High-flux nanofiltration membrane based on multi-element oil phase monomer and application of high-flux nanofiltration membrane to removal of fluoroquinolone antibiotic micropollutants

Abstract

The invention discloses a high-flux nanofiltration membrane based on a multi-element oil-phase monomer and application of the high-flux nanofiltration membrane to removal of fluoroquinolone antibiotic micropollutants, and belongs to the technical field of membrane separation.The method comprises the steps that polyphenol with a rigid distortion structure serves as a water-phase monomer, and a water-phase solution is prepared from the water-phase monomer and an acid-binding agent; the method comprises the following steps: preparing a mixed oil-phase solution by using a multi-component oil-phase monomer which comprises an aroyl chloride monomer and a fatty acyl chloride monomer in a mass ratio of (0.5-2): 1; the preparation method comprises the following steps: infiltrating a polymer porous support membrane by using an aqueous phase solution, removing redundant aqueous phase solution on the surface, placing a mixed oil phase solution on the surface of the membrane treated by the aqueous phase solution, and carrying out interfacial polymerization reaction and crosslinking on an oil phase monomer and an aqueous phase monomer to prepare the high-flux nanofiltration membrane based on the multi-element oil phase monomer, the nanofiltration membrane can give consideration to high permeation flux and high rejection rate of fluoroquinolone antibiotic micropollutants such as ciprofloxacin and the like.

Description

Technical Field

[0001] This invention belongs to the field of membrane separation technology, specifically relating to a high-flux nanofiltration membrane based on multi-component oil phase monomers and its application in removing micro-pollutants from fluoroquinolone antibiotics. Background Technology

[0002] Fluoroquinolone antibiotics (including ciprofloxacin and enrofloxacin) possess broad-spectrum antibacterial activity, but they also exhibit environmental persistence, bioaccumulation, and ecotoxicity. They can remain in the aquatic environment for extended periods and induce the spread of antibiotic resistance genes, posing potential risks to ecosystems and public health. Developing efficient and specific removal technologies is crucial for blocking their environmental migration, controlling antibiotic pollution, and ensuring water safety. Nanofiltration technology, through the synergistic effect of pore size sieving and electrostatic repulsion, achieves highly efficient retention of organic pollutants in water. Compared to traditional water treatment processes, it offers advantages such as high separation precision, low operating energy consumption, and wide applicability, demonstrating significant technological competitiveness and application prospects in the field of deep removal of antibiotic pollutants.

[0003] Currently, mainstream commercial nanofiltration membranes are polyamide composite membranes prepared through interfacial polymerization. In interfacial polymerization, the diffusion of the traditional aqueous monomer, small-molecule piperazine, into the oil phase is a rapid and disordered process. This leads to uneven distribution at the water-oil interface, resulting in localized reaction differences and a wider pore size distribution in the formed polyamide separation layer. Ultimately, this results in poor removal efficiency for small-molecule organic matter, failing to meet the requirements for efficient removal of fluoroquinolone antibiotics such as ciprofloxacin in aquatic environments. Optimizing the structure and composition of the reactants and controlling the microstructure of the nanofiltration membrane aims to improve its pollutant removal capacity.

[0004] Existing technologies for removing fluoroquinolone antibiotics such as ciprofloxacin, including adsorption, oxidation, and biodegradation, have been widely reported, but still have certain limitations in practical applications. Chinese patent document CN118439688A discloses a method for removing ciprofloxacin, utilizing biochar from the pyrolysis of cypress wood chips to remove ciprofloxacin from water. Since cypress wood chips are lignocellulosic biomass, they have a large specific surface area after pyrolysis, which is beneficial for the adsorption of ciprofloxacin. Chinese patent document CN106629977A discloses the application of EDTA-β-CD material in removing ciprofloxacin from aqueous solutions. EDTA-β-CD is a cross-linked polymer obtained by cross-linking EDTA and β-CD. The hydrophobic cavity of β-CD can combine with ciprofloxacin to form inclusion compounds, thereby adsorbing and removing ciprofloxacin. Furthermore, EDTA-β-CD has a strong electrostatic attraction to ciprofloxacin. However, all of the above methods suffer from problems such as difficulty in recovering the adsorbent and high energy consumption for further separation. Although the introduction of magnetic materials can improve separation efficiency, problems such as limited adsorption capacity and insufficient material stability still exist.

