CN112226224A - Method for increasing crude oil recovery ratio - Google Patents

Abstract

The invention relates to a method for improving the recovery ratio of crude oil, which mainly solves the problems that the prior surfactant has low interfacial efficiency, poor capability of emulsifying and solubilizing the crude oil and large adsorption retention capacity and can not meet the oil displacement requirement of a high-temperature and high-salinity oil reservoir. The invention adopts a method for improving the recovery ratio of crude oil, which comprises the following steps: 1) mixing an oil displacement agent with water to obtain an oil displacement system; 2) contacting the oil displacing system with an oil-bearing stratum to displace crude oil in the oil-bearing stratum; the oil displacement agent comprises the following components in parts by weight: 1)1 part of a surfactant composition; 2)0 to 20 parts of a polymer and more than 0 part of a polymer; the surfactant composition comprises the following components in parts by mole: 1)1 part of quaternary ammonium salt surfactant; 2) the technical scheme of 0.1-30 parts of the surfactant containing the amino polyether well solves the problem and can be used for improving the yield of crude oil in an oil field.

Description

Method for increasing crude oil recovery ratio

Technical Field

The invention relates to a method for improving the recovery ratio of crude oil.

Background

Chemical flooding is a strengthening measure for improving the recovery rate 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.

The use of temperature and salt tolerant polymers is a key factor in enhanced oil recovery. Early commercial products of polymer flooding, commonly used for Enhanced Oil Recovery (EOR), were only partially Hydrolyzed Polyacrylamides (HPAMs), which relied on the exclusion of high molecular weight and ionic and strongly polar side groups on the polymer molecular chain to achieve viscosifying effects. However, high molecular weight polymers are susceptible to mechanical degradation and loss of viscosity when subjected to high tensile and shear stresses, particularly when injected into low permeability formations. Cations, especially divalent ions, in the aqueous solution can shield ionic groups in the polymer, so that polymer molecular chains are curled, the hydrodynamic volume is reduced, even the polymer is precipitated, and the tackifying property is greatly reduced. When the temperature of a stratum oil layer is higher (more than 93 ℃), amide groups in Polyacrylamide (PAM) are easy to hydrolyze in a high-temperature aqueous solution, so that the salt resistance of a polymer solution is reduced rapidly. In recent years, the research on temperature and salt resistant polyacrylamide mainly improves the thermal stability of the polymer by introducing large side groups or rigid side groups to the main chain of the polymer, improves the hydrolysis resistance and salt resistance of the polymer by introducing monomers inhibiting hydrolysis or copolymerizing monomers insensitive to salt, or improves the temperature and salt resistance of the polymer by hydrophobic association of hydrophobic groups.

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 most anionic surfactant types are currently used in tertiary oil recovery studies, followed by nonionic and zwitterionic surfactants, and the least cationic surfactant is used. The results of displacement of oil with alkaline water, displacement of oil with surfactant or alkaline water and displacement of oil with zwitterionic surfactant, and the use of zwitterionic surfactant for displacement of oil, are reported successively in US3927716, US4018281 and US4216097 of Mobil Petroleum LtdThe sex agent is carboxylic acid or sulfonate betaine surfactant with different chain lengths, and the interfacial tension on the crude oil in south Texas reaches 10 in simulated saline with total mineralization of 62000-160000 mg/L and calcium and magnesium ions of 1500-18000 mg/L^-1～10^-4mN/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 surfactant composition has 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 a surfactant composition 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 of meifu petroleum company reports an oil displacement system composed of oil-soluble alcohol, betaine sulfonate and quaternary ammonium salt, which can function as both 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% hexanol are used as oil displacement agents, after 1.9PV is injected, the crude oil can be 100% displaced, but the adsorption loss of the surfactant is as large as 6mg/g, and 2.0% tetraethylammonium bromide with a relatively low price is added as a sacrificial agent to reduce the adsorption capacity of the surfactant.

The surfactants of different types have synergistic action, and particularly, the compounding of the surfactants with opposite electrical properties has extremely high surface activity, so that the surfactant has very wide application prospect. For example, the application of the regular solution theory to the traditional surfactant of isoelectronic property, Sodium Dodecyl Sulfate (SDS) and bola type amphiphilic molecule [ (Me) has been studied in Hades, et al (see "journal of Physics and chemistry" No. 9 in 2002, 830-834)₃N⁺(CH₂)₆OC₆H₄O(CH₂)₆N⁺(Me)₃]2Br^-The synergistic effect of the bola molecules and the SDS mixed system is mainly generated by electrostatic interaction between hydrophilic groups, the hydrophobic part in the bola molecular structure has no obvious influence on the interaction, the Cao Chong Long (see physical chemistry report 7 th 2014, 1297-1302) of China petrochemical Shengli oil field division company researches the emulsification and the viscosity increasing behaviors of the anionic and cationic surfactant mixed system on crude oil, systematic researches the influence of the oil-water volume ratio, the concentration, the temperature, the pH value and the ionic strength on the emulsification and viscosity increase are carried out, a formula system with the optimal viscosity increasing effect is obtained, and the viscosity increase of about 80 times is realized compared with the viscosity of the crude oil.

In the preparation method of the surfactant, the anionic-nonionic surfactant is usually prepared by carboxymethylation modification of the nonionic surfactant, for example, U.S. Pat. No. 4,4818440 reports the preparation and application of fatty amide polyoxyethylene ether acetic acid, wherein carboxymethylation reaction adopts the step of adding sodium hydroxide and sodium chloroacetate solid in batches, the final polyether conversion rate reaches 75-80%, and the synthesized crude product is acidified and purified to obtain the fatty amide polyoxyethylene ether acetic acid with higher purity, and the fatty amide polyoxyethylene ether acetic acid is used as a main component for daily chemical products such as shampoo and the like. In the report, polyether carboxylate needs to be purified, the synthesis process is complex, the generated three wastes are more, the preparation cost is higher, and the application in the aspect of improving the crude oil recovery ratio is not involved.

The research results at home and abroad show that the key for improving the recovery ratio of crude oil is to reduce the preparation cost of the oil-displacing agent and improve the oil-displacing efficiency of the oil-displacing agent. The invention relates to a surfactant composition and an oil displacement agent with stable structure under oil reservoir conditions, and a preparation method and a method for improving the recovery ratio of crude oil.

Disclosure of Invention

The invention aims to solve the technical problems that an oil displacement agent system containing a surfactant in the prior art has the problems of poor emulsification and compatibilization capacity of the surfactant on crude oil, low oil displacement efficiency, poor temperature and salt resistance, large adsorption retention and incapability of meeting the oil displacement requirement of a high-temperature and high-salt reservoir, and provides a method for improving the recovery ratio of the crude oil^-3～10^-4mN/m, has the advantages of good temperature resistance and salt resistance and low adsorption retention, thereby effectively improving the oil displacement efficiency of 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 surfactant composition for oil displacement corresponding to the solution of the first technical problem.

The third technical problem to be solved by the invention is to provide a preparation method of the surfactant composition for oil displacement, which corresponds to the second technical problem.

The fourth technical problem to be solved by the invention is to provide an application method of the surfactant composition for oil displacement, which corresponds to the second technical problem.

The fifth technical problem to be solved by the present invention is to provide an oil-displacing agent corresponding to one of the technical problems, which contains the surfactant composition for oil displacement.

The sixth technical problem to be solved by the present invention is to provide a method for preparing an oil displacement agent corresponding to the fifth 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 method for enhanced oil recovery comprising the steps of:

(1) mixing an oil displacement agent with water to obtain an oil displacement system;

(2) contacting the oil displacing system with an oil-bearing stratum to displace crude oil in the oil-bearing stratum;

the oil displacement agent comprises the following components in parts by weight:

(1)1 part of a surfactant composition;

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

the surfactant composition comprises the following components in parts by mole:

(1)1 part of quaternary ammonium salt surfactant;

(2) 0.1-30 parts of an amine polyether-containing surfactant;

wherein the molecular general formula of the quaternary ammonium salt surfactant is shown as a formula (I):

in the formula (I), R₁、R₂Is optionally selected from hydrogen, (CH R')_cOH、(CH R')_dCH₃One of phenyl, substituted phenyl or benzyl, R₄Is hydrogen, C₂～C₃₂Alkyl or substituted alkyl (CHR')_cOne of OH, phenyl, substituted phenyl or benzyl, R₃Is hydrogen, C₂～C₃₂Alkyl or substituted alkyl (CHR')_eOH, halogen or amino, R' are independently selected from H, CH₃Or C₂H₅C is any integer of 1 to 4D is any integer of 0 to 5, e is any integer of 0 to 4; x^j-Is an anion or anionic group having a negative charge number j;

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

in the formula (II), R₅Is C₈～C₃₀Or linear or branched, saturated or unsaturated alkyl or from C₄～C₂₀Saturated and unsaturated hydrocarbon radicals, straight-chain or branched, or cumyl (C)₆H₅C(CH₃)₂) Substituted benzene or naphthalene rings, or R₅N 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 H or R₆Z; y 'is H or R'₆Z′；R₆And R'₆Is independently selected from C₁～C₅At least one of alkylene or hydroxy-substituted alkylene of (a); z and Z' are independently selected from COOA and SO₃B or hydrogen, A, B is selected from cation or cation group.

