Hyperbranched polymer, preparation method therefor, and use thereof

Abstract

A hyperbranched polymer, a preparation method therefor, and a use thereof. The hyperbranched polymer has a structure represented by formula 1, wherein R1, R2, R3, and R are each independently selected from a C8-C22 alkyl group and a C8-C22 alkenyl group. The hyperbranched polymer, as a demulsifier, is used for crude oil emulsion demulsification, and has the advantages of high demulsification efficiency, low use amount, low demulsification temperature, high acid and alkali resistance, and high salt resistance.

Description

Hyperbranched polymer and preparation method and application thereof

[0001] The present application claims priority to the Chinese patent application No. 2024113187128 filed on September 20, 2024, and entitled "Hyperbranched polymer and preparation method and application thereof", the whole content of which is incorporated herein by reference. TECHNICAL FIELD

[0002] The present application belongs to the field of oil field chemical additives, and specifically relates to a hyperbranched polymer and a preparation method and application thereof. BACKGROUND

[0003] Emulsion is a kind of multi-phase dispersion system, which plays an important role in pharmaceutical, biochemical and even food industry. However, stable crude oil emulsion is not conducive to the oil industry and oil refining operation. Stable emulsion is mainly formed in the process of crude oil exploitation. In the process of crude oil exploitation, it is difficult to avoid mixing with water, and the existence of natural emulsifiers such as resin, asphaltene, solid particles and paraffin crystals, combined with a large amount of formation water and artificial injection of surfactant in the process of oil displacement, under the action of heating, shearing and extrusion, more stable emulsion is formed. The formation of emulsion will bring a series of serious hazards to the exploitation, transportation and processing of oil.

[0004] The methods for breaking emulsion of crude oil mainly adopt physical, chemical, biological and other simple and efficient demulsification methods and composite treatment methods. In the actual production process of oil field, chemical demulsification method has always been the most commonly used demulsification technology. From the patents or research and application of demulsifiers at home and abroad, it can be known that the main synthesis method of demulsifier is still the modification or compounding of block polyether based on ethylene oxide and propylene oxide. Chinese patent CN113684054A develops a demulsifier composed of polyether and ionic liquid mixed and compounded according to a certain proportion and solvent; CN101642692B discloses a composite demulsifier and a preparation method thereof, which is composed of block polyether and aromatic ring containing sulfonic acid mixed and compounded according to a certain proportion and solvent. However, the above-mentioned chemical demulsifiers all use ethylene oxide, propylene oxide and other raw materials, which do not meet the development concept of green environmental protection, and at the same time, the demulsifiers require synthesis under certain pressure, the reaction conditions are complex, and the process requirements are high. At present, with the use of various new crude oil exploitation technologies, the stability of oil-water emulsion is getting stronger and stronger, and conventional reagents have been unable to meet the dehydration demand, therefore, the technical personnel in the field urgently need to develop a demulsifier with green and environmentally friendly raw materials, low usage amount, high demulsification efficiency, low demulsification temperature, high acid and alkali resistance and high salt resistance. SUMMARY

[0005] The application provides a hyperbranched polymer, which has the advantages of low use amount, high demulsification efficiency, low demulsification temperature, high acid and alkali resistance and high salt resistance as a demulsifier.

[0006] The application provides a demulsifier, which is applied to crude oil demulsification and can have low use amount, high demulsification efficiency, low demulsification temperature, high acid and alkali resistance and high salt resistance.

[0007] The application provides a crude oil emulsion demulsification method, which can demulsify crude oil emulsion and has high demulsification efficiency, low use amount, low demulsification temperature, high acid and alkali resistance and high salt resistance.

[0008] The application provides a hyperbranched polymer, which has the advantages of low use amount, high demulsification efficiency, low demulsification temperature, high acid and alkali resistance and high salt resistance as a demulsifier.

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

[0010] The hyperbranched polymer is prepared by the following steps.

[0011] The first fatty acid amide is subjected to ring-opening reaction with glycidol, and the product obtained by the ring-opening reaction is subjected to 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] R4 is at least one selected from R1, R2, R3 and R.

[0014] The application provides a preparation method of the hyperbranched polymer.

[0015] The first fatty acid amide is subjected to ring-opening reaction with glycidol, and the product obtained by the ring-opening reaction is subjected to first reaction with the second fatty acid amide to obtain the hyperbranched polymer.

[0016] The first fatty acid amide and the second fatty acid amide have the structural formula shown in formula 2.

[0017] R4 is at least one selected from R1, R2, R3 and R.

[0018] The preparation method of the hyperbranched polymer further comprises the following steps before the ring-opening reaction.

[0019] the second reaction is performed after the plant oil comprising the fatty acid, diethanolamine and a solvent are uniformly mixed, to obtain the first fatty acid amide; and / or the second reaction is performed after the plant oil comprising the fatty acid, diethanolamine and a solvent are uniformly mixed, to obtain the second fatty acid amide;

[0020] The second reaction has a reaction temperature of 60-100°C and a reaction time of 2-6h.

