Glycosyl sulfamic acid betaine type 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 sulfamic acid betaine type surfactant and a preparation method and application thereof.The glycosyl sulfamic acid betaine type surfactant is prepared according to the following steps that firstly, taurine and sodium methoxide with the required amount are mixed and then react, and a first reactant is obtained; 2, adding a required amount of glucose into the first reactant, and reacting to obtain an intermediate product; and step 3, adding N, N-dimethyl-2, 3-epoxypropyl alkyl ammonium chloride into the intermediate product for reaction, and recovering generated sodium chloride to obtain the glycosyl sulfamic acid betaine type surfactant. The method is easy and convenient to operate, the raw materials are green and degradable, environmental pollution is avoided, the obtained glycosyl sulfamic acid betaine type surfactant is used for preparing the acid fracturing discharge aiding agent, the surface tension of an aqueous solution can be effectively reduced, the technical requirements of the acid fracturing discharge aiding agent can be met, the overall production cost can be reduced, and the method is suitable for industrial production. The acid fracturing device is suitable for acid fracturing operation in different operation environments.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of oilfield chemical technology, and is a glycosyl amino sulfonic betaine surfactant, a preparation method and application thereof, and a cleanup aid for acid fracturing using the glycosyl amino sulfonic betaine surfactant as one of raw materials. BACKGROUND

[0002] Acid fracturing reconstruction technology is one of important measures 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 and yield increase and yield stabilization of conventional oil and gas fields. In the process of acid fracturing, the well return fluid is usually rapidly discharged to the ground by relying on the formation pressure. When the formation pressure gradually decreases, the return rate is obviously reduced, and the residues in the return fluid are precipitated to cause plugging, resulting in secondary pollution of the formation, and thus seriously affecting the recovery rate. In order to solve the problem of difficult return of the return fluid after oil acid fracturing, the use of cleanup aid is a conventional means.

[0003] The cleanup aid is one of fracturing fluid additives, which can effectively reduce the surface tension and interfacial tension, reduce the capillary resistance, and improve the return rate and return rate, so as to reduce the formation damage. The cleanup aid is mainly composed of a certain surfactant and other surfactants, and usually an organic solvent such as alcohol ether is added to increase the oil-water mutual solubility or improve the utilization rate of the surfactant. The added inorganic salt can enhance the ability of the surfactant to reduce the surface tension and oil-water interfacial tension.

[0004] The Chinese patent document with publication number CN93120030.X discloses that after the reaction of bromoalkane and diethyltriamine, and then the reaction with chloroacetic acid, an amino carboxylic acid type amphoteric surfactant is also obtained. However, since the scheme is to synthesize a carboxylic acid type amphoteric surfactant, a non-long-chain fatty amine is used in the selection of raw materials, which relatively reduces the raw material cost. However, the generated hydrogen halide gas in the reaction process is not treated in time, but is treated by escaping or neutralization after the reaction is completed. If the hydrogen halide gas does not escape in time, the reverse reaction will be intensified, which affects the product yield, and the escaping of the hydrogen halide gas will pollute the environment.

[0005] The Chinese patent document with publication number CN106609136A discloses a fluorocarbon surfactant oil displacement system, a preparation method and application thereof. The fluorocarbon surfactant oil displacement system is prepared by using fluorocarbon surfactant, fatty alcohol polyoxyethylene ether sulfate and anionic polyacrylamide as combined components of the oil displacement agent, and has good oil displacement effect, no alkali oil displacement system, good temperature resistance, and is suitable for the oil displacement system for oil field oil displacement. However, the fluorocarbon surfactant has high surface activity, and can reduce the surface tension to 23 mN / m. However, the fluorocarbon surfactant is expensive and difficult to degrade completely, and has high biological toxicity.

[0006] Therefore, it is urgent to develop a green and environmentally friendly cleanup agent system. SUMMARY

[0007] The present application provides a glycosyl betaine sulfamate surfactant, a preparation method and application thereof, which overcomes the shortcomings of the prior art, and effectively solves the problems of high price, difficult degradation, high biological toxicity and environmental pollution of the existing fluorocarbon surfactant.

[0008] One of the technical solutions of the present application is achieved by the following measures: a glycosyl betaine sulfamate surfactant, the chemical structural formula of which is: Among them, R is a C 12 to C 16 fatty alkyl group.

[0009] The following is a further optimization or / and improvement of the above-mentioned one of the technical solutions: The above is prepared by the following steps: First, a certain amount of taurine is mixed with sodium methoxide to obtain a first reactant; Second, a certain amount of glucose is added to the first reactant to obtain an intermediate product; Third, N,N-dimethyl-2,3-epoxypropyl alkyl ammonium chloride is added to the intermediate product to obtain a glycosyl betaine sulfamate surfactant, and the generated sodium chloride is recovered.

