CN112694878A

CN112694878A - Ester-group-containing polyether cationic surfactant composition and preparation and application thereof

Info

Publication number: CN112694878A
Application number: CN201911004118.0A
Authority: CN
Inventors: 沈之芹; 李应成; 何秀娟; 李斌
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2019-10-22
Filing date: 2019-10-22
Publication date: 2021-04-23
Anticipated expiration: 2039-10-22
Also published as: CN112694878B

Abstract

The invention relates to an ester group-containing polyether cationic surfactant composition, and preparation and application thereof, and mainly solves the problems of poor effect, poor viscosity reduction effect and low interface efficiency of the conventional surfactant and thick oil. The invention adopts an ester group-containing polyether cationic surfactant composition, which comprises the following components in parts by mole: (1)1 part of ester polyether cationic surfactant; (2) 1-100 parts of cosurfactant; the molecular general formula of the ester-based polyether cationic surfactant is shown in the formula (I), and the cosurfactant is at least one of a nonionic surfactant, an anionic surfactant, an amphoteric surfactant and a tetraalkyl quaternary ammonium salt surfactant.

Or

Or

Description

Ester-group-containing polyether cationic surfactant composition and preparation and application thereof

Technical Field

The invention relates to an ester group-containing polyether cationic surfactant composition, and preparation and application thereof.

Background

The thickened oil refers to crude oil with high content of asphaltene and colloid and high viscosity. The relative density is usually more than 0.92g/cm³(20 ℃) and the underground viscosity of the crude oil is more than 50 mPas, which is called thick oil and also called heavy oil. At present, the exploitation modes of the thickened oil mainly comprise cold exploitation and hot exploitation. Wherein the thermal recovery mode comprises: steam flooding, steam stimulation, Steam Assisted Gravity Drainage (SAGD); the cold mining method comprises the following steps: polymer flooding, surfactant flooding, foam flooding, solvent extraction (VAPEX), microbial flooding, and the like.

The low-permeability oil reservoir generally has the characteristics of poor physical property of a reservoir layer, low porosity, low permeability and serious heterogeneity, the initial capacity of the oil reservoir is low, and the yield is reduced rapidly. The water absorption capacity of a water injection well is low during water injection development; more serious problems of water lock, water sensitivity, quick sensitivity and the like can occur in the water injection process, and the stratum is damaged; the rock physical property is poor, the pore throat is fine, and the Jamin effect is serious. These problems all result in low water injection recovery ratio of low permeability oil field and unsatisfactory development effect. Particularly for low-permeability heavy oil reservoirs, due to the dual influences of low permeability and high crude oil viscosity, effective exploitation cannot be realized by some conventional methods such as steam flooding.

The surfactant as an important oil displacement mode can be divided into two categories, namely ionic type and non-ionic type, according to different chemical compositions and molecular structures of the surfactant. 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, which is carboxylic acid or sulfonate betaine surfactant with different chain lengths, are reported successively in US3927716, US4018281 and US4216097 of Mobil Petroleum CoThe agent has an interfacial tension of 10 to Texas south crude oil in simulated saline water 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 instance, the application of the rule solution theory to bola type amphiphilic molecules [ (Me) has been studied in the Hades and the like (see "Physics and chemistry journal of academic, No. 9, 830-834 in 2002)₃N⁺(CH₂)₆OC₆H₄O(CH₂)₆N⁺(Me)₃]2Br^-The synergistic effect of the bola molecule and the SDS mixed system is mainly generated by electrostatic interaction between hydrophilic groups, a hydrophobic part in the bola molecular structure has no obvious influence on the interaction, the Cao-Shulong (see physical chemistry report 7 in 2014, 1297-1302) of China petrochemical Shengli oilfield division researches the emulsification and tackifying behaviors of the anionic and cationic surfactant mixed system on crude oil, systematic researches are carried out on the influence of oil-water volume ratio, concentration, temperature, pH value and ionic strength on emulsification and tackifying, a formula system with the optimal tackifying effect is obtained, and compared with the viscosity of crude oil, the viscosity is increased by about 80 times.

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

Disclosure of Invention

The invention aims to solve the technical problems that in the prior art, a surfactant which is mainly used as an oil displacement agent system has poor effect on thick oil, poor viscosity reducing effect and low interface efficiency, and provides a novel ester group-containing polyether cationic surfactant composition. The aqueous solution containing the ester-based polyether cationic surfactant composition has good capabilities of stripping and solubilizing thick oil, effectively reduces the viscosity of the thick oil, and has the viscosity reduction rate of more than 98 percent, thereby being beneficial to starting the thick oil, improving the displacement efficiency of the thick oil and having good application prospect of improving the recovery ratio.

The second technical problem to be solved by the invention is to provide a preparation method of the ester group-containing polyether cationic surfactant composition corresponding to the solution of the first technical problem.

The third technical problem to be solved by the invention is to provide an application of the ester group-containing polyether cationic surfactant composition corresponding to the solution of one of the technical problems.

In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: the cationic surfactant composition containing the ester-based polyether comprises the following components in parts by mole:

(1)1 part of ester polyether cationic surfactant;

(2)1 part to 100 parts of cosurfactant;

the surfactant composition further comprises at least one of a small molecule alcohol, a small molecule amine, a salt and an inorganic base;

wherein the molecular general formula of the ester-based polyether cationic surfactant is shown as the formula (I):

in the formula (I), R₁Is C₂～C₃₂A hydrocarbyl or substituted hydrocarbyl group of (a); r₂、R₃And R₄Independently selected from OH or (CH)₂)_eH and e are any integer of 0-4; r₅、R₆And R₇Independently selected from hydrogen, C₁～C₃₂Alkyl or substituted alkyl (CHR')_fOne of OH, benzyl and naphthalene methylene, R' is selected fromH、CH₃Or C₂H₅F is any integer of 1-4; x^j-Is an anion or anionic group having a negative charge number j; a is the number of carbonyl groups, and a is 0 or 1; b. c and d are the addition number of polyether groups, b is 0-50, c is 0-50, d is 0-50, and b, c and d are not 0 at the same time;

the cosurfactant is at least one of nonionic surfactant, anionic surfactant, amphoteric surfactant and tetraalkyl quaternary ammonium salt surfactant.

