CN114479811A - Anionic-nonionic surfactant and preparation method and application thereof - Google Patents

Abstract

The invention discloses an anion-nonionic surfactant, a preparation method and an application thereof, wherein the structure of the anion-nonionic surfactant is shown as the following formula:

R₁is selected from C₆～C₃₆A hydrocarbyl or substituted hydrocarbyl radical of R₂Selected from hydrogen, C₁～C₁₀A hydrocarbon group of₁～C₁₀Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a); a. b and c are independently selected from any integer of 0-50 and are not 0 at the same time; r₃、R₄And R₅Each independently selected from hydroxy or (CH)₂)_dH and d are any integer of 0-4; r₆Selected from hydrogen, C₁～C₅A hydrocarbon group of₁～C₅Substituted hydrocarbyl carboxylate of (A), C₁～C₅Substituted hydrocarbyl sulfonates of (A) and (B)₁～C₅Substituted hydrocarbyl phosphates or C₁～C₅Is gotAlkyl sulfate salts; n is the charge number of the cation or cationic group, and M is selected from hydrogen, alkali metal, alkaline earth metal or ammonium. The foam-free high-temperature-resistant oil pool has excellent temperature resistance and salt resistance, is more practical for high-temperature and high-salt oil pools, and is more beneficial to the formation of foam.

Description

Anionic-nonionic surfactant and preparation method and application thereof

Technical Field

The invention belongs to the field of surfactants, and particularly relates to an anionic-nonionic surfactant.

Background

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 oil displacement by using alkaline water, surfactant or alkaline water oil displacement and oil displacement by using zwitterionic surfactant are sequentially reported by US3927716, US4018281 and US4216097 of Mofu Petroleum company, the zwitterionic surfactant is carboxylic acid or sulfonate type betaine surfactant with different chain lengths, and the interfacial tension on crude oil in Texas south Texas is 10 in simulated saline with total mineralization of 62000-160000 mg/L and calcium and magnesium ions of 1500-18000 mg/L^-1～10^-4mN/m. For example, chinese patents CN1528853A, CN1817431A, CN1066137A 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.

U.S. Pat. No. 2,8211837, the university of Texas, USA, reports that linear alcohol with low cost is adopted to catalyze dimerization reaction at high temperature to obtain branched long carbon alcohol, and then sulfuric acid esterification reaction is carried out after polymerization with propylene oxide and ethylene oxide, compared with expensive sulfonate type surfactant, large hydrophilic group polyether sulfate surfactant is synthesized at low cost, due to existence of large hydrophilic group, the sulfate surfactant has excellent high-temperature stability under alkaline condition, and 0.3% branched alcohol polyether sulfate (C-alcohol polyether sulfate) is used₃₂-7PO-6EO sulfate) with 0.3% of an internal olefin sulfonate (C)_20～24IOS) brine solution was mixed with the same amount of crude oil at 85 ℃ with a solubilization parameter of 14. The surfactant used in foreign research is limited in practical application as an oil displacement agent due to large usage amount and high cost.

Surfactants used as blowing agents are mainly of two types, anionic and nonionic. However, for high-temperature and high-salinity oil reservoirs, due to the poor compatibility of the single anionic foaming agent and the formation water, the anionic foaming agent is easy to form precipitates with high-valence ions such as calcium, magnesium and the like in the formation water, and the nonionic temperature resistance is insufficient. Document CN1648199A discloses an enhanced oil recovery foam formulation for conventional oil reservoirs, wherein the main agent of the foaming agent is dodecyl polyoxyethylene ether sulfate sodium salt, but the existence of a sulfate ester bond in the main agent makes the system only suitable for oil reservoirs below 100 ℃. US7122509 reports a high temperature foam drainage agent formulation, which adopts a research idea of neutralization of anionic surfactant and amine to improve the temperature resistance of the system, but the patent does not relate to drainage effect and use concentration. CN102212348A discloses a salt-tolerant methanol-resistant foam drainage agent, which comprises the following components in percentage by weight: 20-40% of cocamidopropyl betaine, 45-65% of amine oxide, 5-20% of alpha-olefin sulfonate, 5-15% of triethanolamine, 0.2-2% of fluorocarbon surfactant and 0-5% of methanol, wherein the mineralization resistance can reach 18 ten thousand, and the amount of a foaming agent is 5000ppm, but the agent contains the fluorocarbon surfactant, so that not only the cost is greatly improved, but also the environmental impact is large.

Research results at home and abroad show that the surfactant has certain limitation in practical application as an oil displacement agent and a foaming agent due to large use amount, high adsorption amount, complex composition and environmental problems caused by fluorine-containing carbon. The invention relates to the anion-nonionic surfactant with stable structure under the condition of an oil-gas reservoir, a preparation method and application in an oil-gas field.

Disclosure of Invention

The invention aims to solve the technical problems that in the prior art, the recovery ratio of the anionic surfactant for improving crude oil, particularly thick oil, is low, and the gas production efficiency of the oil is low due to the fact that foam formed by the surfactant cannot form effective plugging and liquid carrying in the prior art, and provides a novel anionic-nonionic surfactant. The surfactant or the aqueous solution of the composition containing the surfactant can well emulsify and solubilize the crude oil to form microemulsion, thereby being beneficial to improving the oil displacement efficiency of the crude oil. The foam formed by the surfactant or the composition aqueous solution containing the surfactant is used as a fluidity control agent for plugging a stratum core in an oil displacement process or used in a gas well foam liquid drainage process, and has the advantages of strong foaming capability under acidic high-temperature high-salt conditions, long foam stabilizing time, high liquid carrying rate, high condensate oil resistance, simple formula and the like.

The invention aims to provide an anionic-nonionic surfactant, which has a structure shown in a formula (I):

in the formula (I), R₁Is selected from C₆～C₃₆A hydrocarbyl or substituted hydrocarbyl radical of R₂Selected from hydrogen, C₁～C₁₀A hydrocarbon group of₁～C₁₀Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a); a. b and c are independently selected from any integer of 0-50, and a, b and c are not 0 at the same time; r₃、R₄And R₅Each independently selected from hydroxy or (CH)₂)_dH and d are any integer of 0-4; r₆Selected from hydrogen, C₁～C₅A hydrocarbon group of (C)₁～C₅Substituted hydrocarbyl carboxylate of (1), C₁～C₅Substituted alkylsulfonic acid salt of (2), C₁～C₅Substituted hydrocarbyl phosphate or C₁～C₅Substituted hydrocarbyl sulfate salts of (a); n is the charge number of the cation or cationic group, and M is selected from hydrogen, alkali metal, alkaline earth metal or ammonium.

In a preferred embodiment, in formula (I), R₁Is selected from C₁₀～C₂₂Hydrocarbyl or C₁₀～C₂₂A substituted hydrocarbyl group of (a).

In a preferred embodiment, in formula (I), R₂Selected from hydrogen, C₁～C₃A hydrocarbon group of (C)₁～C₃The substituted hydrocarbyl, phenyl or substituted phenyl of (a) is preferably selected from methyl, ethyl, phenyl or tolyl.

In a preferred embodiment, in formula (I), a is 0 to 30, b is 0 to 30, and c is 0 to 30, and a, b, and c are not 0 at the same time, preferably, a is 0 to 20, b is 0 to 20, c is 0 to 20, and a, b, and c are not 0 at the same time.

