CN113930249B - Benzyloxy-oleoyl quaternary ammonium surfactant and its preparation method and use - Google Patents

Abstract

The present invention relates to a kind of benzyloxy-oleoyl quaternary ammonium surfactant and its preparation method and application, wherein the structural formula of the surfactant is as shown in formula (I) or formula (II):

Wherein, m=0-11, n=4-15, and m+n=15. The preparation method comprises: firstly fatty acid, anisole, FeCl ₃ are mixed and carried out alkylation reaction; Then mixed with 3-dimethylaminopropylamine and carried out amidation reaction; The surfactant is obtained by mixing sodium in ethanol/water solution and performing quaternization reaction. Compared with the prior art, the present invention uses oleic acid obtained from animals and plants, and anisole extracted from fennel instead of benzene as raw materials, optimizes the structure of traditional phenyl octadecanoic acid, and passes through the alkyl After chemical reaction, amidation reaction, and quaternization reaction, the oil-water interfacial tension of the obtained surfactant can reach a minimum of 5×10 ^‑4 mN/m, which has great application potential in the tertiary oil recovery industry.

Description

Benzyloxy-oleoyl quaternary ammonium surfactant and its preparation method and application

technical field

The invention belongs to the technical field of surfactants, and relates to a benzyloxy-oleoyl quaternary ammonium surfactant and a preparation method and application thereof.

Background technique

Surfactants can be divided into petroleum-based surfactants, bio-surfactants, bio-based surfactants, etc. according to the source of the hydrophobic group. Currently the most widely used surfactants are petroleum-based surfactants, the main source of which is petrochemicals. Bio-based surfactants, unlike traditional petroleum-based surfactants, refer to surfactants whose main source is renewable biomass. Petroleum products have been widely used as sources of hydrophobic groups for surfactants since the 1950s. Since the 1990s, due to factors such as safety, environmental protection and sustainable development, the share of petroleum-based surfactants in the total production of surfactants has gradually declined. Biomass resources are considered to be one of the best sources to replace fossil resources. For more than 100 years, oil and natural gas have provided a large amount of fuel and other chemical raw materials for people's production and life, supporting the rapid development of the global economy. Over the past few decades, shrinking oil reserves, increasing product costs, and worsening environmental pollution have prompted the search for alternative chemicals derived from oil and natural gas. Safety has become the focus of social attention, and sustainable development is the theme of social development. Sustainable chemistry includes not only resources, but also the sustainability of chemical production processes. In the production of chemical reagents, skin care products and pharmaceuticals, the most important goals of sustainable chemistry are the development of non-toxic and biodegradable compounds, improved reaction conditions (e.g. use of clean solvents, biotechnology, etc.), and the use of renewable raw materials.

There has been a trend to replace traditional petroleum-based surfactants with more environmentally friendly surfactants. Both manufacturers and consumers prefer to use new environmentally friendly surfactants derived from renewable resources and produced by clean and sustainable technologies. The key to realizing this expectation is how to obtain surfactants that are mild, biodegradable, have good performance and are economical.

Most of the renewable hydrophobic groups of bio-based surfactants come from fatty acids in vegetable or animal oils, as well as proteins and carbohydrates. Due to the characteristics of high yield, low cost, strong universal applicability, and good environmental compatibility, natural oils and fats have been widely used in the synthesis of bio-based surfactants in recent years, and have become a research hotspot in the industrial and academic fields. Fatty acids obtained from vegetable oils, the common ones are lauric acid (C12), myristic acid (C14), palmitic acid (C16) and stearic acid (C18), oleic acid (C18), linoleic acid (C18) and ricin Sesame Acid (C18). From raw oil to desired surfactants and surfactant precursors, use oleochemical methods to convert triglycerides, such as hydrogenation, hydrolysis, transesterification reduction, sulfonation, chlorination, glycosidation, etc. .

Liquid-liquid interfacial tension, like surface tension, is one of the main means to measure the properties of two-phase interfaces. Unlike the surface tension of gas-liquid two-phase, the other phase of interfacial tension is usually oil phase besides the water phase. In the study of tertiary oil recovery, interfacial tension is a very important measurement index, and it is the main means of laboratory research on chemical flooding. Whether ultra-low interfacial tension (<10 ^-2 mN/m) can be achieved is considered to be one of the most important indicators of enhanced oil recovery. At present, most of the surfactants that can significantly reduce the interfacial tension are alkylbenzene sulfonate, alkylbenzene quaternary ammonium salt type and alkylbenzene betaine type surfactants, etc., and their interfacial tension can even be reduced to 10 ^-3 mN/ m below, but because of the use of carcinogenic and highly toxic compound benzene as raw material in the synthesis process, it is contrary to the development of green chemistry, thus limiting its further application.

