CN113731297A - Amido sulfonate gemini surfactant as well as preparation method and application thereof - Google Patents
Amido sulfonate gemini surfactant as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an amido sulfonate gemini surfactant as well as a preparation method and application thereof, wherein the method comprises the following steps: mixing maleic anhydride, n-hexadecanol and anhydrous sodium acetate, heating to 85-95 ℃, and reacting for 2-4 hours to obtain maleic acid monoester; heating and dissolving maleic acid monoester, adding diethanol amine, a catalyst and a solvent after completely dissolving, stirring and reacting for 5-7 h at the temperature of 60-70 ℃, then cooling to below 10 ℃, adding a mixed solution of acryloyl chloride and the solvent, heating to 55-65 ℃, and reacting for 5-7 h to obtain an intermediate product; and adding a sodium bisulfite aqueous solution consisting of sodium bisulfite and water into the intermediate product, and carrying out heat preservation reaction for 2-4 h at the temperature of 110-130 ℃ to obtain the amido sulfonate gemini surfactant. The surfactant solves the problem of low recovery ratio of crude oil in tertiary oil recovery, has certain degradability, and reduces or avoids the harm to the environment.
Description
Technical Field
The invention relates to the technical field of surfactants, in particular to an amido sulfonate gemini surfactant as well as a preparation method and application thereof.
Background
The reactive surfactant is an important functional monomer, and has reactive groups, and can form polymer surfactants with different structures and different properties through copolymerization or self-polymerization, so that the functions and application range of the surfactant are greatly expanded. Compared with the traditional surfactant, the gemini surfactant has lower critical micelle concentration, abundant aggregate morphology, adjustable rheological behavior and the like; when the gemini surfactant contains a reactive group, a polymer with a novel structure can be formed, so that the gemini surfactant has a better application prospect. The surfactant has the advantages of high surface activity, strong solubilization, good emulsibility and wettability, strong interfacial activity, good compatibility with crude oil, less adsorption on the sandstone surface, simple production process, low cost, easy biodegradation and the like. Therefore, the amido sulfonate gemini surfactant has great application potential in the field of tertiary oil recovery, and has wide application prospect and market value.
However, the existing preparation method of the amido sulfonate gemini surfactant has the defects of complex route, high price of raw materials and poor repeatability, and influences the application value of the amido sulfonate gemini surfactant in the field of oil recovery.
Disclosure of Invention
The invention aims to provide an amido sulphonate gemini surfactant, a preparation method and application thereof, aiming at the excellent characteristics of the amido sulphonate gemini surfactant and the special requirements of tertiary oil recovery and the like on the surfactant. The amido sulfonate gemini surfactant is used as a chemical oil displacement agent to improve the recovery ratio of crude oil in tertiary oil recovery.
The technical scheme adopted by the invention is as follows:
an amido sulphonate gemini surfactant has a structural formula as follows:
a preparation method of amido sulfonate gemini surfactant comprises the following steps:
mixing maleic anhydride, n-hexadecanol and anhydrous sodium acetate, heating to 85-95 ℃, and reacting for 2-4 hours to obtain maleic acid monoester;
heating and dissolving maleic acid monoester, adding diethanol amine, a catalyst and a solvent after completely dissolving, stirring and reacting for 5-7 h at the temperature of 60-70 ℃, then cooling to below 10 ℃, adding a mixed solution of acryloyl chloride and the solvent, heating to 55-65 ℃, and reacting for 5-7 h to obtain an intermediate product;
and adding a sodium bisulfite aqueous solution consisting of sodium bisulfite and water into the intermediate product, and carrying out heat preservation reaction for 2-4 h at the temperature of 110-130 ℃ to obtain the amido sulfonate gemini surfactant.
As a further improvement of the invention, the molar ratio of the maleic anhydride to the n-hexadecanol is (1-1.1): 1.
As a further improvement of the invention, the addition amount of the anhydrous sodium acetate is 0.5 wt% of the total mass of the maleic anhydride, the hexadecanol and the anhydrous sodium acetate.
