Benzalkonium chloride surfactants, methods of making and using the same

Abstract

The application relates to the technical field of oil field chemistry, and is a preparation method and application of an aminosulfonic betaine type surfactant. The aminosulfonic betaine surfactant and the preparation method thereof are simple in operation, high in product yield, green in biodegradation, and green in environmental protection; the product does not need to be separated and purified, and can be directly used, thereby reducing the cost. The cleanup aid for acid fracturing, which takes the surfactant as a main component, can effectively reduce the surface and interfacial tension of a fracturing fluid of an oil and gas field, and the surfactant in the cleanup aid is low in use amount, thereby reducing the use cost.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of oilfield chemical technology, and is an aminosulfonic betaine surfactant, a preparation method and application thereof, and a cleanup agent for acid fracturing. BACKGROUND

[0002] Acid fracturing 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, yield increase and yield stability of conventional oil and gas fields, and improvement of reservoir reconstruction effect. In the acid fracturing process, 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 significantly reduced, and the residues in the return fluid are precipitated to cause plugging, resulting in secondary pollution of the formation, thereby seriously affecting the construction efficiency and the acid fracturing reconstruction effect. In order to solve the problem of difficult return of the return fluid after the acid fracturing, the cleanup agent is a conventional means.

[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 the interfacial tension, reduce the capillary resistance, and improve the return rate and the 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. The fluorocarbon surfactant has high surface activity, and can reduce the surface tension to 23 mN / m. However, it is expensive and difficult to degrade, and has high biological toxicity, so the European Union has banned the use of fluorocarbon surfactants since June 2008. Therefore, it is urgent to develop green and environmentally friendly surfactants suitable for cleanup agents and cleanup agent systems. SUMMARY

[0004] The present application provides an aminosulfonic betaine surfactant, a preparation method and application thereof, which overcomes the shortcomings of the prior art, and effectively solves the problems of high price and difficult degradation of the surfactant for the cleanup agent.

[0005] One of the technical solutions of the present application is achieved by the following measures: an aminosulfonic betaine surfactant, the chemical structural formula of which is

[0006]

[0007] Among them, R is a fatty hydrocarbon group of C 12 to C 16 .

[0008] The following is a further optimization or / and improvement of the above-mentioned one of the technical solutions:

[0009] The above-mentioned aminosulfonic betaine surfactant is prepared by the following steps:

[0010] The first step, the required amount of N, N-dimethyl alkyl tertiary amine and epichlorohydrin are mixed, stirred uniformly, reacted at the required temperature, and the intermediate product 2, 3-epoxy propyl-N, N-dimethyl long chain alkyl ammonium chloride is obtained;

[0011] The second step, the required amount of intermediate product 2, 3-epoxy propyl-N, N-dimethyl long chain alkyl ammonium chloride, taurine, sodium hydroxide are dissolved in water, stirred uniformly, reacted at the required temperature, and the amino sulfonic acid betaine type surfactant is obtained.

[0012] In the above first step, the molar ratio of N, N-dimethyl alkyl tertiary amine to epichlorohydrin is 1:4 to 1:10.

[0013] In the above first step, the reaction temperature is 50-80℃, and the reaction time is 1-6h.

[0014] In the above second step, the molar ratio of intermediate product 2, 3-epoxy propyl-N, N-dimethyl long chain alkyl ammonium chloride, taurine and sodium hydroxide is 1:1:1.

[0015] In the above second step, the reaction temperature is 50-80℃, and the reaction time is 4-12h.

[0016] The second technical scheme of the present application is realized by the following measures: a preparation method of an amino sulfonic acid betaine type surfactant, comprising the following steps:

[0017] The first step, the required amount of N, N-dimethyl alkyl tertiary amine and epichlorohydrin are mixed, stirred uniformly, reacted at the required temperature, and the intermediate product 2, 3-epoxy propyl-N, N-dimethyl long chain alkyl ammonium chloride is obtained;

[0018] The second step, the required amount of intermediate product 2, 3-epoxy propyl-N, N-dimethyl long chain alkyl ammonium chloride, taurine, sodium hydroxide are dissolved in water, stirred uniformly, reacted at the required temperature, and the amino sulfonic acid betaine type surfactant is obtained.

[0019] The third technical scheme of the present application is realized by the following measures: an application of an amino sulfonic acid betaine type surfactant in a fracturing fluid additive.

