CN113930249B - Benzyloxy-oleoyl quaternary ammonium surfactant and its preparation method and use - Google Patents
Benzyloxy-oleoyl quaternary ammonium surfactant and its preparation method and use Download PDFInfo
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Abstract
The invention relates to a benzyloxy-oleoyl quaternary ammonium surfactant, a preparation method and application thereof, wherein the structural formula of the surfactant is shown as the formula (I) or the formula (II):
wherein m =0-11, n =4-15, and m + n =15. The preparation method comprises the following steps: firstly, fatty acid, anisole and FeCl are added 3 Mixing and carrying out alkylation reaction; then mixing with 3-dimethylaminopropylamine and carrying out amidation reaction; and finally, mixing the intermediate product with chlorinated organic acid salt and sodium carbonate in an ethanol/water solution, and carrying out quaternization reaction to obtain the surfactant. Compared with the prior art, the invention adopts oleic acid obtained from animals and plants and anisole extracted from fennel to replace benzene as raw materials, carries out structure optimization on the traditional phenyloctadecanoic acid, and obtains the surfactant with the lowest oil-water interfacial tension of 5 multiplied by 10 after alkylation reaction, amidation reaction and quaternization reaction in sequence ‑4 mN/m has larger application potential in the tertiary oil recovery industry.
Description
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
Surfactants can be classified as petroleum-based surfactants, biosurfactants, and the like, depending on the source of the hydrophobic group. The most widely used surfactant at present is a petroleum-based surfactant, the main source of which is petrochemical. The bio-based surfactant is different from the traditional petroleum-based surfactant and is a surfactant which takes renewable biomass as a main source. Since the 50 s of the 20 th century, petroleum products were widely used as a source of hydrophobic groups for surfactants. The share of petroleum-based surfactants in the total surfactant production has declined since the 90 s due to safety, environmental protection, and sustainable development. Biomass resources are considered to be one of the best sources of replacement for fossil resources. For over a hundred years, petroleum and natural gas have provided a large number of fuels and other chemical feedstocks for people's productive life, supporting the rapid development of global economy. Over the past decades, depletion of oil reservoirs, increased production costs and worsening of environmental pollution have forced people to find chemicals that can replace those from oil and gas. Safety has become a focus of social attention, and sustainable development is the subject of social development. Sustainable chemistry includes not only resources, but also sustainability of chemical production processes. In the production of chemical agents, skin care products and pharmaceutical agents, the most important goals of sustainable chemistry are the development of non-toxic biodegradable compounds, the improvement of 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 that are derived from renewable resources and that are produced by means of clean and sustainable technologies. The focus on achieving this desire is how to obtain surfactants that are both mild, biodegradable and excellent in performance and are cost effective.
The renewable hydrophobic base of bio-based surfactants is mostly derived from fatty acids in vegetable or animal oils, as well as proteins and carbohydrates. The natural oil has the characteristics of high yield, low cost, strong general applicability, good environmental compatibility and the like, is widely applied to the synthetic source of the bio-based surfactant in recent years, and becomes a research hotspot in the industrial and academic fields. Fatty acids obtained from vegetable oils are commonly lauric (C12), myristic (C14), palmitic (C16) and stearic (C18), oleic (C18), linoleic (C18) and ricinoleic (C18) acids. In the process from the feedstock oil to the desired surfactants and surfactant precursors, oleochemical processes are used to convert triglycerides, such as hydrogenation, hydrolysis, transesterification reduction, sulfonation, chlorination, glycosidation, and the like.
