Polymerizable glycosyl surfactant as well as preparation method and application thereof
By using polymerizable glycoside surfactants synthesized by glucose, long-chain alkyl primary amines, maleic anhydride and NaOH, the insufficient ability of existing surfactants to reduce the interfacial tension of oil-water meter and chromatographic separation during oil production is solved. The problem has achieved a more efficient oil dispelling effect.
Patent Information
- Application Number
- CN202311024910.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-08-15
- Publication Date
- 2025-02-21
Smart Images
Figure BDA0004395125040000021 
Figure BDA0004395125040000031 
Figure BDA0004395125040000032
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of oilfield chemistry, and is a polymerizable sugar-based surfactant, a preparation method and application thereof, and a drainage aid for acid fracturing. Background Art
[0002] Surfactants have both hydrophilic and lipophilic groups and can be adsorbed at the oil, gas and water three-phase interface, thereby changing the wetting effect and reducing the surface interfacial tension. This property is widely used in various fields of oil and gas field development.
[0003] During the acid fracturing process, it is usually necessary to rely on the formation pressure to quickly discharge the flowback fluid from the well to the ground. When the formation pressure gradually decreases, the flowback rate decreases significantly, and the residue in the flowback 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. In order to solve the problem of difficult flowback of flowback fluid after oil acid fracturing, the use of drainage aids is a conventional means. Drainage aids are one of the fracturing fluid additives that can effectively reduce surface tension and interfacial tension, reduce capillary resistance, and increase the flowback rate, thereby reducing formation damage. At present, many targeted drainage aids have been formed at home and abroad, but most of them contain fluorocarbon surfactants. Fluorocarbon surfactants have problems such as difficulty in degradation and persistent bioaccumulation.
[0004] In the tertiary oil recovery process, chemical flooding is usually used to improve the recovery rate, mainly including polymer flooding, alkaline water flooding, surfactant flooding, binary composite flooding and ternary composite flooding. In recent years, with the increasing attention paid to environmental protection issues, green, low-carbon, cost reduction and efficiency improvement have become the inevitable choice for sustainable development of oil fields. Due to the use of alkali (NaOH or Na2CO3, etc.), the most commonly used ternary composite flooding in tertiary oil recovery will cause serious reservoir damage and formation water pollution problems, making chemical flooding gradually tilt towards alkali-free polymer binary flooding. Surfactant is an important component of polymer flooding agent, which can greatly reduce the interfacial tension between oil and water and greatly improve the recovery rate. In the absence of alkali, the oil flooding agent has higher requirements on the performance of surfactant. When the oil flooding agent does not contain alkali, the ability to reduce the interfacial tension between oil and water is weak, and chromatographic separation is prone to occur, making it difficult to achieve the expected oil displacement effect.
[0005] In view of this, synthesizing an environmentally friendly and high-performance surfactant has become an urgent problem to be solved. Summary of the invention
[0006] The present invention provides a polymerizable sugar-based surfactant and a preparation method thereof, which overcomes the deficiencies of the above-mentioned prior art and can effectively solve the problems that the surfactants used in the existing oil recovery process have a weak ability to reduce the interfacial tension of the oil-water surface, are prone to chromatographic separation, and are difficult to achieve the expected oil recovery effect.
[0007] One of the technical solutions of the present invention is achieved by the following measures: a polymerizable sugar-based surfactant is synthesized using glucose, long-chain alkyl primary amine, maleic anhydride and NaOH as raw materials, and the chemical structure is:
[0008]
[0009] Where R is C 12 To C 18 Saturated or unsaturated aliphatic hydrocarbon group.
[0010] The following is a further optimization and / or improvement of one of the above-mentioned technical solutions:
[0011] The above polymerizable sugar-based surfactant is prepared by the following method:
[0012] The first step is to add the required amount of glucose and long-chain alkyl primary amine into the first reactor, add the solvent into the first reactor, and perform reflux reaction. After the reaction is complete, solid-liquid separation and drying are performed to obtain N-alkyl glucosamine;
[0013] The second step is to add the required amount of maleic anhydride and N-alkylglucosamine into the second reactor, add the solvent into the second reaction vessel, and perform a reflux reaction;
[0014] The third step is to drop NaOH solution into the second reactor, adjust the pH and continue the reaction. After the reaction is completed, the mixed liquid in the second reactor is separated and purified to obtain a polymerizable sugar-based surfactant.
[0015] In the first step, the molar ratio of glucose to long-chain alkyl primary amine is 1.1 to 1.2:1.
