CN113930226A - Surfactant composition containing polyether quaternary ammonium salt, preparation method thereof and method for improving oil and gas yield - Google Patents

Surfactant composition containing polyether quaternary ammonium salt, preparation method thereof and method for improving oil and gas yield Download PDF

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CN113930226A
CN113930226A CN202010672990.9A CN202010672990A CN113930226A CN 113930226 A CN113930226 A CN 113930226A CN 202010672990 A CN202010672990 A CN 202010672990A CN 113930226 A CN113930226 A CN 113930226A
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quaternary ammonium
ammonium salt
surfactant
polyether
surfactant composition
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CN113930226B (en
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沈之芹
李应成
虞辰敏
吴国英
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a surfactant composition containing polyether quaternary ammonium salt, a preparation method thereof and a method for improving oil and gas yield, and mainly solves the problems that the existing surfactant has poor injectivity in a low-permeability reservoir, so that the degree of improving the crude oil recovery is low, and foams formed by the surfactant in the prior art cannot form effective plugging and liquid carrying, so thatThe gas production efficiency of the produced oil is low. The invention adopts a surfactant composition containing polyether quaternary ammonium salt, which comprises the following components in parts by mole: (1)1 part of polyether quaternary ammonium salt; (2) 0.01-30 parts of cosurfactant; wherein the molecular general formula of the polyether quaternary ammonium salt is shown as a formula (I); the cosurfactant is selected from the technical scheme of the zwitterionic surfactant shown in the formula (III), so that the problem is solved well, and the cosurfactant can be used for production of oil and gas fields for improving oil and gas yield.
Figure DDA0002583020760000011

Description

Surfactant composition containing polyether quaternary ammonium salt, preparation method thereof and method for improving oil and gas yield
Technical Field
The invention relates to a surfactant composition containing polyether quaternary ammonium salt, a preparation method thereof and a method for improving oil and gas yield.
Background
The enhanced oil recovery technology, namely the Enhanced Oil Recovery (EOR) and Improved Oil Recovery (IOR) technology generally referred to abroad, can be summarized into six aspects of improving water flooding, chemical flooding, heavy oil thermal recovery, gas flooding, microbial oil recovery, physical oil recovery and the like. Currently, the enhanced oil recovery techniques that enter large-scale applications in mines are concentrated in three major categories, thermal recovery, gas flooding and chemical flooding. Chemical flooding is a strengthening measure for improving the recovery ratio by adding a chemical agent into an aqueous solution and changing the physicochemical property and rheological property of an injected fluid and the interaction characteristic with reservoir rocks, and is rapidly developed in China, mainly because the reservoir deposits in China have strong heterogeneity, the viscosity of the continental-phase crude oil is high, and the method is more suitable for chemical flooding in an EOR method.
Surfactants 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. US20120279715 reports a foam fluid for increasing oil yield by recovering gas in a gas well, which is an amido group-containing quaternary ammonium salt surfactant with foam drainage and sterilization functions, a hydrophobic chain is a hydrophobic segment in substituted naphthalene ring, benzene ring or natural oil ester, and has strong chlorine resistance and condensate oil resistance, and also has good corrosion inhibition performance, the foam agent with the active matter concentration of 400ppm has the foam drainage rate of 86.8% in tap water and the foam drainage rate of 79.1% in simulated salt water with the mineralization degree of 130000 mg/L. Chinese patent CN102212348A discloses a salt-resistant and 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 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 and gas reservoir conditions, a preparation method and application thereof in improving oil and gas yield.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, the surfactant has poor injectivity in a low-permeability reservoir, the degree of improving the crude oil recovery is low, and foams formed by the surfactant cannot form effective plugging and liquid carrying in the prior art, so that the oil production and gas production efficiency is low, and provides a novel surfactant composition containing polyether quaternary ammonium salt. The water solution of the surfactant composition can well strip crude oil to form microemulsion, is beneficial to improving the injectivity of a low-permeability reservoir, and thus effectively improves the oil displacement efficiency of the crude oil and can reduce the injection pressure by 70%. The aqueous solution of the surfactant composition 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 capacity under acidic high-temperature and high-salt conditions, long foam stabilizing time, high liquid carrying rate, good oil displacement efficiency, low preparation cost and the like.
The second technical problem to be solved by the present invention is to provide a method for preparing a surfactant composition containing polyether quaternary ammonium salt corresponding to the solution of the first technical problem.
The invention also provides application of the surfactant composition containing polyether quaternary ammonium salt, which corresponds 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 surfactant composition containing polyether quaternary ammonium salt comprises the following components in parts by mole:
(1)1 part of polyether quaternary ammonium salt;
(2) 0.01-30 parts of cosurfactant;
the molecular general formula of the polyether quaternary ammonium salt is shown as the formula (I):
Figure BDA0002583020740000021
in the formula (I), R1Is C2~C32A hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyl group of4~C20Saturated and unsaturated hydrocarbon radicals, straight-chain or branched, or cumyl (C)6H5C(CH3)2) Any one of substituted benzene ring or naphthalene ring, hydrocarbon carbonyl; r2、R3And R4Independently selected from OH or (CH)2)eH and e are any integer of 0-4; r5、R6And R7Independently selected from the substituent group shown in the formula (II), hydrogen and C1~C32Alkyl or substituted alkyl (CHR')fOne of OH, benzyl and naphthylmethylene; r' is selected from H, CH3Or C2H5F is any integer of 1-4; xj-Is a number of negative charges ofThe anion or anionic group of j; a is any integer of 2-4; 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;
Figure BDA0002583020740000031
the cosurfactant is optionally selected from a zwitterionic surfactant shown as a formula (III);
Figure BDA0002583020740000032
in the formula (III), R8And R9Is independently selected from C1~C30Any one of the hydrocarbon groups of (1), or R9、R10Is independently selected from C1~C5Any one of the hydrocarbyl or substituted hydrocarbyl of (a); r11Is 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 co-surfactant is preferably selected from a nonionic surfactant or an anionic surfactant represented by formula (IV), and a hydrocarbyl quaternary ammonium salt surfactant represented by formula (V):
Figure BDA0002583020740000033
in the formula (IV), R12Is C8~C30Or one of a substituted hydrocarbon group or C4~C20A phenyl or naphthyl ring substituted by a hydrocarbon or cumyl group, or R12O 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;
Figure BDA0002583020740000034
in the formula (V), 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 (V) electrically neutral.
