CN113731297B - 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 h to obtain maleic acid monoester; heating and dissolving maleic acid monoester, adding diethanol amine, a catalyst and a solvent after the maleic acid monoester is completely dissolved, stirring and reacting for 5-7 hours at the temperature of 60-70 ℃, then cooling to below 10 ℃, adding a mixed solution of acryloyl chloride and the solvent, and heating to 55-65 ℃ to react for 5-7 hours to obtain an intermediate product; and adding a sodium bisulfite aqueous solution consisting of sodium bisulfite and water into the intermediate product, and reacting for 2-4 h at the temperature of 110-130 ℃ to obtain the amido sulfonate gemini surfactant. The surfactant solves the problem of low crude oil recovery rate 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:
the preparation method of the 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 h 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 reacting 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 0.5wt% of the total mass of the maleic anhydride, the n-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 sodium bisulfite is 1; the mass ratio of sodium bisulfite in the sodium bisulfite aqueous solution is 40wt%.
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 CaCl 2 Drying, standing overnight, filtering to remove CaCl 2 A pale yellow oily liquid was obtained to give the final intermediate product.
As a further improvement of the invention, the obtained amido sulfonate gemini surfactant further comprises a post-treatment step:
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 crude oil recovery rate 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 obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection 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) Maleic anhydride, n-hexadecanol and a certain amount of anhydrous sodium acetate are sequentially added into a 250mL three-neck flask provided 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 0.5wt%. Heating to 85-95 ℃ under the protection of nitrogen, 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 diethanol amine after the maleic acid monoester is completely dissolved, adding 10mL of catalyst triethylamine and acetone, and stirring and reacting for 5-7 h at the temperature of 60-70 ℃. Then the temperature is reduced to below 10 ℃, 2.6g of mixed solution of acryloyl chloride and acetone is slowly dripped by a constant pressure dropping funnel, and the temperature is raised to 55-65 ℃ after the dripping is finished to react for 5-7 h. Wherein the molar ratio of the maleic acid monoester to the diethanol amine is (2-2.2): 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 CaCl 2 Drying, standing overnight, filtering to remove CaCl 2 Obtaining 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 dropwise 3 ) And water, wherein the molar ratio of the product I to the sodium bisulfite is 1.1, the mass ratio of the sodium bisulfite in the sodium bisulfite aqueous solution is 40wt%, and the reaction is carried out for 2 to 4 hours at the temperature of between 110 and 130 ℃ under the condition of heat preservation. And (3) filtering the crude product by using absolute ethyl alcohol, carrying out rotary evaporation, adding water for 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 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 an 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 is 15000mg/L. Vacuumizing a rock core (experimental rock core with the length of 10cm and the diameter of 2.5 cm), saturating with crude oil, and measuring the amount of saturated adsorbed crude oil. 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 examples in conjunction with the accompanying drawings:
example 1
Maleic anhydride, n-hexadecanol and 0.5% by weight of anhydrous sodium acetate were added in this order 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. 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 mixed solution of acryloyl chloride and acetone is slowly dripped by a constant pressure dropping funnel, and the temperature is raised to 65 ℃ after the dripping is finished for reaction for 7 hours. Wherein, the molar ratio of the maleic acid monoester to the diethanol amine is 2. Filtering, rotary steaming, washing with water, separating, collecting upper oily liquid, and adding anhydrous CaCl 2 Drying, standing overnight, filtering to remove CaCl 2 A pale 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, the mass ratio of the sodium bisulfite in the sodium bisulfite aqueous solution is 40wt%, and the reaction is carried out for 4h at 110 ℃ under the condition that the dripping is finished within 20 min. Filtering the crude product with anhydrous ethanol, rotary steaming, adding waterSeparating, washing to remove the unreacted product I, removing water by rotary evaporation, 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 15000mg/L. Vacuumizing a rock core (experimental rock core with the length of 10cm and the diameter of 2.5 cm), saturating the rock core with crude oil, and measuring the amount of saturated adsorbed crude oil. 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% by weight of anhydrous sodium acetate were added in this order 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. 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. Filtering, rotary steaming, water washing and liquid separating the crude product, taking the upper oily liquid, and adding anhydrous CaCl 2 Drying, standing overnight, filtering to remove CaCl 2 A pale 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 product I and the product II are obtained after 20min of droppingThe molar ratio of sodium bisulfate is 1.1, the mass ratio of sodium bisulfite in the sodium bisulfite aqueous solution is 40wt%, and the reaction is carried out for 3h under the condition of 120 ℃. 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 15000mg/L. Vacuumizing a rock core (experimental rock core with the length of 10cm and the diameter of 2.5 cm), saturating the rock core with crude oil, and measuring the amount of saturated adsorbed crude oil. 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% by weight of anhydrous sodium acetate were added in this order 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. Heating to 95 ℃ under the protection of nitrogen, and reacting for 2h 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 all maleic acid monoester is dissolved, 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 mixed solution of acryloyl chloride and acetone is slowly dripped by a constant pressure dropping funnel, and the temperature is raised to 65 ℃ after the dripping is finished for reaction for 5 hours. Wherein, the molar ratio of the maleic acid monoester to the diethanol amine is 2. Filtering, rotary steaming, water washing and liquid separating the crude product, taking the upper oily liquid, and adding anhydrous CaCl 2 Drying, standing overnight, filtering to remove CaCl 2 To obtain a slightYellow oily liquid 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, the mass ratio of the sodium bisulfite in the sodium bisulfite aqueous solution is 40wt%, and the reaction is carried out for 2h at 130 ℃ under the condition of heat preservation. And (3) filtering the crude product by using absolute ethyl alcohol, carrying out rotary evaporation, adding water for 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 ring-pull liquid film method. Preparing the product II into a 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.