As a further improvement of the invention, the molar ratio of the maleic acid monoester to the diethanolamine is (2-2.2): 1.
As a further improvement of the invention, the catalyst is triethylamine; the solvent is acetone, and the mass ratio of the acetone is 70-80 wt% of the total mass.
As a further improvement of the invention, the molar ratio of the intermediate product to the sodium bisulfite is 1: 1.1; the mass ratio of sodium bisulfite in the sodium bisulfite aqueous solution is 40 wt%.
As a further development of the invention, the intermediate product is also subjected to a work-up step:
filtering, rotary steaming, washing with water, separating, collecting upper oily liquid, and adding anhydrous CaCl2Drying, standing overnight, filtering to remove CaCl2Obtaining a light yellow oily liquidTo the final intermediate product.
As a further improvement of the invention, the method for obtaining the amido sulfonate gemini surfactant further comprises the following post-treatment steps:
and filtering the crude product by using absolute ethyl alcohol, carrying out rotary evaporation, adding water, separating liquid, washing to remove an unreacted intermediate product, carrying out rotary evaporation to remove water, and drying to obtain the amido sulfonate gemini surfactant.
The amido sulfonate gemini surfactant is applied as a chemical oil displacement agent and is used for tertiary oil recovery; the amido sulfonate gemini surfactant is prepared into a surfactant aqueous solution, and the concentration of the surfactant aqueous solution is 0.1-0.5 wt%.
The invention has the following advantages:
the invention has simple preparation route, cheap and easily obtained raw materials and good repeatability. The amido bond is introduced, so that the surfactant has better biodegradability and stability, and the introduction of the unsaturated double bond enables the gemini surfactant to form rod-shaped micelles in a solution when the gemini surfactant has a certain concentration, and the rod-shaped micelles are continuously aggregated and intertwined with each other in the solution, so that a three-dimensional network structure is formed, the viscosity of the solution is increased, and the sand carrying capacity is improved. The invention solves the problem of low recovery ratio of crude oil in tertiary oil recovery, has certain degradability and reduces or avoids the harm to the environment.
The amido sulfonate gemini surfactant can improve the wettability, permeability and diffusivity of stratum rock and the flowability of crude oil, and is used as a chemical oil displacement agent to improve the recovery ratio.
Drawings
FIG. 1 is a surface tension diagram of an amido sulfonate gemini surfactant obtained in example 4;
FIG. 2 is a graph of the interfacial tension of an amidosulfonate gemini surfactant obtained in example 4.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to an amido sulfonate gemini surfactant and a preparation method and application thereof, wherein the surfactant has the following structural formula:
specifically, the amido sulfonate gemini surfactant and the preparation method and the application thereof comprise the following steps:
(1) sequentially adding maleic anhydride, n-hexadecanol and a certain amount of anhydrous sodium acetate into a 250mL three-neck flask with a stirring and reflux condenser, wherein the molar ratio of the maleic anhydride to the n-hexadecanol is (1-1.1): 1, and the addition amount of the anhydrous sodium acetate is 0.5 wt%. And under the protection of nitrogen, heating to 85-95 ℃ and reacting for 2-4 h to obtain a maleic monoester crude product. Recrystallizing the crude product with acetone for 2 times to obtain white crystals;
(2) heating a certain amount of maleic acid monoester to dissolve, adding diethanolamine after the maleic acid monoester is completely dissolved, adding 10mL of catalyst triethylamine and acetone, and stirring and reacting for 5-7 h at 60-70 ℃. And then, reducing the temperature to below 10 ℃, slowly dripping 2.6g of a mixed solution of acryloyl chloride and acetone by using a constant-pressure dropping funnel, and heating to 55-65 ℃ after dripping for reaction for 5-7 hours. Wherein the molar ratio of the maleic acid monoester to the diethanolamine is (2-2.2): 1, and the mass percentage of the solvent acetone is 70-80 wt%. Filtering, rotary steaming, washing with water, separating, collecting upper oily liquid, and adding anhydrous CaCl2Drying, standing overnight, filtering to remove CaCl2Obtaining light yellow oily liquid as a product I;
(3) the product I was introduced into a 250mL three-necked flask equipped with stirring and reflux condenser, and sodium hydrogen sulfite (NaHSO) was added dropwise3) And water, wherein the molar ratio of the product I to the sodium bisulfite is 1:1.1, and the sulfurous acid in the sodium bisulfite aqueous solution is obtained after 20min of drippingThe mass ratio of the sodium hydrogen is 40 wt%, and the reaction is carried out for 2-4 h at the temperature of 110-130 ℃. And filtering the crude product by using absolute ethyl alcohol, carrying out rotary evaporation, adding water, separating liquid, washing to remove the unreacted product I, carrying out rotary evaporation to remove water, and drying to obtain the amido sulfonate gemini surfactant (product II).