[0005] Therefore, there is an urgent need to improve existing nanofiltration processes and develop nanofiltration membranes that can balance high permeation flux and high rejection rate in order to achieve efficient removal of micropollutants from fluoroquinolone antibiotics such as ciprofloxacin. Summary of the Invention

[0006] This invention provides a method for preparing a high-flux nanofiltration membrane based on a multi-component oil-phase monomer. The method is simple and efficient, and the prepared nanofiltration membrane can balance high permeation flux with high rejection rate of micro-pollutants such as ciprofloxacin fluoroquinolone antibiotics.

[0007] The specific technical solution adopted is as follows: A method for preparing a high-flux nanofiltration membrane based on a multi-component oil-phase monomer includes the following steps: (1) Using a polyphenol with a rigid twisted structure as an aqueous monomer, an aqueous solution is prepared using the aqueous monomer and an acid-binding agent; a mixed oil phase solution is prepared using a multi-component oil phase monomer, which includes aromatic acyl chloride monomer and fatty acyl chloride monomer, with a mass ratio of aromatic acyl chloride monomer to fatty acyl chloride monomer of 0.5-2:1; (2) After the polymer porous support membrane is wetted with an aqueous solution, the excess aqueous solution on the surface is removed, and then the mixed oil solution is placed on the membrane surface after the aqueous solution treatment, so that the oil monomer and the aqueous monomer undergo interfacial polymerization reaction and crosslinking to prepare the high-throughput nanofiltration membrane based on the multi-component oil monomer. The polyphenol with a rigid twisted structure is selected from at least one of bisphenol fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 3,3,3',3'-tetramethyl-1,1'-spirobinobi(indane)-6,6'-diol, and 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobinobiindane; The aromatic acyl chloride monomer is selected from pyromellitic acyl chloride; the fatty acyl chloride monomer is selected from at least one of oxaloyl chloride, succinic chloride, and adipoyl chloride.

[0008] This invention selects a polyphenol monomer with a rigid twisted structure as the aqueous phase monomer, which reduces the diffusion rate of the monomer and the interfacial polymerization reaction rate, and effectively increases the free volume of the membrane separation layer. At the same time, by mixing rigid aromatic acyl chlorides and sterically hindrance-free fatty acyl chlorides to form a multi-component mixed oil phase monomer, the polymer network structure of the separation layer formed by interfacial polymerization is synergistically regulated, which can improve the nanofiltration membrane's pollutant rejection rate while maintaining its high permeation flux.

[0009] Further preferred, the polyphenol with a rigid twisted structure is 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane, the aromatic acyl chloride monomer is pyromellitic acid chloride, and the fatty acyl chloride monomer is succinic acid chloride.

[0010] Specifically, the acid-binding agent is at least one of potassium hydroxide, sodium hydroxide, pyridine, triethylamine, N,N-diisopropylethylamine, sodium carbonate, and trisodium phosphate dodecahydrate; in the aqueous solution, the mass concentration of the acid-binding agent is 0.1-5 wt%.

[0011] Preferably, the mass concentration of aqueous monomers in the aqueous solution is 1-10 wt%; and the total mass concentration of oil monomers in the mixed oil solution is 0.1-5 wt%.

[0012] Preferably, the solvent in the mixed oil phase solution is at least one of n-hexane, Isopar G, and toluene.

[0013] Optionally, the polymer porous support membrane includes, but is not limited to, any one of polysulfone ultrafiltration membrane, polyethersulfone ultrafiltration membrane, polyacrylonitrile ultrafiltration membrane, cellulose acetate ultrafiltration membrane, polyethylene ultrafiltration membrane, and polyamide ultrafiltration membrane.