[0021] The preparation method of the hyperbranched polymer as described above, wherein the ring-opening reaction and the first reaction comprise the following steps:

[0022] The ring-opening reaction is performed after the first fatty acid amide and glycidol are uniformly mixed in a solvent, and then the second fatty acid amide is added to the product of the ring-opening reaction to perform the first reaction, to obtain the hyperbranched polymer.

[0023] The ring-opening reaction has a reaction temperature of 80-120°C and a reaction time of 4-10h; and the first reaction has a reaction temperature of 80-120°C and a reaction time of 4-10h.

[0024] The preparation method of the hyperbranched polymer as described above, wherein the plant oil comprises at least one of soybean oil, tung oil, palm oil, corn oil and cottonseed oil; and the molar ratio of the plant oil to diethanolamine is 1:(3-6).

[0025] And / or, the molar ratio of the first fatty acid amide to glycidol is 1:(2-15).

[0026] And / or, the molar ratio of the second fatty acid amide to the first fatty acid amide is (2-6):1.

[0027] The preparation method of the hyperbranched polymer as described above, wherein the second reaction is performed under the action of a first catalyst, the first catalyst comprising at least one of sodium hydride, potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide and potassium ethoxide; and the molar ratio of the first catalyst to the plant oil is (0.01-0.05):1.

[0028] The preparation method of the hyperbranched polymer as described above, wherein the ring-opening reaction is performed 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; and the molar ratio of the second catalyst to the first fatty acid amide is (0.01-0.05):1.

[0029] And / or, the solvent comprises at least one of methanol, chloroform, dioxane, N-methyl pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide.

[0030] The application also provides a demulsifier comprising the hyperbranched polymer as described above.

[0031] The application also provides a crude oil emulsion demulsification method, comprising the following steps: dissolving the demulsifier as described above in a solvent, and then mixing the obtained demulsifier solution with the crude oil emulsion to perform demulsification.

[0032] The hyperbranched polymer provided by the application has a specific structural formula, wherein the center is a hydrophilic hyperbranched polyglycerol structure, and the tail end is a hydrophobic long-chain fatty acid structure. This structure enables the hyperbranched polymer to exhibit amphiphilicity and high interfacial activity. The hyperbranched polymer can quickly adsorb to the oil-water interface, greatly reduce the interfacial tension, soften or destroy the interfacial film, thereby reducing the stability of the interfacial film and promoting the occurrence of the demulsification process, so that the hyperbranched polymer can efficiently demulsify at a low usage amount.

[0033] In the preparation method of the hyperbranched polymer provided by the application, first, the first fatty acid amide is subjected to ring-opening reaction with glycidol to obtain a product having a structural formula of formula 2, and then the product obtained by the ring-opening reaction is subjected to first reaction with the second fatty acid amide to obtain the hyperbranched polymer having a structural formula of formula 1. Through this preparation method, the hyperbranched polymer can have a special chemical structure, so that the hyperbranched polymer exhibits amphiphilicity and high interfacial activity, and further has high demulsification efficiency, low usage amount, low demulsification temperature, and high salt resistance. Moreover, the structure of the hyperbranched polymer is controllable, which is conducive to regulating the number of hydrophobic chains and hydrophilic chains according to the changes of the crude oil emulsion.

[0034] The application also provides a demulsifier comprising the hyperbranched polymer described above, which can efficiently demulsify the crude oil emulsion, has low usage amount, low demulsification temperature, and high acid and alkali resistance and high salt resistance.

[0035] The application provides a crude oil emulsion demulsification method, and the demulsifier can demulsify the crude oil emulsion, has high demulsification efficiency, low usage amount, low demulsification temperature, high acid and alkali resistance, high salt resistance, and other advantages. BRIEF DESCRIPTION OF DRAWINGS

[0036] FIG. 1 is an infrared spectrum of the hyperbranched polymer of Example 1. DETAILED DESCRIPTION

[0037] In order to make the purposes, technical solutions and advantages of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely in combination with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the scope of protection of the present application.

[0038] The present application provides a hyperbranched polymer, wherein the hyperbranched polymer has a structural formula shown in Formula 1:

[0039] In the formula, R1, R2, R3, R are each independently selected from substituted or unsubstituted C8-C22 alkyl, C8-C22 alkenyl.

[0040] The hyperbranched polymer of the present application has a structural formula shown in Formula 1, wherein R1, R2, R3, R are each independently selected from C8-C22 alkyl, C8-C22 alkenyl. The C8-C22 alkyl of the present application refers to alkyl having 8-22 carbon atoms; the C8-C22 alkenyl refers to alkenyl having 8-22 carbon atoms. When the substituent is specified as a group having a specific number of carbons, all geometric isomers having the number of carbons are included. For example, R1, R2, R3, 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 -(CH2) 11 CH3, -(CH2)6-CH=CH2, etc. The wavy line in the compound shown in Formula 1 of the present application connected to the oxygen atom can be selected or hydrogen, the carbon atom at * in is connected to the oxygen atom in the compound of Formula 1, and the wavy line in can also be selected or hydrogen.