Chinese patent CN201310287422.7 discloses a fatty acyl (-N,N-dialkyl) diamine surfactant, and discloses a preparation method of the surfactant at the same time. The method uses oleic acid as the initial reactant, followed by Prepared by alkylation reaction, acid chloride reaction, tertiary amination reaction, etc. In addition, the application of the fatty acyl (-N, N-dialkyl) diamine surfactant in oil field development is also disclosed. The obtained aliphatic diamide surfactant has good properties and is a potential substitute for most of the surfactants (such as petroleum sulfonate and alkylbenzene sulfonate) currently used in oilfields. However, this patent still has the following disadvantages and deficiencies: 1) Benzene and its homologues are used as alkylation raw materials, and benzene, toluene and other benzene homologues have been listed as carcinogens (benzene is a first-class carcinogen, and toluene is three carcinogens, ethylbenzene is a 2B carcinogen), and the LD50 of benzene is 930mg/kg, which is moderately toxic. Toluene is a precursor compound, subject to application restrictions, ethylbenzene is highly irritating to human skin; 2) Thionyl chloride is used as the acyl chloride reagent in the synthesis process, and thionyl chloride is more irritating to humans , when meeting with water and high temperature, it is easy to decompose and form toxic gases such as sulfur dioxide and hydrogen chloride, which is not conducive to environmental protection; 3) The obtained surfactant is a diamine-type surfactant, which is a cationic surfactant. Easy to decompose characteristics, thus limiting its scope of application.

Contents of the invention

The purpose of the present invention is exactly to provide benzyloxy-oleoyl quaternary ammonium surfactant and preparation method thereof and application, specifically to provide a kind of high benzyloxy-oleoyl quaternary ammonium surfactant of surface activity and its A preparation method with short reaction time and mild reaction conditions and its application in tertiary oil recovery.

The purpose of the present invention can be achieved through the following technical solutions:

A kind of benzyloxy-oleoyl quaternary ammonium surfactant, its structural formula is as shown in formula (I) or formula (II):

(I) (II)

Wherein, m and n are the number of methylene groups (-CH ₂ -) at corresponding positions, and m+n=15, m is an integer of 0-11, and n is an integer of 4-15.

A kind of preparation method of benzyloxy-oleoyl quaternary ammonium surfactant, comprises the following steps:

1) Mix fatty acid, anisole, and FeCl ₃ and carry out alkylation reaction to obtain the first intermediate product;

2) mixing the first intermediate product with 3-dimethylaminopropylamine and performing amidation reaction to obtain the second intermediate product;

3) Mix the second intermediate product, chlorinated organic acid salt, and sodium carbonate in ethanol/water solution, and perform quaternization reaction to obtain the surfactant.

Further, in step 1), the fatty acid is oleic acid or its methyl ester, methyl oleate;

The position of the double bond of oleic acid is 9-10, and the reaction product with anisole has two situations of ortho and para. However, due to positional isomerization at the carbon chain, the benzyloxy group in the product will The 6-17 position of the chain appears, and this rearrangement has no effect on the adjacent-para position reaction. It can be determined that m+n=15, but due to positional isomerism, all products will appear within this range, so it is impossible to determine m and The specific value of n (should be normal distribution trend). Fig. 1 is the proton nuclear magnetic resonance spectrogram of a kind of benzyloxy group-oleoyl quaternary ammonium type surfactant prepared by the present invention, because nuclear magnetic resonance spectrogram can't distinguish the isomer that produces because of positional isomerism, so proton nuclear magnetic resonance spectrum The whole is orderly but the details are messy, such as the split peaks of the methyl peak and the methylene peak. After zooming in, it will be found that there are more than 20 split peaks.

The molar ratio between the fatty acid, anisole, and FeCl is 1:( _3-8 ):(0.5-1.2), and there is no sequence requirement for adding the above-mentioned reactants, and _FeCl is solid and insoluble in The reaction system, therefore, can be recovered by filtration after the reaction, so as to be reused and reduce the cost of raw materials.