In the above technical solution, the nonionic surfactant or the anionic surfactant preferably has a structure represented by formula (II):

in the formula (II), R₈Is C₈～C₃₀Or one of a substituted hydrocarbon group or C₄～C₂₀A phenyl or naphthyl ring substituted by a hydrocarbon or cumyl group, or R₈O is abietate; m1 and m2 are the addition number of ethoxy groups, m1 is 0-50, and m2 is 0-50; n is the addition number of the propoxy groups, and n is 0-100; k is 0 or 1; when k is 1, Y is hydrogen or R 'Z, R' is C₁～C₅Z is COOM, SO₃M’、OSO₃M ' or one of hydrogen, M, M ' and M ' are optionally selected from hydrogen ions, cations or cationic groups; when k is 0, Y is COOM or SO₃M’、OSO₃One of M ", M, M' and M", is optionally selected from hydrogen ions, cations or cationic groups.

In the above technical solution, the zwitterionic surfactant preferably has a structure represented by formula (III): :

in the formula (III), R₉Is selected from C₁～C₃₀Any one of the hydrocarbon groups of (1); r₁₀Is selected from C₁～C₃₀Or is selected from C₁～C₅Any one of the hydrocarbyl or substituted hydrocarbyl of (a); r₁₁Is selected from C₁～C₅Any one of the hydrocarbyl or substituted hydrocarbyl of (a); r₁₂Is selected from C₁～C₅Any of the alkylene groups or substituted alkylene groups of (a); a. the^-Selected from anionic or anionic groups which render the molecule of formula (III) electrically neutral.

In the above technical solution, the tetraalkylammonium salt surfactant preferably has a structure represented by formula (IV):

in the formula (IV), R₁₃Is selected from C₁～C₃₀Any one of the hydrocarbon groups of (1); r₁₄Is selected from C₁～C₃₀Any one of the hydrocarbon groups of (1) or selected from C₁～C₅Any one of the hydrocarbyl or substituted hydrocarbyl of (a); r₁₅And R₁₆Independently selected from hydrogen, (CHR')_gOne of OH, benzyl and naphthalene methylene, R' ″ is selected from H, CH₃Or C₂H₅G is any integer of 1-4; b is^-Selected from anionic or anionic groups which render the molecule of formula (IV) electrically neutral.

In the above technical solution, the co-surfactant is preferably one or more of a nonionic surfactant or an anionic surfactant represented by formula (II), a zwitterionic surfactant represented by formula (III), or a quaternary ammonium salt surfactant represented by formula (IV).

In the above technical scheme, R₁Preferably C₁₂～C₂₄Or an aliphatic or substituted aliphatic radical of (A), or from C₄～C₂₀Linear or branched saturated and unsaturated hydrocarbon groups or cumyl-substituted benzene or naphthalene rings.

In the above technical scheme, R₅、R₆And R₇Preferably C₈～C₂₄Or a hydrocarbon radical ofOne of substituted alkyl, methyl, ethyl, propyl, butyl, benzyl and naphthalene methylene.

In the above technical solution, R' is preferably H, CH₃Or C₂H₅One kind of (1).

In the technical scheme, preferably, e is 0-2, and f is 1-2; b is 0-20, c is 0-20, d is 0-20, and b, c and d are not 0 at the same time.

In the above technical scheme, R₈Preferably C₈～C₂₄Or from C₄～C₂₀Straight or branched chain saturated and unsaturated alkyl or cumyl substituted benzene or naphthalene rings.

In the above technical scheme, R' is preferably C₁～C₃An alkylene group of (a).

In the above technical solution, preferably, m1 is 0 to 10, m2 is 0 to 10, and n is 0 to 20.

In the above technical scheme, R₉Preferably C₈～C₂₄Any one of the alkyl groups of (1).

In the above technical scheme, R₁₀Preferably hydrogen, C₁～C₃Alkyl of (C)₈～C₂₄Any one of the alkyl groups of (1).

In the above technical scheme, R₁₁Preferably hydrogen, C₁～C₃One of the alkyl groups of (1).

In the above technical scheme, R₁₂Preferably C₁～C₃Any one of alkylene or substituted alkylene of (a).

In the above technical scheme, A^-Preferably COO^-Or SO₃ ^-。

In the above technical scheme, R₁₃Preferably C₈～C₂₄Any one of the alkyl groups of (1).

In the above technical scheme, R₁₄Preferably C₈～C₂₄Alkyl of (2), hydrogen, (CH R')_gOH, benzyl and naphthalene methylene.

In the above technical scheme, R₁₅And R₁₆Preferably hydrogen, (ii) isCH R’”)_gOH, benzyl and naphthalene methylene.

In the above-mentioned embodiment, R' "is preferably H, CH₃Or C₂H₅One kind of (1).

In the technical scheme, g is preferably any integer of 1-4.

In the above technical scheme, B^-Preferably Cl^-、Br^-And CH₃COO^-。

In the above technical solution, the surfactant composition further includes at least one of a small molecule alcohol, a small molecule amine, a salt, and an inorganic base.

In the above technical scheme, the small molecular alcohol is preferably C₁～C₈Alcohol or alcohol ether of (a); more preferably, the solvent is at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, glycerol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether.

In the technical scheme, the preferable small molecular amine is C₁～C₈The aliphatic amine of (3) is more preferably a primary amine, a secondary amine or a tertiary amine, and still more preferably selected from ethylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and cyclohexylamine.

In the above technical solution, the salt is preferably at least one selected from a metal halide, a metal silicate, a metal phosphate, a metal carboxylate, and a metal sulfonate; the metal halide is selected from alkali metal halide, preferably at least one of sodium chloride, potassium chloride, sodium bromide and potassium bromide; the metal silicate is selected from at least one of sodium silicate, sodium metasilicate, potassium silicate and potassium metasilicate; the metal phosphate is at least one of sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium polyphosphate and potassium polyphosphate; the metal carboxylate is at least one selected from sodium acetate, sodium glycolate, potassium acetate, potassium glycolate, sodium benzoate, sodium methyl benzoate, sodium hydroxy benzoate, potassium methyl benzoate, potassium hydroxy benzoate, sodium citrate, potassium citrate and EDTA sodium salt; the metal sulfonate is at least one selected from sodium ethanesulfonate, potassium ethanesulfonate, sodium benzenesulfonate, potassium benzenesulfonate, sodium methylbenzenesulfonate, potassium methylbenzenesulfonate, sodium hydroxybenzenesulfonate, potassium hydroxybenzenesulfonate, sodium naphthalenesulfonate and potassium naphthalenesulfonate.

