Hesperidin-regulated polyamide nanofiltration membrane, preparation method and application thereof

Abstract

The application discloses a preparation method of a hesperidin-regulated polyamide nanofiltration membrane. The preparation method comprises the following steps: S1, contacting the surface of a base membrane with an aqueous solution, standing, and removing the aqueous solution; S2, contacting the surface of the base membrane after removing the aqueous solution in step S1 with an organic phase solution, and performing interfacial polymerization to obtain a hesperidin-regulated polyamide nanofiltration membrane; the aqueous solution contains hesperidin, an amine monomer and water; the mass-volume ratio of hesperidin and water is 5-10:1 g / L, and the mass-volume ratio of the amine monomer and water is 4-6:1 g / L; the organic phase solution contains an acid chloride monomer and an organic solvent; the mass-volume ratio of the acid chloride monomer and the organic solvent is 1.3-2:1 g / L. The polyamide nanofiltration membrane has excellent water flux and antibiotic retention rate, and also has excellent inorganic salt / antibiotic selectivity, and can be applied to sewage treatment equipment, seawater desalination equipment, industrial wastewater treatment and reuse equipment and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of wastewater and sewage treatment, and more particularly relates to a hesperidin-regulated polyamide nanofiltration membrane, a preparation method therefor and an application thereof. BACKGROUND

[0002] Rational utilization and protection of water resources is an important and arduous task. Wastewater and sewage treatment and resource utilization are key measures to solve the crisis of freshwater resources in China. As a typical pressure-driven membrane separation technology, nanofiltration (NF) has attracted much attention in the field of antibiotic desalination in recent years due to its ability to effectively separate divalent and multivalent ions and organic molecules with a molecular weight of 200-1000 daltons (Da). Currently, the nanofiltration membranes on the market are mainly of thin layer composite (TFC) structure, that is, water-phase amine monomers and organic-phase acyl chloride monomers are generated into polyamide nanofiltration membranes on the surface of ultrafiltration or microfiltration base membranes through an interfacial polymerization process.

[0003] Currently, the preparation of antibiotics is mainly carried out by fermentation process for mass production, which includes the following main steps: seed fermentation, fermentation broth pretreatment, plate and frame filtration, exchange resin adsorption, exchange resin elution, desalination, crystallization, drying and the like. In order to ensure the stability of the fermentation broth system during the fermentation process, a certain amount of inorganic salt is usually added to the fermentation broth, and therefore, it is necessary to separate the wastewater containing antibiotics and salt after the fermentation is completed.

[0004] Membrane separation is a newly emerging antibiotic desalination technology in recent years, which has the characteristics of efficient and continuous process, simple equipment and no use of organic solvents in the process. However, due to the strong reactivity of traditional monomers, the interfacial polymerization (IP) process is fast and difficult to control, resulting in a very dense and thick polyamide nanofiltration membrane. This not only leads to a high rejection rate of the polyamide nanofiltration membrane to antibiotics and inorganic salts (i.e. low salt / antibiotic separation efficiency), but also results in a low water flux, which seriously limits the application of polyamide nanofiltration membranes in the field of antibiotic desalination. How to regulate the interfacial polymerization process while improving the antibiotic desalination efficiency and water permeability is the key to popularize the application of polyamide nanofiltration membranes. SUMMARY

[0005] In view of the above existing problems in the prior art, the primary object of the present application is to provide a preparation method of a hesperidin-regulated polyamide nanofiltration membrane, which regulates the reaction of amine monomers and acyl chloride monomers in the interfacial polymerization process by adding an additive hesperidin to the water-phase solution, so that the prepared polyamide nanofiltration membrane not only maintains excellent water flux and antibiotic rejection rate, but also has excellent inorganic salt / antibiotic selectivity.

[0006] The second object of the present application is to provide a hesperidin-regulated polyamide nanofiltration membrane prepared by the preparation method.

[0007] The third object of the present application is to provide an application of the hortesin-regulated polyamide nanofiltration membrane in wastewater and sewage treatment.

[0008] The fourth object of the present application is to provide an application of the hortesin-regulated polyamide nanofiltration membrane in selective separation of inorganic salts / antibiotics or recovery of antibiotics.

