Preparation method and application of sulfamic acid betaine type surfactant containing polyoxyethylene ether chain segment

Abstract

The invention relates to the technical field of oilfield chemistry, in particular to a preparation method and application of a sulfamic acid betaine type surfactant containing a polyoxyethylene ether chain segment, and the sulfamic acid betaine type surfactant containing the polyoxyethylene ether chain segment comprises the following raw materials in parts by mass. The sulfamic acid betaine type surfactant containing the polyoxyethylene ether chain segment is green, environment-friendly and biodegradable, is simple and convenient to prepare and operate, does not use inflammable, explosive and volatile organic solvents in the process, and is safe and reliable; and industrial production, popularization and application are facilitated, and the market prospect is wide. The discharge aiding agent for acid fracturing, which takes the surfactant as the raw material, can effectively reduce the surface and interfacial tension of fracturing fluid of an oil and gas field, and meanwhile, the use amount of the surfactant in the discharge aiding agent is relatively low, so that the use cost is saved.

Description

Technical Field

[0001] The invention relates to the technical field of oilfield chemistry, and is an aminosulfonic acid betaine type surfactant containing a polyoxyethylene ether chain segment, a preparation method and application thereof, and an acid fracturing drainage aid using the aminosulfonic acid betaine type surfactant containing a polyoxyethylene ether chain segment as a raw material. Background Art

[0002] Fracturing transformation technology is an important measure for the transformation of low-permeability and ultra-low-permeability oil and gas reservoirs. It is the leading technology for achieving efficient development of unconventional oil and gas resources, increasing and stabilizing the production of conventional oil and gas fields, and improving the effect of reservoir transformation. During the fracturing process, it is usually necessary to rely on the formation pressure to quickly discharge the return fluid from the well to the ground. When the formation pressure gradually decreases, the return rate decreases significantly, and the residue in the return fluid will cause blockage after precipitation, resulting in secondary pollution of the formation, which seriously affects the construction efficiency and the effect of acid fracturing transformation. In order to solve the problem of difficulty in returning the return fluid after oil acid fracturing, the use of drainage aids is a conventional method.

[0003] A drainage aid is one of the fracturing fluid additives. Its main component is a surfactant, which can effectively reduce surface tension and interfacial tension, reduce capillary resistance, increase backflow rate and backflow rate, and thus reduce formation damage. At present, fluorocarbon surfactants are mostly used as the main components of drainage aids at home and abroad. They are prepared by compounding fluorocarbon surfactants, other surfactants and low-carbon alcohols. Fluorocarbon surfactants have high surface activity and can reduce surface tension to 23mN / m. However, they are expensive, difficult to degrade, have high biological toxicity, and are easy to cause damage to the human body and the environment. Low-carbon alcohols (such as methanol, ethanol, and isopropanol) are highly volatile, and there are health and safety hazards in the production environment and on-site construction. Developing a surfactant without biological toxicity, and based on this, developing a green and environmentally friendly drainage aid system that does not contain low-carbon alcohols and fluorocarbon surfactants has become an urgent problem to be solved. Summary of the invention

[0004] The present invention provides an aminosulfonic acid betaine type surfactant containing a polyoxyethylene ether segment, a preparation method and an application thereof, which overcome the deficiencies of the above-mentioned prior art and can effectively solve the problems that the surfactants and drainage aids used in the existing fracturing fluids have biological toxicity and health and safety risks.

[0005] One of the technical solutions of the present invention is achieved by the following measures: an aminosulfonic acid betaine surfactant containing a polyoxyethylene ether segment, the chemical structural formula of which is

[0006]

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

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

[0009] The aminosulfonic acid betaine type surfactant containing polyoxyethylene ether chain segments is prepared according to 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 chain segments.

[0010] The above reaction temperature is 50°C to 80°C.

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

[0012] The molar ratio of the aminosulfonic acid betaine type surfactant to the 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 a polyoxyethylene ether chain segment, which is carried out according to 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 them evenly and reacting them to obtain an aminosulfonic acid betaine type surfactant containing a polyoxyethylene ether chain segment.

[0014] The following is a further optimization and / or improvement of the second technical solution of the above invention:

[0015] The above reaction temperature is 50°C to 80°C.

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

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

[0018] The third technical solution of the present invention is achieved by the following measures: application of an aminosulfonic acid betaine type surfactant containing a polyoxyethylene ether segment in a fracturing fluid additive.

[0019] The fourth technical solution of the present invention is achieved by the following measures: a drainage aid for acid fracturing, wherein the raw materials, calculated by weight, include: 8.0 to 9.5 parts of an aminosulfonic acid betaine type surfactant containing a polyoxyethylene ether chain segment, 0.5 to 2.0 parts of an anionic surfactant, and the rest is water; the aminosulfonic acid betaine type surfactant containing a polyoxyethylene ether chain segment, the anionic surfactant and water are stirred and mixed uniformly at room temperature to obtain the drainage aid for acid fracturing.