In the above technical scheme, R1Preferably C12~C24Or with a hydrocarbon or substituted hydrocarbon radical of4~C20Linear or branched saturated and unsaturated hydrocarbon groups or cumyl-substituted benzene or naphthalene rings, or hydrocarbon carbonyl groups.
In the above technical scheme, R1Preferably C12~C24In the case of the hydrocarbon carbonyl group, the structural formula is preferably
Figure BDA0002583020740000041
R'1The number of carbon atoms is 11 to 23.
In the above technical scheme, R5Preferred is a substituent represented by the formula (V).
In the above technical scheme, R5、R6And R7Preferably C8~C24The alkyl or substituted alkyl, methyl, ethyl, propyl, butyl, benzyl and naphthalene methylene.
In the above technical schemeR' 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 solution, a is preferably 2.
In the above technical scheme, R8And R9Preferably C8~C24Any one of the alkyl groups of (1).
In the above technical scheme, R9、R10Preferably C1~C3One of the alkyl groups of (1).
In the above technical scheme, R11Preferably C1~C3Any one of alkylene or substituted alkylene of (a).
In the above technical means, A is preferred-Is COO-Or SO3 -
In the above technical scheme, R12Preferably C8~C24Alkyl group of (1).
In the above technical scheme, R12Preferably C4~C20Linear or branched 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, R13Preferably C8~C24Any one of the alkyl groups of (1).
In the above technical scheme, R14Preferably C8~C24Alkyl of (2), hydrogen, (CHR')gOH, benzyl and naphthalene methylene.
In the above technical scheme, R15And R16Preferably hydrogen, (CHR')gOH, benzyl and naphthalene methylene.
In the above-mentioned technical scheme, R' ″ is preferablyIs 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 preferably 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 preferable small molecular alcohol is C1~C8More preferably, the alcohol or alcohol ether of (b) 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 above technical scheme, the preferable small molecule amine is C1~C8The aliphatic amine of (b) is more preferably at least one of primary amine, secondary amine and tertiary amine, and most preferably at least one 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 and a hydroxy-substituted carboxylate; the metal halide is preferably an alkali metal halide, and is more preferably one of sodium chloride, potassium chloride, sodium bromide and potassium bromide; the metal carboxylate is 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, sodium EDTA.
In the above-mentioned technical means, the inorganic base is preferably an alkali metal hydroxide, an alkali metal carbonate or an alkali metal hydrogencarbonate, and more preferably selected from the group consisting of potassium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate and potassium carbonate.
In the technical scheme, the surfactant composition contains an ester-based polyether cationic surfactant, a cosurfactant, a small molecular alcohol, a small molecular amine, a salt and an alkali, and the molar ratio of the surfactant composition to the surfactant composition is preferably 1 to (0.1-10): (0-15): (0-5).
In the above technical solution, the co-surfactant is preferably one or more selected from a nonionic surfactant or an anionic surfactant represented by formula (III), a zwitterionic surfactant represented by formula (IV), and a quaternary ammonium salt surfactant represented by formula (V).
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: one of the above technical problems is a method for preparing a surfactant composition containing polyether quaternary ammonium salt, comprising the steps of:
(a) preparation of polyether quaternary ammonium salt:
in the presence of a catalyst, R1COOH or R1Reacting OH with a desired amount of an epoxy compound to obtain a polyether compound;
② mixing the polyether compound obtained in the step I and SOCl2Reacting to obtain a chlorinated polyether intermediate, and reacting with tertiary amine NR5R6R7Carrying out quaternization reaction to obtain polyether quaternary ammonium salt with the structure shown in the formula (I);
or: secondly, in the presence of a multi-element composite catalyst, carrying out amination reaction on the polyether compound obtained in the first step and micromolecular amine to obtain dimeric polyether tertiary amine, and carrying out quaternization reaction to obtain polyether quaternary ammonium salt with the structure shown in the formula (I);
(b) preparation of surfactant composition:
mixing the aqueous solution or the alcohol aqueous solution of the polyether quaternary ammonium salt 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 solutions, the epoxy compound is preferably ethylene oxide, propylene oxide and butylene oxide.
In the above technical solution, the multi-component composite catalyst is preferably a copper composite metal catalyst.
In the above technical scheme, X' is preferably OH, Cl or CH3O、C2H5O, X' are preferably Cl, Br.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the method for improving oil and gas yield of the surfactant composition containing polyether quaternary ammonium salt in any one of the technical schemes comprises the following steps:
(1) mixing the surfactant composition containing polyether quaternary ammonium salt in the technical scheme with water to obtain an oil displacing system;
(2) contacting the oil displacement system 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 displacing crude oil in the oil-bearing stratum;
or: (1') mixing the surfactant composition containing polyether quaternary ammonium salt in the technical scheme with water or water oil to obtain a foaming agent solution;
(2') 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. In the technical scheme, the stratum permeability range is preferably 0.5-100 multiplied by 10-3μm2
In the above technical solution, the gas is preferably at least one of nitrogen, carbon dioxide, methane or natural gas.