For the alkylation reaction in step 1), experiments have shown that if the traditional Lewis acid catalyst _AlCl3 is used, the structure of the product will change, and some benzyloxy products will be decomposed into phenylhydroxy products, thereby affecting the structure and performance of the product; if using A protonic acid catalyst (such as methanesulfonic acid) will intensify the isomerization of the product and form more rearrangement products, so the present invention uses _FeCl3 as the catalyst for the alkylation reaction.

Further, in step 1), in the alkylation reaction, the reaction temperature is 50-85°C, and the reaction time is 2-8h. Wherein the high temperature of the alkylation reaction will aggravate the isomerization of the product, so that a large amount of 9 or 10-benzyloxy group is converted into a positional isomer at the 6-17 position, and too little catalyst consumption will reduce the product conversion rate. If only 0.02 mol FeCl ₃ is added, the conversion rate of alkylation is less than 50%.

Further, the molar ratio of the 3-dimethylaminopropylamine in step 2) to the fatty acid in step 1) is (1-3):1.

Further, in step 2), in the amidation reaction, the reaction temperature is 135-165° C., the reaction time is 5-12 h, and the reaction solvent is preferably ethylbenzene. Wherein the amidation reaction temperature is too low can cause the added 3-dimethylaminopropylamine to fail to reach the boiling point, and the reaction cannot be refluxed, resulting in the inability to separate the formed water (or methanol), which affects the progress of the reaction.

Further, the molar ratio of the chlorinated organic acid salt in step 3), sodium carbonate to the fatty acid in step 1) is (1-2):(1-2):1;

For the surfactant with the structural formula shown in formula (I), the chlorinated organic acid salt is sodium 3-chloro-2-hydroxypropanesulfonate;

For the surfactant with the structural formula (II), the chlorinated organic acid salt is sodium chloroacetate.

Wherein, the too low amount of organic acid salt will cause the yield to decline, because the interfacial tension of the amidation product is very poor, if a large amount of amidation products are mixed in the product, the interfacial tension performance will be poor.

Further, in step 3), in the quaternization reaction, the reaction temperature is 85-105° C., and the reaction time is 6-12 h.

Further, the volume ratio of ethanol/water solution to fatty acid in step 3) is (3-10):1, and the volume ratio of ethanol to water is (1-2):1.

Further, in step 3), after the quaternization reaction product is removed from the reaction solvent ethanol/water solution, it can be extracted with methanol, and after separation, the extraction solvent methanol can be evaporated to obtain the surfactant.

The application of a benzyloxy-oleoyl quaternary ammonium surfactant comprises using the surfactant for tertiary oil recovery.

Oil-water interfacial tension, as the name suggests, is the surface tension between crude oil and aqueous solution interface. The value of interfacial tension is closely related to the structure of each component. Usual tensio-active agent is made up of hydrophilic group and hydrophobic group two parts, because the composition of crude oil contains alkane and aromatic compound of different lengths, consider this point, the present invention introduces benzyloxyl group at long-chain hydrophobic group, Due to the relatively weak polarity of the benzyloxy group, it can further interact with crude oil at the hydrophobic chain end. Due to their strong hydrophilicity, the hydroxyl and sulfonic acid groups act as hydrophilic groups in the compound, thus forming Oil-in-water structure. In addition, a good surfactant needs to achieve a hydrophilic-lipophilic balance, usually expressed by HLB value. The HLB value of the benzyloxysulfonic acid type quaternary ammonium salt surfactant in the present invention is calculated to be 18.053, which proves that its hydrophilic-lipophilic balance is good.

Compared with the prior art, the present invention has the following characteristics:

1) The present invention uses oleic acid as the main chain of the surfactant, replaces benzene series with anisole as the raw material for the alkylation reaction, optimizes the structure of the traditional phenyl octadecanoic acid, and undergoes alkylation reaction, amide After chemical reaction and quaternization reaction, the obtained surfactant is a quaternary ammonium salt type amphoteric surfactant, the oil-water interfacial tension can reach 5×10 ^-4 mN/m at the lowest, and it has good salt resistance, and its anti-calcium The ion concentration can reach 2g/L, so it has great application potential in the tertiary oil recovery industry;

2) The raw material anisole used in the present invention can be extracted from fennel, also known as anisole, which is derived from tarragon essential oil and can be applied to food spices. Its LD50 is 3750mg/kg, which belongs to the low toxicity category and is There is no significant harm to the environment and humans; the oleic acid used can be obtained from animals and plants, has a wide range of sources, and is cheap and easy to obtain;

3) The present invention omits the acid chlorination reaction, and uses diamine and alkylation product to directly react at a certain temperature, thereby avoiding the generation of toxic gas;

4) The present invention has the advantages of raw materials, mild reaction conditions, low energy consumption, less side reactions, high yield, stable product properties, low toxicity, good degradability, etc., and conforms to the development concept of green chemistry.

