A zeolite molecular sieve-polyamide pervaporation composite membrane, a preparation method therefor and applications thereof

Abstract

The present application relates to the technical field of separation membrane, and provides a zeolite molecular sieve-polyamide pervaporation composite membrane, a preparation method and application thereof.The preparation method of the zeolite molecular sieve-polyamide pervaporation composite membrane provided by the present application comprises the following steps: firstly, immersing a porous base film into an amine monomer aqueous solution, taking out and drying, then immersing into an acyl chloride monomer organic phase solution, taking out and heating, to obtain the zeolite molecular sieve-polyamide pervaporation composite membrane; the amine monomer aqueous solution comprises polyvinyl alcohol (PVA) and a zeolite molecular sieve.The preparation method of the zeolite molecular sieve-polyamide pervaporation composite membrane provided by the present application is simple, easy to control, short in preparation period and low in cost, and the prepared zeolite molecular sieve-polyamide pervaporation composite membrane has excellent compactness and permeation selectivity, and has good separation performance in the pervaporation process of isopropyl alcohol and water.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of separation membranes, and more particularly to a zeolite molecular sieve-polyamide pervaporation composite membrane, a preparation method therefor and an application thereof. BACKGROUND

[0002] Compared with traditional separation technologies such as distillation, extraction and absorption, membrane separation technology has the advantages of low energy consumption, high efficiency, green environmental protection and the like. At present, membrane separation technologies such as microfiltration, ultrafiltration, gas separation, reverse osmosis and pervaporation have been widely applied in the fields of chemical industry, energy, medicine and the like.

[0003] Pervaporation membrane separation technology is a process for separating a mixture by relying on the difference in the transmembrane mass transfer rate of each component, with the difference in the vapor pressure of each component as the driving force. Pervaporation membrane dehydration technology is a high-efficiency solvent separation and refining technology, and is particularly suitable for the production fields of azeotropic systems, high-boiling solvent systems and ppm-level water content solvents. Compared with traditional azeotropic distillation, the energy consumption of the pervaporation membrane separation process is only 30% of that of the azeotropic distillation, and the operating cost is less than 50% of that of the azeotropic distillation, and the pervaporation membrane separation process has replaced the traditional azeotropic distillation to a certain extent. Compared with molecular sieve adsorption technology and salt-extraction solvent dehydration technology, the pervaporation membrane separation process does not need to add an external component, does not produce waste and pollutants, and has higher product cleanliness.

[0004] Membrane materials are the key to the development of pervaporation membrane separation technology. Organic pervaporation membranes have the advantage of low cost, but the separation performance is limited by the dissolution-diffusion mechanism, and there is a trade-off effect between permeation flux and selectivity. Inorganic pervaporation membranes are prepared from porous materials such as zeolite molecular sieves, and have a regular pore structure and high porosity, and based on the molecular sieve effect, exhibit high permeability and selectivity, but have the disadvantages of complex preparation process and high price. In order to solve the respective limitations of organic membranes and inorganic membranes, combining polymer materials with porous materials to prepare hybrid matrix membranes is an effective strategy to improve the performance of membranes (Journal of Materials Chemistry A, 2019, 7, 20293-20301).

[0005] The methods for preparing organic pervaporation membranes mainly include surface coating method, phase inversion method, and interfacial polymerization method. The interfacial polymerization method is a commonly used method for preparing commercial composite membranes, and has the advantages of simple operation, high film-forming property, and easy industrial scale-up. At present, the separation membranes prepared by the interfacial polymerization method are mainly applied to ultrafiltration membrane and nanofiltration membrane processes, and there are still limitations in the separation of liquid mixtures with small size differences. The main reason is that the polyamide separation layer prepared by the interfacial polymerization method is not dense enough, and there are membrane defects that affect the separation effect of the membrane. In addition, the intrinsic chemical structure of the separation layer has limited hydrophilicity, and the adsorption selectivity of water / organic molecules is poor. It has been reported that polyamide pervaporation composite membranes are prepared by the interfacial polymerization method (Desalination, 2019, 469, 114090; CN 115518525A; Journal of Membrane Science, 2013, 448, 34-43; Journal of Membrane Science, 2012, 405-406, 123-133), but the separation performance of the pure polyamide membrane is limited by the solubility-diffusion model, and there is a trade-off effect in the separation performance. The membrane with high flux often has low selectivity, and vice versa. In addition, by depositing a porous material on the substrate membrane through vacuum filtration, and then preparing a polyamide composite membrane by the interfacial polymerization method, the performance of the membrane can be improved. However, it is difficult to precisely control the thickness of the deposited layer and the dispersity and uniformity of the porous material in the polyamide layer. SUMMARY

[0006] The purpose of the present application is to provide a zeolite molecular sieve@polyamide pervaporation composite membrane and a preparation method thereof, which improves the dispersity and uniformity of the porous material in the polyamide layer and solves the technical problems of poor compactness and limited separation performance of the polyamide pervaporation membrane in the prior art.