Preparing the amido sulfonate gemini surfactant (product II) into surfactant aqueous solutions with different concentrations, and measuring the surface tension of the system by adopting a circular ring pull-up liquid film method.
Preparing amido sulfonate gemini surfactant (product II) into surfactant aqueous solution with the concentration of 0.3%, enabling the surfactant aqueous solution and simulated crude oil to form an oil/water interface system, and measuring the interfacial tension of the system by using a rotary drop interfacial tension meter at the temperature of 45 ℃ and the rotating speed of 5000 r/min.
Preparing the amido sulfonate gemini surfactant (product II) into aqueous solutions (0.1-0.5 wt%) with different concentrations by using mineralized water, wherein the total mineralization degree is 15000 mg/L. The core (the experimental core, the length of which is 10cm and the diameter of which is 2.5cm) is vacuumized, saturated with crude oil, and the amount of saturated adsorbed crude oil is measured. And injecting water into the rock core to perform a water flooding experiment, and measuring the oil displacement until the water flooding recovery ratio is stable and unchanged. And then injecting an amido sulfonate gemini surfactant (oil displacement agent) with a certain concentration to perform an oil displacement experiment of the oil displacement agent.
The invention is further illustrated by the following specific examples and figures:
example 1
Maleic anhydride, n-hexadecanol and 0.5 wt% anhydrous sodium acetate were sequentially charged into a 250mL three-necked flask equipped with stirring and a reflux condenser, wherein the molar ratio of maleic anhydride to n-hexadecanol was 1:1. Heating to 85 ℃ under the protection of nitrogen, and reacting for 4h to obtain a maleic monoester crude product. The crude product was recrystallized 2 times from acetone to give white crystals. Heating a certain amount of maleic acid monoester to dissolve, adding diethanol amine after completely dissolving, adding 10mL of catalyst triethylamine and acetone, and stirring and reacting for 7 hours at 60 ℃. Then the temperature is reduced to below 10 ℃, 2.6g of the mixed solution of acryloyl chloride and acetone is slowly dripped by a constant pressure dropping funnel, and the temperature is raised to 65 ℃ after dripping for reaction for 7 hours. Wherein the maleic acid monoester is reacted withThe mol ratio of the diethanol amine is 2:1, and the mass ratio of the solvent acetone is 70-80 wt%. Filtering, rotary steaming, washing with water, separating, collecting upper oily liquid, and adding anhydrous CaCl2Drying, standing overnight, filtering to remove CaCl2A light yellow oily liquid was obtained as product I. Adding the product I into a three-neck flask, and dropwise adding sodium bisulfite (NaHSO)3) And water, wherein the molar ratio of the product I to the sodium bisulfite is 1:1.1, the mass ratio of the sodium bisulfite in the sodium bisulfite aqueous solution is 40 wt%, and the reaction is carried out for 4h at 110 ℃ under the condition of heat preservation. And filtering the crude product by using absolute ethyl alcohol, carrying out rotary evaporation, adding water, separating liquid, washing to remove the unreacted product I, carrying out rotary evaporation to remove water, and drying to obtain the amido sulfonate gemini surfactant (product II). And preparing the product II into surfactant aqueous solutions with different concentrations, and measuring the surface tension of the system by adopting a circular ring pull-up liquid film method. Preparing the product II into a surfactant aqueous solution with the concentration of 0.3 percent, enabling the surfactant aqueous solution and simulated crude oil to form an oil/water interface system, and measuring the interfacial tension of the system by using a rotary drop interfacial tension meter at the temperature of 45 ℃ and the rotating speed of 5000 r/min.