Liquid-liquid interfacial tension is also one of the main means of determining interfacial properties of two phases, as is surface tension, unlike the usually gas-liquid two phases, where the other phase, besides the aqueous phase, is usually the oil phase. In the research of tertiary oil recovery, interfacial tension is a very important measurement index and is a main means for researching chemical flooding in a laboratory. Whether or not ultra low interfacial tension can be achieved: (<10 -2 mN/m) is considered to be one of the most important indexes for enhancing oil recovery. Most of the prior surfactants capable of remarkably reducing the interfacial tension are alkylbenzene sulfonate, alkylbenzene quaternary ammonium salt type and alkylbenzene betaine type surfactants, and the interfacial tension can be reduced to 10 -3 The mN/m is less than that, but the method is contrary to the development of green chemistry because a high-toxicity compound benzene which is easy to cause cancer is adopted as a raw material in the synthetic process, thereby limiting the further application of the method.
Chinese patent CN201310287422.7 discloses a fatty acyl (-N, N-dialkyl) diamine surfactant and a preparation method of the surfactant, wherein oleic acid is used as an initial reactant, and alkylation reaction, acyl chlorination reaction, tertiary amination reaction and the like are sequentially adopted for preparation. In addition, the application of the fatty acyl (-N, N-dialkyl) diamine surfactant in oil field development is also disclosed. The resulting fatty acid amide surfactants have good performance and are potential replacements for most of the surfactants currently used in oil fields, such as petroleum sulfonates and alkylbenzene sulfonates. However, the patent has the following disadvantages and shortcomings: 1) Benzene and homologues thereof are used as alkylation raw materials, and the homologues of benzene such as benzene and toluene are listed as carcinogenic substances (benzene belongs to a class of carcinogenic substances, toluene is a class III carcinogenic substance, and ethylbenzene is a class 2B carcinogenic substance), wherein the LD50 of the benzene is 930mg/kg, and the benzene belongs to medium toxicity. Toluene belongs to a compound easy to prepare toxin and is limited by application, and ethylbenzene has strong irritation to human skin; 2) In the synthesis process, thionyl chloride is used as an acyl chlorination reagent, has large irritation to people, is easily decomposed to form toxic gases such as sulfur dioxide, hydrogen chloride and the like when meeting high temperature in water, and is not beneficial to environmental protection; 3) The obtained surfactant is a diamine surfactant, belongs to a cationic surfactant, and has the characteristic that an amine surfactant is easily decomposed by alkali, so that the application range of the surfactant is limited.
Disclosure of Invention
The invention aims to provide a benzyloxy-oleoyl quaternary ammonium surfactant, a preparation method and application thereof, in particular to a benzyloxy-oleoyl quaternary ammonium surfactant with high surface activity, a preparation method with short reaction time and mild reaction conditions and application thereof in tertiary oil recovery.
The purpose of the invention can be realized by the following technical scheme:
a benzyloxy-oleoyl quaternary ammonium surfactant has a structural formula shown as formula (I) or formula (II):
（I） （II）
wherein m and n are methylene (-CH) groups in the corresponding positions 2 -) and m + n =15, m being an integer from 0 to 11 and n being an integer from 4 to 15.
A preparation method of benzyloxy-oleoyl quaternary ammonium surfactant comprises the following steps:
1) Mixing fatty acid, anisole and FeCl 3 Mixing and carrying out alkylation reaction to obtain a first intermediate product;
2) Mixing the first intermediate product with 3-dimethylaminopropylamine and carrying out amidation reaction to obtain a second intermediate product;
3) And mixing the second intermediate product, the chlorinated organic acid salt and the sodium carbonate in an ethanol/water solution, and performing quaternization reaction to obtain the surfactant.
Further, in the step 1), the fatty acid is oleic acid or methyl ester thereof, methyl oleate;
the position of the double bond of the oleic acid is 9-10, the reaction product of the oleic acid and anisole has two conditions of ortho position and para position, but the position isomerization can occur in the carbon chain, so that the benzyloxy group in the product can appear in 6-17 positions of the carbon chain, the rearrangement has no influence on the reaction of the ortho position and the para position, and m + n =15 can be determined, but the position isomerization exists, so that all the products can appear in the range, and the specific values of m and n cannot be determined (the normal distribution trend should be presented). FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a benzyloxy-oleoyl quaternary ammonium surfactant prepared by the present invention, because the nuclear magnetic resonance spectrum can not distinguish isomers generated by position isomerism, the hydrogen spectrum is overall ordered and has disordered details, for example, the splitting peaks of methyl peak and methylene peak are amplified, and more than twenty splitting peaks are found.
