.5 mol) of rosin acid polyoxyethylene (5) ether ester synthesized in the step (b) (1) and 60.0 g (1.5 mol) of sodium hydroxide into a 2000 ml reaction bottle with a mechanical stirring, a thermometer and a reflux condenser pipe, slowly dropping 135.8 g (0.75 mol) of n-propyl bromoacetate, controlling the reaction temperature to be 95 ℃ for reaction for 5 hours, cooling, adding 400 g of water and 75 g of 95% isopropanol, and continuously heating until reflux reaction is carried out for 3 hours. After cooling to 40 ℃, an aqueous isopropanol solution containing 249.1 g (0.75 mol) of the inner salt of (N-carboxymethyl-N-dodecyl-N-methyl) phenylammonium was added and stirring was continued at 45 ℃ for 3 hours to obtain the desired composite surfactant composition S03.

Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 16 ], except that S03 was used instead of S01, a hydrophobically associating polymer (P3, molar ratio of co-AM/AMPS/2-acrylamidododecylsulfonic acid =1/0.35/0.0015, viscosity average molecular weight 2055 ten thousand) was used instead of the modified polyacrylamide polymer (P1, molar ratio of co-AM/AMPS =1/0.05, viscosity average molecular weight 2500 ten thousand), diethanolamine was used instead of sodium carbonate, 12# simulated water, and an oil displacement agent aqueous solution was prepared at 90 ℃, the viscosity of crude oil was 2.1mpa.s, and the results are shown in table 7.

[ example 19 ] to provide

(b) Preparation of composite surfactant composition S04

RO(CHCH ₃ CH ₂ O) ₁₂ (CH ₂ CH ₂ O) ₂ CH ₂ COONa

Wherein R = iso-C ₁₃ H ₂₇ 。

(1) Adding 200 g (1 mol) of isomeric tridecanol, 4 g of potassium hydroxide and 2.6 g of anhydrous potassium carbonate into a pressure reactor provided with a stirring device, heating to the reaction temperature of 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 701.8 g (12.1 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.50MPa, cooling after the propylene oxide reaction is finished, slowly introducing 88.0 g (2.0 mol) of ethylene oxide at 130 ℃, and controlling the pressure to be less than or equal to 0.60MPa. After the reaction, the temperature was reduced to 90 ℃ and the low boiling point material was removed in vacuo, after cooling, neutralization and dehydration were carried out to obtain 955.5 g of isomeric tridecanol polyoxypropylene (12) polyoxyethylene (2) ether with a yield of 97.1%.

(2) Adding 492 g (0.5 mol) of isomeric tridecanol polyoxypropylene (12) polyoxyethylene (2) ether synthesized in the step (b) (1) and 60.0 g (1.5 mol) of sodium hydroxide into a 5000 ml reaction bottle provided with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, slowly dripping 79.6 g (0.65 mol) of ethyl chloroacetate, controlling the reaction temperature to be 90 ℃ for reaction for 4 hours, cooling, adding 700 g of water and 50 g of 95% ethanol, and continuously heating until reflux reaction is carried out for 5 hours. After cooling to 40 deg.C, an aqueous isopropanol solution containing 80.6 g (0.2 mole) of the inner salt of (N-carboxymethyl-N, N-dimethyl) -4-hexadecylphenylammonium was added and stirring was continued at 40 deg.C for 4 hours to obtain the desired composite surfactant composition S04. Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 18 ] except that S04 was used in place of S03 and 10# simulated water to prepare an oil-displacing agent aqueous solution at a temperature of 85 ℃ and a dehydrated crude oil viscosity of 33.5mPa.s, the results are shown in Table 7.