And preparing the product II into aqueous solutions (0.1-0.5 wt%) with different concentrations by using mineralized water, wherein the total mineralization is 15000 mg/L. The core (the experimental core, the length of which is 10cm and the diameter of which is 2.5cm) is vacuumized, saturated with crude oil, and the amount of saturated adsorbed crude oil is measured. And injecting water into the rock core to perform a water flooding experiment, and measuring the oil displacement until the water flooding recovery ratio is stable and unchanged. And then injecting an amido sulfonate gemini surfactant (oil displacement agent) with a certain concentration to perform an oil displacement experiment of the oil displacement agent.
Example 2
Maleic anhydride, n-hexadecanol and 0.5 wt% anhydrous sodium acetate were added sequentially to a 250mL three-necked flask equipped with stirring and a reflux condenser, wherein the molar ratio of maleic anhydride to n-hexadecanol was 1.05: 1. Heating to 90 ℃ under the protection of nitrogen, and reacting for 3h to obtain a maleic monoester crude product. The crude product was recrystallized 2 times from acetone to give white crystals. Heating a certain amount of maleic acid monoester to dissolve, adding diethanol amine after completely dissolving, adding catalyst triethylamine 10mL and acetone, stirring at 65 DEG CAnd reacting for 6 h. Then the temperature is reduced to below 10 ℃, 2.6g of the mixed solution of acryloyl chloride and acetone is slowly dripped by a constant pressure dropping funnel, and the temperature is raised to 60 ℃ after dripping for reaction for 6 hours. Wherein the molar ratio of the maleic acid monoester to the diethanolamine is 2.1:1, and the mass ratio of the solvent acetone is 70-80 wt%. Filtering, rotary steaming, washing with water, separating, collecting upper oily liquid, and adding anhydrous CaCl2Drying, standing overnight, filtering to remove CaCl2A light yellow oily liquid was obtained as product I. Adding the product I into a three-neck flask, and dropwise adding sodium bisulfite (NaHSO)3) And water, wherein the molar ratio of the product I to the sodium bisulfite is 1:1.1, the mass ratio of the sodium bisulfite in the sodium bisulfite aqueous solution is 40 wt%, and the reaction is carried out for 3h at 120 ℃ under the condition that the dripping is finished after 20 min. And filtering the crude product by using absolute ethyl alcohol, carrying out rotary evaporation, adding water, separating liquid, washing to remove the unreacted product I, carrying out rotary evaporation to remove water, and drying to obtain the amido sulfonate gemini surfactant (product II). And preparing the product II into surfactant aqueous solutions with different concentrations, and measuring the surface tension of the system by adopting a circular ring pull-up liquid film method. Preparing the product II into a surfactant aqueous solution with the concentration of 0.3 percent, enabling the surfactant aqueous solution and simulated crude oil to form an oil/water interface system, and measuring the interfacial tension of the system by using a rotary drop interfacial tension meter at the temperature of 45 ℃ and the rotating speed of 5000 r/min.
And preparing the product II into aqueous solutions (0.1-0.5 wt%) with different concentrations by using mineralized water, wherein the total mineralization is 15000 mg/L. The core (the experimental core, the length of which is 10cm and the diameter of which is 2.5cm) is vacuumized, saturated with crude oil, and the amount of saturated adsorbed crude oil is measured. And injecting water into the rock core to perform a water flooding experiment, and measuring the oil displacement until the water flooding recovery ratio is stable and unchanged. And then injecting an amido sulfonate gemini surfactant (oil displacement agent) with a certain concentration to perform an oil displacement experiment of the oil displacement agent.
