Hyperbranched polymer, demulsifier and preparation method and application thereof
The hyperbranched polymer synthesized through three graft reactions is used as a deemulsion agent, which solves the problems of high risk of synthesis, large amount of use and insufficient tolerance in the prior art, and achieves rapid deemulsion at low temperatures and good thermal stability and acid-base tolerance.
Patent Information
- Application Number
- CN202411735017.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-29
- Publication Date
- 2025-03-11
AI Technical Summary
The existing demulsifier synthesis technology has problems such as high risks, large amounts of use, insufficient tolerance to acid and alkali salts, poor flocculation and coagulation effects, and poor demulsification effects.
Hyperbranched polymers are synthesized by three grafting reactions and used as deemulsion agents, which have excellent interfacial activity, can quickly deemulsify at low temperatures, and have good thermal stability and acid-base tolerance.
It achieves rapid demulsification at low temperatures, has good thermal stability and acid-base tolerance, and improves demulsification efficiency and safety.
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Figure CN119591891A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of oilfield chemicals, and in particular relates to a hyperbranched polymer, a demulsifier, and a preparation method and application thereof. Background Art
[0002] With the advancement of enhanced oil recovery technology in the oil extraction industry, methods such as thermal oil recovery, miscible oil recovery, chemical oil recovery and microbial oil recovery have been widely used in actual production, but the application of these technologies inevitably produces a large amount of oil-water emulsions.
[0003] Emulsion is a polydisperse system formed by one or more liquids dispersed in another immiscible liquid in the form of droplets. Oil-in-water emulsion refers to an emulsion in which water is the dispersed phase and crude oil is the continuous phase. Compounds such as colloidal acid and cycloalkanes in crude oil, as well as substances such as asphaltene and wax particles, are the main emulsifiers of this type of emulsion. The formation and stability of emulsions are affected by many factors, such as moderate interfacial tension helps the formation of emulsions; the formation of oil-water interface film can provide a physical barrier; the existence of diffuse double layer increases the electrostatic repulsion between droplets; the adsorption of solid particles can enhance the stability of the droplet surface; specific production temperature helps to maintain the state of the emulsion; the pH value and salinity of the emulsion also affect its stability. Oil-water emulsions not only shorten the service life of pipelines and increase storage and transportation risks, but also cause serious corrosion of equipment in the crude oil production process. Therefore, it is crucial to demulsify oil-water emulsions. Chemical demulsification has been widely used in the petroleum industry due to its high efficiency and low dosage.
[0004] Chemical demulsifiers are a class of amphiphilic compounds with hydrophilic and hydrophobic ends. They act on the oil-water interface to reduce interfacial tension and may replace natural emulsifiers on the interface to promote the aggregation and separation of dispersed phase droplets. Common crude oil demulsifiers include alkyl phenolic resin block polyether type and polyoxyethylene polyoxypropylene type. However, the synthesis process of these demulsifiers is relatively complicated, there are certain risks, and they often require large amounts of use. Summary of the invention
[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a hyperbranched polymer, a demulsifier and a preparation method and application thereof, aiming to solve the problems existing in the existing demulsifier synthesis technology, such as high risk, large usage amount, insufficient tolerance to acids, alkalis and salts, poor flocculation and coagulation effects, and unsatisfactory demulsification effect.
[0006] The purpose of the present invention is achieved through the following technical solutions: A method for preparing a hyperbranched polymer comprises the following steps: S1. In a solvent, a tricarboxylic acid ester compound and a first diamine compound are reacted at a molar ratio of 1:3 to obtain a primary grafted product; the primary grafted product is reacted with a first methyl olefinate compound at a molar ratio of 1:6 to obtain a first intermediate product; S2, reacting the first intermediate product with the second diamine compound in a molar ratio of 1:6 to obtain a secondary grafted product; reacting the secondary grafted product with the second methyl olefinate compound in a molar ratio of 1:12 to obtain a second intermediate product; S3, reacting the second intermediate product with the third diamine compound in a molar ratio of 1:12 to obtain a tertiary grafted product; S4, reacting the tertiary grafting product with alkyl glycidyl ether to obtain a hyperbranched polymer.
[0007] Preferably, in step S1, the solvent is at least one of methanol, ethanol and N,N-dimethylformamide.
