Aminoethanesulfonic acid type surfactant as well as preparation method and application thereof

Abstract

The invention relates to the technical field of oilfield chemistry, in particular to an aminoethanesulfonic acid type surfactant and a preparation method and application thereof.The preparation method of the aminoethanesulfonic acid type surfactant comprises the steps that firstly, fatty amine is dissolved in a first solvent, a sodium chloroethanesulfonate aqueous solution is added, and N-long-chain alkyl-2-sodium aminoethanesulfonate is obtained through a reaction; and 2, dissolving a required amount of N-long-chain alkyl-2-sodium aminoethanesulfonate in a second solvent, adding a required amount of methyl acrylate, and reacting to obtain the aminoethanesulfonic acid type surfactant. The aminoethanesulfonic acid type surfactant disclosed by the invention contains long-chain alkyl, amino, ester groups and sulfonic acid groups, so that the aminoethanesulfonic acid type surfactant has good surface activity and can meet the development requirements of oil and gas fields. The microemulsion cleanup additive prepared from the aminoethanesulfonic acid type surfactant can effectively reduce the surface tension and the interfacial tension of an aqueous solution, and the preparation method is easy and convenient to operate, mild in condition and suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of oilfield chemical technology, and is an aminoethanesulfonic acid type surfactant, a preparation method and application, and a microemulsion cleanup agent. BACKGROUND

[0002] Acidification and hydraulic fracturing are effective means for unconventional reservoir reconstruction, and the fluid entering the formation after the construction should be timely flowed back to reduce the formation damage. The cleanup method is a commonly used method for improving the flowback rate, and the addition of the cleanup agent in the reconstruction fluid can reduce the interfacial tension, increase the contact angle, thereby reducing the capillary resistance, making the reconstruction fluid smoothly flow back to the formation, reducing the reservoir damage, improving the conductivity, and having the characteristics of low cost, simple operation, high flowback rate and the like.

[0003] The Chinese patent document with the publication number CN106244131A discloses a high-temperature microemulsion cleanup agent for fracturing and a preparation method thereof, which comprises 20-40% of a gemini surfactant, 3-4% of a nonionic surfactant, 40-60% of a co-surfactant, and the balance of water; the gemini surfactant is ethylene-based bisalkyldimethyl ammonium chloride, propylene-based bisalkyldimethyl ammonium chloride, ethylene-based bisalkyldimethyl ammonium bromide or propylene-based bisalkyldimethyl ammonium bromide; the alkyl in the ethylene-based bisalkyldimethyl ammonium chloride, propylene-based bisalkyldimethyl ammonium chloride, ethylene-based bisalkyldimethyl ammonium bromide and propylene-based bisalkyldimethyl ammonium bromide is dodecyl, tetradecyl, hexadecyl or octadecyl; the nonionic surfactant is coconut oil fatty acid monoethanolamide, coconut oil fatty acid diethanolamide, lauric acid monoethanolamide or lauric acid diethanolamide; and the co-surfactant is ethanol, n-propanol, isopropanol or isobutanol. The Chinese patent document with the publication number CN105176511A discloses an acidification and fracturing cleanup agent with excellent performance and a preparation method thereof, wherein the cleanup agent is prepared by compounding 15%-20% of alkyl polyoxyethylene ether, 2%-5% of fatty alcohol polyoxyethylene ether, 3%-6% of fatty alcohol, 5%-8% of quaternary ammonium salt and 2%-6% of methanol, the amount of the cleanup agent is 1.0-2.0%, and the surface tension of the cleanup agent aqueous solution is less than 28.0 mN / m.

[0004] At present, the cleanup agent mostly uses fluorocarbon surfactant, and uses low-molecular alcohol such as methanol, ethanol and n-butanol as a solubilizer, which not only has high cost, but also has biological toxicity and safety risk. Therefore, it is urgent to develop a new type of green and environmentally friendly, safe and reliable cleanup agent. SUMMARY

[0005] The present application provides an aminoethanesulfonic acid type surfactant and a preparation method thereof, which overcomes the deficiencies of the prior art, and effectively solves the problems that the surfactant used in the existing fracturing construction is difficult to degrade and has high biological toxicity.