[0010] In the above first step, second step and third step, the molar ratio of taurine, sodium methoxide, glucose and N,N-dimethyl-2,3-epoxypropyl alkyl ammonium chloride is 1:1.05 to 1.1:1.05 to 1.1:1 to 1.1.

[0011] In the above first step, the reaction temperature is room temperature, and the reaction time is 20 min to 40 min.

[0012] In the above second step, the reaction temperature is 40℃ to 60℃, and the reaction time is 4h to 24h.

[0013] In the above third step, the reaction temperature is 40℃ to 60℃, and the reaction time is 4h to 12h.

[0014] The second technical solution of the present application is achieved by the following measures: a preparation method of a glycosyl betaine sulfamate surfactant, which is carried out according to the following steps: First, a certain amount of taurine is mixed with sodium methoxide to obtain a first reactant; Second, a certain amount of glucose is added to the first reactant to obtain an intermediate product; The third step is to add N,N-dimethyl-2,3-epoxypropyl alkyl ammonium chloride to the intermediate product, then react and recover the generated NaCl to obtain the sugar-based amidosulfobetaine surfactant.

[0015] The third technical solution of the present application is realized by the following measures: application of a sugar-based amidosulfobetaine surfactant in preparation of a cleanup agent for acid fracturing.

[0016] The fourth technical solution of the present application is realized by the following measures: a cleanup agent for acid fracturing taking a sugar-based amidosulfobetaine surfactant as one of raw materials, the raw materials including 0.5% to 9.5% anionic surfactant, 0.5% to 9.5% sugar-based amidosulfobetaine surfactant, and the rest being water, according to the following method: uniformly mixing the required amount of anionic surfactant, sugar-based amidosulfobetaine surfactant and water to obtain the cleanup agent for acid fracturing.

[0017] The following is a further optimization or / and improvement of the fourth technical solution of the present application: The anionic surfactant is sodium fatty alcohol polyoxyethylene ether carboxylate, and the molecular structure is as follows: , wherein R1 is a fatty alkyl group of C 12 to C 18 , and n is an integer greater than or equal to 2.

[0018] The method is simple to operate, the raw materials are green and degradable, and will not cause environmental pollution. The obtained sugar-based amidosulfobetaine surfactant used as a cleanup agent for acid fracturing can not only effectively reduce the surface tension of the aqueous solution to meet the technical requirements of the cleanup agent for acid fracturing, but also reduce the overall production cost, and is suitable for acid fracturing operations in different operating environments. DETAILED DESCRIPTION

[0019] 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 products mentioned in the present application are well-known and commonly used chemical reagents and chemical products in the prior art unless otherwise specified; the percentages in the present application are mass percentages unless otherwise specified; the solutions in the present application are aqueous solutions with water as the solvent unless otherwise specified, for example, a hydrochloric acid solution is an aqueous hydrochloric acid solution; 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℃.

[0020] The present application will be further described below in combination with examples: Example 1: The sugar-based amidosulfobetaine surfactant has a chemical structural formula as follows: wherein R is C 12 to C 16 fatty hydrocarbon group.

[0021] The glycosylaminosulfonic betaine surfactant and anionic surfactant compound can effectively reduce the surface tension of the aqueous solution. Therefore, it can be used to prepare acidizing fracturing cleanup agent, which can effectively reduce the surface tension of the aqueous solution and meet the technical specification of acidizing fracturing cleanup agent.

[0022] Example 2: As an optimization of the above examples, the glycosylaminosulfonic betaine surfactant is prepared according to the following steps: First, the required amount of taurine is mixed with sodium methoxide to obtain the first reactant; Second, the required amount of glucose is added to the first reactant to obtain the intermediate product; Third, N,N-dimethyl-2,3-epoxypropyl alkyl ammonium chloride is added to the intermediate product to obtain the glycosylaminosulfonic betaine surfactant, and the generated sodium chloride is recovered.

[0023] In the second step, the intermediate product is N-glucosyl aminoethanesulfonic acid sodium, wherein the chemical reaction process of N-glucosyl aminoethanesulfonic acid sodium is as follows: In the third step, the chemical reaction process of the glycosylaminosulfonic betaine surfactant is as follows: Example 3: As an optimization of the above examples, in the first step, the second step and the third step, the molar ratio of taurine, sodium methoxide, glucose and N,N-dimethyl-2,3-epoxypropyl alkyl ammonium chloride is 1:1.05 to 1.1:1.05 to 1.1:1 to 1.1.