[0008] Preferably, in step S1, the tricarboxylic acid ester compound is at least one of trimethyl citrate, trimethyl 1,2,4-benzenetricarboxylate, triethyl citrate, triethyl methanetricarboxylate, triethyl 1,3,5-benzenetricarboxylate and triethyl 1,1,2-ethanetricarboxylate.
[0009] Preferably, in step S1, the first diamine compound is at least one of ethylenediamine, 1,3-propylenediamine and p-phenylenediamine.
[0010] Preferably, in step S1, the first methyl olefinate compound is at least one of methyl acrylate and methyl 3-butyleneate.
[0011] Preferably, in step S1, the tricarboxylic acid ester compound and the first diamine compound are reacted at 25-60° C. for 8-12 hours to obtain a primary grafted product.
[0012] Preferably, in step S2, the second diamine compound is at least one of ethylenediamine, 1,3-propylenediamine and p-phenylenediamine.
[0013] Preferably, in step S2, the second methyl olefinate compound is at least one of methyl acrylate and methyl 3-butyleneate.
[0014] Preferably, in step S2, the first intermediate product reacts with the second diamine compound in a molar ratio of 1:6, the reaction temperature is 25-60° C., and the reaction time is 8-12 h to obtain a secondary grafted product.
[0015] Preferably, in step S3, the third diamine compound is at least one of ethylenediamine, 1,3-propylenediamine and p-phenylenediamine.
[0016] Preferably, in step S3, the second intermediate product reacts with the third diamine compound in a molar ratio of 1:12, the reaction temperature is 25-60° C., and the reaction time is 8-12 h to obtain a tertiary grafted product.
[0017] Preferably, in step S4, the alkyl glycidyl ether is octyl glycidyl ether, C 8 -C 10 Alkyl glycidyl ether, C 12 -C 14 At least one of alkyl glycidyl ether, polyethylene glycol glycidyl dodecyl ether and glycidyl hexadecyl ether.
[0018] Preferably, in step S4, the molar ratio of the tertiary grafting product to the alkyl glycidyl ether is 1:6-12.
[0019] Preferably, in step S4, the reaction temperature is 80-120° C., and the reaction time is 4-6 hours.
[0020] The hyperbranched polymer is prepared by the above-mentioned method for preparing the hyperbranched polymer.
[0021] A demulsifier comprises the above hyperbranched polymer.
[0022] The application of the above demulsifier in demulsifying crude oil emulsion.
[0023] The use of the demulsifier in crude oil emulsion demulsification comprises the following steps: firstly dissolving the hyperbranched polymer in a solvent to obtain a solution, then mixing the solution with the crude oil emulsion at 40-70° C. and standing for 0.5-3 hours.
[0024] Preferably, the mass percentage of the hyperbranched polymer in the solution is 0.1-1 wt %, more preferably 0.2-1 wt %.
[0025] Preferably, the solvent is at least one of water, ethanol and xylene.
[0026] Preferably, the volume ratio of the solution to the crude oil emulsion is 1:(10-20).
[0027] Preferably, the crude oil emulsion is a water-in-oil type crude oil emulsion.
[0028] Compared with the prior art, the beneficial effects of the present invention include: The invention synthesizes a hyperbranched polymer through three grafting reactions and uses the hyperbranched polymer as a demulsifier, which has excellent interfacial activity and can achieve rapid demulsification at low temperatures. In addition, the demulsifier of the invention also has the characteristics of good thermal stability and acid-base tolerance. BRIEF DESCRIPTION OF THE DRAWINGS
[0029] Figure 1 This is a schematic diagram of the synthesis principle of the hyperbranched polymer described in Example 1 (Part 1).
[0030] Figure 2 Schematic diagram of the synthesis principle of the hyperbranched polymer described in Example 1 (Part 2).
[0031] Figure 3 This is the infrared spectrum of the hyperbranched polymer described in Example 1. DETAILED DESCRIPTION
[0032] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.