[0006] One of the technical solutions of the present application is realized by the following measures: a preparation method of aminoethanesulfonic acid type surfactant, comprising the following steps: Step one, the fatty amine is dissolved in the first solvent, and the sodium chloroethyl sulfonate aqueous solution is added, and N-long chain alkyl-2-aminoethanesulfonic acid sodium is obtained by reaction; Step two, a certain amount of N-long chain alkyl-2-aminoethanesulfonic acid sodium is dissolved in the second solvent, and a certain amount of methyl acrylate is added, and the aminoethanesulfonic acid type surfactant is obtained after reaction.

[0007] The following is a further optimization or / and improvement of one of the above technical solutions of the application: In the above step one, the reaction is a reflux reaction, and the reaction time is 8h to 24h.

[0008] In the above step one, during the reaction, the pH of the reaction system is between 7.0 and 7.5. Specifically, sodium hydroxide solution is used to adjust the pH during the reaction of fatty amine and sodium chloroethyl sulfonate to keep it weakly alkaline.

[0009] In the above step one, the molar ratio of fatty amine to sodium chloroethyl sulfonate is 1.1 to 1.5:1.

[0010] The above first solvent is anhydrous ethanol, and the second solvent is or methanol.

[0011] In the above step two, the molar ratio of methyl acrylate to N-long chain alkyl-2-aminoethanesulfonic acid sodium is 1.1 to 1.5:1.

[0012] In the above step two, the reaction is a reflux reaction, and the reaction time is 4h to 12h.

[0013] The second technical solution of the present application is realized by the following measures: a preparation method of aminoethanesulfonic acid type surfactant, and the chemical structural formula of the aminoethanesulfonic acid type surfactant prepared by the preparation method is Wherein, R is a fatty alkyl group of C 12 to C 16 .

[0014] The third technical solution of the present application is realized by the following measures: the application of aminoethanesulfonic acid type surfactant in reservoir fracturing construction.

[0015] The fourth technical solution of the present application is realized by the following measures: a microemulsion cleanup agent, the raw materials include: the amount of aminoethanesulfonic acid type surfactant is 2 to 10 parts, the oil phase is 50 to 100 parts, the anionic surfactant is 0.5 to 5 parts, and the water is 50 to 100 parts.

[0016] The following is a further optimization or / and improvement of the fourth technical scheme of the above-mentioned application: The above-mentioned microemulsion cleanup agent is prepared by the following steps: A desired amount of aminoethanesulfonic acid surfactant is dissolved in the oil phase, and after mixing, a first mixed solution is obtained; A desired amount of anionic surfactant is dissolved in water, and after mixing, a second mixed solution is obtained; The second mixed solution is added to the first mixed solution, stirred and mixed, and after uniform emulsification, it is left to separate into layers, and the lower microemulsion phase is taken to obtain the microemulsion cleanup agent.

[0017] The above-mentioned oil phase is one or more of white oil, kerosene, and cyclohexane.

[0018] The above-mentioned anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium fatty acid methyl ester sulfonate, and sodium fatty alcohol polyoxyethylene ether carboxylate.

[0019] The present application provides an aminoethanesulfonic acid surfactant containing long-chain alkyl, amino, ester, and sulfonic acid groups, which has good surface activity and can meet the needs of oil and gas field development. The microemulsion cleanup agent prepared using the aminoethanesulfonic acid surfactant can effectively reduce the surface and interfacial tension of an aqueous solution, and the preparation method is simple and easy to operate, and the conditions are mild, making it suitable for industrial production. DETAILED DESCRIPTION

[0020] The present application is not limited by the following examples, and the specific implementation can be determined according to the technical scheme of the present application and the actual situation. The various chemical reagents and chemical supplies mentioned in the present application are well-known and commonly used chemical reagents and chemical supplies in the prior art unless otherwise specified; the percentages in the present application are mass percentages unless otherwise specified; and normal temperature and room temperature generally refer to a temperature of 15℃ to 25℃, and are generally defined as 25℃.

