Preparation method of cationic aromatic side chain demulsifier

Abstract

The invention relates to a preparation method of a cationic aromatic side chain demulsifier, and belongs to the technical field of chemical demulsification, and the preparation method comprises the following steps: S1, preparing used drugs and reagents including polysuccinimide, 1, 4-dibromobutane, N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylformamide, N, N- The cleaning agent is prepared from N, N-dimethyl benzylamine, quinoline, triethylamine, dimethyl sulfoxide, acetonitrile, ethylene diamine tetraacetic acid disodium. Dihydrate, anhydrous sodium sulfate, sodium hydroxide, hydrochloric acid, absolute ethyl alcohol, anhydrous calcium chloride, petroleum ether, n-heptane, sodium bicarbonate, complex black T, deionized water, acetone and diethyl ether. S2, preparing required equipment including a double-neck round-bottom bottle provided with a cooling system, heating equipment, cooling equipment, a thermometer, a test tube, a dropper, a beaker and a weighing device; according to the preparation method of the cationic aromatic side chain demulsifier, a relatively good demulsification effect can be displayed at room temperature and in a strong acid environment, and enough surfactant molecules are provided, so that an adsorption layer is formed on the surface of an emulsion, the surface tension is reduced, and an emulsion structure is destroyed.

Description

Technical Field

[0001] The invention relates to the technical field of chemical demulsification, in particular to a method for preparing a cationic aromatic side chain demulsifier. Background Art

[0002] In recent years, with the development and application of tertiary oil recovery technology, the content of asphaltene and colloid in crude oil, which are the main factors affecting the stability of emulsions, has continued to increase, which not only makes the performance of crude oil emulsions more stable, but also always causes problems such as equipment corrosion, greatly increasing the cost of production and operation, and untreated wastewater will endanger human health and the social environment. Therefore, the preparation of a low-temperature, efficient and environmentally friendly demulsifier for O / W emulsions has become an urgent problem to be solved. The current demulsification technologies include physical demulsification, chemical demulsification and biological demulsification. Among them, chemical demulsification technology has the advantages of high efficiency, flexibility, controllability, multi-function and economy, and is currently the most commonly used demulsification method.

[0003] In the prior art, polysuccinimide-3-dimethylaminopropylamine, polysuccinimide-dopamine-3-dimethylaminopropylamine and polysuccinimide-phenylethylamine-3-dimethylaminopropylamine can be successfully used for demulsification of water-in-oil crude oil emulsions. However, the polysuccinimide-phenylethylamine-3-dimethylaminopropylamine demulsifier, which has excellent demulsification ability at extremely low dosages, is very easy to agglomerate, and the above three demulsifiers are still powerless against demulsification under strong acids and alkalis.

[0004] The present invention tests the existing components according to the existing implementation scheme, and finds that the surfactant with a longer alkyl chain has higher lipophilicity and dispersibility, can effectively reduce the surface tension of the emulsion system, and form a stable micelle structure on the interface. Due to the characteristics of its long chain structure, the demulsifier with a long alkyl chain is more likely to penetrate into the colloidal particle layer in the emulsion, destroying the adsorption force and charge balance between the colloidal particles, and the surfactant with a positive charge can interact with the emulsifier or colloidal particles with a negative charge, destroying the stability of the colloidal particles, and promoting their aggregation and sedimentation. Based on this, the present invention provides a method for preparing a cationic aromatic side chain demulsifier, and prepares three quaternary ammonium salt cationic demulsifiers of triethylamine-polysuccinimide (TEA-PS I), N,N-dimethylbenzylamine-polysuccinimide (BZK-PS I) and quinoline-polysuccinimide (QA-PS I) with a long alkyl chain to solve the problems existing in the prior art. Summary of the invention

[0005] 1. Technical issues to be solved

[0006] In view of the shortcomings of the prior art, the present invention provides a method for preparing a cationic aromatic side chain demulsifier, which has the advantages of being able to prepare a demulsifier that can show better demulsification effect in a strong acid environment by changing the grafting raw materials, thereby solving the problem that the existing demulsifiers are unable to perform demulsification work in a strong acid or strong alkali environment.