[0007] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is:

[0008] In a first aspect, the present application provides a preparation method of a zeolite molecular sieve@polyamide pervaporation composite membrane, comprising: first immersing a porous substrate membrane in an amine monomer aqueous solution, taking it out and drying, then immersing it in an acyl chloride monomer organic phase solution, and heating after taking it out to prepare the zeolite molecular sieve@polyamide pervaporation composite membrane; the amine monomer aqueous solution comprises polyvinyl alcohol (PVA) and a zeolite molecular sieve.

[0009] The application provides a preparation method of a zeolite molecular sieve-polyamide pervaporation composite membrane. The method is characterized in that a porous base film is used as a substrate, and a separation layer with high permeation selectivity is prepared through one-step interfacial polymerization. PVA is added to an amine monomer aqueous solution to adjust the diffusion rate of the amine monomer, and the viscosity of the amine monomer aqueous solution is adjusted, so that the dispersibility and uniformity of the zeolite molecular sieve in the amine monomer aqueous solution are improved, the zeolite molecular sieve can be uniformly dispersed in the polyamide membrane, the defect density of the polyamide membrane is effectively reduced, and the problem of poor membrane compactness is solved. In addition, the zeolite molecular sieve has regular channels, which can improve the selective separation performance of the membrane on target substances (such as water / isopropyl alcohol), and the separation effect of the membrane is better.

[0010] In the application, the PVA can be selected from commonly used brands and types, for example, at least one of PVA 17-88, PVA 17-92 and PVA 17-99.

[0011] According to some embodiments of the application, the concentration of the polyvinyl alcohol in the amine monomer aqueous solution is 0.05-0.15% w / v, for example, 0.05% w / v, 0.06% w / v, 0.08% w / v, 0.1% w / v, 0.11% w / v, 0.12% w / v, 0.13% w / v or 0.15% w / v.

[0012] According to some embodiments of the application, the concentration of the polyvinyl alcohol in the amine monomer aqueous solution is 0.10-0.15% w / v.

[0013] According to some embodiments of the application, the concentration of the zeolite molecular sieve in the amine monomer aqueous solution is 0.01-1.0% w / v, for example, 0.01% w / v, 0.03% w / v, 0.05% w / v, 0.08% w / v, 0.1% w / v, 0.15% w / v, 0.18% w / v, 0.2% w / v, 0.25% w / v, 0.3% w / v, 0.35% w / v, 0.4% w / v, 0.5% w / v, 0.6% w / v, 0.7% w / v, 0.8% w / v, 0.9% w / v or 1.0% w / v.

[0014] According to some embodiments of the application, the concentration of the zeolite molecular sieve in the amine monomer aqueous solution is 0.2-0.3% w / v.

[0015] According to some embodiments of the application, the zeolite molecular sieve comprises at least one of MCM-22 and ZSM-35.

[0016] In the present application, the zeolite molecular sieve as the porous filler, the specific type of which will affect the performance of the prepared zeolite molecular sieve-polyamide pervaporation composite membrane to some extent. Selecting a suitable type of zeolite molecular sieve can not only improve the separation performance of the prepared zeolite molecular sieve-polyamide pervaporation composite membrane, but also be conducive to improving the film-forming property and compactness and integrity of the composite membrane.

[0017] According to some embodiments of the present application, the amine monomer includes at least one of m-phenylenediamine (MPD), piperazine (PIP), ethylenediamine (ED), and polyimide (PEI), preferably m-phenylenediamine (MPD).

[0018] According to some embodiments of the present application, the concentration of the amine monomer in the aqueous amine monomer solution is 1-5% w / v, preferably 2-3% w / v.

[0019] According to some embodiments of the present application, the acyl chloride monomer includes at least one of trimesoyl chloride (TMC), terephthaloyl chloride, liminophthaloyl chloride, isophthaloyl chloride, and biphenyl tetracarboxylic acid chloride, preferably trimesoyl chloride (TMC).