[0024] Example 4: As an optimization of the above examples, in the first step, the reaction temperature is room temperature, and the reaction time is 20 min to 40 min.

[0025] Example 5: As an optimization of the above examples, in the second step, the reaction temperature is 40℃ to 60℃, and the reaction time is 4h to 24h.

[0026] Example 6: As an optimization of the above examples, in the third step, the reaction temperature is 40℃ to 60℃, and the reaction time is 4h to 12h.

[0027] Example 7: The preparation method of the glycosylaminosulfonic betaine surfactant is carried out according to the following steps: First step, the desired amount of taurine is mixed with sodium methoxide to obtain the first reactant; Second step, the desired amount of glucose is added to the first reactant to obtain the intermediate product; Third step, N, N-dimethyl-2, 3-epoxypropyl alkyl ammonium chloride is added to the intermediate product to obtain the glycosyl aminosulfonic betaine surfactant, and the generated NaCl is recovered.

[0028] Example 8: the application of the glycosyl aminosulfonic betaine surfactant in the preparation of the cleanup agent for acidizing fracturing.

[0029] Example 9: the cleanup agent for acidizing fracturing, which takes the glycosyl aminosulfonic betaine surfactant as one of the raw materials, the raw materials are 0.5% to 9.5% anionic surfactant, 0.5% to 9.5% glycosyl aminosulfonic betaine surfactant by mass fraction, and the rest is water, which is obtained by mixing the desired amount of anionic surfactant, glycosyl aminosulfonic betaine surfactant and water uniformly to obtain the cleanup agent for acidizing fracturing.

[0030] Example 10: as an optimization of the above examples, the anionic surfactant is sodium fatty alcohol polyoxyethylene ether carboxylate, and the molecular structure is as follows: , Wherein, R1 is a fatty alkyl group of C 12 to C 18 , and n is an integer greater than or equal to 2.

[0031] Example 11: (1) Preparation of the glycosyl aminosulfonic betaine surfactant 0.11 mol of sodium methoxide and 0.1 mol of taurine are dissolved in 400 mL of methanol (solvent), and the reaction is carried out at room temperature for 30 min, 0.11 mol of glucose is added, the temperature is raised to 45℃, and the reaction is carried out for 24 h, 0.1 mol of N, N-dimethyl-2, 3-epoxypropyl hexadecyl ammonium chloride is added, and the reaction is continued for 4 h, and then cooled, filtered, and the filtrate is evaporated to recover methanol to obtain the glycosyl aminosulfonic betaine surfactant. The obtained product does not need to be purified and can be used directly.

[0032] (2) Preparation of the cleanup agent for acidizing fracturing 9 parts of the glycosyl aminosulfonic betaine surfactant, 1 part of sodium fatty alcohol polyoxyethylene ether carboxylate and 90 parts of water are mixed uniformly to obtain the cleanup agent for acidizing fracturing.

[0033] The indoor experimental test results of the above-mentioned acid fracturing cleanup additive show that the surface tension is 23.356 mN / m and the interfacial tension is 0.069 mN / m at a mass percentage concentration of 0.3%, meeting the non-fluorocarbon cleanup additive industry use standard.

[0034] Example 12: (1) Preparation of the sugar-based amidosulfamic betaine surfactant 0.11 mol of sodium methoxide and 0.1 mol of taurine were dissolved in 400 mL of methanol (solvent), reacted at room temperature for 30 min, 0.11 mol of glucose was added, the temperature was raised to 45°C and reacted for 12 h, 0.1 mol of N,N-dimethyl-2,3-epoxypropyl hexadecyl ammonium chloride was added, and the reaction was continued for 4 h. After cooling and filtering, the filtrate was evaporated to recover methanol, and the sugar-based amidosulfamic betaine surfactant was obtained. The product obtained need not be purified and can be used directly.

[0035] (2) Preparation of the acid fracturing cleanup additive 9 parts of the sugar-based amidosulfamic betaine surfactant, 1 part of sodium fatty alcohol polyoxyethylene ether carboxylate and 90 parts of water were uniformly mixed to obtain the acid fracturing cleanup additive.

[0036] The indoor experimental test results of the above-mentioned acid fracturing cleanup additive show that the surface tension is 23.361 mN / m and the interfacial tension is 0.068 mN / m at a mass percentage concentration of 0.3%, meeting the non-fluorocarbon cleanup additive industry use standard.