[0041] According to the above scheme provided in the application, the hyperbranched polymer is used as a demulsifier in crude oil emulsion demulsification, has the advantages of high demulsification efficiency, low use amount, low demulsification temperature, and excellent demulsification effect in acid-base environment or high-salt conditions. The applicant analyzes the principle and considers that the reason may be that the hyperbranched polymer has the structural formula shown in formula 1, the center is a hyperbranched polyglycerol structure with hydrophilicity, and the tail end is a long-chain fatty acid structure with hydrophobicity, so that the hyperbranched polymer exhibits excellent amphiphilicity and high interfacial activity, thereby greatly reducing the oil-water interfacial tension, replacing the active substances in the interfacial film, softening or destroying the interfacial film, promoting the occurrence of the demulsification process, and enabling the hyperbranched polymer to demulsify efficiently.

[0042] Specifically, the hyperbranched polymer can be obtained by infrared absorption spectrum test.

[0043] In a specific embodiment, the hyperbranched polymer is prepared by the following steps:

[0044] The first fatty acid amide is subjected to ring-opening reaction with glycidol, and the product obtained by the ring-opening reaction is subjected to first reaction with the second fatty acid amide to obtain the hyperbranched polymer;

[0045] The first fatty acid amide and the second fatty acid amide have the structural formula shown in formula 2:

[0046] R4 is selected from at least one of R1, R2, R3, and R.

[0047] Specifically, first, the first fatty acid amide is subjected to ring-opening reaction with glycidol to obtain a ring-opening reaction product, and then the product obtained by the ring-opening reaction is subjected to first reaction with the second fatty acid amide to obtain the hyperbranched polymer, wherein the first fatty acid amide and the second fatty acid amide both have the structural formula shown in formula 2.

[0048] It is worth noting that the first fatty acid amide includes at least one of the fatty acid amide with R1, the fatty acid amide with R2, the fatty acid amide with R3, and the fatty acid amide with R4, that is, the first fatty acid amide can be one fatty acid amide, or a mixture of any two or more of the four fatty acid amides. The second fatty acid amide is similar to the first fatty acid amide, and can also be one fatty acid amide, or a mixture of any two or more of the four fatty acid amides. In addition, 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.

[0049] The application does not limit the specific parameter selection of the ring-opening reaction, which can be selected according to actual needs.

[0050] The application does not limit the specific parameter selection of the first reaction, which can be selected according to actual needs.

[0051] The application does not limit the specific ratio of the first fatty acid amide and glycidol, which can be selected according to actual needs.

[0052] The application does not limit the specific ratio of the second fatty acid amide and the first fatty acid amide, which can be selected according to actual needs.

[0053] The application, through the above preparation method, first performs ring-opening reaction on the first fatty acid amide and glycidol, and then performs the first reaction on the product obtained by the ring-opening reaction and the second fatty acid amide to obtain the hyperbranched polymer with the structure of formula 1. Through the preparation method, the hyperbranched polymer has a special chemical structure, so that the hyperbranched polymer exhibits amphiphilicity and high interfacial activity, and further has high demulsification efficiency, low use amount, low demulsification temperature and high salt resistance, and the structure of the hyperbranched polymer is controllable, which is conducive to the number regulation of hydrophobic chains and hydrophilic chains according to the change of crude oil emulsion.

[0054] The application provides a preparation method of the above hyperbranched polymer, which comprises the following steps:

[0055] After the ring-opening reaction of the first fatty acid amide and glycidol, the first reaction is performed on the product obtained by the ring-opening reaction and the second fatty acid amide to obtain the hyperbranched polymer.

[0056] The first fatty acid amide and the second fatty acid amide have the structural formula shown in formula 2:

[0057] R4 is selected from at least one of R1, R2, R3 and R.

[0058] Specifically, the ring-opening reaction is performed on the first fatty acid amide and glycidol to obtain a ring-opening reaction product, and then the first reaction is performed on the product obtained by the ring-opening reaction and the second fatty acid amide to obtain the hyperbranched polymer. The first fatty acid amide and the second fatty acid amide both have the structural formula shown in formula 2.

[0059] The first fatty acid amide and the second fatty acid amide of the application are similar, and can be one fatty acid amide or a mixture of any two or more of the four fatty acid amides. In addition, the first fatty acid amide and the second fatty acid amide can be the same or different, which can be selected according to actual needs.

[0060] The application does not limit the specific parameter selection of the ring-opening reaction, which can be selected according to actual needs.

[0061] The application does not limit the specific parameter selection of the first reaction, which can be selected according to actual needs.

[0062] The application does not limit the specific ratio of the addition of the first fatty acid amide and the glycidol, which can be selected according to actual needs.

[0063] The application does not limit the specific ratio of the addition of the second fatty acid amide and the first fatty acid amide, which can be selected according to actual needs.

[0064] The preparation method of the hyperbranched polymer of the application can prepare a hyperbranched polymer with the structural formula of formula 1. The hyperbranched polymer has a special chemical structure, so that the hyperbranched polymer exhibits amphiphilicity and high interfacial activity, thereby having high demulsification efficiency, low use amount, low demulsification temperature and high salt resistance, and the structure of the hyperbranched polymer is controllable.