In the above technical solution, the inorganic base is preferably an alkali metal hydroxide, an alkali metal carbonate or an alkali metal bicarbonate, and more preferably at least one of potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate.

In the technical scheme, the mole ratio of the ester-based polyether cationic surfactant, the cosurfactant, the small molecular alcohol, the small molecular amine, the salt and the alkali in the composition is preferably 1 to (1-20): (0-15): (0-5).

The surfactant composition of the invention can also comprise oil displacement components commonly used in the field, such as oil displacement polymers, oil displacement foam agents, oil displacement mineral substances (such as sodium chloride and potassium chloride), alkaline substances (such as sodium hydroxide, sodium carbonate, sodium bicarbonate, diethanolamine, triethanolamine and other micromolecular organic amines), and organic micromolecular auxiliary agents including short-chain fatty alcohols, low-carbon-chain ketones, DMSO and the like.

The key active ingredients of the surfactant compositions of the present invention are (1) and (2), and those skilled in the art will recognize that they can be supplied in various forms, such as a non-aqueous solid form, an aqueous paste form, or an aqueous solution form, for convenience of transportation and storage or on-site use; the aqueous solution form comprises a form of preparing a concentrated solution by water and a form of directly preparing a solution with concentration required by on-site oil displacement, for example, a solution with the key active ingredient content of 0.01-1.0 wt% by weight is a form suitable for 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.

To solve the second technical problem, the technical solution adopted by the present invention is as follows: the preparation method of the ester group-containing polyether cationic surfactant composition in one of the technical problems comprises the following steps:

(a) preparation of ester-based polyether cationic surfactant:

in the presence of a catalyst, R₁COOH or R₁Reacting OH with a desired amount of an epoxy compound to obtain a polyether compound represented by the formula (V); or: in the presence of a catalyst, R₁OH reacts with halogenated epoxy compound to obtain glycidyl ether compound intermediate, and then the glycidyl ether compound intermediate reacts with the required amount of epoxy compound to obtain polyether compound shown in formula (VI);

② mixing the polyether compound obtained in the step I with

Carrying out esterification reaction, and carrying out quaternary ammonification reaction to obtain an ester-based polyether cationic surfactant;

(b) preparation of surfactant composition:

mixing the aqueous solution or the alcohol aqueous solution of the ester-based polyether cationic surfactant obtained in the step (a) with a cosurfactant and optional small molecular alcohol, small molecular amine, salt and inorganic base according to a required molar ratio to obtain the surfactant composition.

In the above technical solution, the catalyst is preferably at least one of potassium hydroxide or anhydrous potassium carbonate.

In the above technical solution, the epoxy compound is preferably ethylene oxide or propylene oxide butylene oxide.

In the above technical scheme, the halogenated epoxy compound is preferably epichlorohydrin.

In the above technical scheme, X' is preferably OH, Cl or CH₃O、C₂H₅O。

In the above technical solution, X' is preferably NR₅R₆、Cl、Br。

In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the application of the cationic surfactant composition containing the ester group polyether, which is described in any one of the technical schemes for solving the technical problems, in improving the yield of heavy oil reservoirs.

In the technical scheme, the surfactant composition can be applied according to the prior art, can be used independently, and can also be compounded with common oil field auxiliaries for use; as a preferable scheme: the total salinity of stratum brine of the application-preferred oil reservoir is 1000-100000 mg/L, wherein HCO₃ ^-0 to 10000 mg/L; the viscosity of the crude oil is 100-7000.0 mPa.s; the formation temperature is 30-70 ℃.

The surfactant composition prepared by the invention is shown in the aspects of increasing the surface activity, reducing the critical micelle concentration, improving the crude oil solubilizing capability and the like due to the synergistic interaction between the components. Especially, the electrostatic effect of the surfactants with opposite electric properties promotes the association between two surfactant ions with different charges, and the hydrophobic hydrocarbon chains of the hydrophobic groups of the two surfactants have certain hydrophobic effect to promote different surfactant molecules to adopt a tighter arrangement mode, so that micelles are easily formed in a solution, and higher surface activity and lower critical micelle concentration than a single surfactant are generated. In addition, the molecules of the surfactant composition adopted by the invention can simultaneously contain aromatic and fatty hydrophobic groups and hetero atoms, so that the surfactant composition is easy to peel off from the thickened oil through pi-pi action, hydrogen bonds and the like to start the thickened oil, and the viscosity of the thickened oil is reduced.

The present invention refers to the total concentration of the components of the above technical schemes, such as the molecular formula (I), the molecular formula (II), the molecular formula (III) or the molecular formula (IV), when the content or concentration of the surfactant composition is referred to.

The method for measuring viscosity reduction rate of thickened oil comprises the following steps: keeping the temperature of the thickened oil at 50 ℃ for 1-2 h, stirring to remove free water and bubbles in the thickened oil, and rapidly measuring the viscosity eta at 50 ℃ by using a rheometer₀. Weighing a certain amount of thick oil, adding a surfactant composition aqueous solution according to the oil-water mass ratio of 7:3, keeping the temperature at 50 ℃ for 40 minutes, stirring to convert the thick oil into an oil-in-water type emulsion, and rapidly measuring the viscosity eta of the thick oil emulsion by using a rheometer₁The viscosity reduction rate is calculated according to the formula (1):

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 (2):

γ＝0.25ω²r³Δ ρ (L/D ≧ 4) formula (2);

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 surfactant composition is used for the formation temperature of 30-70 ℃ and the degree of mineralization of 1000-100000 mg/L, wherein HCO₃ ^-The viscosity of the simulated saline water and the crude oil is 0-10000 mg/L, and the viscosity of the crude oil is 100-10000.0 mPa.s. The viscosity reducing rate of the surfactant composition with the dosage of 0.03 percent on the thickened oil can reach more than 90.0 percent, the viscosity reducing rate of the surfactant composition with the dosage of 0.3w percent on the thickened oil can reach more than 93.0 percent, the highest viscosity reducing rate can reach 98.5 percent, and the dynamic interfacial tension value between the surfactant composition with the dosage of 0.01wt percent and the oil field dehydrated crude oil can reach 0.0232 to0.0041mN/m, the dynamic interfacial tension value between the surfactant composition with the dosage of 0.15 wt% and the oil field dehydration crude oil can reach 0.0033-0.0005 mN/m, and a better technical effect is obtained.