[ example 20 ]

(b) Preparation of composite surfactant composition S05

(1) 276 g (1 mol) of dodecyl benzyl alcohol and 4.6 g of potassium hydroxide are added into a 2L pressure reactor provided with a stirring device, when the temperature is heated to 80-90 ℃, a vacuum system is started, dehydration is carried out for 1 hour under high vacuum, then nitrogen is used for replacing for 3-4 times, the reaction temperature of the system is adjusted to 140 ℃, 178.2 g (4.05 mol) of ethylene oxide is slowly introduced, 469.8 g (8.1 mol) of propylene oxide is slowly introduced at 150 ℃, the pressure is controlled to be less than or equal to 0.60MPa, after the reaction of the propylene oxide is finished, the temperature is adjusted to 140 ℃, 44.0 g (1.0 mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.40MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, 925.4 g of dodecyl benzyl alcohol polyoxyethylene (4), polyoxypropylene (8) and polyoxyethylene (1) ether are obtained, and the yield is 96.4%.

(2) And (b) adding 96.0 g (0.1 mol) of the dodecyl benzyl alcohol polyoxyethylene (4) polyoxypropylene (8) polyoxyethylene (1) ether synthesized in the step (b) (1) and 9.6 g (0.25 mol) of sodium hydroxide into a 5000-ml reaction bottle with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, slowly dripping 21.7 g (0.12 mol) of isopropyl bromoacetate, controlling the reaction temperature to be 90 ℃ for reaction for 4 hours, cooling, adding 160 g of water, and continuously heating until the reflux reaction is carried out for 3 hours. After cooling to 40 ℃, 434.7 g (0.9 mol) of an aqueous ethanol solution containing (N- (2-hydroxy-3-propanesulfonic acid) -N-methyl-N-hexadecyl) -4-methylphenylammonium inner salt was added, and stirring was continued at 45 ℃ for 3 hours to obtain the desired complex surfactant composition S05. Phase and static adsorption experiments were carried out as in [ example 16 ], with the results shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 16 ] except that S01 was replaced with S05, and a modified polyacrylamide polymer (P1, copolymerization AM/AMPS molar ratio =1/0.05, viscosity average molecular weight 2500 ten thousand) was replaced with high molecular weight anionic polyacrylamide P4 (viscosity average molecular weight 2300 ten thousand), and 11# simulated water was added to prepare an oil displacement agent aqueous solution at a temperature of 55 ℃ and a crude oil viscosity of 125.9mpa.s, the results of which are shown in table 6.

[ example 21 ]

(a) Preparation of (N-carboxymethyl-N, N-dimethyl) phenyl ammonium inner salt

(b) Preparation of composite surfactant composition S06

(1) 242 g (1 mol) of isomeric hexadecanol, 8 g of potassium hydroxide and 5.5 g of anhydrous potassium carbonate are added into a 2L pressure reactor provided with a stirring device, when the temperature is heated to 80-90 ℃, a vacuum system is started, dehydration is carried out for 1 hour under high vacuum, then nitrogen is used for replacing for 3-4 times, the reaction temperature of the system is adjusted to 140 ℃, 178.2 g (4.05 mol) of ethylene oxide is slowly introduced, 350.9 g (6.05 mol) of propylene oxide is slowly introduced at 150 ℃, the pressure is controlled to be less than or equal to 0.60MPa, after the reaction of the propylene oxide is finished, the temperature is adjusted to 140 ℃, 88.0 g (2.0 mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.40MPa. After the reaction, the temperature was reduced to 90 ℃, the low boiling point material was removed in vacuum, and after cooling, neutralization and dehydration were carried out, so that 894.9 g of isomeric hexadecanol polyoxyethylene (4) polyoxypropylene (6) polyoxyethylene (2) ether was obtained, with a yield of 94.2%.

(2) Adding 475.0 g (0.5 mol) of isomeric hexadecyl alcohol polyoxyethylene (4) polyoxypropylene (6) polyoxyethylene (2) ether synthesized in the step (b) (1) and 87.0 g (1.5 mol) of potassium hydroxide into a 2000 ml reaction bottle provided with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, slowly dropping 102.4 g (0.75 mol) of isopropyl chloroacetate, controlling the reaction temperature to be 100 ℃, reacting for 3 hours, cooling, adding 600 g of water, and continuously heating until the reflux reaction is carried out for 3 hours. After cooling to 40 deg.C, an aqueous isopropanol solution containing 9.0 g (0.05 mole) of the inner salt of (N-carboxymethyl-N, N-dimethyl) phenylammonium was added and stirring was continued at 40 deg.C for 5 hours to obtain the desired composite surfactant composition S06. Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 19 ] except that an aqueous displacement agent solution was prepared by substituting S06 for S04, the results are shown in table 7.