[0065] In a specific embodiment, the method further comprises, before the ring-opening reaction:

[0066] The plant oil including fatty acids and diethanolamine are uniformly mixed in a solvent, and then a second reaction is performed to obtain a first fatty acid amide; and / or the plant oil including fatty acids and diethanolamine are uniformly mixed in a solvent, and then a second reaction is performed to obtain a second fatty acid amide.

[0067] The fatty acid includes at least one of the fatty acids with R1, R2 or R3; the reaction temperature of the second reaction is 60-100℃, and the reaction time is 2-6h.

[0068] Specifically, the plant oil and diethanolamine are mixed in a solvent, and after uniform mixing, a second reaction is performed. 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 a first fatty acid amide. The plant oil includes fatty acids, and the fatty acids include at least one of the fatty acids with R1, R2 or R3, i.e., the plant oil can only include one kind of fatty acid, or can be a mixture including two or three kinds of the three fatty acids.

[0069] Similarly, the vegetable oil and the diethanolamine are mixed in a solvent, and after being uniformly mixed, a second reaction is performed. The reaction temperature of the second reaction is 60-100°C, such as 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, or 100°C, etc. The reaction time is 2-6h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, or 6h, etc. After the reaction is completed, impurities and the solvent are removed, and the first fatty acid amide is obtained.

[0070] The present application does not limit the specific operation of mixing the vegetable oil and the diethanolamine in a solvent, which can be selected according to actual needs.

[0071] The present application does not limit the specific selection of the solvent, which can be selected according to actual needs.

[0072] The present application does not limit the specific process of removing impurities and the solvent, which can be selected according to actual needs.

[0073] The present application can make the fatty acid in the vegetable oil react with the diethanolamine by the preparation method to obtain the fatty acid amide with the structure of Formula 2. The preparation method has low reaction temperature, short reaction time, low preparation condition requirement, and the vegetable oil is easy to obtain and has no environmental pollution.

[0074] In one specific embodiment, the ring-opening reaction and the first reaction include the following steps:

[0075] After the first fatty acid amide and the glycidol are uniformly mixed in a solvent, a ring-opening reaction is performed, and then a second fatty acid amide is added to the product obtained by the ring-opening reaction to perform a first reaction, and a hyperbranched polymer is obtained.

[0076] The reaction temperature of the ring-opening reaction is 80-120°C, and the reaction time is 4-10h. The reaction temperature of the first reaction is 80-120°C, and the reaction time is 4-10h.

[0077] Specifically, first, the first fatty acid amide and glycidol are mixed in a solvent, after being uniformly mixed, ring-opening reaction is carried out, the reaction temperature of the ring-opening reaction is 80-120°C, for example, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C or 120°C, etc., the reaction time is 4-10h, for example, 4h, 5h, 6h, 7h, 8h, 9h or 10h, etc., to obtain a product, then the second fatty acid amide is added to the product to carry out the first reaction, the reaction temperature of the first reaction is 80-120°C, for example, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C or 120°C, etc., 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.

[0078] The application does not limit the specific mixing parameters of the first fatty acid amide and glycidol in the solvent, which can be selected according to actual needs.

[0079] The application can make the first fatty acid amide and glycidol carry out efficient ring-opening reaction through the above method, then the second fatty acid amide and the product obtained by the ring-opening reaction carry out ring-opening reaction, to realize the successful preparation of the hyperbranched polymer. In addition, the preparation process of the preparation method is simple, the equipment requirement is low, energy is saved, and the structure of the hyperbranched polymer can be effectively controlled through the preparation method, which is conducive to the wide application of the hyperbranched polymer.

[0080] In a specific embodiment, the plant oil includes at least one of soybean oil, tung oil, palm oil, corn oil, cottonseed oil; the molar ratio of the plant 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, etc. When the plant oil is selected from the above plant oils, the plant oil contains suitable fatty acids, and the fatty acids can fully react with diethanolamine to generate fatty acid amide, which is conducive to the subsequent preparation of the hyperbranched polymer, and at the same time, other substances in the plant oil do not react with other raw materials in the preparation method of the application, avoiding the generation of side reactions, and improving the purity of the hyperbranched polymer. When the molar ratio of the plant oil to diethanolamine is in the above range, the fatty acids in the plant oil can fully react with diethanolamine to generate enough fatty acid amide, which is conducive to the subsequent preparation of the hyperbranched polymer.

[0081] In an embodiment, the molar ratio of the first fatty acid amide to glycidol is 1:(2-15), such as 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, etc. When the molar ratio of the first fatty acid amide to glycidol is within the above range, the first fatty acid amide and glycidol can undergo sufficient ring-opening reaction, which is conducive to the preparation of hyperbranched polyglycerol structure with hydrophilicity, and lays the foundation for the preparation of hyperbranched polymers.

[0082] In an embodiment, the molar ratio of the second fatty acid amide to the first fatty acid amide is (2-6):1, such as 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, or 6:1, etc. 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 grafted to the product obtained by ring-opening reaction, so as to realize that the center of the hyperbranched polymer is the hyperbranched polyglycerol structure with hydrophilicity, and the tail end is the long-chain fatty acid structure with hydrophobicity.