[0033] Example 1 A method for preparing a hyperbranched polymer comprises the following steps: S1. In 15 mL of methanol, trimethyl citrate and ethylenediamine are reacted in a molar ratio of 1:3 at a temperature of 60°C for 12 hours to obtain a primary grafted product; the primary grafted product is reacted with methyl acrylate in a molar ratio of 1:6 at a temperature of 60°C for 8 hours to obtain a first intermediate product; S2, reacting the first intermediate product with ethylenediamine in a molar ratio of 1:6, the reaction temperature is 60°C, and the reaction time is 12 hours to obtain a secondary grafted product; reacting the secondary grafted product with methyl acrylate in a molar ratio of 1:12, the reaction temperature is 60°C, and the reaction time is 8 hours to obtain a second intermediate product; S3, reacting the second intermediate product with ethylenediamine in a molar ratio of 1:12 at a temperature of 60° C. for 8 h to obtain a tertiary grafted product; S4, the three grafted products and C 8 -C 10 The alkyl glycidyl ether is reacted at a molar ratio of 1:12, the reaction temperature is 120° C., and the reaction time is 4 hours to obtain the hyperbranched polymer.
[0034] Figure 1~2 This is a schematic diagram of the synthesis principle of the hyperbranched polymer described in Example 1. Since many steps are involved, it is divided into a first part and a second part for display.
[0035] Figure 3 is the infrared spectrum of the hyperbranched polymer described in Example 1, from Figure 3 It can be seen that at 3270 cm -1The peak at 2956 cm is caused by the stretching vibration of the NH bond within the secondary amide group. -1 With 2869 cm -1 The peak at is the -CH 2 -Antisymmetric stretching vibration and symmetric stretching vibration peaks. 1654 cm -1 The peak at 1550 cm-1 is attributed to the C=O stretching vibration in the amide group. -1 The peak at 1382 cm is attributed to the CNH bending vibration of the secondary amide. -1 , 1255 cm -1 and 1093 cm -1 These are the CN stretching vibrations of primary amides, secondary amides and fatty tertiary amines. 661 cm -1 The peak at 400 nm is attributed to the in-plane bending vibration of the O=CN of the amide group. The above infrared spectroscopy characterization results indicate that the target product was successfully synthesized.
[0036] Example 2 A method for preparing a hyperbranched polymer comprises the following steps: S1. In 15 mL of ethanol, triethyl methanetricarboxylate and ethylenediamine are reacted in a molar ratio of 1:3, the reaction temperature is 25°C, and the reaction time is 12 hours to obtain a primary grafted product; the primary grafted product is reacted with methyl acrylate in a molar ratio of 1:6, the reaction temperature is 25°C, and the reaction time is 12 hours to obtain a first intermediate product; S2, reacting the first intermediate product with ethylenediamine in a molar ratio of 1:6, the reaction temperature is 25°C, and the reaction time is 12h to obtain a secondary grafted product; reacting the secondary grafted product with methyl acrylate in a molar ratio of 1:12, the reaction temperature is 25°C, and the reaction time is 12h to obtain a second intermediate product; S3, reacting the second intermediate product with ethylenediamine in a molar ratio of 1:12 at a temperature of 25° C. for 12 h to obtain a tertiary grafted product; S4, the three grafted products and C 8 -C 10 The alkyl glycidyl ether is reacted at a molar ratio of 1:12, the reaction temperature is 120° C., and the reaction time is 4 hours to obtain the hyperbranched polymer.
[0037] Example 3 A method for preparing a hyperbranched polymer comprises the following steps: S1. In 15 mL of ethanol, trimethyl citrate and 1,3-propylenediamine were reacted in a molar ratio of 1:3 at a temperature of 60°C for 12 hours to obtain a primary grafted product; the primary grafted product was reacted with 3-butenoic acid methyl ester in a molar ratio of 1:6 at a temperature of 60°C for 12 hours to obtain a first intermediate product; S2, reacting the first intermediate product with 1,3-propylenediamine in a molar ratio of 1:6, the reaction temperature is 60°C, and the reaction time is 12 hours to obtain a secondary grafted product; reacting the secondary grafted product with 3-butenoic acid methyl ester in a molar ratio of 1:12, the reaction temperature is 60°C, and the reaction time is 12 hours to obtain a second intermediate product; S3, reacting the second intermediate product with 1,3-propylenediamine in a molar ratio of 1:12 at a reaction temperature of 60° C. for 12 h to obtain a tertiary grafted product; S4, the three grafted products and C 12 -C 14 The alkyl glycidyl ether is reacted at a molar ratio of 1:12, the reaction temperature is 120° C., and the reaction time is 4 hours to obtain the hyperbranched polymer.