Example 3
Maleic anhydride, n-hexadecanol and 0.5 wt% anhydrous sodium acetate were added sequentially to a 250mL three-necked flask equipped with stirring and a reflux condenser, wherein the molar ratio of maleic anhydride to n-hexadecanol was 1.1: 1. Heating to 95 ℃ under the protection of nitrogen, and reacting for 2h to obtain a maleic monoester crude product. The crude product is usedAcetone was recrystallized 2 times to obtain white crystals. Heating a certain amount of maleic acid monoester to dissolve, adding diethanol amine after completely dissolving, adding 10mL of catalyst triethylamine and acetone, and stirring and reacting for 5 hours at 70 ℃. Then the temperature is reduced to below 10 ℃, 2.6g of the mixed solution of acryloyl chloride and acetone is slowly dripped by a constant pressure dropping funnel, and the temperature is raised to 65 ℃ after dripping for reaction for 5 hours. Wherein the molar ratio of the maleic acid monoester to the diethanolamine is 2:1, and the mass ratio of the solvent acetone is 70-80 wt%. Filtering, rotary steaming, washing with water, separating, collecting upper oily liquid, and adding anhydrous CaCl2Drying, standing overnight, filtering to remove CaCl2A light yellow oily liquid was obtained as product I. Adding the product I into a three-neck flask, and dropwise adding sodium bisulfite (NaHSO)3) And water, wherein the molar ratio of the product I to the sodium bisulfite is 1:1.1, the mass ratio of the sodium bisulfite in the sodium bisulfite aqueous solution is 40 wt%, and the reaction is carried out for 2h at 130 ℃ under the condition of heat preservation. And filtering the crude product by using absolute ethyl alcohol, carrying out rotary evaporation, adding water, separating liquid, washing to remove the unreacted product I, carrying out rotary evaporation to remove water, and drying to obtain the amido sulfonate gemini surfactant (product II). And preparing the product II into surfactant aqueous solutions with different concentrations, and measuring the surface tension of the system by adopting a circular ring pull-up liquid film method. Preparing the product II into a surfactant aqueous solution with the concentration of 0.3 percent, enabling the surfactant aqueous solution and simulated crude oil to form an oil/water interface system, and measuring the interfacial tension of the system by using a rotary drop interfacial tension meter at the temperature of 45 ℃ and the rotating speed of 5000 r/min.
And preparing the product II into aqueous solutions (0.1-0.5 wt%) with different concentrations by using mineralized water, wherein the total mineralization is 15000 mg/L. The core (the experimental core, the length of which is 10cm and the diameter of which is 2.5cm) is vacuumized, saturated with crude oil, and the amount of saturated adsorbed crude oil is measured. And injecting water into the rock core to perform a water flooding experiment, and measuring the oil displacement until the water flooding recovery ratio is stable and unchanged. And then injecting an amido sulfonate gemini surfactant (oil displacement agent) with a certain concentration to perform an oil displacement experiment of the oil displacement agent.