Description of drawings

Fig. 1 is the proton nuclear magnetic resonance spectrogram of final product benzyloxy group-oleoyl quaternary ammonium type surfactant in embodiment 1;

Fig. 2 is the gas chromatography-mass spectrogram of the first intermediate product benzyloxy octadecanoic acid in embodiment 2; Wherein the upper figure is a gas chromatogram (total ion flow diagram), and the lower figure is a mass spectrogram;

Fig. 3 is the gas chromatography-mass spectrogram of the second intermediate product benzyloxy octadecamide in embodiment 2; Wherein the upper figure is a gas chromatogram (total ion flow diagram), and the lower figure is a mass spectrogram;

Fig. 4 is the liquid chromatogram of sulfoquaternary ammonium salt type surfactant in embodiment 2.

Fig. 5 is the high-efficiency liquid chromatography-mass spectrum of the final product benzyloxy-oleoyl quaternary ammonium surfactant in Example 3; the upper figure is an ultraviolet detection figure (wavelength 216nm), and the lower figure is a mass spectrum;

Fig. 6 is the high-efficiency liquid chromatography-mass spectrum of the final product benzyloxy-oleoyl quaternary ammonium surfactant in Example 4; the upper figure is an ultraviolet detection figure (wavelength 216nm), and the lower figure is a mass spectrum;

Fig. 7, Fig. 8 are the measurement data figure that the interfacial tension of sulfoquaternary ammonium salt type surfactant solution changes with concentration in embodiment 7;

Fig. 9 is the measurement data figure that the interfacial tension of carboxylate quaternary ammonium salt type surfactant solution changes with concentration in embodiment 7;

Fig. 10 is the measurement data diagram of the interfacial tension of the sulfoquaternary ammonium salt type surfactant solution under different oil sand adsorption times in embodiment 8;

Fig. 11 is the measurement data figure of the interfacial tension of sulfoquaternary ammonium salt type surfactant solution under different NaCl concentrations in embodiment 9;

Fig. 12 is the measurement data figure of the interfacial tension of carboxylate quaternary ammonium salt type surfactant solution under different NaCl concentrations in embodiment 9;

Fig. 13, Fig. 14 are the measurement data figure of the interfacial tension of sulfoquaternary ammonium salt type surfactant solution in different Ca in embodiment ¹⁰ under the concentration;

Fig. 15 is a measurement data diagram of the interfacial tension of the carboxylic acid-based quaternary ammonium salt surfactant solution in Example 10 at different Ca ²⁺ concentrations.

Detailed ways

The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments.

A kind of benzyloxy-oleoyl quaternary ammonium surfactant, its structural formula is as shown in formula (I) or formula (II):

(I) (II)

Wherein, m and n are the number of methylene groups (-CH ₂ -) at corresponding positions, and m+n=15, m is an integer ranging from 0-11, and n is an integer ranging from 4-15.

A kind of preparation method of benzyloxy-oleoyl quaternary ammonium surfactant, comprises the following steps:

1) Mix fatty acid, anisole, and FeCl ₃ and carry out alkylation reaction at 50-85°C for 2-8 h to obtain the first intermediate product;

2) Mix the first intermediate product with 3-dimethylaminopropylamine and perform amidation reaction at 135-165°C for 5-12 h to obtain the second intermediate product;

3) Mix the second intermediate product, chlorinated organic acid salt, and sodium carbonate in ethanol/water solution, and perform a quaternization reaction at 85-105°C for 6-12 h to obtain benzyloxy-oleoyl quaternary Ammonium type surfactant.

Wherein, fatty acid is oleic acid or its methyl ester compound, methyl oleate; The mol ratio of fatty acid, anisole, FeCl ₃ , 3-dimethylaminopropylamine, chlorinated organic acid salt, sodium carbonate is 1:(3- 8):(0.5-1.2):(1-3):(1-2):(1-2).

For the surfactant shown in the formula (I), the chlorinated organic acid salt is sodium 3-chloro-2-hydroxypropanesulfonate; for the surfactant shown in the formula (II), the chlorinated organic acid The salt is sodium chloroacetate.