In the above technical scheme, the polymer is preferably at least one of anionic polyacrylamide, temperature-resistant and salt-resistant modified polyacrylamide, hydrophobically associating polyacrylamide or polymer microspheres; further preferably, the temperature-resistant and salt-resistant modified polyacrylamide molecular chain preferably comprises an acrylamide structural unit and a 2-acrylamido-2-methylpropanesulfonic acid structural unit, wherein the molar ratio of the acrylamide structural unit to the 2-acrylamido-2-methylpropanesulfonic acid structural unit is preferably (0.1-40) to 1, and the viscosity-average molecular weight is preferably 800-2500 ten thousand; the molecular chain of the hydrophobic association polymer preferably 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 preferably 1: (0.1-40): (0.001 to 0.05) and preferably has a viscosity average molecular weight of 500 to 2500 ten thousand; the oil displacement agent further preferably comprises 0-30 parts of alkali, and the mass ratio of the surfactant composition to the polymer to the alkali is preferably 1 to (0.1-2): (0-5).

In the above technical scheme, the A, B is selected from hydrogen ion, alkali metal cation or formula NR₇(R₈)(R₉)(R₁₀) At least one of the groups shown, wherein R₇、R₈、R₉、R₁₀Is independently selected from H, (CHR)⁰)_fOH or (CHR)⁰)_gCH₃One of (1), R⁰Is H, CH₃Or C₂H₅Wherein f is any integer from 1 to 4, and g is any integer from 0 to 5.

In the above technical scheme, R₁、R₂Any one of hydrogen, methyl, ethyl, hydroxyethyl, hydroxypropyl, phenyl and benzyl; r₄Is hydrogen, C₈～C₂₄One of alkyl or substituted alkyl, methyl, ethyl, hydroxyethyl, hydroxypropyl, phenyl and benzyl, R₃Is hydrogen, C₈～C₂₄One of alkyl or substituted alkyl, hydrogen, methyl, ethyl, phenyl, hydroxyl and amino; r ', R', R⁰Independently selected from H or CH₃(ii) a c is 1-2, d is 0-1, e is 0-1, f is 1-2, and g is 0-1; the R is₅Is C₁₂～C₂₄Or with a hydrocarbon or substituted hydrocarbon radical of₄～C₂₀Saturated and unsaturated hydrocarbon radicals, straight-chain or branched, or cumyl (C)₆H₅C(CH₃)₂) Substituted benzene or naphthalene rings, or R₅N is abietylamine radical; r₆And R'₆Is C₁～C₃One of alkylene or hydrogen of (a); the r1+ r2 is 1-10, r3+ r4 is 1-10, and s1+ s2 is 1-20.

In the technical scheme, j is any integer from 1 to 3; when j is 1, X^-Is Cl^-、Br^-、I^-、CH₃OSO₃ ^-、HCO₃ ^-、HCOO^-、CH₃COO-、C₂H₅COO^-、C₃H₇COO^-、HOC₆H₄COO^-、C₆H₅SO₃ ^-Or CH₃C₆H₄SO₃ ^-Is more preferably Cl^-、Br^-、HCO₃ ^-、CH₃COO^-、HOC₆H₄COO^-、C₆H₅SO₃ ^-Or CH₃C₆H₄SO₃ ^-One of (1); when j is 2, X^2-Is SO₄ ^2-、HPO₄ ^2-、(COO^-)₂、CH₂(COO^-)₂、C₂H₄(COO^-)₂、C₂H₂(COO^-)₂Or C₆H₄(COO^-)₂One of (1); further preferred is SO₄ ^2-、(COO^-)₂、C₂H₂(COO^-)₂Or C₆H₄(COO^-)₂One of (1); when j is 3, X^3-Is PO₄ ^3-Or CH₂(COO^-)CH(OH)(COO^-)CH₂(COO^-) Is more preferably CH₂(COO^-)CH(OH)(COO^-)CH₂(COO^-)。

In the above technical solution, the surfactant composition further comprises:

(3) 0-20 parts of small molecular alcohol;

(4) 0-20 parts of small molecular amine;

(5) 0-10 parts of salt;

(6) 0-10 parts of inorganic base;

wherein the small molecular alcohol is selected from C₁～C₈The fatty alcohol of (a); the small molecule amine is selected from C₁～C₈At least one of a primary amine, a secondary amine, or a tertiary amine; the salt is at least one of metal halide and hydroxyl substituted carboxylate; the inorganic base is selected from alkali metal hydroxide, alkali metal carbonate orAt least one of alkali metal bicarbonate; further preferably: the preferred molar ratio of the quaternary ammonium salt surfactant, the amine polyether-containing surfactant, the small molecular alcohol, the small molecular amine, the salt and the alkali is 1 (0.2-20): 0-15): 0-5.

To solve the second technical problem, the technical solution adopted by the present invention is as follows: the surfactant composition comprises the following components in parts by mole:

(1)1 part of quaternary ammonium salt surfactant;

(2) 0.1-30 parts of an amine polyether-containing surfactant;

wherein the molecular general formula of the quaternary ammonium salt surfactant is shown as a formula (I):

in the formula (I), R₁、R₂Is optionally selected from hydrogen, (CH R')_cOH、(CH R')_dCH₃One of phenyl, substituted phenyl or benzyl, R₄Is hydrogen, C₂～C₃₂Alkyl or substituted alkyl (CHR')_cOne of OH, phenyl, substituted phenyl or benzyl, R₃Is hydrogen, C₂～C₃₂Alkyl or substituted alkyl (CHR')_eOH, halogen or amino, R' are independently selected from H, CH₃Or C₂H₅C is any integer from 1 to 4, d is any integer from 0 to 5, and e is any integer from 0 to 4; x^j-Is an anion or anionic group having a negative charge number j;

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

in the formula (II), R₅Is C₈～C₃₀Linear or branched saturated and unsaturatedAlkyl or from C₄～C₂₀Saturated and unsaturated hydrocarbon radicals, straight-chain or branched, or cumyl (C)₆H₅C(CH₃)₂) Substituted benzene or naphthalene rings, or R₅N 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 H or R₆Z; y 'is H or R'₆Z′；R₆And R'₆Is independently selected from C₁～C₅At least one of alkylene or hydroxy-substituted alkylene of (a); z and Z' are independently selected from COOM, SO₃N or hydrogen, M, N is selected from any cationic or cationic group.

In the above technical scheme, R₁、R₂Preferably one of hydrogen, methyl, ethyl, hydroxyethyl, hydroxypropyl, phenyl and benzyl.

In the above technical scheme, R₃Preferably hydrogen, C₈～C₂₄Hydrogen, methyl, ethyl, phenyl, hydroxyl, amino, carboxylic acid or sulfonic acid.

In the above technical scheme, R₄Preferably hydrogen, C₈～C₂₄The alkyl or substituted alkyl, methyl, ethyl, hydroxyethyl, hydroxypropyl, phenyl and benzyl.

In the above technical scheme, R 'and R' are preferably H or CH₃。

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 hydrogen, an alkali metal cation or a compound of formula NR₇(R₈)(R₉)(R₁₀) At least one of the groups shown.

In the above technical scheme, R₇、R₈、R₉、R₁₀Preferably H, (CHR)⁰)_fOH or (CHR)⁰)_gCH₃One kind of (1).

In the above technical scheme, R⁰Preferably H, CH₃Or C₂H₅One kind of (1).

In the above-described embodiment, f is preferably 1 to 2, and g is preferably 0 to 1.

In the above technical scheme, Y^-Preferably Cl^-、Br^-、I^-、CH₃OSO₃ ^-、HCO₃ ^-、HCOO^-、CH₃COO-、C₂H₅COO^-、C₃H₇COO^-、HOC₆H₄COO^-、C₆H₅SO₃ ^-Or CH₃C₆H₄SO₃ ^-One of (1), Y^2-Preferably SO₄ ^2-、HPO₄ ^2-、(COO^-)₂、CH₂(COO^-)₂、C₂H₄(COO^-)₂、C₂H₂(COO^-)₂Or C₆H₄(COO^-)₂One of (1), Y^3-Preferably PO₄ ^3-Or CH₂(COO^-)CH(OH)(COO^-)CH₂(COO^-) One kind of (1).

In the above technical scheme, Y^-More preferably Cl^-、Br^-、HCO₃ ^-、CH₃COO^-、HOC₆H₄COO^-、C₆H₅SO₃ ^-Or CH₃C₆H₄SO₃ ^-One of (1), Y^2-More preferably SO₄ ^2-、(COO^-)₂、C₂H₂(COO^-)₂Or C₆H₄(COO^-)₂One of (1), Y^3-More preferably CH₂(COO^-)CH(OH)(COO^-)CH₂(COO^-)。

In the above technical scheme, R₅Preferably C₁₂～C₂₄Or with a hydrocarbon or substituted hydrocarbon radical of₄～C₂₀Saturated and unsaturated hydrocarbon radicals, straight-chain or branched, or cumyl (C)₆H₅C(CH₃)₂) Substituted benzene or naphthalene rings, or R₅N is abietylamine radical.

In the above technical scheme, R₆And R'₆Preferably C₁～C₃Alkylene or hydrogen.

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 20.

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 quaternary ammonium salt surfactant, the amine polyether-containing surfactant, the micromolecular alcohol, the micromolecular amine, the salt and the alkali is 1 (0.1-30): 0-20): 0-10; the small molecular alcohol is selected from C₁～C₈The fatty alcohol of (a); the small molecule amine is selected from C₁～C₈At least one of a primary amine, a secondary amine, or a tertiary amine; the salt is at least one of metal halide and hydroxyl substituted carboxylate; the inorganic base is further preferably selected from at least one of alkali metal hydroxides, alkali metal carbonates or alkali metal bicarbonates: the molar ratio of the quaternary ammonium salt surfactant, the surfactant containing polyether segments, the small molecular alcohol, the small molecular amine, the salt and the alkali is preferably 1 (0.2-20): 0-15): 0-5. In the above technical scheme, the preferable small molecular alcohol is C₁～C₅The fatty alcohol of (1).