[0020] The following is a further optimization and / or improvement of the fourth technical solution of the above invention:

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

[0022] The aminosulfonic acid betaine type surfactant containing polyoxyethylene ether chain segments of the present invention is green, environmentally friendly and biodegradable. The preparation process thereof adopts a "one-pot method", which is simple, has a high product yield, and the obtained product does not need to be separated and purified, and can be used directly, thereby reducing costs and shortening production cycles. After being mixed with other types of surfactants, it has good composite synergistic characteristics, can effectively reduce the surface tension and interfacial tension of oil and gas field fracturing fluids, and at the same time significantly reduces the amount of surfactant used in the drainage agent, thereby reducing the use cost. DETAILED DESCRIPTION

[0023] The present invention is not limited by the following embodiments, and the specific implementation method can be determined according to the technical scheme of the present invention and the actual situation. Unless otherwise specified, the various chemical reagents and chemicals mentioned in the present invention are all chemical reagents and chemicals known and used in the prior art; unless otherwise specified, the percentages in the present invention are all mass percentages; unless otherwise specified, the solutions in the present invention are all aqueous solutions with water as the solvent, for example, hydrochloric acid solution is a hydrochloric acid aqueous solution; the normal temperature and room temperature in the present invention generally refer to a temperature of 15°C to 25°C, and are generally defined as 25°C.

[0024] The present invention will be further described below in conjunction with embodiments:

[0025] Example 1: The aminosulfonic acid betaine surfactant containing polyoxyethylene ether chain segments has a chemical structural formula of

[0026]

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

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

[0029] The chemical reaction in the preparation process of the aminosulfonic acid betaine type surfactant containing polyoxyethylene ether chain segment is 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 example, the reaction time is 4 h to 12 h.

[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 chain segments in fracturing fluid additives.

[0035] Example 7: The drainage aid for acid fracturing comprises, in each hundred parts by mass, 8.0 to 9.5 parts of an aminosulfonic acid betaine type surfactant containing a polyoxyethylene ether segment, 0.5 to 2.0 parts of an anionic surfactant, and the remainder water; the aminosulfonic acid betaine type surfactant containing a polyoxyethylene ether segment, the anionic surfactant and water are stirred and mixed uniformly at room temperature to obtain the drainage aid for acid fracturing.

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

[0037] The invention provides an aminosulfonic acid betaine type surfactant containing a polyoxyethylene ether segment and a preparation method thereof, as well as a drainage aid for acid fracturing. In actual use, the drainage aid for acid fracturing can be directly prepared with oilfield sewage such as oilfield produced water and fracturing flowback fluid and used in fracturing construction.

[0038] The preparation method of the aminosulfonic acid betaine type surfactant containing polyoxyethylene ether chain segments of the present invention is simple to operate, the raw materials are green and degradable, and no environmental pollution is caused; 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 used directly; it is conducive to industrial production and promotion and application, and has broad market prospects. The drainage agent for acid fracturing using the raw material can effectively reduce the surface tension of the aqueous solution and meet the requirements of the technical specifications of the acid fracturing drainage agent.

[0039] Embodiment 9:

[0040] 218.5 parts of aminosulfonic acid betaine surfactant (effective concentration is about 20%, and the aliphatic hydrocarbon group R1 in its chemical structure is hexadecyl), 36.3 parts of lauryl alcohol polyoxyethylene ether (3) glycidyl ether and 725.3 parts of water were weighed by mass, stirred at room temperature to dissolve evenly, heated to 70°C for reaction for 6 hours, and an aminosulfonic acid betaine surfactant aqueous solution containing polyoxyethylene ether segments was obtained.

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

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

[0043] Embodiment 10:

[0044] 18.60 parts of aminosulfonic acid betaine surfactant (effective concentration is about 20%, and the aliphatic hydrocarbon group R1 in its chemical structure is hexadecyl), 5.28 parts of lauryl alcohol polyoxyethylene ether (3) glycidyl ether and 72.53 parts of water were weighed by mass, stirred at room temperature to dissolve evenly, heated to 70°C for reaction for 6 hours, and an aminosulfonic acid betaine surfactant aqueous solution containing polyoxyethylene ether segments was obtained.

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

[0046] The laboratory test results of the acid fracturing drainage agent show that at a concentration of 0.3% by mass, the surface tension of the acid fracturing drainage agent is 23.282 mN / m, and the interfacial tension is 0.174 mN / m, which meets the industry standards for non-fluorocarbon drainage agents.