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 infrared spectroscopy (ATR)^-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 the cationic nonionic surfactant prepared in example 1. Wherein, 2923.3cm^-1And 2846.1m^-1Is a characteristic peak of C-H stretching of methyl and methylene, 1629.9cm^-1Is C ═ O stretching vibration absorption peak, 1546.8cm^-1And 1602.8cm^-1Is the stretching vibration peak of benzene ring, 1465.1cm^-1Is a C-N bending vibration absorption peak, 1167.0cm^-1And 1239.1cm^-1Is the C-N stretching vibration peak, 1098.9cm^-1Is C-O stretching vibration peak, 1046.2cm^-1Is a C-O-C stretching vibration peak of 700.0-800.0 cm^-1Is the in-plane rocking absorption peak of CH plane in the benzene ring. The invention is further illustrated by the following examples.

Detailed Description

[ example 1 ]

(a) Preparation of cationic nonionic surfactants

Firstly, adding 282.5 g (1 mol) of 9-ene octadecanoic acid and 5.5 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 664.4 g (15.1 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, thus obtaining 921.8 g of 9-ene octadecanoic acid polyoxyethylene (15) ester with the yield of 97.8 percent.

② mixing 51.6 g (0.5 mol) of N, N-dimethylglycine and 119.1 g (1.0 mol) of thionyl chloride, refluxing for 5 hours under the protection of nitrogen, decompressing and evaporating excessive thionyl chloride to obtain N, N-dimethylglycine chloride. N, N-dimethylglycinoyl chloride is slowly dropped into 471.3 g (0.5 mol) of 9-octadecenoic acid polyoxyethylene (15) ester to react to obtain a tertiary amine intermediate containing an ester group, and then 131.2 g (0.55 mol) of octyl benzyl chloride is added to carry out quaternization reaction to obtain the cationic nonionic surfactant.

(b) Preparation of surfactant composition S01

Adding the cationic non-ionic surfactant synthesized in the step (a), cetyl dihydroxyethyl hydroxypropyl sulfonic acid betaine), sodium silicate and isopropanol into the mixture at about 40 ℃ according to a molar ratio of 1:1.2:0.5:2.5, adding water until the content of the surfactant is about 30%, and continuously stirring the mixture at 40 ℃ for 4 hours to obtain the ester-containing polyether cationic surfactant composition S01.

[ example 2 ]

(a) Preparation of cationic nonionic surfactants

Adding 282.5 g (1 mol) of 9-ene octadecanoic acid and 6.5 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 116.0 g (2.0 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the propylene oxide, slowly introducing 132.0 g (3.0 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction, the temperature was reduced to 90 ℃, the low boiling point material was removed in vacuum, and neutralization and dehydration were carried out after cooling to obtain 511.4 g of 9-eneoctadecylic acid polyoxypropylene (2) epoxy ethylene (3) ester with a yield of 96.4%.

② mixing 51.6 g (0.5 mol) of N, N-dimethylglycine and 119.1 g (1.0 mol) of thionyl chloride, refluxing for 5 hours under the protection of nitrogen, decompressing and evaporating excessive thionyl chloride to obtain N, N-dimethylglycine chloride. Slowly dripping N, N-dimethyl glycine acyl chloride into 256.3 g (0.5 mol) of 9-ene octadecanoic acid polyoxypropylene (2) epoxy ethylene (3) ester to react to obtain a tertiary amine intermediate containing an ester group, adding 50.5 g (1.0 mol) of methyl chloride to perform quaternization under a pressurized condition, and after the reaction is finished, decompressing and removing low-boiling-point substances to obtain the cationic nonionic surfactant.

(b) Preparation of surfactant composition S02

Adding the cationic non-ionic surfactant synthesized in the step (a), cetyl dihydroxyethyl hydroxypropyl sulfonate betaine, glycerol, diethylenetriamine and sodium benzoate according to the molar ratio of 1:2:0.4:0.1:0.2 at about 40 ℃, adding water until the content of the surfactant is about 30%, and continuously stirring at 45 ℃ for 3 hours to obtain the ester-group-containing polyether cationic surfactant composition S02.

[ example 3 ]

(a) Preparation of cationic nonionic surfactants

Firstly, adding 282.5 g (1 mol) of 9-ene octadecanoic acid and 6.5 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 132.0 g (3.0 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 160 ℃ after the reaction of the ethylene oxide, slowly introducing 288.0 g (4.0 mol) of butylene oxide, controlling the pressure to be less than or equal to 0.40MPa, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 308.0 g (7.0 mol) of ethylene oxide, cooling to 90 ℃, removing low-content substances in vacuum, cooling, neutralizing and dehydrating to obtain 940.8 g of 9-ene octadecanoic acid polyoxyethylene (3) polyoxybutylene (4) polyoxyethylene (7) ester, wherein the yield is 93.1%.

② mixing 51.6 g (0.5 mol) of N, N-dimethylglycine and 119.1 g (1.0 mol) of thionyl chloride, refluxing for 5 hours under the protection of nitrogen, decompressing and evaporating excessive thionyl chloride to obtain N, N-dimethylglycine chloride. N, N-dimethylglycinoyl chloride is slowly dropped into 505.3 g (0.5 mol) of 9-octadecenoic acid polyoxyethylene (3) polyoxybutylene (4) polyoxyethylene (7) ester to react to obtain a tertiary amine intermediate containing an ester group, and then 75.8 g (1.5 mol) of methyl chloride is added to carry out quaternization under a pressurized condition to obtain the cationic nonionic surfactant.