In the alkylation reaction, the reaction temperature is preferably 65°C, and the reaction time is preferably 6 h; in the amidation reaction, the reaction temperature is preferably 160°C, the reaction time is preferably 8 h, and the reaction solvent is preferably ethylbenzene; the quaternization reaction Among them, the reaction temperature is preferably 95°C, the reaction time is preferably 10 h, the volume ratio of ethanol/water solution to fatty acid is 7:1, and the volume ratio of ethanol to water is 2:1.

For the separation and purification method of the reaction product, after the alkylation reaction, since _FeCl3 is added as a catalyst and is a solid insoluble in the reaction system, it can be recovered by filtration after the reaction for repeated use, reducing the cost of raw materials. For the quaternization reaction product, after removing the reaction solvent ethanol/water solution, it can be extracted with methanol, and after separation, the extraction solvent methanol can be evaporated to obtain the benzyloxy-oleoyl quaternary ammonium surfactant.

The application of a kind of benzyloxy-oleoyl quaternary ammonium surfactant comprises that the surfactant is used in the tertiary use industry.

The following examples are carried out on the premise of the technical solutions of the present invention, and detailed implementation methods and specific operation processes are provided, but the protection scope of the present invention is not limited to the following examples.

In the following examples, the test conditions for interfacial tension include: using a spinning drop interfacial tensiometer (model TX500C), operating temperature 45°C, operating speed 4500rpm, and operating time 2h;

The oil used in the test is crude oil from Daqing Refining & Chemical Co., Ltd., with a density of 0.85g/cm ³ and a viscosity of 19.8 mPa*s (45°C). The formula of Daqing simulated formation water used in the test: NaCl 1588.3mg/L, CaCl ₂ 112.2mg/L, Na ₂ CO ₃ 381.6 mg/L, MgCl ₂ ·6H ₂ O 91.6 mg/L, Na ₂ SO ₄ 17.1 mg/L, NaHCO ₃ 3176.0 mg/L.

Example 1:

A kind of benzyloxy-oleoyl quaternary ammonium surfactant, its structural formula is as follows:

。

.

The preparation method of this tensio-active agent comprises the following steps:

1) Add 0.08 mol anisole and 0.005 mol catalyst FeCl ₃ to 0.01 mol oleic acid, and stir the reaction at 65°C for 6 h to obtain the first intermediate product;

2) Add 0.03 mol of 3-dimethylaminopropylamine to 10 mL of ethylbenzene and mix well, then add the first intermediate product, and stir the reaction at 160°C for 5 h, then evaporate the unreacted 3-dimethylaminopropylamine Propylamine, ethylbenzene and anisole, obtain the second intermediate product;

3) Prepare ethanol/water solution by mixing 30 mL ethanol and 15 mL water, then add the second intermediate product, 0.01 mol Na ₂ CO ₃ and 0.012 mol 3-chloro-2-hydroxypropanesulfonate sodium to the solution, and Stir and react at 95°C for 10 h, then distill off ethanol and water, and dissolve the remaining solid with methanol, separate the methanol phase, and evaporate methanol to dryness to obtain the above-mentioned benzyloxy-oleoyl quaternary ammonium surfactant ( The yield was 91.9%).

The H NMR spectrum is shown in Figure 1, Chemical Formula: C ₃₃ H ₆₁ N ₂ O ₆ S ⁺ , Exact Mass: 613.42.

The above-mentioned benzyloxy-oleoyl quaternary ammonium surfactant was mixed with Daqing simulated formation water to obtain 0.5 g/L and 3.0 g/L surfactant flooding system, and the interface between it and Daqing refining crude oil was characterized Tension, the results are as follows: the equilibrium interfacial tension of 0.5g/L surfactant is 5.2×10 ^-4 mN/m, and the equilibrium interfacial tension of 3.0 g/L surfactant is 2.0×10 ^-3 mN/m, all reaching super Low interfacial tension level.

Example 2:

A kind of benzyloxy-oleoyl quaternary ammonium surfactant, its structural formula is as follows:

。

.