In the above technical solution, the oil is preferably at least one of kerosene and condensate.
In the technical scheme, the surfactant composition containing polyether quaternary ammonium salt 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 mineralization degree of stratum saline water of the application-preferred oil reservoir is 3000-200000 mg/L, wherein Ca2++Mg2+10 to 15000mg/L, HCO3 -0 to 2000 mg/L; the viscosity of the crude oil is 0.8-50.0 mPa.s; the formation temperature is 50-120 ℃.
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 testing the interfacial tension comprises the following steps: (1) presetting the temperature to the temperature required by the measurement, and waiting for the temperature to be stable; (2) injecting external phase liquid, filling the centrifuge tube, injecting internal phase liquid, removing bubbles, and tightly covering; (3) the centrifuge tube is arranged in a rotating shaft of the instrument, the rotating speed is set, and a microscope is adjusted to enable inner phase liquid drops or bubbles in the visual field to be very clear; (4) reading and calculating, and calculating the interfacial tension according to the formula (1):
γ=0.25ω2r3Δ ρ (L/D ≧ 4) formula (1);
wherein γ is the interfacial tension (mN. m)-1) Δ ρ is the two-phase density difference (Kg. m)-3.) Omega is angular velocity (rad · s)-1),r is the minor axis radius (m)) of the droplets, L is the major axis (tube axis) diameter, and D is the minor axis (tube axis) diameter.
The invention adopts an injection physical simulation displacement evaluation method for effect evaluation, and the specific evaluation method comprises the following steps: and drying the rock core at constant temperature to constant weight, and measuring the gas logging permeability of the rock core. The method comprises the steps of firstly, saturating a rock core with water, then saturating the rock core with crude oil, carrying out water flooding until the water content reaches 99%, calculating the recovery ratio of the crude oil enhanced by the water flooding, injecting a certain PV number (rock core pore volume) of surfactant composition aqueous solution, finally carrying out the water flooding until the water content reaches 100%, and calculating the recovery ratio percentage of the enhanced crude oil and the injection pressure reduction percentage.
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 (2);
wherein RF is a resistance factor, P1Is water drive differential pressure (MPa), P2The foam displacement pressure (MPa).
The surfactant composition prepared by the invention is used in an amount of 0.01-0.15 wt% in percentage by mass, and can be used for treating the formation temperature of 30-100 ℃, the mineralization degree of 5000-100000 Mg/L and Mg2++Ca2+20 to 12000 mg/l, HCO3 -The dynamic interfacial tension value between the surfactant aqueous solution and the crude oil is measured to be 0-2000 mg/L of oilfield water and crude oil and can reach 10-2~10-4Interfacial tension of mN/m. The evaluation in a physical simulation displacement laboratory shows that the oil displacement agent can reduce the injection pressure by 72.4 percent, and obtains better technical effect.
The method for increasing the oil and gas yield by adopting the foaming agent composition can be used for, but not limited to, the formation temperature is 60-150 ℃, the total mineralization degree of water is 0-200000 mg/L, and H2And (3) a high-temperature oil-gas reservoir with the S content of 5-35%. Measuring the initial foaming height, the foaming height after 5 minutes and the liquid carrying rate by using 0.05-0.2 wt% of foaming agent composition water solution or foaming agent composition oil-water mixed solution in percentage by mass, wherein the foaming height reaches 173mm, the liquid carrying rate reaches 95.9%, and the foaming agent composition has excellent temperature resistance, salt resistance, foaming stability and liquid carrying performance in an acid environment; the plugging factor of the core tube filled with the quartz sand reaches 125, the plugging performance is strong, and a good technical effect is achieved.
Drawings
The polyether 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 polyether quaternary ammonium salt surfactant prepared in example 1. Wherein, 3352.8cm-1And 3297.4cm-1Is the characteristic peak of O-H stretching vibration, 2926.3cm-1And 2862.4m-1Is a characteristic peak of C-H stretching of methyl and methylene, 1454.7cm-1Is a C-N bending vibration absorption peak, 1092.2cm-1Is C-O stretching vibration peak, 1066.6cm-1Is the C-O-C stretching vibration peak.
Fig. 2 is a flow chart of an indoor core displacement experiment.
FIG. 3 is a schematic view showing a 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. 4 is a schematic structural view of a high-temperature and high-pressure foam evaluation device.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
(a) Preparation of polyether quaternary ammonium salt
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 536.8 g (12.2 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 775.4 g of octadecanol polyoxyethylene (12) ether are obtained, and the yield is 97.3%.
② at 80 ℃, 142.9 g (1.2 mol) of thionyl chloride is dropped into 200 ml of mixed solution of 398.4 g (0.5 mol) of DMF of octadecyl alcohol polyoxyethylene (12) ether, after 7 hours of reaction, unreacted thionyl chloride and DMF solvent are removed, thus obtaining the chlorinated polyether intermediate. And transferring the chlorinated polyether intermediate into a high-pressure reaction kettle, introducing dimethylamine according to the proportion of 1:2, reacting for 10 hours at about 135 ℃, and vacuumizing to remove low-boiling-point substances to obtain the N, N-dimethyl polyether tertiary amine. And cooling, adding ethanol, replacing with nitrogen again, introducing 95.0 g (1.0 mol) of methyl bromide to perform quaternization reaction, keeping the reaction pressure at 0.5-0.8 MPa, and reacting at 60 ℃ for 6-8 hours to obtain the polyether quaternary ammonium salt surfactant.
