Process for the preparation of aminosulphonic betaine surfactants containing polyoxyethylene ether segments and use thereof

Abstract

The present application relates to the oil field chemical technology field, it is a kind of preparation method and application of amino sulfonic acid betaine type surfactant containing polyoxyethylene ether chain segment, the amino sulfonic acid betaine type surfactant containing polyoxyethylene ether chain segment raw material includes by mass fraction.The amino sulfonic acid betaine type surfactant containing polyoxyethylene ether chain segment of the present application is green environmental protection, biodegradable, preparation operation is simple, and flammable, explosive, volatile organic solvent is not used in process, safe and reliable;It is beneficial to industrial production and popularization and application, and has broad market prospect.The acidizing fracturing cleanup aid with it as raw material can effectively reduce the oil and gas field fracturing fluid surface, interfacial tension, while the amount of surfactant in cleanup aid is lower, and the use cost is saved.

Description

Technical Field

[0001] This invention relates to the field of oilfield chemical technology, specifically to an aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments, its preparation method and application, and an acid fracturing aid using an aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments as a raw material. Background Technology

[0002] Fracturing technology is a crucial measure for the stimulation of low-permeability and ultra-low-permeability oil and gas reservoirs. It is a leading technology for achieving efficient development of unconventional oil and gas resources, increasing and stabilizing production in conventional oil and gas fields, and improving reservoir stimulation effectiveness. During fracturing, formation pressure is typically required to rapidly expel flowback fluid from the well to the surface. As formation pressure gradually decreases, the flowback rate drops significantly. Residue in the flowback fluid can precipitate and cause blockages, leading to secondary formation contamination and severely impacting operational efficiency and the effectiveness of acid fracturing. To address the difficulty of flowback fluid after acid fracturing, the use of flowback aids is a conventional method.

[0003] Fracturing fluid aids are a type of fracturing fluid additive, primarily composed of surfactants. They effectively reduce surface and interfacial tension, decrease capillary resistance, and increase flowback rate and efficiency, thereby minimizing formation damage. Currently, fluorocarbon surfactants are widely used as the main component of fracturing fluid aids both domestically and internationally, prepared by compounding fluorocarbon surfactants with other surfactants and low-carbon alcohols. Fluorocarbon surfactants have high surface activity, capable of reducing surface tension to 23 mN / m; however, they are expensive, difficult to degrade, and highly biotoxic, potentially causing harm to humans and the environment. Low-carbon alcohols (such as methanol, ethanol, and isopropanol) are highly volatile, posing health and safety hazards in production environments and on-site operations. Developing a non-biotoxic surfactant, and based on this, developing a green and environmentally friendly fracturing fluid aid system free of low-carbon alcohols and fluorocarbon surfactants, has become an urgent problem to be solved. Summary of the Invention

[0004] This invention provides an aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments, its preparation method, and its application, overcoming the shortcomings of the prior art. It can effectively solve the problems of biotoxicity and health and safety risks posed by existing surfactants and drainage aids used in fracturing fluids.

[0005] One of the technical solutions of this invention is achieved through the following measures: an aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments, with the chemical structural formula as follows:

[0006]

[0007] Where R1 is C 12 To C 16aliphatic hydrocarbon group, R2 is C 12 To C 18 The aliphatic hydrocarbon group, where n is an integer greater than or equal to 2.

[0008] The following are further optimizations and / or improvements to one of the above-mentioned technical solutions:

[0009] The above-mentioned aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments is prepared by the following steps: adding an equimolar amount of fatty alcohol polyoxyethylene glycidyl ether to an aqueous solution of the aminosulfonic acid betaine type surfactant, mixing evenly and reacting to obtain the aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments.

[0010] The reaction temperature is between 50°C and 80°C.

[0011] The reaction time is 4 to 12 hours.

[0012] The molar ratio of the above-mentioned aminosulfonic acid betaine-type surfactant to fatty alcohol polyoxyethylene glycidyl ether is 1:1.