The fatty acid, the anisole and the FeCl 3 The mol ratio of the reactants is 1 (3-8) to 0.5-1.2, and the addition of the reactants does not require the order, feCl 3 Is solid and insoluble in a reaction system, so the catalyst can be recovered by a filtration mode and the like after reaction so as to be repeatedly used, and the cost of raw materials is reduced.
As for the alkylation reaction in the step 1), experiments show that if the traditional Lewis acid catalyst AlCl is adopted 3 The structure of the product is changed, and partial benzyloxy products are decomposed into phenoxy products, so that the structure and the performance of the product are influenced; if a protonic acid catalyst (such as methanesulfonic acid) is used, isomerization of the product is promoted, and more rearrangement products are formed, so FeCl is used in the invention 3 As alkylation reaction catalyst.
Further, in the step 1), in the alkylation reaction, the reaction temperature is 50-85 ℃ and the reaction time is 2-8 h. Wherein, the isomerization of the product is intensified by over high alkylation reaction temperature, a large amount of 9 or 10-benzyloxy is converted into 6-17 position isomer, the conversion rate of the product is reduced by over low catalyst consumption, and if only 0.0 is added2 mol FeCl 3 Then the alkylation conversion is less than 50%.
Further, the molar ratio of 3-dimethylaminopropylamine in step 2) to the fatty acid in step 1) is (1-3): 1.
Further, in the step 2), in the amidation reaction, the reaction temperature is 135-165 ℃, the reaction time is 5-12 h, and the reaction solvent is preferably ethylbenzene. Wherein, the amidation reaction temperature is too low, which can cause that the added 3-dimethylamino propylamine can not reach the boiling point, the reaction can not flow back, the formed water (or methanol) can not be separated, and the reaction is influenced.
Further, the molar 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): 1;
for the surfactant with the structural formula shown in the formula (I), the chlorinated organic acid salt is 3-chloro-2-hydroxy sodium propanesulfonate;
for the surfactant with the structural formula shown in the formula (II), the chlorinated organic acid salt is sodium chloroacetate.
Among them, too low an amount of the organic acid salt results in a decrease in yield, and poor interfacial tension properties if a large amount of the amidation product is mixed into the product due to poor interfacial tension of the amidation product.
Further, in the step 3), in the quaternization reaction, the reaction temperature is 85-105 ℃, and the reaction time is 6-12 h.
Further, the volume ratio of the ethanol/water solution to the fatty acid in the step 3) is (3-10): 1, and the volume ratio of the ethanol to the water is (1-2): 1.
Further, in the step 3), after removing the reaction solvent ethanol/water solution from the quaternization reaction product, methanol can be adopted for extraction, and after separation, the extraction solvent methanol is removed by evaporation, so that the surfactant can be obtained.
The application of the benzyloxy-oleoyl quaternary ammonium surfactant includes applying the surfactant in tertiary oil recovery.
The oil-water interfacial tension, as the name suggests, is the surface tension between the crude oil and the aqueous solution interface. The value of the interfacial tension is closely related to the structure of each component. The conventional surfactant is composed of two parts of a hydrophilic group and a hydrophobic group, and because the components of crude oil contain alkane and aromatic compounds with different lengths, in view of the point, the invention introduces a benzyloxy group into a long-chain hydrophobic group, and because the benzyloxy group is relatively weak in polarity, the benzyl group can perform further action with the crude oil at the end of a hydrophobic chain, and a hydroxyl group and a sulfonic acid group act as hydrophilic groups in the compounds due to strong hydrophilicity, so that an oil-in-water structure is formed. In addition, a good surfactant is required to achieve the hydrophilic-lipophilic balance, usually expressed in terms of HLB value. The HLB value of the benzyloxy sulfonic acid type quaternary ammonium salt surfactant is calculated to be 18.053, which proves that the hydrophile-lipophile balance is good.