[0009] In order to achieve the above object, the present application is implemented by the following technical solutions:

[0010] The present application claims a preparation method of a hortesin-regulated polyamide nanofiltration membrane, comprising the following steps:

[0011] S1. The surface of the base film is contacted with an aqueous solution, and the aqueous solution is removed after standing;

[0012] S2. The surface of the base film after removing the aqueous solution in step S1 is contacted with an organic phase solution, and interfacial polymerization is carried out to obtain a polyamide nanofiltration membrane;

[0013] The aqueous solution is an aqueous solution containing hortesin, amine monomer and water; in the aqueous solution, the mass-volume ratio of hortesin and water is 5-10:1 g / L, and the mass-volume ratio of amine monomer and water is 4-6:1 g / L;

[0014] The organic phase solution is a mixed solution containing acyl chloride monomer and organic solvent; in the organic phase solution, the mass-volume ratio of the acyl chloride monomer and the organic solvent is 1.3-2:1 g / L;

[0015] The structure of the hortesin is shown in the following formula (I):

[0016]

[0017] (I).

[0018] The inventors found that, in the preparation process of the polyamide nanofiltration membrane, the addition of the aurantiamarin with a twisted structure in the reaction system can make part of the aurantiamarin molecules enter the organic phase solution with the amine monomers in the water phase, and the aurantiamarin can occupy the distribution space of the amine monomers and the acyl chloride monomers in the IP process and does not participate in the IP reaction, thus creating free cavities (forming free volumes) in the polyamide layer. These free cavities can increase the water permeation flux of the polyamide nanofiltration membrane and reduce the inorganic salt retention (while the antibiotic retention remains unchanged), thereby improving the selective separation of inorganic salts / antibiotics. In addition, the aurantiamarin can be adsorbed on the surface of the base membrane through π-π interaction and hydrophobic-hydrophobic interaction, and the aurantiamarin molecules have abundant alcohol and phenolic hydroxyl groups, which are conducive to the enrichment of more amine monomers on the surface of the base membrane through hydrogen bonding or electrostatic interaction. The aurantiamarin molecules in the aqueous solution can also reduce the interfacial tension of the aqueous solution, which can promote the reaction of the amine monomers and the acyl chloride monomers at the water-organic interface, increase the interfacial instability of the IP reaction, and be conducive to the formation of a patterned polyamide layer, thereby further significantly improving the water permeation flux of the polyamide nanofiltration membrane.

[0019] Further, the inventors found that the concentrations of the aurantiamarin and the amine monomers in the aqueous phase solution and the concentration of the acyl chloride monomers in the organic phase solution have a great influence on the formation of the polyamide nanofiltration membrane during the polymerization process. Under specific concentrations of the aurantiamarin and the amine monomers and specific concentrations of the acyl chloride monomers, the prepared polyamide nanofiltration membrane has excellent water flux and antibiotic retention rate, and also has excellent inorganic salt / antibiotic selectivity.

[0020] Compared with the conventional polyamide nanofiltration membrane, the polyamide nanofiltration membrane prepared by the present application has higher free volume and higher effective filtration area, which can effectively enhance the inorganic salt / antibiotic selectivity of the polyamide nanofiltration membrane and greatly reduce the operating pressure and energy consumption of the conventional nanofiltration membrane. The present application uses the environmentally friendly and low-cost aurantiamarin with a twisted structure, which does not need to add a catalyst during the reaction process, and solves the problems of toxicity overflow and high cost of the additives used in the conventional interfacial polymerization process.

[0021] Preferably, the amine monomer is selected from one or more of piperazine, m-phenylenediamine, ethylenediamine, polyvinylamine, diethylenetriamine, and polyethyleneimine; and / or

[0022] The acyl chloride monomer is selected from one or more of 1,3,5-benzene tricarbonyl chloride, p-phenylenediformyl chloride, and m-phenylenediformyl chloride; and / or

[0023] The base membrane is poly sulfone, poly ether sulfone, polyvinylidene fluoride, polyacrylonitrile, polyethylene, polyvinyl chloride, or polytetrafluoroethylene.