[0016] In the first and second steps above, the solvent is dry ethanol or methanol.
[0017] In the first step, the reaction conditions of the reflux reaction are a reaction temperature of 40° C. to 60° C. and a reaction time of 6 h to 8 h.
[0018] In the second step, the molar ratio of maleic anhydride to N-alkylglucosamine is 1.1 to 1.2:1.
[0019] In the above second step, the reaction conditions of the reflux reaction are reaction temperature of 40° C. to 60° C. and reaction time of 2 h to 6 h.
[0020] In the third step, NaOH solution is added dropwise to the second reactor, and the pH value is adjusted to 7.0 to 7.5 and the reaction is continued for 1.5 to 3 hours.
[0021] In the third step, the specific operation of separation and purification is as follows: the mixed liquid in the second reactor is distilled under reduced pressure to remove methanol and water to obtain a viscous liquid; the viscous liquid is extracted with acetone to precipitate a light yellow solid, and the light yellow solid is vacuum dried after filtering to remove the acetone to obtain a polymerizable sugar-based surfactant.
[0022] The third technical solution of the present invention is achieved by the following measures: A method for preparing a polymerizable sugar-based surfactant is carried out according to the following steps:
[0023] The first step is to add the required amount of glucose and long-chain alkyl primary amine into the first reactor, add the solvent into the first reactor, and perform reflux reaction. After the reaction is complete, solid-liquid separation and drying are performed to obtain N-alkyl glucosamine;
[0024] The second step is to add the required amount of maleic anhydride and N-alkylglucosamine into the second reactor, add the solvent into the second reaction vessel, and perform a reflux reaction;
[0025] The third step is to drop NaOH solution into the second reactor, adjust the pH and continue the reaction. After the reaction is completed, the mixed liquid in the second reactor is separated and purified to obtain a polymerizable sugar-based surfactant.
[0026] The third technical solution of the present invention is achieved by the following measures: application of a polymerizable sugar-based surfactant in an oil displacement agent, an oil removal agent additive or a fracturing fluid additive.
[0027] The fourth technical solution of the present invention is achieved by the following measures: a drainage aid for acid fracturing, wherein the raw materials are calculated by mass, and each hundred parts are composed of: 8.0 to 9.5 parts of a polymerizable sugar-based surfactant, 0.5 to 2.0 parts of a sugar-based cationic surfactant, and the rest is water; the preparation process is: the polymerizable sugar-based surfactant, the sugar-based cationic surfactant and water are stirred and mixed uniformly at room temperature to obtain the drainage aid for acid fracturing.
[0028] The following is a further optimization and / or improvement of the fourth technical solution of the above invention:
[0029] The sugar-based cationic surfactant is glucosylamidopropyl-N,N-dimethyl-N-alkylammonium bromide, and its chemical structure is:
[0030]
[0031] Where R1 is C 12 To C 16 aliphatic hydrocarbon group.
[0032] The present invention provides a polymerizable sugar-based surfactant and a preparation method and application thereof. The polymerizable sugar-based surfactant has excellent surface activity, a simple preparation method, a high product yield, safety and reliability, can be used for oil displacement agents, polymer surface displacement agents, emulsifiers, drainage agents, heavy oil viscosity reducers, etc., has a wide range of uses, and meets the green development needs of composite oil fields. DETAILED DESCRIPTION
[0033] 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 known and commonly used chemical reagents and chemicals in the prior art; unless otherwise specified, the percentages in the present invention are all mass percentages; the normal temperature and room temperature in the present invention generally refer to the temperature of 15°C to 25°C, and are generally defined as 25°C.
[0034] The present invention will be further described below in conjunction with embodiments:
[0035] Example 1: The polymerizable sugar-based surfactant is synthesized using glucose, long-chain alkyl primary amine, maleic anhydride and NaOH as raw materials, and has the chemical structural formula:
[0036]
[0037] Where R is C 12 To C 18 Saturated or unsaturated aliphatic hydrocarbon group.
[0038] Example 2: As an optimization of the above example, the polymerizable sugar-based surfactant is obtained by the following method: In the first step, the required amount of glucose and long-chain alkyl primary amine are added to the first reactor, and a solvent is added to the first reactor to perform a reflux reaction. After the reaction is complete, the solid-liquid separation and drying are performed to obtain N-alkyl glucosamine;
[0039] The second step is to add the required amount of maleic anhydride and N-alkylglucosamine into the second reactor, add the solvent into the second reaction vessel, and perform a reflux reaction;
[0040] The third step is to drop NaOH solution into the second reactor, adjust the pH and continue the reaction. After the reaction is completed, the mixed liquid in the second reactor is separated and purified to obtain a polymerizable sugar-based surfactant.