[0020] According to some embodiments of the present application, the solvent in the acyl chloride monomer organic phase solution includes at least one of n-hexane, n-heptane, and cyclohexane, preferably n-hexane.

[0021] According to some embodiments of the present application, the concentration of the acyl chloride monomer in the acyl chloride monomer organic phase solution is 0.1-0.4% w / v, preferably 0.15-0.2% w / v.

[0022] According to some embodiments of the present application, the porous base membrane includes a flat sheet membrane or a tubular membrane.

[0023] According to some embodiments of the present application, the porous base membrane includes any one of polyvinylidene fluoride / non-woven fabric, polyacrylonitrile / non-woven fabric, polyethersulfone / non-woven fabric, and alumina ceramic membrane.

[0024] According to some embodiments of the present application, the time for immersing the porous base membrane in the aqueous amine monomer solution is 90-900 s, preferably 600-800 s.

[0025] According to some embodiments of the present application, the time for immersing the porous base membrane in the acyl chloride monomer organic phase solution is 30-240 s, preferably 120-200 s.

[0026] According to some embodiments of the present application, the heating temperature is 50-90℃, preferably 70-85℃; and the heating time is 5-10 min, preferably 5-7 min.

[0027] In a second aspect, the present application provides a zeolite molecular sieve-polyamide pervaporation composite membrane prepared by the preparation method of the first aspect.

[0028] According to some embodiments of the present application, the zeolite molecular sieve-polyamide pervaporation composite membrane comprises a porous base film layer and a zeolite molecular sieve-polyamide layer.

[0029] According to some embodiments of the present application, the thickness of the zeolite molecular sieve-polyamide layer is 80-500 nm.

[0030] In a third aspect, the present application provides an application of the zeolite molecular sieve-polyamide pervaporation composite membrane of the second aspect in the field of pervaporation, in particular in the dehydration of alcohols, acids, ketones and esters.

[0031] The present application has at least the following beneficial effects:

[0032] The preparation method of the zeolite molecular sieve-polyamide pervaporation composite membrane provided by the present application is simple, easy to control, short in preparation period and low in cost, and the prepared zeolite molecular sieve-polyamide pervaporation composite membrane has excellent compactness and permeation selectivity and has good separation performance in the pervaporation process of alcohols and water, acids and water, ketones and water, and esters and water. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 SEM image of the zeolite molecular sieve-polyamide pervaporation composite membrane of Example 1 of the present application;

[0034] Figure 2 SEM image of the zeolite molecular sieve nanosheet of Example 1 of the present application. DETAILED DESCRIPTION

[0035] In order to make the technical problems to be solved by the present application, the technical solutions and beneficial effects more clear and explicit, the present application will be further described in detail below in combination with specific examples. It should be understood that the specific examples described herein are only used to illustrate the present application in detail, and do not limit the protection scope of the present application in any way.

[0036] Unless otherwise defined, the technical terms used in the following examples have the same meanings as generally understood by those skilled in the art to which the present application belongs. The reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the raw materials, instruments and equipment used in the following examples, unless otherwise specified, can be purchased on the market or obtained by existing methods; the reagent amount, unless otherwise specified, is the reagent amount in conventional experimental operation; the experimental methods, unless otherwise specified, are conventional methods.

[0037] In each of the embodiments and comparative examples of the present application, the evaluation method of the pervaporation separation performance is as follows:

[0038] The prepared separation membrane was sealed in a pervaporation membrane cell, the temperature of the feed liquid was controlled at 60°C, and the pressure on the permeation side was maintained below 100 Pa. Before the test, the device was pre-operated for more than 60 min to make the system reach an equilibrium state, and the liquid on the permeation side was collected by cooling in liquid nitrogen. The concentration of the feed liquid on the feed side and the concentration of the liquid on the permeation side were determined by gas chromatography. The test was performed with isopropanol aqueous solution (isopropanol / water = 90 wt%:10 wt%).

[0039] The pervaporation membrane flux J was determined by the following formula:

[0040]

[0041] The separation factor β was determined by the following formula:

[0042]

[0043] wherein W is the mass of the collected liquid on the permeation side (g), t is the test time (h), A is the effective membrane area (m 2 ), y B and x B are the concentrations of water on the feed side and the permeation side (wt%), respectively, y A and x A are the concentrations of isopropanol on the feed side and the permeation side (wt%) respectively.