[0020] The fourth technical scheme of the present application is realized by the following measures: a cleanup aid for acid fracturing, which comprises, in terms of mass fraction, 9-9.5 parts of anionic surfactant, 0.5-1 part of amino sulfonic acid betaine type surfactant, and the rest is water; the anionic surfactant, the amino sulfonic acid betaine type surfactant and the water are stirred and mixed uniformly at room temperature to obtain the cleanup aid for acid fracturing.

[0021] The following is a further optimization or / and improvement of the fourth technical scheme of the above invention:

[0022] The anionic surfactant is sodium fatty alcohol polyoxyethylene ether carboxylate, and its chemical structural formula is as follows:

[0023]

[0024] In the formula, R1 is a fatty alkyl group of C12-C16, and n is an integer greater than or equal to 3. 12 to C 18 n is an integer greater than or equal to 3.

[0025] The amino sulfonic betaine surfactant of the present application has simple preparation method, is green and biodegradable, and can be directly used without separation and purification, so it is convenient and low in cost. The cleanup aid for acidizing fracturing containing the amino sulfonic betaine surfactant as a main component can effectively reduce the surface and interfacial tension of fracturing fluid, and the surfactant has low dosage and low use cost. DETAILED DESCRIPTION

[0026] 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 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 15-25℃, and is generally defined as 25℃.

[0027] The present application will be further described below in combination with examples:

[0028] Example 1: The amino sulfonic betaine surfactant has a chemical structural formula as follows:

[0029]

[0030] In the formula, R is a fatty alkyl group of C12-C16.

[0031] Example 2: As an optimization of the above example, the amino sulfonic betaine surfactant is prepared by the following steps:

[0032] Firstly, a required amount of N,N-dimethylalkyl tertiary amine is mixed with epichlorohydrin, stirred uniformly, and reacted at a required temperature to obtain an intermediate product 2,3-epoxypropyl-N,N-dimethyl long-chain alkyl ammonium chloride;

[0033] Second step, the required amount of intermediate product 2, 3-epoxy propyl-N, N-dimethyl long chain alkyl ammonium chloride, taurine, sodium hydroxide is dissolved in water, stirring, reaction at the required temperature, namely the preparation of aminosulfonic betaine surfactant. The aminosulfonic betaine surfactant can be directly used.

[0034] Example 3: as the optimization of the above examples, in the first step, the molar ratio of N, N-dimethyl alkyl tertiary amine to epichlorohydrin is 1:4 to 1:10.

[0035] Example 4: as the optimization of the above examples, in the first step, the reaction temperature is 50-80℃, and the reaction time is 1-6h.

[0036] Example 5: as the optimization of the above examples, in the second step, the molar ratio of intermediate product 2, 3-epoxy propyl-N, N-dimethyl long chain alkyl ammonium chloride, taurine and sodium hydroxide is 1:1:1.

[0037] Example 6: as the optimization of the above examples, in the second step, the reaction temperature is 50-80℃, and the reaction time is 4-12h.

[0038] The chemical reaction process of the above preparation method is as follows:

[0039] (1) Preparation of 2, 3-epoxy propyl-N, N-dimethyl long chain alkyl ammonium chloride:

[0040]

[0041] (2) Preparation of aminosulfonic betaine surfactant:

[0042]

[0043] The preparation method of the aminosulfonic betaine surfactant prepared by the application is simple, the product yield is high, the product is green and biodegradable; no flammable, explosive and volatile organic solvents are used in the synthesis process, which is safe and reliable; the product does not need to be separated and purified, and can be directly used, which reduces the cost and shortens the production cycle.

[0044] Example 7: the preparation method of the aminosulfonic betaine surfactant, comprising the following steps:

[0045] First step, the required amount of N, N-dimethyl alkyl tertiary amine and epichlorohydrin are mixed, stirred uniformly, and reacted at the required temperature to obtain intermediate product 2, 3-epoxy propyl-N, N-dimethyl long chain alkyl ammonium chloride;

[0046] Secondly, the required amount of intermediate product 2,3-epoxypropyl-N,N-dimethyl long chain alkyl ammonium chloride, taurine and sodium hydroxide are dissolved in water, stirred uniformly, and reacted at a required temperature to obtain the sulfamate betaine surfactant.

[0047] Example 8: Application of the sulfamate betaine surfactant to a fracturing fluid additive.

[0048] Example 9: A cleanup agent for acid fracturing, which comprises, in terms of mass fraction per 100 parts, 9 to 9.5 parts of an anionic surfactant, 0.5 to 1 part of the sulfamate betaine surfactant, and the rest is water; the anionic surfactant, the sulfamate betaine surfactant and water are stirred and mixed uniformly at room temperature to obtain the cleanup agent for acid fracturing.