[0041] The chemical reaction process of the polymerizable sugar-based surfactant of the present invention is as follows:
[0042]
[0043] In the above structural formula, R is C 12 To C 18Saturated or unsaturated aliphatic hydrocarbon group.
[0044] Specifically, in the first step, the reflux reaction is cooled, filtered, recrystallized with anhydrous ethanol, and vacuum dried to obtain N-alkylglucosamine.
[0045] When preparing the polymerizable sugar-based surfactant of the present invention, a hydrophobic group is first introduced into the glucose molecule, and then a double bond and a carboxyl group are connected to make it have excellent surface activity. Glucose is widely available, low in cost, environmentally friendly and easy to biodegrade. The polymerizable sugar-based surfactant of the present invention has a reliable principle, simple operation, and excellent performance. It can be used to synthesize high molecular surfactants, temperature-resistant and salt-resistant polymer oil-displacing agents, and can also be used as polymer surface-displacing agents, emulsifiers, drainage aids, heavy oil viscosity reducers, etc. It has a wide range of uses and meets the green development needs of composite oil fields.
[0046] Example 3: As an optimization of the above example, in the first step, the molar ratio of glucose to long-chain alkyl primary amine is 1.1 to 1.2:1.
[0047] Example 4: As an optimization of the above example, in the first step and the second step, the solvent is dry ethanol or methanol.
[0048] Example 5: As an optimization of the above example, in the first step, the reaction conditions of the reflux reaction are a reaction temperature of 40°C to 60°C and a reaction time of 6h to 8h.
[0049] Example 6: As an optimization of the above example, in the second step, the molar ratio of maleic anhydride to N-alkylglucosamine is 1.1 to 1.2:1.
[0050] Example 7: As an optimization of the above example, in the second step, the reaction conditions of the reflux reaction are a reaction temperature of 40°C to 60°C and a reaction time of 2h to 6h.
[0051] Example 8: As an optimization of the above example, in the third step, NaOH solution is added dropwise to the second reactor, and the pH value is adjusted to 7.0 to 7.5 and the reaction is continued for 1.5 to 3 hours.
[0052] Example 9: As an optimization of the above example, in the third step, the specific operation of separation and purification is: the mixed liquid in the second reactor is distilled under reduced pressure to remove methanol and water to obtain a viscous liquid; the viscous liquid is extracted with acetone to precipitate a light yellow solid, and the light yellow solid is vacuum dried after filtering to remove the acetone to obtain a polymerizable sugar-based surfactant.
[0053] Example 10: Application of the polymerizable sugar-based surfactant in oil displacement agents, oil removal agent additives or fracturing fluid additives.
[0054] Example 11: The drainage aid for acid fracturing, the raw materials are calculated by mass, and the composition per 100 parts is: 8.0 to 9.5 parts of a polymerizable sugar-based surfactant, 0.5 to 2.0 parts of a sugar-based cationic surfactant, and the rest is water; the preparation process is: the polymerizable sugar-based surfactant, the sugar-based cationic surfactant and water are stirred and mixed uniformly at room temperature to obtain the drainage aid for acid fracturing.
[0055] Example 12: As an optimization of the above example, the sugar-based cationic surfactant is glucosylamidopropyl-N,N-dimethyl-N-alkylammonium bromide, and the chemical structure is:
[0056]
[0057] Where R1 is C 12 To C 16 aliphatic hydrocarbon group.
[0058] Embodiment 13:
[0059] Preparation of polymerizable sugar-based surfactants:
[0060] In the first step, the required amount of glucose and dodecylamine (molar ratio of 1.2) are added into the first reactor, and dry ethanol is used as solvent, and refluxed at 50° C. for 6 hours, cooled, filtered, recrystallized from anhydrous ethanol, and vacuum dried to obtain white solid N-dodecyl glucosamine;
[0061] In the second step, the required amount of maleic anhydride and N-dodecyl glucosamine (molar ratio of 1.2) are added into the second reactor, and an appropriate amount of dry methanol is used as solvent, and the reaction is refluxed at 50° C. for 4 hours;
[0062] In the third step, a 10% NaOH solution was added dropwise to the second reactor, the pH was adjusted to 7.2, and the reaction was continued for 2 hours. Methanol and water were removed by distillation under reduced pressure to obtain a viscous liquid, which was extracted with acetone to precipitate a light yellow solid, which was filtered and vacuum dried to obtain a polymerizable glycoside surfactant. Specifically, the polymerizable glycoside surfactant obtained in this embodiment is sodium N-dodecyl glucosyl maleamate.