[0024] Preferably, the mass / volume ratio of hesperidin and water in the aqueous solution is 6.5-8.5:1 g / L. Further preferably, the mass / volume ratio of hesperidin and water in the aqueous solution is 7-8:1 g / L. More preferably, the mass / volume ratio of hesperidin and water in the aqueous solution is 7.5:1 g / L. Under the premise of the preferred amount of hesperidin added, the polyamide nanofiltration membrane prepared has more excellent water flux, antibiotic retention rate and inorganic salt / antibiotic selectivity.

[0025] Preferably, the mass / volume ratio of the amine monomer and water in the aqueous solution is 4.5-5.5:1 g / L. Further preferably, the mass / volume ratio of the amine monomer and water is 5:1 g / L. Under the premise of the preferred amount of amine monomer added, the polyamide nanofiltration membrane prepared has more excellent water flux, antibiotic retention rate and inorganic salt / antibiotic selectivity.

[0026] Preferably, the mass / volume ratio of the acid chloride monomer and the organic solvent in the organic solution is 1.4-1.7:1 g / L. Further preferably, the mass / volume ratio of the acid chloride monomer and the organic solvent is 1.5-1.6:1 g / L. More preferably, the mass / volume ratio of the acid chloride monomer and the organic solvent is 1.5:1 g / L. Under the premise of the preferred amount of amine monomer added, the polyamide nanofiltration membrane prepared has more excellent water flux, antibiotic retention rate and inorganic salt / antibiotic selectivity.

[0027] Preferably, the organic solvent is selected from one or more of hexane, heptane, octane, decane, cyclohexane.

[0028] Preferably, in the step S1, the standing time is 0.5-15 min; and / or in the step S2, the interfacial polymerization time is 0.05-5 min.

[0029] Further, the present application claims to protect the hesperidin-regulated polyamide nanofiltration membrane prepared by the above preparation method.

[0030] Preferably, the molecular weight cut-off of the hesperidin-regulated polyamide nanofiltration membrane is 330-350 Da. More specifically, the molecular weight cut-off of the hesperidin-regulated polyamide nanofiltration membrane is 340 Da.

[0031] Further, the present application claims to protect the above hesperidin-regulated polyamide nanofiltration membrane for use in wastewater and sewage treatment.

[0032] Further, the present application claims to protect the above hesperidin-regulated polyamide nanofiltration membrane for use in inorganic salt / antibiotic selective separation or antibiotic recovery.

[0033] Preferably, the antibiotic is selected from at least one of a tetracycline antibiotic, a fluoroquinolone antibiotic, a macrolide antibiotic, a fluoroquinolone antibiotic. More particularly, the tetracycline antibiotic includes but is not limited to tetracycline. The fluoroquinolone antibiotic includes but is not limited to enrofloxacin. The macrolide antibiotic includes but is not limited to erythromycin. The fluoroquinolone antibiotic includes but is not limited to norfloxacin. The polyamide nanofiltration membrane provided by the present application has not only more excellent antibiotic rejection rate but also more excellent inorganic salt / antibiotic selectivity for the above-mentioned antibiotics relative to other antibiotics.

[0034] Preferably, the molecular weight of the antibiotic is ≥ 300 Da. More preferably, the molecular weight of the antibiotic is ≥ 340 Da. More preferably, the molecular weight of the antibiotic is ≥ 400 Da. Further preferably, the molecular weight of the antibiotic is 400-2000 Da. The polyamide nanofiltration membrane provided by the present application has more excellent rejection effect for the antibiotic with the above-mentioned preferred molecular weight.

[0035] Preferably, the inorganic salt includes but is not limited to NaCl.

[0036] Compared with the prior art, the present application has the following beneficial effects:

[0037] The present application provides a preparation method of hesperidin-regulated polyamide nanofiltration membrane. By adding hesperidin as an additive in an aqueous solution, the reaction of amine monomers and acyl chloride monomers in the interfacial polymerization process is regulated, so that the polyamide nanofiltration membrane prepared has excellent water flux and antibiotic rejection rate, and also has excellent inorganic salt / antibiotic selectivity. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 The scanning electron microscope graph of the surface of the polyamide nanofiltration membrane synthesized in Example 2 and Comparative Example 1 is shown in FIG. 1, wherein, Figure 1 a in FIG. 1 is the scanning electron microscope graph of the surface of the polyamide nanofiltration membrane synthesized in Comparative Example 1; Figure 1 b in FIG. 1 is the scanning electron microscope graph of the surface of the polyamide nanofiltration membrane synthesized in Example 1.