[0021] The present application will be further described below in conjunction with examples: Example 1: The preparation method of the aminoethanesulfonic acid surfactant includes the following steps: Step one, the fatty amine is dissolved in a first solvent, and a sodium chloroethyl sulfonate aqueous solution is added, and N-long-chain alkyl-2-aminoethanesulfonic acid sodium is obtained by reaction; Step two, a desired amount of N-long-chain alkyl-2-aminoethanesulfonic acid sodium is dissolved in a second solvent, and a desired amount of methyl acrylate is added, and the aminoethanesulfonic acid surfactant is obtained after reaction.

[0022] Example 2: As an optimization of the above-mentioned example, in step one, the reaction is a reflux reaction, and the reaction time is 8h to 24h.

[0023] Example 3: As an optimization of the above-mentioned examples, in step one, the pH of the reaction system during the reaction is between 7.0 and 7.5. Specifically, the pH is adjusted to be weakly alkaline during the reaction of the fatty amine and sodium chloroethyl sulfonate using a sodium hydroxide solution.

[0024] Example 4: As an optimization of the above-mentioned examples, in step one, the molar ratio of the fatty amine to sodium chloroethyl sulfonate is 1.1 to 1.5:1.

[0025] Example 5: As an optimization of the above-mentioned examples, the first solvent is anhydrous ethanol, and the second solvent is or methanol.

[0026] Example 6: As an optimization of the above-mentioned examples, in step two, the molar ratio of methyl acrylate to N-long-chain alkyl-2-aminoethanesulfonic acid sodium is 1.1 to 1.5:1.

[0027] Example 7: As an optimization of the above-mentioned examples, in step two, the reaction is a reflux reaction, and the reaction time is 4h to 12h.

[0028] Example 8: The aminoethanesulfonic acid type surfactant prepared by the preparation method of the aminoethanesulfonic acid type surfactant has a chemical structural formula of wherein R is a fatty alkyl group of C 12 to C 16 .

[0029] The aminoethanesulfonic acid type surfactant of the present application is prepared through a substitution reaction and a Michael addition reaction, and the chemical reaction process of the preparation method is as follows: (1) Preparation of N-long-chain alkyl-2-aminoethanesulfonic acid sodium: (2) Preparation of the aminoethanesulfonic acid type surfactant: In the above structural formula, R is a fatty alkyl group of C 12 to C 16 .

[0030] Example 9: Application of the aminoethanesulfonic acid type surfactant in reservoir fracturing construction.

[0031] Example 10: The microemulsion cleanup agent is prepared according to the following steps, and the raw materials include, by mass fraction: the amount of aminoethanesulfonic acid type surfactant is 2 to 10 parts, the oil phase is 50 to 100 parts, the anionic surfactant is 0.5 to 5 parts, and the water is 50 to 100 parts.

[0032] Example 11: As an optimization of the above-mentioned example 10, the microemulsion cleanup agent is prepared according to the following steps: Dissolve the desired amount of aminoethanesulfonic acid surfactant in the oil phase, mix to obtain a first mixture; Dissolve the desired amount of anionic surfactant in water, mix to obtain a second mixture; Add the second mixture to the first mixture, mix and emulsify, then stand to separate the layers, take the lower microemulsion phase to obtain the microemulsion cleanup agent.

[0033] Example 12: As an optimization of the above Example 10, the oil phase is one or more of white oil, kerosene, and cyclohexane; the anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium fatty acid methyl ester sulfonate, and sodium fatty alcohol polyoxyethylene ether carboxylate.

[0034] Example 13: (1) Preparation of aminoethanesulfonic acid surfactant: Dissolve 0.15 mol of dodecylamine in 200 mL of anhydrous ethanol, mix well, add 0.1 mol of sodium chloroethyl sulfonate (dissolved in 20 mL of tap water), and reflux for 24 h, during which 50 mL of 10% NaOH solution is slowly added. After the reaction is complete, store at low temperature, and filter to obtain white solid intermediate product N-dodecyl-2-aminoethanesulfonic acid sodium, with a yield of 97.8%.