[0013] The second technical solution of the present invention is achieved by the following measures: a method for preparing an aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments, comprising the following steps: adding an equimolar amount of fatty alcohol polyoxyethylene glycidyl ether to an aqueous solution of the aminosulfonic acid betaine type surfactant, mixing evenly and reacting to obtain an aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments.

[0014] The following are further optimizations and / or improvements to the second technical solution of the above invention:

[0015] The reaction temperature is between 50°C and 80°C.

[0016] The reaction time is 4 to 12 hours.

[0017] The molar ratio of the above-mentioned aminosulfonic acid betaine-type surfactant to fatty alcohol polyoxyethylene glycidyl ether is 1:1.

[0018] The third technical solution of the present invention is achieved through the following measures: the application of an aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments in fracturing fluid additives.

[0019] The fourth technical solution of the present invention is achieved through the following measures: an acid fracturing pumping aid, wherein every 100 parts by mass of the raw materials include: 8.0 to 9.5 parts of aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments, 0.5 to 2.0 parts of anionic surfactant, and the remainder being water; the aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments, the anionic surfactant, and water are stirred and mixed evenly at room temperature to obtain the acid fracturing pumping aid.

[0020] The following are further optimizations and / or improvements to the fourth technical solution of the invention described above:

[0021] The aforementioned anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium oleate, sodium dodecanoate, sodium tetradecanoate, and sodium hexadecanoate.

[0022] The aminosulfonic acid betaine-type surfactant of this invention, containing polyoxyethylene ether segments, is green, environmentally friendly, and biodegradable. Its preparation process employs a one-pot method, which is simple, yields a high product, and the obtained product can be used directly without separation and purification, reducing costs and shortening the production cycle. When mixed with other types of surfactants, it exhibits excellent synergistic effects, effectively reducing the surface and interfacial tension of fracturing fluids in oil and gas fields, while significantly reducing the amount of surfactant used in drainage aids, thus lowering usage costs. Detailed Implementation

[0023] This invention is not limited to the following embodiments, and specific implementation methods can be determined according to the technical solutions and actual conditions of this invention. Unless otherwise specified, all chemical reagents and chemicals mentioned in this invention are well-known and commonly used chemical reagents and chemicals in the prior art; unless otherwise specified, all percentages in this invention are mass percentages; unless otherwise specified, all solutions in this invention are aqueous solutions with water as the solvent, for example, hydrochloric acid solution is an aqueous solution of hydrochloric acid; room temperature in this invention generally refers to a temperature between 15°C and 25°C, generally defined as 25°C.

[0024] The present invention will be further described below with reference to embodiments:

[0025] Example 1: The aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments has the following chemical structural formula:

[0026]

[0027] Where R1 is C 12 To C 16 aliphatic hydrocarbon group, R2 is C 12 To C 18 The aliphatic hydrocarbon group, where n is an integer greater than or equal to 2.

[0028] Example 2: As an optimization of the above example, the preparation method of aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments is carried out according to the following steps: an equimolar amount of fatty alcohol polyoxyethylene glycidyl ether is added to an aqueous solution of aminosulfonic acid betaine type surfactant, and after mixing evenly, the mixture is reacted to obtain aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments.

[0029] The chemical reactions involved in the preparation of the aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments are as follows:

[0030]

[0031] Example 3: As an optimization of the above example, the reaction temperature is 50°C to 80°C.

[0032] Example 4: As an optimization of the above examples, the reaction time is 4h to 12h.

[0033] Example 5: As an optimization of the above example, the molar ratio of aminosulfonic acid betaine type surfactant to fatty alcohol polyoxyethylene glycidyl ether is 1:1.

[0034] Example 6: Application of the aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments in fracturing fluid additives.

[0035] Example 7: The acid fracturing flow aid comprises, by weight, 8.0 to 9.5 parts of aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments, 0.5 to 2.0 parts of anionic surfactant, and the remainder being water; the aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments, the anionic surfactant, and water are stirred and mixed evenly at room temperature to obtain the acid fracturing flow aid.