[0014] Preferably, the aqueous solution is immersed in the surface of the polymer porous support membrane for 1-10 minutes.

[0015] Furthermore, the interfacial polymerization reaction was carried out at room temperature for 1-10 minutes.

[0016] Furthermore, after the interfacial polymerization reaction is completed, the membrane surface is rinsed 1-5 times with an oil-phase solvent. The resulting nascent membrane is then heated for crosslinking at a temperature of 50-100℃ for 1-10 min.

[0017] This invention also provides a high-flux nanofiltration membrane based on a multi-component oil-phase monomer, prepared by the aforementioned method. This nanofiltration membrane balances high permeation flux with high rejection rates for micropollutants such as ciprofloxacin from fluoroquinolone antibiotics. When used to treat wastewater containing micropollutants from fluoroquinolone antibiotics, it exhibits high treatment efficiency and high pollutant removal rate, overcoming the problem of difficult recovery of traditional adsorbents.

[0018] The present invention also provides a method for removing micropollutants of fluoroquinolone antibiotics from an aquatic environment, utilizing the aforementioned high-flux nanofiltration membrane based on multi-component oil-phase monomers.

[0019] The fluoroquinolone antibiotic micropollutants include ciprofloxacin. Specifically, after adjusting the pH of the wastewater containing fluoroquinolone antibiotic micropollutants to ≥7.5, the wastewater is filtered using the high-flux nanofiltration membrane based on a multi-component oil-phase monomer to achieve the retention and removal of fluoroquinolone antibiotic micropollutants. Adjusting the influent pH to ≥7.5 enhances the electrostatic repulsion between the high-flux nanofiltration membrane based on a multi-component oil-phase monomer and fluoroquinolone antibiotic micropollutants such as ciprofloxacin, further improving the retention rate.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) By designing the structure and composition of the reaction monomers, the present invention uses polyphenols with rigid twisted structures as aqueous phase monomers and uses rigid aromatic acyl chlorides and flexible fatty acyl chlorides as mixed oil phase monomers to synergistically optimize the polymer network structure and reduce the membrane pore size, thus achieving both high permeation flux and high rejection rate of micro-pollutants such as ciprofloxacin fluoroquinolone antibiotics.

[0021] (2) The nanofiltration membrane preparation method of the present invention does not require the introduction of complex additives or cumbersome post-processing steps. Its process is simple, the reaction conditions are mild, the equipment requirements are low, and it has excellent process controllability and repeatability, making it very suitable for large-scale continuous production.

[0022] (3) The nanofiltration membrane prepared by the present invention can balance high permeation flux with high rejection rate of micropollutants such as fluoroquinolone antibiotics such as ciprofloxacin. The high flux characteristic means that the water production is greater under the same operating pressure, which directly translates into higher water treatment efficiency and lower unit water production energy consumption. The water flux of the nanofiltration membrane prepared by the present invention is ≥12.0 L·m -2 ·h -1 ·bar -1The rejection rate for ciprofloxacin is ≥95.0%. Attached Figure Description

[0023] Figure 1 This is a schematic diagram illustrating the design principle of a high-throughput nanofiltration membrane based on multi-component oil phase monomers.

[0024] Figure 2 The image shows a surface electron microscope (SEM) image of the high-throughput nanofiltration membrane based on a multi-component oil-phase monomer prepared in Example 4. Detailed Implementation

[0025] To make the objectives, features, and advantages of this invention more apparent and understandable, a detailed description is provided below through specific embodiments. Many specific details are set forth in the following description to provide a thorough understanding of the invention. However, the invention can be practiced in many other ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below. Technical features in various embodiments of the invention can be combined appropriately without mutual conflict.

[0026] Unless otherwise specified, the operating methods in the following examples are generally performed under conventional conditions or as recommended by the manufacturer. Contents not described in detail in this specification are prior art known to those skilled in the art. Unless otherwise specified, the experimental materials used in the examples below can be purchased from conventional biochemical reagent companies.