In a preferred embodiment, in formula (I), R₃、R₄And R₅Each independently selected from (CH)₂)_dH, wherein d is 0, 1 or 2.

In a preferred embodiment, in formula (I), R₆Is H, C₁～C₃Hydrocarbyl or substituted hydrocarbyl carboxylates, C₁～C₃Alkyl or substituted alkyl sulfonates or C₁～C₃One of alkyl or substituted alkyl sulfate.

In a preferred embodiment, in formula (I), n is 1 or 2.

In a preferred embodiment, in formula (I), M is selected from hydrogen, alkali metals or ammonium.

The second purpose of the invention is to provide a preparation method of the anionic-nonionic surfactant, which comprises the following steps:

step 1, in the presence of a catalyst, R₁CHYCOOR′₀And R₂COCH₂COOR″₀Carrying out (condensation) reaction to obtain an ester compound shown as a formula (II);

step 2, reacting the ester compound (neutralization R) shown in the formula (II)₂The connected carbonyl group) is reduced to obtain an intermediate compound shown as a formula (III);

step 3, in the presence of an alkaline catalyst, reacting the intermediate compound shown in the formula (III) with an epoxy compound to obtain a polyether compound I shown in the formula (IV);

optionally, step 4, reacting the polyether compound of formula (IV) with Y' R₆' X is reacted to obtain a polyether compound II shown as a formula (V);

and 5, saponifying the polymer compound I shown in the formula (IV) or the polyether compound II shown in the formula (V) to obtain the anionic-nonionic surfactant shown in the formula (I).

In a preferred embodiment, in step 1, the catalyst is selected from metals, metal compounds and/or metal alkyl compounds.

In a further preferred embodiment, in step 1, the catalyst is selected from at least one of an alkali metal, an alkali metal compound, and an alkali metal alkyl compound.

In a still further preferred embodiment, in step 1, the catalyst is selected from at least one of metallic sodium, butyl lithium, butyl sodium.

In a preferred embodiment, at R₁CHYCOOR′₀And R₂COCH₂COOR″₀In, R₁Is selected from C₆～C₃₆A hydrocarbyl or substituted hydrocarbyl group of (a); and/or, R₂Selected from hydrogen, C₁～C₁₀A hydrocarbon group of₁～C₁₀Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a); and/or, R'₀And R ″)₀Each independently selected from C₁～C₁₀Alkyl groups of (a); and/or Y is selected from halogen elements.

In a further preferred embodiment, in R₁CHYCOOR′₀And R₂COCH₂COOR″₀In, R₁Is selected from C₁₀～C₂₂Hydrocarbyl or C₁₀～C₂₂Substituted hydrocarbyl groups of (a); and/or, R₂Selected from hydrogen, C₁～C₃A hydrocarbon group of₁～C₃Substituted hydrocarbyl, phenyl or substituted phenyl of (a), preferably selected from methyl, ethyl, phenyl or tolyl; and/or, R'₀And R ″)₀Each independently selected from C₁～C₅Preferably one selected from methyl, ethyl or propyl; and/or Y is selected from chlorine or bromine.

In a preferred embodiment, R₁CHYCOOR′₀And R₂COCH₂COOR″₀The molar ratio of (1): (1-2), preferably 1: (1-1.2).

In a preferred embodiment, the reaction described in step 1 is carried out at reflux temperature.

In a preferred embodiment, step 2 is performed as follows: with NaHB₄And/or NaHB₄The ester compound shown in the formula (II) reacts at room temperature to reflux temperature to obtain the intermediate compound shown in the formula (III). Preferably, the small molecule alcohol is selected from at least one of methanol, ethanol, isopropanol and n-propanol.

In a further preferred embodiment, the metal ion is selected from Bi³⁺、Ni²⁺、Cd²⁺Preferably, when NaHB is used₄When metal ion is used as catalyst, NaHB₄The molar ratio to metal ions is 1: (0.01 to 0.5), preferably 1: (0.05-0.3).

In a still further preferred embodiment, NaHB is used₄And/or NaHB₄When metal ions are used as the catalyst, the reaction is carried out at 30-60 ℃, preferably at 40-50 ℃.

In the present invention, the "small molecules" all refer to molecular compounds having a molecular weight of less than 500.

In the reduction method, in step 2, the molar ratio of the catalyst to the ester-based compound represented by the formula (II) is 1: (2-10), preferably 1: (3-8).

In another preferred embodiment, step 2 is performed as follows: an ester-based compound of the formula (II) in a Pd/C catalyst and H₂The reaction is carried out in the presence of a catalyst to obtain an intermediate compound shown as a formula (III).

In a further preferred embodiment, the molar ratio of the Pd/C catalyst to the ester-based compound is 1: (5 to 100), preferably 1: (10-50).

In a further preferred embodiment, the reaction is carried out at 5 to 90 ℃, preferably 25 to 80 ℃.

In a preferred embodiment, in step 3, the basic catalyst is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, anhydrous potassium carbonate, anhydrous potassium bicarbonate, anhydrous sodium carbonate, and anhydrous sodium bicarbonate.

In a further preferred embodiment, in step 3, the molar ratio of the basic catalyst to the intermediate compound represented by formula (III) is (0.02-1): 1, preferably (0.05-0.5): 1.

in a preferred embodiment, in step 3, the epoxy compound is selected from C₁～C₆The epoxy compound of (b) is preferably at least one selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide.

In a further preferred embodiment, in step 3, the molar ratio of the epoxy compound to the intermediate compound is (2 to 200): 1, preferably (3-100: 1).

In a further preferred embodiment, in step 3, the reaction is carried out at 100 to 200 ℃, preferably 120 to 160 ℃.

In a preferred embodiment, Y' R is as described in step 4₆In 'X, Y' is selected from halogen elements, and/or, R₆' selected from C₁～C₅Or C is a hydrocarbon group₁～C₅And/or X is selected from SO₃M ', COOM' or OSO₃M ', M ' and M ' are selected from alkali metals or ammonium.

In a further preferred embodiment, Y' R is as described in step 4₆In 'X, Y' is selected from chlorine, bromine or iodine, and/or, R₆' selected from C₁～C₃Or a hydrocarbon radical of C₁～C₃And/or X is selected from SO₃M 'or COOM ", M' and M" are selected from potassium and/or sodium.

In a preferred embodiment, in step 4, a polyether compound of the formula (IV) I is reacted with Y' R₆The molar ratio of' X used is 1: (1 to 10), preferably 1: (1.5-5).

In a preferred embodiment, in step 5, the saponification treatment is carried out in an alkaline solution (preferably at pH 13 to 14) and/or an aqueous alcohol solution.

In a further preferred embodiment, the saponification treatment in step 5 is carried out at reflux temperature.

In a preferred embodiment, in step 5, R is obtained by saponification of the first polymeric compound of formula (IV)₆An anionic-nonionic surfactant represented by the formula (I) H, wherein R is obtained by saponifying a polymer compound II represented by the formula (V)₆Is R₆'X is an anionic-nonionic surfactant represented by the formula (I) wherein Y' is chlorine, bromine or iodine; r₆' is C₁～C₅Hydrocarbyl or substituted hydrocarbyl; x is SO₃M ', COOM' or OSO₃M ', M ' and M ' are one of alkali metal or ammonium.