[0047] Embodiment 11:

[0048] 150.8 parts of aminosulfonic acid betaine surfactant (effective concentration is about 20%, and the aliphatic hydrocarbon group R1 in its chemical structure is hexadecyl), 49.8 parts of lauryl alcohol polyoxyethylene ether (9) glycidyl ether and 784.4 parts of water were weighed by mass, stirred at room temperature to dissolve evenly, heated to 80°C for reaction for 6 hours, and an aminosulfonic acid betaine surfactant aqueous solution containing polyoxyethylene ether segments was obtained.

[0049] At room temperature, 10.0 parts by mass of sodium oleate and 5.0 parts by mass of sodium dodecylbenzene sulfonate were added to the aqueous solution of the aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments, and stirred evenly to obtain about 1000 parts of drainage aid.

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

[0051] Embodiment 12:

[0052] 186.0 parts of aminosulfonic acid betaine surfactant (effective concentration is about 20%, and the aliphatic hydrocarbon group R1 in its chemical structure is hexadecyl), 52.8 parts of lauryl alcohol polyoxyethylene ether (9) glycidyl ether and 751.2 parts of water were weighed by mass, stirred at room temperature to dissolve evenly, heated to 80°C for reaction for 6 hours, and an aminosulfonic acid betaine surfactant aqueous solution containing polyoxyethylene ether segments was obtained.

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

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

[0055] In summary, the aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments of the present invention is green, environmentally friendly, biodegradable, easy to prepare and operate, does not use flammable, explosive, and volatile organic solvents in the process, is safe and reliable, is conducive to industrial production and promotion and application, and has broad market prospects. The acid fracturing drainage agent using it as a raw material can effectively reduce the surface and interfacial tension of oil and gas field fracturing fluids, and at the same time, the amount of surfactant in the drainage agent is low, saving the use cost.

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

Claims

1. An aminosulfonic acid betaine type surfactant containing a polyoxyethylene ether segment, characterized in that The chemical structure is Where R1 is C 12 To C 16 aliphatic hydrocarbon group, R2 is C 12 To C 18 Aliphatic hydrocarbon group, n is an integer greater than or equal to 2.

2. The aminosulfonic acid betaine type surfactant containing polyoxyethylene ether chain segments according to claim 1, characterized in that The preparation method is prepared by the following steps: adding an equimolar amount of fatty alcohol polyoxyethylene glycidyl ether to an aqueous solution of aminosulfonic acid betaine type surfactant, mixing them evenly and reacting them to obtain an aminosulfonic acid betaine type surfactant containing a polyoxyethylene ether chain segment.

3. The aminosulfonic acid betaine type surfactant containing polyoxyethylene ether chain segment according to claim 2, characterized in that The reaction temperature is 50°C to 80°C.

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

5. The aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segment according to claim 2, 3 or 4, characterized in that The molar ratio of the aminosulfonic acid betaine type surfactant to the fatty alcohol polyoxyethylene glycidyl ether is 1:

1.

6. A method for preparing an aminosulfonic acid betaine type surfactant containing a polyoxyethylene ether segment according to claim 1, characterized in that The method is carried out according to the following steps: adding an equimolar amount of fatty alcohol polyoxyethylene glycidyl ether to an aqueous solution of aminosulfonic acid betaine type surfactant, mixing them evenly and reacting them to obtain an aminosulfonic acid betaine type surfactant containing polyoxyethylene ether chain segments.

7. The aminosulfonic acid betaine type surfactant containing polyoxyethylene ether chain segments according to claim 6, characterized in that The reaction temperature is 50° C. to 80° C.; or / and the reaction time is 4 h to 12 h; or / and the molar ratio of the aminosulfonic acid betaine surfactant to the fatty alcohol polyoxyethylene glycidyl ether is 1:

1.

8. Use of the aminosulfonic acid betaine type surfactant containing a polyoxyethylene ether segment according to any one of claims 1 to 5 in a fracturing fluid additive.

9. A drainage aid for acid fracturing using the aminosulfonic acid betaine type surfactant containing polyoxyethylene ether segments as described in any one of claims 1 to 6 as a raw material, characterized in that The raw materials include, by weight, 8.0 to 9.5 parts of an aminosulfonic acid betaine surfactant containing a polyoxyethylene ether chain segment, 0.5 to 2.0 parts of an anionic surfactant, and the remainder is water. The aminosulfonic acid betaine surfactant containing a polyoxyethylene ether chain segment, the anionic surfactant and water are stirred and mixed uniformly at room temperature to obtain a drainage agent for acid fracturing.

10. The drainage aid for acid fracturing according to claim 9, characterized in that The anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium oleate, sodium dodecanoate, sodium myristate, and sodium hexadecanoate.

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