CN112708411B

CN112708411B - Oil displacement zwitterionic surfactant and polyether amine surfactant composition, and preparation method and application thereof

Info

Publication number: CN112708411B
Application number: CN201911020227.1A
Authority: CN
Inventors: 沈之芹; 李应成; 沙鸥
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: 2019-10-25
Filing date: 2019-10-25
Publication date: 2022-09-06
Anticipated expiration: 2039-10-25
Also published as: CN112708411A

Abstract

The invention relates to a zwitterionic surfactant and a polyether amine surface for oil displacementThe active agent composition, the preparation method and the application thereof mainly solve the problems that the existing surfactant has low oil displacement efficiency, poor temperature resistance and salt resistance and large adsorption retention capacity and cannot meet the oil displacement requirement of an oil reservoir. The invention adopts a surfactant composition, which comprises the following components: (1) a zwitterionic compound; (2) a polyetheramine surfactant; wherein the molar ratio of the zwitterionic compound to the polyether amine surfactant is 1 (0.01-50); the molecular general formula of the zwitterionic compound is shown in the formula (I), and the molecular general formula of the polyether amine surfactant is shown in the formula (II), so that the problem is solved well, and the zwitterionic compound can be used in oil fields to improve the yield of crude oil.

Description

Oil displacement zwitterionic surfactant and polyether amine surfactant composition, and preparation method and application thereof

Technical Field

The invention relates to a zwitterionic surfactant and polyether amine surfactant composition for oil displacement, 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.

Surfactants as an important component of chemical flooding can be classified into two major classes, namely ionic and nonionic, according to their chemical composition and molecular structure. The type of surfactant currently used in tertiary oil recovery studiesAnionic is the most, followed by nonionic and zwitterionic, and cationic is the least used. The results of oil displacement by using alkaline water, surfactant or alkaline water oil displacement and oil displacement by using zwitterionic surfactant are sequentially reported by US3927716, US4018281 and US4216097 of Mofu Petroleum company, 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 Texas 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. For example, chinese patents CN 1528853, CN 1817431, CN 1066137 and the like sequentially report bisamide type cationic, fluorine-containing cationic and pyridyl-containing cationic gemini surfactants, but the use of cations in oil fields is limited due to the disadvantages of large adsorption loss, high cost and the like.

After the surfactants of different types are compounded with each other, the defects of a single surfactant can be overcome, and the advantages of each component are exerted, so that the oil displacement agent is endowed with more excellent performance. Chinese patent CN1458219A discloses a surfactant/polymer binary ultra-low interfacial tension composite flooding formula for tertiary oil recovery, wherein the used surfactant is petroleum sulfonate or an oil displacement agent compounded by petroleum sulfonate serving 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 United states Texas university patent US8211837 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 sulfuric acid esterification reaction, compared with an expensive sulfonate surfactant, a large hydrophilic group polyether sulfate surfactant is synthesized at low cost, the sulfate surfactant has excellent high-temperature stability under an alkaline condition due to the existence of large hydrophilic groups, 0.3 percent of branched alcohol polyether sulfate (C32-7PO-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 by meifu petroleum company reports an oil displacement system composed of oil-soluble alcohol, betaine sulfonate and quaternary ammonium salt, which can function as both a surfactant and a fluidity control agent, wherein the quaternary ammonium salt is a cationic surfactant with a lipophilic carbon chain length of 16-20, 2% octadecyl dihydroxyethyl propyl betaine sulfonate and 1.0% n-hexanol are used as oil displacement agents, after 1.9PV is injected, the crude oil can be displaced by 100%, but the adsorption loss of the surfactant is as large as 6mg/g, and 2.0% tetraethylammonium bromide with a relatively low price is added as a 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 an oil displacement surfactant composition with stable structure under oil reservoir conditions, an oil displacement agent, a preparation method and application in oil displacement.

Disclosure of Invention

One of the technical problems to be solved by the invention is that the surfactant in the prior art has poor solubilization capacity on crude oil, low oil displacement efficiency, poor temperature and salt resistance and large adsorption retention, and cannot meet the oil displacement requirement of a high-temperature and high-salt oil reservoir, and a novel surfactant composition for oil displacement is provided, so that an aqueous solution of the surfactant composition can well emulsify the crude oil, has strong solubilization capacity, has the maximum solubilization parameter of 16.6-20.5, and has the advantages of good temperature and salt resistance and low adsorption retention, thereby effectively improving the oil displacement efficiency of the crude oil, and having good application prospect of improving the recovery ratio.

The second technical problem to be solved by the present invention is to provide a method for preparing the surfactant composition described in the first technical problem.

The invention also provides an application of the surfactant composition in oil displacement, which solves one of the technical problems.

The fourth technical problem to be solved by the invention is the problem that the oil displacement agent system containing the surfactant in the prior art has poor crude oil capacity-increasing capability, low oil displacement efficiency, poor temperature resistance and salt resistance, large adsorption retention and can not meet the oil displacement requirement of a high-temperature and high-salt reservoir, and the invention provides a novel oil displacement agent, the water solution oil-water interfacial tension of which can reach 10 ^-3 ～10 ^-4 mN/m, thereby effectively improving the oil displacement efficiency of crude oil and having good application prospect of improving the recovery ratio.

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 above technical problems, the technical solution adopted by the present invention is as follows: a surfactant composition comprising the following components:

(1) a zwitterionic compound;

(2) a polyetheramine surfactant;

wherein the molar ratio of the zwitterionic compound to the polyether amine surfactant is 1 (0.01-50); 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 of (CH R') _c OH、(CH R') _d CH ₃ One of phenyl, substituted phenyl or benzyl, R ₂ Is C ₁ ～C ₅ Alkylene or substituted alkylene, X ^- Is radical carboxylate, sulfonate, phosphate or sulfate radical, R ₃ Is hydrogen, C ₂ ～C ₃₂ Alkyl or substituted alkyl (CHR') _e One of OH, halogen, amino, carboxylic acid group or sulfonic groupR 'and R' are independently selected from H, CH ₃ Or C ₂ H ₅ C is any integer from 1 to 4, d is any integer from 0 to 5, and e is any integer from 0 to 4.

The molecular general formula of the polyether amine surfactant is as follows:

in the formula (II), R ₅ Is C ₈ ～C ₃₀ Or linear or branched, saturated or unsaturated alkyl or from C 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 Is abietylamine radical; r1, r2, r3 or r4 are independently selected from 0-50, but r1 and r2, and r3 and r4 cannot be 0 at the same time; s1 and s2 are independently selected from 0-100, but s1 and s2 cannot be 0 at the same time; y is R ₆ Z; y 'is R' ₆ Z′；R ₆ And R' ₆ Is independently selected from C ₁ ～C ₅ At least one of alkylene or hydroxy-substituted alkylene of (a); z and Z' are independently selected from COOM, SO ₃ And one of N, M, N is selected from cation or cation group. In the above technical scheme, R ₁ Or R ₄ Preferably hydrogen, C ₈ ～C ₂₄ The alkyl or substituted alkyl, methyl, ethyl, hydroxyethyl, hydroxypropyl, phenyl or benzyl.

In the above technical scheme, R ₂ X ^- Preferably C ₁ ～C ₃ Alkylene or substituted alkylene carboxylates, C ₁ ～C ₃ Alkylene or substituted alkylene 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 technical means, c is preferably 1 to 2, d is preferably 0 to 1, and e is preferably 0 to 1.

In the above embodiments, M, N is preferably a hydrogen ion, an alkali metal cation, or a compound 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 technical means, f is preferably 1 to 2, and g is preferably 0 to 1.

In the above technical scheme, R ₅ Preferably C ₁₂ ～C ₂₄ Or with a hydrocarbon or substituted hydrocarbon 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 N is abietylamine radical.

In the above technical scheme, R ₆ And R' ₆ Preferably C ₁ ～C ₃ An alkylene group of (a).

In the above technical solution, r1+ r2 is preferably 1 to 10, r3+ r4 is preferably 1 to 10, and s1+ s2 is preferably 1 to 40.

In the above technical solution, the surfactant composition preferably further comprises the following components in parts by mole:

(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 polyether amine surfactant, the small molecular alcohol, the small molecular amine, the salt and the inorganic base is 1 (0.01-50): (0-20): 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 To a primary, secondary or tertiary amine ofOne kind of the compound is used; 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 molar preferred ratio of the zwitterionic compound, the surfactant containing polyether segments, the micromolecular alcohol, the micromolecular amine, the salt and the inorganic base is 1 (0.02-30): 0-15): 0-5.