[0044] In each of the embodiments and comparative examples of the present application, the PVA used was PVA 17-99 produced by Shanghai Maikelin Biochemical Technology Co., Ltd.

[0045] Example 1

[0046] (1) Preparation of the aqueous solution of amine monomers for the interfacial polymerization process: the amine monomer was m-phenylenediamine (MPD), and the concentration of MPD was 2.0% w / v; PVA and zeolite nanosheet MCM-22 (SEM image as shown in Figure 2 ) were added to the aqueous solution of amine monomers, the concentration of PVA was 0.10% w / v, and the concentration of zeolite nanosheet was 0.2% w / v;

[0047] (2) Preparation of the organic phase solution of acyl chloride monomers for the interfacial polymerization process: the acyl chloride monomer was trimesoyl chloride (TMC), the solvent was n-hexane, and the concentration of TMC was 0.15% w / v;

[0048] (3) Interfacial polymerization reaction: the microporous PVDF / non-woven fabric support layer was immersed in the aqueous solution of amine monomers for 600 s, then taken out, and the excess solution on the surface was removed in air, and then immersed in the organic phase solution of acyl chloride monomers for interfacial polymerization reaction, and the reaction time was 180 s;

[0049] (4) Interfacial polymerization heat treatment and post-treatment: the film was taken out from the organic phase solution of acyl chloride monomers, and then placed in an oven for heat treatment, the temperature was 75 ℃, the heating time was 5 min, then washed with methanol, and finally immersed in deionized water to obtain a zeolite molecular sieve-polyamide pervaporation composite membrane, and a SEM image is shown in FIG. 2. Figure 1

[0050] The zeolite molecular sieve-polyamide pervaporation composite membrane prepared in this example was used for pervaporation dehydration test of isopropyl alcohol / water (mass ratio 90:10) mixed solution, and when the temperature was 60 ℃, the flux and separation factor were 2.2 kg m - 2 h -1 and 190.

[0051] Example 2

[0052] (1) Preparation of aqueous solution of amine monomers in interfacial polymerization process: the amine monomer was m-phenylenediamine (MPD), and the concentration of MPD was 2.5% w / v; PVA and zeolite molecular sieve nanosheet MCM-22 were added to the aqueous solution of amine monomers, the concentration of PVA was 0.12% w / v, and the concentration of zeolite molecular sieve nanosheet was 0.3% w / v.

[0053] (2) Preparation of organic phase solution of acyl chloride monomers in interfacial polymerization process: the acyl chloride monomer was trimesoyl chloride (TMC), the solvent was n-hexane, and the concentration of TMC was 0.2% w / v.

[0054] (3) Interfacial polymerization reaction: the microporous PVDF / non-woven fabric support layer was immersed in the aqueous solution of amine monomers for 700 s, then taken out, and the excess solution on the surface was removed in air, and then immersed in the organic phase solution of acyl chloride monomers for interfacial polymerization reaction, and the reaction time was 150 s.

[0055] (4) Interfacial polymerization heat treatment and post-treatment: the film was taken out from the organic phase solution of acyl chloride monomers, and then placed in an oven for heat treatment, the temperature was 70 ℃, the heating time was 7 min, then washed with methanol, and finally immersed in deionized water to obtain a zeolite molecular sieve-polyamide pervaporation composite membrane.

[0056] The zeolite molecular sieve-polyamide pervaporation composite membrane prepared in this example was used for pervaporation dehydration test of isopropyl alcohol / water (mass ratio 90:10) mixed solution, and when the temperature was 60 ℃, the flux and separation factor were 2.10 kg m​- 2 h -1 and 225.

[0057] Example 3

[0058] (1) Preparation of amine monomer aqueous solution for interfacial polymerization: the amine monomer is m-phenylenediamine (MPD), and the concentration of MPD is 2.5% w / v; PVA and zeolite nanosheet MCM-22 are added to the amine monomer aqueous solution, the concentration of PVA is 0.10% w / v, and the concentration of zeolite nanosheet is 0.25% w / v;

[0059] (2) Preparation of acyl chloride monomer organic solution for interfacial polymerization: the acyl chloride monomer is trimesoyl chloride (TMC), the solvent is n-hexane, and the concentration of TMC is 0.15% w / v;

[0060] (3) Interfacial polymerization reaction: microporous polyacrylonitrile (PAN) / non-woven fabric support layer is immersed in the amine monomer aqueous solution for 600 s, and then the surface excess solution is removed in the air, and then the interfacial polymerization reaction is carried out by immersing in the acyl chloride monomer organic solution, and the reaction time is 180 s;

[0061] (4) Interfacial polymerization heat treatment and post-treatment: the film is taken out from the acyl chloride monomer organic solution, and then placed in an oven for heat treatment, the temperature is 80 ℃, the heating time is 6 min, then washed with methanol, and finally immersed in deionized water to obtain a zeolite@polyamide pervaporation composite membrane.