In the above technical scheme, the preferable small molecule amine is C₁～C₅The 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.

In the above technical scheme, the core of the cationic surfactant represented by formula (I) is the cationic moiety in the structure, Y^j-The anion is not particularly limited as long as it is an anion capable of forming an electrically neutral system with the cationic moiety in the formula (I). Examples of simple anions are, for example, Y^j-Inorganic anions (for example, chloride, bromide, hydroxide, dihydrogen phosphate, etc.) of j ═ 1, organic anions (for example, monocarboxylate such as acetate, etc.) of j ═ 1, inorganic anions (for example, sulfate, dibasic hydrogen phosphate, etc.) of j ═ 2, organic anions (for example, tartrate, phthalate, maleate, etc.) of j ═ 2; also polyvalent inorganic or organic anions with j > 2, such as phosphate, citrate. In addition to the simple anions described above, polyanions (e.g., tripolyphosphate, polyphosphate, etc.), polymeric anions (e.g., polyacrylate), and the like are also included. However, Y is a simple and convenient method of preparation at least^j-Preferably chloride, bromide hydroxide or acetate.

In the absence of an ionizing reaction, represented by formula (I)

Can be obtained from commercial sources or synthesized by the conventional technology in the field; at Y^j-The quaternary ammonium salt compound other than chloride, bromide or hydroxide ions can be synthesized by a conventional technique in the art, for example, at least Y^j-Neutralizing the quaternary ammonium base which is hydroxide ion with corresponding acid to a required degree to obtain a quaternary ammonium salt compound shown in a formula (I); y is^j-Quaternary ammonium base compounds being hydroxide ions, e.g. by Y^j-Cationic surfactants of chloride and bromide ions are obtained by reacting silver oxide, and further, for example, Y^j--The quaternary ammonium salt compound of chloride ion and bromide ion is obtained by treating with strong alkaline hydroxide type anion exchange resin.

The key active ingredients of the surfactant composition are quaternary ammonium salt surfactant shown in formula (I) and surfactant containing polyether fragment shown in formula (II), and the surfactant composition can be obtained by mixing the quaternary ammonium salt surfactant and/or the surfactant containing polyether fragment shown in formula (I) with the salt and the alcohol according to a required ratio, and is preferably obtained by the following technical scheme for solving the third technical problem.

In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: a method for preparing a surfactant composition for solving the second technical problem, comprising the steps of:

(a) preparing a quaternary ammonium salt surfactant:

will be provided with

And R₄Uniformly mixing the X in water or small molecular alcohol water to carry out quaternization reaction to obtain a water solution or a small molecular alcohol water solution of the quaternary ammonium salt surfactant shown in the formula (I); wherein the concentration of the small molecular alcohol aqueous solution is 0-100 wt% (the mass percentage of alcohol in the alcohol aqueous solution), and the small molecular alcohol is selected from C₁～C₅The fatty alcohol of (a);

(b) preparation of surfactant composition:

in the presence of an alkaline catalyst, R₅NH₂Reacting with ethylene oxide, propylene oxide and ethylene oxide with required amount to obtain polyether compound; mixing a required amount of polyether compound with the quaternary ammonium salt surfactant aqueous solution or the small molecular alcohol aqueous solution obtained in the step (a) to obtain the surfactant composition;

or by a second reaction to obtain the surfactant composition:

② the polyether compound obtained in the step I and an ionizing agent Y₀R₆Z or Y₀R'₆Mixing Z' and alkali metal hydroxide or alkali metal alkoxide in a molar ratio of 1 (0.1-20) to 0.1-20, reacting at 50-120 ℃ for 3-15 hours under stirring, adding the quaternary ammonium salt surfactant aqueous solution or the small molecular 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 required surfactant composition oil-displacing agent; wherein, Y₀Selected from chlorine, bromine or iodine;

or: ② the polyether compound obtained in the step I and an ionizing agent Y₀R₆COOR₀Or Y₀R'₆COOR₀And 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, quaternary ammonium salt surfactant aqueous solution or small molecular alcohol aqueous solution obtained in the step (a) is added according to the required molar ratio, the temperature is raised to 40-100 ℃, and stirring is carried out for 1-5 hours, so that the required surfactant composition is obtained; wherein, Y₀Selected from chlorine, bromine or iodine, R₀Is selected from C₁～C₈Alkyl group of (1).

In the technical scheme, the pressure in the step (a) is preferably 0.1-0.6 MPa.

In the above technical scheme, the small molecule alcohol in the step (a) is preferably C₁～C₄The fatty alcohol of (1).

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 1₀Preferably C₁～C₄Alkyl group of (1).

Y₀R₆Z and Y₀R’₆Examples of Z' include, but are not limited to, chloroacetic acid, sodium chloroacetate, sodium 1-chloro-2-hydroxypropanesulfonate, and the like.

Y₀R₆COOR₀And Y₀R'₆COOR₀Examples 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 fourth technical problem, the technical scheme adopted by the invention is as follows: the application of the surfactant composition in any one of the two technical schemes for solving the technical problems in oil displacement in oil fields.

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 is²⁺+Mg²⁺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 surfactant composition prepared by the invention has the advantages that the surfactant containing the amino polyether and the aniline structure in the quaternary ammonium salt present the synergistic interaction, the surface activity and the critical micelle concentration are higher and lower than those of a single surfactant in the aspects of increasing the surface activity, reducing the critical micelle concentration, improving the crude oil solubilizing capability and the like, so that the oil displacement agent has excellent crude oil emulsifying capability and interface efficiency, the problem that the crude oil cannot be well washed due to the poor crude oil emulsifying and solubilizing capability of the surfactant in the field use process of an oil field can be solved, and the ultra-high interface efficiency can ensure that the low-concentration surfactant can still keep ultra-low oil-water interfacial tension, thereby improving the oil displacement efficiency. In addition, the preparation method of the surfactant composition adopted by the invention has the advantage that the high-purity ionic surfactant is high in price and can be obtained only by complex purification steps such as extraction, column chromatography and the like, so that the preparation cost of the surfactant for oil displacement is greatly increased. Polyether carboxylate or polyether carboxylate is generated by polyether and halogenated carboxylate or halogenated carboxylate under the catalysis of alkali metal hydroxide or alkali metal alkoxide, the polyether carboxylate is obtained without separation or direct saponification, a required amount of aniline structure-containing compound water or small molecular alcohol aqueous solution is added and mixed, the small molecular alcohol or amine in the system and a surfactant can form a composite membrane at an interface and are distributed to an oil phase and an aqueous phase, the properties of the oil phase and the aqueous phase are improved, the oil-water interfacial tension is reduced and microemulsion is formed, the generated inorganic salt has a promoting effect on the interfacial performance and does not need to be removed, the excessive alkali metal hydroxide can neutralize acid substances in the crude oil to form soap, so that the emulsification and solubilization capacity of the surfactant on the crude oil is further improved, the oil washing efficiency of the 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 fifth technical problem, the invention adopts the technical scheme that: an oil displacement agent comprises the following components in parts by weight:

(1)1 part of the surfactant composition according to any one of the above-mentioned means for solving the second technical problem or the surfactant composition produced by the production method according to any one of the above-mentioned means for solving the third 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) to 1, the viscosity average molecular weight is 800-2500 ten thousand, and further, the preferable molecular chain of the 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 molar preferred ratio of the acrylamide to the temperature-resistant salt-resistant monomer in the temperature-resistant salt-resistant modified polyacrylamide is (0.1-40) to 1.

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

In the technical scheme, the temperature-resistant 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 C₁～C₈At 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 a foaming agent, small molecular organic substances (e.g., ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, DMSO, etc.) and the like which are commonly used in the art.

In 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.

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 is²⁺+Mg²⁺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 ℃.

In order to solve the sixth technical problem, the invention adopts the technical scheme that: the preparation method of the oil displacement agent in any one of the five technical schemes for solving the technical problems comprises the following steps:

(a) preparing a quaternary ammonium salt surfactant:

will be provided with

And R₄Uniformly mixing the X in water or small molecular alcohol water to carry out quaternization reaction to obtain a water solution or a small molecular alcohol water solution of the quaternary ammonium salt surfactant shown in the formula (I); wherein the concentration of the small molecular alcohol aqueous solution is 0-100 wt% (the mass percentage of alcohol in the alcohol aqueous solution), and the small molecular alcohol is selected from C₁～C₅The fatty alcohol of (a);

(b) preparation of surfactant composition:

in the presence of an alkaline catalyst, R₅NH₂Reacting with ethylene oxide, propylene oxide and ethylene oxide with required amount to obtain polyether compound; mixing a required amount of polyether compound with the quaternary ammonium salt surfactant aqueous solution or the small molecular alcohol aqueous solution obtained in the step (a) to obtain the surfactant composition;

or by a second reaction to obtain the surfactant composition:

② the polyether compound obtained in the step I and an ionizing agent Y₀R₆Z or Y₀R'₆Mixing Z' and alkali metal hydroxide or alkali metal alkoxide in a molar ratio of 1 (0.1-20) to 0.1-20, reacting at 50-120 ℃ for 3-15 hours under stirring, adding the quaternary ammonium salt surfactant aqueous solution or the small molecular 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 required surfactant composition oil-displacing agent; wherein, Y₀Selected from chlorine, bromine or iodine;

or: ② the polyether compound obtained in the step I and an ionizing agent Y₀R₆COOR₀Or Y₀R'₆COOR₀And 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, quaternary ammonium salt surfactant aqueous solution or small molecular alcohol aqueous solution obtained in the step (a) is added according to the required molar ratio, the temperature is raised to 40-100 ℃, and stirring is carried out for 1-5 hours, so that the required surfactant composition is obtained; wherein, Y₀Selected from chlorine, bromine or iodine, R₀Is selected from C₁～C₈Alkyl 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.