Example 4
Maleic anhydride, n-hexadecanol and 0.5 wt% anhydrous sodium acetate were added sequentially to 250mL of a solution containing stirring andin a reflux condenser three-neck flask, the molar ratio of maleic anhydride to n-hexadecanol was 1.05: 1. Heating to 90 ℃ under the protection of nitrogen, and reacting for 3h to obtain a maleic monoester crude product. The crude product was recrystallized 2 times from acetone to give white crystals. Heating a certain amount of maleic acid monoester to dissolve, adding diethanol amine after completely dissolving, adding 10mL of catalyst triethylamine and acetone, and stirring and reacting for 6 hours at 65 ℃. Then the temperature is reduced to below 10 ℃, 2.6g of the mixed solution of acryloyl chloride and acetone is slowly dripped by a constant pressure dropping funnel, and the temperature is raised to 60 ℃ after dripping for reaction for 6 hours. Wherein the molar ratio of the maleic acid monoester to the diethanolamine is 2:1, and the mass ratio of the solvent acetone is 70-80 wt%. Filtering, rotary steaming, washing with water, separating, collecting upper oily liquid, and adding anhydrous CaCl2Drying, standing overnight, filtering to remove CaCl2A light yellow oily liquid was obtained as product I. Adding the product I into a three-neck flask, and dropwise adding sodium bisulfite (NaHSO)3) And water, wherein the molar ratio of the product I to the sodium bisulfite is 1:1.1, the mass ratio of the sodium bisulfite in the sodium bisulfite aqueous solution is 40 wt%, and the reaction is carried out for 3h at 120 ℃ under the condition that the dripping is finished after 20 min. And filtering the crude product by using absolute ethyl alcohol, carrying out rotary evaporation, adding water, separating liquid, washing to remove the unreacted product I, carrying out rotary evaporation to remove water, and drying to obtain the amido sulfonate gemini surfactant (product II). And preparing the product II into surfactant aqueous solutions with different concentrations, and measuring the surface tension of the system by adopting a circular ring pull-up liquid film method. Preparing the product II into a surfactant aqueous solution with the concentration of 0.3 percent, enabling the surfactant aqueous solution and simulated crude oil to form an oil/water interface system, and measuring the interfacial tension of the system by using a rotary drop interfacial tension meter at the temperature of 45 ℃ and the rotating speed of 5000 r/min.
And preparing the product II into aqueous solutions (0.1-0.5 wt%) with different concentrations by using mineralized water, wherein the total mineralization is 15000 mg/L. The core (the experimental core, the length of which is 10cm and the diameter of which is 2.5cm) is vacuumized, saturated with crude oil, and the amount of saturated adsorbed crude oil is measured. And injecting water into the rock core to perform a water flooding experiment, and measuring the oil displacement until the water flooding recovery ratio is stable and unchanged. And then injecting an amido sulfonate gemini surfactant (oil displacement agent) with a certain concentration to perform an oil displacement experiment of the oil displacement agent.
Example 5
Maleic anhydride, n-hexadecanol and 0.5 wt% anhydrous sodium acetate were added sequentially to a 250mL three-necked flask equipped with stirring and a reflux condenser, wherein the molar ratio of maleic anhydride to n-hexadecanol was 1.1: 1. Heating to 90 ℃ under the protection of nitrogen, and reacting for 3h to obtain a maleic monoester crude product. The crude product was recrystallized 2 times from acetone to give white crystals. Heating a certain amount of maleic acid monoester to dissolve, adding diethanol amine after completely dissolving, adding 10mL of catalyst triethylamine and acetone, and stirring and reacting for 6 hours at 65 ℃. Then the temperature is reduced to below 10 ℃, 2.6g of the mixed solution of acryloyl chloride and acetone is slowly dripped by a constant pressure dropping funnel, and the temperature is raised to 60 ℃ after dripping for reaction for 6 hours. Wherein the molar ratio of the maleic acid monoester to the diethanolamine is 2.1:1, and the mass ratio of the solvent acetone is 70-80 wt%. Filtering, rotary steaming, washing with water, separating, collecting upper oily liquid, and adding anhydrous CaCl2Drying, standing overnight, filtering to remove CaCl2A light yellow oily liquid was obtained as product I. Adding the product I into a three-neck flask, and dropwise adding sodium bisulfite (NaHSO)3) And water, wherein the molar ratio of the product I to the sodium bisulfite is 1:1.1, the mass ratio of the sodium bisulfite in the sodium bisulfite aqueous solution is 40 wt%, and the reaction is carried out for 3h at 120 ℃ under the condition that the dripping is finished after 20 min. And filtering the crude product by using absolute ethyl alcohol, carrying out rotary evaporation, adding water, separating liquid, washing to remove the unreacted product I, carrying out rotary evaporation to remove water, and drying to obtain the amido sulfonate gemini surfactant (product II). And preparing the product II into surfactant aqueous solutions with different concentrations, and measuring the surface tension of the system by adopting a circular ring pull-up liquid film method. Preparing the product II into a surfactant aqueous solution with the concentration of 0.3 percent, enabling the surfactant aqueous solution and simulated crude oil to form an oil/water interface system, and measuring the interfacial tension of the system by using a rotary drop interfacial tension meter at the temperature of 45 ℃ and the rotating speed of 5000 r/min.