(b) Preparation of surfactant composition S03

Adding the cationic non-ionic surfactant synthesized in the step a, cetyl dihydroxyethyl hydroxypropyl sulfonate betaine, ethylene glycol monomethyl ether and sodium silicate according to the molar ratio of 1:4:0.05:0.8 at about 40 ℃, adding water until the content of the surfactant is about 30%, and continuously stirring at 40 ℃ for 4 hours to obtain the ester-group-containing polyether cationic surfactant composition S03.

[ example 4 ]

(a) Preparation of cationic nonionic surfactants

Firstly, adding 282.5 g (1 mol) of 9-ene octadecanoic acid and 6.5 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 664.4 g (15.1 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction is finished, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, thus obtaining 921.8 g of 9-ene octadecanoic acid polyoxyethylene (15) ester with the yield of 97.8 percent.

② mixing 51.6 g (0.5 mol) of N, N-dimethylglycine and 119.1 g (1.0 mol) of thionyl chloride, refluxing for 5 hours under the protection of nitrogen, decompressing and evaporating excessive thionyl chloride to obtain N, N-dimethylglycine chloride. N, N-dimethylglycinoyl chloride is slowly dropped into 471.3 g (0.5 mol) of 9-octadecenoic acid polyoxyethylene (15) ester to react to obtain a tertiary amine intermediate containing an ester group, and then 131.2 g (0.55 mol) of octyl benzyl chloride is added to carry out quaternization reaction to obtain the cationic nonionic surfactant. (b) Preparation of surfactant composition S04

Adding the cationic nonionic surfactant synthesized in the step (a), isomeric tridecanol polyoxypropylene (2) polyoxyethylene (6) sodium acetate, ethylene glycol and sodium polyphosphate into the mixture at the temperature of about 40 ℃ according to the mol ratio of 1:1.5:3:2, adding water until the content of the surfactant is about 30%, and continuously stirring the mixture at the temperature of 40 ℃ for 4 hours to obtain the ester group-containing polyether cationic surfactant composition S04.

[ example 5 ]

(a) Preparation of cationic nonionic surfactants

Adding 282.5 g (1 mol) of 9-ene octadecanoic acid and 6.5 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 116.0 g (2.0 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the propylene oxide, slowly introducing 440.2 g (10.0 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction, the temperature was reduced to 90 ℃, the low boiling point material was removed in vacuo, and after cooling, neutralization and dehydration were carried out to obtain 796.6 g of 9-eneoctadecylic acid polyoxypropylene (2) polyoxyethylene (10) ester with a yield of 95.0%.

② mixing 51.6 g (0.5 mol) of N, N-dimethylglycine and 119.1 g (1.0 mol) of thionyl chloride, refluxing for 5 hours under the protection of nitrogen, decompressing and evaporating excessive thionyl chloride to obtain N, N-dimethylglycine chloride. N, N-dimethylglycinoyl chloride is slowly dropped into 419.3 g (0.5 mol) of 9-octadecenoic acid polyoxypropylene (2) polyoxyethylene (10) ester to react to obtain a tertiary amine intermediate containing an ester group, and then 75.8 g (1.5 mol) of methyl chloride is added to carry out quaternization reaction to obtain the cationic nonionic surfactant. (b) Preparation of surfactant composition S05

Adding the cationic nonionic surfactant synthesized in the step (a), ammonium dodecylbenzene sulfonate, propane diamine and sodium benzenesulfonate into the mixture at a molar ratio of 1:1.05:3:0.5 at about 50 ℃, adding water until the content of the surfactant is about 30%, and continuously stirring the mixture for 2 hours at 50 ℃ to obtain the ester group-containing polyether cationic surfactant composition S05.

[ example 6 ]

(a) Preparation of cationic nonionic surfactants

Adding 269.0 g (1 mol) of octadecanol and 10.2 g of potassium carbonate into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 396.0 g (9.0 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. 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 646.4 g of octadecanol polyoxyethylene (9) ether are obtained, and the yield is 97.2%.

② 58.6 g (0.5 mol) of N, N-dimethyl glycine methyl ester, 332.5 g (0.5 mol) of octadecyl alcohol polyoxyethylene (9) ether and 4.1 g of solid potassium hydroxide are added into a four-neck flask with a distillation device, the temperature is slowly increased until obvious methanol is distilled off, the reaction is stopped until the collected methanol amount reaches more than 95 percent of the theoretical amount, a tertiary amine intermediate containing ester groups is obtained, 95.1 g (1.0 mol) of methyl bromide is added for quaternization reaction under the pressurization condition, and the cationic nonionic surfactant is obtained.

(b) Preparation of surfactant composition S06

Adding the cationic non-ionic surfactant synthesized in the step a, sodium dodecyl benzene sulfonate, propanol and potassium citrate into the mixture at a temperature of about 40 ℃ according to a mol ratio of 1:1.5:8:0.7, adding water until the content of the surfactant is about 30%, and continuously stirring the mixture for 4 hours at a temperature of 40 ℃ to obtain the ester-group-containing polyether cationic surfactant composition S06.

[ example 7 ]

(a) Preparation of cationic nonionic surfactants

185.0 g (1 mol) of dodecanol and boron trifluoride diethyl etherate are added into a three-neck flask with a stirring dropping funnel and stirred uniformly. When the temperature is raised to a certain temperature, 92.5 g (1 mol) of epichlorohydrin is slowly dripped, and after the dripping is finished, the solution is maintained for 2 hours. Vacuum distilling to remove unreacted epichlorohydrin, adding ethanol solution of sodium hydroxide, and stirring. Filtering to remove the generated sodium chloride, then distilling under reduced pressure to remove ethanol, water and the like, and filtering to remove residual sodium chloride while the solution is hot to obtain the dodecanol glycidyl ether.

Adding 240.0 g (1 mol) of dodecanol glycidyl ether and 7.8 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 130 ℃, slowly introducing 90.2 g (2.05 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction, the temperature is reduced to 80 ℃, low-boiling-point substances are removed in vacuum, and neutralization and dehydration are carried out after cooling, so that 317.9 g of dodecanol hydroxyl polyoxypropylene (1) polyoxyethylene (2) ether are obtained, and the yield is 92.7%.