[0083] In an embodiment, the second reaction is carried out under the action of the first catalyst, and the first catalyst comprises 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 plant oil is (0.01-0.05):1, such as 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, etc. The plant oil and diethanolamine in the present application are subjected to the second reaction under the action of the first catalyst. When the first catalyst is selected from the above compounds and the molar ratio is within the above range, the first catalyst can promote the plant oil and diethanolamine to undergo rapid and sufficient second reaction, which lays the foundation for the efficient preparation of hyperbranched polymers.

[0084] In an embodiment, the ring-opening reaction is carried out under the action of the second catalyst, and the second catalyst comprises 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, such as 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, etc. The first fatty acid amide and glycidol in the present application are subjected to ring-opening reaction under the action of the second catalyst. When the second catalyst is selected from the above compounds and the molar ratio is within the above range, the second catalyst can promote the first fatty acid amide and glycidol to undergo ring-opening reaction, which is conducive to the efficient preparation of hyperbranched polymers.

[0085] In one embodiment, the solvent comprises at least one of methanol, chloroform, dioxane, N-methylpyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide. When the solvent is selected from the above compounds, the first fatty acid amide and glycidol can be fully dissolved in the solvent, which is conducive to the ring-opening reaction and the first reaction, and the components do not react with the solvent, avoiding the occurrence of side reactions, thereby ensuring the successful preparation of the hyperbranched polymer.

[0086] The application also provides a demulsifier comprising the hyperbranched polymer. The demulsifier is applied to crude oil emulsion demulsification, has high demulsification efficiency, and has high demulsification efficiency in a low use amount, a low demulsification temperature, an acid and alkali environment, or a high salt content environment.

[0087] The application also provides a crude oil emulsion demulsification method, comprising the following steps: dissolving the demulsifier in a solvent, and then uniformly mixing the demulsifier solution with the crude oil emulsion to perform demulsification. The method can realize rapid and efficient demulsification, save the use amount of the demulsifier, and save energy and time costs, thereby laying a foundation for large-scale application of the demulsifier in crude oil emulsion.

[0088] The application will be further described in detail through specific embodiments.

[0089] Embodiment 1

[0090] The preparation process of the hyperbranched polymer provided in the embodiment comprises the following steps:

[0091] 1. 30 mmol of soybean oil, 90 mmol of diethanolamine, and 1 mmol of potassium methoxide are added to a reaction kettle, uniformly mixed, and then reacted at 80°C for 4 h, and then the solvent and impurities are removed to obtain a fatty acid amide;

[0092] The molar ratio of the soybean oil to the diethanolamine is 1:3, and the molar ratio of the potassium methoxide to the soybean oil is 0.033:1;

[0093] 2. 10 mmol of the fatty acid amide and 0.2 mmol of sodium methoxide are added to 20 mL of methanol, uniformly mixed, and then placed in a nitrogen atmosphere, and then 30 mmol of glycidol is added dropwise to the above solution at 75°C within 2 h, and then reacted at 100°C for 5 h, and then 30 mmol of the fatty acid amide is added again and reacted at 100°C for 5 h, and then the solvent and impurities are removed to obtain a hyperbranched polymer;

[0094] The molar ratio of the first added fatty acid amide to the glycidol is 1:3, the molar ratio of the second added fatty acid amide to the first added fatty acid amide is 3:1, and the molar ratio of the sodium methoxide to the first added fatty acid amide is 0.02:1.

[0095] Example 2

[0096] The preparation process of the hyperbranched polymer provided in this example includes the following steps:

[0097] 1. 30 mmol of palm oil, 90 mmol of diethanolamine and 0.8 mmol of potassium methoxide were added to a reaction kettle, mixed uniformly, and then reacted at 90°C for 3h, and then the solvent and impurities were removed to obtain a fatty acid amide;

[0098] The molar ratio of palm oil to diethanolamine was 1:3, and the molar ratio of potassium methoxide to palm oil was 0.027:1.

[0099] 2. 10 mmol of fatty acid amide and 0.3 mmol of sodium methoxide were added to 20 mL of methanol, mixed uniformly, and then placed in a nitrogen atmosphere, and then 30 mmol of glycidol was added dropwise to the above solution at 60°C within 2h, and then reacted at 110°C for 3h, and then 30 mmol of fatty acid amide was added again and reacted at 110°C for 3h, and then the solvent and impurities were removed to obtain a hyperbranched polymer;

[0100] 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.

[0101] Example 3

[0102] The preparation process of the hyperbranched polymer provided in this example includes the following steps:

[0103] 1. 30 mmol of corn oil, 90 mmol of diethanolamine and 1 mmol of potassium methoxide were added to a reaction kettle, mixed uniformly, and then reacted at 90°C for 5h, and then the solvent and impurities were removed to obtain a fatty acid amide;

[0104] The molar ratio of corn oil to diethanolamine was 1:3, and the molar ratio of potassium methoxide to corn oil was 0.033:1.

