Hyperbranched polymer as well as preparation method and application thereof

Abstract

The invention provides a hyperbranched polymer as well as a preparation method and application thereof, the hyperbranched polymer has a structural formula as shown in formula 1, and R1, R2, R3 and R are independently selected from C8-C22 alkyl and C8-C22 alkenyl respectively. The hyperbranched polymer provided by the invention is used as a demulsifier, is applied to demulsification of crude oil emulsion, and has the advantages of high demulsification efficiency, low usage amount, low demulsification temperature, high acid and alkali resistance and high salt resistance.

Description

Technical Field

[0001] This invention relates to a hyperbranched polymer, and more particularly to a hyperbranched polymer, its preparation method, and its application, belonging to the field of oilfield chemical additives technology. Background Technology

[0002] Emulsions are multiphase dispersion systems that play a vital role in the pharmaceutical, biochemical, and even food industries. However, stable crude oil emulsions are detrimental to the petroleum industry and refining operations. Stable emulsions primarily form during crude oil extraction. During extraction, mixing with water and the presence of natural emulsifiers such as gums, asphaltene, solid particles, and paraffin crystals are unavoidable. Combined with the large amounts of formation water and artificially injected surfactants during oil displacement, the resulting emulsions become even more stable under heating, shearing, and compression. The formation of emulsions poses a series of serious hazards to oil extraction, transportation, and processing.

[0003] Crude oil demulsification mainly employs a variety of simple and efficient methods, including physical, chemical, and biological methods, as well as combined treatment methods. In actual oilfield production, chemical demulsification remains the most commonly used technology. From domestic and international patents, research, and applications of demulsifiers, it is clear that the main synthesis methods for demulsifiers currently still rely on modifications or compounding of ethylene oxide and propylene oxide block polyethers. Chinese patent CN113684054A developed a demulsifier composed of polyether and ionic liquid mixed in a certain proportion with solvents; CN101642692B disclosed a composite demulsifier and its preparation method, which uses block polyether and aromatic sulfonic acid mixed in a certain proportion with solvents. However, the above-mentioned chemical demulsifiers all use raw materials such as ethylene oxide and propylene oxide, which does not meet the concept of green and environmentally friendly development. Furthermore, they require synthesis of demulsifiers under certain pressure, resulting in complex reaction conditions and high process requirements. Currently, with the use of various new crude oil extraction technologies, the stability of oil-water emulsions is becoming stronger and stronger. Conventional agents can no longer meet the dehydration requirements. Therefore, those skilled in the art urgently need to develop a demulsifier that is environmentally friendly in terms of raw material acquisition, has low usage, high demulsification efficiency and low demulsification temperature, and has high acid and alkali resistance and high salt resistance. Summary of the Invention

[0004] This invention provides a hyperbranched polymer, which, as a demulsifier, has advantages such as low dosage, high demulsification efficiency and low demulsification temperature, high acid and alkali resistance and high salt resistance.

[0005] This invention provides a demulsifier that, when applied to crude oil demulsification, exhibits low dosage, high demulsification efficiency, low demulsification temperature, and high acid and alkali resistance as well as high salt resistance.

[0006] This invention provides a method for demulsifying crude oil emulsions. The demulsifier can demulsify crude oil emulsions and has high demulsification efficiency, low usage, low demulsification temperature, high acid and alkali resistance, and high salt resistance.

[0007] This invention provides a hyperbranched polymer, wherein the hyperbranched polymer has the structural formula shown in Formula 1:

[0008]

[0009] In the formula, R1, R2, R3, and R are each independently selected from C8-C22 alkyl groups and C8-C22 alkenyl groups.

[0010] The hyperbranched polymer as described above is prepared by the following steps:

[0011] The first fatty acid amide is subjected to a ring-opening reaction with glycidyl ether, and the product obtained from the ring-opening reaction is subjected to a first reaction with the second fatty acid amide to obtain the hyperbranched polymer.

[0012] The first fatty acid amide and the second fatty acid amide have the structural formula shown in Formula 2:

[0013]

[0014] R4 is selected from at least one of R1, R2, R3, and R.

[0015] This invention provides a method for preparing the hyperbranched polymer as described above, comprising the following steps:

[0016] After the first fatty acid amide is subjected to a ring-opening reaction with glycidyl ether, the product obtained from the ring-opening reaction is subjected to the first reaction with the second fatty acid amide to obtain the hyperbranched polymer.

[0017] The first fatty acid amide and the second fatty acid amide have the structural formula shown in Formula 2:

[0018]

[0019] R4 is selected from at least one of R1, R2, R3, and R.

[0020] The method for preparing hyperbranched polymers as described above further includes, prior to the ring-opening reaction:

[0021] After uniformly mixing vegetable oil containing the fatty acid and diethanolamine in a solvent, the second reaction is carried out to obtain the first fatty acid amide; and / or, after uniformly mixing vegetable oil containing the fatty acid and diethanolamine in a solvent, the second reaction is carried out to obtain the second fatty acid amide;

[0022] The fatty acid includes at least one of fatty acids having R1, R2 or R3; the reaction temperature of the second reaction is 60-100℃ and the reaction time is 2-6h.

[0023] The method for preparing the hyperbranched polymer as described above, wherein the ring-opening reaction and the first reaction include the following steps:

[0024] After the first fatty acid amide and glycidyl ether are mixed evenly in a solvent, a ring-opening reaction is carried out. Then, the second fatty acid amide is added to the product obtained from the ring-opening reaction to carry out the first reaction, thereby obtaining the hyperbranched polymer.