The anionic-nonionic surfactant has the advantages of both anionic surfactants and nonionic surfactants, is excellent in temperature resistance and salt resistance, can flexibly regulate and control the hydrophilic-lipophilic balance value (HLB value) of the surfactant due to the fact that molecules of the anionic-nonionic surfactant contain two hydrophilic head groups and polyether chain segments, is particularly easy to regulate towards a strong hydrophilic direction, is more practical for high-temperature and high-salt oil reservoirs, and is more beneficial to forming foams. Aiming at crude oil with higher viscosity (such as common thick oil), the viscosity of the thick oil can be effectively reduced by introducing an aromatic ring, the requirement on the viscosity of the displacement fluid is reduced, the using amount of a polymer is reduced, and the viscosity of a binary system is further increased due to the hydrophobic effect between polymer surface binaries, so that the improvement of the recovery ratio is facilitated. The introduction of polyether segment can raise the liquid carrying capacity of anionic-nonionic surfactant foam greatly and obtain unexpected effect.

It is a further object of the present invention to provide a composition comprising: small molecule auxiliary agent and/or polymer and the anion-nonionic surfactant of one purpose of the invention or the anion-nonionic surfactant obtained by the preparation method of the second purpose of the invention.

In a preferred embodiment, the small molecule assistant is selected from at least one of organic alcohol and/or alcohol ether, organic amine, salt and inorganic base.

In a further preferred embodiment, the molar ratio of the anionic-nonionic surfactant, the organic alcohol and/or alcohol ether, the organic amine, the salt and the inorganic base is 1 (0-20): 0-1.

In a further preferred embodiment, the molar ratio of the anionic-nonionic surfactant, the organic alcohol and/or alcohol ether, the organic amine, the salt and the inorganic base is 1 (0-1.2): 0-5): 0-20): 0-1.

The occasion of the surfactant is referred to in the invention, which refers to the mole number of the effective substances in the molecular general formula (I) in the technical scheme; when the content or concentration of the surfactant is concerned, the concentration of the component containing the molecular general formula (I) in the technical scheme is referred to. In a preferred embodiment, the organic alcohol and/or alcohol ether is selected from C₁～C₈Alcohol and/or alcohol ether of (a).

In a further preferred embodiment, the organic alcohol and/or alcohol 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, ethylene glycol dibutyl ether.

In a preferred embodiment, the organic amine is selected from C₁～C₈Primary, secondary or tertiary amines of (a).

In a further preferred embodiment, the organic amine is selected from at least one of ethylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, cyclohexylamine.

In a preferred embodiment, the salt is selected from at least one of a metal halide, a metal carboxylate and a metal phosphate.

In a further preferred embodiment, the metal halide is preferably an alkali metal halide, more preferably at least one selected from the group consisting of sodium chloride, potassium chloride, sodium bromide, potassium bromide; and/or, the metal carboxylate is preferably an alkali metal carboxylate, more preferably selected from sodium acetate, sodium glycolate, potassium acetate, potassium glycolate, sodium benzoate, sodium methylbenzoate, sodium hydroxybenzoate, potassium benzoate, potassium methylbenzoate, potassium hydroxybenzoate, sodium citrate, potassium citrate, sodium EDTA; the inorganic base is selected from potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate; and/or the metal phosphate is at least one selected from sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium polyphosphate and potassium polyphosphate.

The salt can enable a hydrophobic chain of the surfactant to be more stretched due to the electrostatic effect, so that the viscosity of a system can be effectively improved, and the adsorption of the surfactant on a stratum can be reduced.

In a preferred embodiment, the inorganic base is selected from at least one of an alkali metal hydroxide, an alkali metal carbonate or an alkali metal bicarbonate.

In a further preferred embodiment, the inorganic base is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.

In a preferred embodiment, the polymer is selected from at least one of anionic polyacrylamide, temperature and salt resistant modified polyacrylamide, hydrophobically associating polyacrylamide and polymeric microspheres.

In a further preferred embodiment, the temperature-resistant salt-tolerant modified polyacrylamide is prepared by copolymerizing two monomers, namely acrylamide and 2-acrylamido-2-methylpropanesulfonic acid, wherein the molar ratio of the acrylamide to the 2-acrylamido-2-methylpropanesulfonic acid is (0.1-40): 1, the viscosity-average molecular weight is preferably 800-2500 ten thousand; and/or the hydrophobic association polymer is formed by copolymerizing acrylamide, a temperature-resistant salt-resistant monomer and a hydrophobic monomer, wherein the molar ratio of the acrylamide to the temperature-resistant salt-resistant monomer to the hydrophobic monomer is 1: (0.1-40): (0.001-0.05), the viscosity-average molecular weight is preferably 500-2500 ten thousand, and the molar ratio of the acrylamide, the temperature-resistant salt-resistant monomer and the hydrophobic monomer is preferably 1: (0.1-20): (0.001-0.01) and a viscosity average molecular weight of 1200-2200 ten thousand.

In a still further preferred embodiment, the weight ratio of anionic-nonionic surfactant to polymer is 1: (0 to 2), preferably 1: (0 to 0.8).

The fourth purpose of the invention is to provide the application of the composition of the third purpose of the invention in an oil displacement agent or a foaming agent.

In a preferred embodiment, the oil-displacing agent comprises the composition of the third object of the present invention and water.

In a further preferred embodiment, the oil displacement agent is contacted with an oil-bearing stratum under the conditions that the temperature is 25-120 ℃ and the total mineralization is more than 500 mg/L, and crude oil in the oil-bearing stratum is displaced.

The anion-nonionic surfactant and the oil displacement agent formed by the surfactant, the small molecular auxiliary agent and the polymer prepared by the method can be used for but not limited to formation temperature of 40-100 ℃, and mineralization degree of 1000-100000 mg/L, Mg²⁺+Ca ²⁺20 to 2000mg/L, HCO₃ ^-0-2000 mg/L of oil field simulated water and dehydrated crude oil with the viscosity of 1-1000 mPa.

The dynamic interfacial tension value between the water solution and the crude oil is measured within the range of 0.05-0.6 percent in percentage by mass and can reach 10^-3～10^-4An interfacial tension of 5X 10 at the lowest^-4mN/m; the oil displacement agent is evaluated in a physical simulation displacement laboratory, so that the maximum recovery ratio of the oil displacement agent is 24.53%; the viscosity reduction rate of the aqueous solution with the concentration of 0.03 percent and 0.3 percent to crude oil (common thickened oil) is respectively 86.6 percent and 92.8 percent to the maximum, thereby obtaining better technical effect.

In a preferred embodiment, the foaming agent comprises water and/or oil and the composition of the third object of the invention.

Fully contacting the foaming agent solution with gas at the temperature of 0-180 ℃ to form a foam fluid to plug the core or/and carry out water or an oil-water mixture in the foaming agent solution; as a preferable scheme: the gas is preferably selected from at least one of nitrogen, carbon dioxide, methane or natural gas; the oil is at least one of kerosene or condensate.

The foaming agent can be used for oil and gas reservoirs with the formation temperature of 50-150 ℃ and the total mineralization degree of water of 1000-200000 mg/L, but not limited to the oil and gas reservoirs. For the condition of a high-temperature acid gas-containing ultra-deep gas well, the acid resistance of a 0.15 wt% foaming agent aqueous solution reaches pH4, the highest foaming height is 176mm, and the liquid carrying rate is 95.1%; for the condition of a shallow gas well containing condensate oil, the condensate oil resistant content reaches 70%, 0.15 wt% and 0.3 wt% of foaming agent aqueous solution, and the liquid carrying rates are 55.9% and 60.7% respectively; for the high-temperature heterogeneous oil reservoir conditions, the maximum plugging factor in the core tube filled with quartz sand reaches 163, and a better technical effect is achieved.