[0039] Figure 2 The schematic diagram of the free volume (FFV) of the polyamide nanofiltration membrane in Example 2 and Comparative Example 1 by molecular dynamics simulation is shown in FIG. 2, wherein, Figure 2 a in FIG. 2 is the schematic diagram of the FFV of the polyamide nanofiltration membrane in Comparative Example 1 by molecular dynamics simulation; Figure 2 b in FIG. 2 is the schematic diagram of the FFV of the polyamide nanofiltration membrane in Example 2 by molecular dynamics simulation.

[0040] Figure 3The polyamide nanofiltration membrane synthesized in Example 1-3 was used to test the rejection rate of neutral organic molecules with different molecular weights. DETAILED DESCRIPTION

[0041] The present application is further illustrated by the following description and examples, which do not limit the present application in any manner. Unless otherwise specified, the reagents, methods and apparatus used in the present application are conventional in the art.

[0042] Example 1 Preparation of polyamide nanofiltration membrane

[0043] (1) 5.0 g of piperazine and 7.5 g of hesperidin (Yuzhou Bio, CAS: 520-26-3, the structure of which is shown in formula (I) below) were added to 1 L of deionized water solution, and stirred at a stirring speed of 100 rpm for 10 min to obtain a piperazine-hesperidin mixed aqueous solution;

[0044]

[0045] (I) Molecular structure of hesperidin;

[0046] (2) The piperazine-hesperidin mixed aqueous solution was poured onto the surface of a polysulfone-based membrane (US020, Zhongke Liyang), and left to stand for 3 min. After the solution was poured off, the excess droplets on the surface of the base membrane were removed by an air knife to obtain a base membrane adsorbed with piperazine-hesperidin;

[0047] (3) 1.5 g of 1,3,5-benzene tricarbonyl chloride was added to 1 L of n-hexane solution, and after complete dissolution, an organic phase solution was obtained. The organic phase solution was poured onto the surface of the base membrane treated in step (2), and left to stand for 1 min for interfacial polymerization. After the solution on the surface of the base membrane was poured off, the unreacted 1,3,5-benzene tricarbonyl chloride on the surface of the base membrane was removed by n-hexane solution, and placed in a 60°C oven for heat treatment for 10 min to obtain a polyamide nanofiltration membrane.

[0048] Example 2 Preparation of polyamide nanofiltration membrane

[0049] The difference between this example and Example 1 is that in step (1), the amount of hesperidin added is 5.0 g.

[0050] Example 3 Preparation of polyamide nanofiltration membrane

[0051] The difference between this example and Example 1 is that in step (1), the amount of hesperidin added is 10.0 g.

[0052] Example 4 Preparation of polyamide nanofiltration membrane

[0053] The difference between this example and Example 1 is that in step (2), the mass-volume ratio of 1,3,5-benzene tricarbonyl chloride to n-hexane solution is 2.0:1 g / L.

[0054] Comparative Example 1

[0055] The difference between this comparative example and Example 1 is that in step (1), no hesperidin is added.

[0056] Comparative Example 2

[0057] The difference between this comparative example and Example 1 is that in step (1), aloe glycoside is used instead of hesperidin.

[0058] Comparative Example 3

[0059] This comparative example uses commercial polyamide nanofiltration membrane Dow-Filmtec NF270.

[0060] Comparative Example 4

[0061] This comparative example uses commercial polyamide nanofiltration membrane Dow-Filmtec NF90.

[0062] Comparative Example 5

[0063] The difference between this comparative example and Example 1 is that in step (1), 2.5 g of piperazine is added in 1 L of deionized water solution.

[0064] Comparative Example 6

[0065] The difference between this comparative example and Example 1 is that in step (1), 7.5 g of piperazine is added in 1 L of deionized water solution.

[0066] Comparative Example 7

[0067] The difference between this comparative example and Example 1 is that in step (1), 2.5 g of piperazine is added in 1 L of deionized water solution, and no hesperidin is added.