③ 51.6 g (0.5 mol) of N, N-dimethylglycine and 119.1 g (1.0 mol) of thionyl chloride are mixed, and after refluxing for 5 hours under the protection of nitrogen, excessive thionyl chloride is distilled off under reduced pressure to obtain N, N-dimethylglycine chloride. N, N-dimethylglycinoyl chloride is slowly dropped into 171.5 g (0.5 mol) of dodecanol hydroxy polyoxypropylene (1) polyoxyethylene (2) ether to react to obtain an ester group-containing tertiary amine intermediate, and then 178.9 g (0.75 mol) of benzyl chloride is added to carry out quaternization reaction to obtain the cationic nonionic surfactant.

(b) Preparation of the surfactant composition S07, adding the cationic nonionic surfactant synthesized in the step (a), potassium acetate of behenyl polyoxyethylene ether (5) and tetrasodium EDTA at a molar ratio of 1:3:0.1 at about 40 ℃, adding water until the content of the surfactant is about 30%, and continuously stirring at 40 ℃ for 4 hours to obtain the ester-containing polyether cationic surfactant composition S07.

[ example 8 ]

(a) Preparation of cationic nonionic surfactants

185.0 g (1 mol) of dodecanol and boron trifluoride diethyl etherate are added into a three-neck flask with a stirring dropping funnel and stirred uniformly. When the temperature is raised to a certain temperature, 92.5 g (1 mol) of epichlorohydrin is slowly dripped, and after the dripping is finished, the solution is maintained for 2 hours. Vacuum distilling to remove unreacted epichlorohydrin, adding ethanol solution of sodium hydroxide, and stirring. Filtering out the generated sodium chloride, then removing ethanol, water and the like by reduced pressure distillation, and filtering to remove residual sodium chloride while the solution is hot to obtain the dodecanol glycidyl ether.

(b) Preparation of surfactant composition S08

Adding the cationic nonionic surfactant synthesized in the step (a), sodium dodecyl phenol polyoxypropylene (5) polyoxyethylene (5) ether acetate, cyclohexylamine and isopropanol into the mixture at a molar ratio of 1:2:0.7:5 at about 40 ℃, adding water until the content of the surfactant is about 30%, and continuously stirring the mixture for 4 hours at 40 ℃ to obtain the ester group-containing polyether cationic surfactant composition S08.

[ example 9 ]

(a) Preparation of cationic nonionic surfactants

(b) Preparation of surfactant composition S09

Adding the cationic non-ionic surfactant synthesized in the step (a), cetyl dihydroxyethyl hydroxypropyl sulfonate betaine, bromocetyl pyridine and sodium citrate according to the molar ratio of 1:5:3.5:1 at about 35 ℃, adding water until the content of the surfactant is about 30%, and continuously stirring at 35 ℃ for 6 hours to obtain the ester-containing polyether cationic surfactant composition S09.

[ example 10 ]

(a) Preparation of cationic nonionic surfactants

Adding 228.0 g (1 mol) of coconut oil acid, 3.5 g of potassium hydroxide and 6.0 g of potassium carbonate into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 308.0 g (7.0 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction, the temperature is reduced to 90 ℃, low-boiling-point substances are removed in vacuum, and after cooling, neutralization and dehydration are carried out, so that 492.1 g of polyoxyethylene (7) cocoate is obtained, and the yield is 91.8%.

② under the protection of nitrogen, slowly dripping 56.6 g (0.5 mol) of chloracetyl chloride into 268.1 g (0.5 mol) of polyoxyethylene (7) cocoate to react to obtain a chlorinated compound intermediate containing ester group, then adding 127.8 g (0.6 mol) of N, N-dimethyldodecylamine and 400 g of isopropanol to carry out quaternization reaction to obtain the cationic non-ionic surfactant.

(b) Preparation of surfactant composition S10

Adding the cationic nonionic surfactant synthesized in the step a, dodecyl dimethyl carboxyl betaine, dodecyl trimethyl ammonium chloride and diethanol amine according to the molar ratio of 1:4:0.2:1.5 at about 30 ℃, adding water until the content of the surfactant is about 30%, and continuously stirring at 30 ℃ for 6 hours to obtain the ester-containing polyether cationic surfactant composition S10.

[ example 11 ]

(a) Preparation of cationic nonionic surfactants

② 58.6 g (0.5 mol) of N, N-dimethyl glycine methyl ester, 332.5 g (0.5 mol) of octadecyl alcohol polyoxyethylene (9) ether and 4.7 g of solid potassium hydroxide are added into a four-neck flask with a distillation device, the temperature is slowly increased until obvious methanol is distilled off, the reaction is stopped until the collected methanol amount reaches more than 95 percent of the theoretical amount, a tertiary amine intermediate containing ester groups is obtained, 50.5 g (1.0 mol) of methyl chloride is added for quaternization reaction under the pressure condition, and the cationic nonionic surfactant is obtained.

(b) Preparation of surfactant composition S11

Adding the cationic nonionic surfactant synthesized in the step a and alpha-olefin sulfonate (AOS) at the temperature of about 40 ℃ according to the mol ratio of 1:2:0.9:5:3_14-18) And (3) adding water into the mixture until the content of the surfactant is about 30%, and continuing stirring at 40 ℃ for 4 hours to obtain the ester group-containing polyether cationic surfactant composition S11.

[ example 12 ]

(a) Preparation of cationic nonionic surfactants

Firstly, adding 185.0 g (1 mol) of dodecanol and 7.3 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 116.0 g (2.0 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the propylene oxide, slowly introducing 406.0 g (7.0 mol) of ethylene oxide, and controlling the pressure to be less than or equal to 0.40 MPa. After the reaction, the temperature was reduced to 90 ℃, low boiling point substances were removed in vacuo, and after cooling, neutralization and dehydration were carried out to obtain 597.3 g of lauryl polyoxypropylene (2) polyoxyethylene (7) ether with a yield of 98.1%.

58.6 g (0.5 mol) of N, N-dimethyl glycine methyl ester, 304.5 g (0.5 mol) of lauryl alcohol polyoxypropylene (2) polyoxyethylene (7) ether and 5.6 g of solid potassium hydroxide are added into a four-neck flask with a distillation device, the temperature is slowly increased until obvious methanol is distilled off, the reaction is stopped until the amount of the collected methanol reaches more than 95 percent of the theoretical amount, a tertiary amine intermediate containing ester groups is obtained, and 122.7 g (0.6 mol) of 1-chlorododecane is added for quaternization reaction, so that the cationic nonionic surfactant is obtained.