[0025] The ring-opening reaction is carried out at a temperature of 80-120℃ for 4-10 hours; the first reaction is carried out at a temperature of 80-120℃ for 4-10 hours.

[0026] The method for preparing hyperbranched polymers as described above, wherein the vegetable oil includes at least one of soybean oil, tung oil, palm oil, corn oil, and cottonseed oil; and the molar ratio of the vegetable oil to diethanolamine is 1:(3-6).

[0027] And / or, the molar ratio of the first fatty acid amide to glycidyl is 1:(2-15);

[0028] And / or, the molar ratio of the second fatty acid amide to the first fatty acid amide is (2-6):1.

[0029] In the preparation method of the hyperbranched polymer as described above, the second reaction is carried out under the action of a first catalyst, the first catalyst including at least one of sodium hydride, potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide; the molar ratio of the first catalyst to vegetable oil is (0.01-0.05):1.

[0030] The method for preparing the hyperbranched polymer as described above, wherein the ring-opening reaction is carried out under the action of a second catalyst, the second catalyst comprising at least one of sodium hydride, potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide; the molar ratio of the second catalyst to the first fatty acid amide is (0.01-0.05):1;

[0031] And / or, the solvent includes at least one of methanol, chloroform, dioxane, N-methylpyrrolidone, N,N-dimethylformamide, and dimethyl sulfoxide.

[0032] The present invention also provides a demulsifier comprising the hyperbranched polymer described above.

[0033] The present invention also provides a method for demulsifying crude oil emulsion, comprising the following steps: dissolving the demulsifier as described above in a solvent, and then mixing the resulting demulsifier solution with the crude oil emulsion evenly to perform demulsification.

[0034] The hyperbranched polymer provided by this invention has a specific structural formula, with a hydrophilic hyperbranched polyglycerol structure at the center and a hydrophobic long-chain fatty acid structure at the tail end. This structure enables the hyperbranched polymer to exhibit amphiphilicity and high interfacial activity. The hyperbranched polymer can be rapidly adsorbed onto the oil-water interface, significantly reducing interfacial tension, softening or destroying the interfacial film, thereby reducing the stability of the interfacial film, promoting the demulsification process, and thus enabling the hyperbranched polymer to achieve efficient demulsification at low dosage.

[0035] The method for preparing hyperbranched polymers provided by this invention first involves a ring-opening reaction between a first fatty acid amide and glycidyl ether to obtain a product having the structure of Formula 2. Subsequently, the product obtained from the ring-opening reaction is reacted with a second fatty acid amide to obtain a hyperbranched polymer having the structure of Formula 1. This preparation method enables the hyperbranched polymer to possess a unique chemical structure, thereby exhibiting amphiphilicity and high interfacial activity. This results in high demulsification efficiency, low usage, low demulsification temperature, and high salt resistance. Furthermore, the structure of the hyperbranched polymer is controllable, which is beneficial for adjusting the number of hydrophobic and hydrophilic chains according to changes in the crude oil emulsion.

[0036] The present invention also provides a demulsifier comprising the above-mentioned hyperbranched polymer, which can efficiently demulsify crude oil emulsions, and has the advantages of low dosage, low demulsification temperature, high acid and alkali resistance and high salt resistance.

[0037] This invention provides a method for demulsifying crude oil emulsions. The demulsifier can demulsify crude oil emulsions and has advantages such as high demulsification efficiency, low usage, low demulsification temperature, high acid and alkali resistance, and high salt resistance. Attached Figure Description

[0038] Figure 1 The image shows the infrared spectrum of the hyperbranched polymer from Example 1. Detailed Implementation

[0039] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0040] This invention provides a hyperbranched polymer, wherein the hyperbranched polymer has the structural formula shown in Formula 1:

[0041]

[0042] In the formula, R1, R2, R3, and R are each independently selected from substituted or unsubstituted C8-C22 alkyl or C8-C22 alkenyl groups.

[0043] The hyperbranched polymer of the present invention has the structural formula shown in Formula 1, wherein R1, R2, R3, and R are each independently selected from C8-C22 alkyl groups and C8-C22 alkenyl groups. The C8-C22 alkyl groups of the present invention refer to alkyl groups having 8-22 carbon atoms; the C8-C22 alkenyl groups refer to alkenyl groups having 8-22 carbon atoms. When a substituent is specified as a group having a specific number of carbon atoms, all geometric isomers having that number of carbon atoms are included. For example, R1, R2, R3, and R can each be independently selected from -(CH2)7CH3, -CH(CH3)(CH2)5CH3, -CH2CH(CH3)(CH2)4CH3, -CH2C(CH3)2(CH2)3CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 10 CH3, -(CH2) 11 CH3, -(CH2)6-CH=CH2, etc. The wavy line connecting the oxygen atom in the compound represented by Formula 1 of this invention can be selected... Or hydrogen, The carbon atom at the * position is bonded to the oxygen atom in the compound of formula 1, and The wavy line in the image can also be selected. Or hydrogen.

[0044] According to the above-mentioned solution provided by the present invention, hyperbranched polymers are used as demulsifiers in crude oil emulsion demulsification, which has advantages such as high demulsification efficiency, low dosage, and low demulsification temperature, and exhibits excellent demulsification effect under acidic or alkaline environments or high-salt conditions. The inventors analyzed the principle and believe that the reason may be that the hyperbranched polymer exhibits the structural formula shown in Formula 1, with a hydrophilic hyperbranched polyglycerol structure at the center and a hydrophobic long-chain fatty acid structure at the tail end. This makes the hyperbranched polymer exhibit excellent amphiphilicity and high interfacial activity, thereby significantly reducing the oil-water interfacial tension, replacing the active substances on the interfacial film, softening or destroying the interfacial film, promoting the demulsification process, and enabling the hyperbranched polymer to perform efficient demulsification.