[0049] The cleanup agent for acid fracturing of the present application can be directly prepared using oilfield produced water, flowback fluid and other oilfield sewage for acid fracturing construction.

[0050] Example 10: As an optimization of the above examples, the anionic surfactant is a sodium fatty alcohol polyoxyethylene ether carboxylate, and its chemical structural formula is:

[0051]

[0052] wherein R1 is a fatty alkyl group of C 12 to C 18 n is an integer greater than or equal to 3.

[0053] The present application provides a sulfamate betaine surfactant and a preparation method thereof, which is simple in operation, green in raw materials, safe and reliable in synthesis process, and does not cause environmental pollution; the product does not need to be separated and purified, and can be directly used to effectively reduce the surface tension of aqueous solution; is conducive to industrialized production and popularization and application, and has a broad market prospect. The cleanup agent with the sulfamate betaine surfactant as a main component effectively reduces the surface and interfacial tension of a fracturing fluid of an oil and gas field, has good composite synergistic characteristics between the two surfactants in the raw material, significantly reduces the amount of surfactant in the cleanup agent, and reduces the use cost.

[0054] Example 11:

[0055] 1 mol of hexadecyl dimethyl tertiary amine is uniformly mixed with 5.5 mol of epichlorohydrin, heated to 55℃, refluxed for 5 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.

[0056] Sodium 2,3-epoxypropyl-N,N-dimethyltetradecyl ammonium chloride was prepared by mixing 1 mol of tetradecyl dimethyl tertiary amine with 5.0 mol of epichlorohydrin, heating to 50°C, refluxing for 6 h, and recovering epichlorohydrin by rotary evaporation to obtain yellow viscous liquid.

[0057] Sodium lauryl alcohol polyoxyethylene ether (3) carboxylate was prepared by mixing 9.5 parts by mass of lauryl alcohol polyoxyethylene ether (3) with 2.5 parts by mass of the aqueous sulfobetaine surfactant solution, dissolving in 88.0 parts by mass of water, and stirring at room temperature until dissolved to obtain 100 parts of the cleanup additive for acid fracturing.

[0058] The laboratory test results of the cleanup additive for acid fracturing showed that the surface tension of the cleanup additive for acid fracturing was 23.071 mN / m and the interfacial tension was 0.139 mN / m at a mass percentage concentration of 0.3%, which met the industry use standard of non-fluorocarbon cleanup additives.

[0059] Example 12:

[0060] The aqueous sulfobetaine surfactant solution with a mass concentration of about 20% was prepared according to the method of Example 11.

[0061] Sodium lauryl alcohol polyoxyethylene ether (23) carboxylate was prepared by mixing 9.0 parts by mass of lauryl alcohol polyoxyethylene ether (23) with 5.0 parts by mass of the aqueous sulfobetaine surfactant solution, dissolving in 86.0 parts by mass of water, and stirring at room temperature until dissolved to obtain 100 parts of the cleanup additive for acid fracturing.

[0062] The laboratory test results of the cleanup additive for acid fracturing showed that the surface tension of the cleanup additive for acid fracturing was 24.037 mN / m and the interfacial tension was 0.172 mN / m at a mass percentage concentration of 0.3%, which met the industry use standard of non-fluorocarbon cleanup additives.

[0063] Example 13:

[0064] Sodium 2,3-epoxypropyl-N,N-dimethyltetradecyl ammonium chloride was prepared by mixing 1 mol of tetradecyl dimethyl tertiary amine with 5.0 mol of epichlorohydrin, heating to 50°C, refluxing for 6 h, and recovering epichlorohydrin by rotary evaporation to obtain yellow viscous liquid.

[0065] Sodium 2,3-epoxypropyl-N,N-dimethyltetradecyl ammonium chloride was prepared by mixing 1 mol of tetradecyl dimethyl tertiary amine with 5.0 mol of epichlorohydrin, heating to 50°C, refluxing for 6 h, and recovering epichlorohydrin by rotary evaporation to obtain yellow viscous liquid.

[0066] 9.5 parts by mass of sodium octadecanol polyoxyethylene ether (9) carboxylate, 2.5 parts by mass of an aqueous solution of aminobenzoate betaine surfactant, and 88.0 parts by mass of water were weighed, stirred at room temperature, and uniformly dissolved to prepare 100 parts of a cleanup additive for acid fracturing.

[0067] The laboratory test results of the cleanup additive for acid fracturing show that the surface tension of the cleanup additive for acid fracturing is 23.738 mN / m and the interfacial tension is 0.039 mN / m at a mass percentage concentration of 0.3%, which meets the industry use standard of non-fluorocarbon cleanup additives.

