Glycosyl cationic surfactant as well as preparation method and application thereof

Abstract

The invention relates to the technical field of oilfield chemistry, in particular to a glycosyl cationic surface active agent and a preparation method and application thereof.The glycosyl cationic surface active agent is prepared according to the following steps that firstly, a required amount of N, N-dimethyl alkyl tertiary amine and epoxy chloropropane are mixed to react, and an intermediate product is obtained; and step 2, mixing a required amount of the intermediate product with glucosamine hydrochloride for reaction to obtain the glycosyl cationic surfactant. The glycosyl cationic surfactant provided by the invention can be directly used without separation and purification, and is simple to operate and suitable for large-scale production. The discharge aiding agent for acid fracturing, which is obtained by compounding the glycosyl cationic surfactant and the anionic surfactant, can effectively reduce the surface tension and the interfacial tension, meanwhile, remarkably reduces the use amount of the surfactant, is free of biotoxicity, green and environment-friendly, does not contain inflammable, explosive and volatile substances, and is suitable for acid fracturing in different operation environments.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of oil field chemistry, and is a glycosyl cationic surfactant, a preparation method and application thereof, and an acid fracturing cleanup agent. BACKGROUND

[0002] Reservoir reconstruction technology is an important measure for efficient development of oil and gas fields, and is a main technical means for realizing exploration and development of unconventional oil and gas resources, increasing production and stabilizing production of conventional oil and gas fields, and improving reservoir reconstruction effect. After the gel of the reconstruction fluid is broken, the fluid is usually returned to the ground in time by relying on the formation pressure. When the formation pressure gradually decreases, the return rate is significantly reduced, and the residue in the return fluid is precipitated to cause plugging, resulting in secondary pollution of the formation, thereby seriously affecting the reconstruction effect. In order to solve the problem of difficult return of the return fluid after acid fracturing, the use of a cleanup agent is a conventional means. The main component of the cleanup agent is a surfactant, which can reduce the surface and interfacial tension and increase the wetting angle to achieve the purpose of rapid return.

[0003] The cleanup agent is one of the fracturing fluid additives, and the surfactant is the main component of the cleanup agent, which can effectively reduce the surface tension and interfacial tension, reduce the capillary resistance, and improve the return rate and return rate, thereby reducing the formation damage. At present, many types of cleanup agents are used at home and abroad, but most of them are prepared by compounding fluorocarbon surfactants and other surfactants. This type of surfactant can effectively reduce the surface tension, interfacial tension and capillary force, and improve the wettability of the formation rock, so that the spent acid is easily discharged from the formation. Usually, this type of cleanup agent is mainly compounded by a polymer nonionic surfactant, a cationic quaternary ammonium salt and a fluorocarbon surfactant. The Chinese patent document with the publication number CN101538462A discloses an oil well cleanup agent, which comprises: dodecyl dimethyl benzyl ammonium chloride: 7.5-13.5%; fatty alcohol polyoxyethylene ether: 2-3.5%; fluorocarbon surfactant FN-3 (containing only one active group): 0.05-0.1%; and the rest is water. The final decomposition products of fluorine compounds in the environment and organisms are perfluorooctane sulfonic acid and perfluorooctane carboxylic acid, which are difficult to continue to degrade, have biological accumulation, are highly toxic, cause serious pollution, and are expensive. Therefore, it is urgent to develop a green and environmentally friendly cleanup agent system. SUMMARY

[0004] The present application provides a glycosyl cationic surfactant and a preparation method thereof, which overcomes the shortcomings of the prior art, and effectively solves the problems of difficult degradation and high biological toxicity of the existing fracturing surfactant.

[0005] One of the technical solutions of the present application is realized by the following measures: a glycosyl cationic surfactant, the chemical structural formula of which is wherein R is C 12 to C 16 fatty hydrocarbon group.

[0006] The following is a further optimization or / and improvement of one of the above technical solutions: The above sugar-based cationic surfactant is prepared by the following steps: Step one, the required amount of N,N-dimethyl alkyl tertiary amine and epichlorohydrin are mixed to obtain an intermediate product; Step two, the required amount of intermediate product and glucosamine hydrochloride are mixed to obtain a sugar-based cationic surfactant.