The preparation method of this tensio-active agent comprises the following steps:

1) Add 0.03 mol anisole and 0.01 mol catalyst FeCl ₃ to 0.01 mol oleic acid, and stir the reaction at 50°C for 8 h to obtain the first intermediate product;

2) Add 0.01 mol of 3-dimethylaminopropylamine to 10 mL of ethylbenzene and mix well, then add the first intermediate product, and stir and react at 160°C for 5 h, then evaporate unreacted 3-dimethylaminopropylamine Propylamine, ethylbenzene and anisole, obtain the second intermediate product;

3) Prepare ethanol/water solution by mixing 30 mL ethanol and 15 mL water, then add the second intermediate product, 0.01 mol Na ₂ CO ₃ and 0.02 mol sodium 3-chloro-2-hydroxypropanesulfonate to the solution, and Stir and react at 85°C for 6 h, then distill off ethanol and water, and use methanol to dissolve the remaining solids. After separating the methanol phase, evaporate the methanol to dryness to obtain the above-mentioned benzyloxy-oleoyl quaternary ammonium surfactant ( The yield was 47.6%).

Product structure characterization:

The gas chromatography-mass spectrogram of the first intermediate product benzyloxy octadecanoic acid is as shown in Figure 2; the gas chromatography-mass spectrogram of the second intermediate product benzyloxy octadecanoic acid is as shown in Figure 3, two kinds of intermediate products The detection conditions include: injection volume: 1 μL; initial temperature: 120°C; gradient conditions: 0-12 min, 120-300°C, 12-62 min, 300°C, split ratio 30:1;

The high-performance liquid chromatography-mass spectrogram of the final product benzyloxy-oleoyl quaternary ammonium surfactant is shown in Figure 4. The detection conditions include: injection volume: 5 μL; detection wavelength: 216 nm; flow rate: 1.0 mL /min; gradient conditions: 0-2 min, 95% methanol, 2-12 min, 95-100% methanol, 12-30 min, 100% methanol.

Example 3:

A kind of benzyloxy group-oleoyl quaternary ammonium surfactant, its preparation method comprises the following steps:

1) Add 0.08 mol anisole and 0.005 mol catalyst FeCl ₃ to 0.01 mol oleic acid, and stir the reaction at 65°C for 2 h to obtain the first intermediate product;

2) Add 0.03 mol 3-dimethylaminopropylamine to 10 mL ethylbenzene and mix well, then add the first intermediate product, and stir at 160°C for 12 h, then distill off the unreacted 3-dimethylaminopropylamine Propylamine, ethylbenzene and anisole, obtain the second intermediate product;

3) Prepare ethanol/water solution by mixing 30 mL ethanol and 15 mL water, then add the second intermediate product, 0.01 mol Na ₂ CO ₃ and 0.02 mol sodium 3-chloro-2-hydroxypropanesulfonate to the solution, and Stir and react at 95°C for 12 h, then evaporate ethanol and water, and use methanol to dissolve the remaining solids. After separating the methanol phase, evaporate methanol to dryness to obtain the above-mentioned benzyloxy-oleoyl quaternary ammonium surfactant ( The yield was 75.2%).

The characterization spectrum of the final product benzyloxy-oleoyl quaternary ammonium surfactant is shown in Figure 5.

Example 4:

A kind of benzyloxy-oleoyl quaternary ammonium surfactant, its structural formula is as follows:

。

.

The preparation method of this tensio-active agent comprises the following steps:

1) Add 0.08 mol anisole and 0.012 mol catalyst FeCl ₃ to 0.01 mol oleic acid, and stir the reaction at 85°C for 6 h to obtain the first intermediate product;

2) Add 0.012 mol of 3-dimethylaminopropylamine to 10 mL of ethylbenzene and mix well, then add the first intermediate product, and stir the reaction at 130°C for 5 h, then evaporate the unreacted 3-dimethylaminopropylamine Propylamine, ethylbenzene and anisole, obtain the second intermediate product;

3) Prepare ethanol/water solution by mixing 30 mL ethanol and 15 mL water, then add the second intermediate product, 0.02 mol Na ₂ CO ₃ and 0.02 mol sodium chloroacetate to the solution, and stir the reaction at 95°C for 6 h After that, ethanol and water were evaporated, and methanol was used to dissolve the remaining solids. After the methanol phase was separated, methanol was evaporated to dryness to obtain the above-mentioned benzyloxy-oleoyl quaternary ammonium surfactant (yield: 89.3%).

The high-performance liquid chromatography-mass spectrogram of the final product benzyloxy-oleoyl quaternary ammonium surfactant is shown in Figure 6. The detection conditions include: injection volume: 5 μL; detection wavelength: 216 nm; flow rate: 1.0 mL /min; gradient conditions: 0-2 min, 95% methanol, 2-12 min, 95-100% methanol, 12-30 min, 100% methanol.