(b) Preparation of surfactant composition S12

Adding the cationic nonionic surfactant synthesized in the step o (a), isotridecanol polyoxypropylene (2) polyoxyethylene (6) ether sodium acetate, octadecyl trihydroxyethyl ammonium chloride, potassium carbonate and ethylene glycol dimethyl ether into the mixture at a molar ratio of 1:3:1.2:2:0.3 at about 30 ℃, adding water until the content of the surfactant is about 30%, and continuously stirring the mixture at 30 ℃ for 6 hours to obtain the ester group-containing polyether cationic surfactant composition S12.

[ example 13 ]

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 an oil field, the viscosity of the crude oil is shown in the table 1, and the crude oil is used after dehydration and is the viscosity of the ground crude oil.

The viscosity reduction test can well reflect the effect of the surfactant on the thickened oil, and the viscosity reduction result of the surfactant is shown in table 1. The viscosity is determined by a model HAAKE MARS III rotational rheometer.

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 1. 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 difference is that the cationic nonionic surfactant synthesized in the step (a), cetyl dihydroxyethyl hydroxypropyl sulfonic acid betaine, sodium silicate and isopropanol are added at about 40 ℃ in a molar ratio of 1:0:0.5:2.5, water is added until the content of the surfactant is about 30%, and the stirring is continued at 40 ℃ for 4 hours, so that a surfactant composition S13 is obtained.

The difference is that the cationic nonionic surfactant synthesized in the step a, cetyl dihydroxyethyl hydroxypropyl sulfonic acid betaine, sodium silicate and isopropanol are added at about 40 ℃ in a molar ratio of 0:1.2:0.5:2.5, water is added until the content of the surfactant is about 30%, and the stirring is continued at 40 ℃ for 4 hours, so that a surfactant composition S14 is obtained.

The same as [ example 4 ] except that the cationic nonionic surfactant synthesized in step (a), isomeric tridecanol polyoxypropylene (2) polyoxyethylene (6) sodium acetate, ethylene glycol and sodium polyphosphate were added at about 40 ℃ in a molar ratio of 0:1.5:3:2, water was added to a surfactant content of about 30%, and stirring was continued at 40 ℃ for 4 hours to obtain a surfactant composition S15.

[ COMPARATIVE EXAMPLE 2 ]

The difference is as in [ example 6 ]:

58.6 g (0.5 mol) of N, N-dimethyl glycine methyl ester, 135.2 g (0.5 mol) of octadecanol and 4.1 g of solid potassium hydroxide are added into a four-neck flask with a distillation device, the temperature is slowly increased until obvious methanol is distilled off, the reaction is stopped until the collected methanol amount reaches more than 95 percent of the theoretical amount, a tertiary amine intermediate containing an ester group is obtained, 50.5 g (1.0 mol) of methyl chloride is added, and the quaternization reaction is carried out under the pressurized condition, so that the cationic nonionic surfactant is obtained. (b) Adding the cationic surfactant synthesized in the step a, sodium dodecyl benzene sulfonate, propanol and potassium citrate into the mixture at a temperature of about 40 ℃ according to a mol ratio of 1:1.5:8:0.7, adding water until the content of the surfactant is about 30%, and continuously stirring the mixture for 4 hours at a temperature of 40 ℃ to obtain a surfactant composition S16.

[ COMPARATIVE EXAMPLE 3 ]

The difference is that the cationic nonionic surfactant synthesized in the step (a), cetyl dihydroxyethyl hydroxypropyl sulfonate betaine, bromocetyl pyridine and sodium citrate are added at about 35 ℃ in a molar ratio of 0:5:3.5:1, water is added until the content of the surfactant is about 30%, and the mixture is continuously stirred at 35 ℃ for 6 hours to obtain a surfactant composition S17.

TABLE 1

TABLE 2

Claims

1. The cationic surfactant composition containing the ester-based polyether comprises the following components in parts by mole:

(1)1 part of ester polyether cationic surfactant;

(2) 1-100 parts of cosurfactant;

or

Or

In the formula (I), R₁Is C₂～C₃₂A hydrocarbyl or substituted hydrocarbyl group of (a); r₂、R₃And R₄Independently selected from OH or (CH)₂)_eH and e are any integer of 0-4; r₅、R₆And R₇Independently selected from hydrogen, C₁～C₃₂Alkyl or substituted alkyl (CHR')_fOH, benzyl or naphthalene methylene, R' is selected from H, CH₃Or C₂H₅F is any integer of 1-4; x^j-Is an anion or anionic group having a negative charge number j; a is the number of carbonyl groups, and a is 0 or 1; b. c and d are the addition number of polyether groups, b is 0-50, c is 0-50, d is 0-0E50, and b, c and d are not 0 at the same time;

the cosurfactant is at least one of nonionic surfactant, anionic surfactant, zwitterionic surfactant and tetraalkyl quaternary ammonium salt surfactant.

2. The ester group-containing polyether cationic surfactant composition of claim 1, wherein the nonionic surfactant or anionic surfactant has the structure of formula (II), the zwitterionic surfactant has the structure of formula (III), and the tetraalkyl quaternary ammonium salt surfactant has the structure of formula (IV):

in the formula (II), R₈Is C₈～C₃₀Or one of a substituted hydrocarbon group or C₄～C₂₀A phenyl or naphthyl ring substituted by a hydrocarbon or cumyl group, or R₈O is abietate; m1 and m2 are the addition number of ethoxy groups, m1 is 0-50, and m2 is 0-50; n is the addition number of the propoxy groups, and n is 0-100; k is 0 or 1; when k is 1, Y is hydrogen or R 'Z, R' is C₁～C₅Z is COOM, SO₃M’、OSO₃M ' or one of hydrogen, M, M ' and M ' are optionally selected from hydrogen ions, cations or cationic groups; when k is 0, Y is COOM or SO₃M’、OSO₃One of M ", M, M' and M" are optionally selected from hydrogen ions, cations or cationic groups;