[0007] In the above step one, the intermediate product is 2,3-epoxypropyl-N,N-dimethyl alkyl ammonium chloride.

[0008] In the above step one, the molar ratio of N,N-dimethyl alkyl tertiary amine to epichlorohydrin is 1:2 to 1:10.

[0009] In the above step one, the reaction temperature is 50 to 80 DEG C, and the reaction time is 1 to 6 hours.

[0010] In the above step two, the molar ratio of intermediate product to glucosamine hydrochloride is 1:1.

[0011] In the above step two, the reaction temperature is 50 to 80 DEG C, and the reaction time is 4 to 12 hours.

[0012] The second technical solution of the present application is realized by the following measures: a preparation method of a sugar-based cationic surfactant, which is carried out by the following steps: Step one, the required amount of N,N-dimethyl alkyl tertiary amine and epichlorohydrin are mixed to obtain an intermediate product; Step two, the required amount of intermediate product and glucosamine hydrochloride are mixed to obtain a sugar-based cationic surfactant.

[0013] The third technical solution of the present application is realized by the following measures: application of a sugar-based cationic surfactant to a fracturing fluid additive.

[0014] The fourth technical solution of the present application is realized by the following measures: an acid fracturing cleanup agent, the raw materials are calculated by mass fraction, and in every one hundred parts of the acid fracturing cleanup agent, 8.5 to 9 parts of anionic surfactant, 0.5 to 1 part of sugar-based cationic surfactant, and the rest is water.

[0015] The following is a further optimization or / and improvement of the above fourth technical solution: The above anionic surfactant is sodium fatty alcohol polyoxyethylene ether carboxylate, and its chemical structural formula is: wherein R1 is a C 12 to C 18 fatty alkyl group, and n is an integer greater than or equal to 2.

[0016] The sugar-based cationic surfactant of the present application can be directly used without separation and purification, is simple to operate, and is suitable for large-scale production. The cleanup aid for acid fracturing obtained by compounding the sugar-based cationic surfactant with an anionic surfactant can effectively reduce the surface and interfacial tension, significantly reduce the amount of surfactant, is non-bio-toxic, green and environmentally friendly, does not contain flammable, explosive and volatile substances, and is suitable for acid fracturing operations in different operating environments. DETAILED DESCRIPTION

[0017] The present application is not limited by the following examples, and the specific implementation can be determined according to the technical solutions 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; the normal temperature and room temperature in the present application generally refer to a temperature of 15℃ to 25℃, and is generally defined as 25℃.

[0018] The present application will be further described below in conjunction with examples: Example 1: The sugar-based cationic surfactant has a chemical structural formula of wherein R is a C 12 to C 16 fatty alkyl group.

[0019] Example 2: As an optimization of the above examples, the sugar-based cationic surfactant is prepared according to the following steps: Step 1: A required amount of N,N-dimethylalkyl tertiary amine is mixed with epichlorohydrin to obtain an intermediate product; Step 2: A required amount of the intermediate product is mixed with glucosamine hydrochloride to obtain a sugar-based cationic surfactant.

[0020] Example 3: As an optimization of the above examples, in Step 1, the intermediate product is 2,3-epoxypropyl-N,N-dimethylalkyl ammonium chloride.

[0021] Example 4: As an optimization of the above examples, in Step 1, the molar ratio of N,N-dimethylalkyl tertiary amine to epichlorohydrin is 1:2 to 1:10.

[0022] Example 5: As an optimization of the above examples, in Step 1, the reaction temperature is 50℃ to 80℃, and the reaction time is 1h to 6h.

[0023] Example 6: As an optimization of the above examples, in step two, the molar ratio of the intermediate product to glucosamine hydrochloride is 1:1.

[0024] Example 7: As an optimization of the above examples, in step two, the reaction temperature is 50-80°C and the reaction time is 4-12 hours.