[0045] Specifically, the hyperbranched polymer can be obtained by infrared absorption spectroscopy.

[0046] In one specific embodiment, the hyperbranched polymer is prepared by the following steps:

[0047] The first fatty acid amide is subjected to a ring-opening reaction with glycidyl ether, and the product obtained from the ring-opening reaction is subjected to a first reaction with the second fatty acid amide to obtain a hyperbranched polymer.

[0048] The first fatty acid amide and the second fatty acid amide have the structural formula shown in Formula 2:

[0049]

[0050] R4 is selected from at least one of R1, R2, R3, and R.

[0051] Specifically, the first fatty acid amide is first subjected to a ring-opening reaction with glycidyl to obtain a ring-opening product. Then, the product obtained from the ring-opening reaction is subjected to a first reaction with a second fatty acid amide to obtain a hyperbranched polymer. Both the first and second fatty acid amides have the structural formula shown in Formula 2.

[0052] It is worth noting that the first fatty acid amide includes at least one of the following: a fatty acid amide having R1, a fatty acid amide having R2, a fatty acid amide having R3, and a fatty acid amide having R4. That is, the first fatty acid amide can be a single fatty acid amide or a mixture of any two or more of these four fatty acid amides. Similarly, the second fatty acid amide can also be a single fatty acid amide or a mixture of any two or more of the four fatty acid amides. Furthermore, the first and second fatty acid amides can be the same or different, and can be selected according to actual needs.

[0053] This invention does not limit the specific parameters of the ring-opening reaction; they can be selected according to actual needs.

[0054] The present invention does not limit the specific parameter selection of the first reaction, and can be selected according to actual needs.

[0055] The present invention does not impose a specific limit on the addition ratio of the first fatty acid amide and glycidol, which can be selected according to actual needs.

[0056] The present invention does not impose a specific limit on the addition ratio of the second fatty acid amide and the first fatty acid amide, which can be selected according to actual needs.

[0057] This invention, through the above-described preparation method, firstly involves a ring-opening reaction between a first fatty acid amide and glycidyl ether, followed by a first reaction between the product obtained from the ring-opening reaction and a second fatty acid amide to obtain a hyperbranched polymer with the structure of Formula 1. This preparation method enables the hyperbranched polymer to possess a unique chemical structure, thereby exhibiting amphiphilicity and high interfacial activity. This results in high demulsification efficiency, low dosage, low demulsification temperature, and high salt resistance. Furthermore, the structure of this hyperbranched polymer is controllable, facilitating the adjustment of the number of hydrophobic and hydrophilic chains according to changes in the crude oil emulsion.

[0058] This invention provides a method for preparing the above-mentioned hyperbranched polymer, comprising the following steps:

[0059] After the first fatty acid amide is subjected to a ring-opening reaction with glycidyl, the product obtained from the ring-opening reaction is subjected to a first reaction with the second fatty acid amide to obtain a hyperbranched polymer.

[0060] The first fatty acid amide and the second fatty acid amide have the structural formula shown in Formula 2:

[0061]

[0062] R4 is selected from at least one of R1, R2, R3, and R.

[0063] Specifically, a first fatty acid amide is subjected to a ring-opening reaction with glycidyl ether to obtain a ring-opening product. Then, the product obtained from the ring-opening reaction is subjected to a first reaction with a second fatty acid amide to obtain a hyperbranched polymer. Both the first and second fatty acid amides have the structural formula shown in Formula 2.

[0064] The first fatty acid amide and the second fatty acid amide of the present invention are similar; both can be a single fatty acid amide, or a mixture of any two or more of the four fatty acid amides. Furthermore, the first fatty acid amide and the second fatty acid amide can be the same or different, and can be selected according to actual needs.

[0065] This invention does not limit the specific parameters of the ring-opening reaction; they can be selected according to actual needs.

[0066] The present invention does not limit the specific parameter selection of the first reaction, and can be selected according to actual needs.

[0067] The present invention does not impose a specific limit on the addition ratio of the first fatty acid amide and glycidol, which can be selected according to actual needs.

[0068] The present invention does not impose a specific limit on the addition ratio of the second fatty acid amide and the first fatty acid amide, which can be selected according to actual needs.

[0069] The method for preparing hyperbranched polymers of the present invention can prepare hyperbranched polymers having the structure of Formula 1. This hyperbranched polymer has a unique chemical structure, thereby exhibiting amphiphilicity and high interfacial activity, resulting in high demulsification efficiency, low dosage, low demulsification temperature, and high salt resistance. Furthermore, the structure of the hyperbranched polymer is controllable.

[0070] In one specific embodiment, the process further includes the following prior to the ring-opening reaction:

[0071] After uniformly mixing vegetable oil containing fatty acids and diethanolamine in a solvent, a second reaction is carried out to obtain a first fatty acid amide; and / or, after uniformly mixing vegetable oil containing fatty acids and diethanolamine in a solvent, a second reaction is carried out to obtain a second fatty acid amide.

[0072] The fatty acids include at least one of fatty acids having R1, R2, or R3; the reaction temperature of the second reaction is 60-100℃, and the reaction time is 2-6h.