[0007] (II) Technical solution

[0008] In order to achieve the above-mentioned purpose of preparing a demulsifier that can show a better demulsification effect in a strong acid environment by changing the grafting raw materials, the present invention provides the following technical solution: a method for preparing a cationic aromatic side chain demulsifier, comprising the following steps:

[0009] S1: Prepare the drugs and reagents used, including polysuccinimide, 1,4-dibromobutane, N,N-dimethylbenzylamine, quinoline, triethylamine, dimethyl sulfoxide, acetonitrile, disodium ethylenediaminetetraacetic acid dihydrate, anhydrous sodium sulfate, sodium hydroxide, hydrochloric acid, anhydrous ethanol, anhydrous calcium chloride, petroleum ether, n-heptane, sodium bicarbonate, chromatograph, deionized water, acetone, and ether;

[0010] S2: Prepare the necessary equipment, including a double-necked round-bottom flask equipped with a cooling system, a heating device, a cooling device, a thermometer, a test tube, a dropper, a beaker, and a weighing machine;

[0011] S3: Add 13 ml of 1,4-dibromobutane to a double-necked round-bottom flask equipped with a cooling system, and then slowly add 3 ml of N,N-dimethylbenzylamine to 50 mL of acetonitrile after purging the system with nitrogen. Then heat the mixture to 50°C, stir for 16 hours, and then reflux for 1 hour to evaporate the solvent, and then filter and wash with ether to obtain a white paste, which is finally freeze-dried to obtain 4-bromobutylbenzalkonium bromide (BZK-Br);

[0012] S4: According to the above principle, 4-bromobutyltriethylammonium bromide (TEA-Br) and 4-bromobutylquinolammonium bromide (QA-Br) are prepared;

[0013] S5: After obtaining enough ammonium salt, further chemical modification is performed, 1.0 g of polysuccinimide is fully dissolved in 5.0 ml of dimethyl sulfoxide, and then 1.33 g of N, N-dimethylbenzylamine is fully dissolved in 10.0 ml of dimethyl sulfoxide, and the dissolved N, N-dimethylbenzylamine solution is slowly dripped into the polysuccinimide solution at a temperature of 80°C and reacted for a period of time, and then precipitated with acetone and freeze-dried to obtain N, N-dimethylbenzylamine-polysuccinimide (BZK-PSI);

[0014] S6: Triethylamine-polysuccinimide (TEA-PSI) and quinoline-polysuccinimide (QA-PSI) were prepared according to the above principle.

[0015] Furthermore, in S4, 4-bromobutyltriethylammonium bromide (TEA-Br) and 4-bromobutylquinol ammonium bromide (QA-Br) need to be prepared. The preparation method is similar to the preparation method of 4-bromobutylbenzalkonium bromide (BZK-Br) in S3, but in the synthesis process, N, N-dimethylbenzylamine needs to be replaced by triethylamine or quinoline.

[0016] Furthermore, in S3, S4, S5 and S6, a dropper, a beaker and a weighing machine are required to be used for taking out a quantitative amount of reagent.

[0017] Furthermore, the heating device in S2 is an alcohol lamp, and the cooling device in S2 consists of a refrigerator and a metal water tank.

[0018] Furthermore, when the polysuccinimide in S5 is dissolved in dimethyl sulfoxide, it is necessary to stir continuously in a clockwise direction until no obvious particles are visible.

[0019] Furthermore, the specific operation of freeze drying in S3, S4, S5 and S6 is to use a refrigerator to cool the metal water tank, and then use the principle of water bath freezing to cool the test tube or beaker containing the reagent.

[0020] Furthermore, in S5, products with different grafting rates can be obtained by varying the reaction time or the amount of solvent.

[0021] Furthermore, in S6, 4-bromobutyltriethylammonium bromide (TEA-Br) is used to prepare triethylamine-polysuccinimide (TEA-PS I) according to the step of S5.

[0022] Furthermore, in S6, 4-bromobutylquinol ammonium bromide (QA-Br) is used to prepare quinoline-polysuccinimide (QA-PS I) according to the step of S5.

[0023] Furthermore, after the preparation of triethylamine-polysuccinimide (TEA-PS I) and quinoline-polysuccinimide (QA-PS I) in S6 is completed, N,N-dimethylbenzylamine-polysuccinimide (BZK-PS I) can be added to obtain three demulsifiers.