Compared with the prior art, the invention has the following characteristics:
1) The invention adopts oleic acid as a main chain of a surfactant, anisole replaces benzene series to be used as a raw material for alkylation reaction, the structure of the traditional phenyloctadecanoic acid is optimized, the obtained surfactant belongs to a quaternary ammonium salt type amphoteric surfactant after alkylation reaction, amidation reaction and quaternization reaction are carried out in sequence, and the lowest oil-water interfacial tension can reach 5 multiplied by 10 -4 mN/m, and has better salt resistance, and the calcium ion resistance concentration can reach 2g/L, so that the composite material has greater application potential in the tertiary oil recovery industry;
2) The anisole used as the raw material can be extracted from fennel, is also called anisole, is derived from tarragon essential oil, can be applied to food spices, has LD50 of 3750mg/kg, belongs to low-toxicity class, and has no obvious harm to the environment and human beings; the oleic acid can be obtained from animals and plants, and has wide sources, low price and easy obtainment;
3) The invention omits the acyl chlorination reaction, and adopts diamine and alkylation product to directly react at a certain temperature, thereby avoiding the generation of toxic gas;
4) The method has the advantages of mild raw material and reaction conditions, low energy consumption, less side reactions, high yield, stable product property, low toxicity, good degradability and the like, and conforms to the development concept of green chemistry.
Drawings
FIG. 1 is the NMR spectrum of the final product of benzyloxy-oleoyl quaternary ammonium type surfactant in example 1;
FIG. 2 is a GC-MS of a first intermediate, benzyloxyoctadecanoic acid, of example 2; wherein the upper graph is a gas chromatogram (total ion flow graph), and the lower graph is a mass spectrum graph;
FIG. 3 is a GC-MS spectrum of a second intermediate product, benzyloxy octadecanamide, obtained in example 2; wherein the upper graph is a gas chromatogram (total ion flow graph), and the lower graph is a mass spectrum graph;
fig. 4 is a liquid chromatogram of the sulfoquaternary surfactant of example 2.
FIG. 5 is a HPLC-mass spectrum of the final product of the surfactant of benzyloxy-oleoyl quaternary ammonium type in example 3; the upper graph is an ultraviolet detection graph (with the wavelength of 216 nm), and the lower graph is a mass spectrum graph;
FIG. 6 is a HPLC-MS spectrum of the final product of example 4, i.e., a benzyloxy-oleoyl quaternary ammonium surfactant; the upper graph is an ultraviolet detection graph (with the wavelength of 216 nm), and the lower graph is a mass spectrum graph;
FIGS. 7 and 8 are graphs showing the data obtained by measuring the interfacial tension of the solution of the sulfoquaternary surfactant in example 7 as a function of the concentration;
FIG. 9 is a graph of measured data for interfacial tension as a function of concentration for a quaternary ammonium carboxylate surfactant solution of example 7;
FIG. 10 is a graph of the measured data for interfacial tension of the sulfoquat type surfactant solution of example 8 at different oil sand adsorption times;
FIG. 11 is a graph showing data obtained by measuring the interfacial tension of a sulfoquaternary surfactant solution in example 9 at different NaCl concentrations;
FIG. 12 is a graph of data obtained from measurements of interfacial tension of a quaternary ammonium carboxylate surfactant solution at different NaCl concentrations in example 9;
FIGS. 13 and 14 show that the interfacial tension of the sulfoquaternary surfactant solutions of example 10 is different for Ca 2+ A graph of measured data at concentration;
FIG. 15 shows interfacial tensions at different Ca for solutions of quaternary ammonium carboxylate surfactants of example 10 2+ Graph of measurement data at concentration.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A benzyloxy-oleoyl quaternary ammonium type surfactant has a structural formula shown as formula (I) or formula (II):
（I） （II）
wherein m and n are methylene (-CH) groups in the corresponding positions 2 -) and m + n =15, m being an integer ranging from 0 to 11 and n being an integer ranging from 4 to 15.