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

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.

The oil-displacing surfactant composition can also comprise oil-displacing components commonly used in the field, such as oil-displacing polymers, oil-displacing foam agents, oil-displacing 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, such as short-chain fatty alcohols, low-carbon-chain ketones, DMSO and the like.

The key active ingredients of the oil-displacing surfactant composition are (1) and (2), and those skilled in the art know that the oil-displacing surfactant composition can be supplied in various forms, such as a non-aqueous solid form, an aqueous paste form or an aqueous solution form, for convenience of transportation and storage or on-site use; the aqueous solution form comprises a form of preparing a concentrated solution by water, and a form of directly preparing a solution with a concentration required by 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 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.

To solve the second technical problem, the technical solution adopted by the present invention is as follows: a method for producing the surfactant composition according to any one of the above-mentioned means for solving the technical problems, comprising the steps of:

(a) preparation of zwitterionic Compounds:

will be provided with

With ionizing agent X ₀ R ₂ Uniformly mixing the X 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 alcohol accounts for 0-100 wt% of the alcohol aqueous solution in percentage by mass, and the alcohol is selected from C ₁ ～C ₅ Fatty alcohol of (2), X ₀ Selected from chlorine, bromine or iodine;

(b) preparation of surfactant composition:

in the presence of an alkaline catalyst, R ₅ NH ₂ Reacting with ethylene oxide, propylene oxide and ethylene oxide in required amount in sequence to obtain a polyether compound; mixing a desired amount of a polyether compound with the aqueous or aqueous alcoholic solution of the zwitterionic compound from step (a) to provide said surfactant composition;

or obtaining the surfactant composition by a second reaction:

② the polyether compound obtained in the step I and an ionizing agent Y ₀ R ₆ Z or Y ₀ R' ₆ Mixing Z' and alkali metal hydroxide or alkali metal alkoxide according to a molar ratio of 1 (0.1-20) to 0.1-20, reacting at a reaction temperature of 50-120 ℃ for 3-15 hours under stirring, adding the zwitterionic compound aqueous solution or alcohol aqueous solution obtained in the step (a) according to a required molar ratio, heating to 40-100 ℃, and stirring for 1-5 hours to obtain the surfactant composition; wherein Y is ₀ Selected from chlorine, bromine or iodine;

or: ② the polyether compound obtained in the step I and an ionizing agent Y ₀ R ₆ COOR ₀ Or Y ₀ R' ₆ COOR 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 at the reaction temperature of 50-120 ℃ for 3-15 hours, water is continuously added for saponification reaction, after the mixture is refluxed for 1-10 hours, the zwitterionic compound aqueous solution or alcohol aqueous solution obtained in the step (a) is added according to the required molar ratio, the mixture is heated to 40-100 ℃ and stirred for 1-5 hours, and the required surfactant composition is obtained; wherein R is ₀ Is selected from C ₁ ～C ₈ Alkyl group of (1).

In the above technical scheme, the ionizing agent X in the step (a) ₀ R ₂ X 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 X ₀ R ₂ The preferable molar ratio of X is 1: 1-3.

In the above technical scheme, the reaction temperature in the step (b) 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 pressure.

In the above technical solution, the alkali metal hydroxide in the step (b) 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 (2-10) to (2-10), and R is preferably 1 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 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 surfactant composition in any technical scheme for solving the technical problem in oil displacement in an oil field is disclosed.

In the technical scheme, the 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 salinity of stratum saline water of the oil reservoir is preferably selected from 5000-200000 mg/L in the application, wherein Ca is ²⁺ +Mg ²⁺ 10 to 15000mg/L, HCO ₃ ^- 0 to 2000 mg/L; the viscosity of the crude oil is 1.0-200.0 mPa.s; the formation temperature is 50-120 ℃.

The oil displacement agent prepared by the invention shows synergistic interaction among the components, and shows the aspects of increasing surface activity, reducing critical micelle concentration, improving crude oil solubilizing capability and the like. Especially, the electrostatic action of the surfactants with opposite electric properties promotes the association between two surfactant ions with different charges, and the hydrophobic hydrocarbon chains of the two have certain hydrophobic action 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 oil displacement agent 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 oil and water phases, 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 property 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 an oil displacement agent is improved, and the green production of the surfactant is realized.

The present invention refers to the total concentration of the components of the molecular formula (I) and the molecular formula (II) in the above technical scheme, when the content or concentration of the surfactant composition is referred to.

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

1)1 part of the surfactant composition according to any one of the above-mentioned means for solving the first technical problem or the surfactant composition obtained by the production method according to any one of the above-mentioned means for solving the second technical problem;

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

3) 0-30 parts 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): 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 to 0.05) and a viscosity average molecular weight of 500 to 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 and 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, the temperature-resistant and salt-resistant monomer is preferably 2-acrylamido-2-methylpropanesulfonic acid, and the hydrophobic monomer is preferably 2-acrylamidododecyl sulfonic acid.

In the above technical scheme, the mole ratio of acrylamide to the temperature-resistant salt-resistant monomer to the hydrophobic monomer in the hydrophobic association polymer is preferably 1: (0.1-40): (0.001 to 0.05) and a viscosity average molecular weight of 500 to 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 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 salt-resistant modified polyacrylamide is preferably prepared by copolymerizing acrylamide and 2-acrylamide-2-methylpropanesulfonic acid, the molar ratio of the acrylamide to the 2-acrylamide-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 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 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, 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 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.

The oil displacement agent composition of the present invention may further contain oil recovery aids such as foaming agents, small molecular organic substances (e.g., ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, DMSO, etc.) 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 oil displacement agent in any one of the four technical solutions for solving the technical problems, comprising the following steps:

(a) preparation of zwitterionic Compounds:

will be provided with

With ionizing agents X ₀ R ₂ Uniformly mixing the X 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 alcohol accounts for 0-100 wt% of the alcohol aqueous solution in percentage by mass, and the alcohol is selected from C ₁ ～C ₅ Fatty alcohol of (2), X ₀ Selected from chlorine, bromine or iodine;

(b) preparation of surfactant composition:

in the presence of an alkaline catalyst, R ₅ NH ₂ Reacting with required amount of ethylene oxide, propylene oxide and ethylene oxide in sequence to obtain a polyether compound; mixing a desired amount of a polyether compound with the aqueous or aqueous alcoholic solution of the zwitterionic compound obtained in step (a) to obtain said surfactant composition;

or obtaining the surfactant composition through a second reaction:

② the polyether compound obtained in the step I and an ionizing agent Y ₀ R ₆ Z or Y ₀ R' ₆ Z' and alkali metal hydroxide or alkali metal alkoxide are mixed according to the mol 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, according to the requirementAdding the zwitterionic compound aqueous solution or alcohol aqueous solution obtained in the step (a) according to the molar ratio, heating to 40-100 ℃, and stirring for 1-5 hours to obtain the surfactant composition; wherein, Y ₀ Selected from chlorine, bromine or iodine;

or: ② mixing the polyether compound obtained in the step I and an ionizing agent Y ₀ R ₆ COOR ₀ Or Y ₀ R' ₆ COOR 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 reacted at the reaction temperature of 50-120 ℃ for 3-15 hours, water is continuously added for saponification reaction, after refluxing for 1-10 hours, the zwitterionic compound aqueous solution or 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 is obtained; wherein R is ₀ Is selected from C ₁ ～C ₈ The alkyl group of (1).

(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.

In the above technical solution, the preferable solution is: the ionizing agent X ₀ R ₂ X 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 (a); the described

And X ₀ R ₂ The preferred molar ratio of X is 1: 1-3; the step of (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; the second step is as follows: the alkali metal hydroxide is preferably at least one of potassium hydroxide or sodium hydroxide, and the molar ratio of the polyether compound to the ionizing agent and the alkali metal hydroxide or the alkali metal alkoxide is preferably 1 (2-10): 2-10), and X ₀ And Y ₀ Preference is given toIs 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: the application of the oil displacement agent comprises the following steps:

(1) mixing the 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 salinity 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 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 oil displacement agent, the components in the oil displacement composition are respectively dissolved in water to obtain the oil displacement agent for oil displacement. The water used in the preparation can be tap water, river water, seawater and oil field formation water.

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 the 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, driving the oil displacement agent to the water content of 100% at the speed of 0.2mL/min, 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 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 the interfacial tension (mN. m) ^-1 ) Δ ρ is the two-phase density difference (Kg. m) ^-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 static adsorption capacity (mg/g), W is weight (g) of the surfactant solution, Co is initial concentration (mg/g) of the surfactant solution calculated according to commodity content, A is effective content (%) of the surfactant product, effective concentration (mg/g) of the Ce surfactant solution after adsorption, and m is mass (g) of the adsorbent.