[0068] Comparative Example 8

[0069] The difference between this comparative example and Example 1 is that in step (1), 7.5 g of piperazine is added in 1 L of deionized water solution, and no hesperidin is added.

[0070] Comparative Example 9

[0071] The difference between this comparative example and Example 1 is that in step (2), the mass-volume ratio of 1,3,5-benzene tricarbonyl chloride to n-hexane solution is 1.0:1 g / L.

[0072] Test Example 1 Characterization of Polyamide Nanofiltration Membrane

[0073] The surface morphology of the polyamide nanofiltration membranes synthesized in Example 2 and Comparative Example 1 was observed by field emission scanning electron microscopy (FESEM, model Quanta 400). The polyamide nanofiltration membranes were dried in advance in a vacuum drying oven; before observation, conductive glue was pasted on the sample copper platform, and the square-shaped polyamide nanofiltration membranes were fixed on the conductive glue; the sample surface was treated with gold spraying, and observation was performed under an acceleration voltage of 5 kV.

[0074] Figure 1 The scanning electron microscope images of the surface of the polyamide nanofiltration membranes prepared in Example 1 and Comparative Example 1. It can be seen from Figure 1 that the polyamide selective layer of Comparative Example 1 is a typical nodular morphology, which is generated by the reaction of piperazine and 1,3,5-benzene tricarbonyl chloride on the surface of the porous base membrane. Example 1 is a polyamide nanofiltration membrane prepared by adding hesperidin, and the polyamide selective layer is a folded morphology. Figure 1 It can be seen that after adding hesperidin in the aqueous solution, the polyamide selective layer on the membrane surface changes from a nodular morphology to a folded morphology, which means that the polyamide controlled by hesperidin has a larger specific surface area, which will significantly increase the water permeation flux of the membrane.

[0075] The free volume of the polyamide nanofiltration membranes in Example 2 and Comparative Example 1 was explored by molecular dynamics simulation. In the simulation box of Example 2 (the simulation box was established by software Packmol), 120 piperazine molecules, 90 1,3,5-benzene tricarbonyl chloride molecules and 20 hesperidin molecules were placed, and in Comparative Example 1, only 120 piperazine molecules and 90 1,3,5-benzene tricarbonyl chloride molecules were placed, the crosslinking monomers were only set as piperazine and 1,3,5-benzene tricarbonyl chloride, and the crosslinking degree was set as 65.5%. After the simulation was completed, the hesperidin molecules in the simulation box of Example 2 were removed, and the simulation box of Comparative Example 1 was not changed, and then the free volumes of the two systems were analyzed.

[0076] Figure 2 The crosslinking simulation products of Example 2 and Comparative Example 1 after simulation and their respective free volumes are shown. It can be seen from Figure 2 that after the addition of hesperidin, the FFV of the corresponding polyamide selective layer has a significant increase, which helps to improve the permeation flux of the membrane. The free volume of the polyamide selective layer in Comparative Example 1 without adding hesperidin is 18.56%, and the free volume of the polyamide selective layer in Example 2 after adding hesperidin is 43.21%.

[0077] Test Example 2 Water permeation flux, antibiotic and salt retention rate experiment of polyamide nanofiltration membrane

[0078] The pure water permeation flux, NaCl retention rate and tetracycline retention rate of the polyamide nanofiltration membranes prepared in the comparative example and the example were tested, and the specific method was as follows:

[0079] (1) Pure water flux determination:

[0080] The filtration experiment was carried out by using a cross-flow filtration device (CF016D; Sterlitech, USA), and the experimental parameters were as follows: the effective area of the polyamide nanofiltration membrane was 16 x 10 -4 m 2 , the temperature of the filtration experiment was 25 ± 2 ℃, and the test pressure was 5 bar.

[0081] At the beginning of the test, after the pure water was pre-pressed at a pressure of 5 bar for 60 min to reach a stable flux, the volume of the pure water passing through the nanofiltration membrane was continuously determined within a certain time, and the permeation flux J W (Lm -2 h -1 bar -1 ) of the composite nanofiltration membrane to be tested was calculated, and the calculation formula was as follows:

[0082] (1)

[0083] In the formula, V is the permeation volume, m 3 ; A is the effective area of the membrane, m 2 ; t is the sample filtration time, s; and ΔP is the pressure at which the device operates, bar.