The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.

Compared with the prior art, the invention has the following beneficial effects:

(1) the anionic-nonionic surfactant has the advantages of both anionic surfactants and nonionic surfactants, is excellent in temperature resistance and salt resistance, can flexibly regulate and control the hydrophilic-lipophilic balance value (HLB value) of the surfactant due to the fact that molecules of the anionic-nonionic surfactant contain two hydrophilic head groups and polyether chain segments, is particularly easy to regulate towards a strong hydrophilic direction, is more practical for high-temperature and high-salt oil reservoirs, and is more beneficial to forming foams.

(2) Aiming at crude oil with higher viscosity (such as common thick oil), the viscosity of the thick oil can be effectively reduced by introducing an aromatic ring, the requirement on the viscosity of the displacement fluid is reduced, the using amount of a polymer is reduced, and the viscosity of a binary system is further increased due to the hydrophobic effect between polymer surface binaries, so that the improvement of the recovery ratio is facilitated. The introduction of polyether segment can raise the liquid carrying capacity of anionic-nonionic surfactant foam greatly and obtain unexpected effect.

(3)When the oil displacement agent is applied to the oil displacement agent, the dosage is 0.05-0.6% by mass percent, and the dynamic interfacial tension value between the aqueous solution and the crude oil is measured and can reach 10^-3～10^-4An interfacial tension of 5X 10 at the lowest^-4mN/m; the oil displacement agent is evaluated in a physical simulation displacement laboratory, so that the maximum recovery ratio of the oil displacement agent is 24.53%; the viscosity reduction rate of the aqueous solution with the concentration of 0.03 percent and 0.3 percent to crude oil (common thickened oil) is respectively 86.6 percent and 92.8 percent to the maximum, thereby obtaining better technical effect.

(4) When the foam agent is applied to the foaming agent, the foam agent can be used for but not limited to oil and gas reservoirs with the formation temperature of 50-150 ℃ and the total mineralization degree of water of 1000-200000 mg/L. For the condition of a high-temperature acid gas-containing ultra-deep gas well, the acid resistance of a 0.15 wt% foaming agent aqueous solution reaches pH4, the highest foaming height is 176mm, and the liquid carrying rate is 95.1%; for the condition of a shallow gas well containing condensate oil, the condensate oil resistant content reaches 70 percent, and the foaming agent aqueous solutions with the weight percent of 0.15 percent and 0.3 percent respectively have liquid carrying rates of 55.9 percent and 60.7 percent; for the high-temperature heterogeneous oil reservoir conditions, the maximum plugging factor in the core tube filled with quartz sand reaches 163, and a better technical effect is achieved.

Drawings

FIG. 1 is an infrared spectrum of the anionic-nonionic surfactant prepared in example 1. Wherein, 3471.2cm^-1Is the characteristic peak of O-H stretching vibration, 2927.2cm^-1And 2860.7m^-1Is a characteristic peak of C-H stretching of methyl and methylene, 11760.6cm^-1Is C ═ O flexural vibration absorption peak, 1092.2cm^-1Is C-O stretching vibration peak, 1066.6cm^-1Is the C-O-C stretching vibration peak. 1458.5cm^-1Is the stretching vibration peak of the benzene ring, 1098.8cm^-1Is a C-O-C stretching vibration peak, 570-930 cm^-1Is the in-plane rocking absorption peak of CH plane in the benzene ring.

Fig. 2 is a graph of concentration-interfacial tension of the anionic-nonionic surfactant a1 prepared in example 1. Wherein, the simulated water composition is as follows: TDS 23000mg/L, Ca²⁺＝200mg/L，Mg²⁺50mg/L, crude oil viscosity 895.2mPa.s (50 ℃), temperature 65 ℃.

Fig. 3 is a flow chart of an indoor core displacement experiment.

FIG. 4 is a graph of concentration-viscosity reduction for the anionic-nonionic surfactant A1 and A1/Diethanolamine (DEA) systems prepared in example 1. Wherein the initial viscosity of the crude oil is 895.2mPa.s (50 ℃).

FIG. 5 is a schematic view showing the flow of measuring the amount of liquid carried by the foam drainage agent. Wherein, 1 is a constant temperature water bath, 2 is a measuring cup, 3 is circulating water, 4 is a foam collector, 5 is a foaming pipe, 6 is a test solution, 7 is a rotameter, and 8 is a gas cylinder.

FIG. 6 is a graph showing the concentration-viscosity reduction ratio of the surfactant behenyl alcohol polyoxyethylene ether (23), sodium acetate A8, and A8/Diethanolamine (DEA) systems obtained in comparative example 1. Wherein the initial viscosity of the crude oil is 895.2mPa.s (50 ℃).

Detailed Description

While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.

It is to be further understood that the various features described in the following detailed description may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention can be made, as long as the technical solution formed by the combination does not depart from the idea of the present invention, and the technical solution formed by the combination is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.

The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art. NaHB₄/BiCl₃In the catalyst, NaHB₄The molar ratio of Bi ions is 1: (0.01-0.1) the NaHB₄/BiCl₃Mixing the catalysts according to the required molar ratio, and purchasing the raw materials from Chinese medicamentsA group; NaHB₄/Ni(NO₃)₂In the catalyst, NaHB₄The molar ratio to Ni ions was 1: (0.01-0.1) the NaHB₄/BiCl₃The required molar ratio of the catalyst is mixed, and the raw materials are purchased from the national medicine group.

The surfactant prepared by the invention can be applied to a 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.

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 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 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 mu at 50 ℃ by using a rheometer₀. Weighing a certain amount of thickened 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 thickened oil into an oil-in-water emulsion, rapidly measuring the viscosity mu of the thickened oil emulsion by using a rheometer, and calculating the viscosity reduction rate according to the formula (1):

wherein, f is viscosity reduction rate; mu.s₀The viscosity of the thick oil sample at 50 ℃,mPa.s; mu, viscosity of the thick oil emulsion after the sample solution is added, mPa & s.

The method for measuring the foaming, foam stabilizing and liquid carrying performances of the surfactant composition comprises the following steps: the foaming ability and foam stability of the foam composition were evaluated by measuring the initial height of foaming and the height of foaming after a certain time using a Roche foam meter (ROSS-Miles method). With reference to SY/T6465-2000 evaluation method for foam generation for water drainage and gas recovery, gas at a certain flow rate is continuously introduced into a foam agent composition solution or a foam agent composition solution and oil mixed solution to form foam, the amount of liquid (water, oil and water) carried out by the foam after a certain time is measured, the liquid carrying rate is calculated, and the liquid carrying capacity is evaluated. Wherein the oil is at least one of kerosene, crude oil or condensate oil.

The method for determining the core plugging performance of the surfactant composition comprises the following steps: the plugging performance experiment of the surfactant composition is carried out by adopting a core barrel filled with quartz sand. And (3) injecting the foaming agent composition aqueous solution into the sand pipe, then injecting a certain amount of gas, measuring the plugging pressure difference before and after injection, and calculating a resistance factor.