[0073] Specifically, vegetable oil and diethanolamine are mixed in a solvent. After the mixture is homogeneous, a second reaction is carried out. The reaction temperature of the second reaction is 60-100℃, for example, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, or 100℃, and the reaction time is 2-6 hours, for example, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours. After the reaction is completed, impurities and solvent are removed to obtain the first fatty acid amide. The vegetable oil includes fatty acids, and the fatty acids include at least one of the following: fatty acids having R1, fatty acids having R2, and fatty acids having R3. That is, the vegetable oil may contain only one fatty acid, or it may be a mixture of two or three of these three fatty acids.

[0074] Similarly, vegetable oil and diethanolamine are mixed in a solvent. After the mixture is homogeneous, a second reaction is carried out. The reaction temperature of the second reaction is 60-100℃, for example, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃ or 100℃, etc., and the reaction time is 2-6h, for example, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, etc. After the reaction is completed, impurities and solvents are removed to obtain the second fatty acid amide.

[0075] This invention does not limit the specific operation of mixing vegetable oil and diethanolamine in a solvent, and can be selected according to actual needs.

[0076] This invention does not limit the specific choice of solvent, which can be selected according to actual needs.

[0077] This invention does not limit the specific process for removing impurities and solvents, and can be selected according to actual needs.

[0078] The present invention enables the reaction of fatty acids in vegetable oil with diethanolamine to obtain fatty acid amides with the structure of Formula 2. Furthermore, the preparation method has low reaction temperature, short reaction time, low requirements for preparation conditions, and vegetable oil is readily available and does not pollute the environment.

[0079] In one specific embodiment, the ring-opening reaction and the first reaction include the following steps:

[0080] After the first fatty acid amide and glycidyl ether are mixed evenly in a solvent, a ring-opening reaction is carried out. Then, the second fatty acid amide is added to the product obtained from the ring-opening reaction to carry out the first reaction, thereby obtaining a hyperbranched polymer.

[0081] The ring-opening reaction is carried out at a temperature of 80-120℃ for 4-10 hours; the first reaction is carried out at a temperature of 80-120℃ for 4-10 hours.

[0082] Specifically, the first fatty acid amide and glycidyl ether are first mixed in a solvent. After the mixture is homogeneous, a ring-opening reaction is carried out. The reaction temperature for the ring-opening reaction is 80-120℃, for example, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, or 120℃, and the reaction time is 4-10h, for example, 4h, 5h, 6h, 7h, 8h, 9h, or 10h, to obtain the product. Then, the second fatty acid amide is added to the product to carry out the first reaction. The reaction temperature for the first reaction is 80-120℃, for example, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, or 120℃, and the reaction time is 4-10h, for example, 4h, 5h, 6h, 7h, 8h, 9h, or 10h, etc. After the reaction is completed, impurities and solvents are removed to obtain the hyperbranched polymer.

[0083] This invention does not limit the specific mixing parameters of the first fatty acid amide and glycidol in the solvent, and can be selected according to actual needs.

[0084] This invention enables a highly efficient ring-opening reaction between a first fatty acid amide and glycidyl ether, followed by a ring-opening reaction between a second fatty acid amide and the product obtained from the ring-opening reaction, thus achieving the successful preparation of hyperbranched polymers. Furthermore, this preparation method is simple, requires minimal equipment, saves energy, and allows for effective control of the structure of hyperbranched polymers, which is beneficial for their widespread application.

[0085] In one specific embodiment, the vegetable oil includes at least one selected from soybean oil, tung oil, palm oil, corn oil, and cottonseed oil; the molar ratio of vegetable oil to diethanolamine is 1:(3-6), for example, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, or 1:6. When the above-mentioned vegetable oil is selected, the vegetable oil contains suitable fatty acids, and these fatty acids can react fully with diethanolamine to generate fatty acid amides, which is beneficial to the subsequent preparation of hyperbranched polymers. At the same time, other substances in the vegetable oil do not react with other raw materials in the preparation method of this invention, avoiding the generation of side reactions and improving the purity of the hyperbranched polymer. When the molar ratio of vegetable oil to diethanolamine is within the above range, the fatty acids in the vegetable oil can react fully with diethanolamine to generate a sufficient amount of fatty acid amides, which is beneficial to the subsequent preparation of hyperbranched polymers.

[0086] In one specific embodiment, the molar ratio of the first fatty acid amide to glycidyl glycerol is 1:(2-15), for example, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, or 1:15. When the molar ratio of the first fatty acid amide to glycidyl glycerol is within the above range, the first fatty acid amide and glycidyl glycerol can undergo a sufficient ring-opening reaction, which is beneficial for preparing a hydrophilic hyperbranched polyglycerol structure and lays the foundation for the preparation of hyperbranched polymers.

[0087] In one specific embodiment, the molar ratio of the second fatty acid amide to the first fatty acid amide is (2-6):1, for example, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, or 6:1. When the molar ratio of the second fatty acid amide to the first fatty acid amide is within the above range, the second fatty acid amide can be sufficiently grafted onto the product obtained from the ring-opening reaction, thereby achieving a hyperbranched polymer with a hydrophilic hyperbranched polyglycerol structure at the center and a hydrophobic long-chain fatty acid structure at the tail end.