[0027] Example 1 An aqueous solution was prepared using bisphenol fluorene and sodium hydroxide, with a bisphenol fluorene concentration of 2.0 wt% and a sodium hydroxide concentration of 0.5 wt%. A mixed oil phase solution containing 0.1 wt% trimesoyl chloride and 0.2 wt% oxaloyl chloride was prepared using n-hexane as a solvent. The aqueous solution was poured onto the surface of a fixed polysulfone ultrafiltration membrane and allowed to soak for 5 min at room temperature. The aqueous solution was then discarded, and residual solution on the polysulfone ultrafiltration membrane surface was removed using a rubber roller. The mixed oil phase solution was then poured onto the membrane surface treated with the aqueous solution for interfacial polymerization, reacting at room temperature for 2 min. Afterward, the mixed oil phase solution was discarded, and the membrane surface was rinsed twice with the oil phase solvent n-hexane to obtain a nascent membrane. Finally, the nascent membrane was placed in an oven at 80°C for crosslinking treatment and kept at that temperature for 10 min before being removed, thus obtaining the high-flux nanofiltration membrane based on a multi-component oil phase monomer.

[0028] The design principle diagram of the high-flux nanofiltration membrane based on multi-component oil phase monomers is shown below. Figure 1 As shown in the figure, the pure water flux of this nanofiltration membrane is 18.2 L·m⁻¹. -2 ·h -1 ·bar-1 (Test temperature was 25℃, test pressure was 0.5 MPa). After adjusting the pH of the aqueous solution containing ciprofloxacin (concentration of 10 ppm) to 7.5, the nanofiltration membrane had a ciprofloxacin rejection rate of 95.3%.

[0029] Example 2 An aqueous solution was prepared using 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and potassium hydroxide, with a mass concentration of 2.5 wt% for 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and 0.6 wt% for potassium hydroxide. A mixed oil phase solution containing 0.1 wt% trimesoyl chloride and 0.1 wt% succinyl chloride was prepared using n-hexane as a solvent. The aqueous solution was poured onto the surface of a fixed polyethersulfone ultrafiltration membrane and allowed to soak at room temperature for 4 min. The aqueous solution was then discarded, and the residual solution on the surface of the polyethersulfone ultrafiltration membrane was removed using a rubber roller. Then, the mixed oil phase solution was poured onto the membrane surface after the aqueous phase solution was treated to carry out the interfacial polymerization reaction. The reaction was carried out at room temperature for 4 min. After that, the mixed oil phase solution was poured off, and the membrane surface was rinsed 3 times with the oil phase solvent n-hexane to obtain the nascent membrane. Finally, the nascent membrane was placed in an oven at 80°C for crosslinking treatment. After keeping it at that temperature for 7 min, it was taken out to obtain the high-flux nanofiltration membrane based on multi-component oil phase monomers.

[0030] Tests showed that the pure water flux of this nanofiltration membrane was 16.3 L·m. -2 ·h -1 ·bar -1 (Test temperature was 25℃, test pressure was 0.5 MPa). After adjusting the pH of the aqueous solution containing ciprofloxacin (concentration of 10 ppm) to 7.5, the nanofiltration membrane had a ciprofloxacin rejection rate of 96.1%.

[0031] Example 3 An aqueous solution was prepared using 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and potassium hydroxide, with a mass concentration of 3.0 wt% for 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and 0.4 wt% for potassium hydroxide. A mixed oil phase solution containing 0.1 wt% trimesoyl chloride and 0.1 wt% succinyl chloride was prepared using Isopar G as solvent. The aqueous solution was poured onto the surface of a fixed polysulfone ultrafiltration membrane and allowed to soak at room temperature for 5 min. The aqueous solution was then discarded, and the residual solution on the surface of the polysulfone ultrafiltration membrane was removed using a rubber roller. Then, the mixed oil phase solution was poured onto the membrane surface after the aqueous phase solution was treated to carry out the interfacial polymerization reaction. The reaction was carried out at room temperature for 5 min. After that, the mixed oil phase solution was poured off, and the membrane surface was rinsed 3 times with the oil phase solvent IsoparG to obtain the nascent membrane. Finally, the nascent membrane was placed in an oven at 85°C for crosslinking treatment. After keeping it at that temperature for 5 min, it was taken out to obtain the high-flux nanofiltration membrane based on multi-component oil phase monomers.