And preparing the product II into aqueous solutions (0.1-0.5 wt%) with different concentrations by using mineralized water, wherein the total mineralization is 15000 mg/L. The core (the experimental core, the length of which is 10cm and the diameter of which is 2.5cm) is vacuumized, saturated with crude oil, and the amount of saturated adsorbed crude oil is measured. And injecting water into the rock core to perform a water flooding experiment, and measuring the oil displacement until the water flooding recovery ratio is stable and unchanged. And then injecting an amido sulfonate gemini surfactant (oil displacement agent) with a certain concentration to perform an oil displacement experiment of the oil displacement agent.
Example 6
Maleic anhydride, n-hexadecanol and 0.5 wt% anhydrous sodium acetate were sequentially charged into a 250mL three-necked flask equipped with stirring and a reflux condenser, wherein the molar ratio of maleic anhydride to n-hexadecanol was 1:1. Heating to 90 ℃ under the protection of nitrogen, and reacting for 3h to obtain a maleic monoester crude product. The crude product was recrystallized 2 times from acetone to give white crystals. Heating a certain amount of maleic acid monoester to dissolve, adding diethanol amine after completely dissolving, adding 10mL of catalyst triethylamine and acetone, and stirring and reacting for 6 hours at 65 ℃. Then the temperature is reduced to below 10 ℃, 2.6g of the mixed solution of acryloyl chloride and acetone is slowly dripped by a constant pressure dropping funnel, and the temperature is raised to 60 ℃ after dripping for reaction for 6 hours. Wherein the molar ratio of the maleic acid monoester to the diethanolamine is 2.2:1, and the mass ratio of the solvent acetone is 70-80 wt%. Filtering, rotary steaming, washing with water, separating, collecting upper oily liquid, and adding anhydrous CaCl2Drying, standing overnight, filtering to remove CaCl2A light yellow oily liquid was obtained as product I. Adding the product I into a three-neck flask, and dropwise adding sodium bisulfite (NaHSO)3) And water, wherein the molar ratio of the product I to the sodium bisulfite is 1:1.1, the mass ratio of the sodium bisulfite in the sodium bisulfite aqueous solution is 40 wt%, and the reaction is carried out for 3h at 120 ℃ under the condition that the dripping is finished after 20 min. And filtering the crude product by using absolute ethyl alcohol, carrying out rotary evaporation, adding water, separating liquid, washing to remove the unreacted product I, carrying out rotary evaporation to remove water, and drying to obtain the amido sulfonate gemini surfactant (product II). And preparing the product II into surfactant aqueous solutions with different concentrations, and measuring the surface tension of the system by adopting a circular ring pull-up liquid film method. Preparing the product II into a surfactant aqueous solution with the concentration of 0.3 percent, enabling the surfactant aqueous solution and simulated crude oil to form an oil/water interface system, and measuring the interfacial tension of the system by using a rotary drop interfacial tension meter at the temperature of 45 ℃ and the rotating speed of 5000 r/min.
And preparing the product II into aqueous solutions (0.1-0.5 wt%) with different concentrations by using mineralized water, wherein the total mineralization is 15000 mg/L. The core (the experimental core, the length of which is 10cm and the diameter of which is 2.5cm) is vacuumized, saturated with crude oil, and the amount of saturated adsorbed crude oil is measured. And injecting water into the rock core to perform a water flooding experiment, and measuring the oil displacement until the water flooding recovery ratio is stable and unchanged. And then injecting an amido sulfonate gemini surfactant (oil displacement agent) with a certain concentration to perform an oil displacement experiment of the oil displacement agent.