The test method of the solubilization parameter of the invention comprises the following steps: (1) 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) sealing the upper opening of the glass pipette after the sample is added; (4) uniformly mixing by adopting vortex oscillation or rotation; (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 test method of the carboxylation degree and the sulfonation degree comprises the following steps: an analytical method for determining the end point of titration by indicating the change of potential difference (or electrode potential) during titration analysis with a potential measuring device. The measurement is performed by using the relationship between the electrode potential of the electrode and the activity of the component to be measured.

Halmin cation solution as titrant

S ^－ +Hyamine＝S-Hyamine

Under alkaline conditions (pH 11), both carboxylate and sulfonate surfactants exist in salt form and are able to react with hallisin cations, and the amount of both surfactants can be measured using hallisin cation solution as a titrant. The carboxylation degree or sulfonation degree of the anionic surfactant can be measured by adopting a two-phase potentiometric titration method and taking hallisin cationic solution as a titrant and judging equivalent potential by a potentiometric titrator.

Accurately weighing 5.0g of surfactant sample solution to be measured, sampling 3-4 parts in parallel each time, and recording the weighed weight W _S (g) Respectively adding 40mL of distilled water, and adjusting the pH value of each parallel sample to be about 11.00 by using 0.2M NaOH standard solution; adding 10mL of ethanol and 10mL of methyl isobutyl ketone (MIBK) into the solution with the adjusted pH value in sequence, titrating by adopting 0.004M hamming 1622 standard solution, and recording the volume V of consumed halmin _H (mL). The degree of carboxylation or sulfonation of the surfactant samples was calculated using the following formulaAnd (4) degree. Where Mw is the molecular weight of the surfactant sample to be tested.

The surfactant composition prepared by the invention is used in an amount 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, 4 wt% of surfactant can well emulsify the crude oil, the maximum solubilization parameter is 20.5, and a better technical effect is achieved.

The 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 surfactant composition with the dosage of 0.01-0.15 wt%, the polymer with the dosage of 0-0.3 wt% and the alkali with the dosage of 0-1.2 wt% form the oil displacement agent 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 The mN/m is evaluated in a physical simulation displacement laboratory, and the oil displacement agent can improve the crude oil recovery rate on the basis of water displacement by 27.74 percent to the maximum extent, so that a better technical effect is achieved.

Drawings

The zwitterionic compound and the surfactant containing polyether fragments prepared by the invention can be applied to a U.S. Nicolet-5700 spectrometer and subjected to infrared spectrum analysis (with the scanning range of 4000-400 cm) by total reflection (ATR) ^-1 ) And determining the chemical structure of the tested sample so as to achieve infrared characterization of the compound.

FIG. 1 is a reaction solution HPLC chart of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt prepared in [ example 1 ]. Evaporative light detector (ELSD), Xcharge C18 chromatography column (2.1 × 150mm, 5 μm); gradient elution is carried out by acetonitrile-0.1% trifluoroacetic acid water solution, the flow rate is 1.0mL/min, and the column temperature is 30 ℃. Wherein 1 is a solvent group peak, 2 is unreacted tertiary amine (N-octadecyl-N-methylaniline), and 3 is (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt.

FIG. 2 is an infrared spectrum of (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt. Wherein, 2918.4cm ^-1 And 2850.4cm ^-1 Is a characteristic peak of C-H stretching of methyl and methylene, 1629.9cm ^-1 Is C ═ O stretching vibration absorption peak, 1546.8cm ^-1 And 1602.8cm ^-1 Is the stretching vibration peak of benzene ring, 1465.1cm ^-1 Is a C-N bending vibration absorption peak, 1167.0cm ^-1 And 1239.1cm ^-1 Is a C-N stretching vibration peak of 700.0-800.0 cm ^-1 Is the in-plane rocking absorption peak of CH plane in the benzene ring.

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, 174.8 g (1.5 mol) of sodium chloroacetate, and 750 g of a 50 wt% 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 for 8 hours to stop the reaction. A small amount of the reaction solution was taken for HPLC analysis, and the ratio of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt to N-octadecyl-N-methylaniline was 96.7:3.3, as shown in FIG. 1. Dissolving in ethyl acetate, desalting for several times, removing organic solvent to obtain zwitterionic surfactant, and performing total reflection (ATR) with Nicolet-5700 infrared spectrometerInfrared spectroscopic analysis (scanning range 4000-400 cm) ^-1 ) The infrared spectrum is shown in figure 2. The remaining samples were left untreated and were ready for use.

(b) Preparation of surfactant composition S01

Z ₁ ＝Z ₂ ＝CH ₂ COOH.HN(CH ₂ CH ₂ OH) ₂ ；r ₁ +r ₂ ＝4，s ₁ +s ₂ ＝15，r ₃ +r ₄ ＝3。

Adding 261 g (1 mol) of dodecylaniline, 5.9 g of sodium hydroxide and 11.9 g of anhydrous potassium carbonate into a 5L 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 110 ℃, slowly introducing 178.2 g (4.05 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.50MPa, after the reaction of the ethylene oxide is finished, slowly introducing 881.6 g (15.2 mol) of propylene oxide at 150 ℃, controlling the pressure to be less than or equal to 0.60MPa, and after the reaction of the propylene oxide is finished, adjusting the temperature to 140 ℃, and slowly introducing 134.2 g (3.05 mol) of ethylene oxide. 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, 1394.4 g of dodecylaniline polyoxyethylene (4), polyoxypropylene (15) and polyoxyethylene (3) ether are obtained, and the yield is 96.9%.

Dodecylaniline polyoxyethylene (4) polyoxypropylene (15) polyoxyethylene (3) ether 719.5 g (0.5 mol), 60 g (1.5 mol) sodium hydroxide, 235.0 g (2.0 mol) sodium chloroacetate and 800 ml toluene/benzene (v/v ═ 1) were mixed in a 5000 ml four-neck flask equipped with mechanical stirrer, thermometer and reflux condenser, and heated to reflux for 8 hours. After the reaction, all reaction solutions were acidified, washed with saturated brine 3 times, and toluene/benzene was distilled off under reduced pressure, and the obtained product was subjected to carboxylation of 190.4% using halmin cation solution as a titrant using a mertler T90 autopotentiometric titrator, and 1500g of water, 126.0 g (1.2 mol) of diethanolamine, 83.4 g (0.2 mol) of an aqueous ethanol solution of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt were added, and uniformly mixed to obtain the desired 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 reaction bottle 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-carboxymethyl oxyethyl-N-dodecyl) phenyl ammonium inner salt to N-dodecyl-N-hydroxyethyl aniline is 89.6:8.4, and the rest samples are not processed.

(b) Preparation of surfactant composition S02

Wherein r is ₁ +r ₂ ＝5，s ₁ +s ₂ ＝5，r ₃ +r ₄ ＝3。

325 g (1 mol) of icosaediamine, 2.3 g of potassium hydroxide and 8.4 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 120 ℃, 222.2 g (5.05 mol) of ethylene oxide is slowly introduced, the pressure is controlled to be less than or equal to 0.60MPa, the temperature is adjusted to 130 ℃ after the reaction of the ethylene oxide, 295.8 g (5.1 mol) of propylene oxide is slowly introduced, the pressure is controlled to be less than or equal to 0.60MPa, and the temperature is adjusted to 140 ℃ after the reaction of the propylene oxide, 134.2 g (3.05 mol) of ethylene oxide is slowly introduced. After the reaction, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and neutralization and dehydration are carried out after cooling, so that 925.4 g of the icosapolyoxyethylene (5) polyoxypropylene (5) polyoxyethylene (3) ether are obtained, and the yield is 95.7%.

Icosanediamine polyoxyethylene (5) polyoxypropylene (5) polyoxyethylene (3) ether 478.5 g (0.5 mol), 160 g (4 mol) sodium hydroxide, 589.5 g (3 mol) sodium 3-chloro-2-hydroxypropanesulfonate and 800 ml toluene/benzene (v/v ═ 2) were mixed in a 5000 ml four-neck flask equipped with a mechanical stirrer, thermometer and reflux condenser, and heated to 85 ℃ for reaction for 9 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 20 wt% hydrochloric acid, separating water and inorganic salt, evaporating to remove the solvent, adopting a Mettler company T90 automatic potentiometric titrator, taking a Heimemin cation solution as a titrant, and measuring the sulfonation degree to be 175.8% through potentiometric drop. . The solvent was distilled off from the remaining untreated reaction solution, 600 g of water, 80.0 g (2.0 mol) of sodium hydroxide, and an aqueous solution containing 630.0 g (1.5 mol) of (N-carboxymethyl-N-carboxymethyloxyethyl-N-dodecyl) phenylammonium inner salt were added, and stirring was continued at 40 ℃ for 4 hours to obtain the desired 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 5 wt% 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 94.7:6.3, and the rest samples are not processed for later use.