[0036] Example 8: As an optimization of the above examples, the anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium oleate, sodium dodecanoate, sodium tetradecanoate, and sodium hexadecanoate.

[0037] This invention provides an aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments and its preparation method, as well as an acid fracturing flow aid. In practical use, the acid fracturing flow aid can be directly prepared from oilfield wastewater such as oilfield produced water and fracturing flowback fluid and used in fracturing operations.

[0038] This invention discloses a method for preparing aminosulfonic acid betaine-type surfactants containing polyoxyethylene ether segments. This method is simple to operate, uses green and biodegradable raw materials, and will not cause environmental pollution. The synthesis process does not use flammable, explosive, or volatile organic solvents, making it safe and reliable. The product does not require separation and purification and can be used directly. It is conducive to industrial production and widespread application, and has broad market prospects. Acid fracturing flow aids made from this method can effectively reduce the surface tension of aqueous solutions, meeting the requirements of acid fracturing flow aid technical specifications.

[0039] Example 9:

[0040] Weigh 218.5 parts by weight of aminosulfonic acid betaine surfactant (effective concentration of about 20%, the aliphatic hydrocarbon group R1 in its chemical structure is hexadecyl), 36.3 parts by weight of lauryl alcohol polyoxyethylene ether (3) glycidyl ether and 725.3 parts by weight of water, stir at room temperature, dissolve evenly, heat to 70°C and react for 6 hours to obtain an aqueous solution of aminosulfonic acid betaine type surfactant containing polyoxyethylene ether chain segments.

[0041] At room temperature, 15.0 parts (by weight) of sodium oleate and 5.0 parts (by weight) of sodium dodecyl sulfate were added to the above aqueous solution of aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments, and stirred evenly to obtain a discharge aid of about 1000 parts by weight.

[0042] Laboratory test results of the acid fracturing pumping agent: at a concentration of 0.3% by mass, the surface tension of the acid fracturing pumping agent is 22.987 mN / m and the interfacial tension is 0.655 mN / m, which meets the industry standards for non-fluorocarbon pumping agents.

[0043] Example 10:

[0044] Weigh out 18.60 parts by weight of aminosulfonic acid betaine surfactant (effective concentration of about 20%, the aliphatic hydrocarbon group R1 in its chemical structure is hexadecyl), 5.28 parts by weight of lauryl alcohol polyoxyethylene ether (3) glycidyl ether and 72.53 parts by weight of water, stir at room temperature, dissolve evenly, heat to 70°C and react for 6 hours to obtain an aqueous solution of aminosulfonic acid betaine type surfactant containing polyoxyethylene ether chain segments.

[0045] At room temperature, 1.5 parts (by weight) of sodium oleate and 0.5 parts (by weight) of sodium hexadecanoate were added to the above aqueous solution of aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments, and stirred evenly to obtain a discharge aid of about 1000 parts by weight.

[0046] Laboratory test results of the acid fracturing pumping aid: at a concentration of 0.3% by mass, the surface tension of the acid fracturing pumping aid is 23.282 mN / m and the interfacial tension is 0.174 mN / m, which meets the industry standards for non-fluorocarbon pumping aids.

[0047] Example 11:

[0048] Weigh out 150.8 parts by weight of aminosulfonic acid betaine surfactant (effective concentration of about 20%, the aliphatic hydrocarbon group R1 in its chemical structure is hexadecyl), 49.8 parts by weight of lauryl alcohol polyoxyethylene ether (9) glycidyl ether and 784.4 parts by weight of water, stir at room temperature, dissolve evenly, and heat to 80°C for 6 hours to obtain an aqueous solution of aminosulfonic acid betaine type surfactant containing polyoxyethylene ether chain segments.

[0049] At room temperature, 10.0 parts (by weight) of sodium oleate and 5.0 parts (by weight) of sodium dodecylbenzenesulfonate were added to the above aqueous solution of aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments, and stirred evenly to obtain about 1000 parts of discharge aid.