A preparation method of a benzyloxy-oleoyl quaternary ammonium surfactant comprises the following steps:
1) Mixing fatty acid, anisole and FeCl 3 Mixing and carrying out alkylation reaction for 2-8 h at 50-85 ℃ to obtain a first intermediate product;
2) Mixing the first intermediate product with 3-dimethylaminopropylamine and carrying out amidation reaction at 135-165 ℃ for 5-12 h to obtain a second intermediate product;
3) And mixing the second intermediate product, the chlorinated organic acid salt and sodium carbonate in an ethanol/water solution, and carrying out quaternization reaction for 6-12 h at 85-105 ℃ to obtain the benzyloxy-oleoyl quaternary ammonium surfactant.
Wherein the fatty acid is oleic acid or methyl ester thereof, methyl oleate; fatty acid, anisole, feCl 3 The mol ratio of the 3-dimethylamino propylamine to the chlorinated organic acid salt to the sodium carbonate is 1 (3-8) to (0.5-1.2) to (1-3) to (1-2).
For the surfactant with the structural formula shown as the formula (I), the chlorinated organic acid salt is 3-chloro-2-hydroxy sodium propane sulfonate; for the surfactant with the structural formula shown in the formula (II), the chlorinated organic acid salt is sodium chloroacetate.
In the alkylation reaction, the reaction temperature is preferably 65 ℃, and the reaction time is preferably 6 hours; in the amidation reaction, the reaction temperature is preferably 160 ℃, the reaction time is preferably 8 hours, and the reaction solvent is preferably ethylbenzene; in the quaternization reaction, the reaction temperature is preferably 95 ℃, the reaction time is preferably 10 h, the volume ratio of the ethanol/water solution to the fatty acid is 7.
For the separation and purification method of the reaction product, after the alkylation reaction, the reaction product is separated from FeCl 3 The catalyst is added as a solid which is insoluble in a reaction system, so the catalyst can be recovered by a filtration mode and the like after the reaction so as to be reused, thereby reducing the cost of raw materials. For the quaternization reaction product, after removing the reaction solvent ethanol/water solution, methanol can be adopted for extraction, and after separation, the extraction solvent methanol is removed by evaporation, thus obtaining the benzyloxy-oleoyl quaternary ammonium surfactant.
The application of the benzyloxy-oleoyl quaternary ammonium surfactant comprises that the surfactant is used in the industry of tertiary adoption.
The following examples are given in detail to illustrate the embodiments and specific procedures of the present invention, but the scope of the present invention is not limited to the following examples.
In the following examples, the interfacial tension test conditions include: adopting a rotary drop interfacial tension meter (model TX 500C), wherein the working temperature is 45 ℃, the running speed is 4500rpm, and the running time is 2h;
the oil for testing is Daqing refined crude oil with the density of 0.85g/cm 3 Viscosity 19.8 mpa · s (45 ℃), test daqing simulated formation water formulation: 1588.3mg/L of NaCl, caCl 2 112.2mg/L，Na 2 CO 3 381.6mg/L，MgCl 2 ·6H 2 O 91.6mg/L，Na 2 SO 4 17.1mg/L，NaHCO 3 3176.0mg/L。
Example 1:
a benzyloxy-oleoyl quaternary ammonium surfactant, its structural formula is as follows:
the preparation method of the surfactant comprises the following steps:
1) 0.08 mol of anisole and 0.005 mol of catalyst FeCl are added into 0.01 mol of oleic acid 3 Stirring and reacting for 6 hours at 65 ℃ to obtain a first intermediate product;
2) Adding 0.03 mol of 3-dimethylaminopropylamine into 10 mL of ethylbenzene, uniformly mixing, then adding a first intermediate product, stirring at 160 ℃ for reacting for 5 hours, and then evaporating unreacted 3-dimethylaminopropylamine, ethylbenzene and anisole to obtain a second intermediate product;
3) Mixing 30 mL of ethanol and 15 mL of water to prepare an ethanol/water solution, and adding a second intermediate product and 0.01 mol of Na into the solution 2 CO 3 And 0.012 mol of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, stirring and reacting for 10 hours at 95 ℃, then evaporating to remove ethanol and water, dissolving the residual solid by adopting methanol, separating the methanol phase, and evaporating to dryness the methanol to obtain the benzyloxy-oleoyl quaternary ammonium surfactant (the yield is 91.9%).