[0038] Example 4 A method for preparing a hyperbranched polymer comprises the following steps: S1. In 15 mL of ethanol, 1,2,4-trimethyl benzoate and 1,3-propylenediamine were reacted in a molar ratio of 1:3 at a temperature of 60°C for 12 hours to obtain a primary grafted product; the primary grafted product was reacted with methyl acrylate in a molar ratio of 1:6 at a temperature of 60°C for 12 hours to obtain a first intermediate product; S2, reacting the first intermediate product with 1,3-propylenediamine in a molar ratio of 1:6, the reaction temperature is 60°C, and the reaction time is 12 hours to obtain a secondary grafted product; reacting the secondary grafted product with methyl acrylate in a molar ratio of 1:12, the reaction temperature is 60°C, and the reaction time is 12 hours to obtain a second intermediate product; S3, reacting the second intermediate product with 1,3-propylenediamine in a molar ratio of 1:12 at a reaction temperature of 60° C. for 12 h to obtain a tertiary grafted product; S4, the three grafted products and C 8 -C 10 The alkyl glycidyl ether is reacted at a molar ratio of 1:12, the reaction temperature is 120° C., and the reaction time is 4 hours to obtain the hyperbranched polymer.
[0039] Comparative Example 1 Commercial demulsifier PE10100 was purchased from Shanghai Kaiyin Chemical Co., Ltd.
[0040] Comparative Example 2 Commercial demulsifier RI 16A was purchased from Shanghai Kaiyin Chemical Co., Ltd.
[0041] Test Example 1 The demulsifiers (ie, hyperbranched polymers) prepared in Examples 1 to 4 and the commercial demulsifiers described in Comparative Examples 1 and 2 were used to characterize the demulsification performance of the demulsifiers in water-in-oil crude oil emulsions.
[0042] 150 parts by mass of crude oil were added to 350 parts by mass of distilled water, stirred and mixed, and heated to 70° C., and then stirred at a rotation speed of 11,000 rpm for 20 minutes. This process was repeated three times until a stable water-in-oil emulsion was obtained.
[0043] The commercial demulsifiers of comparative examples 1 and 2 prepared in examples 1 to 4 were added into ethanol to prepare demulsifier solutions with a mass fraction of 1%, namely experimental groups 1 to 4 and comparative groups 1 to 2.
[0044] 1 volume part of the above demulsifier solution was added to 20 volume parts of crude oil emulsion and then mixed evenly by inversion, and then transferred to a 45°C water bath and allowed to stand for 2.5 hours. The demulsification efficiency was characterized by measuring its dehydration rate (refer to the Petroleum and Natural Gas Industry Standard SY / T 5281-2000 of the People's Republic of China). The results are shown in Table 1.
[0045] Table 1 Demulsification results of experimental groups 1-5 and comparative groups 1-2
[0046] Note: "Crude oil demulsifier (mg / L)" in the table refers to the concentration of demulsifier in crude oil emulsion.
[0047] It can be seen from Table 1 that the hyperbranched demulsifiers prepared in Examples 1 to 4 all have good demulsification performance, and the demulsification efficiency of Example 1 is the highest.
[0048] Test Example 2 Based on the demulsifier prepared in Example 1, demulsifier solutions of different concentrations were prepared to characterize the demulsification performance of demulsifiers of different concentrations in crude oil emulsions.
[0049] 150 parts by mass of crude oil were added to 350 parts by mass of deionized water, stirred and mixed, heated to 70° C., and then stirred at a rotation speed of 11,000 rpm for 20 minutes. This process was repeated three times until a stable water-in-oil emulsion was obtained.
[0050] Different weight portions of the demulsifier prepared in Example 1 were added to ethanol to prepare crude oil demulsifier solutions with weight fractions of 1%, 0.8%, 0.6%, 0.4% and 0.2%, respectively. The obtained samples were recorded as experimental groups 5 to 9; the blank group was 0%, and the sample was recorded as experimental group 10.