(b) Preparation of surfactant composition S03

R ₅ Is CH ₃ (CH ₂ ) ₇ CH＝CH(CH ₂ ) ₈ ；Z ₁ ＝Z ₂ ＝CH ₂ COONa r ₁ +r ₂ ＝3，s ₁ +s ₂ ＝12，r ₃ +r ₄ ＝4。

Adding 267.0 g (1 mol) of 9-ene-octadecylamine and 9.5 g of potassium hydroxide into a 5L 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 110 ℃, slowly introducing 132.9 g (3.02 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.50MPa, after the reaction of the ethylene oxide is finished, slowly introducing 701.8 g (12.1 mol) of propylene oxide at 150 ℃, controlling the pressure to be less than or equal to 0.60MPa, and after the reaction of the propylene oxide is finished, adjusting the temperature to 130 ℃, and slowly introducing 178.2 g (4.05 mol) of ethylene oxide. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and the 9-ene octadecylamine polyoxyethylene (3), polyoxypropylene (12) polyoxyethylene (4) ether 1230.3 g is obtained through neutralization and dehydration after cooling, and the yield is 96.8%.

Introducing nitrogen into a 5000 ml reaction bottle provided with a mechanical stirring device, a thermometer and a reflux condenser tube to remove moisture, adding 635.5 g (0.5 mol) of 9-ene-octadecylamine polyoxyethylene (3) polyoxypropylene (12) polyoxyethylene (4) ether and 108.0 g (2.0 mol) of sodium methoxide under the protection of nitrogen, slowly dripping 162.8 g (1.5 mol) of methyl chloroacetate, controlling the reaction temperature to be 65 ℃ for reacting for 8 hours, cooling, adding 1000 g of water and 50 g of methanol, and continuously heating until reflux reaction is carried out for 5 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 20 wt% hydrochloric acid, evaporating methanol, adding 100 g of benzene, mixing, removing a water layer, washing with saturated saline solution for 3 times, decompressing, evaporating benzene, and measuring the carboxylation degree to be 185.6% by adopting a Mettler company T90 automatic potentiometric titrator and using a Helminum cation solution as a titrant. The remaining untreated reaction solution was added with 1280 g of water, and an aqueous isopropanol solution containing 166.1 g (0.5 mol) of (N-carboxymethyl-N-dodecyl-N-methyl) phenyl ammonium inner salt, and mixed uniformly to obtain the desired surfactant composition S03.

[ example 4 ]

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

In a 2000 ml four-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, 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 15 wt% aqueous isopropanol solution were mixed, and the mixture was heated to reflux and reacted for 9 hours, thereby stopping the reaction. A small amount of reaction liquid is taken for HPLC analysis, the ratio of the (N-carboxymethyl-N, N-dimethyl) -4-hexadecyl phenyl ammonium inner salt to the N, N-dimethyl- (4-hexadecyl) aniline is 91.2:8.8, and other samples are not processed for later use.

(b) Preparation of surfactant composition S04

Wherein r is ₁ +r ₂ ＝0，s ₁ +s ₂ ＝5，r ₃ +r ₄ ＝15。

325 g (1 mol) of icosamine, 2.3 g of potassium hydroxide and 8.4 g of anhydrous potassium carbonate are added into a 2L pressure reactor provided with a stirring device, a vacuum system is started when the mixture is heated to 80-90 ℃, the mixture is dehydrated 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 130 ℃, 295.8 g (5.1 mol) of propylene oxide is slowly introduced, the pressure is controlled to be less than or equal to 0.60MPa, and after the reaction of the propylene oxide is finished, 664.4 g (15.1 mol) of ethylene oxide is slowly introduced when the temperature is adjusted to 140 ℃. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, neutralization and dehydration are carried out after cooling, 1201.1 g of the icosanediamine polyoxypropylene (5) polyoxyethylene (15) ether are obtained, and the yield is 94.2%.

Icosanediamine polyoxypropylene (5) polyoxyethylene (15) ether 637.5 g (0.5 mol) was mixed with 200 g (5 mol) sodium hydroxide, 589.5 g (3 mol) sodium 3-chloro-2-hydroxypropanesulfonate and 800 ml toluene/benzene (v/v ═ 2) in a 5000 ml four-neck flask equipped with mechanical stirrer, thermometer and reflux condenser, and heated to 85 ℃ for 8 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 20 wt% hydrochloric acid, separating water and inorganic salt, evaporating to remove the solvent, adopting a Mettler company T90 automatic potentiometric titrator, taking a Heimemin cation solution as a titrant, and measuring the sulfonation degree to be 168.7% through potentiometric dropping. The remaining untreated reaction solution was distilled off the solvent, 600 g of water, an aqueous isopropanol solution containing 806.0 g (2.0 mol) of the inner salt of (N-carboxymethyl-N, N-dimethyl) -4-hexadecylphenylammonium were added, and stirring was continued at 40 ℃ for 4 hours to obtain the desired 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 25 wt% aqueous ethanol solution were mixed in a 2000-ml four-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and heated to reflux reaction for 12 hours, and the reaction was stopped. A small amount of the reaction solution was subjected to 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 87.5:12.5, and the remaining sample was left untreated and was used for future use.

(b) Preparation of surfactant composition S05

R ₅ Is C ₁₄ H ₂₉ ；Z ₁ ＝Z ₂ ＝CH ₂ COONa r ₁ +r ₂ ＝3，s ₁ +s ₂ ＝12，r ₃ +r ₄ ＝4。

Adding 213 g (1 mol) of tetradecylamine and 8.2 g of potassium hydroxide into a 5L 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 110 ℃, slowly introducing 132.9 g (3.02 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.50MPa, after the reaction of the ethylene oxide is finished, slowly introducing 701.8 g (12.1 mol) of propylene oxide at 150 ℃, controlling the pressure to be less than or equal to 0.60MPa, and after the reaction of the propylene oxide is finished, adjusting the temperature to 130 ℃, and slowly introducing 178.2 g (4.05 mol) of ethylene oxide. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, neutralization and dehydration are carried out after cooling, 1158.6 g of decatetramine polyoxyethylene (3), polyoxypropylene (12) and polyoxyethylene (4) ether are obtained, and the yield is 95.2%.

Introducing nitrogen into a 5000 ml reaction bottle provided with a mechanical stirring pipe, a thermometer and a reflux condenser pipe to remove water vapor, adding 608.5 g (0.5 mol) of tetradecylamine polyoxyethylene (3), polyoxypropylene (12) polyoxyethylene (4) ether and 108.0 g (2.0 mol) of sodium methoxide under the protection of nitrogen, slowly dripping 162.8 g (1.5 mol) of methyl chloroacetate, controlling the reaction temperature to be 65 ℃ for reacting for 8 hours, cooling, adding 1000 g of water and 50 g of methanol, and continuously heating until the reflux reaction is carried out for 5 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 20 wt% hydrochloric acid, evaporating methanol, adding 100 g of benzene, mixing, removing a water layer, washing with saturated saline solution for 3 times, decompressing, evaporating benzene, and measuring the carboxylation degree to be 180.2% by adopting a Mettler company T90 automatic potentiometric titrator and taking a Halmin cation solution as a titrant. The remaining untreated reaction solution was added with 1000 g of water, 10.5 g (0.1 mol) of diethanolamine, and an aqueous ethanol solution containing 36.2 g (0.05 mol) of an inner salt of (N- (2-hydroxy-3-propanesulfonic acid) -N-methyl-N-hexadecyl) -4-methylphenylammonium, and stirring was continued at 45 ℃ for 3 hours to obtain the desired 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 5 wt% aqueous isopropanol 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 for 8 hours to stop the reaction. 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 95.1:4.9, and the rest samples are not processed for standby.