[0025] The preparation chemical reaction process of the sugar-based cationic surfactant of the present application is as follows: (1) Preparation of the intermediate product 2,3-epoxypropyl-N,N-dimethylalkyl ammonium chloride: (2) Preparation of the sugar-based cationic surfactant: .

[0026] Example 8: Application of the sugar-based cationic surfactant in fracturing fluid additives.

[0027] Example 9: The cleanup agent for acid fracturing, in which, per 100 parts of the acid fracturing cleanup agent, the anionic surfactant is 8.5-9 parts, the sugar-based cationic surfactant is 0.5-1 part, and the rest is water.

[0028] Example 10: As an optimization of the above examples, the anionic surfactant is a fatty alcohol polyoxyethylene ether carboxylic acid sodium, and its chemical structural formula is: wherein, R1 is a fatty alkyl group of C 12 to C 18 , and n is an integer greater than or equal to 2.

[0029] Compared with the prior art, the present application has the following beneficial effects: (1) The sugar-based cationic surfactant of the present application can be directly used without separation and purification, and is simple to operate and suitable for large-scale production.

[0030] (2) The cleanup agent for acid fracturing of the present application uses surfactants that are all degradable, non-bio-toxic, green and environmentally friendly, and can effectively avoid the damage of fluorocarbon cleanup agents to the environment and organisms; at the same time, the cleanup agent for acid fracturing does not contain flammable, explosive and volatile substances, and is suitable for acid fracturing operations in different operating environments.

[0031] (3) The cleanup agent for acid fracturing has good composite synergistic characteristics between different types of surfactants, can effectively reduce the surface and interfacial tension, and significantly reduce the amount of surfactant used and the use cost.

[0032] (4) The acidizing fracturing cleanup additive has simple components, the surfactant accounts for only 10% of the total amount, is low in cost and easy to prepare.

[0033] Example 11: (1) Preparation of the sugar-based cationic surfactant 1 mol of hexadecyl dimethyl tertiary amine is uniformly mixed with 10 mol of epichlorohydrin, heated to 80 DEG C, refluxed for 6 h, cooled to room temperature, filtered, washed with cold acetone, and vacuum dried to obtain white solid 2,3-epoxypropyl-N,N-dimethyl hexadecyl ammonium chloride with a yield of 98.6%.

[0034] 0.1 mol of 2,3-epoxypropyl-N,N-dimethyl hexadecyl ammonium chloride is dissolved in 0.1 mol of glucosamine hydrochloride in an appropriate amount of tap water, heated to 50 DEG C and reacted for 12 h to obtain a sugar-based cationic surfactant aqueous solution with a mass concentration of about 10%.

[0035] (2) Preparation of the acidizing fracturing cleanup additive 10 parts of the sugar-based cationic surfactant aqueous solution, 9 parts of fatty alcohol polyoxyethylene ether (9) carboxylic acid sodium and 81 parts of tap water are uniformly mixed to obtain the acidizing fracturing cleanup additive.

[0036] The indoor experimental test results of the acidizing fracturing cleanup additive are as follows: the surface tension is 24.036 mN / m, the interfacial tension is 0.347 mN / m under the condition of 0.3% mass percentage concentration, and the acidizing fracturing cleanup additive meets the non-fluorocarbon cleanup additive industry use standard.

[0037] Example 12: (1) Preparation of the sugar-based cationic surfactant 1 mol of hexadecyl dimethyl tertiary amine is uniformly mixed with 10 mol of epichlorohydrin, heated to 55 DEG C, refluxed for 6 h, cooled to room temperature, filtered, washed with cold acetone, and vacuum dried to obtain white solid 2,3-epoxypropyl-N,N-dimethyl hexadecyl ammonium chloride with a yield of 98.3%.

[0038] 0.1 mol of 2,3-epoxypropyl-N,N-dimethyl hexadecyl ammonium chloride is dissolved in 0.1 mol of glucosamine hydrochloride in an appropriate amount of tap water, heated to 50 DEG C and reacted for 8 h to obtain a sugar-based cationic surfactant aqueous solution with a mass concentration of about 10%.