[ example 22 ]

(a) Preparation of (N-carboxymethyl-N, N-diethyl) phenyl ammonium inner salt

(b) Preparation of composite surfactant composition S07

(1) Into a 2L pressure reactor equipped with a stirring device was charged 248 g (1 mol) of a mixed alcohol (C) _14～18 ) Heating 6.5 g of potassium hydroxide to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 707.6 g (12.2 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the propylene oxide, slowly introducing 90.2 g (2.05 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out to obtain mixed alcohol (C) _14～18 ) 995.9 g of polyoxypropylene (12) polyoxyethylene (2) ether, and the yield is 96.5%.

Phase and static adsorption experiments were carried out as in example 16, and the results are shown in tables 2 and 3, and the results are shown in table 6, in which S07 was used instead of S01 to prepare an oil-displacing agent aqueous solution.

[ example 23 ]

(a) Preparation of (N-carboxymethyl-N-methyl-N-ethyl) phenylammonium inner salt

(b) Preparation of composite surfactant composition S08

(1) Adding 262 g (1 mol) of dodecylphenol, 4 g of potassium hydroxide and 2.6 g of anhydrous potassium carbonate into a pressure reactor provided with a stirring device, heating to the reaction temperature of 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 121.8 g (2.1 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.50MPa, cooling after the propylene oxide reaction is finished, slowly introducing 312.4 g (7.1 mol) of ethylene oxide at 130 ℃, and controlling the pressure to be less than or equal to 0.60MPa. After the completion of the reaction, the reaction mixture was worked up in the same manner as in example 16 to obtain 665.8 g of dodecylphenol polyoxypropylene (2) polyoxyethylene (7) ether, and the yield thereof was 97.2%.

(2) 342.5 g (0.5 mol) of the dodecylphenol polyoxypropylene (2) polyoxyethylene (7) ether synthesized in the step (b) (1) and 80.0 g (2.0 mol) of sodium hydroxide are added into a 5000 ml reaction bottle provided with a mechanical stirring, a thermometer and a reflux condenser pipe under stirring, 79.6 g (0.65 mol) of ethyl chloroacetate is slowly dropped into the reaction bottle, the reaction temperature is controlled to be 90 ℃ for reaction for 4 hours, 600 g of water and 100 g of 50% isopropanol are added after cooling, and the reaction bottle is continuously heated until reflux reaction is carried out for 3 hours. Cooled to 40 deg.C, 56.4 grams (0.3 moles) of an aqueous isopropanol solution of the inner (N-methyl-N-ethyl) phenylammonium salt was added and stirring continued at 40 deg.C for 4 hours to give the desired composite surfactant composition S08. Phase and static adsorption experiments were carried out as in [ example 16 ], with the results shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 18 ] except that an aqueous displacement agent solution was prepared by replacing S03 with S08, the results are shown in table 7.

[ example 24 ]

(a) The same as [ example 16 ] a.

(b) Preparation of composite surfactant composition S09

In the same manner as [ example 16 ] preparation of Mixed alcohol (C) _14～18 ) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether.

The mixed alcohol (C) added with stirring in a 5000 ml reaction flask equipped with mechanical stirring, thermometer and reflux condenser _14～18 ) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether 560.0 g (0.5 mol), 56.0 g (1.0 mol) potassium hydroxide and 1000 ml benzene were reacted at 70 ℃ for 4 hours, then cooled to 87.4 g (0.75 mol) sodium chloroacetate was slowly added, refluxed for 8 hours, cooled to 30 ℃, concentrated hydrochloric acid was added to adjust pH =3, benzene was evaporated under reduced pressure, 55.5 g (0.55 mol) triethylamine was added to neutralize the resulting carboxylic acid, and an aqueous ethanol solution containing 834.0 g (2.0 mol) (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt was added to obtain the desired composite surfactant composition S09.