The NMR spectrum is shown in FIG. 1, chemical Formula: C 33 H 61 N 2 O 6 S + ，Exact Mass: 613.42。
Mixing the benzyloxy-oleoyl quaternary ammonium type surface activity with Daqing simulated formation water to obtain a 0.5 g/L and 3.0 g/L surfactant oil displacement system, and characterizing the interfacial tension between the surfactant oil displacement system and Daqing refined crude oil, wherein the results are as follows: 0.5 The equilibrium interfacial tension of the g/L surfactant is 5.2X 10 -4 The equilibrium interfacial tension of the surfactant with mN/m,3.0 g/L is 2.0X 10 -3 mN/m, all reach the ultra-low interfacial tension level.
Example 2:
a benzyloxy-oleoyl quaternary ammonium surfactant, its structural formula is as follows:
the preparation method of the surfactant comprises the following steps:
1) 0.03 mol of anisole and 0.01 mol of catalyst FeCl are added into 0.01 mol of oleic acid 3 Stirring and reacting for 8 hours at 50 ℃ to obtain a first intermediate product;
2) Adding 0.01 mol of 3-dimethylaminopropylamine into 10 mL of ethylbenzene, uniformly mixing, then adding the first intermediate product, stirring at 160 ℃ for reaction for 5 hours, and then evaporating unreacted 3-dimethylaminopropylamine, ethylbenzene and anisole to obtain a second intermediate product;
3) Mixing 30 mL of ethanol and 15 mL of water to prepare an ethanol/water solution, and adding a second intermediate product and 0.01 mol of Na into the solution 2 CO 3 And 0.02 mol of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, stirring the mixture at 85 ℃ for reaction for 6 hours, evaporating ethanol and water, dissolving the residual solid by using methanol, separating a methanol phase, and evaporating the methanol to dryness to obtain the benzyloxy-oleoyl quaternary ammonium surfactant (the yield is 47.6%).
And (3) product structure characterization:
the gas chromatography-mass spectrum of the first intermediate product of the benzyloxy octadecanoic acid is shown in figure 2; the gas chromatography-mass spectrum of the second intermediate product benzyloxy-octadecanamide is shown in fig. 3, and the detection conditions of the two intermediate products both comprise: sample injection amount: 1. mu L; initial temperature: 120 ℃; gradient conditions: 0-12 min,120-300 ℃,12-62 min,300 ℃, and a split ratio of 30;
the high performance liquid chromatography-mass spectrum of the final product benzyloxy-oleoyl quaternary ammonium surfactant is shown in figure 4, and the detection conditions comprise: sample introduction amount: 5. mu L; 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 benzyloxy-oleoyl quaternary ammonium type surfactant, its preparation method includes the following steps:
1) 0.08 mol of anisole and 0.005 mol of catalyst FeCl are added into 0.01 mol of oleic acid 3 Stirring and reacting for 2 hours at 65 ℃ to obtain a first intermediate product;
2) Adding 0.03 mol of 3-dimethylaminopropylamine into 10 mL of ethylbenzene, uniformly mixing, then adding a first intermediate product, stirring at 160 ℃ for reaction for 12 hours, and then evaporating unreacted 3-dimethylaminopropylamine, ethylbenzene and anisole to obtain a second intermediate product;
3) Mixing 30 mL of ethanol and 15 mL of water to prepare an ethanol/water solution, and adding a second intermediate product and 0.01 mol of Na into the solution 2 CO 3 And 0.02 mol of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, stirring and reacting for 12 hours at the temperature of 95 ℃, then evaporating ethanol and water, dissolving the residual solid by adopting methanol, separating a methanol phase, and evaporating the methanol to dryness to obtain the benzyloxy-oleoyl quaternary ammonium surfactant (the yield is 75.2%).