[0024] (III) Beneficial effects

[0025] Compared with the prior art, the present invention provides a method for preparing a cationic aromatic side chain demulsifier, which has the following beneficial effects:

[0026] 1. The preparation method of the cationic aromatic side chain demulsifier is to prepare three demulsifiers, namely triethylamine-polysuccinimide (TEA-PS I), quinoline-polysuccinimide (QA-PS I) and N,N-dimethylbenzylamine-polysuccinimide (BZK-PS I), which can show good demulsification effect at room temperature and in a strong acid environment, and can provide sufficient surfactant molecules to form an effective adsorption layer on the surface of the emulsion, thereby reducing the surface tension, destroying the emulsion structure, and promoting the aggregation and separation of droplets, so that the demulsifier has a good demulsification effect.

[0027] 2. The preparation method of the cationic aromatic side chain demulsifier can achieve a demulsification efficiency of up to 99.98% by preparing three demulsifiers, namely triethylamine-polysuccinimide (TEA-PS I), quinoline-polysuccinimide (QA-PS I) and N,N-dimethylbenzylamine-polysuccinimide (BZK-PS I), and can effectively separate oily wastewater and high-oil-content O / W emulsions at room temperature. Therefore, the above three demulsifiers and their preparation methods have great advantages and broad space in the application prospects of demulsifiers. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 A schematic diagram of the synthesis pathway and chemical structure of 4-bromobutyltriethylammonium bromide, 4-bromobutylbenzalkonium bromide and 4-bromobutylquinol ammonium bromide in a method for preparing a cationic aromatic side chain demulsifier proposed by the present invention;

[0029] Figure 2 The present invention provides a schematic diagram of the synthesis pathways and chemical structures of triethylamine-polysuccinimide (TEA-PSI), N,N-dimethylbenzylamine-polysuccinimide (BZK-PSI) and quinoline-polysuccinimide (QA-PSI) in the preparation method of a cationic aromatic side chain demulsifier proposed by the present invention. DETAILED DESCRIPTION

[0030] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] See also Figures 1 to 2 The present invention provides a technical solution: a method for preparing a cationic aromatic side chain demulsifier, comprising the following steps:

[0032] S1: Prepare the drugs and reagents used, including polysuccinimide, 1,4-dibromobutane, N,N-dimethylbenzylamine, quinoline, triethylamine, dimethyl sulfoxide, acetonitrile, disodium ethylenediaminetetraacetic acid dihydrate, anhydrous sodium sulfate, sodium hydroxide, hydrochloric acid, anhydrous ethanol, anhydrous calcium chloride, petroleum ether, n-heptane, sodium bicarbonate, chromatograph, deionized water, acetone, and ether.

[0033] S2: Prepare the necessary equipment, including a double-necked round-bottom flask equipped with a cooling system, a heating device, a cooling device, a thermometer, a test tube, a dropper, a beaker, and a weighing machine. The heating device is an alcohol lamp, and the cooling device consists of a refrigerator and a metal water tank to meet the needs of heating and water bath cooling in chemical experiments.

[0034] S3: Add 13 ml of 1,4-dibromobutane to a double-necked round-bottom flask equipped with a cooling system, and then slowly add 3 ml of N,N-dimethylbenzylamine to 50 mL of acetonitrile after purifying the system with nitrogen. Then heat the mixture to 50°C, stir for 16 hours, and then reflux for 1 hour to evaporate the solvent. Then filter and wash with ether to obtain a white paste, and finally freeze-dry to obtain 4-bromobutylbenzalkonium bromide (BZK-Br). Among them, a dropper, a beaker and a weighing machine are needed to take out a quantitative reagent so that the whole can maintain a certain accuracy. The specific operation of freeze-drying is to use a refrigerator to cool the metal water tank, and then use the principle of water bath freezing to cool the test tube or beaker containing the reagent. The preparation route is as follows: Figure 1 shown.

[0035] S4: According to the above principle, 4-bromobutyltriethylammonium bromide (TEA-Br) and 4-bromobutylquinol bromide (QA-Br) are prepared. Among them, 4-bromobutyltriethylammonium bromide (TEA-Br) and 4-bromobutylquinol bromide (QA-Br) need to be prepared. The preparation method is similar to the preparation method of 4-bromobutylbenzalkonium bromide (BZK-Br) in S3, but in the synthesis process, N, N-dimethylbenzylamine needs to be replaced by triethylamine or quinoline. The preparation route is as follows: Figure 1 shown.