Example 5:

A kind of benzyloxy group-oleoyl quaternary ammonium surfactant, its preparation method comprises the following steps:

1) Add 0.05 mol anisole and 0.01 mol catalyst FeCl ₃ to 0.01 mol oleic acid, and stir the reaction at 65°C for 6 h to obtain the first intermediate product;

2) Add 0.03 mol 3-dimethylaminopropylamine to 10 mL ethylbenzene and mix well, then add the first intermediate product, and stir at 165°C for 5 h, then distill off unreacted 3-dimethylaminopropylamine Propylamine, ethylbenzene and anisole, obtain the second intermediate product;

3) Prepare ethanol/water solution by mixing 30 mL ethanol and 15 mL water, then add the second intermediate product, 0.01 mol Na ₂ CO ₃ and 0.01 mol sodium chloroacetate to the solution, and stir the reaction at 85°C for 6 h After that, ethanol and water were evaporated, and methanol was used to dissolve the remaining solids. After the methanol phase was separated, methanol was evaporated to dryness to obtain the above-mentioned benzyloxy-oleoyl quaternary ammonium surfactant (yield: 73.0%).

Embodiment 6:

A kind of benzyloxy group-oleoyl quaternary ammonium surfactant, its preparation method comprises the following steps:

1) Add 0.08 mol anisole and 0.01 mol catalyst FeCl ₃ to 0.01 mol oleic acid, and stir the reaction at 65°C for 8 h to obtain the first intermediate product;

2) Add 0.03 mol of 3-dimethylaminopropylamine to 10 mL of ethylbenzene and mix well, then add the first intermediate product, and stir the reaction at 160°C for 5 h, then evaporate the unreacted 3-dimethylaminopropylamine Propylamine, ethylbenzene and anisole, obtain the second intermediate product;

3) Prepare ethanol/water solution by mixing 30 mL ethanol and 15 mL water, then add the second intermediate product, 0.02 mol Na ₂ CO ₃ and 0.012 mol sodium chloroacetate to the solution, and stir the reaction at 105°C for 6 h After that, ethanol and water were evaporated, and methanol was used to dissolve the remaining solids. After the methanol phase was separated, the methanol was evaporated to dryness to obtain the above-mentioned benzyloxy-oleoyl quaternary ammonium surfactant (yield: 78.3%).

Embodiment 7:

In this example, the sulfoquaternary ammonium salt surfactant prepared in Example 1 and the carboxylate quaternary ammonium salt surfactant prepared in Example 4 were respectively added to the simulated formation water, and the results obtained under different dosages were investigated. Interfacial tension development of surfactant solutions.

The test results are as follows:

As shown in Figure 7 and Figure 8, the interfacial tension of the sulfoquaternary ammonium salt surfactant solution at a concentration of 0.02-3 g/L can be lower than 1×10 ^-2 mN/m, and the lowest can reach 5.2×10 ^-4 mN/m; as shown in Figure 9, the interfacial tension of the carboxylic acid-based quaternary ammonium salt surfactant solution at a concentration of 0.02-3 g/L can be lower than 10 ^-2 mN/m, and the lowest can reach 4.5 ×10 ^-4 mN/m.

Embodiment 8:

In this example, a sulfoquaternary ammonium salt-type surfactant solution with a concentration of 3 g/L was prepared using the same method as in Example 7, and the interfacial tension change of the surfactant solution after repeated oil sand adsorption was investigated. The test method is as follows :

Mix the surfactant solution and the oil sand at a mass ratio of 9:1, shake and rotate at a constant temperature in a shaker at 120 rpm at 45°C for 24 h, centrifuge to take the supernatant to test its interfacial tension, and then put the supernatant Mix again with oil sand according to the ratio of mass ratio 9:1, repeat above experiment 5 times;

Among them, the oil sand is taken from the oil sand collected by the sixth oil production plant of Daqing Oilfield Co., Ltd., extracted three times in sufficient petroleum ether and chloroform before the experiment, and crushed into 80-120 mesh oil sand particles after drying.

The test results are as follows:

As shown in Figure 10, the interfacial tension of the sample solution can be lower than 1×10 ⁻² mN/m after four times of adsorption.