[0050] Laboratory test results of the acid fracturing pumping agent: at a concentration of 0.3% by mass, the surface tension of the acid fracturing pumping agent is 23.992 mN / m and the interfacial tension is 1.007 mN / m, which meets the industry standards for non-fluorocarbon pumping agents.

[0051] Example 12:

[0052] Weigh out 186.0 parts by weight of aminosulfonic acid betaine surfactant (effective concentration of about 20%, the aliphatic hydrocarbon group R1 in its chemical structure is hexadecyl), 52.8 parts by weight of lauryl alcohol polyoxyethylene ether (9) glycidyl ether and 751.2 parts by weight of water, stir at room temperature, dissolve evenly, heat to 80℃ and react for 6h to obtain an aqueous solution of aminosulfonic acid betaine type surfactant containing polyoxyethylene ether chain segments.

[0053] At room temperature, 10.0 parts (by weight) of sodium oleate were added to the above aqueous solution of aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments and stirred evenly to obtain about 1000 parts of discharge aid.

[0054] Laboratory test results of the acid fracturing pumping agent: at a concentration of 0.3% by mass, the surface tension of the acid fracturing pumping agent is 24.320 mN / m and the interfacial tension is 0.248 mN / m, which meets the industry standards for non-fluorocarbon pumping agents.

[0055] In summary, the aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments of this invention is green, environmentally friendly, and biodegradable. Its preparation is simple, and it does not use flammable, explosive, or volatile organic solvents, making it safe and reliable. It is conducive to industrial production and widespread application, and has broad market prospects. Acid fracturing aids made from this surfactant can effectively reduce the surface and interfacial tension of fracturing fluids in oil and gas fields. Furthermore, the amount of surfactant used in the aid is low, saving on usage costs.

[0056] The above technical features constitute the embodiments of the present invention, which have strong adaptability and implementation effect. Unnecessary technical features can be added or removed according to actual needs to meet the needs of different situations.

Claims

1. A betaine-type surfactant containing polyoxyethylene ether segments, characterized in that... The chemical structural formula is: Where R1 is C 12 To C 16 aliphatic hydrocarbon group, R2 is C 12 To C 18 aliphatic hydrocarbon groups, where n is an integer greater than or equal to 2; The aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments is prepared by the following steps: adding an equimolar amount of fatty alcohol polyoxyethylene glycidyl ether to an aqueous solution of the aminosulfonic acid betaine type surfactant, mixing evenly and reacting to obtain the aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments.

2. The aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments according to claim 1, characterized in that... The reaction temperature is 50℃ to 80℃.

3. The aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments according to claim 1 or 2, characterized in that... The reaction time is 4 to 12 hours.

4. A method for preparing an aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments according to claim 1, characterized in that... The following steps are performed: an equimolar amount of fatty alcohol polyoxyethylene glycidyl ether is added to an aqueous solution of an aminosulfonic acid betaine type surfactant, and after mixing evenly, the mixture is reacted to obtain an aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments.

5. The method for preparing aminosulfonic acid betaine-type surfactants containing polyoxyethylene ether segments according to claim 4, characterized in that... The reaction temperature is 50°C to 80°C; or / and the reaction time is 4 h to 12 h.

6. The application of an aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments according to any one of claims 1 to 3 in fracturing fluid additives.

7. A fracturing aid for acidification using an aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments as described in any one of claims 1 to 3 as a raw material, characterized in that... The raw materials, by mass, comprise 8.0 to 9.5 parts of aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments, 0.5 to 2.0 parts of anionic surfactant, and the remainder is water. The aminosulfonic acid betaine-type surfactant containing polyoxyethylene ether segments, the anionic surfactant, and water are stirred and mixed evenly at room temperature to obtain the acid fracturing aid.

8. The flow aid for acid fracturing according to claim 7, characterized in that... The anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium oleate, sodium dodecanoate, sodium tetradecanoate, and sodium hexadecanoate.

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