[0036] S5: After obtaining enough ammonium salt, further chemical modification is carried out. 1.0g of polysuccinimide is fully dissolved in 5.0ml of dimethyl sulfoxide, and then 1.33g of N,N-dimethylbenzylamine is fully dissolved in 10.0ml of dimethyl sulfoxide. The dissolved N,N-dimethylbenzylamine solution is slowly dripped into the polysuccinimide solution at 80°C for a period of time, and then precipitated with acetone and freeze-dried to obtain N,N-dimethylbenzylamine-polysuccinimide (BZK-PSI). Products with different grafting rates can be obtained by different reaction time or solvent amount. Among them, when polysuccinimide is dissolved in dimethyl sulfoxide, it needs to be stirred continuously in a clockwise direction until no obvious particles are seen. The specific operation of freeze-drying is to use a refrigerator to cool the metal water tank, and then use the principle of water bath freezing to cool the test tube or beaker containing the reagent. The synthetic route and chemical structure are as follows: Figure 2 shown.

[0037] S6: Triethylamine-polysuccinimide (TEA-PS I) and quinoline-polysuccinimide (QA-PS I) are prepared according to the above principle. Specifically, 4-bromobutyltriethylammonium bromide (TEA-Br) is used to prepare triethylamine-polysuccinimide (TEA-PS I) according to the step of S5, and 4-bromobutylquinol ammonium bromide (QA-Br) is used to prepare quinoline-polysuccinimide (QA-PS I) according to the step of S5. After the preparation of triethylamine-polysuccinimide (TEA-PS I) and quinoline-polysuccinimide (QA-PSI) is completed, N,N-dimethylbenzylamine-polysuccinimide (BZK-PS I) can be added to obtain three demulsifiers. The synthesis route and chemical structure are as follows: Figure 2 shown.

[0038] The above three demulsifiers were tested in experiments and all three demulsifiers were able to break emulsions with oil concentrations of 1.0 to 30.0 wt%. The optimal dosage of TEA-PS I for treating emulsions with oil concentrations of 1.0 and 30.0 wt% was 40.0 mg / L, and the oil concentrations in the separated water were 62.61 mg / L and 41.95 mg / L, respectively, and the demulsification efficiencies reached 99.37% and 99.99%, respectively. The optimal dosage of BZK-PS I for treating emulsions with oil concentrations of 1.0 and 30.0 wt% was 50.0 mg / L and 20.0 mg / L, and the oil concentrations in the separated water were 33.97 mg / L and 54.84 mg / L, respectively, and the demulsification efficiencies reached 99.66% and 99.98%, respectively. The optimal dosage of I for treating emulsions with oil concentrations of 1.0 and 30.0wt% is 600.0mg / L and 500.0mg / L. The oil concentrations in the separated water are 49.07mg / L and 53.72mg / L, respectively, and the demulsification efficiencies reach 99.51% and 99.98%, respectively.

[0039] Compared with the prior art, the preparation method of the cationic aromatic side chain demulsifier can show good demulsification effect at room temperature and in a strong acid environment by preparing three demulsifiers of triethylamine-polysuccinimide (TEA-PS I), quinoline-polysuccinimide (QA-PS I) and N,N-dimethylbenzylamine-polysuccinimide (BZK-PS I), and can provide sufficient surfactant molecules to form an effective adsorption layer on the surface of the emulsion, thereby reducing the surface tension, destroying the emulsion structure, and promoting the aggregation and separation of droplets, so that it has a good demulsification effect. I) The three demulsifiers can achieve a demulsification efficiency of up to 99.98%, and can effectively separate oily wastewater and O / W emulsions with high oil content, and the results are achieved at room temperature, so that the above three demulsifiers and their preparation methods have great advantages and broad space in the application prospects of demulsifiers, and solve the problem that existing demulsifiers are unable to perform demulsification work in strong acid and strong alkali environments.