[0035] Dissolve 0.05 mol of N-dodecyl-2-aminoethanesulfonic acid sodium in 250 mL of methanol, mix well, and slowly add 1.1 times the molar amount of methyl acrylate. After addition is complete, reflux for 8 h, and recover the methanol by rotary evaporation to obtain white solid aminoethanesulfonic acid surfactant 2-(dodecyl(3-methoxy-3-oxopropyl)amino)ethanesulfonic acid sodium, with a yield of 98.1%.

[0036] (2) Preparation of microemulsion cleanup agent: Dissolve 4.5 parts of 2-(dodecyl(3-methoxy-3-oxopropyl)amino)ethanesulfonic acid sodium in 50 parts of white oil, mix well to obtain a first mixture; Dissolve 0.5 parts of sodium dodecyl sulfate in 50 parts of tap water, mix well to obtain a second mixture; Start high-speed stirring (500 r / min), slowly add the water phase to the oil phase, emulsify, and then stand to separate the layers. Take the lower microemulsion phase to obtain the microemulsion cleanup agent.

[0037] Example 14: (1) Preparation of aminoethanesulfonic acid surfactant 0.15 mol of dodecylamine was stirred with 200 mL of anhydrous ethanol, 0.1 mol of sodium chloroethyl sulfonate (dissolved in 20 mL of tap water) was added, and the reaction was carried out under reflux for 12 h, during which 50 mL of 10% NaOH solution was slowly added dropwise. After the reaction was completed, the white solid intermediate product N-dodecyl-2-aminoethanesulfonic acid sodium was obtained by low-temperature refrigeration and suction filtration, with a yield of 97.5%.

[0038] 0.05 mol of N-dodecyl-2-aminoethanesulfonic acid sodium was dissolved in 250 mL of methanol, and 1.1 times the molar amount of methyl acrylate was slowly added dropwise. After the addition was completed, the reaction was carried out under reflux for 6 h, and the methanol was recovered by rotary evaporation to obtain the white solid aminoethanesulfonic acid surfactant 2-(dodecyl(3-methoxy-3-oxopropyl)amino)ethanesulfonic acid sodium, with a yield of 98.0%.

[0039] (2) Preparation of microemulsion cleanup agent: 4.0 parts of 2-(dodecyl(3-methoxy-3-oxopropyl)amino)ethanesulfonic acid sodium was dissolved in 50 parts of white oil to obtain a first mixed solution; 0.5 parts of sodium dodecyl sulfate and 0.5 parts of sodium fatty alcohol polyoxyethylene ether carboxylate were dissolved in 50 parts of tap water to obtain a second mixed solution; High-speed stirring (500 r / min) was started, and the aqueous phase was slowly added dropwise into the oil phase. After emulsification, the lower layer of the microemulsion phase was taken to obtain the microemulsion cleanup agent.

[0040] Example 15: (1) Preparation of aminoethanesulfonic acid surfactant: 0.11 mol of dodecylamine was stirred with 200 mL of anhydrous ethanol, 0.1 mol of sodium chloroethyl sulfonate (dissolved in 20 mL of tap water) was added, and the reaction was carried out under reflux for 12 h, during which 50 mL of 10% NaOH solution was slowly added dropwise. After the reaction was completed, the white solid intermediate product N-dodecyl-2-aminoethanesulfonic acid sodium was obtained by low-temperature refrigeration and suction filtration, with a yield of 97.3%. 0.05 mol of N-dodecyl-2-aminoethanesulfonic acid sodium was dissolved in 250 mL of methanol, and 1.1 times the molar amount of methyl acrylate was slowly added dropwise. After the addition was completed, the reaction was carried out under reflux for 4 h, and the methanol was recovered by rotary evaporation to obtain the white solid aminoethanesulfonic acid surfactant 2-(dodecyl(3-methoxy-3-oxopropyl)amino)ethanesulfonic acid sodium, with a yield of 97.8%.

[0041] (2) Preparation of microemulsion cleanup agent 4.0 parts of 2-(dodecyl(3-methoxy-3-oxopropyl)amino)ethanesulfonic acid sodium was dissolved in 50 parts of kerosene to obtain a first mixed solution; 1.0 parts of fatty alcohol polyoxyethylene ether carboxylic acid sodium was dissolved in 50 parts of tap water, stirred uniformly to obtain a second mixture; High-speed stirring (500 r / min) was started, and the water phase was slowly added into the oil phase. After uniform emulsification, it was left to stand and separate into layers. The lower microemulsion phase was taken, and the microemulsion drainage aid was obtained.