(b) Preparation of surfactant composition S01
Adding the polyether quaternary ammonium salt surfactant synthesized in the step (a), cetyl dimethyl carboxylic acid betaine and diethanol amine into the mixture at the temperature of about 40 ℃ according to the molar ratio of 1:1.5:2.5, adding water until the content of the surfactant is about 35%, and continuously stirring the mixture at the temperature of 40 ℃ for 6 hours to obtain a surfactant composition S01 containing polyether quaternary ammonium salt.
[ example 2 ]
(a) Preparation of polyether quaternary ammonium salt
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 536.8 g (12.2 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 775.4 g of octadecanol polyoxyethylene (12) ether are obtained, and the yield is 97.3%.
② at 80 ℃, 142.9 g (1.2 mol) of thionyl chloride is dropped into 200 ml of mixed solution of 398.4 g (0.5 mol) of DMF of octadecyl alcohol polyoxyethylene (12) ether, after 7 hours of reaction, unreacted thionyl chloride and DMF solvent are removed, thus obtaining the chlorinated polyether intermediate. And transferring the chlorinated polyether intermediate into a high-pressure reaction kettle, introducing dimethylamine according to the proportion of 1:2, reacting for 10 hours at about 135 ℃, and vacuumizing to remove low-boiling-point substances to obtain the N, N-dimethyl polyether tertiary amine. And cooling, adding ethanol, replacing with nitrogen again, introducing 95.0 g (1.0 mol) of methyl bromide to perform quaternization reaction, keeping the reaction pressure at 0.5-0.8 MPa, and reacting at 60 ℃ for 6-8 hours to obtain the polyether quaternary ammonium salt surfactant.
(b) Preparation of surfactant composition S02
Adding the polyether quaternary ammonium salt surfactant synthesized in the step (a), octadecyl dimethyl carboxylic acid betaine, diethanolamine and sodium polyphosphate into the mixture at the temperature of about 40 ℃ according to the molar ratio of 1:4:2:0.5, adding water until the content of the surfactant is about 35%, and continuously stirring the mixture at the temperature of 40 ℃ for 6 hours to obtain a polyether quaternary ammonium salt-containing surfactant composition S02.
[ example 3 ]
(a) Preparation of polyether quaternary ammonium salt
Adding 200.0 g (1 mol) of lauric acid and 5.4 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, after the reaction is finished, cooling to 90 ℃, removing low-boiling-point substances in vacuum, cooling, neutralizing and dehydrating to obtain 306.8 g of lauric acid polyoxyethylene (3) ester, wherein the yield is 92.4%.
Adding 166.0 g (0.5 mol) of lauric acid polyoxyethylene (3) ester and 0.9 g of quaternary copper metal catalyst into an autoclave, heating to 150-170 ℃ after nitrogen replacement, activating the catalyst with hydrogen, introducing methylamine gas at a slow speed, heating to about 200 ℃, controlling the reaction pressure to be below 1.0MPa, and reacting for about 6-7 hours to obtain the bis (lauric acid polyoxyethylene (2) ethyl) methyl tertiary amine. And cooling, adding isopropanol, replacing with nitrogen again, introducing 95.0 g (1.0 mol) of methyl bromide to perform quaternization reaction, keeping the reaction pressure at 0.5-0.8 MPa, and reacting at 65 ℃ for 6-8 hours to obtain the polyether quaternary ammonium salt surfactant.
(b) Preparation of surfactant composition S03
Adding the polyether quaternary ammonium salt surfactant synthesized in the step (a), octadecyl dimethyl carboxylic acid betaine, ethylene glycol dimethyl ether and sodium citrate into the mixture at a temperature of about 40 ℃ according to a molar ratio of 1:1.05:0.1:1.5, 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 a polyether quaternary ammonium salt-containing surfactant composition S03.
[ example 4 ]
(a) Preparation of polyether quaternary ammonium salt
Adding 282.5 g (1 mol) of 9-ene octadecanoic acid and 5.1 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 312.4 g (7.1 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, 564.5 g of 9-ene octadecanoic acid polyoxyethylene (7) ester is obtained, and the yield is 95.6%.
295.3 g (0.5 mol) of 9-ene octadecanoic acid polyoxyethylene (7) ester and 142.9 g (1.2 mol) of thionyl chloride are mixed and refluxed for 7 hours, then unreacted thionyl chloride is removed through reduced pressure distillation to obtain a chlorinated polyether intermediate, 65.4 g (0.55 mol) of N-methyldiethanolamine and 200 g of isopropanol are added, and the mixture is heated to 80 ℃ to react for 8 hours to obtain the polyether quaternary ammonium salt surfactant.
(b) Preparation of surfactant composition S04
Adding the polyether quaternary ammonium salt surfactant synthesized in the step (a), cetyl dihydroxyethyl hydroxy sulfonic acid betaine and propane diamine into the mixture at the temperature of about 40 ℃ according to the mol ratio of 1:1.1:1.8, adding water until the content of the surfactant is about 40%, and continuously stirring the mixture for 4 hours at the temperature of 40 ℃ to obtain a polyether quaternary ammonium salt-containing surfactant composition S04.
[ example 5 ]
(a) Preparation of polyether quaternary ammonium salt
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 220.5 g (50 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 578.3 g of 9-eneoctadecylic acid polyoxypropylene (2) polyoxyethylene (5) ester with a yield of 93.5%.