Embodiment 9:

The present embodiment adopts the method preparation concentration with embodiment 7 to be the sulfoquaternary ammonium salt type surfactant solution of 0.5 g/L, and the carboxylate quaternary ammonium salt type surfactant solution that concentration is 0.5 g/L, and Add an appropriate amount of NaCl to it respectively to form NaCl surfactant solutions with different concentrations, and then investigate the development of its interfacial tension. The test results are as follows:

As shown in Figure 11, for the 0.5 g/L sulfoquaternary ammonium salt surfactant solution, when the concentration of NaCl is lower than 50 g/L, the interfacial tension can be reduced to below 1×10 ^-2 mN/m; As shown in Figure 12, for 0.5 g/L carboxylate-based quaternary ammonium salt surfactant solution, when the NaCl concentration is lower than 70 g/L, the interfacial tension can develop below 10 ^-2 mN/m.

Example 10:

The present embodiment adopts the method preparation concentration with embodiment 7 to be the sulfoquaternary ammonium salt type surfactant solution of 0.5 g/L, and the carboxylate quaternary ammonium salt type surfactant solution that concentration is 0.5 g/L, and Add an appropriate amount of CaCl ₂ to it to form Ca ²⁺ surfactant solutions with different concentrations, and then investigate the development of the interfacial tension. The test results are as follows:

As shown in Figure 13 and Figure 14, for the 0.5 g/L sulfoquaternary ammonium salt surfactant solution, when the concentration of Ca ²⁺ is below 2.0 g/L, the interfacial tension is lower than 1×10 ^{- 2} mN/m; as shown in Figure 15, for 0.5 g/L carboxylate quaternary ammonium salt surfactant solution, when the Ca ²⁺ concentration is lower than 2 g/L, the interfacial tension is lower than 10 ^{- 2} mN/m.

The above descriptions of the embodiments are for those of ordinary skill in the art to understand and use the invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described here to other embodiments without creative efforts. Therefore, the present invention is not limited to the above-mentioned embodiments. Improvements and modifications made by those skilled in the art according to the disclosure of the present invention without departing from the scope of the present invention should fall within the protection scope of the present invention.

Claims (6)

1. A preparation method of a benzyloxy-oleoyl quaternary ammonium surfactant is characterized by comprising the following steps:

1) Mixing fatty acid, anisole and FeCl ₃ Mixing and carrying out alkylation reaction to obtain a first intermediate product;

wherein the fatty acid is oleic acid or methyl oleate; the fatty acid, the anisole and the FeCl ₃ The mol ratio of the components is 1 (3-8) to 0.5-1.2; in the alkylation reaction, the reaction temperature is 50-85 ℃ and the reaction time is 2-8 h;

2) Mixing the first intermediate product with 3-dimethylaminopropylamine and carrying out amidation reaction to obtain a second intermediate product;

wherein, in the amidation reaction, the reaction temperature is 135-165 ℃, and the reaction time is 5-12 h;

3) Mixing the second intermediate product, the chlorinated organic acid salt and sodium carbonate in an ethanol/water solution, and carrying out quaternization reaction to obtain the surfactant;

wherein, the mol ratio of the chlorinated organic acid salt and the sodium carbonate in the step 3) to the fatty acid in the step 1) is (1-2) to 1;

the chlorinated organic acid salt is 3-chloro-2-hydroxy sodium propanesulfonate or sodium chloroacetate.

2. The method for preparing a benzyloxy-oleoyl quaternary ammonium surfactant according to claim 1, wherein the molar ratio of 3-dimethylaminopropylamine in step 2) to the fatty acid in step 1) is (1-3): 1.

3. The method for preparing benzyloxy-oleoyl quaternary ammonium surfactant according to claim 1, wherein in step 3), the reaction temperature is 85-105 ℃ and the reaction time is 6-12 h.

4. The method for preparing benzyloxy-oleoyl quaternary ammonium surfactant according to claim 1, wherein the volume ratio of ethanol/water solution to fatty acid in step 3) is (3-10): 1, and the volume ratio of ethanol to water is (1-2): 1.

5. A benzyloxy-oleoyl quaternary ammonium type surfactant, characterized in that it is prepared by the method of any claim 1 to 4, and the structural formula of the surfactant is shown as formula (I) or formula (II):

（I） （II）

wherein m =0-11,n =4-15 and m + n =15.

6. Use of a benzyloxy-oleoyl quaternary ammonium surfactant according to claim 5, characterized in that said surfactant is used for tertiary oil recovery.

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