RF＝P₂/P₁Formula (3);

wherein RF is a resistance factor, P₁Is water drive differential pressure (MPa), P₂The foam displacement pressure (MPa).

[ example 1 ]

Under the protection of nitrogen, 12.7 g (0.55 mol) of fresh sodium metal is cut into threads, carefully added into 150 ml of absolute ethyl alcohol for many times, after the sodium metal reacts, 105.6 g (0.55 mol, M is 192.0) of benzoyl ethyl acetate and 195.6 g (0.5 mol, M is 391) of alpha-bromo ethyl stearate are sequentially added, the mixture is heated to reflux, the reaction is stopped when the pH of the reaction solution is nearly neutral, the excessive ethyl alcohol is evaporated under reduced pressure, and the mixture is cooled to room temperature. 200 ml of cold water was carefully added, the mixture was neutralized, the water layer was separated, and the oil phase was dried over anhydrous sodium sulfate to obtain an ester-based compound (II) (R)₁＝C₁₆H₃₃，R₂＝C₆H₅，R′₀＝R″₀＝C₂H₅)。

② will be provided withAfter water in a three-neck flask device of a reflux condenser tube, a dropping funnel and a thermometer is completely removed, adding NaHB₄/BiCl₃66.0 g of catalyst and 500 ml of dry dioxane are stirred, dispersed and mixed, and 251.0 g (0.5 mol, M ═ 502) of ester-based compound (II) (R) is added dropwise at-10 to 5 DEG C₁＝C₁₆H₃₃，R₂＝C₆H₅，R′₀＝R″₀＝C₂H₅) The 40 wt% dioxane solution is added dropwise and slowly heated to about 40 ℃ for reaction for 3 hours. The reaction solution was carefully poured into ice water, followed by post-treatment to obtain Compound (III) (R)₁＝C₁₆H₃₃，R₂＝C₆H₅，R′₀＝R″₀＝C₂H₅，M＝504)。

③ charging 201.6 g (0.4 mol) of Compound (III) (R) into a pressure reactor equipped with a stirring device₁＝C₁₆H₃₃，R₂＝C₆H₅，R′₀＝R″₀＝C₂H₅M504 and 10.2 g potassium hydroxide, in that order, with 583.2 g (8.1 mol) of butylene oxide and 69.6 g (1.2 mol) of propylene oxide at 140-160 ℃ to obtain a polyether compound (IV) (R)₁＝C₁₆H₃₃，R₂＝C₆H₅，R₃＝C₂H₅，R₄＝CH₃，R′₀＝R″₀＝C₂H₅，a＝20，b＝3，c＝0，M＝2118)。

635.4 g (0.3 mol) of a polyether compound (IV) (R)₁＝C₁₆H₃₃，R₂＝C₆H₅，R₃＝C₂H₅，R₄＝CH₃，R′₀＝R″₀＝C₂H₅And a is 20, b is 3, c is 0, and M is 2118), and 450 g of 15 wt% aqueous sodium hydroxide ethanol solution (ethanol-water volume ratio is 5 to 5), and the mixture is heated and refluxed for 4 to 5 hours to obtain an aqueous ethanol solution of the anionic-nonionic surfactant A1. The structure composition of a1 is shown in table 1. 20 g of the homogeneous reaction solution are acidified with 10 wt% hydrochloric acid and the ethyl is distilled offAdding 50 g of benzene into alcohol, removing a water layer, washing for 3 times by using saturated saline solution, evaporating benzene, and measuring the content of the effective substances to be 90.7% by using a Meiterer company T90 automatic potentiometric titrator and a Halmin cation solution as a titrant. Samples were taken for infrared spectroscopy analysis, see FIG. 1.

[ example 2 ]

In the same way as in example 1, ethanol aqueous solutions of anionic-nonionic surfactants A2, A3 and A4 were obtained, and the structural compositions of A2, A3 and A4 are shown in Table 1.

[ example 3 ]

Oil displacement performance experiment:

firstly, preparing oil field simulation water with different divalent cations and total mineralization degrees respectively, wherein the specific composition is shown in table 2, and the experimental temperature and the crude oil viscosity are shown in table 2.

② 1# simulated water in the table 2 is used for respectively preparing the A1 ethanol aqueous solution, the micromolecule compound and the polymer prepared in the example 1, the mixture is mixed and stirred for 1-3 hours according to the required proportion to obtain the uniform oil displacement agent, the viscosity of the system and the interfacial tension to crude oil (895.2mPa. s, measured at 50 ℃) are measured at 65 ℃, the result is shown in the table 3, and the concentration-interfacial tension curve is shown in the table 2. The polymer P1 was a modified polyacrylamide polymer (molar ratio of copolymer AM/AMPS was 1/0.05, viscosity average molecular weight was 2500 ten thousand), apparent viscosity was measured by a BROODFIELD model III viscometer manufactured by Brookfield corporation, usa, and interfacial tension was measured by a TX500 spinning drop interfacial tensiometer manufactured by texas university, usa.

Thirdly, ethanol aqueous solution i (A2, A3 and A4), a small molecular compound ii and a polymer iii of the surfactant prepared in the example 2 are prepared respectively by using No. 2 simulated water in the table 2, the materials are mixed and stirred for 1-3 hours according to the required proportion to obtain a uniform oil displacement agent, and the viscosity of the system and the interfacial tension on crude oil (1.2mPa.s, 50 ℃) are measured at 90 ℃, and the result is shown in the table 3. Wherein the polymer P2 is a hydrophobic association polymer (the molar ratio of the copolymer AM/AMPS/2-acrylamidododecylsulfonic acid is 1/0.5/0.001, and the viscosity-average molecular weight is 1930 ten thousand), the apparent viscosity is measured by a Brookfield company BroodIELD III viscometer in the United states, and the interfacial tension is measured by a TX500 type rotary drop interfacial tension meter manufactured by the university of Texas in the United states.

And fourthly, 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. And testing the pore volume of the stratum water saturated core. And (4) recording the volume of the saturated crude oil by using the oil field dehydrated crude oil saturated core. Under the experimental temperature, the water content of produced liquid reaches 100% by using oil field simulation water flooding, the recovery ratio of crude oil improved by water flooding is calculated, after the oil displacement agent with 0.3PV (core pore volume) is injected, the water is displaced to 100%, and the percentage of the recovery ratio of crude oil improved on the basis of water flooding is calculated, and the result is shown in Table 3. As can be seen from table 3, there is a higher recovery factor when a surfactant, a small molecule compound, and a polymer are used in combination.

The gas permeability of the core is measured by an HKGP-3 type compact core gas permeability porosity measuring instrument, and the flow of the adopted simulated core displacement test is shown in figure 3.

The influence of the surfactant on the viscosity of crude oil (895.2mPa.s, measured at 50 ℃) refers to a method for measuring the viscosity reduction rate of thick oil, and the result is shown in figure 4. The viscosity is determined by a model HAAKE MARS III rotational rheometer.