Preferably, in the step (a): the pressure is preferably 0.1-0.6 MPa, and the small molecular alcohol is preferably selected from C₁～C₄The fatty alcohol of (a); in the step (b): 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 alkali metal hydroxide is preferably at least one of potassium hydroxide or sodium hydroxide, the molar ratio of the polyether compound to the ionizing agent and the alkali metal hydroxide or the alkali metal alkoxide is preferably 1 (2-10) to (2-10), and Y is preferably 1₀Preferably in chlorine or bromineA 1 of, R₀Preferably C₁～C₄Alkyl group of (1).

The invention adopts a physical simulation displacement evaluation method to evaluate the effect, and the 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 the measurement, and waiting for the temperature to be stable; (2) injecting external phase liquid, filling the centrifuge tube, injecting internal phase liquid, removing bubbles, and tightly covering; (3) the centrifuge tube is arranged in a rotating shaft of the instrument, the rotating speed is set, and a microscope is adjusted to enable inner phase liquid drops or bubbles in the visual field to be very clear; (4) reading and calculating, and calculating the interfacial tension according to the formula (1):

γ＝0.25ω²r³Δ 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, 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) firstly, sealing the tip of a 5mL temperature-resistant glass pipette, and intercepting the required length for later use; (2) preparing a surfactant solution with a certain concentration, measuring a certain volume of aqueous solution by using a pipettor, adding the aqueous solution into a glass pipettor with a sealed tip, simultaneously recording the mass of the added solution by using an analytical balance, adding a certain amount of crude oil or simulated oil (the oil-water ratio is determined according to the experimental requirements) according to the same method, recording the volume and the mass, and recording the scales of a water phase and an oil phase; (3) after the sample is added, sealing the upper opening of the glass pipette; (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 balance, photographing to record the change of a phase state along with time, and calculating solubilization parameters, which are shown in a formula (3);

wherein SP is a solubilization parameter, V_S、V_O、V_WThe 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, 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 the consumed halmin_H(mL). The degree of carboxylation or sulfonation of the surfactant samples was calculated using the following formula. 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 Mg²⁺+Ca ²⁺20 to 12000 mg/l, HCO₃ ^-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^-4The 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 24.8, 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^-4mN/m, and the static adsorption capacity is less than 2 mg/g. Through physical simulation displacement testAccording to indoor evaluation, the oil displacement agent can improve the oil recovery rate of the crude oil by up to 25.01 percent on the basis of water flooding, and obtains better technical effect.

Drawings

The quaternary ammonium salt surfactant prepared by the invention can be applied to an American Nicolet-5700 spectrometer and is subjected to infrared spectrum analysis (scanning range is 4000-400 cm) by Adopting Total Reflection (ATR) infrared spectroscopy^-1) And determining the chemical structure of the tested sample so as to achieve infrared characterization of the compound.

FIG. 1 is an infrared spectrum of N-dodecyl-N, N-di (2-hydroxyethyl) benzeneammonium chloride. Wherein, 3287.3cm^-1Is the characteristic peak of O-H stretching vibration, 2930.3cm^-1And 2853.1m^-1Is a characteristic peak of C-H stretching of methyl and methylene, 1508.6cm^-1And 1599.7cm^-1Is the stretching vibration peak of benzene ring, 1438.4cm^-1Is a C-N bending vibration absorption peak, 1123.4cm^-1And 1228.4cm^-1Is the C-N stretching vibration peak of 1053.5cm^-1Is the stretching vibration peak of C-O in primary alcohol, 745.1cm^-1And 682.2cm^-1Is the in-plane rocking absorption peak of CH plane in the benzene ring.

FIG. 2 is a graph of oil-water interfacial tension of 0.15% surfactant after aging for various periods of time.

Fig. 3 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-dodecyl-N, N-di (2-hydroxyethyl) phenyl ammonium chloride

181.2 g (1 mol) of N, N-dihydroxyethylaniline, 204.8 g (1 mol) of 1-chlorododecane and 750 g of a 20 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 36 hours to stop the reaction. And (3) taking a small amount of reaction liquid for LC-MS analysis, wherein the content of the N-dodecyl-N, N-di (2-hydroxyethyl) phenyl ammonium chloride is 98.5 percent, the content of the N, N-dihydroxyethylaniline is 0.7 percent, and the rest samples are not processed for later use.

(b) Preparation of surfactant composition S01

R₅Is CH₃(CH₂)₇CH＝CH(CH₂)₈；Z₁＝Z₂＝CH₂COONa r₁+r₂＝3，s₁+s₂＝12，r₃+r₄＝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 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 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, 20.0 g (0.5 mol) of sodium hydroxide, and an aqueous ethanol solution containing 77.2 g (0.2 mol) of N-dodecyl-N, N-bis (2-hydroxyethyl) benzeneammonium chloride, and uniformly mixed to obtain the desired surfactant composition S01.

[ example 2 ]

(a) Preparation of N-dodecyl-N, N-di (2-hydroxyethyl) phenyl ammonium chloride

181.2 g (1 mol) of N, N-dihydroxyethylaniline, 204.8 g (1 mol) of 1-chlorododecane and 750 g of a 20 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 36 hours to stop the reaction. And (3) taking a small amount of reaction liquid for LC-MS analysis, wherein the content of the N-dodecyl-N, N-di (2-hydroxyethyl) phenyl ammonium chloride is 98.5 percent, the content of the N, N-dihydroxyethylaniline is 0.7 percent, and the rest samples are not processed for later use.

(b) Preparation of surfactant composition S02

Z₁＝Z₂＝CH₂COOH.HN(CH₂CH₂OH)₂；r₁+r₂＝4，s₁+s₂＝15，r₃+r₄＝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), 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 the toluene/benzene was evaporated 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 1500 g of water, 126.0 g (1.2 mol) of diethanolamine, and an aqueous ethanol solution containing 38.6 g (0.1 mol) of N-dodecyl-N, N-bis (2-hydroxyethyl) benzeneammonium chloride were added and mixed uniformly to obtain the desired surfactant composition S02.

[ example 3 ]

(a) Preparation of N, N, N-trimethyl- (4-dodecyl) phenyl ammonium chloride

289.0 g (1 mol) of N, N-dimethyl- (4-dodecyl) aniline and 500 g of 50 wt% isopropanol aqueous solution are mixed in a 2000 ml pressure kettle, after nitrogen is used for replacing oxygen for many times, 75.8 g (1.5 mol) of chloromethane is slowly introduced, and the pressure is kept between 0.3 MPa and 0.5MPa for reaction for 6 hours. Cooling to normal temperature, emptying, pumping out low-boiling-point substances, taking a small amount of reaction liquid for LC-MS analysis, wherein the content of N, N, N-trimethyl- (4-dodecyl) phenyl ammonium chloride is 96.8 percent, and the content of N, N-dimethyl- (4-dodecyl) aniline is 1.2 percent. The remaining samples were left untreated and were ready for use.

(b) Preparation of surfactant composition S03

Wherein r is₁+r₂＝5，s₁+s₂＝5，r₃+r₄＝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, and 600 g of water, 80.0 g (2.0 mol) of sodium hydroxide, and an aqueous ethanol solution containing 74.7 g (0.22 mol) of N, N-trimethyl- (4-dodecyl) benzeneammonium chloride were added and mixed uniformly to obtain the desired surfactant composition S03.

[ example 4 ]

(a) Preparation of N, N, N-trimethyl- (4-dodecyl) phenyl ammonium chloride

289.0 g (1 mol) of N, N-dimethyl- (4-dodecyl) aniline and 500 g of 50 wt% isopropanol aqueous solution are mixed in a 2000 ml pressure kettle, after nitrogen is used for replacing oxygen for many times, 75.8 g (1.5 mol) of chloromethane is slowly introduced, and the pressure is kept between 0.3 MPa and 0.5MPa for reaction for 6 hours. Cooling to normal temperature, emptying, pumping out low-boiling-point substances, taking a small amount of reaction liquid for LC-MS analysis, wherein the content of N, N, N-trimethyl- (4-dodecyl) phenyl ammonium chloride is 96.8 percent, and the content of N, N-dimethyl- (4-dodecyl) aniline is 1.2 percent. The remaining samples were left untreated and were ready for use.

(b) Preparation of surfactant composition S04

R₅Is CH₃(CH₂)₇CH＝CH(CH₂)₈；Z₁＝Z₂＝CH₂COONa r₁+r₂＝3，s₁+s₂＝12，r₃+r₄＝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 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 company T90 automatic potentiometric titrator and using a Helminum cation solution as a titrant. The remaining untreated reaction solution was distilled off the solvent, 1100 g of water, 12.0 g (0.3 mol) of sodium hydroxide, and an aqueous ethanol solution containing 25.5 g (0.075 mol)) of N, N-trimethyl- (4-dodecyl) benzeneammonium chloride were added, and they were mixed uniformly to obtain the desired surfactant composition S04.