[0084] (2) Inorganic salt and antibiotic rejection rate and selectivity determination:

[0085] The filtration experiment was carried out by using a cross-flow filtration device, and the rejection rate R of the polyamide nanofiltration membrane prepared in the examples and the comparative examples to tetracycline or NaCl was obtained, and the selective permeability of the polyamide nanofiltration membrane to NaCl / tetracycline was characterized.

[0086] 1000 mg L -1 of NaCl solution and 10 mg L -1 of tetracycline were respectively prepared as raw material liquid, and when different raw material liquids were used for testing, the raw material liquid was pre-pressed at 5 bar for 30 min to reach a stable flux, and the concentrated liquid and the permeate were collected, and the concentrations of the two were tested, and the salt rejection rate R (%) was calculated by formula (2). The selectivity coefficient a of NaCl / tetracycline was calculated by formula (3):

[0087] (2)

[0088] (3)

[0089] Among them, C p and C F represent the solute concentrations of the permeate and the concentrated liquid, respectively, mg L -1 .

[0090] (3) Determination of molecular weight cutoff

[0091] A cross-flow filtration device was used to conduct filtration experiments to obtain the retention rate R (%) of the polyamide nanofiltration membrane for four neutral molecules: glycerol (92 Da), glucose (180 Da), sucrose (342 Da) and raffinose (504 Da), and this was used to characterize the molecular weight cutoff of the polyamide nanofiltration membrane.

[0092] Prepare 200 mg L of each -1 The above four neutral molecules are used as raw materials. When different raw materials are used for testing, the raw materials are pre-pressurized at 5 bar for 30 min to achieve a stable flux. The concentrate and permeate are collected and their concentrations are tested by TOC (TOC-L, Shimadzu). The salt rejection rate R (%) is calculated by formula (2).

[0093] The pure water permeate flux, tetracycline rejection rate, and NaCl / tetracycline selectivity of the polyamide nanofiltration membranes prepared in the comparative examples and embodiments were compared with the performance of existing commercial membranes. The specific comparison results are shown in Table 1.

[0094] Table 1

[0095]

[0096] As shown in Table 1, the polyamide nanofiltration membrane prepared by hesperidin-regulated interfacial polymerization in this invention exhibits excellent water permeability, high antibiotic rejection rate, and antibiotic / NaCl selectivity. More specifically, the water flux of the polyamide nanofiltration membrane is ≥22.9 Lm. -2 h -1 bar -1 The tetracycline rejection rate is ≥98.7%, and the NaCl / tetracycline selectivity is ≥49.2. More preferably, the water flux of the polyamide nanofiltration membrane is ≥36.5 Lm. -2 h -1 bar -1 The tetracycline rejection rate is ≥98.7%, and the NaCl / tetracycline selectivity is ≥50.4; most preferably, the water flux of the polyamide nanofiltration membrane is ≥36.9 Lm. -2 h -1 bar -1 Tetracycline rejection rate ≥99.2%, NaCl / tetracycline selectivity ≥95.6.

[0097] As can be seen from Examples 1, 2 and 3, when the amount of hesperidin added to the aqueous solution is within a specific range, the prepared polyamide nanofiltration membrane has a better antibiotic rejection rate and antibiotic / NaCl selectivity.

[0098] As can be seen from Example 1, Example 4, Comparative Examples 5-6 and Comparative Example 9, when the addition amount of piperazine in the aqueous phase solution or the addition amount of 1,3,5-benzene tricarbonyl chloride in the organic phase solution is within a certain range, the polyamide nanofiltration membrane prepared has more excellent water flux, antibiotic rejection rate and antibiotic / NaCl selectivity.

[0099] As can be seen from Example 1, Comparative Example 1 and Comparative Examples 7-8, when no hesperidin is added in the system, the water flux and NaCl / antibiotic selectivity sharply decrease, which indicates that hesperidin can form a patterned polyamide selective layer and a larger free volume, and is more conducive to improving the water permeation flux and NaCl / antibiotic selectivity of the polyamide nanofiltration membrane.