[0040] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0041] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a cationic aromatic side chain demulsifier, characterized in that: The following steps are involved: S1: Prepare the drugs and reagents used, including polysuccinimide, 1,4-dibromobutane, N,N-dimethylbenzylamine, quinoline, triethylamine, dimethyl sulfoxide, acetonitrile, disodium ethylenediaminetetraacetic acid dihydrate, anhydrous sodium sulfate, sodium hydroxide, hydrochloric acid, anhydrous ethanol, anhydrous calcium chloride, petroleum ether, n-heptane, sodium bicarbonate, chromatograph, deionized water, acetone, and ether; S2: Prepare the necessary equipment, including a double-necked round-bottom flask equipped with a cooling system, a heating device, a cooling device, a thermometer, a test tube, a dropper, a beaker, and a weighing machine; S3: Add 13 ml of 1,4-dibromobutane to a double-necked round-bottom flask equipped with a cooling system, and then slowly add 3 ml of N,N-dimethylbenzylamine to 50 mL of acetonitrile after purging the system with nitrogen. Then heat the mixture to 50°C, stir for 16 hours, and then reflux for 1 hour to evaporate the solvent, and then filter and wash with ether to obtain a white paste, which is finally freeze-dried to obtain 4-bromobutylbenzalkonium bromide (BZK-Br); S4: According to the above principle, 4-bromobutyltriethylammonium bromide (TEA-Br) and 4-bromobutylquinolammonium bromide (QA-Br) are prepared; S5: After obtaining enough ammonium salt, further chemical modification is performed, 1.0 g of polysuccinimide is fully dissolved in 5.0 ml of dimethyl sulfoxide, and then 1.33 g of N, N-dimethylbenzylamine is fully dissolved in 10.0 ml of dimethyl sulfoxide, and the dissolved N, N-dimethylbenzylamine solution is slowly dripped into the polysuccinimide solution at a temperature of 80°C and reacted for a period of time, and then precipitated with acetone and freeze-dried to obtain N, N-dimethylbenzylamine-polysuccinimide (BZK-PSI); S6: Triethylamine-polysuccinimide (TEA-PSI) and quinoline-polysuccinimide (QA-PSI) were prepared according to the above principle.

2. The method for preparing a cationic aromatic side chain demulsifier according to claim 1, characterized in that: In S4, 4-bromobutyltriethylammonium bromide (TEA-Br) and 4-bromobutylquinol ammonium bromide (QA-Br) need to be prepared. The preparation method is similar to the preparation method of 4-bromobutylbenzalkonium bromide (BZK-Br) in S3, but in the synthesis process, N,N-dimethylbenzylamine needs to be replaced by triethylamine or quinoline.

3. The method for preparing a cationic aromatic side chain demulsifier according to claim 1, characterized in that: In S3, S4, S5 and S6, a dropper, a beaker and a weighing device are required to take out a quantitative amount of reagent.

4. The method for preparing a cationic aromatic side chain demulsifier according to claim 1, characterized in that: The heating device in S2 is an alcohol lamp, and the cooling device in S2 is composed of a refrigerator and a metal water tank.

5. The method for preparing a cationic aromatic side chain demulsifier according to claim 1, characterized in that: When the polysuccinimide in S5 is dissolved in dimethyl sulfoxide, it needs to be stirred continuously in a clockwise direction until no obvious particles are visible.

6. The method for preparing a cationic aromatic side chain demulsifier according to claim 4, characterized in that: The specific operation of freeze drying in S3, S4, S5 and S6 is to use a refrigerator to cool the metal water tank, and then use the principle of water bath freezing to cool the test tube or beaker containing the reagent.

7. The method for preparing a cationic aromatic side chain demulsifier according to claim 1, characterized in that: In S5, products with different grafting rates can be obtained by varying the reaction time or the amount of solvent.

8. The method for preparing a cationic aromatic side chain demulsifier according to claim 1, characterized in that: In S6, 4-bromobutyltriethylammonium bromide (TEA-Br) is used to prepare triethylamine-polysuccinimide (TEA-PSI) according to the steps of S5.

9. The method for preparing a cationic aromatic side chain demulsifier according to claim 1, characterized in that: In S6, 4-bromobutylquinol ammonium bromide (QA-Br) is used to prepare quinoline-polysuccinimide (QA-PSI) according to the steps of S5.

10. The method for preparing a cationic aromatic side chain demulsifier according to claim 1, characterized in that: After the triethylamine-polysuccinimide (TEA-PSI) and quinoline-polysuccinimide (QA-PSI) are prepared in S6, N,N-dimethylbenzylamine-polysuccinimide (BZK-PSI) can be added to obtain three demulsifiers.

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