CN-122006497-A - Preparation method of composite membrane for tetracycline wastewater treatment

CN122006497ACN 122006497 ACN122006497 ACN 122006497ACN-122006497-A

Abstract

The invention relates to the technical field of antibiotic wastewater treatment, and particularly discloses a preparation method of a composite membrane for tetracycline wastewater treatment, which comprises the following steps of adding 1-vinyl imidazole and equimolar bromo-n-hexane into a three-necked flask, stirring for reaction, cooling to room temperature after the stirring reaction is finished, washing with ethyl acetate to obtain a first product, and drying the first product in a vacuum drying oven to obtain yellow viscous ionic liquid 1-hexyl-3-vinyl imidazole bromide; and preparing the imidazole polyion liquid by using the product I, and preparing the polyion liquid composite membrane by using the obtained polyion liquid through a phase inversion method. Compared with the prior art, the polyion liquid composite membrane prepared by the invention combines the characteristics of ionic liquid and polymer, and has good hydrophilicity, thermal stability, dirt resistance, mechanical property and separation property.

Inventors

Qin Xingxiu
YANG MINNA
WANG LAILIANG
TAO ZERONG
ZHANG QI
CHANG QING
CAO LEI

Assignees

江苏省地质调查研究院

Dates

Publication Date: 20260512
Application Date: 20260407

Claims (10)

1. The preparation method of the composite membrane for tetracycline wastewater treatment is characterized by comprising the following steps of: s1, adding 1-vinyl imidazole and equimolar bromo-n-hexane into a three-necked flask, stirring for reaction, cooling to room temperature after the stirring reaction is completed, washing with ethyl acetate to obtain a product I, and drying the product I in a vacuum drying oven to obtain yellow viscous ionic liquid 1-hexyl-3-vinyl imidazole bromide; S2, dissolving the ionic liquid 1-hexyl-3-vinylimidazole bromide in methanol, adding ethylene glycol dimethacrylate and azodiisobutyronitrile, heating and refluxing for reaction, cooling to room temperature after the reaction is finished, washing with methanol to obtain a product II, and drying the product II in a vacuum drying oven to obtain the poly 1-hexyl-3-vinylimidazole bromide; S3, uniformly dispersing poly 1-hexyl-3-vinylimidazole bromide in N, N-dimethylformamide, adding polyvinylidene fluoride to obtain a mixture, continuously stirring the mixture until a uniform mixed solution is formed, standing at room temperature to remove bubbles, casting a certain volume of the mixed solution on a glass plate, fixing the shape of the film by a circular die, immersing the glass plate in deionized water to cause phase inversion, and finally stripping the film from the glass plate to obtain the polyion liquid composite film.
2. The method for preparing the composite membrane for tetracycline wastewater treatment according to claim 1, wherein the molar ratio of 1-vinylimidazole to bromohexane in S1 is 0.10mol, and 1:1.
3. The method for preparing the composite membrane for tetracycline wastewater treatment as defined in claim 1, wherein the temperature of the stirring reaction in S1 is 70 ℃, and the reaction time is 2 hours.
4. The method for preparing the composite membrane for tetracycline wastewater treatment as defined in claim 1, wherein the number of times of washing the product one in S1 is three, the drying temperature of the vacuum drying oven in S1 is 65 ℃, and the drying time is 12 hours.
5. The method for preparing the composite membrane for tetracycline wastewater treatment according to claim 1, wherein the mass of ionic liquid 1-hexyl-3-vinylimidazole bromide in S2 is 2.61g, the volume of methanol is 30mL, the mass of ethylene glycol dimethacrylate is 1.42g, and the mass of azobisisobutyronitrile is 0.05g.
6. The method for preparing the composite membrane for tetracycline wastewater treatment according to claim 1, wherein the heating reflux temperature in S2 is 80 ℃ and the time is 2 hours, the times of washing the product in S2 are three times, the drying temperature of a vacuum drying oven in S2 is 70 ℃, and the drying time is 12 hours.
7. The preparation method of the composite membrane for tetracycline wastewater treatment according to claim 1, wherein the molar ratio of ionic liquid 1-hexyl-3-vinylimidazole bromide solution to ethylene glycol dimethacrylate to azobisisobutyronitrile in S2 is 33:24:1.
8. The method for preparing a composite membrane for tetracycline wastewater treatment as defined in claim 1, wherein the mass of poly 1-hexyl-3-vinylimidazole bromide in S3 is 0.30g, the mass of N, N-dimethylformamide is 15g, and the mass of polyvinylidene fluoride is 1g.
9. The method for preparing a composite membrane for 2-tetracycline wastewater treatment as defined in claim 1, wherein the stirring time of the mixture in the step S3 is 4 hours, the standing time at room temperature is 12 hours, and the diameter of the circular mold is 6cm.
10. The method for preparing the composite membrane for tetracycline wastewater treatment according to claim 1, wherein the molar ratio of poly 1-hexyl-3-vinylimidazole bromide to N, N-dimethylformamide to polyvinylidene fluoride in S3 is 0.3:15:1.