[ example 4 ]

Under the protection of nitrogen, 12.7 g (0.55 mol) of fresh sodium metal is cut into threads, carefully added into 150 ml of absolute ethyl alcohol for many times, after the sodium metal reacts, 71.5 g (0.55 mol, M is 130) of ethyl acetoacetate and 223.6 g (0.5 mol, M is 447) of alpha-bromoeicosanoic acid ethyl ester are sequentially added, the mixture is heated to reflux, the reaction is stopped when the pH of a reaction solution is nearly neutral, the excessive ethyl alcohol is evaporated under reduced pressure, and the mixture is cooled to room temperature. 200 ml of cold water was carefully added, the mixture was neutralized, the water layer was separated, and the oil phase was dried over anhydrous sodium sulfate to obtain an ester-based compound (II) (R)₁＝C₂₀H₄₁，R₂＝CH₃，R′₀＝R″₀＝C₂H₅)。

② after removing the water in the three-neck flask device provided with a reflux condenser tube, a dropping funnel and a thermometer, adding NaHB₄/Ni(NO₃)₂Catalyst 45.1 g and 500 ml of dry dioxahexaCircularly stirring, dispersing and mixing, and dripping 248.1 g (0.5 mol, M is 496) ester-based compound (II) (R) at-10-5 DEG C₁＝C₂₀H₄₁，R₂＝CH₃，R′₀＝R″₀＝C₂H₅) The 40 wt% dioxane solution is added dropwise and slowly heated to about 40 ℃ for reaction for 5 hours. The reaction solution was carefully poured into ice water, followed by post-treatment to obtain Compound (III) (R)₁＝C₂₀H₄₁，R₂＝CH₃，R′₀＝R″₀＝C₂H₅，M＝498)。

③ charging 199.3 g (0.4 mol) of Compound (III) (R) into a pressure reactor equipped with a stirring device₁＝C₂₀H₄₁，R₂＝CH₃，R′₀＝R″₀＝C₂H₅M498, 2.8 g of potassium hydroxide and 49.3 g (0.85 mol) of propylene oxide are reacted at 140 to 160 ℃ to give a polyether compound (IV) (R)₁＝C₂₀H₄₁，R₂＝CH₃，R₅＝CH₃，R′₀＝R″₀＝C₂H₅，a＝0，b＝0，c＝2，M＝614)。

(IV) polyether Compound (R)₁＝C₂₀H₄₁，R₂＝CH₃，R₅＝CH₃，R′₀＝R″₀＝C₂H₅A ═ 0, b ═ 0, c ═ 2, and M ═ 614)184.2 g (0.3 mol) were mixed with 48.0 g (1.2 mol) of sodium hydroxide, 70.1 g (0.6 mol) of sodium chloroacetate, and 500 ml of acetone in a reaction vessel equipped with a mechanical stirrer, a thermometer, and a reflux condenser, and heated to reflux for 7 hours. And (3) distilling off the acetone under reduced pressure, adding 300 g of ethanol water solution (the volume ratio of ethanol to water is 5: 5), and heating and refluxing for 4-5 hours to obtain the ethanol water solution of the anionic-nonionic surfactant A5. The structure composition of a5 is shown in table 4.

[ example 5 ]

Under the protection of nitrogen, 12.7 g (0.55 mol) of fresh sodium metal is cut into threads, carefully added into 150 ml of absolute ethyl alcohol for many times, and added in sequence after the sodium metal reaction is finishedAdding 105.6 g (0.55 mol, M ═ 192.0) of ethyl benzoylacetate and 114.1 g (0.5 mol, M ═ 228) of alpha-bromotetradecanoate, heating to reflux, stopping reaction until the pH of the reaction solution is near neutral, reducing pressure, evaporating excessive ethanol, and cooling to room temperature. 200 ml of cold water was carefully added, the mixture was neutralized, the water layer was separated, and the oil phase was dried over anhydrous sodium sulfate to obtain an ester-based compound (II) (R)₁＝C₁₂H₂₅，R₂＝C₆H₅，R′₀＝R″₀＝C₂H₅)。

② 223.1 g (0.5 mol, M ═ 446) of the ester-based compound (II) (R) was charged in sequence in the high-pressure reactor₁＝C₁₂H₂₅，R₂＝C₆H₅，R′₀＝R″₀＝C₂H₅) After the Pd/C catalyst 11.2 g and 1000 ml of isopropanol are deoxidized for many times, stirring, dispersing and mixing, slowly heating to about 40 ℃, carefully introducing hydrogen for many times until the reaction pressure is basically unchanged, and continuing the reaction for 2 hours. Carefully replacing the reaction hydrogen with nitrogen, filtering to recover Pd/C, and evaporating the solvent from the remaining reaction solution to obtain compound (III) (R)₁＝C₁₂H₂₅，R₂＝C₆H₅，R′₀＝R″₀＝C₂H₅，M＝448)。

③ charging 179.2 g (0.4 mol) of Compound (III) (R) into a pressure reactor equipped with a stirring device₁＝C₁₂H₂₅，R₂＝C₆H₅，R′₀＝R″₀＝C₂H₅M is 448), 2.1 g of potassium hydroxide and 86.4 g (1.2 mol) of epoxybutane are reacted at 140-160 ℃ to obtain the polyether compound (IV) (R)₁＝C₁₂H₂₅，R₂＝C₆H₅，R₃＝C₂H₅，R′₀＝R″₀＝C₂H₅，a＝3，b＝0，c＝0，M＝664)。

(IV) 199.2 g (0.3 mol) of a polyether compound (IV) (R)₁＝C₁₂H₂₅，R₂＝C₆H₅，R₃＝C₂H₅，R′₀＝R″₀＝C₂H₅And a is 3, b is 0, c is 0, M is 664) and 400 g of 15 wt% potassium hydroxide ethanol aqueous solution (ethanol water volume ratio is 7 to 3), and the mixture is heated and refluxed for 5 to 7 hours to obtain the ethanol aqueous solution of the anionic-nonionic surfactant A6. The composition of the a6 structure is shown in table 4.

[ example 6 ]

Under the protection of nitrogen, 12.7 g (0.55 mol) of fresh sodium metal is cut into threads, carefully added into 150 ml of absolute ethyl alcohol for many times, after the sodium metal reacts, 71.5 g (0.55 mol, M is 130) of ethyl acetoacetate and 195.6 g (0.5 mol, M is 391) of alpha-bromo ethyl stearate are sequentially added, the mixture is heated to reflux, the reaction is stopped when the pH of the reaction solution is nearly neutral, the excess ethanol is evaporated under reduced pressure, and the mixture is cooled to room temperature. 200 ml of cold water was carefully added, the mixture was neutralized, the water layer was separated, and the oil phase was dried over anhydrous sodium sulfate to obtain an ester-based compound (II) (R)₁＝C₁₆H₃₃，R₂＝CH₃，R′₀＝R″₀＝C₂H₅)。

② after removing the water in the three-neck flask device provided with a reflux condenser tube, a dropping funnel and a thermometer, adding NaHB₄/Ni(NO₃)₂35.1 g and 500 ml of dry dioxane are stirred, dispersed and mixed, and 220.1 g (0.5 mol, M ═ 440) of ester group compound (II) (R) is dripped into the mixture at-5 to 10 DEG C₁＝C₁₆H₃₁，R₂＝CH₃，R′₀＝R″₀＝C₂H₅) The 40 wt% dioxane solution is added dropwise and slowly heated to about 40 ℃ for reaction for 5 hours. The reaction solution was carefully poured into ice water, followed by post-treatment to obtain Compound (III) (R)₁＝C₁₆H₃₁，R₂＝CH₃，R′₀＝R″₀＝C₂H₅，M＝442)。