[0039] (2) Preparation of the acidizing fracturing cleanup additive 10 parts of the sugar-based cationic surfactant aqueous solution, 9 parts of fatty alcohol polyoxyethylene ether (3) carboxylic acid sodium and 81 parts of tap water are uniformly mixed to obtain the acidizing fracturing cleanup additive.

[0040] The indoor experimental test results of the acidizing fracturing cleanup additive are as follows: surface tension of 23.038 mN / m, interfacial tension of 0.213 mN / m at a mass percentage concentration of 0.3%, meeting the non-fluorocarbon cleanup additive industry use standard.

[0041] Example 13 (1) Preparation of sugar-based cationic surfactant 1 mol of hexadecyl dimethyl tertiary amine is uniformly mixed with 10 mol of epichlorohydrin, warmed to 55°C, refluxed for 6 h, cooled to room temperature, filtered, washed with cold acetone, and vacuum dried to obtain white solid 2,3-epoxypropyl-N,N-dimethyl hexadecyl ammonium chloride with a yield of 98.3%; 0.1 mol of 2,3-epoxypropyl-N,N-dimethyl hexadecyl ammonium chloride is dissolved in an appropriate amount of tap water with 0.1 mol of glucosamine hydrochloride, warmed to 50°C, and reacted for 8 h to obtain a sugar-based cationic surfactant aqueous solution with a mass concentration of about 10%.

[0042] (2) Preparation of acidizing fracturing cleanup additive 5 parts of the sugar-based cationic surfactant aqueous solution, 9.5 parts of fatty alcohol polyoxyethylene ether (3) carboxylic acid sodium, and 86.5 parts of tap water are uniformly mixed to obtain the acidizing fracturing cleanup additive.

[0043] The indoor experimental test results of the acidizing fracturing cleanup additive are as follows: surface tension of 23.038 mN / m, interfacial tension of 0.213 mN / m at a mass percentage concentration of 0.3%, meeting the non-fluorocarbon cleanup additive industry use standard.

[0044] Example 14 (1) Preparation of sugar-based cationic surfactant 1 mol of hexadecyl dimethyl tertiary amine is uniformly mixed with 8 mol of epichlorohydrin, warmed to 55°C, refluxed for 6 h, cooled to room temperature, filtered, washed with cold acetone, and vacuum dried to obtain white solid 2,3-epoxypropyl-N,N-dimethyl hexadecyl ammonium chloride with a yield of 96.6%.

[0045] 0.1 mol of 2,3-epoxypropyl-N,N-dimethyl hexadecyl ammonium chloride is dissolved in an appropriate amount of tap water with 0.1 mol of glucosamine hydrochloride, warmed to 50°C, and reacted for 6 h to obtain a sugar-based cationic surfactant aqueous solution with a mass concentration of about 10%.

[0046] (2) Preparation of acidizing fracturing cleanup additive 5 parts of the sugar-based cationic surfactant aqueous solution, 9.5 parts of fatty alcohol polyoxyethylene ether (23) carboxylic acid sodium, and 86.5 parts of tap water are uniformly mixed to obtain the acidizing fracturing cleanup additive.

[0047] The indoor experiment test result of the acid fracturing cleanup agent is that the surface tension is 24.667 mN / m, the interfacial tension is 0.585 mN / m under the concentration of 0.3% mass percentage, and the acid fracturing cleanup agent meets the non-fluorocarbon cleanup agent industry use standard.

[0048] Example 15: (1) Preparation of the sugar-based cationic surfactant 1 mol of dodecyl dimethyl tertiary amine is uniformly mixed with 10 mol of epichlorohydrin, heated to 55 DEG C, refluxed for 6 h, cooled to room temperature, filtered, washed with cold acetone and vacuum dried to obtain white solid 2,3-epoxypropyl-N,N-dimethyl hexadecyl ammonium chloride with a yield of 97.6%.

[0049] 0.1 mol of 2,3-epoxypropyl-N,N-dimethyl dodecyl ammonium chloride is dissolved in 0.1 mol of glucosamine hydrochloride and an appropriate amount of tap water, heated to 50 DEG C and reacted for 6 h to obtain a sugar-based cationic surfactant aqueous solution with a mass concentration of about 10%.