The characterization spectrum of the final product of the benzyloxy-oleoyl quaternary ammonium surfactant is shown in figure 5.
Example 4:
a benzyloxy-oleoyl quaternary ammonium surfactant, its structural formula is as follows:
the preparation method of the surfactant comprises the following steps:
1) 0.08 mol of anisole and 0.012 mol of catalyst FeCl are added into 0.01 mol of oleic acid 3 Stirring and reacting for 6 h at 85 ℃ to obtain a first intermediate product;
2) Adding 0.012 mol of 3-dimethylaminopropylamine into 10 mL of ethylbenzene, uniformly mixing, then adding the first intermediate product, stirring at 130 ℃ for reaction for 5 hours, and then evaporating unreacted 3-dimethylaminopropylamine, ethylbenzene and anisole to obtain a second intermediate product;
3) Mixing 30 mL of ethanol and 15 mL of waterTo this solution was added a second intermediate product, 0.02 mol Na 2 CO 3 And 0.02 mol of sodium chloroacetate, stirring and reacting for 6 h at 95 ℃, then evaporating ethanol and water, dissolving the residual solid by adopting methanol, separating a methanol phase, and evaporating the methanol to dryness to obtain the benzyloxy-oleoyl quaternary ammonium type surfactant (the yield is 89.3%).
The high performance liquid chromatography-mass spectrum of the final product benzyloxy-oleoyl quaternary ammonium surfactant is shown in fig. 6, and the detection conditions include: sample introduction amount: 5. mu.L; 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 benzyloxy-oleoyl quaternary ammonium type surfactant, its preparation method includes the following steps:
1) 0.05 mol of anisole and 0.01 mol of catalyst FeCl are added into 0.01 mol of oleic acid 3 Stirring and reacting for 6 h at 65 ℃ to obtain a first intermediate product;
2) Adding 0.03 mol of 3-dimethylaminopropylamine into 10 mL of ethylbenzene, uniformly mixing, then adding a first intermediate product, stirring at 165 ℃ for reacting for 5 hours, and then evaporating unreacted 3-dimethylaminopropylamine, ethylbenzene and anisole to obtain a second intermediate product;
3) Mixing 30 mL of ethanol and 15 mL of water to prepare an ethanol/water solution, and adding the second intermediate product and 0.01 mol of Na into the solution 2 CO 3 And 0.01 mol of sodium chloroacetate, stirring and reacting for 6 hours at 85 ℃, then evaporating to remove ethanol and water, dissolving the residual solid by adopting methanol, separating a methanol phase, and evaporating to dryness the methanol to obtain the benzyloxy-oleoyl quaternary ammonium type surfactant (the yield is 73.0%).
Example 6:
a benzyloxy-oleoyl quaternary ammonium type surfactant, its preparation method includes the following steps:
1) 0.08 mol of anisole and 0.01 mol of catalyst FeCl are added into 0.01 mol of oleic acid 3 And stirred at 65 deg.CReacting for 8 hours to obtain a first intermediate product;
2) Adding 0.03 mol of 3-dimethylaminopropylamine into 10 mL of ethylbenzene, uniformly mixing, then adding the first intermediate product, stirring at 160 ℃ for reaction for 5 hours, and then evaporating unreacted 3-dimethylaminopropylamine, ethylbenzene and anisole to obtain a second intermediate product;
3) Mixing 30 mL of ethanol and 15 mL of water to prepare an ethanol/water solution, and adding a second intermediate product and 0.02 mol of Na into the solution 2 CO 3 And 0.012 mol of sodium chloroacetate, stirring and reacting for 6 h at 105 ℃, then evaporating ethanol and water, dissolving the residual solid by adopting methanol, separating a methanol phase, and evaporating the methanol to dryness to obtain the benzyloxy-oleoyl quaternary ammonium type surfactant (the yield is 78.3%).