③ charging 176.8 g (0.4 mol) of Compound (III) (R) into a pressure reactor equipped with a stirring device₁＝C₁₆H₃₁，R₂＝CH₃，R′₀＝R″₀＝C₂H₅M is 442 and 3.8 g of potassium hydroxide, and then sequentially reacts with 208.9 g (2.9 mol) of butylene oxide and 35.2 g (0.8 mol) of ethylene oxide at 140-160 ℃ to obtain a polyether compound (IV) (R)₁＝C₁₄H₂₉，R₂＝CH₃，R₄＝C₂H₅，R₅＝H，R′₀＝R″₀＝C₂H₅，a＝0，b＝7，c＝2，M＝1034)。

(IV) polyether Compound (R)₁＝C₁₄H₂₉，R₂＝CH₃，R₄＝C₂H₅，R₅＝H，R′₀＝R″₀＝C₂H₅A is 0, b is 7, c is 2, M is 1034)310.2 g (0.3 mol) and 48.0 g (1.2 mol) of sodium hydroxide, 118.5 g (0.6 mol) of sodium 1-chloro-2-hydroxypropanesulfonate and 700 ml of toluene are mixed in a 2000 ml three-neck flask equipped with a mechanical stirring, thermometer and reflux condenser, heated to 100 ℃ for 5 hours, decompressed to remove toluene, added with 600 g of ethanol water solution (the volume ratio of ethanol to water is 4 to 6), heated and refluxed for 6 to 7 hours, thus obtaining the ethanol water solution of the anionic-nonionic surfactant a 7. The structure composition of a7 is shown in table 4.

[ example 7 ]

Foam liquid discharge performance experiment: dissolving the iv surfactant (A5) and the v small molecular compound (glycerol) in 100,000mg/L and 200,000mg/L NaCl water respectively according to the required proportion to prepare a uniform foam discharging agent mother solution, adding saline water to dilute to a test concentration, and adjusting the pH value by using sodium citrate/citric acid.

1. The results are shown in Table 5, referring to SY/T6465-2000 evaluation method for foam blowing agent for water drainage and gas recovery, by measuring the performances such as foaming ability, foam stability and liquid carrying ability at a temperature of 80 ℃.

As can be seen from table 5: (1) under the same pH and the same salinity, the composition obtained by compounding the surfactant and the small molecular alcohol is more excellent in foaming capacity, foam stability, liquid carrying capacity and other performances; (2) however, the amount of the small molecular alcohol is not so large that the performance is deteriorated when the molar ratio of the small molecular alcohol to the surfactant is 5: 1.

2. The experiment is carried out by adopting a pressure-resistant and acid-resistant aging device, simulated water is 100000mg/L NaCl, the performances such as foaming power, foam stability, liquid carrying capacity and the like are measured again at 80 ℃ after aging is carried out for 72 hours at 130 ℃, and the result is shown in Table 6. FIG. 5 is a schematic diagram showing measurement of the amount of liquid carried.

As can be seen from table 6, (1) the composition obtained by complexing the surfactant with the small-molecule alcohol is more excellent in foaming power, foam stability, liquid-carrying capacity, and the like at the same pH and the same salinity; (2) however, the amount of the small molecular alcohol is not so large that the performance is rather deteriorated when the molar ratio of the small molecular alcohol to the surfactant is 1.5: 1.

And (3) dissolving the vi surfactant (A6) and the vii small molecular compound (urea) in 100,000mg/L NaCl water according to a required ratio to prepare a uniform foam scrubbing agent mother liquor, and adding saline water and condensate oil to dilute to a tested concentration. The liquid carrying property was measured with reference to SY/T6465-. The schematic diagram of the measurement of the amount of liquid carried is shown in FIG. 5.

As can be seen from table 7, (1) the composition obtained by compounding the surfactant with urea has a higher liquid carrying rate; (2) however, the amount of urea used is not so large that the liquid carrying rate is lowered when the molar ratio of urea to surfactant is 15: 1.

[ example 8 ]

Foam plugging performance experiment:

viii surfactant (a7), ix small molecule compound (diethanolamine) and x hydrophobically associative polymer (P3, copolymerization AM/AMPS/2-acrylamidododecylsulfonic acid molar ratio 1/0.45/0.002, viscosity average molecular weight 1750 ten thousand) were mixed to simulate saline (TDS 100000mg/L, Ca²⁺2000mg/L) and mixing according to the required proportion to obtain a uniform channeling sealing agent aqueous solution.

1. The foaming capacity and half-life of the aqueous solution were measured by the Roche method at a bath temperature of 60 ℃ and the results are shown in Table 8.

As can be seen from table 8, (1) the composition of surfactant with small amine has higher foaming capacity and longer half-life than the surfactant alone, but the amount of diethanolamine is not too high; (2) compared with a pure surfactant and a pure surfactant-small molecule amine composition, the composition formed by the surfactant-small molecule amine-polymer has longer half life.

2. The quartz sand filled core tube was used for the evaluation of plugging performance, the permeability was 2500mD, 0.15% channeling sealing agent aqueous solution was injected into the sand tube at a rate of 2mL/min, while nitrogen gas was injected at a rate of 6mL/min, the plugging differential pressure was measured, and the resistance factor was calculated, the results are shown in Table 9.

As can be seen from Table 9, the compositions formed when using the surfactant-small amine-polymer have a higher drag factor, but the amounts of small amine and polymer are not too high.

[ COMPARATIVE EXAMPLE 1 ]

The behenyl alcohol polyoxyethylene ether (23) sodium acetate A8 is obtained by the polyether reaction with ethylene oxide and the carboxymethylation reaction with sodium chloroacetate. The hydrophile-lipophile balance (HLB value) is basically equal to A1 and the length of the hydrophobic carbon chain is basically consistent by calculation according to an empirical formula.

The oil displacement performance test was performed as in example 3, and the oil-water interfacial tension, viscosity, and enhanced oil recovery results of A8 are shown in table 10.

Effect of A8 on viscosity of crude oil (895.2mpa. s, measured at 50 ℃) the viscosity reduction rate measurement method was referenced and the results are shown in fig. 6. The viscosity is determined by a model HAAKE MARS III rotational rheometer.

[ COMPARATIVE EXAMPLE 2 ]

Synthetic anionic surfactant A9(I) (R)₁＝C₂₀H₄₁，R₂＝CH₃，R₆H, a ═ 0, b ═ 0, and c ═ 0), the process was the same as [ example 4 ] except that propylene oxide was not added.

The foam drainage performance test was carried out as in example 7, and the results of the tests on foaming power, foam stability, liquid carrying capacity and the like of A9 are shown in Table 11. FIG. 5 is a schematic diagram showing measurement of the amount of liquid carried.

[ COMPARATIVE EXAMPLE 3 ]

A sodium polyether dicarboxylate compound similar in structure to a2 was synthesized, except that the hydrophilic group was at the end of the polyether.

Using hexadecyl mono-glycol ether and epoxy chloropropane as raw materials, performing cyclization reaction according to the molar ratio of 1:1.5, and hydrolyzing to obtain C₁₆H₃₃OC₂H₄OCH(OH)CH₂And OH, polymerizing with epoxy butane to obtain a polyether intermediate, and further performing carboxymethylation reaction on the polyether intermediate with sodium chloroacetate and sodium hydroxide to obtain an anionic surfactant A10, wherein the molecular length of the epoxy butane fragment contained in the anionic surfactant A10 is 18 and is consistent with the A2 polyether chain segment.