The results of the phase and static adsorption experiments are shown in tables 2 and 3, and the results of the oil displacement experiments are shown in table 6, in which S09 is used instead of S01 to prepare the oil displacement agent aqueous solution.

[ example 25 ]

The same as [ example 16 ] except that 560.0 g (0.5 mol) of the mixed alcohol (C) _14～18 ) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether need not be followed byAfter the reaction, 600 g of water and 73.0 g (1.0 mol) of N-butylamine were added, and an aqueous ethanol solution containing 166.8 g (0.4 mol) of (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt was added to obtain the desired composite surfactant composition S10.

Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3. S10 is used for replacing S01 to prepare an oil displacement agent aqueous solution, and an oil displacement experiment is carried out, and the result is shown in Table 6.

[ example 26 ]

The same as in example 16, except that the alcohol solvent was distilled off under reduced pressure at the end of the reaction in the steps (a) and (b), to obtain the desired surfactant composition S11.

Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3. S11 is used for replacing S01 to prepare an oil displacement agent aqueous solution, and an oil displacement experiment is carried out, wherein the result is shown in a table 6.

[ example 27 ]

The same as [ example 16 ] except that the mixed alcohol (C) was replaced with 0.5 mol of coconut oil acid triethylamine salt _14～18 ) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether acetic acid triethylamine salt, and an aqueous ethanol solution containing 834.0 g (2.0 mol) of (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt was added to obtain the desired complex surfactant composition S12.

Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3. S12 replaces S01 to prepare an oil displacement agent aqueous solution, and an oil displacement experiment is carried out, wherein the result is shown in Table 6.

[ example 28 ]

The same as [ example 16 ] except that the mixed alcohol (C) was replaced with 0.5 mol of triethylamine dodecylsulfonate _14～18 ) Polyoxyethylene (2) polyoxypropylene (12) polyoxyethylene (2) ether acetic acid triethylamine salt, and an aqueous ethanol solution containing 417.0 g (1.0 mol) of (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt were added to obtain the desired complex surfactant composition S13.

Phase and static adsorption experiments were carried out as in [ example 16 ] and the results are shown in tables 2 and 3. S13 replaces S01 to prepare an oil displacement agent aqueous solution, and an oil displacement experiment is carried out, wherein the result is shown in Table 6.

[ example 29 ] to

(a) The same as [ example 21 ] a.

(b) Preparation of composite surfactant composition S14

(1) 242 g (1 mol) of isomeric hexadecanol, 8 g of potassium hydroxide and 5.5 g of anhydrous potassium carbonate are added into a 2L pressure reactor provided with a stirring device, a vacuum system is started when the 2L pressure reactor is heated to 80-90 ℃, a high vacuum is performed for 1 hour, then nitrogen is used for replacement for 3-4 times, the reaction temperature of the system is adjusted to 140 ℃, 178.2 g (4.05 mol) of ethylene oxide is slowly introduced, and the pressure is controlled to be less than or equal to 0.40MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, so that 397.9 g of isomeric hexadecanol polyoxyethylene (4) ether is obtained, and the yield is 95.2%.

Similarly, (example 19) S14 was used instead of S04, and ethanolamine was used instead of diethanolamine to prepare an oil displacement agent aqueous solution, and oil displacement experiments were performed, and the results are shown in table 7.

[ COMPARATIVE EXAMPLE 4 ]

Octadecyl benzyl methyl betaine

Octadecyl dimethyl betaine

The same as in example 16 except that (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt was replaced with commercially available octadecyl benzyl methyl betaine or octadecyl dimethyl betaine, and the other was the same, surfactant compositions S15 and S16 were obtained. The phase experiment and the static adsorption experiment were carried out as in example 16, and the results are shown in Table 5. The results of preparing the oil-displacing agent aqueous solution by replacing S01 with S15 and S16 are shown in Table 8.