[0088] In one specific embodiment, the second reaction is carried out under the action of a first catalyst, which includes at least one selected from sodium hydride, potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide. The molar ratio of the first catalyst to the vegetable oil is (0.01-0.05):1, for example, 0.01:1, 0.015:1, 0.02:1, 0.025:1, 0.03:1, 0.035:1, 0.04:1, 0.045:1, or 0.05:1. In this invention, the vegetable oil and diethanolamine undergo a second reaction under the action of a first catalyst. When the first catalyst is selected from the above-mentioned compounds and the molar ratio is within the above range, the first catalyst can promote a rapid and complete second reaction between the vegetable oil and diethanolamine, laying the foundation for the efficient preparation of hyperbranched polymers.

[0089] In one specific embodiment, the ring-opening reaction is carried out under the action of a second catalyst, which includes at least one selected from sodium hydride, potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide. The molar ratio of the second catalyst to the first fatty acid amide is (0.01-0.05):1, for example, 0.01:1, 0.015:1, 0.02:1, 0.025:1, 0.03:1, 0.035:1, 0.04:1, 0.045:1, or 0.05:1. In this invention, the first fatty acid amide and glycidyl ether undergo a ring-opening reaction under the action of a second catalyst. When the second catalyst is selected from the above-mentioned compounds and the molar ratio is within the above range, the second catalyst can promote the ring-opening reaction of the first fatty acid amide and glycidyl ether, which is beneficial for the efficient preparation of hyperbranched polymers.

[0090] In one specific embodiment, the solvent includes at least one selected from methanol, chloroform, dioxane, N-methylpyrrolidone, N,N-dimethylformamide, and dimethyl sulfoxide. When the solvent is one of the above compounds, the first fatty acid amide and glycidyl can be fully dissolved in the solvent, which is beneficial to the ring-opening reaction and the first reaction. Furthermore, the components will not react with the solvent, avoiding the occurrence of side reactions, thereby ensuring the successful preparation of the hyperbranched polymer.

[0091] The present invention also provides a demulsifier comprising the above-mentioned hyperbranched polymer. This demulsifier, when applied to crude oil emulsion demulsification, exhibits high demulsification efficiency, particularly under conditions of low dosage, low demulsification temperature, acidic or alkaline environments, or high environmental salinity.

[0092] This invention also provides a method for demulsifying crude oil emulsions, comprising the following steps: dissolving the aforementioned demulsifier in a solvent, and then mixing the demulsifier solution with the crude oil emulsion uniformly to perform demulsification. This crude oil emulsion demulsification method enables rapid demulsification of crude oil emulsions, saving on the amount of demulsifier used, energy, and time costs, thus laying the foundation for the large-scale application of demulsifiers in crude oil emulsions.

[0093] The present invention will be further described in detail below through specific embodiments.

[0094] Example 1

[0095] The preparation process of the hyperbranched polymer provided in this embodiment includes the following steps:

[0096] 1. Add 30 mmol of soybean oil, 90 mmol of diethanolamine and 1 mmol of potassium methoxide to a reaction vessel, mix well and react at 80°C for 4 h, remove solvent and impurities to obtain fatty acid amide.

[0097] The molar ratio of soybean oil to diethanolamine is 1:3, and the molar ratio of potassium methoxide to soybean oil is 0.033:1.

[0098] 2. Add 10 mmol of fatty acid amide and 0.2 mmol of sodium methoxide to 20 mL of methanol, mix well, and place under a nitrogen atmosphere. Then, add 30 mmol of glycidyl ether dropwise to the above solution over 2 hours at 75 °C. Then, react at 100 °C for 5 hours. Then, add 30 mmol of fatty acid amide again and react at 100 °C for 5 hours. Remove the solvent and impurities to obtain the hyperbranched polymer.

[0099] The molar ratio of the first added fatty acid amide to glycidyl ether was 1:3, the molar ratio of the second added fatty acid amide to the first added fatty acid amide was 3:1, and the molar ratio of sodium methoxide to the first added fatty acid amide was 0.02:1.

[0100] Example 2

[0101] The preparation process of the hyperbranched polymer provided in this embodiment includes the following steps:

[0102] 1. Add 30 mmol of palm oil, 90 mmol of diethanolamine and 0.8 mmol of potassium methoxide to a reaction vessel, mix well and react at 90°C for 3 h, remove solvent and impurities to obtain fatty acid amide;

[0103] The molar ratio of palm oil to diethanolamine is 1:3, and the molar ratio of potassium methoxide to palm oil is 0.027:1.

[0104] 2. Add 10 mmol of fatty acid amide and 0.3 mmol of sodium methoxide to 20 mL of methanol, mix well, and place under a nitrogen atmosphere. Then, add 30 mmol of glycidyl ether dropwise to the above solution over 2 hours at 60 °C. Then, react at 110 °C for 3 hours. Then, add 30 mmol of fatty acid amide again and react at 110 °C for 3 hours. Remove the solvent and impurities to obtain the hyperbranched polymer.

[0105] The molar ratio of the first added fatty acid amide to glycidol was 1:3, the molar ratio of the second added fatty acid amide to the first added fatty acid amide was 3:1, and the molar ratio of sodium methoxide to the first added fatty acid amide was 0.03:1.

[0106] Example 3

[0107] The preparation process of the hyperbranched polymer provided in this embodiment includes the following steps:

[0108] 1. Add 30 mmol of corn oil, 90 mmol of diethanolamine and 1 mmol of potassium methoxide to a reaction vessel, mix well and react at 90°C for 5 h, remove solvent and impurities to obtain fatty acid amide.

[0109] The molar ratio of corn oil to diethanolamine is 1:3, and the molar ratio of potassium methoxide to corn oil is 0.033:1.