[0063] Preparation of drainage agent for acid fracturing:
[0064] Weigh 9.5 parts of sodium N-dodecyl glucosyl maleamate, 0.5 parts of glucosylaminopropyl-N,N-dimethyl-N-hexadecyl ammonium bromide and 90 parts of water, stir at room temperature, and dissolve evenly to obtain a drainage agent for acid fracturing.
[0065] The acid fracturing drainage agent was subjected to indoor experimental tests. The test results showed that the surface tension at a concentration of 0.3% by mass was 23.112 mN / m, and the interfacial tension was 0.299 mN / m, which met the industry standards for non-fluorocarbon drainage agents.
[0066] Embodiment 14:
[0067] The preparation of the polymerizable sugar-based surfactant in this example is the same as that in Example 13.
[0068] Preparation of drainage agent for acid fracturing:
[0069] Weigh 9 parts of sodium N-dodecyl glucosyl maleamate, 1 part of glucosylaminopropyl-N,N-dimethyl-N-hexadecyl ammonium bromide and 90 parts of water, stir at room temperature, and dissolve evenly to obtain 100 parts of drainage aid for acid fracturing.
[0070] The acid fracturing drainage agent was tested indoors, and the test results showed that the surface tension was 22.715 mN / m and the interfacial tension was 0.161 mN / m at a concentration of 0.3% by mass, which met the industry standards for non-fluorocarbon drainage agents.
[0071] Embodiment 15:
[0072] Preparation of polymerizable sugar-based surfactants:
[0073] In the first step, the required amount of glucose and oleylamine (molar ratio of 1.1) are added into the first reactor, and dry methanol is used as solvent, and refluxed at 60° C. for 6 hours, cooled, filtered, recrystallized from anhydrous ethanol, and vacuum dried to obtain N-oleyl glucosamine;
[0074] In the second step, the required amount of maleic anhydride and N-oleyl glucosamine (molar ratio of 1.1) were added into the second reactor, and dry methanol was used as solvent, and the reaction was refluxed at 50° C. for 4 h;
[0075] In the third step, NaOH solution is added dropwise to the second reactor, the pH is adjusted to 7.1, and the reaction is continued for 2 hours. Methanol and water are removed by distillation under reduced pressure to obtain a viscous liquid, which is extracted with acetone, filtered, and vacuum dried to obtain a polymerizable sugar-based surfactant. Specifically, the polymerizable sugar-based surfactant obtained in this embodiment is sodium N-oleyl glucosyl maleamate.
[0076] Preparation of drainage agent for acid fracturing:
[0077] Weigh 9.5 parts of sodium N-oleyl glucosyl maleamate, 0.5 parts of glucosylaminopropyl-N,N-dimethyl-N-dodecyl ammonium bromide and 90 parts of water, mix and stir at room temperature, and dissolve evenly to obtain a drainage agent for acid fracturing.
[0078] The acid fracturing drainage agent was tested indoors, and the test results showed that the surface tension was 23.421 mN / m and the interfacial tension was 0.026 mN / m at a concentration of 0.3% by mass, which met the industry standards for non-fluorocarbon drainage agents.
[0079] Embodiment 16:
[0080] The preparation of the polymerizable sugar-based surfactant in this example is the same as in Example 15.
[0081] Preparation of drainage agent for acid fracturing:
[0082] Weigh 9 parts of sodium N-oleyl glucosyl maleamate, 1 part of glucosylaminopropyl-N,N-dimethyl-N-dodecyl ammonium bromide and 90 parts of water, stir at room temperature, and dissolve evenly to obtain a drainage agent for acid fracturing.
[0083] The acid fracturing drainage agent was tested indoors, and the test results showed that the surface tension was 22.605 mN / m and the interfacial tension was 0.002 mN / m at a concentration of 0.3% by mass, which met the industry standards for non-fluorocarbon drainage agents.