[0042] Example 16: (1) Preparation of aminoethanesulfonic acid surfactant 0.11 mol of tetradecylamine was uniformly stirred with 200 mL of anhydrous ethanol, and 0.1 mol of sodium chloroethyl sulfonate (dissolved in 20 mL of tap water) was added. The reaction was carried out at elevated temperature and reflux for 12 h, during which 50 mL of 10% NaOH solution was slowly added. After the reaction was completed, low-temperature refrigeration and suction filtration were carried out to obtain white solid intermediate product N-tetradecyl-2-aminoethanesulfonic acid sodium with a yield of 97.4%. 0.05 mol of N-tetradecyl-2-aminoethanesulfonic acid sodium was dissolved in 250 mL of methanol, and 1.1 times the molar amount of methyl acrylate was slowly added. After the addition was completed, the reaction was carried out at reflux for 4 h. Methyl alcohol was recovered by rotary evaporation to obtain white solid aminoethanesulfonic acid surfactant 2-(tetradecyl(3-methoxy-3-oxopropyl)amino)ethanesulfonic acid sodium with a yield of 97.9%.

[0043] (2) Preparation of microemulsion drainage aid 4.0 parts of 2-(tetradecyl(3-methoxy-3-oxopropyl)amino)ethanesulfonic acid sodium was dissolved in 50 parts of kerosene to obtain a first mixture; 1.0 parts of fatty alcohol polyoxyethylene ether carboxylic acid sodium was dissolved in 50 parts of tap water, stirred uniformly to obtain a second mixture; High-speed stirring (500 r / min) was started, and the water phase was slowly added into the oil phase. After uniform emulsification, it was left to stand and separate into layers. The lower microemulsion phase was taken, and the microemulsion drainage aid was obtained.

[0044] Example 17: (1) Preparation of aminoethanesulfonic acid surfactant 0.11 mol of tetradecylamine was uniformly stirred with 200 mL of anhydrous ethanol, and 0.1 mol of sodium chloroethyl sulfonate (dissolved in 20 mL of tap water) was added. The reaction was carried out at elevated temperature and reflux for 12 h, during which 50 mL of 10% NaOH solution was slowly added. After the reaction was completed, low-temperature refrigeration and suction filtration were carried out to obtain white solid intermediate product N-tetradecyl-2-aminoethanesulfonic acid sodium with a yield of 97.4%.

[0045] 0.05 mol of N-hexadecyl-2-aminoethanesulfonic acid sodium was dissolved in 250 mL of methanol, stirred uniformly, 1.1 times the molar amount of methyl acrylate was slowly added dropwise, and after the addition was completed, the reaction was refluxed for 4 h, methanol was recovered by rotary evaporation, and a white solid aminoethanesulfonic acid surfactant 2-(hexadecyl(3-methoxy-3-oxopropyl)amino)ethanesulfonic acid sodium was obtained, with a yield of 98.0%.

[0046] (2) Preparation of microemulsion cleanup agent 4.0 parts of 2-(hexadecyl(3-methoxy-3-oxopropyl)amino)ethanesulfonic acid sodium was dissolved in 50 parts of kerosene, stirred uniformly, and a first mixed solution was obtained; 1.0 parts of fatty alcohol polyoxyethylene ether carboxylic acid sodium was dissolved in 50 parts of tap water, stirred uniformly, and a second mixed solution was obtained; High-speed stirring (500 r / min) was started, the aqueous phase was slowly added dropwise into the oil phase, emulsified uniformly, and then allowed to stand and separate into layers, and the lower microemulsion phase was taken, to obtain the microemulsion cleanup agent.

[0047] The microemulsion cleanup agents prepared in Examples 13 to 17 were subjected to indoor experimental testing, and the test results are shown in Table 1. The aminoethanesulfonic acid surfactant of the present application has superior water solubility and surface activity, and the microemulsion cleanup agent using the aminoethanesulfonic acid surfactant of the present application as raw material can effectively reduce the interfacial tension, meet the use standards of the non-fluorocarbon cleanup agent industry, has a small amount of surfactant, and has low use cost. In addition, the aminoethanesulfonic acid surfactant of the present application also has the characteristics of biodegradability, non-biological toxicity, and green environmental protection.