[0051] 1 volume part of the above experimental groups 5 to 9 was added to 20 volume parts of crude oil emulsion and then inverted and shaken to mix evenly, and then transferred to a 45°C water bath and allowed to stand for 2.5 hours. The dehydration rate was measured. The results are shown in Table 2.
[0052] Table 2 Demulsification results of experimental groups 5-10
[0053] Note: "Crude oil demulsifier (mg / L)" in the table refers to the concentration of the demulsifier in the crude oil emulsion.
[0054] As shown in Table 2, the hyperbranched demulsifier provided by the present invention has good demulsification performance, and can achieve a demulsification efficiency of 100% at a demulsification concentration of 500 mg / L, and a demulsification efficiency of up to 85% at a demulsification concentration of 400 mg / L.
[0055] Test Example 3 Based on the demulsifier prepared in Example 1, experimental groups 11 to 15 were established in sequence to characterize the demulsification performance of the demulsifier at different temperatures and times.
[0056] 150 parts by mass of crude oil were added to 350 parts by mass of deionized water, stirred and mixed, heated to 70° C., and then stirred at a rotation speed of 11,000 rpm for 20 minutes. This process was repeated three times until a stable water-in-oil emulsion was obtained.
[0057] The demulsifier prepared in Example 1 was added into ethanol to prepare a solution with a mass fraction of 1%.
[0058] 1 volume part of the above crude oil demulsifier solution was added to 20 volume parts of crude oil emulsion and then inverted and shaken to mix evenly, and then transferred to water bath pots set at different temperatures and allowed to stand for 2.5 hours. The dehydration rate was measured. The results are shown in Table 3.
[0059] Table 3 Demulsification results of experimental groups 11-15
[0060] It can be seen from Table 3 that the hyperbranched demulsifier provided by the present invention can achieve a demulsification efficiency of 100% at 45°C for 150 minutes, and can achieve a demulsification efficiency of 100% at 60°C and 65°C for 60 minutes and 30 minutes respectively.
[0061] Test Example 4 Based on the demulsifier prepared in Example 1, experimental groups 16 to 21 were established in sequence to characterize the demulsification performance of the demulsifier under different pH conditions.
[0062] 150 parts by mass of crude oil are added to 350 parts by mass of distilled water and stirred to mix. The pH value is adjusted by adding hydrochloric acid or sodium hydroxide, and then heated to 70°C and stirred at 11,000 rpm for 20 minutes. This process is repeated three times until a stable water-in-oil emulsion is obtained.
[0063] The demulsifier prepared in Example 1 was added into ethanol to prepare a solution with a mass fraction of 1%.
[0064] 1 volume part of the above crude oil demulsifier solution was added to 20 volumes of crude oil emulsions with different pH values and then inverted and shaken to mix evenly. The mixture was then transferred to a 45°C water bath and allowed to stand for 2.5 hours. The demulsification efficiency was measured. The results are shown in Table 4.
[0065] Table 4 Demulsification results of experimental groups 16-21
[0066] It can be seen from Table 4 that the demulsifier provided by the present invention has good acid-base tolerance and has a high demulsification efficiency under strong alkaline and acidic conditions (pH=4-12).
[0067] Test Example 5 Based on the demulsifier prepared in Example 1, experimental groups 22 to 27 were established in sequence to characterize the demulsification performance of the demulsifier under different salinity conditions.
[0068] 150 parts by mass of crude oil were added to 350 parts by mass of distilled water and stirred and mixed. The salinity was adjusted by adding sodium chloride, and then heated to 70° C. and stirred at 11,000 rpm for 20 minutes. This process was repeated three times until a stable water-in-oil emulsion was obtained.
[0069] The demulsifier prepared in Example 1 was added into ethanol to prepare a solution with a mass fraction of 1%.
[0070] 1 volume part of the above crude oil demulsifier solution was added to 20 volumes of crude oil emulsions of different salinities and then inverted and shaken to mix evenly. Then, they were transferred to a 45°C water bath and allowed to stand for 2.5 hours. The demulsification efficiency was measured. The results are shown in Table 5.
[0071] Table 5 Demulsification results of experimental groups 22-27
[0072] It can be seen from Table 5 that the demulsifier provided in Example 1 of the present invention has a stable demulsification efficiency under high salinity conditions.