[0062] The zeolite@polyamide pervaporation composite membrane prepared in the example is used for pervaporation dehydration test of isopropyl alcohol / water (mass ratio 90:10) mixed solution, and when the temperature is 60 ℃, the flux and separation factor are 2.0 kg m - 2 h -1 and 210.

[0063] Example 4

[0064] (1) Preparation of amine monomer aqueous solution for interfacial polymerization: the amine monomer is m-phenylenediamine (MPD), and the concentration of MPD is 2.5% w / v; PVA and zeolite nanosheet MCM-22 are added to the amine monomer aqueous solution, the concentration of PVA is 0.10% w / v, and the concentration of zeolite nanosheet is 0.25% w / v;

[0065] (2) Preparation of acyl chloride monomer organic solution for interfacial polymerization: the acyl chloride monomer is trimesoyl chloride (TMC), the solvent is n-hexane, and the concentration of TMC is 0.15% w / v;

[0066] (3) Interfacial polymerization reaction: the microporous alumina ceramic membrane is immersed in the aqueous solution of the amine monomer for 600 s, and then is placed in air to remove the excess solution on the surface, and then is immersed in the organic phase solution of the acyl chloride monomer for interfacial polymerization reaction, and the reaction time is 200 s;

[0067] (4) Interfacial polymerization heat treatment and post-treatment: the membrane is taken out of the organic phase solution of the acyl chloride monomer, and then is placed in an oven for heat treatment, the temperature is 70 ℃, the heating time is 5 min, then the membrane is washed with methanol, and finally is immersed in deionized water, to obtain the zeolite@polyamide pervaporation composite membrane.

[0068] The zeolite@polyamide pervaporation composite membrane prepared in this example is used for pervaporation dehydration test of isopropyl alcohol / water (mass ratio 90:10) mixed solution, and when the temperature is 60 ℃, the flux and separation factor are 2.3 kg m - 2 h -1 and 178.

[0069] Example 5

[0070] The preparation method of the zeolite@polyamide pervaporation composite membrane is the same as that in Example 1, except that the zeolite nanosheet MCM-22 is replaced by zeolite nanosheet ZSM-35.

[0071] The zeolite@polyamide pervaporation composite membrane prepared in this example is used for pervaporation dehydration test of isopropyl alcohol / water (mass ratio 90:10) mixed solution, and when the temperature is 60 ℃, the flux and separation factor are 2.1 kg m - 2 h -1 and 206.

[0072] Example 6

[0073] The preparation method of the zeolite@polyamide pervaporation composite membrane is the same as that in Example 1, except that the zeolite nanosheet MCM-22 is replaced by ZSM-5 molecular sieve.

[0074] The zeolite@polyamide pervaporation composite membrane prepared in this example is used for pervaporation dehydration test of isopropyl alcohol / water (mass ratio 90:10) mixed solution, and when the temperature is 60 ℃, the flux and separation factor are 2.4 kg m - 2 h -1 and 145.

[0075] Example 7

[0076] The preparation method of the zeolite molecular sieve@polyamide pervaporation composite membrane refers to Example 1, except that the zeolite molecular sieve nanosheet MCM-22 is replaced by SAPO-34 molecular sieve.

[0077] The zeolite molecular sieve@polyamide pervaporation composite membrane prepared in this example is used for pervaporation dehydration test of isopropyl alcohol / water (mass ratio 90:10) mixed solution, and when the temperature is 60 ℃, the flux and separation factor are 2.3 kg m - 2 h -1 and 138.

[0078] Example 8

[0079] The preparation method of the zeolite molecular sieve@polyamide pervaporation composite membrane refers to Example 1, except that the PVA concentration is 0.05% w / v.

[0080] The zeolite molecular sieve@polyamide pervaporation composite membrane prepared in this example is used for pervaporation dehydration test of isopropyl alcohol / water (mass ratio 90:10) mixed solution, and when the temperature is 60 ℃, the flux and separation factor are 2.3 kg m - 2 h -1 and 183.