[0050] (2) Preparation of the acid fracturing cleanup agent 5 parts of the sugar-based cationic surfactant aqueous solution, 9.5 parts of fatty alcohol polyoxyethylene ether (23) sodium carboxylate and 86.5 parts of tap water are uniformly mixed to obtain the acid fracturing cleanup agent.

[0051] The indoor experiment test result of the acid fracturing cleanup agent is that the surface tension is 24.667 mN / m, the interfacial tension is 0.585 mN / m under the concentration of 0.3% mass percentage, and the acid fracturing cleanup agent meets the non-fluorocarbon cleanup agent industry use standard.

[0052] In summary, the sugar-based cationic surfactant provided by the application has the advantages that the preparation method is simple to operate, the raw materials are green and degradable and will not cause environmental pollution, flammable, explosive and volatile organic solvents are not used in the synthesis process, the product can be directly used without separation and purification, the industrial production and popularization and application are facilitated, and the sugar-based cationic surfactant has a broad market prospect. The sugar-based cationic surfactant can be compounded with an anionic surfactant to effectively reduce the surface tension of an aqueous solution. The acid fracturing cleanup agent prepared from the sugar-based cationic surfactant can effectively reduce the surface and interfacial tension of an aqueous solution and meet the acid fracturing cleanup agent technical specification.

[0053] The above technical features constitute the embodiments of the application, have strong adaptability and implementation effect, and can be increased or decreased according to actual needs to meet the needs of different situations.

Claims

1. A glycosyl cationic surfactant characterized in that The chemical structural formula is wherein R is a C 12 to C 16 aliphatic hydrocarbon group.

2. The glycosylated cationic surfactant of claim 1, wherein The following steps are taken to prepare: Step one, a desired amount of N, N-dimethyl alkyl tertiary amine is mixed with epichlorohydrin to obtain an intermediate product. Step two, a desired amount of the intermediate product is mixed with glucosamine hydrochloride to obtain a glycosyl cationic surfactant.

3. The glycosylated cationic surfactant of claim 2, wherein In step one, the intermediate product is 2, 3-epoxypropyl-N, N-dimethyl alkyl ammonium chloride.

4. The glycosylated cationic surfactant according to claim 2 or 3, characterized in that In step one, the molar ratio of N, N-dimethyl alkyl tertiary amine to epichlorohydrin is 1:2 to 1:

10.

5. The glycosylated cationic surfactant according to any one of claims 2 to 4, characterized in that In step one, the reaction temperature is 50-80℃, and the reaction time is 1-6h.

6. The glycosylated cationic surfactant according to any one of claims 2 to 5, characterized in that In step two, the molar ratio of the intermediate product to glucosamine hydrochloride is 1:1; or / and, in step two, the reaction temperature is 50-80℃, and the reaction time is 4-12h.

7. A method of preparing a glycosylated cationic surfactant according to any one of claims 1 to 6, characterized in that The following steps are taken: Step one, a desired amount of N, N-dimethyl alkyl tertiary amine is mixed with epichlorohydrin to obtain an intermediate product. Step two, a desired amount of the intermediate product is mixed with glucosamine hydrochloride to obtain a glycosyl cationic surfactant.

8. The use of a glycosyl cationic surfactant according to any one of claims 1 to 6 as a fracturing fluid additive.

9. An acidizing fracturing cleanup agent using the sugar-based cationic surfactant of any one of claims 1 to 6 as a raw material, characterized by The raw materials are as follows: for every 100 parts of the acidizing fracturing cleanup additive, 8.5-9 parts of anionic surfactant, 0.5-1 part of glycosyl cationic surfactant, and the rest is water.

10. The acidizing fracturing fluid loss additive of claim 9, wherein The anionic surfactant is sodium fatty alcohol polyoxyethylene ether carboxylate, and its chemical structural formula is: The anionic surfactant is sodium fatty alcohol polyoxyethylene ether carboxylate, and its chemical structural formula is: wherein R1is a C 12 to C 18 aliphatic hydrocarbon group, and n is an integer greater than or equal to 2.

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