[ example 5 ]

The same as [ example 3 ] except that 478.5 g (0.5 mol) of icosapolyoxyethylene (5) polyoxypropylene (5) polyoxyethylene (3) ether was added without further reaction, 600 g of water, 100 g of N-propanol, 73.0 g (1.0 mol) of N-butylamine, 8.5 g (0.025 mol) of an aqueous isopropanol solution of N, N-trimethyl- (4-dodecyl) benzeneammonium chloride, to give the desired surfactant composition S05.

[ example 6 ]

The same as in example 1, except that at the end of the reaction in the step (a), ethanol was distilled off under reduced pressure to obtain a cationic surfactant product, and the rest was the same, to obtain the desired surfactant composition S06.

[ example 7 ]

(a) Preparation of N, N, N-trimethyl- (4-hexadecyl) phenyl ammonium chloride

Mixing 345.0 g (1 mol) of N, N-dimethyl- (4-hexadecyl) aniline and 600 g of 80 wt% isopropanol aqueous solution in a 2000 ml pressure kettle, replacing oxygen by nitrogen for many times, slowly introducing 101.0 g (2.0 mol) of chloromethane, and reacting for 8 hours under the pressure of 0.3-0.5 MPa. Cooling to normal temperature, emptying, pumping out low-boiling-point substances, taking a small amount of reaction liquid for LC-MS analysis, wherein the content of N, N, N-trimethyl- (4-hexadecyl) phenyl ammonium chloride is 95.4 percent, and the content of N, N-dimethyl- (4-hexadecyl) aniline is 1.9 percent. The remaining samples were left untreated and were ready for use.

(b) Preparation of surfactant composition S07

The same procedure as in example 3 was repeated to obtain a remaining untreated disulfonate reaction solution, after distilling off the solvent, 600 g of water, 80.0 g (2.0 mol) of sodium hydroxide and an aqueous ethanol solution containing 59.3 g (0.15 mol) of N, N, N-trimethyl- (4-hexadecyl) benzeneammonium chloride were added and mixed uniformly to obtain the desired surfactant composition S07.

[ example 8 ]

(a) Preparation of N-dodecyl-N, N-diethyl- (3-hydroxy) phenyl ammonium bromide

165.0 g (1 mol) of N, N-diethyl- (3-hydroxy) aniline, 249.0 g (1 mol) of 1-bromododecane and 600 g of a 50 wt% aqueous isopropanol solution were mixed in a 2000-ml four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux for 36 hours to stop the reaction. And (3) performing LC-MS analysis on a small amount of reaction liquid, wherein the content of the N-dodecyl-N, N-diethyl- (3-hydroxy) phenyl ammonium bromide is 98.8 percent, the content of the N, N-diethyl- (3-hydroxy) aniline is 0.3 percent, and the rest samples are not processed for later use.

(b) Preparation of surfactant composition S08

The same procedure as in example 1 was repeated to obtain a residual untreated reaction solution, after distilling off the solvent, 1780 g of water, 20.0 g (0.5 mol) of sodium hydroxide and an aqueous ethanol solution containing 372.6 g (0.9 mol) of N-dodecyl-N, N-diethyl- (3-hydroxy) phenylammonium bromide were added, and the mixture was uniformly mixed to obtain the desired surfactant composition S08.

[ example 9 ]

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. The crude oil for the experiment comes from oil fields, the properties of the crude oil are shown in table 2, and the crude oil is used after dehydration.

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

The static adsorption test is mainly based on the research of adsorption loss amount of the surfactant on the formation rock core, and the economy and the formability of the surfactant synthesized in the embodiment in the field application of improving the crude oil recovery rate are explored. The experimental process is as follows: mixing 3g of simulated saline solution of the surfactant and 1g of clay-containing quartz sand, oscillating for 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 result is 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 20 ml anbei bottle, sealing, placing into oven, and measuring differentThe oil-water interfacial tension after the aging time is found to be still kept at 10^-3～10^-4Ultra low values of mN/m are shown in FIG. 2. The oil-water interfacial tension (IFT) was measured by a model TX500 spinning drop interfacial tensiometer, produced by Texas university, USA.

[ COMPARATIVE EXAMPLE 1 ]

The same as in example 3 except that "303.0 g (1 mol)" of N, N-dimethyl- (4-dodecyl) benzylamine was used in place of "289.0 g (1 mol)" of N, N-dimethyl- (4-dodecyl) aniline in the step (a), the rest was the same, whereby a surfactant composition S09 was obtained. The performance test was carried out as in example 9, and the results are shown in Table 5.

[ COMPARATIVE EXAMPLE 2 ]

The same as [ example 3 ] except that commercially available phenyltrimethylammonium chloride and benzyltriethylammonium chloride were used in place of N, N-trimethyl- (4-dodecyl) phenylammonium chloride, and the same was used, the surfactant compositions S10 and S11 were obtained. The performance test was carried out as in example 9, and the results are shown in Table 5.

[ COMPARATIVE EXAMPLE 3 ]

The same as [ example 3 ] except that commercially available N-dodecyl-N, N-di (2-hydroxyethyl) benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, and octadecyl dimethyl benzyl ammonium chloride were used instead of N, N-trimethyl- (4-dodecyl) benzyl ammonium chloride, respectively, and the rest were the same, surfactant compositions S12, S13, and S14 were obtained. The performance test was carried out as in example 9, and the results are shown in Table 5.

[ COMPARATIVE EXAMPLE 4 ]

C₁₈H₃₇(CH₂CH₂OH)₂N⁺(CH₂)₄N⁺(CH₂CH₂OH)₂C₁₈H₃₇.2Br^-(18-4-18,2Br^-)

The same as [ example 1 ] except that a gemini cationic quaternary ammonium surfactant (18-4-18,2 Br)^-) The same was repeated except for N-dodecyl-N, N-bis (2-hydroxyethyl) phenylammonium chloride, to obtain surfactant composition S15. At the same time (implement)Example 9 Performance tests were performed and the results are shown in Table 5.

[ COMPARATIVE EXAMPLE 5 ]

The same as in example 1, except that the reaction with propylene oxide and ethylene oxide was not carried out stepwise in succession, but carried out in one step after mixing, and the same as in example 9, S16 was obtained, and the results of the performance test were shown in Table 5.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

[ example 10 ]

(a) Preparation of N-dodecyl-N, N-di (2-hydroxyethyl) phenyl ammonium chloride

181.2 g (1 mol) of N, N-dihydroxyethylaniline, 204.8 g (1 mol) of 1-chlorododecane and 750 g of a 20 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 36 hours to stop the reaction. And (3) taking a small amount of reaction liquid for LC-MS analysis, wherein the content of the N-dodecyl-N, N-di (2-hydroxyethyl) phenyl ammonium chloride is 98.5 percent, the content of the N, N-dihydroxyethylaniline is 0.7 percent, and the rest samples are not processed for later use.

(b) Preparation of surfactant composition S01

R₅Is CH₃(CH₂)₇CH＝CH(CH₂)₈；Z₁＝Z₂＝CH₂COONa r₁+r₂＝3，s₁+s₂＝12，r₃+r₄＝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 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 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, 20.0 g (0.5 mol) of sodium hydroxide, and an aqueous ethanol solution containing 77.2 g (0.2 mol) of N-dodecyl-N, N-bis (2-hydroxyethyl) benzeneammonium chloride, 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. Crude oil was used for the experiments in the oil field, the properties of which are shown in table 2, after dehydration.

The phase state experiment can well reflect the solubilizing capability of the surfactant to the crude oil, and the solubilizing parameters of the surfactant to the crude oil and the optimal salt content of the surfactant are obtained. The experimental process is as follows: first, 4.0 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 diethanol amine by using simulated water, and mixing and diluting the aqueous solution according to a required proportion to obtain the 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 pore volume was tested with the above simulated brine saturated core. And (4) recording the volume of the saturated crude oil by using the oil field dehydrated crude oil saturated core. At 70 ℃, 11# simulated 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 ratio of the surfactant and the polymer injected with the same PV is compared, and the calculation is shown in table 6. The flow of the simulated core displacement test used is shown in fig. 3. The viscosity of the dehydrated crude oil is 1.9 mPa.s.

[ example 11 ]

(a) Preparation of N-dodecyl-N, N-di (2-hydroxyethyl) phenyl ammonium chloride

181.2 g (1 mol) of N, N-dihydroxyethylaniline, 204.8 g (1 mol) of 1-chlorododecane and 750 g of a 20 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 36 hours to stop the reaction. And (3) taking a small amount of reaction liquid for LC-MS analysis, wherein the content of the N-dodecyl-N, N-di (2-hydroxyethyl) phenyl ammonium chloride is 98.5 percent, the content of the N, N-dihydroxyethylaniline is 0.7 percent, and the rest samples are not processed for later use.

(b) Preparation of surfactant composition S02

Z₁＝Z₂＝CH₂COOH.HN(CH₂CH₂OH)₂；r₁+r₂＝4，s₁+s₂＝15，r₃+r₄＝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), 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 the toluene/benzene was evaporated 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 1500 g of water, 126.0 g (1.2 mol) of diethanolamine, and an aqueous ethanol solution containing 38.6 g (0.1 mol) of N-dodecyl-N, N-bis (2-hydroxyethyl) benzeneammonium chloride were added and mixed uniformly to obtain the desired surfactant composition S02.

Phase and static adsorption experiments were carried out as in [ example 10 ] and the results are shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 10 ] except that S02 was used instead of S01 and potassium carbonate was used instead of diethanolamine, the temperature was 65 ℃ and the viscosity of dehydrated crude oil was 122.6mPa.s, and the results are shown in Table 6.