[0105] 2. 10 mmol of fatty acid amide and 0.3 mmol of sodium methoxide were added to 20 mL of methanol, mixed uniformly, and then placed in a nitrogen atmosphere, and then 30 mmol of glycidol was added dropwise to the above solution at 75°C within 2h, and then reacted at 100°C for 4h, and then 40 mmol of fatty acid amide was added again and reacted at 100°C for 4h, and then the solvent and impurities were removed to obtain a hyperbranched polymer;

[0106] The molar ratio of the first added fatty acid amide to glycidol is 1:3, the molar ratio of the second added fatty acid amide to the first added fatty acid amide is 4:1, and the molar ratio of sodium methoxide to the first added fatty acid amide is 0.03:1.

[0107] Example 4

[0108] The preparation process of the hyperbranched polymer provided in the embodiment includes the following steps:

[0109] 1. 30 mmol of soybean oil, 90 mmol of diethanolamine and 1 mmol of potassium methoxide were added into a reaction kettle, and after being uniformly mixed, they were reacted at 80℃ for 4h, and then the solvent and impurities were removed to obtain a fatty acid amide;

[0110] The molar ratio of the soybean oil to diethanolamine is 1:3, and the molar ratio of the potassium methoxide to the soybean oil is 0.033:1.

[0111] 2. 10 mmol of the fatty acid amide and 0.2 mmol of sodium methoxide were added into 20 mL of methanol, and after being uniformly mixed, they were placed in a nitrogen atmosphere, and then 60 mmol of glycidol was added dropwise into the above solution at 75℃ within 2h, and then reacted at 100℃ for 5h, and then 30 mmol of the fatty acid amide was added again and reacted at 100℃ for 5h, and then the solvent and impurities were removed to obtain a hyperbranched polymer;

[0112] The molar ratio of the first added fatty acid amide to glycidol is 1:6, the molar ratio of the second added fatty acid amide to the first added fatty acid amide is 3:1, and the molar ratio of sodium methoxide to the first added fatty acid amide is 0.02:1.

[0113] Example 5

[0114] The preparation process of the hyperbranched polymer provided in the embodiment includes the following steps:

[0115] 1. 30 mmol of soybean oil, 90 mmol of diethanolamine and 1 mmol of potassium methoxide were added into a reaction kettle, and after being uniformly mixed, they were reacted at 80℃ for 4h, and then the solvent and impurities were removed to obtain a fatty acid amide;

[0116] The molar ratio of the soybean oil to diethanolamine is 1:3, and the molar ratio of the potassium methoxide to the soybean oil is 0.033:1.

[0117] 2. 10 mmol of fatty acid amide and 0.2 mmol of sodium methoxide were added to 20 mL of methanol, mixed uniformly, and then placed in a nitrogen atmosphere, and then 90 mmol of glycidol was added dropwise to the above solution at 75°C within 2h, and then reacted at 110°C for 5h, and then 50 mmol of fatty acid amide was added again and reacted at 110°C for 5h, and then the solvent and impurities were removed to obtain a hyperbranched polymer;

[0118] The molar ratio of the first added fatty acid amide to glycidol 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.

[0119] Example 6

[0120] The preparation process of the hyperbranched polymer provided in this example is substantially the same as that of Example 1, except that the soybean oil, diethanolamine and potassium methoxide are reacted at 60°C for 6h.

[0121] Example 7

[0122] The preparation process of the hyperbranched polymer provided in this example is substantially the same as that of Example 1, except that the soybean oil, diethanolamine and potassium methoxide are reacted at 100°C for 2h.

[0123] Example 8

[0124] The preparation process of the hyperbranched polymer provided in this example is substantially the same as that of Example 1, except that the molar ratio of soybean oil to diethanolamine is 1:4.

[0125] Example 9

[0126] The preparation process of the hyperbranched polymer provided in this example is substantially the same as that of Example 1, except that the molar ratio of soybean oil to diethanolamine is 1:6.

[0127] Example 10

[0128] The preparation process of the hyperbranched polymer provided in this example is substantially the same as that of Example 1, except that the molar ratio of potassium methoxide to soybean oil is 0.01:1.

[0129] Example 11

[0130] The preparation process of the hyperbranched polymer provided in this example is substantially the same as that of Example 1, except that the molar ratio of potassium methoxide to soybean oil is 0.05:1.

[0131] Example 12

[0132] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of the first added fatty acid amide to glycidol is 1:2.

[0133] Embodiment 13

[0134] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of the first added fatty acid amide to glycidol is 1:9.

[0135] Embodiment 14

[0136] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of the first added fatty acid amide to glycidol is 1:15.

[0137] Embodiment 15

[0138] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of the second added fatty acid amide to the first added fatty acid amide is 2:1.

[0139] Embodiment 16

[0140] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of the second added fatty acid amide to the first added fatty acid amide is 6:1.

[0141] Embodiment 17

[0142] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of sodium methoxide to the first added fatty acid amide is 0.01:1.

[0143] Embodiment 18

[0144] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of sodium methoxide to the first added fatty acid amide is 0.03:1.

[0145] Embodiment 19

[0146] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of sodium methoxide to the first added fatty acid amide is 0.05:1.