[0037] Example 13: (1) Preparation of the sugar-based amidosulfamic betaine surfactant 0.11 mol of sodium methoxide and 0.1 mol of taurine were dissolved in 400 mL of methanol (solvent), reacted at room temperature for 30 min, 0.11 mol of glucose was added, the temperature was raised to 45°C and reacted for 8 h, 0.1 mol of N,N-dimethyl-2,3-epoxypropyl hexadecyl ammonium chloride was added, and the reaction was continued for 4 h. After cooling and filtering, the filtrate was evaporated to recover methanol, and the sugar-based amidosulfamic betaine surfactant was obtained. The product obtained need not be purified and can be used directly.

[0038] (2) Preparation of the acid fracturing cleanup additive 9 parts of the sugar-based amidosulfamic betaine surfactant, 1 part of sodium fatty alcohol polyoxyethylene ether carboxylate and 90 parts of water were uniformly mixed to obtain the acid fracturing cleanup additive.

[0039] The indoor experimental test results of the above-mentioned acid fracturing cleanup additive show that the surface tension is 23.363 mN / m and the interfacial tension is 0.068 mN / m at a mass percentage concentration of 0.3%, meeting the non-fluorocarbon cleanup additive industry use standard.

[0040] Example 14 (1) Preparation of the sugar-based amidosulfamic betaine surfactant 0.11 mol of sodium methoxide and 0.1 mol of taurine were dissolved in 400 mL of methanol (solvent) and reacted at room temperature for 30 min. Then, 0.11 mol of glucose was added, and the reaction was continued at 45°C for 8 h. Then, 0.1 mol of N,N-dimethyl-2,3-epoxypropyl hexadecyl ammonium chloride was added, and the reaction was continued for 12 h. After cooling and filtration, the filtrate was evaporated to recover methanol, and the sugar-based amidosulfamic betaine surfactant was obtained. The obtained product was used directly without purification.

[0041] (2) Preparation of the cleanup agent for acid fracturing 9 parts of the sugar-based amidosulfamic betaine surfactant, 1 part of sodium fatty alcohol polyoxyethylene ether carboxylate, and 90 parts of water were uniformly mixed to obtain the cleanup agent for acid fracturing.

[0042] The indoor experimental test results of the above-mentioned cleanup agent for acid fracturing showed that the surface tension was 23.372 mN / m and the interfacial tension was 0.071 mN / m at a mass percentage concentration of 0.3%, which met the industry use standard of non-fluorocarbon cleanup agents.

[0043] Example 15 (1) Preparation of the sugar-based amidosulfamic betaine surfactant 0.11 mol of sodium methoxide and 0.1 mol of taurine were dissolved in 400 mL of methanol (solvent) and reacted at room temperature for 30 min. Then, 0.11 mol of glucose was added, and the reaction was continued at 45°C for 8 h. Then, 0.1 mol of N,N-dimethyl-2,3-epoxypropyl hexadecyl ammonium chloride was added, and the reaction was continued for 12 h. After cooling and filtration, the filtrate was evaporated to recover methanol, and the sugar-based amidosulfamic betaine surfactant was obtained. The obtained product was used directly without purification.

[0044] (2) Preparation of the cleanup agent for acid fracturing 9 parts of the sugar-based amidosulfamic betaine surfactant, 1 part of sodium fatty alcohol polyoxyethylene ether carboxylate, and 90 parts of water were uniformly mixed to obtain the cleanup agent for acid fracturing.

[0045] The indoor experimental test results of the above-mentioned cleanup agent for acid fracturing showed that the surface tension was 23.374 mN / m and the interfacial tension was 0.078 mN / m at a mass percentage concentration of 0.3%, which met the industry use standard of non-fluorocarbon cleanup agents.

[0046] Example 16 (1) Preparation of the sugar-based amidosulfamic betaine surfactant Sodium methoxide 0.11 mol and taurine 0.1 mol were dissolved in 400 mL of methanol (solvent) at room temperature for 30 min, then glucose 0.11 mol was added, and the temperature was raised to 45 DEG C for 8 h, then N, N-dimethyl-2, 3-epoxypropyl hexadecyl ammonium chloride 0.1 mol was added, and the reaction was continued for 6 h, then the mixture was cooled, filtered, and the filtrate was evaporated to recover methanol, to obtain a sugar-based amidosulfobetaine surfactant, which was used directly without purification.

[0047] (2) Preparation of a cleanup agent for acid fracturing The cleanup agent for acid fracturing was prepared by mixing 9 parts of the sugar-based amidosulfobetaine surfactant, 1 part of sodium fatty alcohol polyoxyethylene ether carboxylate, and 90 parts of water.