[ example 12 ]

(a) Preparation of N, N, N-trimethyl- (4-dodecyl) phenyl ammonium chloride

289.0 g (1 mol) of N, N-dimethyl- (4-dodecyl) aniline and 500 g of 50 wt% isopropanol aqueous solution are mixed in a 2000 ml pressure kettle, after nitrogen is used for replacing oxygen for many times, 75.8 g (1.5 mol) of chloromethane is slowly introduced, and the pressure is kept between 0.3 MPa and 0.5MPa for reaction for 6 hours. Cooling to normal temperature, emptying, pumping out low-boiling-point substances, taking a small amount of reaction liquid for LC-MS analysis, wherein the content of N, N, N-trimethyl- (4-dodecyl) phenyl ammonium chloride is 96.8 percent, and the content of N, N-dimethyl- (4-dodecyl) aniline is 1.2 percent. The remaining samples were left untreated and were ready for use.

(b) Preparation of surfactant composition S03

Wherein r is₁+r₂＝5，s₁+s₂＝5，r₃+r₄＝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, and 600 g of water, 80.0 g (2.0 mol) of sodium hydroxide, and an aqueous ethanol solution containing 74.7 g (0.22 mol) of N, N-trimethyl- (4-dodecyl) benzeneammonium chloride were added and mixed uniformly to obtain the desired surfactant composition S03.

Phase and static adsorption experiments were carried out as in [ example 10 ] and the results are shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 10 ] except that S03 was used instead of S01, P2 (the molar ratio of the copolymer AM/AMPS/2-acrylamidododecylsulfonic acid was 1/0.45/0.002, and the viscosity average molecular weight was 1750 ten thousand) was used instead of P1, and ethanolamine was used instead of diethanolamine to prepare an oil-displacing agent aqueous solution, wherein water was 12# simulated water, the temperature was 98 ℃, and the viscosity of dehydrated crude oil was 3.2mpa.s, and the results are shown in table 7.

[ example 13 ]

(a) Preparation of N, N, N-trimethyl- (4-dodecyl) phenyl ammonium chloride

289.0 g (1 mol) of N, N-dimethyl- (4-dodecyl) aniline and 500 g of 50 wt% isopropanol aqueous solution are mixed in a 2000 ml pressure kettle, after nitrogen is used for replacing oxygen for many times, 75.8 g (1.5 mol) of chloromethane is slowly introduced, and the pressure is kept between 0.3 MPa and 0.5MPa for reaction for 6 hours. Cooling to normal temperature, emptying, pumping out low-boiling-point substances, taking a small amount of reaction liquid for LC-MS analysis, wherein the content of N, N, N-trimethyl- (4-dodecyl) phenyl ammonium chloride is 96.8 percent, and the content of N, N-dimethyl- (4-dodecyl) aniline is 1.2 percent. The remaining samples were left untreated and were ready for use.

(b) Preparation of surfactant composition S04

R₅Is CH₃(CH₂)₇CH＝CH(CH₂)₈；Z₁＝Z₂＝CH₂COONa r₁+r₂＝3，s₁+s₂＝12，r₃+r₄＝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 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, collecting 50 g of homogeneous reaction solution, acidifying with 20 wt% hydrochloric acid, distilling off methanol, adding 100 g of benzene, mixing, removing water layer, washing with saturated saline solution for 3 times, distilling off benzene under reduced pressure, and measuring carboxylation degree of 185.6% with Helmin cation solution as titrant by using Mettler's T90 automatic potentiometric titrator, and infrared analysis chromatogram shown in figure 1. The remaining untreated reaction solution was distilled off the solvent, 1100 g of water, 12.0 g (0.3 mol) of sodium hydroxide, and an aqueous ethanol solution containing 25.5 g (0.075 mol)) of N, N-trimethyl- (4-dodecyl) benzeneammonium chloride were added, and they were mixed uniformly to obtain the desired surfactant composition S04.

Phase and static adsorption experiments were carried out as in [ example 10 ] and the results are shown in tables 2 and 3.

(c) Performance test of oil-displacing agent

The same as [ example 10 ] except that S04 was used instead of S01 and sodium carbonate was used instead of diethanolamine, and the results are shown in table 6.

[ example 14 ]

The same as [ example 3 ] except that 478.5 g (0.5 mol) of icosapolyoxyethylene (5) polyoxypropylene (5) polyoxyethylene (3) ether was added without further reaction, 600 g of water, 100 g of N-propanol, 73.0 g (1.0 mol) of N-butylamine, 8.5 g (0.025 mol) of an aqueous isopropanol solution of N, N-trimethyl- (4-dodecyl) benzeneammonium chloride, to give the desired surfactant composition S05.

Phase and static adsorption experiments were carried out as in [ example 10 ] and the results are shown in tables 2 and 3.

An oil displacement agent aqueous solution was prepared by substituting S07 for S03, and oil displacement experiments were performed in the same manner as in example 12, and the results are shown in table 7.

[ example 15 ]

The same as in example 1, except that at the end of the reaction in the step (a), ethanol was distilled off under reduced pressure to obtain a cationic surfactant product, and the rest was the same, to obtain the desired surfactant composition S06. Phase and static adsorption experiments were carried out as in [ example 10 ] and the results are shown in tables 2 and 3. The oil displacement experiment was carried out as in example 10, and the results are shown in table 6.

[ example 16 ]

(a) Preparation of N, N, N-trimethyl- (4-hexadecyl) phenyl ammonium chloride

Mixing 345.0 g (1 mol) of N, N-dimethyl- (4-hexadecyl) aniline and 600 g of 80 wt% isopropanol aqueous solution in a 2000 ml pressure kettle, replacing oxygen by nitrogen for many times, slowly introducing 101.0 g (2.0 mol) of chloromethane, and reacting for 8 hours under the pressure of 0.3-0.5 MPa. Cooling to normal temperature, emptying, pumping out low-boiling-point substances, taking a small amount of reaction liquid for LC-MS analysis, wherein the content of N, N, N-trimethyl- (4-hexadecyl) phenyl ammonium chloride is 95.4 percent, and the content of N, N-dimethyl- (4-hexadecyl) aniline is 1.9 percent. The remaining samples were left untreated and were ready for use.

(b) Preparation of surfactant composition S07

The same procedure as in example 3 was repeated to obtain a remaining untreated disulfonate reaction solution, after distilling off the solvent, 600 g of water, 80.0 g (2.0 mol) of sodium hydroxide and an aqueous ethanol solution containing 59.3 g (0.15 mol) of N, N, N-trimethyl- (4-hexadecyl) benzeneammonium chloride were added and mixed uniformly to obtain the desired surfactant composition S07. Phase and static adsorption experiments were carried out as in [ example 10 ] and the results are shown in tables 2 and 3. The oil displacement experiment was carried out as in example 12, and the results are shown in Table 7.

[ example 17 ]

(a) Preparation of N-dodecyl-N, N-diethyl- (3-hydroxy) phenyl ammonium bromide

165.0 g (1 mol) of N, N-diethyl- (3-hydroxy) aniline, 249.0 g (1 mol) of 1-bromododecane and 600 g of a 50 wt% aqueous isopropanol solution were mixed in a 2000-ml four-neck flask equipped with a mechanical stirrer, a thermometer and a reflux condenser, and the mixture was heated to reflux for 36 hours to stop the reaction. And (3) performing LC-MS analysis on a small amount of reaction liquid, wherein the content of the N-dodecyl-N, N-diethyl- (3-hydroxy) phenyl ammonium bromide is 98.8 percent, the content of the N, N-diethyl- (3-hydroxy) aniline is 0.3 percent, and the rest samples are not processed for later use.

(b) Preparation of surfactant composition S08

The same procedure as in example 1 was repeated to obtain a residual untreated reaction solution, after distilling off the solvent, 1780 g of water, 20.0 g (0.5 mol) of sodium hydroxide and an aqueous ethanol solution containing 372.6 g (0.9 mol) of N-dodecyl-N, N-diethyl- (3-hydroxy) phenylammonium bromide were added, and the mixture was uniformly mixed to obtain the desired surfactant composition S08. The performance results are shown in tables 2, 3 and 6.

[ COMPARATIVE EXAMPLE 6 ]

The same as in example 12 except that in step (a), 289.0 g (1 mol) of N, N-dimethyl- (4-dodecyl) aniline was replaced with 303.0 g (1 mol) of N, N-dimethyl- (4-dodecyl) benzylamine, and the rest was the same, a surfactant composition S09 was obtained, and the results are shown in Table 5 and Table 8.

[ COMPARATIVE EXAMPLE 7 ]

The same as [ example 12 ] except that commercially available phenyltrimethylammonium chloride and benzyltriethylammonium chloride were used in place of N, N, N-trimethyl- (4-dodecyl) phenylammonium chloride and the same as above, surfactant compositions S10 and S11 were obtained, and the results are shown in Table 5 and Table 8.

[ COMPARATIVE EXAMPLE 8 ]

The same as [ example 12 ] except that commercially available N-dodecyl-N, N-di (2-hydroxyethyl) benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, and octadecyl dimethyl benzyl ammonium chloride were used instead of N, N-trimethyl- (4-dodecyl) benzyl ammonium chloride, respectively, and the same was used, surfactant compositions S12, S13, and S14 were obtained, and the results are shown in tables 5 and 8.

[ COMPARATIVE EXAMPLE 9 ]

C₁₈H₃₇(CH₂CH₂OH)₂N⁺(CH₂)₄N⁺(CH₂CH₂OH)₂C₁₈H₃₇.2Br^-(18-4-18,2Br^-)

The same as [ example 10 ] except that a gemini cationic quaternary ammonium surfactant (18-4-18,2 Br)^-) The same was used instead of N-dodecyl-N, N-bis (2-hydroxyethyl) phenylammonium chloride to obtain surfactant composition S15, and the results are shown in Table 5 and Table 8.