309.3 g (0.5 mol) of 9-ene octadecanoic acid polyoxypropylene (2) polyoxyethylene (5) ester and 142.9 g (1.2 mol) of thionyl chloride are mixed and refluxed for 7 hours, then unreacted thionyl chloride is removed through reduced pressure distillation to obtain a chlorinated polyether intermediate, 124.5 g (0.5 mol) of N, N-dimethyl octyl benzyl amine and isopropanol are added to carry out quaternization reaction, and the reaction is carried out for 6 to 8 hours at 70 ℃ to obtain the polyether quaternary ammonium salt surfactant.
(b) Preparation of surfactant composition S05
Adding the polyether quaternary ammonium salt surfactant synthesized in the step (a), cetyl dihydroxyethyl hydroxy sulfonic acid betaine and propylene diamine into the mixture at the temperature of about 50 ℃ according to the mol ratio of 1:1.3:2, adding water until the content of the surfactant is about 35%, and continuously stirring the mixture for 2 hours at the temperature of 50 ℃ to obtain a polyether quaternary ammonium salt-containing surfactant composition S05.
[ example 6 ]
(a) Preparation of polyether quaternary ammonium salt
Adding 282.5 g (1 mol) of 9-ene octadecanoic acid, 6.5 g of potassium hydroxide and 1.3 g of anhydrous potassium carbonate into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 88.2 g (2.0 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 160 ℃, slowly introducing 144.2 g (2.0 mol) of butylene oxide after the reaction of propylene oxide is finished, controlling the pressure to be less than or equal to 0.40MPa, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 132.1 g (3.0 mol) of ethylene oxide, cooling to 90 ℃, removing low-boiling substances in vacuum, cooling, neutralizing, and dehydrating to obtain 616.6 g of 9-ene octadecanoic acid polyoxyethylene (2) polyoxybutylene (2) polyoxyethylene (3) ester, the yield thereof was found to be 95.4%.
323.2 g (0.5 mol) of 9-ene octadecanoic acid polyoxyethylene (2) polyoxybutylene (2) polyoxyethylene (3) ester and 178.2 g (1.5 mol) of thionyl chloride are mixed and refluxed for 8 hours, then unreacted thionyl chloride is removed through reduced pressure distillation to obtain a chlorinated polyether intermediate, 65.4 g (0.55 mol) of N-methyldiethanolamine and 300 g of isopropanol are added, and the mixture is heated to 80 ℃ to react for 8 hours to obtain the polyether quaternary ammonium salt surfactant.
(b) Preparation of surfactant composition S06
Adding the polyether quaternary ammonium salt surfactant synthesized in the step (a) and hexadecyl dihydroxyethyl hydroxy sulfonic acid betaine according to the molar ratio of 1:2 at about 40 ℃, adding water until the content of the surfactant is about 35%, and continuously stirring at 40 ℃ for 4 hours to obtain a polyether quaternary ammonium salt-containing surfactant composition S06.
[ example 7 ]
(a) Preparation of polyether quaternary ammonium salt
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 536.8 g (12.2 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 775.4 g of octadecanol polyoxyethylene (12) ether are obtained, and the yield is 97.3%.
② at 80 ℃, 142.9 g (1.2 mol) of thionyl chloride is dropped into 200 ml of mixed solution of 398.4 g (0.5 mol) of DMF of octadecyl alcohol polyoxyethylene (12) ether, after 7 hours of reaction, unreacted thionyl chloride and DMF solvent are removed, thus obtaining the chlorinated polyether intermediate. And transferring the chlorinated polyether intermediate into a high-pressure reaction kettle, introducing dimethylamine according to the proportion of 1:2, reacting for 10 hours at about 135 ℃, and vacuumizing to remove low-boiling-point substances to obtain the N, N-dimethyl polyether tertiary amine. And cooling, adding ethanol, replacing with nitrogen again, introducing 95.0 g (1.0 mol) of methyl bromide to perform quaternization reaction, keeping the reaction pressure at 0.5-0.8 MPa, and reacting at 60 ℃ for 6-8 hours to obtain the polyether quaternary ammonium salt surfactant.
(b) Preparation of surfactant composition S07
Adding the polyether quaternary ammonium salt surfactant synthesized in the step (a), sodium acetate, ethanolamine and ethylene glycol in a molar ratio of 1:1.2:2.0:0.7 at about 40 ℃, adding water until the content of the surfactant is about 35%, and continuously stirring for 4 hours at 40 ℃ to obtain the polyether quaternary ammonium salt-containing surfactant composition S07.
[ example 8 ]
(a) Preparation of polyether quaternary ammonium salt
Adding 282.5 g (1 mol) of 9-ene octadecanoic acid and 5.1 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 312.4 g (7.1 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 neutralization and dehydration are carried out after cooling, so that 564.5 g of 9-ene octadecanoic ethylene oxide (7) ester is obtained, and the yield is 95.6%.
295.3 g (0.5 mol) of 9-ene octadecanoic acid polyoxyethylene (7) ester and 178.2 g (1.5 mol) of thionyl chloride are mixed and refluxed for 8 hours, then unreacted thionyl chloride is removed through reduced pressure distillation to obtain a chlorinated polyether intermediate, 65.4 g (0.55 mol) of N-methyldiethanolamine and 300 g of isopropanol are added, and the mixture is heated to 80 ℃ to react for 8 hours to obtain the polyether quaternary ammonium salt surfactant.
(b) Preparation of surfactant composition S08
Adding the polyether quaternary ammonium salt surfactant synthesized in the step (a), ammonium dodecylbenzene sulfonate, diethylenetriamine and propanol in a molar ratio of 1:1.5:0.2:1.2 at about 40 ℃, adding water until the content of the surfactant is about 40%, and continuously stirring for 4 hours at 40 ℃ to obtain the polyether quaternary ammonium salt-containing surfactant composition S08.