(b) Preparation of surfactant composition S06

Adding 267.0 g (1 mol) of 9-ene-octadecylamine and 9.5 g of potassium hydroxide into a 5L 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 110 ℃, slowly introducing 132.9 g (3.02 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.50MPa, after the reaction of the ethylene oxide is finished, slowly introducing 701.8 g (12.1 mol) of propylene oxide at 150 ℃, controlling the pressure to be less than or equal to 0.60MPa, and after the reaction of the propylene oxide is finished, adjusting the temperature to 130 ℃, and slowly introducing 178.2 g (4.05 mol) of ethylene oxide. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and neutralization and dehydration are carried out after cooling, so that 1230.3 g of 9-ene octadecylamine polyoxyethylene (3), polyoxypropylene (12) polyoxyethylene (4) ether are obtained, and the yield is 96.8%.

Introducing nitrogen into a 5000 ml reaction bottle provided with a mechanical stirring device, a thermometer and a reflux condenser tube to remove moisture, adding 635.5 g (0.5 mol) of 9-ene-octadecylamine polyoxyethylene (3) polyoxypropylene (12) polyoxyethylene (4) ether and 108.0 g (2.0 mol) of sodium methoxide under the protection of nitrogen, slowly dripping 162.8 g (1.5 mol) of methyl chloroacetate, controlling the reaction temperature to be 65 ℃ for reacting for 8 hours, cooling, adding 1000 g of water and 50 g of methanol, and continuously heating until reflux reaction is carried out for 5 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 20 wt% hydrochloric acid, evaporating methanol, adding 100 g of benzene, mixing, removing a water layer, washing with saturated saline solution for 3 times, decompressing, evaporating benzene, and measuring the carboxylation degree to be 185.6% by adopting a Mettler corporation T90 automatic potentiometric titrator and taking a Helminum cation solution as a titrant. The remaining untreated reaction solution was added 1200 g of water, an aqueous isopropanol solution containing 3.6 g (0.02 mol) of the inner salt of (N-carboxymethyl-N, N-dimethyl) phenylammonium, and mixed well to obtain the desired 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 15 wt% 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 92.5:7.5, and the rest samples are not processed for later use.

(b) Preparation of surfactant composition S07

Introducing nitrogen into a 5000 ml reaction bottle provided with a mechanical stirring device, a thermometer and a reflux condenser tube to remove moisture, adding 635.5 g (0.5 mol) of 9-ene-octadecylamine polyoxyethylene (3) polyoxypropylene (12) polyoxyethylene (4) ether and 108.0 g (2.0 mol) of sodium methoxide under the protection of nitrogen, slowly dripping 162.8 g (1.5 mol) of methyl chloroacetate, controlling the reaction temperature to be 65 ℃ for reacting for 8 hours, cooling, adding 1000 g of water and 50 g of methanol, and continuously heating until reflux reaction is carried out for 5 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 20 wt% hydrochloric acid, evaporating methanol, adding 100 g of benzene, mixing, removing a water layer, washing with saturated saline solution for 3 times, decompressing, evaporating benzene, and measuring the carboxylation degree to be 185.6% by adopting a Mettler corporation T90 automatic potentiometric titrator and taking a Helminum cation solution as a titrant. The remaining untreated reaction solution was added 1200 g of water, an aqueous isopropanol solution containing 10.3 g (0.05 mole) of the inner salt of (N-carboxymethyl-N, N-diethyl) phenylammonium, and mixed well to give the desired 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 15 wt% 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-ethylaniline is 93.7:6.3, and the rest samples are not processed for later use.

(b) Surfactant composition S08 was prepared

Introducing nitrogen into a 5000 ml reaction bottle with a mechanical stirrer, a thermometer and a reflux condenser tube to remove water vapor, adding 635.5 g (0.5 mol) of 9-ene-octadecylamine polyoxyethylene (3) polyoxypropylene (12) polyoxyethylene (4) ether and 108.0 g (2.0 mol) of sodium methoxide under the protection of nitrogen, slowly dripping 162.8 g (1.5 mol) of methyl chloroacetate, controlling the reaction temperature to 65 ℃ for reacting for 8 hours, cooling, adding 1000 g of water and 50 g of methanol, and continuously heating until reflux reaction is carried out for 5 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 20 wt% hydrochloric acid, evaporating methanol, adding 100 g of benzene, mixing, removing a water layer, washing with saturated saline solution for 3 times, decompressing, evaporating benzene, and measuring the carboxylation degree to be 185.6% by adopting a Mettler company T90 automatic potentiometric titrator and using a Helminum cation solution as a titrant. The remaining untreated reaction solution was added with 1200 g of water, an aqueous isopropanol solution containing 18.8 g (0.1 mol) of (N-methyl-N-ethyl) phenyl ammonium inner salt, and mixed well to obtain the desired surfactant composition S08.

[ example 9 ]

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 step (a), to obtain the desired surfactant composition S09.

[ example 10 ]

359.0 g (1 mol) of N-octadecyl-N-methylaniline, 174.8 g (1.5 mol) of sodium chloroacetate, and 750 g of a 50 wt% 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 for 8 hours to stop the reaction. A small amount of the reaction solution was taken for HPLC analysis, and the ratio of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt to N-octadecyl-N-methylaniline was 96.7:3.3, as shown in FIG. 1. Dissolving ethyl acetate for desalting for multiple times, removing organic solvent to obtain zwitterionic surfactant, and performing infrared spectrum analysis (scan range 4000-400 cm) by liquid membrane method with Nicolet-5700 infrared spectrometer ^-1 ) The infrared spectrum is shown in figure 2. The remaining samples were left untreated and were ready for use.

(b) Preparation of surfactant composition S10

Z ₁ ＝Z ₂ ＝H；r ₁ +r ₂ ＝4，s ₁ +s ₂ ＝15，r ₃ +r ₄ ＝3。

261 g (1 mol) of dodecylaniline, 5.9 g of sodium hydroxide and 11.9 g of anhydrous potassium carbonate are added into a 5L 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 110 ℃, 178.2 g (4.05 mol) of ethylene oxide is slowly introduced, the pressure is controlled to be less than or equal to 0.50MPa, 881.6 g (15.2 mol) of propylene oxide is slowly introduced at 150 ℃ after the reaction of the ethylene oxide is finished, the pressure is controlled to be less than or equal to 0.60MPa, and 134.2 g (3.05 mol) of ethylene oxide is slowly introduced after the reaction of the propylene oxide is finished. 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, 1394.4 g of dodecylaniline polyoxyethylene (4), polyoxypropylene (15) and polyoxyethylene (3) ether are obtained, and the yield is 96.9%.

Dodecylaniline polyoxyethylene (4) polyoxypropylene (15) polyoxyethylene (3) ether 5.8 g (0.004 mol), 200 g water, 126.0 g (1.2 mol) diethanolamine, 83.4. g (0.2 mol) aqueous ethanol of (N-carboxymethyl-N-octadecyl-N-methyl) phenyl ammonium inner salt, and mixing them uniformly to obtain the desired surfactant composition S10.

[ example 11 ]

Performance experiments of the surfactant composition as an oil displacement agent.

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 parameter 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 are prepared (1) ^# ～9 ^# Simulated water) was added 2.5mL into a 5mL pipette sealed at one end, and addedAdding 2.5mL of dehydrated crude oil (the volume ratio of oil to water is 1:1), sealing the upper end of the dehydrated crude oil, recording the initial volume of the oil to water, fully mixing, putting the dehydrated crude oil into a stainless steel sealed container, placing the stainless steel sealed container in an oven, standing at constant temperature until the volume of each phase is not changed, recording the volume of each phase, calculating the solubilization parameter of the surfactant on the crude oil, and taking the salinity with the maximum solubilization parameter as the optimal salt content, wherein the results are shown in Table 2.

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 with 1g of clay-containing quartz sand, oscillating for 24 hours at a set temperature, cooling, performing centrifugal separation, taking supernatant, measuring the concentration of effective components of the surfactant by using a TOC method, and calculating the adsorption capacity of the surfactant in unit mg/g, wherein the results are shown in Table 3. Wherein, the clay-containing quartz sand comprises the following components: 10 wt% of kaolin and 90 wt% of 100-200 mesh quartz sand.

The surfactant composition was dissolved in the 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 0.15 wt% surfactant composition simulated saline solution into a 20 ml anbei bottle, sealing, placing into an oven, measuring 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, the rest was the same, to give surfactant compositions S11 and S12. The performance test was carried out as in example 11, and the results are shown in Table 5.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

[ example 12 ]

359.0 g (1 mol) of N-octadecyl-N-methylaniline and 174.8 g (1.5 mol) of sodium chloroacetate,750 g of a 50 wt% aqueous ethanol solution was 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. A small amount of the reaction solution was taken for HPLC analysis, and the ratio of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt to N-octadecyl-N-methylaniline was 96.7:3.3, as shown in FIG. 1. Dissolving ethyl acetate for desalting for multiple times, removing organic solvent to obtain zwitterionic surfactant, and performing infrared spectrum analysis (scan range 4000-400 cm) by total reflection (ATR) with Nicolet-5700 infrared spectrometer ^-1 ) The infrared spectrum is shown in figure 2. The remaining samples were left untreated and were ready for use.