[0032] Tests show that the pure water flux of this nanofiltration membrane is 14.4 L·m⁻¹. -2 ·h -1 ·bar -1 (Test temperature was 25℃, test pressure was 0.5 MPa). After adjusting the pH of the aqueous solution containing ciprofloxacin (concentration of 10 ppm) to 7.5, the nanofiltration membrane had a ciprofloxacin rejection rate of 98.1%.

[0033] Example 4 An aqueous solution was prepared using 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane and sodium hydroxide. The mass concentration of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane in the aqueous solution was 2.0 wt%, and the mass concentration of sodium hydroxide was 0.5 wt%. A mixed oil phase solution containing 0.1 wt% trimesoyl chloride and 0.2 wt% succinyl chloride was prepared using n-hexane as a solvent. The aqueous solution was poured onto the surface of a fixed polyacrylonitrile ultrafiltration membrane and allowed to soak for 5 min at room temperature. The aqueous solution was then discarded, and the residual solution on the surface of the polyacrylonitrile ultrafiltration membrane was removed using a rubber roller. The mixed oil phase solution was then poured onto the membrane surface treated with the aqueous phase solution for interfacial polymerization. The reaction was carried out at room temperature for 5 min. Afterward, the mixed oil phase solution was discarded, and the membrane surface was rinsed three times with the oil phase solvent n-hexane to obtain the nascent membrane. Finally, the nascent membrane was placed in an oven at 85°C for crosslinking treatment and kept at that temperature for 10 min before being removed, thus obtaining the high-flux nanofiltration membrane based on multi-component oil phase monomers. Its surface SEM image is shown below. Figure 2 As shown.

[0034] Tests show that the pure water flux of this nanofiltration membrane is 12.8 L·m.-2 ·h -1 ·bar -1 (Test temperature was 25℃, test pressure was 0.5 MPa). After adjusting the pH of the aqueous solution containing ciprofloxacin (concentration of 10 ppm) to 7.5, the nanofiltration membrane had a ciprofloxacin rejection rate of 99.5%.

[0035] Example 5 An aqueous solution was prepared using 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane and sodium hydroxide. The mass concentration of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane in the aqueous solution was 2.5 wt%, and the mass concentration of sodium hydroxide was 0.7 wt%. A mixed oil phase solution containing 0.1 wt% trimesoyl chloride and 0.2 wt% adipicoyl chloride was prepared using Isopar G as solvent. The aqueous solution was poured onto the surface of a fixed polyacrylonitrile ultrafiltration membrane and allowed to soak at room temperature for 3 min. After soaking, the aqueous solution was discarded, and the residual solution on the surface of the polyacrylonitrile ultrafiltration membrane was removed using a rubber roller. Then, the mixed oil phase solution was poured onto the membrane surface after the aqueous phase solution was treated to carry out the interfacial polymerization reaction. The reaction was carried out at room temperature for 5 min. After that, the mixed oil phase solution was poured off, and the membrane surface was rinsed twice with the oil phase solvent Isopar G to obtain the nascent membrane. Finally, the nascent membrane was placed in an oven at 90°C for crosslinking treatment. After keeping it at that temperature for 5 min, it was taken out to obtain the high-flux nanofiltration membrane based on multi-component oil phase monomers.