[ example 9 ]
(a) Preparation of polyether quaternary ammonium salt
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 220.5 g (50 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 578.3 g of 9-eneoctadecylic acid polyoxypropylene (2) polyoxyethylene (5) ester with a yield of 93.5%.
309.3 g (0.5 mol) of 9-ene octadecanoic acid polyoxypropylene (2) polyoxyethylene (5) ester and 142.9 g (1.2 mol) of thionyl chloride are mixed and refluxed for 7 hours, then unreacted thionyl chloride is removed through reduced pressure distillation to obtain a chlorinated polyether intermediate, 124.5 g (0.5 mol) of N, N-dimethyl octyl benzyl amine and isopropanol are added to carry out quaternization reaction, and the reaction is carried out for 6 to 8 hours at 70 ℃ to obtain the polyether quaternary ammonium salt surfactant.
(b) Preparation of surfactant composition S09
Adding the polyether quaternary ammonium salt surfactant synthesized in the step (a), ammonium dodecylbenzene sulfonate, diethylenetriamine and propanol in a molar ratio of 1:1.5:0.5:0.3 at about 35 ℃, adding water until the content of the surfactant is about 35%, and continuously stirring at 35 ℃ for 6 hours to obtain a polyether quaternary ammonium salt-containing surfactant composition S09.
[ example 10 ]
(a) Preparation of polyether quaternary ammonium salt
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 536.8 g (12.2 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 775.4 g of octadecanol polyoxyethylene (12) ether are obtained, and the yield is 97.3%.
② at 80 ℃, 142.9 g (1.2 mol) of thionyl chloride is dropped into 200 ml of mixed solution of 398.4 g (0.5 mol) of DMF of octadecyl alcohol polyoxyethylene (12) ether, after 7 hours of reaction, unreacted thionyl chloride and DMF solvent are removed, thus obtaining the chlorinated polyether intermediate. And transferring the chlorinated polyether intermediate into a high-pressure reaction kettle, introducing dimethylamine according to the proportion of 1:2, reacting for 10 hours at about 135 ℃, and vacuumizing to remove low-boiling-point substances to obtain the N, N-dimethyl polyether tertiary amine. And cooling, adding ethanol, replacing with nitrogen again, introducing 95.0 g (1.0 mol) of methyl bromide to perform quaternization reaction, keeping the reaction pressure at 0.5-0.8 MPa, and reacting at 60 ℃ for 6-8 hours to obtain the polyether quaternary ammonium salt surfactant.
(b) Preparation of surfactant composition S10
Adding the polyether quaternary ammonium salt surfactant synthesized in the step (a), octadecylpyridine chloride, diethanolamine and tetrasodium EDTA at the temperature of about 30 ℃ according to the molar ratio of 1:0.3:0.3, adding water until the content of the surfactant is about 35%, and continuously stirring at the temperature of 30 ℃ for 6 hours to obtain the polyether quaternary ammonium salt-containing surfactant composition S10.
[ example 11 ]
(a) Preparation of polyether quaternary ammonium salt
Firstly, adding 282.5 g (1 mol) of 9-ene octadecanoic acid and 5.1 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 312.4 g (7.1 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, 564.5 g of 9-ene octadecanoic acid polyoxyethylene (7) ester is obtained, and the yield is 95.6%.
295.3 g (0.5 mol) of 9-ene octadecanoic acid polyoxyethylene (7) ester and 178.2 g (1.5 mol) of thionyl chloride are mixed and refluxed for 8 hours, then unreacted thionyl chloride is removed through reduced pressure distillation to obtain a chlorinated polyether intermediate, 65.4 g (0.55 mol) of N-methyldiethanolamine and 300 g of isopropanol are added, and the mixture is heated to 80 ℃ to react for 8 hours to obtain the polyether quaternary ammonium salt surfactant.
(b) Preparation of surfactant composition S11
Adding the polyether quaternary ammonium salt surfactant synthesized in the step (a), cetyl dihydroxyethyl hydroxy sulfonic acid betaine and dodecyl trimethyl ammonium chloride at the molar ratio of 1:1.8:0.2 at about 40 ℃, adding water until the content of the surfactant is about 40%, and continuously stirring at 40 ℃ for 4 hours to obtain a polyether quaternary ammonium salt-containing surfactant composition S11.
[ example 12 ]
(a) Preparation of polyether quaternary ammonium salt
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 536.8 g (12.2 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 775.4 g of octadecanol polyoxyethylene (12) ether are obtained, and the yield is 97.3%.
② at 80 ℃, 142.9 g (1.2 mol) of thionyl chloride is dropped into 200 ml of mixed solution of 398.4 g (0.5 mol) of DMF of octadecyl alcohol polyoxyethylene (12) ether, after 7 hours of reaction, unreacted thionyl chloride and DMF solvent are removed, thus obtaining the chlorinated polyether intermediate. And transferring the chlorinated polyether intermediate into a high-pressure reaction kettle, introducing dimethylamine according to the proportion of 1:2, reacting for 10 hours at about 135 ℃, and vacuumizing to remove low-boiling-point substances to obtain the N, N-dimethyl polyether tertiary amine. And cooling, adding ethanol, replacing with nitrogen again, introducing 95.0 g (1.0 mol) of methyl bromide to perform quaternization reaction, keeping the reaction pressure at 0.5-0.8 MPa, and reacting at 60 ℃ for 6-8 hours to obtain the polyether quaternary ammonium salt surfactant.