(b) Preparation of surfactant composition S01

Adding 261 g (1 mol) of dodecylaniline, 5.9 g of sodium hydroxide and 11.9 g of anhydrous potassium carbonate into a 5L 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 110 ℃, slowly introducing 178.2 g (4.05 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.50MPa, after the reaction of the ethylene oxide is finished, slowly introducing 881.6 g (15.2 mol) of propylene oxide at 150 ℃, controlling the pressure to be less than or equal to 0.60MPa, and after the reaction of the propylene oxide is finished, adjusting the temperature to 140 ℃, and slowly introducing 134.2 g (3.05 mol) of ethylene oxide. 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, 1394.4 g of dodecylaniline polyoxyethylene (4), polyoxypropylene (15), polyoxyethylene (3) ether are obtained, and the yield is 96.9%.

In a 5000 ml four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, 719.5 g (0.5 mol) of dodecylaniline polyoxyethylene (4) polyoxypropylene (15) polyoxyethylene (3) ether, 235.0 g (2.0 mol) of sodium chloroacetate and 800 ml of toluene/benzene (v/v ═ 1) were mixed, and the mixture was heated to reflux reaction for 8 hours. After the reaction, all reaction solutions were acidified, washed with saturated brine 3 times, and toluene/benzene was distilled off under reduced pressure, and the obtained product was subjected to carboxylation of 190.4% using halmin cation solution as a titrant using a mertler T90 autopotentiometric titrator, and 1500g of water, 126.0 g (1.2 mol) of diethanolamine, 83.4 g (0.2 mol) of an aqueous ethanol solution of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt were added, and uniformly mixed to obtain the desired surfactant composition S01.

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 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 (the volume ratio of oil to water is 1:1), sealing the upper end, recording the initial volume of oil and water, fully mixing, placing the mixture into a stainless steel sealed container, placing the container in an oven, standing at constant temperature until the volume of each phase is not changed, recording the volume of each phase, calculating the solubilization parameter of the surfactant to the crude oil, and taking the salinity when the solubilization parameter is maximum as the optimal salt content, wherein the result is shown in Table 2.

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: 10 wt% of kaolin and 90 wt% of 100-200 mesh quartz sand.

(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 is 1/0.05, and the viscosity average molecular weight is 2500 ten thousand) and an aqueous solution of sodium carbonate by using 11# simulated water, and mixing and diluting the aqueous solution according to a required ratio 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. The apparent viscosity was measured by a model HAAKE MARS III rotational rheometer, and the interfacial tension was measured by a model TX500 rotational drop interfacial tension meter, manufactured by texas university, usa.

(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 simulated brine saturated cores were tested for pore volume. 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 2.5 mPa.s.

[ example 13 ] to prepare a suspension

(b) Preparation of surfactant composition S02

Wherein r is ₁ +r ₂ ＝5，s ₁ +s ₂ ＝5，r ₃ +r ₄ ＝3。

Icosanediamine polyoxyethylene (5) polyoxypropylene (5) polyoxyethylene (3) ether 478.5 g (0.5 mol), 160 g (4 mol) sodium hydroxide, 589.5 g (3 mol) sodium 3-chloro-2-hydroxypropanesulfonate and 800 ml toluene/benzene (v/v ═ 2) were mixed in a 5000 ml four-neck flask equipped with a mechanical stirrer, thermometer and reflux condenser, and heated to 85 ℃ for reaction for 9 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 20 wt% hydrochloric acid, separating water and inorganic salt, evaporating to remove the solvent, adopting a Mettler company T90 automatic potentiometric titrator, taking a Heimemin cation solution as a titrant, and measuring the sulfonation degree to be 175.8% through potentiometric drop. . The solvent was distilled off from the remaining untreated reaction solution, 600 g of water, 80.0 g (2.0 mol) of sodium hydroxide, and an aqueous solution containing 630.0 g (1.5 mol) of (N-carboxymethyl-N-carboxymethyloxyethyl-N-dodecyl) phenylammonium inner salt were added, and stirring was continued at 40 ℃ for 4 hours to obtain the desired surfactant composition S02. Phase and static adsorption experiments were carried out as in [ example 12 ] and the results are shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 12 ], except that S02 was used instead of S01, a hydrophobically associating polymer P2 (copolymerization AM/AMPS/2-acrylamidododecylsulfonic acid molar ratio 1/0.45/0.002, viscosity average molecular weight 1750 ten thousand) was used instead of the modified polyacrylamide polymer (P1, copolymerization AM/AMPS molar ratio 1/0.05, viscosity average molecular weight 2500 ten thousand), diethanolamine was used instead of sodium carbonate, 9# simulated water, an oil-displacing agent aqueous solution was prepared, the temperature was 110 ℃, and the viscosity of crude oil was 1.9mpa.s, and the results are shown in table 7.

[ example 14 ]

(b) Preparation of surfactant composition S03

Introducing nitrogen into a 5000 ml reaction bottle with a mechanical stirrer, a thermometer and a reflux condenser tube to remove water vapor, adding 635.5 g (0.5 mol) of 9-ene-octadecylamine polyoxyethylene (3) polyoxypropylene (12) polyoxyethylene (4) ether and 108.0 g (2.0 mol) of sodium methoxide under the protection of nitrogen, slowly dripping 162.8 g (1.5 mol) of methyl chloroacetate, controlling the reaction temperature to 65 ℃ for reacting for 8 hours, cooling, adding 1000 g of water and 50 g of methanol, and continuously heating until reflux reaction is carried out for 5 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 20 wt% hydrochloric acid, evaporating methanol, adding 100 g of benzene, mixing, removing a water layer, washing with saturated saline solution for 3 times, decompressing, evaporating benzene, and measuring the carboxylation degree to be 185.6% by adopting a Mettler company T90 automatic potentiometric titrator and using a Helminum cation solution as a titrant. The remaining untreated reaction solution was added with 1280 g of water, and an aqueous isopropanol solution containing 166.1 g (0.5 mol) of (N-carboxymethyl-N-dodecyl-N-methyl) phenyl ammonium inner salt, and mixed uniformly to obtain the desired surfactant composition S03. Phase and static adsorption experiments were carried out as in [ example 12 ] and the results are shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 12 ] 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 was used to prepare an oil displacement agent aqueous solution at 90 ℃ and crude oil viscosity 2.1mpa.s, and the results are shown in table 7.

[ example 15 ]

(b) Preparation of surfactant composition S04

Wherein r is ₁ +r ₂ ＝0，s ₁ +s ₂ ＝5，r ₃ +r ₄ ＝15。

Icosanediamine polyoxypropylene (5) polyoxyethylene (15) ether 637.5 g (0.5 mol) was mixed with 200 g (5 mol) sodium hydroxide, 589.5 g (3 mol) sodium 3-chloro-2-hydroxypropanesulfonate and 800 ml toluene/benzene (v/v ═ 2) in a 5000 ml four-neck flask equipped with mechanical stirrer, thermometer and reflux condenser, and heated to 85 ℃ for 8 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 20 wt% hydrochloric acid, separating water and inorganic salt, evaporating to remove the solvent, adopting a Mettler company T90 automatic potentiometric titrator, taking a Heimemin cation solution as a titrant, and measuring the sulfonation degree to be 168.7% through potentiometric dropping. The remaining untreated reaction solution was distilled to remove the solvent, 600 g of water, an aqueous isopropanol solution containing 806.0 g (2.0 mol) of the inner salt of (N-carboxymethyl-N, N-dimethyl) -4-hexadecylphenylammonium were added, and stirring was continued at 40 ℃ for 4 hours to obtain the desired surfactant composition S04.

Phase and static adsorption experiments were carried out as in [ example 12 ] and the results are shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 14 ] except that S04 was used in place of S03 and 10# simulated water to prepare an aqueous solution of an oil-displacing agent at 85 ℃ and the viscosity of dehydrated crude oil was 59.5mPa.s, the results of which are shown in Table 7.

[ example 16 ] A method for producing a polycarbonate

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 25 wt% 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 subjected to 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 87.5:12.5, and the remaining sample was left untreated and was used for future use.