[ COMPARATIVE EXAMPLE 5 ]

The same as in example 16 except that in step (b) (1), 180.4 g (4.1 mol) of ethylene oxide was introduced followed by 707.6 g (12.2 mol) of propylene oxide to give the isomeric tridecanol polyoxyethylene (4) polyoxypropylene (12) ether and the rest was the same, surfactant composition S17 was obtained.

The phase experiment and the static adsorption experiment were carried out in the same manner as in example 16, and the results are shown in Table 5. The results of preparing an oil-displacing agent aqueous solution by substituting S17 for S01 are shown in table 8.

[ COMPARATIVE EXAMPLE 6 ]

The same as [ example 16 ], except that the reaction with propylene oxide and ethylene oxide was not carried out stepwise in succession, but carried out in one step after mixing, i.e., a mixture of 707.6 g (12.2 mol) of propylene oxide and 180.4 g (4.1 mol) of ethylene oxide was slowly introduced at 110 to 150 ℃ under a pressure of 0.60MPa or less, and the remainder was the same, to obtain S18.

The phase experiment and the static adsorption experiment were carried out as in example 16, and the results are shown in Table 5. The results of preparing an oil-displacing agent aqueous solution by substituting S18 for S01 are shown in table 8.

[ COMPARATIVE EXAMPLE 7 ]

The same as example 16, except that the hydrophobically associating polymer P1 was replaced with a high molecular weight anionic polyacrylamide P4 (having a viscosity average molecular weight of 2300 ten thousand), and the rest was the same, the results are shown in FIG. 8.

TABLE 6

TABLE 7

TABLE 8

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Claims

1. A composite surfactant composition comprising the following components:

(1) A zwitterionic compound;

(2) A surfactant containing polyether segments or no polyether segments;

wherein the molar ratio of the zwitterionic compound to the surfactant containing polyether or no polyether segment is (1: 0.02) - (1: 20); the molecular general formula of the zwitterionic compound is shown as the formula (I):

formula (I);

in the formula (I), R ₁ And R ₄ Is hydrogen, C ₂ ～C ₃₂ One of a hydrocarbyl or substituted hydrocarbyl group of (A), R ₂ Y ^- Is C ₁ ~C ₅ Alkylene or substituted alkylene carboxylates、C ₁ ~C ₅ Alkyl or substituted alkyl sulfonates, C ₁ ~C ₅ Hydrocarbyl or substituted hydrocarbyl phosphate or C ₁ ~C ₅ At least one of hydrocarbyl or substituted hydrocarbyl sulfate, R ₃ Is hydrogen, C ₂ ～C ₃₂ Alkyl or substituted alkyl (CHR '') _e OH, halogen, amino, carboxylic acid group or sulfonic group, R' is independently selected from H and CH ₃ Or C ₂ H ₅ E is any integer from 0 to 4;

formula (II);

in the formula (II), R ₅ Is C ₈ ～C ₃₀ One of the aliphatic or substituted aliphatic groups of (a), or R ₅ O is abietate; m1 and m2 are the addition number of the ethoxy groups, and m1= 0-50 and m2= 0-50; n is the addition number of the propoxy groups, and n = 0-100; k =0 or 1; when k =1, X is hydrogen or R ₆ Z，R ₆ Is C ₁ ～C ₅ Z is COOM, SO ₃ N or hydrogen, M and N are selected from cation or cation group; when k =0, X is COOM or SO ₃ N, M and N are selected from cation or cation group.

2. The composite surfactant composition according to claim 1, wherein M and N are selected from hydrogen ions, alkali metal cations, or compounds of formula NR ₇ (R ₈ )(R ₉ )(R ₁₀ ) At least one of the groups shown, wherein R ₇ 、R ₈ 、R ₉ 、R ₁₀ Is independently selected from H, (CHR) ⁰ ) _f OH or (CHR) ⁰ ) _g CH ₃ One of (1), R ⁰ Is H, CH ₃ Or C ₂ H ₅ Wherein f is an integer from 1 to 4, and g is an integer from 0 to 5.