(b) Preparation of surfactant composition S12
Adding the polyether quaternary ammonium salt surfactant synthesized in the step (a), alpha-olefin sulfonate (AOS14-18), octadecyl trihydroxyethyl ammonium chloride and sodium salicylate into the mixture at the temperature of about 30 ℃ according to the molar ratio of 1:3.0:0.5:1.2, adding water until the content of the surfactant is about 35%, and continuously stirring the mixture at the temperature of 30 ℃ for 6 hours to obtain a polyether quaternary ammonium salt-containing surfactant composition S12.
[ example 13 ]
(a) Preparation of polyether quaternary ammonium salt
Firstly, adding 282.5 g (1 mol) of 9-ene octadecanoic acid and 5.1 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 312.4 g (7.1 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, 564.5 g of 9-ene octadecanoic acid polyoxyethylene (7) ester is obtained, and the yield is 95.6%.
295.3 g (0.5 mol) of 9-ene octadecanoic acid polyoxyethylene (7) ester and 178.2 g (1.5 mol) of thionyl chloride are mixed and refluxed for 8 hours, then unreacted thionyl chloride is removed through reduced pressure distillation to obtain a chlorinated polyether intermediate, 65.4 g (0.55 mol) of N-methyldiethanolamine and 300 g of isopropanol are added, and the mixture is heated to 80 ℃ to react for 8 hours to obtain the polyether quaternary ammonium salt surfactant. (b) Preparation of surfactant composition S13
Adding the polyether quaternary ammonium salt surfactant synthesized in the step (a), isotridecanol polyoxypropylene (2) polyoxypropylene (3) sodium acetate, chlorooctadecyl pyridine, urea and ethylene glycol dimethyl ether into the mixture at a temperature of about 40 ℃ according to a molar ratio of 1:0.3:2.5:3:0.1, adding water until the content of the surfactant is about 40%, and continuously stirring the mixture at the temperature of 40 ℃ for 4 hours to obtain a polyether quaternary ammonium salt-containing surfactant composition S13.
[ example 14 ]
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 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.
Drying the core at constant temperature to constant weight, and measuring the gas logging permeability of the core; calculating the pore volume of the simulated oil field stratum water saturated core, recording the volume of saturated crude oil by using a crude oil saturated core at the stratum temperature, pumping the stratum water at the speed of 0.2mL/min, driving the stratum water until the water content reaches 100%, calculating the recovery ratio of the crude oil improved by water drive, then transferring 0.1-1 PV (core pore volume) surfactant composition aqueous solution at the speed of 0.1mL/min, driving the stratum water at the speed of 0.2mL/min until the water content reaches 100%, and calculating the percent of the recovery ratio of the crude oil improved on the basis of the water drive and the percent of the reduction of injection pressure, wherein the percent is shown in Table 2.
[ example 15 ]
S10 and S13 are respectively dissolved in deionized water, 100,000mg/L and 200,000mg/L NaCl water to prepare 0.3 wt% of surfactant mother liquor, and the surfactant mother liquor is diluted to a test concentration by adding saline or condensate oil.
The performance of the surfactant solution, such as foaming power, foam stability, liquid carrying capacity and the like, was measured according to SY/T6465-2000 evaluation method for foam-generating agent for water drainage and gas production, and the results are shown in Table 3.
[ example 16 ]
Dissolving S11 in simulated saline to obtain the desired aqueous solution of surfactant composition. The foaming capacity and half-life of the composition were measured by the Roche method at a bath temperature of 60 ℃ and the results are shown in Table 4. The foaming height and half-life of the surfactant at high temperature and high pressure were measured using the high temperature and high pressure foam evaluation apparatus shown in FIG. 4, and the results are shown in Table 4. A quartz sand filled core tube is adopted for carrying out a plugging performance evaluation experiment, the permeability is 2500mD, 0.15% of surfactant composition aqueous solution is injected into the sand tube at the speed of 2mL/min, nitrogen is pressed at the speed of 6mL/min, the plugging differential pressure is measured to be 1.54MPa, and the calculated resistance factor is 125.
[ COMPARATIVE EXAMPLE 1 ]
The same as in example 1, except that the polyether quaternary ammonium salt surfactant synthesized in step (a), cetyl dimethyl carboxylic acid betaine and diethanolamine were added at about 40 ℃ in a molar ratio of 1:0:2.5, water was added until the surfactant content was about 35%, and stirring was continued at 40 ℃ for 6 hours to obtain a surfactant composition S14.
The same as [ example 1 ] except that the polyether quaternary ammonium salt surfactant synthesized in the step (a), cetyl dimethyl carboxylic betaine and diethanolamine were added at about 40 ℃ in a molar ratio of 0:1.5:2.5, water was added until the surfactant content was about 35%, and stirring was continued at 40 ℃ for 6 hours to obtain a surfactant composition S15.
[ COMPARATIVE EXAMPLE 2 ]
The difference is as in [ example 1 ]: 144.3 g (0.5 mol) of 1-chlorooctadecane, 65.4 g (0.55 mol) of N-methyldiethanolamine and 1600 g of water are heated to 80 ℃ to react for 8 hours to obtain the quaternary ammonium salt surfactant.
Adding the quaternary ammonium salt surfactant synthesized in the step (a), cetyl dimethyl carboxylic acid betaine and diethanol amine into the mixture at the temperature of about 40 ℃ according to the mol ratio of 1:1.5:2.5, adding water until the content of the surfactant is about 35%, and continuously stirring the mixture at the temperature of 40 ℃ for 6 hours to obtain a surfactant composition S16 containing polyether quaternary ammonium salt.