[0036] Tests show that the pure water flux of this nanofiltration membrane is 13.5 L·m. -2 ·h -1 ·bar -1 (Test temperature was 25℃, test pressure was 0.5 MPa). After adjusting the pH of the aqueous solution containing ciprofloxacin (concentration of 10 ppm) to 7.5, the nanofiltration membrane had a ciprofloxacin rejection rate of 98.4%.

[0037] Example 6 An aqueous solution was prepared using 3,3,3',3'-tetramethyl-1,1'-spiroBI(indane)-6,6'-diol and potassium hydroxide. The mass concentration of 3,3,3',3'-tetramethyl-1,1'-spiroBI(indane)-6,6'-diol in the aqueous solution was 2.0 wt%, and the mass concentration of potassium hydroxide was 0.4 wt%. A mixed oil phase solution containing 0.2 wt% trimesoyl chloride and 0.1 wt% oxaloyl chloride was prepared using Isopar G as solvent. The aqueous solution was poured onto the surface of a fixed polyethersulfone ultrafiltration membrane and allowed to soak for 5 min at room temperature. The aqueous solution was then discarded, and the residual solution on the surface of the polyethersulfone ultrafiltration membrane was removed using a rubber roller. Then, the mixed oil phase solution was poured onto the membrane surface after the aqueous phase solution was treated to carry out the interfacial polymerization reaction. The reaction was carried out at room temperature for 3 min. After that, the mixed oil phase solution was poured off, and the membrane surface was rinsed 3 times with the oil phase solvent Isopar G to obtain the nascent membrane. Finally, the nascent membrane was placed in an oven at 85°C for crosslinking treatment. After keeping it at the temperature for 5 min, it was taken out to obtain the high-flux nanofiltration membrane based on multi-component oil phase monomers.

[0038] Tests show that the pure water flux of this nanofiltration membrane is 15.1 L·m⁻¹. -2 ·h -1 ·bar -1 (Test temperature was 25℃, test pressure was 0.5 MPa). After adjusting the pH of the aqueous solution containing ciprofloxacin (concentration of 10 ppm) to 7.5, the nanofiltration membrane had a ciprofloxacin rejection rate of 97.2%.

[0039] Comparative Example 1 The only difference between this comparative example and Example 4 is that the oil phase solution is a hexane oil phase solution of pyromellitic trimethylol chloride with a mass concentration of 0.3 wt%. All other processes and parameters are the same as in Example 4, and a nanofiltration membrane is prepared.

[0040] Tests show that the pure water flux of this nanofiltration membrane is 9.6 L·m. -2 ·h -1 ·bar -1 (Test temperature was 25℃, test pressure was 0.5 MPa). After adjusting the pH of the aqueous solution containing ciprofloxacin (concentration of 10 ppm) to 7.5, the nanofiltration membrane had a ciprofloxacin rejection rate of 84.5%.

[0041] Compared with Example 4, this comparative example only added rigid aromatic acyl chloride to the oil phase solution, resulting in poor retention performance of the prepared nanofiltration membrane for the small molecule antibiotic ciprofloxacin.

[0042] Comparative Example 2 The only difference between this comparative example and Example 5 is that the oil phase solution is an Isopar G oil phase solution with a mass concentration of 0.3 wt% adipicoyl chloride. All other processes and parameters are the same as in Example 5, and a nanofiltration membrane is prepared.

[0043] Tests show that the pure water flux of this nanofiltration membrane is 5.5 L·m. -2 ·h -1 ·bar -1 (Test temperature was 25℃, test pressure was 0.5 MPa). After adjusting the pH of the aqueous solution containing ciprofloxacin (concentration of 10 ppm) to 7.5, the nanofiltration membrane had a ciprofloxacin rejection rate of 85.7%.

[0044] Compared with Example 5, this comparative example only added flexible fatty acyl chloride to the oil phase solution, resulting in fewer effective water transport channels in the membrane separation layer. This led to a significant decrease in the flux of the prepared nanofiltration membrane and poor retention performance for the small molecule antibiotic ciprofloxacin.