[0084] The present invention adopts a "one-pot method" to prepare a polymerizable sugar-based surfactant. The surfactant first introduces a hydrophobic group on the glucose molecule, and then connects a double bond and a carboxyl group to make it have excellent surface activity. Glucose is widely available, low in cost, environmentally friendly and easy to biodegrade. The preparation principle of the polymerizable sugar-based surfactant described in the present invention is reliable, the operation is simple, and the performance is excellent. It can be used to synthesize high molecular surfactants, temperature-resistant and salt-resistant polymer oil-displacing agents, and can also be used as polymer surface-displacing agents, emulsifiers, drainage aids, heavy oil viscosity reducers, etc. It has a wide range of uses and meets the green development needs of composite oil fields.
[0085] 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. A polymerizable sugar-based surfactant, characterized in that It is synthesized from glucose, long-chain alkyl primary amine, maleic anhydride and NaOH, and its chemical structure is: Where R is C 12 To C 18 Saturated or unsaturated aliphatic hydrocarbon group.
2. The polymerizable sugar-based surfactant according to claim 1, characterized in that Prepared as follows: The first step is to add the required amount of glucose and long-chain alkyl primary amine into the first reactor, add the solvent into the first reactor, perform reflux reaction, and after the reaction is complete, perform solid-liquid separation and dry to obtain N-alkyl glucosamine; The second step is to add the required amount of maleic anhydride and N-alkylglucosamine into the second reactor, add the solvent into the second reaction vessel, and perform a reflux reaction; The third step is to drop NaOH solution into the second reactor, adjust the pH and continue the reaction. After the reaction is completed, the mixed liquid in the second reactor is separated and purified to obtain a polymerizable sugar-based surfactant.
3. The polymerizable sugar-based surfactant according to claim 2, characterized in that In the first step, the molar ratio of glucose to long-chain alkyl primary amine is 1.1 to 1.2:1; or / and, in the first step, the reaction conditions of the reflux reaction are a reaction temperature of 40° C. to 60° C. and a reaction time of 6 h to 8 h.
4. The polymerizable sugar-based surfactant according to claim 2 or 3, characterized in that In the first step and the second step, the solvent is dry ethanol or methanol; or / and, in the second step, the molar ratio of maleic anhydride to N-alkylglucosamine is 1.1 to 1.2:
1.
5. The polymerizable sugar-based surfactant according to any one of claims 2 to 4, characterized in that In the second step, the reaction conditions of the reflux reaction are a reaction temperature of 40°C to 60°C and a reaction time of 2h to 6h; or / and, in the third step, NaOH solution is added dropwise to the second reactor, the pH value is adjusted to 7.0 to 7.5, and the reaction is continued for 1.5h to 3h.
6. The polymerizable sugar-based surfactant according to any one of claims 2 to 5, characterized in that In the third step, the specific operation of separation and purification is: the mixed liquid in the second reactor is distilled under reduced pressure to remove methanol and water to obtain a viscous liquid, the viscous liquid is extracted with acetone to precipitate a light yellow solid, the acetone is removed by filtration, and the light yellow solid is vacuum dried to obtain a polymerizable sugar-based surfactant.
7. A method for preparing a polymerizable sugar-based surfactant according to any one of claims 2 to 6, characterized in that Follow these steps: The first step is to add the required amount of glucose and long-chain alkyl primary amine into the first reactor, add the solvent into the first reactor, perform reflux reaction, and after the reaction is complete, perform solid-liquid separation and dry to obtain N-alkyl glucosamine; The second step is to add the required amount of maleic anhydride and N-alkylglucosamine into the second reactor, add the solvent into the second reaction vessel, and perform a reflux reaction; The third step is to drop NaOH solution into the second reactor, adjust the pH and continue the reaction. After the reaction is completed, the mixed liquid in the second reactor is separated and purified to obtain a polymerizable sugar-based surfactant.
8. Use of the polymerizable sugar-based surfactant according to any one of claims 1 to 6 in an oil displacement agent, an oil removal agent additive or a fracturing fluid additive.
9. A drainage aid for acid fracturing using the polymerizable sugar-based surfactant according to any one of claims 1 to 6 as a raw material, characterized in that The raw materials are calculated by weight, and the composition of each 100 parts is: 8.0 to 9.5 parts of a polymerizable sugar-based surfactant, 0.5 to 2.0 parts of a sugar-based cationic surfactant, and the rest is water; the preparation process is: the polymerizable sugar-based surfactant, the sugar-based cationic 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 sugar-based cationic surfactant is glucosylamidopropyl-N,N-dimethyl-N-alkylammonium bromide, and its chemical structure is: Where R1 is C 12 To C 16 aliphatic hydrocarbon group.