Description

Preparation method of composite membrane for tetracycline wastewater treatment Technical Field The invention belongs to the technical field of antibiotic wastewater treatment, and particularly relates to a preparation method of a composite membrane for tetracycline wastewater treatment. Background Antibiotics are a medicine for treating various bacterial infections or diseases caused by pathogenic microorganisms. However, along with the increase of the demand of antibiotics and the prominent abuse problem, the antibiotics are accumulated and enriched in various environments and organisms to induce microbial communities to generate evolution and spread of drug-resistant genes, so that potential threats are caused to human health and ecological environment, and Tetracycline (TC) is a common broad-spectrum antibiotic which has a strong inhibition effect on gram bacteria, chlamydia, mycoplasma and the like, is low in cost, is widely applied to the fields of livestock and poultry, aquaculture and the like, and is discharged from pharmaceutical factory wastewater, aquaculture manure, domestic sewage and the like, so that tetracycline is detected in groundwater, surface water and other water environments, thereby causing potential ecological risks. The tetracycline has the characteristics of concentrated pollution sources, large consumption, good water solubility, stable structure, difficult treatment in water and the like, so that the tetracycline has the durability in groundwater, surface water, rivers and wastewater, and the water pollution problem is particularly prominent; The main stream treatment method of the antibiotic polluted wastewater comprises an adsorption method, a chemical oxidation method, a photocatalytic degradation method, an electrochemical degradation method and the like, wherein the adsorption method is regarded as a preferred scheme of sewage treatment due to simple operation and low cost, various high-capacity adsorbents such as metal oxides, metal organic frameworks and the like which are developed at present are difficult to be practically applied due to poor separation performance and mechanical performance, and the membrane material is used as the adsorbent, shows excellent separation and mechanical performance and can make up the defects of the traditional particle adsorbent. Disclosure of Invention The invention aims to provide a preparation method of a composite membrane for tetracycline wastewater treatment, which aims to solve the problems in the background technology. In order to achieve the above purpose, the present invention provides the following technical solutions: The preparation method of the composite membrane for tetracycline wastewater treatment comprises the following steps: s1, adding 1-vinyl imidazole and equimolar bromo-n-hexane into a three-necked flask, stirring for reaction, cooling to room temperature after the stirring reaction is completed, washing with ethyl acetate to obtain a product I, and drying the product I in a vacuum drying oven to obtain yellow viscous ionic liquid 1-hexyl-3-vinyl imidazole bromide; S2, dissolving the ionic liquid 1-hexyl-3-vinylimidazole bromide in methanol, adding ethylene glycol dimethacrylate (EDGMA) and Azodiisobutyronitrile (AIBN), heating and refluxing for reaction, cooling to room temperature after the reaction is finished, washing the reaction product to obtain a product II, and drying the product II in a vacuum drying oven to obtain poly (1-hexyl-3-vinylimidazole bromide) (P [ HVIM ] [ Br ]); S3, uniformly dispersing poly (1-hexyl-3-vinylimidazole bromide) (P [ HVIM ] [ Br ]) in N, N-Dimethylformamide (DMF), adding polyvinylidene fluoride (PVDF) to obtain a mixture, continuously stirring the mixture until a uniform mixed solution is formed, standing at room temperature to remove bubbles, casting a certain volume of the mixed solution on a glass plate, fixing the shape of the film by a circular mold, immersing the glass plate in deionized water to cause phase inversion, and finally stripping the film from the glass plate to obtain the polyion liquid composite film, thereby obtaining the composite film for tetracycline wastewater treatment. Preferably, the 1-vinyl imidazole in the S1 is 0.10mol, and the molar ratio of the 1-vinyl imidazole to the bromon-hexane is 1:1. Preferably, the temperature of the stirring reaction in the step S1 is 70 ℃, and the reaction time is 2 hours. Preferably, the number of times of washing the product one in the step S1 is three, the drying temperature of the vacuum drying oven in the step S1 is 65 ℃, and the drying time is 12 hours. Preferably, in the S2, the mass of the ionic liquid 1-hexyl-3-vinylimidazole bromide is 2.61g, the volume of methanol is 30mL, the mass of ethylene glycol dimethacrylate (EDGMA) is 1.42g, and the mass of Azobisisobutyronitrile (AIBN) is 0.05g. Preferably, the heating reflux temperature in the step S2 is 80 ℃, the time is 2h, the times of washing the second product