The oil displacement performance test was performed as in example 3, and the oil-water interfacial tension, viscosity, and enhanced oil recovery results of a10 are shown in table 12.

TABLE 1

TABLE 2

TABLE 5

TABLE 6

TABLE 7

TABLE 8

TABLE 9

Watch 10

TABLE 11

The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (14)

1. An anionic-nonionic surfactant having the structure of formula (I):

in the formula (I), R₁Is selected from C₆～C₃₆A hydrocarbyl or substituted hydrocarbyl radical of R₂Selected from hydrogen, C₁～C₁₀A hydrocarbon group of₁～C₁₀Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a); a. b and c are independently selected from any integer of 0-50, and a, b and c are not 0 at the same time; r₃、R₄And R₅Each independently selected from hydroxy or (CH)₂)_dH and d are any integer of 0-4; r₆Selected from hydrogen, C₁～C₅A hydrocarbon group of₁～C₅Substituted hydrocarbyl carboxylate of (A), C₁～C₅Substituted hydrocarbyl sulfonates of (A) and (B)₁～C₅Substituted hydrocarbyl phosphate or C₁～C₅Substituted hydrocarbyl sulfate salts of (a); n is the charge number of the cation or cationic group, and M is selected from hydrogen, alkali metal, alkaline earth metal or ammonium.

2. The anionic-nonionic surfactant according to claim 1, characterized in that in formula (I):

R₁is selected from C₁₀～C₂₂Hydrocarbyl or C₁₀～C₂₂Substituted hydrocarbyl groups of (a); and/or

R₂Selected from hydrogen, C₁～C₃A hydrocarbon group of₁～C₃Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a); and/or

a is 0-30, b is 0-30, c is 0-30, and a, b and c are not 0 at the same time; and/or

R₃、R₄And R₅Each independently selected from (CH)₂)_dH, wherein d is 0, 1 or 2; and/or

R₆Is H, C₁～C₃Hydrocarbyl or substituted hydrocarbyl carboxylates, C₁～C₃Alkyl or substituted alkyl sulfonates or C₁～C₃Alkyl or substituted alkyl sulfatesOne of (1); and/or

n is 1 or 2; and/or

M is selected from hydrogen, alkali metal or ammonium.

3. A process for preparing the anionic-nonionic surfactant of claim 1 or 2, comprising the steps of:

step 1, in the presence of a catalyst, R₁CHYCOOR′₀And R₂COCH₂COOR″₀Reacting to obtain an ester compound;

step 2, reducing the ester-based compound to obtain an intermediate compound;

step 3, in the presence of an alkaline catalyst, reacting the intermediate compound with an epoxy compound to obtain a polyether compound I;

optionally, step 4, reacting the polyether compound one with Y' R₆' X is reacted to obtain a polyether compound II;

and 5, saponifying the polymer compound I or the polyether compound II to obtain the anionic-nonionic surfactant shown in the formula (I).

4. The production method according to claim 3,

in step 1, the catalyst is selected from metals, metal compounds and/or metal alkyl compounds, preferably at least one selected from alkali metals, alkali metal compounds, alkali metal alkyl compounds; and/or

The reaction described in step 1 is carried out at reflux temperature.

5. The method according to claim 3, wherein R is₁CHYCOOR′₀And R₂COCH₂COOR″₀In, R₁Is selected from C₆～C₃₆A hydrocarbyl or substituted hydrocarbyl group of (a); and/or, R₂Selected from hydrogen, C₁～C₁₀A hydrocarbon group of₁～C₁₀Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a); and/or, R'₀And R ″)₀Each independently selected from C₁～C₁₀Alkyl groups of (a); and/or, Y is selected from halogen elements; preferably, R₁CHYCOOR′₀And R₂COCH₂COOR″₀The molar ratio of (1): (1-2), preferably 1: (1-1.2).

6. The method according to claim 3, wherein step 2 is carried out by: with NaHB₄And/or NaHB₄Metal ions are used as a catalyst, micromolecular alcohol is used as a solvent, and an ester-based compound is reacted between room temperature and reflux temperature to obtain an intermediate compound; preferably, the metal ion is selected from Bi³⁺、Ni²⁺、Cd²⁺More preferably, when NaHB is used₄When metal ion is used as catalyst, NaHB₄The molar ratio to metal ions is 1: (0.01 to 0.5), preferably 1: (0.05-0.3).

7. The production method according to claim 6,

in step 2, the weight ratio of the catalyst to the ester-based compound is 1: (2-10), preferably 1: (3-8); and/or

In step 2, the reaction is carried out at 30 to 60 ℃, preferably 40 to 50 ℃.

8. The method according to claim 3, wherein step 2 is carried out by: an ester-based compound of the formula (II) in a Pd/C catalyst and H₂The reaction is carried out in the presence of a catalyst to give an intermediate compound.

Preferably, the molar ratio of the Pd/C catalyst to the ester-based compound is 1: (5 to 100), preferably 1: (10-50); and/or the reaction is carried out at 5-90 ℃, preferably at 25-80 ℃.

9. The production method according to claim 3,

in step 3, the basic catalyst is at least one of potassium hydroxide, sodium hydroxide, anhydrous potassium carbonate, anhydrous potassium bicarbonate, anhydrous sodium carbonate and anhydrous sodium bicarbonate; and/or

In the step 3, the molar use ratio of the basic catalyst to the intermediate compound is (0.02-1): 1, preferably (0.05-0.5): 1; and/or

In step 3, the epoxy compound is selected from C₁～C₆The epoxy compound of (b) is preferably at least one selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide.

10. The method of claim 3, wherein the Y' R is in step 4₆In 'X, Y' is selected from halogen elements, and/or, R₆' selected from C₁～C₅Or C is a hydrocarbon group₁～C₅And/or X is selected from SO₃M ', COOM' or OSO₃M ', M ' and M ' are selected from alkali metals or ammonium;

preferably, in step 4, the polyether compound one is reacted with Y' R₆The molar ratio of' X used is 1: (1 to 10), preferably 1: (1.5-5).

11. The production method according to any one of claims 3 to 10, wherein the saponification treatment is performed in an alkaline water and/or an aqueous alcohol solution in step 5, and preferably the saponification treatment is performed at a reflux temperature.

12. A composition, comprising: the small molecular auxiliary agent and/or the polymer and the anionic-nonionic surfactant as described in claim 1 or 2 or the anionic-nonionic surfactant obtained by the preparation method as described in any one of claims 3 to 11, wherein the small molecular auxiliary agent is at least one selected from organic alcohol and/or alcohol ether, organic amine, salt and inorganic base; preferably, the molar ratio of the anionic-nonionic surfactant, the organic alcohol and/or alcohol ether, the organic amine, the salt and the inorganic base is 1 (0-20): 0-1.

13. The composition of claim 12,

the organic alcohol and/or alcohol ether is at least one selected from 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; and/or

The organic amine is selected from C₁～C₈Primary, secondary or tertiary amines of (a); and/or

The salt is selected from at least one of a metal halide, a metal carboxylate and a metal phosphate; and/or

The inorganic base is at least one of alkali metal hydroxide, alkali metal carbonate or alkali metal bicarbonate; and/or

The polymer is selected from at least one of anionic polyacrylamide, temperature-resistant salt-resistant modified polyacrylamide, hydrophobically associating polyacrylamide and polymer microspheres.

14. Use of a composition according to claim 12 or 13 in an oil displacing agent or a foam.

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