TABLE 1
Figure BDA0002583020740000171
TABLE 2
Figure BDA0002583020740000181
TABLE 3
Figure BDA0002583020740000182
TABLE 4
Figure BDA0002583020740000183
TABLE 5
Figure BDA0002583020740000191

Claims (10)

1. The surfactant composition containing polyether quaternary ammonium salt comprises the following components in parts by mole:
(1)1 part of polyether quaternary ammonium salt;
(2) 0.01-30 parts of cosurfactant;
the molecular general formula of the polyether quaternary ammonium salt is shown as the formula (I):
Figure FDA0002583020730000011
in the formula (I), R1Is C2~C32A hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyl group of4~C20Saturated and unsaturated hydrocarbon radicals, straight-chain or branched, or cumyl (C)6H5C(CH3)2) Any one of substituted benzene ring or naphthalene ring, hydrocarbon carbonyl, R2、R3And R4Independently selected from OH or (CH)2)eH, e is any integer of 0-4, R5、R6And R7Independently selected from the substituent group shown in the formula (II), hydrogen and C1~C32Alkyl group of (1), (CHR')fOne of OH, benzyl and naphthalene methylene, R' is selected from H, CH3Or C2H5F is an integer of 1 to 4,Xj-is an anion or anionic group having a negative charge number j; a is any integer of 2-4; 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;
Figure FDA0002583020730000012
the cosurfactant is optionally selected from zwitterionic surfactants represented by formula (III):
Figure FDA0002583020730000013
in the formula (III), R8And R9Is independently selected from C1~C30Any one of the hydrocarbon groups of (1), or R9、R10Is independently selected from C1~C5Any one of the hydrocarbyl or substituted hydrocarbyl of (a); r11Is 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.
2. The surfactant composition according to claim 1, wherein the co-surfactant is selected from the group consisting of a nonionic surfactant or an anionic surfactant of formula (IV), a hydrocarbyl quaternary surfactant of formula (V):
Figure FDA0002583020730000021
in the formula (IV), R12Is C8~C30Or one of a substituted hydrocarbon group or C4~C20A phenyl or naphthyl ring substituted by a hydrocarbon or cumyl group, or R12O is abietate; m1 and m2 are the addition number of ethoxy groups, m1 is 0-50, and m2 is 0-50; n is CN is 0 to 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;
Figure FDA0002583020730000022
in the formula (V), 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 (V) electrically neutral.
3. The surfactant composition comprising polyether quaternary ammonium salt according to claim 1, wherein R is1Is C12~C24A hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyl group of4~C20Saturated and unsaturated hydrocarbon radicals, straight-chain or branched, or cumyl (C)6H5C(CH3)2) Any one of substituted benzene ring or naphthalene ring, and hydrocarbon carbonyl group.
4. The surfactant composition comprising polyether quaternary ammonium salt according to claim 1, wherein R is5Is a substituent shown as a formula (II) or R5、R6And R7Is C8~C24Alkyl or substituted alkyl, methyl, ethyl, propylOne of butyl, benzyl and naphthalene methylene; e is 0-2, and f is 1-2; b is 0-20, c is 0-20, and d is 0-20; a is 2; the R is8And R9Is C8~C24Any one of the alkyl groups of (a); or R9、R10Independently of one another are selected from C1~C3One of the alkyl groups of (a); r11Is C1~C3Any one of alkylene groups of (a); a. the-Is COO-Or SO3 -
5. The surfactant composition comprising polyether quaternary ammonium salt according to claim 2, wherein R is12Is C12~C24Or from C4~C20Straight or branched chain saturated 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 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-
6. The surfactant composition containing polyether quaternary ammonium salt according to claim 1, characterized in that the surfactant composition further comprises at least one of small molecule alcohol, small molecule amine, salt and inorganic base.
7. The surfactant composition containing polyether quaternary ammonium salt according to claim 6, wherein the molar ratio of the polyether quaternary ammonium salt, the cosurfactant, the small molecular alcohol, the small molecular amine, the salt and the alkali is 1 to (0.1-10): (0-15): (0-5).
8. A preparation method of the surfactant composition containing polyether quaternary ammonium salt according to any one of claims 1 to 7, comprising the following steps:
(a) preparation of polyether quaternary ammonium salt:
in the presence of a catalyst, R1COOH or R1Reacting OH with a desired amount of an epoxy compound to obtain a polyether compound;
② mixing the polyether compound obtained in the step I and SOCl2Reacting to obtain a chlorinated polyether intermediate, and reacting with tertiary amine NR5R6R7Carrying out quaternization reaction to obtain polyether quaternary ammonium salt with the structure shown in the formula (I);
or: secondly, in the presence of a multi-element composite catalyst, carrying out amination reaction on the polyether compound obtained in the first step and micromolecular amine to obtain dimeric polyether tertiary amine, and carrying out quaternization reaction to obtain polyether quaternary ammonium salt with the structure shown in the formula (I);
(b) preparation of surfactant composition:
mixing the aqueous solution or the alcohol aqueous solution of the polyether quaternary ammonium salt 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.
9. The method for preparing surfactant composition containing polyether quaternary ammonium salt according to claim 8, characterized in that the catalyst is at least one of potassium hydroxide or anhydrous potassium carbonate; the epoxy compound is ethylene oxide, propylene oxide and butylene oxide, and the multi-component composite catalyst is a copper composite metal catalyst.
10. A method of increasing oil and gas production comprising the steps of:
(1) mixing the surfactant composition containing polyether quaternary ammonium salt according to any one of claims 1 to 7 with water to obtain an oil displacing system;
(2) contacting the oil displacement system 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 displacing crude oil in the oil-bearing stratum;
or:
(1') mixing the polyether quaternary ammonium salt-containing surfactant composition according to any one of claims 1 to 7 with water or water oil to obtain a foaming agent solution;
(2') 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.
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