[0048] In summary, the present application provides an aminoethanesulfonic acid surfactant which is biodegradable, non-biologically toxic, green and environmentally friendly, and has superior water solubility, surface activity, temperature resistance and salt resistance. Meanwhile, the present application prepares a microemulsion cleanup agent using the aminoethanesulfonic acid surfactant, and the microemulsion cleanup agent can effectively reduce the interfacial tension of the aqueous solution. The preparation method of the aminoethanesulfonic acid surfactant and the microemulsion cleanup agent of the present application has low reaction temperature, is safe and reliable, is simple to operate, has low equipment requirements, and has high yield, and is suitable for industrial production.

[0049] The above technical features constitute an embodiment of the present application, which has strong adaptability and implementation effect, and unnecessary technical features can be added or reduced according to actual needs to meet the needs of different situations.

Claims

1. A process for the preparation of an aminoethylsulfonic acid type surfactant, characterized by The method comprises the following steps: Step one, the fatty amine is dissolved in a first solvent, and a sodium chloroethyl sulfonate aqueous solution is added, and a reaction is performed to obtain N-long-chain alkyl-2-aminoethanesulfonic acid sodium; Step two, a required amount of N-long-chain alkyl-2-aminoethanesulfonic acid sodium is dissolved in a second solvent, and a required amount of methyl acrylate is added, and a reaction is performed to obtain an aminoethanesulfonic acid type surfactant.

2. The method for preparing an aminoethylsulfonic acid surfactant according to claim 1, characterized by In step one, the reaction is a reflux reaction, and the reaction time is 8h to 24h; or / and, the molar ratio of the fatty amine to the sodium chloroethyl sulfonate is 1.1 to 1.5:

1.

3. The method for producing an aminoethylsulfonic acid surfactant according to claim 1 or 2, characterized by In step one, the pH value of the reaction system during the reaction is between 7.0 and 7.

5.

4. The process for the preparation of an aminoethylsulfonic surfactant according to any one of claims 1 to 3, characterized in that The first solvent is anhydrous ethanol, and the second solvent is or methanol.

5. The process for the preparation of an aminoethylsulfonic surfactant according to any one of claims 1 to 4, characterized in that In step two, the molar ratio of the methyl acrylate to the N-long-chain alkyl-2-aminoethanesulfonic acid sodium is 1.1 to 1.5:1; or / and, in step two, the reaction is a reflux reaction, and the reaction time is 4h to 12h.

6. An aminoethyl sulfonic acid surfactant prepared according to the method of any one of claims 1 to 5, characterized by The chemical structural formula is wherein R is a C 12 to C 16 aliphatic hydrocarbon group.

7. The aminoethanesulfonic acid type surfactant according to claim 6 is applied in reservoir fracturing construction.

8. A microemulsion cleanup agent using the aminoethylsulfonic acid surfactant of claim 6 as a raw material, characterized by The raw materials include, by mass fraction: 2 to 10 parts of the aminoethanesulfonic acid type surfactant, 50 to 100 parts of an oil phase, 0.5 to 5 parts of an anionic surfactant, and 50 to 100 parts of water.

9. The microemulsion flushing aid of claim 8, wherein The microemulsion cleanup aid is prepared by the following steps: A required amount of the aminoethanesulfonic acid type surfactant is dissolved in the oil phase, and a first mixed solution is obtained after mixing; A required amount of the anionic surfactant is dissolved in water, and a second mixed solution is obtained after mixing; The second mixed solution is added to the first mixed solution, and stirring and mixing are performed, and after emulsification, the lower layer microemulsion phase is taken to obtain the microemulsion cleanup aid.

10. The microemulsion flushing aid of claim 8 or 9, wherein The oil phase is one or more of white oil, kerosene, and cyclohexane; or / and, the anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium fatty acid methyl ester sulfonate, and sodium fatty alcohol polyoxyethylene ether carboxylate.

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