[0110] 2. Add 10 mmol of fatty acid amide and 0.3 mmol of sodium methoxide to 20 mL of methanol, mix well, and place under a nitrogen atmosphere. Then, add 30 mmol of glycidyl ether dropwise to the above solution over 2 hours at 75 °C. Then, react at 100 °C for 4 hours. Then, add 40 mmol of fatty acid amide again and react at 100 °C for 4 hours. Remove the solvent and impurities to obtain the hyperbranched polymer.

[0111] The molar ratio of the first added fatty acid amide to glycidyl ether was 1:3, the molar ratio of the second added fatty acid amide to the first added fatty acid amide was 4:1, and the molar ratio of sodium methoxide to the first added fatty acid amide was 0.03:1.

[0112] Example 4

[0113] The preparation process of the hyperbranched polymer provided in this embodiment includes the following steps:

[0114] 1. Add 30 mmol of soybean oil, 90 mmol of diethanolamine and 1 mmol of potassium methoxide to a reaction vessel, mix well and react at 80°C for 4 h, remove solvent and impurities to obtain fatty acid amide.

[0115] The molar ratio of soybean oil to diethanolamine is 1:3, and the molar ratio of potassium methoxide to soybean oil is 0.033:1.

[0116] 2. Add 10 mmol of fatty acid amide and 0.2 mmol of sodium methoxide to 20 mL of methanol, mix well, and place under a nitrogen atmosphere. Then, add 60 mmol of glycidyl ether dropwise to the above solution over 2 hours at 75 °C. Then, react at 100 °C for 5 hours. Then, add 30 mmol of fatty acid amide again and react at 100 °C for 5 hours. Remove the solvent and impurities to obtain the hyperbranched polymer.

[0117] The molar ratio of the first added fatty acid amide to glycidyl ether was 1:6, the molar ratio of the second added fatty acid amide to the first added fatty acid amide was 3:1, and the molar ratio of sodium methoxide to the first added fatty acid amide was 0.02:1.

[0118] Example 5

[0119] The preparation process of the hyperbranched polymer provided in this embodiment includes the following steps:

[0120] 1. Add 30 mmol of soybean oil, 90 mmol of diethanolamine and 1 mmol of potassium methoxide to a reaction vessel, mix well and react at 100°C for 4 h, remove solvent and impurities to obtain fatty acid amide.

[0121] The molar ratio of soybean oil to diethanolamine is 1:3, and the molar ratio of potassium methoxide to soybean oil is 0.033:1.

[0122] 2. Add 10 mmol of fatty acid amide and 0.2 mmol of sodium methoxide to 20 mL of methanol, mix well, and place under a nitrogen atmosphere. Then, add 90 mmol of glycidyl ether dropwise to the above solution over 2 hours at 75 °C. Then, react at 110 °C for 5 hours. Then, add 50 mmol of fatty acid amide again and react at 110 °C for 5 hours. Remove the solvent and impurities to obtain the hyperbranched polymer.

[0123] The molar ratio of the first added fatty acid amide to glycidyl is 1:9, the molar ratio of the second added fatty acid amide to the first added fatty acid amide is 5:1, and the molar ratio of sodium methoxide to the first added fatty acid amide is 0.02:1.

[0124] Example 6

[0125] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1, except that soybean oil, diethanolamine and potassium methoxide are reacted at 60°C for 6 hours.

[0126] Example 7

[0127] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1, except that soybean oil, diethanolamine and potassium methoxide are reacted at 100°C for 2 hours.

[0128] Example 8

[0129] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1, except that the molar ratio of soybean oil to diethanolamine is 1:4.

[0130] Example 9

[0131] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1, except that the molar ratio of soybean oil to diethanolamine is 1:6.

[0132] Example 10

[0133] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1, except that the molar ratio of potassium methoxide to soybean oil is 0.01:1.

[0134] Example 11

[0135] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1, except that the molar ratio of potassium methoxide to soybean oil is 0.05:1.

[0136] Example 12

[0137] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1, except that the molar ratio of the fatty acid amide to glycidol added for the first time is 1:2.

[0138] Example 13

[0139] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1. The difference is that the molar ratio of the fatty acid amide to glycidol added for the first time is 1:9.

[0140] Example 14

[0141] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1. The difference is that the molar ratio of the fatty acid amide to glycidol added for the first time is 1:15.

[0142] Example 15

[0143] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1. The difference is that the molar ratio of the second added fatty acid amide to the first added fatty acid amide is 2:1.

[0144] Example 16

[0145] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1. The difference is that the molar ratio of the second added fatty acid amide to the first added fatty acid amide is 6:1.

[0146] Example 17

[0147] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1, except that the molar ratio of sodium methoxide to the fatty acid amide added for the first time is 0.01:1.

[0148] Example 18

[0149] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1, except that the molar ratio of sodium methoxide to the fatty acid amide added for the first time is 0.03:1.

[0150] Example 19

[0151] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1, except that the molar ratio of sodium methoxide to the fatty acid amide added for the first time is 0.05:1.

[0152] Example 20

[0153] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1. The difference is that the fatty acid amide, sodium methoxide, and glycidyl are reacted at 80°C for 10 hours, and then reacted with the fatty acid amide at 80°C for 10 hours.

[0154] Example 21

[0155] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1. The difference is that the fatty acid amide, sodium methoxide, and glycidyl are reacted at 120°C for 4 hours, and then reacted with the fatty acid amide at 120°C for 4 hours.

[0156] Example 22

[0157] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1, except that soybean oil, diethanolamine and potassium methoxide are reacted at 110°C for 1.5 h.