(b) Preparation of surfactant composition S05

Introducing nitrogen into a 5000 ml reaction bottle provided with a mechanical stirring pipe, a thermometer and a reflux condenser pipe to remove water vapor, adding 608.5 g (0.5 mol) of tetradecylamine polyoxyethylene (3), polyoxypropylene (12) polyoxyethylene (4) ether and 108.0 g (2.0 mol) of sodium methoxide under the protection of nitrogen, slowly dripping 162.8 g (1.5 mol) of methyl chloroacetate, controlling the reaction temperature to be 65 ℃ for reacting for 8 hours, cooling, adding 1000 g of water and 50 g of methanol, and continuously heating until the reflux reaction is carried out for 5 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 20 wt% hydrochloric acid, evaporating methanol, adding 100 g of benzene, mixing, removing a water layer, washing with saturated saline solution for 3 times, decompressing, evaporating benzene, and measuring the carboxylation degree to be 180.2% by adopting a Mettler company T90 automatic potentiometric titrator and taking a Halmin cation solution as a titrant. The remaining untreated reaction solution was added with 1000 g of water, 10.5 g (0.1 mol) of diethanolamine, and an aqueous ethanol solution containing 36.2 g (0.05 mol) of an inner salt of (N- (2-hydroxy-3-propanesulfonic acid) -N-methyl-N-hexadecyl) -4-methylphenylammonium, and stirred at 45 ℃ for 3 hours to obtain the desired surfactant composition S05. Phase and static adsorption experiments were carried out as in [ example 12 ] and the results are shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

Except that S05 is used for replacing S01, high molecular weight anionic polyacrylamide P4 (viscosity average molecular weight is 2300 ten thousand) is used for replacing modified polyacrylamide polymer (P1, the molar ratio of the copolymer AM/AMPS is 1/0.05, and the viscosity average molecular weight is 2500 ten thousand), 11# simulated water is used for preparing an oil displacement agent aqueous solution, the temperature is 55 ℃, the viscosity of crude oil is 125.9mPa.s, and the result is shown in Table 6.

[ example 17 ] to provide

(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 5 wt% aqueous isopropanol 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 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-dimethyl) phenyl ammonium inner salt to the N, N-dimethylaniline is 95.1:4.9, and the rest samples are not processed for later use.

(b) Preparation of surfactant composition S06

Introducing nitrogen into a 5000 ml reaction bottle provided with a mechanical stirring device, a thermometer and a reflux condenser tube to remove moisture, adding 635.5 g (0.5 mol) of 9-ene-octadecylamine polyoxyethylene (3) polyoxypropylene (12) polyoxyethylene (4) ether and 108.0 g (2.0 mol) of sodium methoxide under the protection of nitrogen, slowly dripping 162.8 g (1.5 mol) of methyl chloroacetate, controlling the reaction temperature to be 65 ℃ for reacting for 8 hours, cooling, adding 1000 g of water and 50 g of methanol, and continuously heating until reflux reaction is carried out for 5 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 20 wt% hydrochloric acid, evaporating methanol, adding 100 g of benzene, mixing, removing a water layer, washing with saturated saline solution for 3 times, decompressing, evaporating benzene, and measuring the carboxylation degree to be 185.6% by adopting a Mettler company T90 automatic potentiometric titrator and using a Helminum cation solution as a titrant. The remaining untreated reaction solution was added 1200 g of water, an aqueous isopropanol solution containing 3.6 g (0.02 mol) of the inner salt of (N-carboxymethyl-N, N-dimethyl) phenylammonium, and mixed well to obtain the desired surfactant composition S06. Phase and static adsorption experiments were carried out as in [ example 12 ] and the results are shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 14 ] except that an aqueous displacement agent solution was prepared by replacing S03 with S06, and the results are shown in table 7.

[ example 18 ]

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

(b) Preparation of surfactant composition S07

Phase and static adsorption experiments were carried out as in [ example 12 ], with the results shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 14 ] except that an aqueous displacement agent solution was prepared in place of S03 by S07, and the results are shown in table 7.

[ example 19 ] to provide

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

(b) Surfactant composition S08 was prepared

Introducing nitrogen into a 5000 ml reaction bottle provided with a mechanical stirring device, a thermometer and a reflux condenser tube to remove moisture, adding 635.5 g (0.5 mol) of 9-ene-octadecylamine polyoxyethylene (3) polyoxypropylene (12) polyoxyethylene (4) ether and 108.0 g (2.0 mol) of sodium methoxide under the protection of nitrogen, slowly dripping 162.8 g (1.5 mol) of methyl chloroacetate, controlling the reaction temperature to be 65 ℃ for reacting for 8 hours, cooling, adding 1000 g of water and 50 g of methanol, and continuously heating until reflux reaction is carried out for 5 hours. Cooling, taking 50 g of uniform reaction liquid, acidifying with 20 wt% hydrochloric acid, evaporating methanol, adding 100 g of benzene, mixing, removing a water layer, washing with saturated saline solution for 3 times, decompressing, evaporating benzene, and measuring the carboxylation degree to be 185.6% by adopting a Mettler company T90 automatic potentiometric titrator and using a Helminum cation solution as a titrant. The remaining untreated reaction solution was added with 1200 g of water, an aqueous isopropanol solution containing 18.8 g (0.1 mol) of (N-methyl-N-ethyl) phenyl ammonium inner salt, and mixed well to obtain the desired surfactant composition S08. Phase and static adsorption experiments were carried out as in [ example 12 ] and the results are shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 14 ] except that an aqueous displacement agent solution was prepared by replacing S03 with S08, and the results are shown in table 7.

[ example 20 ]

S09 is used for replacing S01 to prepare an oil displacement agent aqueous solution, and the results of adsorption and oil displacement experiments are shown in Table 6.

[ example 21 ]

359.0 g (1 mol) of N-octadecyl-N-methylaniline, 174.8 g (1.5 mol) of sodium chloroacetate, and 750 g of a 50 wt% 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 for 8 hours to stop the reaction. A small amount of the reaction solution was taken for HPLC analysis, and the ratio of (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt to N-octadecyl-N-methylaniline was 96.7:3.3, as shown in FIG. 1. Dissolving ethyl acetate for desalting for multiple times, removing organic solvent to obtain zwitterionic surfactant, and performing infrared spectrum analysis (scan range 4000-400 cm) by liquid membrane method with Nicolet-5700 infrared spectrometer ^-1 ) The infrared spectrum is shown in figure 2. Rest sampleThe product is not processed and is ready for use.

(b) Preparation of surfactant composition S10

Dodecylaniline polyoxyethylene (4) polyoxypropylene (15) polyoxyethylene (3) ether 5.8 g (0.004 mol), 200 g water, 126.0 g (1.2 mol) diethanolamine, 83.4 g (0.2 mol) aqueous ethanol (N-carboxymethyl-N-octadecyl-N-methyl) anilinium inner salt, and mixing to obtain the desired surfactant composition S10.

S11。

S10 is used for replacing S01 to prepare an oil displacement agent aqueous solution, and the results of adsorption and oil displacement experiments are shown in Table 6.

[ COMPARATIVE EXAMPLE 2 ]

Octadecyl benzyl methyl betaine

Octadecyl dimethyl betaine

The same as in example 12 except that (N-carboxymethyl-N-octadecyl-N-methyl) phenylammonium inner salt was replaced with commercially available octadecyl benzyl methyl betaine or octadecyl dimethyl betaine, the rest was the same, to give surfactant compositions S11 and S12. The results of preparing the oil-displacing agent aqueous solution by replacing S01 with S11 and S12 are shown in Table 8.

[ COMPARATIVE EXAMPLE 3 ]

The same as [ example 12 ] except that the hydrophobically associative polymer P1 was replaced with a high molecular weight anionic polyacrylamide P4 (having a viscosity average molecular weight of 2300 ten thousand), and the results were as shown in table 8.