[0100] As can be seen from Example 1 and Comparative Examples 2-4, the effect of the polyamide nanofiltration membrane provided by the present application is far superior to the performance of the existing commercial membranes NF270 and NF90; in addition, the water flux and NaCl / tetracycline selectivity are both low when the existing aloin is used as an additive.

[0101] As shown in Figure 3 , the polyamide nanofiltration membrane provided by the present application has excellent rejection effect on molecules with a molecular weight of ≥340 Da.

[0102] Test Example 3 Test experiment of polyamide nanofiltration membrane on different antibiotics

[0103] (1) According to the test method of Test Example 2, the polyamide nanofiltration membrane prepared in Example 1 was tested on sulfamethoxazole, and the specific results are shown in Table 2 below.

[0104] Table 2

[0105]

[0106] As shown in Table 2 above, the polyamide nanofiltration membrane provided by the present application has a lower rejection rate on sulfamethoxazole and a lower NaCl / sulfamethoxazole selectivity.

[0107] The foregoing examples are merely illustrative, serving to explain some features of the method described in the present application. The appended claims are intended to claim as broad a scope as can be conceived, and the examples presented herein are demonstrated by the true experimental results of the applicant. Therefore, the intention of the applicant is that the appended claims are not limited by the selection of examples illustrating the features of the present application. Some numerical ranges used in the claims also include sub-ranges within them, and the variations in these ranges should also be interpreted as covered by the appended claims, if possible.

Claims

1. A method for preparing a hesperidin-modulated polyamide nanofiltration membrane, characterized in that, The method comprises the following steps: S1. contacting the surface of the base film with an aqueous solution, standing, and removing the aqueous solution; S2. contacting the surface of the base film after removing the aqueous solution in step S1 with an organic phase solution, and performing interfacial polymerization to obtain a polyamide nanofiltration membrane; The aqueous solution comprises hesperidin, an amine monomer, and water; in the aqueous solution, the mass-volume ratio of hesperidin to water is 5-10:1 g / L, and the mass-volume ratio of the amine monomer to water is 4-6:1 g / L; The organic phase solution is a mixed solution comprising an acid chloride monomer and an organic solvent; in the organic phase solution, the mass-volume ratio of the acid chloride monomer to the organic solvent is 1.3-2:1 g / L; The structure of the hesperidin is shown in the following formula (I): （I）。 2. The method of claim 1, wherein, The amine monomer is selected from one or more of piperazine, m-phenylenediamine, ethylenediamine, polyvinylamine, diethylenetriamine, and polyethyleneimine; and / or The acid chloride monomer is selected from one or more of 1,3,5-benzene tricarbonyl chloride, terephthaloyl chloride, and isophthaloyl chloride; and / or The base film is poly sulfone, poly ether sulfone, polyvinylidene fluoride, polyacrylonitrile, polyethylene, polyvinyl chloride, or polytetrafluoroethylene.

3. The preparation method according to claim 1, characterized in that, In the aqueous solution, the mass-volume ratio of hesperidin to water is 6.5-8.5:1 g / L.

4. The preparation method according to claim 3, characterized in that, In the aqueous solution, the mass-volume ratio of the amine monomer to water is 4.5-5.5:1 g / L.

5. The preparation method according to claim 3 or 4, characterized in that, In the organic phase solution, the mass-volume ratio of the acid chloride monomer to the organic solvent is 1.4-1.7:1 g / L.

6. The method of claim 1, wherein the step of forming the first and second layers is performed by a process selected from the group consisting of: sputtering, evaporation, and chemical vapor deposition. The organic solvent is selected from one or more of hexane, heptane, octane, decane, and cyclohexane.

7. The method of claim 1, wherein the step of forming the first and second layers is performed by a process selected from the group consisting of: sputtering, evaporation, and chemical vapor deposition. In step S1, the standing time is 0.5-15 min; and / or In step S2, the interfacial polymerization time is 0.05-5 min.

8. The hesperidin-regulated polyamide nanofiltration membrane obtained by the preparation method of any one of claims 1-7.

9. The hesperidin-regulated polyamide nanofiltration membrane of claim 8 for use in wastewater and sewage treatment.

10. The hesperidin-regulated polyamide nanofiltration membrane of claim 8 for use in selective separation of inorganic salts / antibiotics or recovery of antibiotics.

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