[0158] Example 23

[0159] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1, except that the molar ratio of soybean oil to diethanolamine is 1:7.

[0160] Example 24

[0161] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1, except that the molar ratio of potassium methoxide to soybean oil is 0.06:1.

[0162] Example 25

[0163] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1. The difference is that the molar ratio of the fatty acid amide to glycidol added for the first time is 1:16.

[0164] Example 26

[0165] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1. The difference is that the molar ratio of the second added fatty acid amide to the first added fatty acid amide is 7:1.

[0166] Example 27

[0167] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1, except that the molar ratio of sodium methoxide to the fatty acid amide added for the first time is 0.06:1.

[0168] Example 28

[0169] The preparation process of the hyperbranched polymer provided in this embodiment is roughly the same as that in Example 1. The difference is that the fatty acid amide, sodium methoxide, and glycidyl are reacted at 130°C for 3 hours, and then reacted with the fatty acid amide at 130°C for 3 hours.

[0170] Comparative Example 1

[0171] The preparation process of the hyperbranched polymer provided in this embodiment includes the following steps:

[0172] 1. Add 30 mmol of soybean oil, 90 mmol of diethanolamine and 1 mmol of potassium methoxide to a reaction vessel, mix well and react at 80°C for 4 h, remove solvent and impurities to obtain fatty acid amide.

[0173] The molar ratio of soybean oil to diethanolamine is 1:3, and the molar ratio of potassium methoxide to soybean oil is 0.033:1.

[0174] 2. Add 10 mmol of fatty acid amide and 0.2 mmol of sodium methoxide to 20 mL of methanol, mix well, and place under a nitrogen atmosphere. Then, add 30 mmol of glycidyl ether dropwise to the above solution over 2 hours at 75 °C. After that, react at 100 °C for 5 hours to remove solvent and impurities and obtain hyperbranched polymer.

[0175] The molar ratio of fatty acid amide to glycidol is 1:3, and the molar ratio of sodium methoxide to fatty acid amide is 0.02:1.

[0176] Comparative Example 2

[0177] This comparative example uses commercial demulsifier SA-003, purchased from Nantong Shenai Water Treatment Reagent Co., Ltd.

[0178] Experimental Example 1

[0179] Infrared absorption spectroscopy was performed on the hyperbranched polymer of Example 1, such as... Figure 1 As shown. By Figure 1 It can be known that 3328cm -1 The absorption peak at 2919 cm⁻¹ is the stretching vibration of -OH. -1 and 2850cm -1 The peak at 1733 cm⁻¹ represents the absorption peaks of the -CH symmetric and antisymmetric vibrations. -1 The absorption peak at 1457 cm⁻¹ is the -CON- stretching vibration peak. -1 The absorption peak at 1108 cm⁻¹ is the in-plane bending vibration absorption peak of -CH. -1 The absorption peak at this point is the COC stretching vibration peak, therefore the hyperbranched polymer of Example 1 was successfully synthesized.

[0180] Experimental Example 2

[0181] Add 150 parts by weight of crude oil to 350 parts by weight of water and stir to mix. Heat to 70°C and then stir at 11,000 r / min for 20 minutes. Repeat this process three times until a stable emulsion is obtained.

[0182] The hyperbranched polymers prepared in Examples and Comparative Example 1 were added to alcohol to prepare demulsifier solutions with a mass fraction of 0.4%.

[0183] One volume of the above demulsifier solution was added to 20 volume of crude oil emulsion and mixed evenly. The mixture was then transferred to a 60°C water bath and allowed to stand for 3 hours. The demulsification efficiency was characterized by measuring the dehydration rate. The results are shown in Table 1.

[0184] Table 1

[0185]

[0186]

[0187] Experimental Example 3

[0188] Different weight parts of hyperbranched polymer were added to ethanol to prepare demulsifier solutions with mass fractions of 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, and 0.1%, respectively; the blank group was 0%.

[0189] One volume of the above demulsifier solution was added to 20 volume of crude oil emulsion and mixed evenly. The mixture was then transferred to a 60°C water bath and allowed to stand for 3 hours. The dehydration rate was measured, and the results are shown in Table 2.

[0190] Table 2

[0191]

[0192]

[0193] Test Example 4

[0194] The hyperbranched polymers prepared in the examples and comparative examples were added to ethanol to prepare a demulsifier solution with a mass fraction of 0.4%.

[0195] One volume of demulsifier solution was added to 20 volumes of crude oil emulsion and mixed evenly. The mixture was then transferred to water baths at different temperatures and allowed to stand for 3 hours. The dehydration rate was measured, and the results are shown in Table 3.

[0196] Table 3

[0197]

[0198] Experimental Example 5

[0199] Add 150 parts by weight of crude oil to 350 parts by weight of water and stir to mix. Heat to 70°C, adjust the pH value with hydrochloric acid and sodium hydroxide, and then stir at 11,000 r / min for 20 min. Repeat this process three times until a stable emulsion is obtained.

[0200] The hyperbranched polymers prepared in the examples and comparative examples were added to ethanol to prepare a demulsifier solution with a mass fraction of 0.4%.

[0201] One volume of demulsifier solution was added to 20 volume of crude oil emulsions with different pH values ​​and mixed evenly. The mixtures were then transferred to a 60°C water bath and allowed to stand for 3 hours. The dehydration rate was measured, and the results are shown in Table 4.

[0202] Table 4

[0203]

[0204] Experimental Example 6

[0205] Add 150 parts by weight of crude oil to 350 parts by weight of water and stir to mix. Heat to 70°C, adjust the salinity with sodium chloride, and then stir at 11,000 r / min for 20 min. Repeat this process three times until a stable crude oil emulsion is obtained.