In order to characterize the surface activity of the amidosulfonate gemini surfactant, the amidosulfonate gemini surfactant synthesized in example 4 was subjected to a surface tension test, and the results are shown in fig. 1.
In order to characterize the interfacial activity of the amidosulfonate gemini surfactant, the amidosulfonate gemini surfactant synthesized in example 4 was subjected to an interfacial tension test, and the results are shown in fig. 2.
In order to characterize the oil displacement efficiency of the amido sulfonate gemini surfactant, an oil displacement agent oil displacement experiment was performed on the amido sulfonate gemini surfactant synthesized in example 4, and the results are shown in table 1.
Table 1 displacement efficiency of different concentration oil displacement agent system
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (10)
1. The amido sulfonate gemini surfactant is characterized in that the structural formula is as follows:
2. the preparation method of the amido sulfonate gemini surfactant is characterized by comprising the following steps:
mixing maleic anhydride, n-hexadecanol and anhydrous sodium acetate, heating to 85-95 ℃, and reacting for 2-4 hours to obtain maleic acid monoester;
heating and dissolving maleic acid monoester, adding diethanol amine, a catalyst and a solvent after completely dissolving, stirring and reacting for 5-7 h at the temperature of 60-70 ℃, then cooling to below 10 ℃, adding a mixed solution of acryloyl chloride and the solvent, heating to 55-65 ℃, and reacting for 5-7 h to obtain an intermediate product;
and adding a sodium bisulfite aqueous solution consisting of sodium bisulfite and water into the intermediate product, and carrying out heat preservation reaction for 2-4 h at the temperature of 110-130 ℃ to obtain the amido sulfonate gemini surfactant.
3. The method for preparing the amido sulfonate gemini surfactant according to claim 2, wherein the molar ratio of the maleic anhydride to the n-hexadecanol is (1-1.1): 1.
4. The method for preparing the amidosulfonate gemini surfactant according to claim 2, wherein the anhydrous sodium acetate is added in an amount of 0.5 wt% based on the total mass of the maleic anhydride, the cetyl alcohol and the anhydrous sodium acetate.
5. The method for preparing the amido sulfonate gemini surfactant according to claim 2, wherein the molar ratio of the maleic acid monoester to the diethanolamine is (2-2.2): 1.
6. The method for preparing the amido sulfonate gemini surfactant according to claim 2, wherein the catalyst is triethylamine; the solvent is acetone, and the mass ratio of the acetone is 70-80 wt% of the total mass.
7. The method for preparing the amidosulfonate gemini surfactant according to claim 2, wherein the molar ratio of the intermediate product to the sodium bisulfite is 1: 1.1; the mass ratio of sodium bisulfite in the sodium bisulfite aqueous solution is 40 wt%.
8. The method of claim 2 wherein the intermediate product is further subjected to a post-treatment step comprising:
filtering, rotary steaming, washing with water, separating, collecting upper oily liquid, and adding anhydrous CaCl2Drying, standing overnight, filtering to remove CaCl2A pale yellow oily liquid was obtained, giving the final intermediate product.
9. The method for preparing the amido sulfonate gemini surfactant according to claim 2, wherein the step of obtaining the amido sulfonate gemini surfactant further comprises the step of post-treatment:
and filtering the crude product by using absolute ethyl alcohol, carrying out rotary evaporation, adding water, separating liquid, washing to remove an unreacted intermediate product, carrying out rotary evaporation to remove water, and drying to obtain the amido sulfonate gemini surfactant.
10. Use of the amidosulfonate gemini surfactant of claim 1 as an oil displacing agent for tertiary oil recovery; the amido sulfonate gemini surfactant is prepared into a surfactant aqueous solution, and the concentration of the surfactant aqueous solution is 0.1-0.5 wt%.
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