3. The composite surfactant composition according to claim 2, wherein R is ₁ And R ₄ Is hydrogen, C ₈ ～C ₂₄ One of a hydrocarbyl group or a substituted hydrocarbyl group of (a); r ₂ Y ^- Is C ₁ ~C ₃ Alkylene or substituted alkylene carboxylates, C ₁ ~C ₃ One of alkyl or substituted alkyl sulfonate, R ₃ Is hydrogen, C ₈ ～C ₂₄ One of hydrocarbyl or substituted hydrocarbyl, hydroxyl, amino, carboxylic acid group or sulfonic acid group; r', R ⁰ Independently selected from H or CH ₃ (ii) a e =0 to 1,f =1 to 2,g =0 to 1,j =0 or 1; the R is ₅ Is composed of C ₄ ～C ₂₀ Straight-chain or branched-chain saturated and unsaturated alkyl-substituted benzene rings or naphthalene rings; r ₆ Is C ₁ ～C ₃ An alkylene group of (a); m1=0 to 10, m2=0 to 10, n =0 to 20.

4. The composite surfactant composition according to claim 3, characterized in that

R ₁ And R ₄ Is hydrogen, (CH R') _c OH、 (CH R') _d CH ₃ One of phenyl, substituted phenyl and benzyl, (CH R') _c OH and (CH R') _d CH ₃ Wherein R' is independently selected from H and CH ₃ Or C ₂ H ₅ C is any integer from 1 to 4, and d is any integer from 0 to 5.

5. The composite surfactant composition according to claim 4, wherein R' is independently selected from H or CH ₃ ；c=1~2，d=0~1。

6. The composite surfactant composition according to claim 3, characterized in that

The R is ₁ And R ₄ Is one of hydrogen, methyl, ethyl, hydroxyethyl, hydroxypropyl, phenyl and benzyl;

R ₃ is hydrogen, methyl, ethyl, phenyl, hydroxyl, amino, carboxylOne of an acid group or a sulfonic acid group.

7. The composite surfactant composition according to claim 3, characterized in that

Said R is ₅ Is cumyl (C) ₆ H ₅ C(CH ₃ ) ₂ ) A substituted benzene or naphthalene ring.

8. The composite surfactant composition according to claim 1, characterized in that the composite surfactant composition further comprises:

(3) A small molecule alcohol;

(4) A small molecule amine;

(5) Salt;

(6) An inorganic base;

wherein the molar ratio of the zwitterionic compound, the surfactant containing polyether segments or no polyether segments, the small molecular alcohol, the small molecular amine, the salt and the inorganic base is (0.02) - (20) - (0-10); the small molecular alcohol is selected from C ₁ ~C ₈ The fatty alcohol of (4); the small molecule amine is selected from C ₁ ~C ₈ At least one of a primary amine, a secondary amine, or a tertiary amine; the salt is at least one of metal halide and hydroxyl-substituted carboxylate; the inorganic base is at least one selected from alkali metal hydroxide, alkali metal carbonate or alkali metal bicarbonate.

9. The composite surfactant composition according to claim 8, wherein the molar ratio of the zwitterionic compound, the surfactant containing polyether segments or no polyether segments, the small-molecule alcohol, the small-molecule amine, the salt and the base is 1: 0.05 to 20): 0 to 15, 0 to 5 and 0 to 5.

10. A method for preparing the composite surfactant composition of any one of claims 1 to 9, comprising the steps of:

(a) Preparation of zwitterionic compound:

will be provided with

And can provide R ₂ Uniformly mixing the ionizing agent of Y in water or alcohol water for quaternization to obtain an aqueous solution or an alcohol aqueous solution of the zwitterionic compound shown in the formula (I); wherein the concentration of the alcohol-water solution is 0 to 100wt% (mass percent of alcohol in the alcohol-water solution), and the alcohol is selected from C ₁ ~C ₅ The fatty alcohol of (4);

(b) Preparation of the composite surfactant composition:

(1) in the presence of a basic catalyst, R ₅ OH sequentially reacts with required amount of ethylene oxide, propylene oxide and ethylene oxide to obtain a nonionic polyether compound with a structure shown in a formula (II); or further reacting by an optional step (2) to obtain an ionic polyether compound having a structure represented by formula (II):