[ COMPARATIVE EXAMPLE 10 ]

The same as in example 10, except that the reaction with propylene oxide and ethylene oxide was not carried out stepwise one after another but was carried out one after mixing, S16 was obtained, and the results are shown in tables 5 and 8.

[ COMPARATIVE EXAMPLE 11 ]

The same as [ example 10 ] except that the modified associative polymer P1 was replaced with a high molecular weight anionic polyacrylamide P3 (having a viscosity average molecular weight of 2300 ten thousand), and the results were as shown in FIG. 8.

TABLE 6

TABLE 7

TABLE 8

Claims (15)

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

(1) mixing an oil displacement agent with water to obtain an oil displacement system;

(2) contacting the oil displacing system with an oil-bearing stratum to displace crude oil in the oil-bearing stratum;

the oil displacement agent comprises the following components in parts by weight:

(1)1 part of a surfactant composition;

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

the surfactant composition comprises the following components in parts by mole:

(1)1 part of quaternary ammonium salt surfactant;

(2) 0.1-30 parts of an amine polyether-containing surfactant;

wherein the molecular general formula of the quaternary ammonium salt surfactant is shown as a formula (I):

in the formula (I), R₁、R₂Is optionally selected from hydrogen, (CH R')_cOH、(CH R')_dCH₃One of phenyl, substituted phenyl or benzyl, R₄Is hydrogen, C₂～C₃₂Alkyl or substituted alkyl (CHR')_cOne of OH, phenyl, substituted phenyl or benzyl, R₃Is hydrogen, C₂～C₃₂Alkyl or substituted alkyl (CHR')_eOH, halogen or amino, R' are independently selected from H, CH₃Or C₂H₅C is any integer from 1 to 4, d is any integer from 0 to 5, and e is any integer from 0 to 4; x^j-Is an anion or anionic group having a negative charge number j;

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

in the formula (II), R₅Is C₈～C₃₀Or linear or branched, saturated or unsaturated alkyl or from C₄～C₂₀Saturated and unsaturated hydrocarbon radicals, straight-chain or branched, or cumyl (C)₆H₅C(CH₃)₂) Substituted benzene or naphthalene rings, or R₅N 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 H or R₆Z; y 'is H or R'₆Z′；R₆And R'₆Is independently selected from C₁～C₅At least one of alkylene or hydroxy-substituted alkylene of (a); z and Z' are independently selected from COOA and SO₃B or hydrogen, A, B is selected from cation or cation group.

2. The method for enhanced oil recovery according to claim 1, wherein the polymer is preferably at least one of anionic polyacrylamide, temperature-resistant salt-resistant modified polyacrylamide, hydrophobically-associated polyacrylamide, or polymer microspheres; further preferably, the temperature-resistant and salt-resistant modified polyacrylamide molecular chain preferably comprises an acrylamide structural unit and a 2-acrylamido-2-methylpropanesulfonic acid structural unit, wherein the molar ratio of the acrylamide structural unit to the 2-acrylamido-2-methylpropanesulfonic acid structural unit is preferably (0.1-40) to 1, and the viscosity-average molecular weight is preferably 800-2500 ten thousand; the molecular chain of the hydrophobic association polymer preferably 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 preferably 1: (0.1-40): (0.001 to 0.05) and preferably has a viscosity average molecular weight of 500 to 2500 ten thousand; the oil displacement agent further preferably comprises 0-30 parts of alkali, and the mass ratio of the surfactant composition to the polymer to the alkali is preferably 1 to (0.1-2): (0-5).

3. The method for enhanced oil recovery as claimed in claim 1, wherein said A, B is selected from any of hydrogen ions, alkali metal cations or compounds of formula NR₇(R₈)(R₉)(R₁₀) At least one of the groups shown, wherein R₇、R₈、R₉、R₁₀Is independently selected from H, (CHR)⁰)_fOH or (CHR)⁰)_gCH₃One of (1), R⁰Is H, CH₃Or C₂H₅Wherein f is any integer from 1 to 4, and g is any integer from 0 to 5.

4. The method for enhanced oil recovery as claimed in claim 1, wherein the R is₁、R₂Any one of hydrogen, methyl, ethyl, hydroxyethyl, hydroxypropyl, phenyl and benzyl; r₄Is hydrogen, C₈～C₂₄One of alkyl or substituted alkyl, methyl, ethyl, hydroxyethyl, hydroxypropyl, phenyl and benzyl, R₃Is hydrogen, C₈～C₂₄One of alkyl or substituted alkyl, hydrogen, methyl, ethyl, phenyl, hydroxyl and amino; r ', R', R⁰Independently selected from H or CH₃(ii) a c is 1-2, d is 0-1, e is 0-1, f is 1-2, and g is 0-1; the R is₅Is C₁₂～C₂₄Or with a hydrocarbon or substituted hydrocarbon radical of₄～C₂₀Saturated and unsaturated hydrocarbon radicals, straight-chain or branched, or cumyl (C)₆H₅C(CH₃)₂) Substituted benzene or naphthalene rings, or R₅N is abietylamine radical; r₆And R'₆Is C₁～C₃One of alkylene or hydrogen of (a); the r1+ r2 is 1-10, r3+ r4 is 1-10, and s1+ s2 is 1-20.

5. The method for enhanced oil recovery as claimed in claim 1, wherein j is an integer of 1-3; when j is 1, X^-Is Cl^-、Br^-、I^-、CH₃OSO₃ ^-、HCO₃ ^-、HCOO^-、CH₃COO-、C₂H₅COO^-、C₃H₇COO^-、HOC₆H₄COO^-、C₆H₅SO₃ ^-Or CH₃C₆H₄SO₃ ^-Is more preferably Cl^-、Br^-、HCO₃ ^-、CH₃COO^-、HOC₆H₄COO^-、C₆H₅SO₃ ^-Or CH₃C₆H₄SO₃ ^-One of (1); when j is 2, X^2-Is SO₄ ^2-、HPO₄ ^2-、(COO^-)₂、CH₂(COO^-)₂、C₂H₄(COO^-)₂、C₂H₂(COO^-)₂Or C₆H₄(COO^-)₂One of (1); further preferred is SO₄ ^2-、(COO^-)₂、C₂H₂(COO^-)₂Or C₆H₄(COO^-)₂One of (1); when j is 3, X^3-Is PO₄ ^3-Or CH₂(COO^-)CH(OH)(COO^-)CH₂(COO^-) Is more preferably CH₂(COO^-)CH(OH)(COO^-)CH₂(COO^-)。

6. The method for enhanced oil recovery according to claim 1, characterized in that the surfactant composition further comprises:

(3) 0-20 parts of small molecular alcohol;

(4) 0-20 parts of small molecular amine;

(5) 0-10 parts of salt;

(6) 0-10 parts of inorganic base;

wherein the small molecular alcohol is selected from C₁～C₈The fatty alcohol of (a); the small molecule amine is selected from C₁～C₈At least one of a primary amine, a secondary amine, or a tertiary amine; the salt is at least one of metal halide and hydroxyl substituted carboxylate; the inorganic base is at least one selected from alkali metal hydroxide, alkali metal carbonate or alkali metal bicarbonate; further preferably: the quaternary ammonium salt surfactant, the surfactant containing amino polyether, the micromolecular alcohol, the micromolecular amine, the salt and the alkaliThe preferred molar ratio is 1 (0.2-20): (0-15): (0-5): 0-5).

7. The surfactant composition comprises the following components in parts by mole:

(1)1 part of quaternary ammonium salt surfactant;

(2) 0.1-30 parts of an amine polyether-containing surfactant;

wherein the molecular general formula of the quaternary ammonium salt surfactant is shown as a formula (I):

in the formula (I), R₁、R₂Is optionally selected from hydrogen, (CH R')_cOH、(CH R')_dCH₃One of phenyl, substituted phenyl or benzyl, R₄Is hydrogen, C₂～C₃₂Alkyl or substituted alkyl (CHR')_cOne of OH, phenyl, substituted phenyl or benzyl, R₃Is hydrogen, C₂～C₃₂Alkyl or substituted alkyl (CHR')_eOH, halogen or amino, R' are independently selected from H, CH₃Or C₂H₅C is any integer from 1 to 4, d is any integer from 0 to 5, and e is any integer from 0 to 4; x^j-Is an anion or anionic group having a negative charge number j;

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

in the formula (II), R₅Is C₈～C₃₀Or linear or branched, saturated or unsaturated alkyl or from C₄～C₂₀Saturated and unsaturated hydrocarbon radicals, straight-chain or branched, or cumyl (C)₆H₅C(CH₃)₂) Substituted benzene or naphthalene rings, or R₅N 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 H or R₆Z; y 'is H or R'₆Z′；R₆And R'₆Is independently selected from C₁～C₅At least one of alkylene or hydroxy-substituted alkylene of (a); z and Z' are independently selected from COOM, SO₃N or hydrogen, M, N is selected from any cationic or cationic group.

8. The surfactant composition of claim 7, wherein said M, N is selected from the group consisting of hydrogen ions, alkali metal cations, and mixtures thereof₇(R₈)(R₉)(R₁₀) At least one of the groups shown, wherein R₇、R₈、R₉、R₁₀Is independently selected from H, (CHR)⁰)_fOH or (CHR)⁰)_gCH₃One of (1), R⁰Is H, CH₃Or C₂H₅Wherein f is any integer from 1 to 4, and g is any integer from 0 to 5.