[0147] Embodiment 20

[0148] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the fatty acid amide, sodium methoxide and glycidol are reacted at 80°C for 10 h, and then the fatty acid amide is added again and reacted at 80°C for 10 h.

[0149] Embodiment 21

[0150] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the fatty acid amide, sodium methoxide and glycidol are reacted at 80°C for 10 h, and then the fatty acid amide is added again and reacted at 80°C for 10 h.

[0151] Embodiment 22

[0152] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the soybean oil, diethanolamine and potassium methoxide are reacted at 110°C for 1.5 h.

[0153] Embodiment 23

[0154] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of the soybean oil to diethanolamine is 1:7.

[0155] Embodiment 24

[0156] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of the potassium methoxide to the soybean oil is 0.06:1.

[0157] Embodiment 25

[0158] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of the first added fatty acid amide to glycidol is 1:16.

[0159] Embodiment 26

[0160] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of the second added fatty acid amide to the first added fatty acid amide is 7:1.

[0161] Embodiment 27

[0162] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of the sodium methoxide to the first added fatty acid amide is 0.06:1.

[0163] Embodiment 28

[0164] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the fatty acid amide, sodium methoxide and glycidol are reacted at 130°C for 3h, and then the fatty acid amide is reacted at 130°C for another 3h.

[0165] Comparative Example 1

[0166] The preparation process of the hyperbranched polymer provided in the embodiment includes the following steps:

[0167] 1. 30mmol of soybean oil, 90mmol of diethanolamine and 1mmol of potassium methoxide are added into a reaction kettle, and after being uniformly mixed, they are reacted at 80°C for 4h, and then the solvent and impurities are removed to obtain a fatty acid amide;

[0168] 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.

[0169] 2. 10mmol of the fatty acid amide and 0.2mmol of sodium methoxide are added into 20mL of methanol, and after being uniformly mixed, they are placed in a nitrogen atmosphere, and then 30mmol of glycidol is added dropwise into the above solution at 75°C within 2h, and then the reaction is carried out at 100°C for 5h, and then the solvent and impurities are removed to obtain a hyperbranched polymer;

[0170] The molar ratio of the fatty acid amide to glycidol is 1:3, and the molar ratio of sodium methoxide to the fatty acid amide is 0.02:1.

[0171] Comparative Example 2

[0172] The commercial demulsifier SA-003 used in the comparative example is purchased from Nantong Shina Water Treatment Reagent Co., Ltd.

[0173] Test Example 1

[0174] The hyperbranched polymer of Embodiment 1 is subjected to infrared absorption spectrum test, as shown in FIG. 1. As shown in FIG. 1, 3328cm -1 is the stretching vibration absorption peak of -OH, 2919cm -1 and 2850cm -1 are the symmetric and asymmetric vibration absorption peaks of -C-H, 1733cm -1 is the stretching vibration absorption peak of -CON-, 1457cm -1 is the in-plane bending vibration absorption peak of -CH, and 1108cm -1 is the C-O-C stretching vibration absorption peak, so the hyperbranched polymer of Embodiment 1 is successfully synthesized.

[0175] Test Example 2

[0176] 150 parts by mass of crude oil was added to 350 parts by mass of water and mixed by stirring, heated to 70°C, and then stirred at 11000 r / min for 20 min, and this process was repeated three times until a stable emulsion was obtained.

[0177] The hyperbranched polymer prepared in the example and comparative example 1 was added to alcohol to prepare a demulsifier solution having a mass fraction of 0.4%.

[0178] 1 part by volume of the above demulsifier solution was added to 20 parts by volume of crude oil emulsion and mixed uniformly, and then transferred to a water bath at 60°C and left to stand for 3 h. The dehydration rate was measured to characterize the demulsification efficiency, and the results are shown in Table 1.

[0179] Table 1

[0180] Test Example 3

[0181] Different amounts of hyperbranched polymer were added to ethanol to prepare demulsifier solutions having mass fractions of 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, and 0.1%, respectively. The blank group was 0%.

[0182] 1 part by volume of the above demulsifier solution was added to 20 parts by volume of crude oil emulsion and mixed uniformly, and then transferred to a water bath at 60°C and left to stand for 3 h. The dehydration rate was measured, and the results are shown in Table 2.

[0183] Table 2

[0184] Test Example 4

[0185] The hyperbranched polymer prepared in the example and comparative example was added to ethanol to prepare a demulsifier solution having a mass fraction of 0.4%.

[0186] 1 part by volume of the above demulsifier solution was added to 20 parts by volume of crude oil emulsion and mixed uniformly, and then transferred to a water bath at different temperatures and left to stand for 3 h. The dehydration rate was measured, and the results are shown in Table 3.

[0187] Table 3

[0188] Test Example 5

[0189] 150 parts by mass of crude oil was added to 350 parts by mass of water and mixed by stirring, heated to 70°C, and then stirred at 11000 r / min for 20 min, and this process was repeated three times until a stable emulsion was obtained.

[0190] The hyperbranched polymers prepared in the examples and comparative examples were added into ethanol to prepare a demulsifier solution with a mass fraction of 0.4%.