(2) mixing the polyether compound obtained in the step (1) with an ionizing agent Y ₀ R ₆ Z and alkali metal hydroxide or alkali metal alkoxide are mixed according to the molar ratio of 1, (0.1 to 20), and the mixture is stirred to react for 3 to 15 hours at the reaction temperature of 50 to 120 ℃ to obtain the ionic polyether compound; wherein, Y ₀ Selected from chlorine, bromine or iodine;

or: (2) mixing the polyether compound obtained in the step (1) with an ionizing agent Y ₀ R ₆ Z ₀ And alkali metal hydroxide or alkali metal alkoxide are mixed according to the molar ratio of 1 (0.1 to 20) to (0.1 to 20), the mixture is stirred and reacted at the reaction temperature of 50 to 120 ℃ for 3 to 15 hours, water is continuously added for saponification reaction, and the ionic polyether compound is obtained after refluxing for 1 to 10 hours; wherein Y is ₀ Selected from chlorine, bromine or iodine, Z ₀ Is selected from COOR ₀ , R ₀ Is selected from C ₁ ～C ₈ The alkyl group of (1).

11. The method for preparing a composite surfactant composition according to claim 10, wherein said surfactant is capable of providing R ₂ The ionizing agent of Y is at least one of alkali metal salts of 3-chloro-2-hydroxypropanesulfonic acid, 2-chloroethanesulfonic acid, 1, 3-propanesultone, chloroacetic acid and chloroacetic acid, and the alcohol is selected from C ₁ ~C ₄ The fatty alcohol of (a); the above-mentioned

And can provide R ₂ The mol ratio of the ionizing reagent of Y is 1: 1-3; the reaction temperature in the step (1) is 120 to 160 ℃, the pressure is 0.3 to 0.6MPa, and the alkaline catalyst is at least one of potassium hydroxide or anhydrous potassium carbonate; in the step (2), the alkali metal hydroxide is at least one of potassium hydroxide or sodium hydroxide, the molar ratio of the polyether compound to the ionizing agent and the alkali metal hydroxide or the alkali metal alkoxide is 1 (0.3 to 3) to (0.2 to 6), and Y is ₀ Is one of chlorine or bromine, R ₀ Is C ₁ ～C ₄ The alkyl group of (1).

12. Use of the composite surfactant composition according to any one of claims 1 to 9 or the surfactant composition prepared by the preparation method according to any one of claims 10 to 11 in oil fields.

13. The composite oil displacement agent comprises the following components in parts by weight:

(1) 1 part of the composite surfactant composition as defined in any one of claims 1 to 9 or the surfactant composition prepared by the preparation method as defined in any one of claims 10 to 11;

(2) 0 to 20 parts of polymer and more than 0 part of polymer;

(3) 0 to 30 portions of alkali.

14. The composite oil-displacing agent according to claim 13,

the polymer is at least one of anionic polyacrylamide, temperature-resistant salt-resistant modified polyacrylamide, hydrophobically associating polyacrylamide or polymer microspheres.

15. The composite oil-displacing agent according to claim 14,

the temperature-resistant and salt-resistant modified polyacrylamide molecular chain comprises an acrylamide structural unit and a 2-acrylamide-2-methylpropanesulfonic acid structural unit; the hydrophobic association polyacrylamide molecular chain comprises an acrylamide structural unit, a temperature-resistant salt-resistant monomer structural unit and a hydrophobic monomer structural unit.

16. The composite oil-displacing agent according to claim 15,

the molar ratio of an acrylamide structural unit to a 2-acrylamido-2-methylpropanesulfonic acid structural unit in the temperature-resistant salt-resistant modified polyacrylamide molecular chain is (0.1 to 40) to 1, and the viscosity average molecular weight is 800 to 2500 ten thousand; the molar ratio of the acrylamide structural unit, the temperature-resistant salt-resistant monomer structural unit and the hydrophobic monomer structural unit in the hydrophobically associating polyacrylamide molecular chain is 1: (0.1 to 40): (0.001 to 0.05) and a viscosity average molecular weight of 500 to 2500 ten thousand.