Example 7:
in this example, the sulfoquaternary surfactant prepared in example 1 and the carboxylic quaternary surfactant prepared in example 4 were added to simulated formation water, respectively, and the interfacial tension development of the resulting surfactant solutions was examined at different dosages.
The test results were as follows:
as shown in FIGS. 7 and 8, the interfacial tension of the sulfoquaternary surfactant solution can be lower than 1X 10 at a concentration of 0.02-3 g/L -2 mN/m, at least 5.2X 10 -4 mN/m; as shown in FIG. 9, the carboxylic acid quaternary ammonium salt surfactant solution has an interfacial tension of less than 10 at a concentration of 0.02-3 g/L -2 mN/m, at least 4.5X 10 -4 mN/m。
Example 8:
in this example, a sulfoquaternary ammonium salt type surfactant solution with a concentration of 3 g/L was prepared in the same manner as in example 7, and the change in interfacial tension of the surfactant solution after multiple times of oil sand adsorption was examined, as follows:
mixing the surfactant solution with the oil sand according to the mass ratio of 9 to 1, oscillating and rotating for 24 hours in a shaking table at constant temperature of 45 ℃ and 120 rpm, centrifuging to take supernatant liquid, testing the interfacial tension of the supernatant liquid, mixing the supernatant liquid with the oil sand again according to the mass ratio of 9 to 1, and repeating the experiment for 5 times;
the oil sand is collected from the oil reservoir sand collected by the sixth oil production plant of the Daqing oilfield Limited liability company, is extracted for three times in sufficient petroleum ether and chloroform before an experiment, and is dried and crushed into 80-120-mesh oil sand particles.
The test results were as follows:
as shown in FIG. 10, the interfacial tension of the sample solution after four times of adsorption may be lower than 1X 10 -2 mN/m。
Example 9:
in this example, a solution of a sulfoquaternary ammonium salt surfactant with a concentration of 0.5 g/L and a solution of a carboxylic quaternary ammonium salt surfactant with a concentration of 0.5 g/L were prepared by the same method as in example 7, and appropriate amounts of NaCl were added to the solutions to form NaCl surfactant solutions with different concentrations, and then the development of interfacial tension was examined, and the test results were as follows:
as shown in FIG. 11, for a 0.5 g/L sulfoquaternary surfactant solution, the interfacial tension can be reduced to 1X 10 when NaCl is added at a concentration of less than 50 g/L -2 mN/m or less; as shown in FIG. 12, for 0.5 g/L surfactant solution of quaternary ammonium carboxylate, the interfacial tension can be increased to 10 when NaCl is added at a concentration of less than 70 g/L -2 mN/m or less.
Example 10:
in this example, a solution of a sulfoquaternary ammonium salt surfactant having a concentration of 0.5 g/L and a solution of a carboxyquaternary ammonium salt surfactant having a concentration of 0.5 g/L were prepared in the same manner as in example 7, and an appropriate amount of CaCl was added to each of the solutions 2 Form Ca at different addition concentrations 2+ The surfactant solution is examined later on the development of the interfacial tension, and the test results are as follows:
as shown in FIGS. 13 and 14, ca was added to a 0.5 g/L solution of a sulfoquaternary surfactant 2+ When the concentration is below 2.0 g/L, the interfacial tension is lower than 1 x 10 -2 mN/m; as shown in FIG. 15, the concentration of Ca in the 0.5 g/L carboxylic acid quaternary ammonium salt surfactant solution was measured 2+ When the concentration is lower than 2g/L,the interfacial tension is less than 10 -2 mN/m。
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the 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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