[0045] The embodiments described above provide a detailed explanation of the technical solutions of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, additions, or similar substitutions made within the scope of the principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a high-flux nanofiltration membrane based on a multi-component oil-phase monomer, characterized in that, Includes the following steps: (1) Using a polyphenol with a rigid twisted structure as an aqueous monomer, an aqueous solution is prepared by using the aqueous monomer and an acid-binding agent; A mixed oil phase solution was prepared using a multi-component oil phase monomer, which included aromatic acyl chloride monomer and fatty acyl chloride monomer, with a mass ratio of aromatic acyl chloride monomer to fatty acyl chloride monomer of 0.5-2:

1. (2) After the polymer porous support membrane is wetted with an aqueous solution, the excess aqueous solution on the surface is removed, and then the mixed oil solution is placed on the membrane surface after the aqueous solution treatment, so that the oil monomer and the aqueous monomer undergo interfacial polymerization reaction and crosslinking to prepare the high-throughput nanofiltration membrane based on the multi-component oil monomer. The polyphenol with a rigid twisted structure is selected from at least one of bisphenol fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 3,3,3',3'-tetramethyl-1,1'-spirobinobi(indane)-6,6'-diol, and 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobinobiindane; The aromatic acyl chloride monomer is selected from pyromellitic acyl chloride; the fatty acyl chloride monomer is selected from at least one of oxaloyl chloride, succinic chloride, and adipoyl chloride.

2. The method for preparing a high-flux nanofiltration membrane based on a multi-component oil-phase monomer according to claim 1, characterized in that, The acid-binding agent is at least one of potassium hydroxide, sodium hydroxide, pyridine, triethylamine, N,N-diisopropylethylamine, sodium carbonate, and trisodium phosphate dodecahydrate; in the aqueous solution, the mass concentration of the acid-binding agent is 0.1-5 wt%.

3. The method for preparing a high-flux nanofiltration membrane based on a multi-component oil-phase monomer according to claim 1, characterized in that, The mass concentration of aqueous monomers in the aqueous solution is 1-10 wt%; the total mass concentration of oil monomers in the mixed oil solution is 0.1-5 wt%.

4. The method for preparing a high-flux nanofiltration membrane based on a multi-component oil-phase monomer according to claim 1, characterized in that, The polymer porous support membrane is any one of polysulfone ultrafiltration membrane, polyethersulfone ultrafiltration membrane, polyacrylonitrile ultrafiltration membrane, cellulose acetate ultrafiltration membrane, polyethylene ultrafiltration membrane, and polyamide ultrafiltration membrane.

5. The method for preparing a high-flux nanofiltration membrane based on a multi-component oil-phase monomer according to claim 1, characterized in that, The aqueous solution was immersed in the surface of the polymer porous support membrane for 1-10 min; the interfacial polymerization reaction was carried out at room temperature for 1-10 min.

6. The method for preparing a high-flux nanofiltration membrane based on a multi-component oil-phase monomer according to claim 1, characterized in that, After the interfacial polymerization reaction is completed, the membrane surface is rinsed 1-5 times with an oil phase solvent. The resulting nascent membrane is then heated for crosslinking at a temperature of 50-100℃ for 1-10 min.

7. A high-flux nanofiltration membrane based on a multi-component oil phase monomer prepared by the preparation method according to any one of claims 1-6.

8. A method for removing micro-pollutants from fluoroquinolone antibiotics in an aquatic environment, characterized in that, The high-throughput nanofiltration membrane based on multi-component oil phase monomers as described in claim 7 is utilized.

9. The method for removing fluoroquinolone antibiotic micropollutants from an aquatic environment according to claim 8, characterized in that, The fluoroquinolone antibiotic micropollutants include ciprofloxacin. After adjusting the pH of the wastewater containing fluoroquinolone antibiotic micropollutants to ≥7.5, the wastewater is filtered using the high-flux nanofiltration membrane based on multi-component oil-phase monomers to achieve the interception and removal of fluoroquinolone antibiotic micropollutants.

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