17. The composite oil-displacing agent according to claim 13,

in the oil displacement agent, the mass ratio of the surfactant composition to the polymer to the alkali is 1 to (0.1 to 2): (0 to 5).

18. A method for preparing the composite oil-displacing agent of any one of claims 13-17, comprising the steps of:

(a) Preparation of zwitterionic compound:

will be provided with

And can provide R ₂ The ionizing agent for Y is mixed in water or alcohol waterUniformly carrying out quaternization reaction to obtain an aqueous solution or an alcohol aqueous solution of the zwitterion compound shown in the formula (I); wherein the concentration of the alcohol-water solution is 0 to 100wt% (mass percent of alcohol in the alcohol-water solution), and the alcohol is selected from C ₁ ~C ₅ The fatty alcohol of (a);

(b) Preparation of surfactant composition:

step (1) in the presence of a basic catalyst, R ₅ OH sequentially reacts with required amount of ethylene oxide, propylene oxide and ethylene oxide to obtain a nonionic polyether compound with a structure shown in a formula (II); or further reacting by an optional step (2) to obtain an ionic polyether compound having a structure represented by formula (II):

step (2) of mixing the polyether compound obtained in the step (1) with an ionizing agent Y ₀ R ₆ Z and alkali metal hydroxide or alkali metal alkoxide are mixed according to the molar ratio of 1 (0.1 to 20) to (0.1 to 20), and the mixture is stirred to react for 3 to 15 hours at the reaction temperature of 50 to 120 ℃ to obtain the ionic polyether compound; wherein, Y ₀ Selected from chlorine, bromine or iodine;

or: step (2) of mixing the polyether compound obtained in the step (1) with an ionizing agent Y ₀ R ₆ Z ₀ And alkali metal hydroxide or alkali metal alkoxide are mixed according to the molar ratio of 1 (0.1 to 20) to (0.1 to 20), the mixture is stirred and reacted at the reaction temperature of 50 to 120 ℃ for 3 to 15 hours, water is continuously added for saponification reaction, and the ionic polyether compound is obtained after refluxing for 1 to 10 hours; wherein Y is ₀ Selected from chlorine, bromine or iodine, Z ₀ Is selected from COOR ₀ , R ₀ Is selected from C ₁ ～C ₈ Alkyl groups of (a);

(c) And (b) uniformly mixing the surfactant composition obtained in the step (b) with a polymer and alkali according to the required amount by mass to obtain the oil-displacing agent.

19. The method of claim 18,

said can provide R ₂ The ionizing agent of Y is at least one of alkali metal salts of 3-chloro-2-hydroxypropanesulfonic acid, 2-chloroethanesulfonic acid, 1, 3-propanesultone, chloroacetic acid and chloroacetic acid, and the alcohol is selected from C ₁ ~C ₄ The fatty alcohol of (a); the above-mentioned

And can provide R ₂ The mol ratio of the ionizing reagent of Y is 1: 1-3; in the step (1): the reaction temperature is 120 to 160 ℃, the pressure is 0.3 to 0.6MPa, and the alkaline catalyst is at least one of potassium hydroxide or anhydrous potassium carbonate; in the step (2): the alkali metal hydroxide is at least one of potassium hydroxide or sodium hydroxide, the molar ratio of the polyether compound to the ionizing agent and the alkali metal hydroxide or the alkali metal alkoxide is 1 (0.3 to 3) to (0.2 to 6), and Y is ₀ Is one of chlorine or bromine, R ₀ Is C ₁ ～C ₄ The alkyl group of (1).

20. A method for enhanced oil recovery comprising the steps of:

(1) Mixing the composite oil-displacing agent of any one of claims 13-17 with water to obtain an oil-displacing system;

(2) And (3) contacting the oil displacement system with an oil-bearing stratum under the conditions that the oil displacement temperature is 25-150 ℃ and the total mineralization is more than 500 mg/L of simulated stratum water, and displacing the crude oil in the oil-bearing stratum.