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 15000mg/L. Vacuumizing a rock core (experimental rock core with the length of 10cm and the diameter of 2.5 cm), saturating with crude oil, and measuring the amount of saturated adsorbed crude oil. And injecting water into the core for water flooding experiment, and measuring the oil displacement amount when the water flooding recovery ratio is stable and unchanged. And then injecting a certain concentration of amido sulfonate gemini surfactant (oil displacement agent) to carry out an oil displacement experiment of the oil displacement agent.
Example 4
Maleic anhydride, n-hexadecanol and 0.5% by weight of anhydrous sodium acetate were added in this order 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. 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 all maleic acid monoester is dissolved, 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 2The proportion is 70-80 wt%. Filtering, rotary steaming, washing with water, separating, collecting upper oily liquid, and adding anhydrous CaCl 2 Drying, standing overnight, filtering to remove CaCl 2 A 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, the mass ratio of the sodium bisulfite in the sodium bisulfite aqueous solution is 40wt%, and the reaction is carried out for 3h at 120 ℃ under the condition that the dropping is finished after 20 min. And (3) filtering the crude product by using absolute ethyl alcohol, carrying out rotary evaporation, adding water for 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 15000mg/L. Vacuumizing a rock core (experimental rock core with the length of 10cm and the diameter of 2.5 cm), saturating with crude oil, and measuring the amount of saturated adsorbed crude oil. 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% by weight of anhydrous sodium acetate were added in this order 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. Heating to 90 ℃ under the protection of nitrogen, and reacting for 3h to obtain a crude maleic monoester 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 reducing the temperature to below 10 ℃, and using constant pressure2.6g of a mixed solution of acryloyl chloride and acetone is slowly dripped into the dropping funnel, and the temperature is raised to 60 ℃ after dripping for reaction for 6 hours. Wherein, the mole ratio of the maleic acid monoester to 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 CaCl 2 Drying, standing overnight, filtering to remove CaCl 2 A pale 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, the mass ratio of the sodium bisulfite in the sodium bisulfite aqueous solution is 40wt%, and the reaction is carried out for 3h at 120 ℃ under the condition that the dripping is finished after 20 min. And (3) filtering the crude product by using absolute ethyl alcohol, carrying out rotary evaporation, adding water for 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 ring-pull 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 15000mg/L. Vacuumizing a rock core (experimental rock core with the length of 10cm and the diameter of 2.5 cm), saturating the rock core with crude oil, and measuring the amount of saturated adsorbed crude oil. And injecting water into the core for water flooding experiment, and measuring the oil displacement amount when the water flooding recovery ratio is stable and unchanged. And then injecting a certain concentration of amido sulfonate gemini surfactant (oil displacement agent) to carry out an oil displacement experiment of the oil displacement agent.
Example 6
Maleic anhydride, n-hexadecanol and 0.5% by weight of anhydrous sodium acetate were added in this order 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. 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. Mixing a certain amount ofHeating maleic acid monoester to dissolve, adding diethanol amine after all maleic acid monoester is dissolved, 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 to 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 CaCl 2 Drying, standing overnight, filtering to remove CaCl 2 A 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, the mass ratio of the sodium bisulfite in the sodium bisulfite aqueous solution is 40wt%, and the reaction is carried out for 3h at 120 ℃ under the condition that the dripping is finished after 20 min. And (3) filtering the crude product by using absolute ethyl alcohol, carrying out rotary evaporation, adding water for 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 15000mg/L. Vacuumizing a rock core (experimental rock core with the length of 10cm and the diameter of 2.5 cm), saturating with crude oil, and measuring the amount of saturated adsorbed crude oil. 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 oil displacement agent systems of different concentrations
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Finally, it should be noted that: although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art 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 (8)
1. The amido sulfonate gemini surfactant is characterized in that the structural formula is as follows:
2. a process for preparing an amidosulfonate gemini surfactant according to claim 1, comprising the steps of:
mixing maleic anhydride, n-hexadecanol and anhydrous sodium acetate, heating to 85-95 ℃, and reacting for 2-4 h to obtain maleic monoester;
heating and dissolving maleic acid monoester, adding diethanolamine, a catalyst and a solvent after the maleic acid monoester is completely dissolved, stirring and reacting for 5 to 7 hours at the temperature of 60 to 70 ℃, then cooling to below 10 ℃, adding a mixed solution of acryloyl chloride and the solvent, heating to the temperature of 55 to 65 ℃, and reacting for 5 to 7 hours to obtain an intermediate product;
adding a sodium bisulfite aqueous solution consisting of sodium bisulfite and water into the intermediate product, and reacting for 2 to 4 hours at the temperature of 110 to 130 ℃ in a heat preservation manner to obtain an amido sulfonate gemini surfactant;
the molar ratio of the maleic anhydride to the n-hexadecanol is (1 to 1.1) to 1;
the molar ratio of the maleic acid monoester to the diethanolamine is (2 to 2.2) to 1.
3. The method for preparing the amido sulfonate gemini surfactant according to claim 2, wherein the anhydrous sodium acetate is added in an amount of 0.5wt% based on the total mass of maleic anhydride, n-hexadecanol and anhydrous sodium acetate.
4. 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 of the acetone accounts for 70 to 80wt% of the total mass.
5. 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 water solution is 40wt%.
6. The method of claim 2 wherein the intermediate product is further subjected to a post-treatment step comprising:
filtering, rotary steaming, water washing and liquid separating the crude product, and taking the crude productAdding anhydrous CaCl into oily liquid 2 Drying, standing overnight, filtering to remove CaCl 2 A pale yellow oily liquid was obtained, giving the final intermediate product.
7. 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 a post-treatment step of:
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.
8. 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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