[0048] According to the laboratory test results of the cleanup agent for acid fracturing, the surface tension was 22.679 mN / m and the interfacial tension was 0.386 mN / m at a mass percentage of 0.3%, which met the non-fluorocarbon cleanup agent industry standard.

[0049] The present application has the following advantages: (1) The sugar-based amidosulfobetaine surfactant is prepared by a safe and reliable method, which is directly used without separation and purification, and is simple to operate and suitable for large-scale production. (2) The cleanup agent for acid fracturing obtained by the present application uses the sugar-based amidosulfobetaine surfactant and anionic surfactant, both of which are biodegradable, non-toxic, and environmentally friendly, and can effectively solve the damage of existing fluorocarbon cleanup agents to the environment and organisms. (3) The cleanup agent for acid fracturing obtained by the present application has simple raw materials, and the mass of the surfactant accounts for only 10% of the total mass of the material, and has good composite synergistic characteristics between different types of surfactants, which can effectively reduce the surface and interfacial tension of the fracturing fluid, significantly reduce the amount of betaine surfactant, and reduce the overall cost. (4) The cleanup agent for acid fracturing obtained by the present application does not contain flammable, explosive, and volatile substances, and is suitable for acid fracturing operations in different operating environments.

[0050] In summary, the method of the present application is simple to operate, and the raw materials are green and biodegradable, which will not cause environmental pollution. The sugar-based amidosulfobetaine surfactant obtained by the method is used to prepare a cleanup agent for acid fracturing, which can not only effectively reduce the surface tension of the aqueous solution and meet the technical requirements of the cleanup agent for acid fracturing, but also reduce the overall production cost and be suitable for acid fracturing operations in different operating environments.

[0051] The above technical features constitute embodiments of the present application, which have strong adaptability and implementation effects. Unnecessary technical features can be added or reduced according to actual needs to meet the needs of different situations.

Claims

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

2. The sugar-based aminosulfonic betaine surfactant according to claim 1, characterized in that The following steps are taken to prepare: In the first step, a desired amount of taurine is mixed with sodium methoxide to obtain a first reactant; In the second step, a desired amount of glucose is added to the first reactant to obtain an intermediate product; In the third step, N,N-dimethyl-2,3-epoxypropyl alkyl ammonium chloride is added to the intermediate product to obtain a glycosyl betaine surfactant, and the generated sodium chloride is recovered.

3. The sugar-based aminosulfonic betaine surfactant according to claim 2, characterized in that In the first, second and third steps, the molar ratio of taurine, sodium methoxide, glucose and N,N-dimethyl-2,3-epoxypropyl alkyl ammonium chloride is 1:1.05 to 1.1:1.05 to 1.1:1 to 1.

1.

4. The sugar-based aminosulfonic betaine surfactant according to claim 2 or 3, characterized in that In the first step, the reaction temperature is room temperature, and the reaction time is 20 min to 40 min.

5. The sugar-based aminosulfonic betaine surfactant according to any one of claims 2 to 4, characterized in that In the second step, the reaction temperature is 40°C to 60°C, and the reaction time is 4 h to 24 h.

6. The sugar-based aminosulfonic betaine surfactant according to any one of claims 2 to 5, characterized in that In the third step, the reaction temperature is 40°C to 60°C, and the reaction time is 4 h to 12 h.

7. A process for the preparation of a glycosylsarcosinide surfactant of the betaine type according to claim 1 or 3 or 4 or 5 or 6, characterized in that The following steps are taken: In the first step, a desired amount of taurine is mixed with sodium methoxide to obtain a first reactant; In the second step, a desired amount of glucose is added to the first reactant to obtain an intermediate product; In the third step, N,N-dimethyl-2,3-epoxypropyl alkyl ammonium chloride is added to the intermediate product to obtain a glycosyl betaine surfactant, and the generated NaCl is recovered.

8. Use of the glycosyl betaine surfactant according to any one of claims 1 to 6 in the preparation of a cleanup agent for acid fracturing.

9. A cleanup additive for acid fracturing, which uses the sugar-based amidosulfamic betaine surfactant according to any one of claims 1 to 6 as one of the raw materials, characterized by The raw materials are 0.5% to 9.5% anionic surfactant, 0.5% to 9.5% glycosyl betaine surfactant, and the rest is water, according to the following method: mix a desired amount of anionic surfactant, glycosyl betaine surfactant and water uniformly to obtain a cleanup agent for acid fracturing.

10. The cleanup aid for acidizing fracturing of claim 9, wherein The anionic surfactant is sodium fatty alcohol polyoxyethylene ether carboxylate, and the molecular structure 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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