TABLE 6

TABLE 7

TABLE 8

Claims

1. A surfactant composition comprising the following components:

(1) a zwitterionic compound;

(2) a polyetheramine surfactant;

in the formula (I), R ₁ And R ₄ Is hydrogen, C ₂ ～C ₃₂ One of the hydrocarbyl or substituted hydrocarbyl and methyl; r ₂ Is C ₁ ～C ₅ Alkylene or substituted alkylene, X ^- Is carboxylate, sulfonate, phosphate or sulfate radical; r ₃ Is hydrogen, methyl, C ₂ ～C ₃₂ One of alkyl or substituted alkyl, OH, halogen, amino, carboxylic acid group or sulfonic group;

the molecular general formula of the polyether amine surfactant is shown as a formula (II):

in the formula (II), R ₅ Is C ₈ ～C ₃₀ Or linear or branched, saturated or unsaturated alkyl or from C ₄ ～C ₂₀ A straight-chain or branched, saturated and unsaturated hydrocarbyl-substituted benzene or naphthalene ring, or R ₅ Is abietylamine radical; r1, r2, r3 or r4 are independently selected from 0-50, but r1 and r2, and r3 and r4 cannot be 0 at the same time; s1 and s2 are independently selected from 0-100, but s1 and s2 cannot be 0 at the same time; y is R ₆ Z; y 'is R' ₆ Z′；R ₆ And R' ₆ Is independently selected from C ₁ ～C ₅ At least one of alkylene or hydroxy-substituted alkylene of (a); z and Z' are independently selected from COOM, SO ₃ One of N, M, N is optionally selected from a cation or a cationic group.

2. The surfactant composition of claim 1, wherein said M, N is selected from the group consisting of hydrogen ions, alkali metal cations, and mixtures thereof ₇ (R ₈ )(R ₉ )(R ₁₀ ) In the group shownWherein R is ₇ 、R ₈ 、R ₉ 、R ₁₀ 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 any integer from 1 to 4, and g is any integer from 0 to 5.

3. The surfactant composition of claim 2, wherein R is ₁ And R ₄ Is hydrogen, C ₈ ～C ₂₄ One of alkyl or substituted alkyl, methyl, ethyl, hydroxyethyl, hydroxypropyl, phenyl and benzyl; r ₂ X ^- Is C ₁ ～C ₃ Alkylene or substituted alkylene carboxylate, C ₁ ～C ₃ One of alkylene or substituted alkylene sulfonate; r ₃ Is hydrogen, C ₈ ～C ₂₄ One of alkyl or substituted alkyl, ethyl, phenyl, hydroxyl, amino, carboxylic acid group or sulfonic acid group; r ⁰ Independently selected from H or CH ₃ (ii) a f is 1-2, g is 0-1; the R is ₅ Is C ₄ ～C ₂₀ Linear or branched saturated and unsaturated hydrocarbyl-substituted benzene or naphthalene rings; r ₆ Is C ₁ ～C ₃ One of alkylene groups of (a); the r1+ r2 is 1-10, r3+ r4 is 1-10, and s1+ s2 is 1-40.

4. The surfactant composition according to claim 1, characterized in that the 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 polyether amine surfactant, the small molecular alcohol, the small molecular amine, the salt and the inorganic base is 1 (0.01-50): (0-20): 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 Primary, secondary or tertiaryAt least one of an amine; the salt is selected from 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.

5. The surfactant composition of claim 4, wherein the molar ratio of the zwitterionic compound, the polyether amine surfactant, the small molecule alcohol, the small molecule amine, the salt and the inorganic base is 1 (0.02-30): (0-15): (0-5): 0-5).

6. A process for preparing a surfactant composition as claimed in any one of claims 1 to 5, comprising the steps of:

(a) preparation of zwitterionic compound:

will be provided with

With ionizing agent X ₀ R ₂ Uniformly mixing the X 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 alcohol is 0-100 wt% and is not 0 or 100% in terms of the mass percentage of the alcohol in the alcohol aqueous solution, and the alcohol is selected from C ₁ ～C ₅ Fatty alcohol of (2), X ₀ Selected from chlorine, bromine or iodine;

(b) preparation of surfactant composition:

in the presence of an alkaline catalyst, R ₅ NH ₂ Reacting with required amount of ethylene oxide, propylene oxide and ethylene oxide in sequence to obtain a polyether compound;

② the polyether compound obtained in the step I and an ionizing agent Y ₀ R ₆ Z or Y ₀ R' ₆ Mixing Z' and alkali metal hydroxide or alkali metal alkoxide according to the molar ratio of 1 (0.1-20) to 0.1-20, reacting at the reaction temperature of 50-120 ℃ for 3-15 hours under stirring, adding the zwitterionic compound aqueous solution or alcohol aqueous solution obtained in the step (a) according to the required molar ratio, heating to 40-100 ℃, and stirring for 1-5 hours to obtain the compoundA surfactant composition; wherein Y is ₀ Selected from chlorine, bromine or iodine;

or: ② the polyether compound obtained in the step I and an ionizing agent Y ₀ R ₆ COOR ₀ Or Y ₀ R' ₆ COOR 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 reacted at the reaction temperature of 50-120 ℃ for 3-15 hours, water is continuously added for saponification reaction, after refluxing for 1-10 hours, the zwitterionic compound aqueous solution or 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 is obtained; wherein R is ₀ Is selected from C ₁ ～C ₈ The alkyl group of (1).

7. The method for preparing the surfactant composition according to claim 6, wherein the ionizing agent X is ₀ R ₂ X is at least one of alkali metal salt of 3-chloro-2-hydroxy propane sulfonic acid, alkali metal salt of 2-chloroethane sulfonic acid, alkali metal salt of 1, 3-propane sultone, chloroacetic acid and chloroacetic acid, and the alcohol is selected from C ₁ ～C ₄ The fatty alcohol of (4); the above-mentioned

And X ₀ R ₂ The molar ratio of X is 1: 1-3; in the first step, the reaction temperature is 120-160 ℃, the pressure is 0.3-0.6 MPa gauge pressure, and the alkaline catalyst is at least one of potassium hydroxide or anhydrous potassium carbonate; in the step (II), 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 to the alkali metal hydroxide or the alkali metal alkoxide is 1 (2-10) to (2-10), and X is ₀ And Y ₀ Is one of chlorine or bromine, R ₀ Is C ₁ ～C ₄ Alkyl group of (1).

8. Use of the surfactant composition according to any one of claims 1 to 5 in oil fields.

9. The oil displacement agent comprises the following components in parts by mass:

(1)1 part of the surfactant composition according to any one of claims 1 to 5 or the surfactant composition prepared by the preparation method according to any one of claims 6 to 7;

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

(3) 0-30 parts of alkali;

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

10. The oil displacement agent according to claim 9, wherein the temperature-resistant and salt-resistant modified polyacrylamide molecular chain comprises an acrylamide structural unit and a 2-acrylamido-2-methylpropanesulfonic acid structural unit, the molar ratio of the acrylamide structural unit to the 2-acrylamido-2-methylpropanesulfonic acid structural unit is (0.1-40) to 1, and the viscosity average molecular weight is 800-2500 ten thousand; 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 to 0.05) having a viscosity average molecular weight of 500 to 2500 ten thousand; in the oil displacement agent, the mass ratio of the surfactant composition to the polymer to the alkali is 1: 0.1-2: (0 to 5).

11. A process for preparing an oil-displacing agent according to claim 9 or 10, comprising the steps of:

(a) preparation of zwitterionic Compounds:

will be provided with

With ionizing agents X ₀ R ₂ Uniformly mixing the X 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 mass percentage of the alcohol in the alcohol water solution is calculatedThe concentration of the alcohol aqueous solution is 0-100 wt% and is not 0 or 100%, and the alcohol is selected from C ₁ ～C ₅ Fatty alcohol of (2), X ₀ Selected from chlorine, bromine or iodine;

(b) preparation of surfactant composition:

in the presence of an alkaline catalyst, R ₅ NH ₂ Reacting with ethylene oxide, propylene oxide and ethylene oxide in required amount in sequence to obtain a polyether compound;

(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 oil-displacing agent.

12. Process for the preparation of an oil-displacing agent according to claim 11, characterized in that the ionizing agent X ₀ R ₂ X is an alkali metal salt of 3-chloro-2-hydroxypropanesulfonic acid, an alkali metal salt of 2-chloroethanesulfonic acid, or 1, 3-propanesulfonic acidAt least one of ester, chloroacetic acid, alkali metal salt of chloroacetic acid, and alcohol selected from C ₁ ～C ₄ The fatty alcohol of (a); the above-mentioned

And X ₀ R ₂ The molar ratio of X is 1: 1-3; the step of (1): the reaction temperature is 120-160 ℃, the pressure is 0.3-0.6 MPa gauge pressure, and the alkaline catalyst is at least one of potassium hydroxide or anhydrous potassium carbonate; in the step II: 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 (2-10): 2-10), and X ₀ And Y ₀ Is one of chlorine or bromine, R ₀ Is C ₁ ～C ₄ Alkyl group of (1).

13. The application of the oil displacement agent comprises the following steps:

(1) mixing the oil-displacing agent of claim 9 or 10 with water to obtain an oil-displacing system;