9. The surfactant composition according to claim 7 or 8, characterized in that R is₁、R₂Any one of hydrogen, methyl, ethyl, hydroxyethyl, hydroxypropyl, phenyl and benzyl; r₄Is hydrogen, C₈～C₂₄One of alkyl or substituted alkyl, methyl, ethyl, hydroxyethyl, hydroxypropyl, phenyl and benzyl, R₃Is hydrogen, C₈～C₂₄One of alkyl or substituted alkyl, hydrogen, methyl, ethyl, phenyl, hydroxyl and amino; r ', R', R⁰Independently selected from H or CH₃(ii) a c is 1-2, d is 0-1, e is 0-1, f is 1-2, and g is 0-1; the R is₅Is C₁₂～C₂₄Or with a hydrocarbon or substituted hydrocarbon radical of₄～C₂₀Saturated and unsaturated hydrocarbon radicals, straight-chain or branched, or cumyl (C)₆H₅C(CH₃)₂) Substituted benzene or naphthalene ringsOr R is₅N is abietylamine radical; r₆And R'₆Is C₁～C₃One of alkylene or hydrogen of (a); the r1+ r2 is 1-10, r3+ r4 is 1-10, and s1+ s2 is 1-20.

10. The surfactant composition according to claim 7, wherein j is an integer of 1 to 3; when j is 1, X^-Is Cl^-、Br^-、I^-、CH₃OSO₃ ^-、HCO₃ ^-、HCOO^-、CH₃COO-、C₂H₅COO^-、C₃H₇COO^-、HOC₆H₄COO^-、C₆H₅SO₃ ^-Or CH₃C₆H₄SO₃ ^-Is more preferably Cl^-、Br^-、HCO₃ ^-、CH₃COO^-、HOC₆H₄COO^-、C₆H₅SO₃ ^-Or CH₃C₆H₄SO₃ ^-One of (1); when j is 2, X^2-Is SO₄ ^2-、HPO₄ ^2-、(COO^-)₂、CH₂(COO^-)₂、C₂H₄(COO^-)₂、C₂H₂(COO^-)₂Or C₆H₄(COO^-)₂One of (1); further preferred is SO₄ ^2-、(COO^-)₂、C₂H₂(COO^-)₂Or C₆H₄(COO^-)₂One of (1); when j is 3, X^3-Is PO₄ ^3-Or CH₂(COO^-)CH(OH)(COO^-)CH₂(COO^-) Is more preferably CH₂(COO^-)CH(OH)(COO^-)CH₂(COO^-)。

11. The surfactant composition according to claim 7, 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 quaternary ammonium salt surfactant, the surfactant containing polyether segments, the micromolecular alcohol, the micromolecular amine, the salt and the alkali is 1 (0.01-100): 0-20): 0-10); the small molecular alcohol is selected from C₁～C₈The fatty alcohol of (a); the small molecule amine is selected from C₁～C₈At least one of a primary amine, a secondary amine, or a tertiary amine; the salt is at least one of metal halide and hydroxyl substituted carboxylate; the inorganic base is further preferably selected from at least one of alkali metal hydroxides, alkali metal carbonates or alkali metal bicarbonates: the preferred molar ratio of the quaternary ammonium salt surfactant, the amine polyether-containing surfactant, the small molecular alcohol, the small molecular amine, the salt and the alkali is 1 (0.2-20): 0-15): 0-5.

12. A process for the preparation of a surfactant composition as claimed in any one of claims 7 to 11 comprising the steps of:

(a) preparing a quaternary ammonium salt surfactant:

will be provided with

And R₄Uniformly mixing the X in water or small molecular alcohol water to carry out quaternization reaction to obtain a water solution or a small molecular alcohol water solution of the quaternary ammonium salt surfactant shown in the formula (I); wherein the concentration of the small molecular alcohol aqueous solution is 0-100 wt% (the mass percentage of alcohol in the alcohol aqueous solution), and the small molecular alcohol is selected from C₁～C₅The fatty alcohol of (a);

(b) preparation of surfactant composition:

in the presence of an alkaline catalyst, R₅NH₂Reacting with the desired amounts of ethylene oxide, propylene oxide, ethylene oxideA polyether compound is obtained; mixing a required amount of polyether compound with the quaternary ammonium salt surfactant aqueous solution or the small molecular alcohol aqueous solution obtained in the step (a) to obtain the surfactant composition;

or by a second reaction to obtain the surfactant composition:

② the polyether compound obtained in the step I and an ionizing agent Y₀R₆Z or Y₀R'₆Mixing Z' and alkali metal hydroxide or alkali metal alkoxide in a molar ratio of 1 (0.1-20) to 0.1-20, reacting at 50-120 ℃ for 3-15 hours under stirring, adding the quaternary ammonium salt surfactant aqueous solution or the small molecular 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 required surfactant composition oil-displacing agent; wherein, Y₀Selected from chlorine, bromine or iodine;

or: ② the polyether compound obtained in the step I and an ionizing agent Y₀R₆ COOR₀Or Y₀R'₆ COOR₀And 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, quaternary ammonium salt surfactant aqueous solution or small molecular alcohol aqueous solution obtained in the step (a) is added according to the required molar ratio, the temperature is raised to 40-100 ℃, and stirring is carried out for 1-5 hours, so that the required surfactant composition is obtained; wherein, Y₀Selected from chlorine, bromine or iodine, R₀Is selected from C₁～C₈Alkyl groups of (a);

as a preferable scheme: the pressure in the step (a) is preferably 0.1-0.6 MPa, and the small molecular alcohol is preferably selected from C₁～C₄The fatty alcohol of (a); the reaction temperature in the step (b) 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 alkali metal hydroxide in the step (b) is preferably at least one of potassium hydroxide and 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 setSelected from 1 (2-10) and (2-10), Y₀Preferably one of chlorine or bromine, R₀Preferably C₁～C₄Alkyl group of (1).

13. Use of the surfactant composition of any of claims 7 to 11 for enhanced oil recovery in oil fields.

14. An oil displacement agent comprises the following components in parts by weight:

(1)1 part of the surfactant composition according to any one of claims 7 to 11 or the surfactant composition prepared by the preparation method according to claim 12;

(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 preferably at least one of anionic polyacrylamide, temperature-resistant and salt-resistant modified polyacrylamide, hydrophobically associating polyacrylamide or polymer microspheres; further preferably, the temperature-resistant and salt-resistant modified polyacrylamide molecular chain preferably comprises an acrylamide structural unit and a 2-acrylamido-2-methylpropanesulfonic acid structural unit, wherein the molar ratio of the acrylamide structural unit to the 2-acrylamido-2-methylpropanesulfonic acid structural unit is preferably (0.1-40) to 1, and the viscosity-average molecular weight is preferably 800-2500 ten thousand; the molecular chain of the hydrophobic association polymer preferably 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 preferably 1: (0.1-40): (0.001 to 0.05) and preferably has 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 preferably 1 to (0.1-2): (0-5).

15. A method for preparing the oil-displacing agent of claim 14, comprising the steps of:

(a) preparing a quaternary ammonium salt surfactant:

will be provided with

And R₄Uniformly mixing the X in water or small molecular alcohol water to carry out quaternization reaction to obtain a water solution or a small molecular alcohol water solution of the quaternary ammonium salt surfactant shown in the formula (I); wherein the concentration of the small molecular alcohol aqueous solution is 0-100 wt% (the mass percentage of alcohol in the alcohol aqueous solution), and the small molecular alcohol is selected from C₁～C₅The fatty alcohol of (a);

(b) preparation of surfactant composition:

in the presence of an alkaline catalyst, R₅NH₂Reacting with ethylene oxide, propylene oxide and ethylene oxide with required amount to obtain polyether compound; mixing a required amount of polyether compound with the quaternary ammonium salt surfactant aqueous solution or the small molecular alcohol aqueous solution obtained in the step (a) to obtain the surfactant composition;

or by a second reaction to obtain the surfactant composition:

② the polyether compound obtained in the step I and an ionizing agent Y₀R₆Z or Y₀R'₆Mixing Z' and alkali metal hydroxide or alkali metal alkoxide in a molar ratio of 1 (0.1-20) to 0.1-20, reacting at 50-120 ℃ for 3-15 hours under stirring, adding the quaternary ammonium salt surfactant aqueous solution or the small molecular 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 required surfactant composition oil-displacing agent; wherein, Y₀Selected from chlorine, bromine or iodine;

or: ② the polyether compound obtained in the step I and an ionizing agent Y₀R₆ COOR₀Or Y₀R'₆ COOR₀And 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, quaternary ammonium salt surfactant aqueous solution or small molecular alcohol aqueous solution obtained in the step (a) is added according to the required molar ratio, the temperature is raised to 40-100 ℃, and stirring is carried out for 1-5 hours, so that the required surfactant composition is obtained; wherein, Y₀Selected from chlorine,Bromine or iodine, R₀Is selected from C₁～C₈Alkyl 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.

Preferably, in the step (a): the pressure is preferably 0.1-0.6 MPa, and the small molecular alcohol is preferably selected from C₁～C₄The fatty alcohol of (a); in the step (b): 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 alkali metal hydroxide is preferably at least one of potassium hydroxide or sodium hydroxide, the molar ratio of the polyether compound to the ionizing agent and the alkali metal hydroxide or the alkali metal alkoxide is preferably 1 (2-10) to (2-10), and Y is preferably 1₀Preferably one of chlorine or bromine, R₀Preferably C₁～C₄Alkyl group of (1).

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