[0191] 1 part by volume of the demulsifier solution was added into 20 parts by volume of crude oil emulsion with different pH values and mixed uniformly, and then transferred into a 60°C water bath respectively and left to stand for 3h, and the dehydration rate was measured. The results are shown in Table 4.

[0192] Table 4

[0193] Test Example 6

[0194] 150 parts by mass of crude oil was added into 350 parts by mass of water and stirred and mixed, heated to 70°C, the salinity was adjusted by sodium chloride, and then stirred at a speed of 11000r / min for 20min, and this process was repeated three times until a stable crude oil emulsion was obtained.

[0195] The hyperbranched polymers prepared in the examples and comparative examples were added into ethanol to prepare a demulsifier solution with a mass fraction of 0.4%.

[0196] 1 part by volume of the demulsifier solution was added into 20 parts by volume of crude oil emulsion with different salinity and mixed uniformly, and then transferred into a 60°C water bath respectively and left to stand for 3h, and the dehydration rate was measured. The results are shown in Table 5.

[0197] Table 5

[0198] As can be seen from Table 1, according to the comparison of examples 1-28 and comparative examples 1-2, the hyperbranched polymer provided in the application can exhibit excellent demulsification performance as a demulsifier; as can be seen from Table 2, the hyperbranched polymer provided in the application can also have good demulsification performance in crude oil emulsion at a lower concentration; as can be seen from Table 3, the hyperbranched polymer provided in the application has good demulsification performance above 50°C and low demulsification temperature; as can be seen from Table 4, the demulsification performance of the hyperbranched polymer provided in the application is less affected by pH, and has high demulsification efficiency in the pH range of 3-11; as can be seen from Table 5, the hyperbranched polymer provided in the application still has stable demulsification efficiency under high salinity conditions, indicating that the hyperbranched polymer has high salt resistance. In summary, the hyperbranched polymer provided in the application has the advantages of high demulsification efficiency, low use amount, low demulsification temperature, and excellent demulsification effect under high acid or alkaline conditions or high salinity conditions when used as a demulsifier in crude oil emulsion demulsification.

[0199] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, but not to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A hyperbranched polymer, wherein, The hyperbranched polymer has a structural formula shown in Formula 1: wherein R1, R2, R3, R are each independently selected from C8-C22 alkyl, C8-C22 alkenyl.

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

3. A process for the preparation of the hyperbranched polymer of claim 1 or 2, wherein, comprising the following steps: ring-opening reaction of the first fatty acid amide with glycidol, and first reaction of the product of the ring-opening reaction with the second fatty acid amide to obtain the hyperbranched polymer; The first fatty acid amide and the second fatty acid amide have a structural formula shown in Formula 2: wherein R4 is selected from at least one of R1, R2, R3, R.

4. The method of claim 3, wherein the hyperbranched polymer is prepared by the reaction of a compound of formula (I) with a compound of formula (II). Further comprising the following steps before the ring-opening reaction: uniformly mixing the plant oil comprising the fatty acid and diethanolamine in a solvent, and then performing the second reaction to obtain the first fatty acid amide; and / or, uniformly mixing the plant oil comprising the fatty acid and diethanolamine in a solvent, and then performing the second reaction to obtain the second fatty acid amide; wherein the fatty acid comprises at least one of the 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 a hyperbranched polymer according to claim 3 or 4, wherein, The ring-opening reaction and the first reaction comprise the following steps: uniformly mixing the first fatty acid amide and glycidol in a solvent, and then performing ring-opening reaction, and subsequently adding the second fatty acid amide to the product of the ring-opening reaction to perform the first reaction to obtain the hyperbranched polymer; wherein the reaction temperature of the ring-opening reaction is 80-120℃, and the reaction time is 4-10h; the reaction temperature of the first reaction is 80-120℃, and the reaction time is 4-10h.

6. The method for preparing a hyperbranched polymer according to claim 4 or 5, wherein, The plant oil comprises at least one of soybean oil, tung oil, palm oil, corn oil, and cottonseed oil; the molar ratio of the plant oil to diethanolamine is 1:(3-6); and / or, the molar ratio of the first fatty acid amide to glycidol 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 of preparing a hyperbranched polymer according to any one of claims 4 to 6, wherein, The second reaction is performed in the presence of a first catalyst, and the first catalyst comprises 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 plant oil is (0.01-0.05):

1.

8. The method of preparing a hyperbranched polymer according to any one of claims 4 to 7, wherein, The ring-opening reaction is performed in the presence of a second catalyst, and the second catalyst comprises 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 comprises at least one of methanol, chloroform, dioxane, N-methyl pyrrolidone, N,N-dimethylformamide, and dimethyl sulfoxide.

9. A demulsifier, wherein, The demulsifier comprises the hyperbranched polymer of claim 1 or 2.

10. A method of breaking an emulsion of a crude oil, wherein, comprising the following steps: dissolving the demulsifier of claim 9 in a solvent, and then uniformly mixing the obtained demulsifier solution with a crude oil emulsion to perform demulsification.

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