[0073] The invention provides a hyperbranched demulsifier for low-temperature demulsification of water-in-oil type crude oil emulsion. The demulsifier has the characteristics of low demulsification temperature, excellent demulsification performance, good acid, alkali and salt tolerance, etc.
[0074] The specific implementation of the present invention described above does not constitute a limitation on the protection scope of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the protection scope of the claims of the present invention.
Claims
1. A method for preparing a hyperbranched polymer, characterized in that: The steps include: S1. In a solvent, a tricarboxylic acid ester compound and a first diamine compound are reacted at a molar ratio of 1:3 to obtain a primary grafted product; the primary grafted product is reacted with a first methyl olefinate compound at a molar ratio of 1:6 to obtain a first intermediate product; S2, reacting the first intermediate product with the second diamine compound in a molar ratio of 1:6 to obtain a secondary grafted product; reacting the secondary grafted product with the second methyl olefinate compound in a molar ratio of 1:12 to obtain a second intermediate product; S3, reacting the second intermediate product with the third diamine compound in a molar ratio of 1:12 to obtain a tertiary grafted product; S4, reacting the tertiary grafting product with alkyl glycidyl ether to obtain the hyperbranched polymer.
2. The method for preparing a hyperbranched polymer according to claim 1, wherein The solvent in step S1 is at least one of methanol, ethanol and N,N-dimethylformamide; The tricarboxylic acid ester compound in step S1 is at least one of trimethyl citrate, trimethyl 1,2,4-benzenetricarboxylate, triethyl citrate, triethyl methanetricarboxylate, triethyl 1,3,5-benzenetricarboxylate and triethyl 1,1,2-ethanetricarboxylate; In step S1, the first diamine compound is at least one of ethylenediamine, 1,3-propylenediamine and p-phenylenediamine.
3. The method for preparing a hyperbranched polymer according to claim 1, wherein Step S1: the first methyl olefinate compound is at least one of methyl acrylate and methyl 3-butyleneate; Step S1: the tricarboxylic acid ester compound and the first diamine compound are reacted at 25-60° C. for 8-12 hours to obtain a primary grafted product; Step S2: the second diamine compound is at least one of ethylenediamine, 1,3-propylenediamine and p-phenylenediamine; Step S2: the second methyl olefinate compound is at least one of methyl acrylate and methyl 3-butyleneate; In step S2, the first intermediate product reacts with the second diamine compound at a molar ratio of 1:6, the reaction temperature is 25-60° C., and the reaction time is 8-12 hours to obtain a secondary grafted product.
4. The method for preparing a hyperbranched polymer according to claim 1, wherein The third diamine compound in step S3 is at least one of ethylenediamine, 1,3-propylenediamine and p-phenylenediamine; In step S3, the second intermediate product reacts with the third diamine compound at a molar ratio of 1:12, the reaction temperature is 25-60° C., and the reaction time is 8-12 h to obtain a tertiary grafted product; The alkyl glycidyl ether in step S4 is octyl glycidyl ether, C8-C 10 Alkyl glycidyl ether, C 12 -C 14 At least one of alkyl glycidyl ether, polyethylene glycol glycidyl dodecyl ether and glycidyl hexadecyl ether.
5. The method for preparing a hyperbranched polymer according to claim 1, characterized in that: The molar ratio of the tertiary grafted product to the alkyl glycidyl ether in step S4 is 1:6-12; The reaction temperature in step S4 is 80-120° C., and the reaction time is 4-6 hours.
6. A hyperbranched polymer prepared by the method for preparing a hyperbranched polymer according to any one of claims 1 to 5.
7. A demulsifier, characterized in that: Comprising the hyperbranched polymer according to claim 6.
8. Use of the demulsifier according to claim 7 in demulsifying crude oil emulsion.
9. The use according to claim 8, characterized in that: The method comprises the following steps: firstly dissolving the hyperbranched polymer in a solvent to obtain a solution, and then mixing the solution with a crude oil emulsion at 40-65° C. and standing the mixture for 2.5 hours.
10. The use according to claim 9, characterized in that: The mass percentage of the hyperbranched polymer in the solution is 0.1-1wt%; The solvent is at least one of water, ethanol and xylene; The volume ratio of the solution to the crude oil emulsion is 1:(10-20); The crude oil emulsion is a water-in-oil type crude oil emulsion.