[0206] The hyperbranched polymers prepared in the examples and comparative examples were added to ethanol to prepare a demulsifier solution with a mass fraction of 0.4%.

[0207] One volume of demulsifier solution was added to 20 volume of crude oil emulsions with different salinities and mixed evenly. The mixtures were then transferred to a 60°C water bath and allowed to stand for 3 hours. The dehydration rate was measured, and the results are shown in Table 5.

[0208] Table 5

[0209]

[0210] Table 1 shows that, based on the comparison between Examples 1-28 and Comparative Examples 1-2, the hyperbranched polymer provided by this invention exhibits excellent demulsification performance as a demulsifier. Table 2 shows that the hyperbranched polymer provided by this invention also demonstrates good demulsification performance in crude oil emulsions at relatively low concentrations. Table 3 shows that the hyperbranched polymer provided by this invention exhibits good demulsification performance above 50°C, with a low demulsification temperature. Table 4 shows that the demulsification performance of the hyperbranched polymer provided by this invention is less affected by pH, exhibiting high demulsification efficiency within a pH range of 3-11. Table 5 shows that the hyperbranched polymer provided by this invention maintains stable demulsification efficiency even under high salinity conditions, indicating that the hyperbranched polymer has high salt resistance. In summary, the hyperbranched polymer provided by this invention, when used as a demulsifier in crude oil emulsion demulsification, offers advantages such as high demulsification efficiency, low dosage, and low demulsification temperature, and demonstrates excellent demulsification effects under high acid / alkaline or high salinity conditions.

[0211] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A hyperbranched polymer, characterized in that, The hyperbranched polymer has the structural formula shown in Formula 1: In the formula, R1, R2, R3, and R are each independently selected from C8-C22 alkyl groups and C8-C22 alkenyl groups.

2. The hyperbranched polymer according to claim 1, characterized in that, The hyperbranched polymer is prepared by the following steps: The first fatty acid amide is subjected to a ring-opening reaction with glycidyl ether, and the product obtained from the ring-opening reaction is subjected to a first reaction with the second fatty acid amide to obtain the hyperbranched polymer. The first fatty acid amide and the second fatty acid amide have the structural formula shown in Formula 2: R4 is selected from at least one of R1, R2, R3, and R.

3. A method for preparing the hyperbranched polymer according to claim 1 or 2, characterized in that, Includes the following steps: After the first fatty acid amide is subjected to a ring-opening reaction with glycidyl ether, the product obtained from the ring-opening reaction is subjected to the first reaction with the second fatty acid amide to obtain the hyperbranched polymer. The first fatty acid amide and the second fatty acid amide have the structural formula shown in Formula 2: R4 is selected from at least one of R1, R2, R3, and R.

4. The method for preparing the hyperbranched polymer according to claim 3, characterized in that, The following steps are included prior to the ring-opening reaction: After uniformly mixing vegetable oil containing the fatty acid and diethanolamine in a solvent, the second reaction is carried out to obtain the first fatty acid amide; and / or, after uniformly mixing vegetable oil containing the fatty acid and diethanolamine in a solvent, the second reaction is carried out to obtain the second fatty acid amide; The fatty acid includes at least one of fatty acids having R1, R2 or R3; the reaction temperature of the second reaction is 60-100℃ and the reaction time is 2-6h.

5. The method for preparing the hyperbranched polymer according to claim 3 or 4, characterized in that, The ring-opening reaction and the first reaction include the following steps: After the first fatty acid amide and glycidyl ether are mixed evenly in a solvent, a ring-opening reaction is carried out. Then, the second fatty acid amide is added to the product obtained from the ring-opening reaction to carry out the first reaction, thereby obtaining the hyperbranched polymer. The ring-opening reaction is carried out at a temperature of 80-120℃ for 4-10 hours; the first reaction is carried out at a temperature of 80-120℃ for 4-10 hours.

6. The method for preparing the hyperbranched polymer according to claim 4 or 5, characterized in that, The vegetable oil includes at least one of soybean oil, tung oil, palm oil, corn oil, and cottonseed oil; the molar ratio of the vegetable oil to diethanolamine is 1:(3-6); And / or, the molar ratio of the first fatty acid amide to glycidyl is 1:(2-15); And / or, the molar ratio of the second fatty acid amide to the first fatty acid amide is (2-6):

1.

7. The method for preparing the hyperbranched polymer according to any one of claims 4-6, characterized in that, The second reaction is carried out under the action of a first catalyst, which includes at least one of sodium hydride, potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide; the molar ratio of the first catalyst to the vegetable oil is (0.01-0.05):

1.

8. The method for preparing the hyperbranched polymer according to any one of claims 4-7, characterized in that, The ring-opening reaction is carried out under the action of a second catalyst, which includes at least one of sodium hydride, potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide; the molar ratio of the second catalyst to the first fatty acid amide is (0.01-0.05):

1. And / or, the solvent includes at least one of methanol, chloroform, dioxane, N-methylpyrrolidone, N,N-dimethylformamide, and dimethyl sulfoxide.

9. A demulsifier, characterized in that, The demulsifier comprises the hyperbranched polymer as described in claim 1 or 2.

10. A method for demulsifying crude oil emulsions, characterized in that, Includes the following steps: The demulsifier according to claim 9 is dissolved in a solvent, and then the resulting demulsifier solution is mixed evenly with the crude oil emulsion to perform demulsification.

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