in the formula (III), R₉Is selected from C₁～C₃₀Any one of the hydrocarbon groups of (1); r₁₀Is selected from C₁～C₃₀Or is selected from C₁～C₅With hydrocarbon or substituted hydrocarbon radicalsAny one of the above; r₁₁Is selected from C₁～C₅Any one of the hydrocarbyl or substituted hydrocarbyl of (a); r₁₂Is selected from C₁～C₅Any of the alkylene groups or substituted alkylene groups of (a); a. the^-Selected from anionic or anionic groups which render the molecule of formula (III) electrically neutral;

in the formula (IV), R₁₃Is selected from C₁～C₃₀Any one of the hydrocarbon groups of (1); r₁₄Is selected from C₁～C₃₀Any one of the hydrocarbon groups of (1) or selected from C₁～C₅Any one of the hydrocarbyl or substituted hydrocarbyl of (a); r₁₅And R₁₆Independently selected from hydrogen, (CH R' ")_gOne of OH, benzyl and naphthalene methylene, R' "is selected from H, CH₃Or C₂H₅G is any integer of 1-4; b is^-Selected from anionic or anionic groups which render the molecule of formula (IV) electrically neutral.

3. The ester group-containing polyether cationic surfactant composition according to claim 1, wherein R is₁Is C₁₂～C₂₄Or an aliphatic or substituted aliphatic radical of (A), or from C₄～C₂₀Straight or branched saturated and unsaturated hydrocarbon radicals or cumyl-substituted benzene or naphthalene rings, R₅、R₆And R₇Is C₈～C₂₄One of alkyl or substituted alkyl, methyl, ethyl, propyl, butyl, benzyl and naphthalene methylene, wherein e is 0-2, and f is 1-2; b is 0-20, c is 0-20, d is 0-20, and b, c and d are not 0 at the same time.

4. The ester group-containing polyether cationic surfactant composition according to claim 2, wherein R is₈Is C₈～C₂₄Or from C₄～C₂₀Straight or branched chainSaturated and unsaturated alkyl or cumyl substituted benzene or naphthalene rings; r' is C₁～C₃An alkylene group of (a); m1 is 0-10, m2 is 0-10, and n is 0-20; the R is₉Is C₈～C₂₄Any one of the alkyl groups of (a); r₁₀Is C₁～C₃Alkyl of (C)₈～C₂₄Any one of the alkyl groups of (a); r₁₁Is selected from C₁～C₃One of the alkyl groups of (a); r₁₂Is C₁～C₃Any one of alkylene or substituted alkylene of (a); a. the^-Is COO^-Or SO₃ ^-(ii) a The R is₁₃Is C₈～C₂₄Any one of the alkyl groups of (a); r₁₄Is C₈～C₂₄Alkyl of (5), hydrogen, (CH R')_gOne of OH, benzyl and naphthalene methylene; r₁₅And R₁₆Independently selected from hydrogen, (CH R' ")_gOne of OH, benzyl and naphthalene methylene, R' "is selected from H, CH₃Or C₂H₅G is any integer of 1-4; b is^-Is Cl^-、Br^-And CH₃COO^-。

5. The ester group-containing polyether cationic surfactant composition of claim 1, characterized in that the surfactant composition further comprises at least one of a small molecule alcohol, a small molecule amine, a salt, and an inorganic base;

further preferably: the small molecular alcohol is preferably selected from C₁～C₈Alcohol or alcohol ether of (a); the small molecular amine is preferably selected from C₁～C₈The fatty amine of (a); the salt is preferably at least one selected from the group consisting of metal halides, metal silicates, metal phosphates, metal carboxylates, and metal sulfonates; the inorganic base is preferably at least one selected from an alkali metal hydroxide, an alkali metal carbonate or an alkali metal bicarbonate.

6. The ester group-containing polyether cationic surfactant composition according to claim 5, characterized in that C₁～C₈Alcohol or alcohol ofThe ether is selected from at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, glycerol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol dibutyl ether; said C is₁～C₈The aliphatic amine is primary amine, secondary amine or tertiary amine, preferably at least one selected from ethylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and cyclohexylamine; the metal halide is selected from alkali metal halide, preferably at least one of sodium chloride, potassium chloride, sodium bromide and potassium bromide; the metal silicate is selected from at least one of sodium silicate, sodium metasilicate, potassium silicate and potassium metasilicate; the metal phosphate is at least one of sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium polyphosphate and potassium polyphosphate; the metal carboxylate is at least one selected from sodium acetate, sodium glycolate, potassium acetate, potassium glycolate, sodium benzoate, sodium methyl benzoate, sodium hydroxy benzoate, potassium methyl benzoate, potassium hydroxy benzoate, sodium citrate, potassium citrate and EDTA sodium salt; the metal sulfonate is at least one of sodium ethanesulfonate, potassium ethanesulfonate, sodium benzenesulfonate, potassium benzenesulfonate, sodium methyl benzenesulfonate, potassium methylbenzenesulfonate, sodium hydroxybenzenesulfonate, potassium hydroxybenzenesulfonate, sodium naphthalenesulfonate and potassium naphthalenesulfonate; the inorganic base is at least one of potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate.

7. The ester group-containing polyether cationic surfactant composition according to any one of claims 1 to 6, wherein the molar ratio of the ester group-containing polyether cationic surfactant, the cosurfactant, the small molecular alcohol, the small molecular amine, the salt and the alkali in the composition is 1:1 (1-20): (0-15): (0-5).

8. A method for preparing the ester group-containing polyether cationic surfactant composition as claimed in any one of claims 1 to 7, comprising the steps of:

(a) preparation of ester-based polyether cationic surfactant:

② mixing the polyether compound obtained in the step I with

(b) preparation of surfactant composition:

9. The method for preparing the ester group-containing polyether cationic surfactant according to claim 8, wherein the catalyst is at least one of potassium hydroxide or anhydrous potassium carbonate; the epoxy compound is ethylene oxide, propylene oxide and butylene oxide; the halogenated epoxy compound is epichlorohydrin; the X' is OH, halogen or CH₃O、C₂H₅O、C₃H₉O, X' are halogen, NR₅R₆。

10. The application of the cationic surfactant composition containing the ester group polyether in any one of claims 1-7 in improving the yield of heavy oil reservoirs.