[0068] Example 14:

[0069] 1 mol of dodecyl dimethyl tertiary amine was uniformly mixed with 6.0 mol of epichlorohydrin, heated to 50 DEG C, refluxed for 6 h, and the epichlorohydrin was recovered by rotary evaporation to obtain yellow viscous liquid 2,3-epoxypropyl-N,N-dimethyl dodecyl ammonium chloride.

[0070] 5.0 parts by mass of taurine was dissolved in 60.0 parts by mass of tap water, 1.6 parts by mass of sodium hydroxide was slowly added, stirred uniformly, 14.5 parts by mass of 2,3-epoxypropyl-N,N-dimethyl dodecyl ammonium chloride was added, heated to 60 DEG C, and reacted for 12 h to obtain an aqueous solution of aminobenzoate betaine surfactant with a mass concentration of about 20%.

[0071] 9.5 parts by mass of sodium hexadecanol polyoxyethylene ether (20) carboxylate, 2.5 parts by mass of an aqueous solution of aminobenzoate betaine surfactant, and 88.0 parts by mass of water were weighed, stirred at room temperature, and uniformly dissolved to prepare 100 parts of a cleanup additive for acid fracturing.

[0072] The laboratory test results of the cleanup additive for acid fracturing show that the surface tension of the cleanup additive for acid fracturing is 23.894 mN / m and the interfacial tension is 0.134 mN / m at a mass percentage concentration of 0.3%, which meets the industry use standard of non-fluorocarbon cleanup additives.

[0073] In summary, the present application provides a kind of aminobenzoate betaine surfactant and preparation method thereof, preparation process is simple, product yield is high, product is biodegradable, green and environmental protection, and does not need to separate and purify, can be directly used.Acid fracturing cleanup additive with aminobenzoate betaine surfactant as main component can effectively reduce the surface and interfacial tension of oil and gas field fracturing fluid, and the amount of surfactant in the acid fracturing cleanup additive is low, which reduces the use cost.

[0074] The above technical features constitute embodiments of the present application, which have strong adaptability and implementation effect. Non-essential technical features can be added or removed according to actual needs to meet different needs.

Claims

1. An aminosulfonic betaine surfactant, characterized by The chemical structural formula is: wherein R is a C 12 to C 16 aliphatic hydrocarbon group.

2. A process for the preparation of aminosulfonic betaine surfactants according to claim 1, characterized in that The following steps are taken to prepare: In the first step, the required amount of N, N-dimethyl alkyl tertiary amine is mixed with epichlorohydrin, stirred uniformly, and reacted at the required temperature to obtain the intermediate product 2, 3-epoxypropyl-N, N-dimethyl long-chain alkyl ammonium chloride; In the second step, the required amount of intermediate product 2, 3-epoxypropyl-N, N-dimethyl long-chain alkyl ammonium chloride, taurine, and sodium hydroxide are dissolved in water, stirred uniformly, and reacted at the required temperature to obtain the aminosulfonic betaine surfactant.

3. The method for preparing aminosulfonic acid betaine-type surfactants according to claim 2, characterized in that... In the first step, the molar ratio of N, N-dimethyl alkyl tertiary amine to epichlorohydrin is 1:4 to 1:

10.

4. The method for producing aminosulfonic betaine surfactant according to claim 2 or 3, characterized by In the first step, the reaction temperature is 50°C to 80°C, and the reaction time is 1h to 6h.

5. The method for preparing aminosulfonic betaine surfactant according to claim 2 or 3, characterized by In the second step, the molar ratio of intermediate product 2, 3-epoxypropyl-N, N-dimethyl long-chain alkyl ammonium chloride, taurine, and sodium hydroxide is 1:1:

1.

6. The method for preparing aminosulfonic acid betaine-type surfactants according to claim 5, characterized in that... In the second step, the reaction temperature is 50°C to 80°C, and the reaction time is 4h to 12h.

7. The aminosulfonic betaine surfactant according to claim 1 for use as a fracturing fluid additive.

8. A cleanup additive for acid fracturing using the aminosulfonic betaine surfactant of claim 1 as a raw material, characterized by The raw materials include 9 to 9.5 parts of anionic surfactant, 0.5 to 1 part of aminosulfonic betaine surfactant, and the rest is water, with each hundred parts by mass; the anionic surfactant, aminosulfonic betaine surfactant, and water are stirred and mixed uniformly at room temperature to obtain the cleanup aid for acidizing fracturing.

9. The cleanup aid for acidizing fracturing of claim 8, wherein 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 3.

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