[0081] Example 9

[0082] The preparation method of the zeolite molecular sieve@polyamide pervaporation composite membrane refers to Example 1, except that the PVA concentration is 0.15% w / v.

[0083] The zeolite molecular sieve@polyamide pervaporation composite membrane prepared in this example is used for pervaporation dehydration test of isopropyl alcohol / water (mass ratio 90:10) mixed solution, and when the temperature is 60 ℃, the flux and separation factor are 2.5 kg m - 2 h -1 and 196.

[0084] Example 10

[0085] The preparation method of the zeolite molecular sieve@polyamide pervaporation composite membrane refers to Example 1, except that the zeolite molecular sieve nanosheet concentration is 0.01% w / v.

[0086] The zeolite molecular sieve@polyamide pervaporation composite membrane prepared in this example is used for pervaporation dehydration test of isopropyl alcohol / water (mass ratio 90:10) mixed solution, and when the temperature is 60 ℃, the flux and separation factor are 2.5 kg m - 2 h -1 and 142.

[0087] Example 11

[0088] The preparation method of the polyamide pervaporation membrane refers to Example 1, and the only difference is that the zeolite molecular sieve nanosheet concentration is 1.0 %w / v.

[0089] The zeolite molecular sieve@polyamide pervaporation composite membrane prepared in this example is used for pervaporation dehydration test of isopropyl alcohol / water (mass ratio 90:10) mixed solution, and when the temperature is 60 ℃, the flux and separation factor are 2.8 kg m - 2 h -1 and 173.

[0090] Comparative Example 1

[0091] The preparation method of the polyamide pervaporation composite membrane refers to Example 1, and the only difference is that PVA and zeolite molecular sieve nanosheets are not added.

[0092] The polyamide pervaporation composite membrane prepared in this example is used for pervaporation dehydration test of isopropyl alcohol / water (mass ratio 90:10) mixed solution, and when the temperature is 60 ℃, the flux and separation factor are 2.5 kg m -2 h -1 and 130.

[0093] Comparative Example 2

[0094] The preparation method of the zeolite molecular sieve@polyamide pervaporation composite membrane refers to Example 1, and the only difference is that PVA is not added.

[0095] The zeolite molecular sieve@polyamide pervaporation composite membrane prepared in this example is used for pervaporation dehydration test of isopropyl alcohol / water (mass ratio 90:10) mixed solution, and when the temperature is 60 ℃, the flux and separation factor are 2.3 kg m - 2 h -1 and 160.

[0096] It should be noted that the above-described examples are only used to explain the present application and do not constitute any limitation on the present application. The present application is described by referring to typical examples, but it should be understood that the words used therein are descriptive and explanatory words, rather than limiting words. The present application can be modified as specified within the scope of the claims of the present application, and the present application can be revised without departing from the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and examples, it does not mean that the present application is limited to the specific examples disclosed therein, on the contrary, the present application can be extended to all other methods and applications having the same function.

Claims

1. A method for preparing a zeolite molecular sieve@polyamide pervaporation composite membrane, characterized in that, include: The porous base membrane is first immersed in an aqueous solution of amine monomers, then removed and dried, and then immersed in an organic solution of acyl chloride monomers. After removal and heating, the zeolite molecular sieve@polyamide pervaporation composite membrane is obtained; the aqueous solution of amine monomers includes polyvinyl alcohol and zeolite molecular sieve. The concentration of amine monomers in the aqueous solution of amine monomers is 1–5% w / v; The concentration of acyl chloride monomer in the organic phase solution of acyl chloride monomer is 0.1–0.4% w / v; The concentration of zeolite molecular sieves in aqueous solutions of amine monomers is 0.05–1.0% w / v; The concentration of polyvinyl alcohol in the aqueous solution of amine monomers is 0.05–0.15% w / v.

2. The preparation method according to claim 1, characterized in that, The concentration of the zeolite molecular sieve in the aqueous solution of amine monomers is 0.2–1.0% w / v; And / or, the concentration of the polyvinyl alcohol in the aqueous solution of the amine monomer is 0.10 to 0.15% w / v.

3. The preparation method according to claim 2, characterized in that, The concentration of the zeolite molecular sieve in the aqueous solution of amine monomers is 0.2–0.3% w / v.

4. The preparation method according to any one of claims 1-3, characterized in that, The zeolite molecular sieve includes at least one of MCM-22 and ZSM-35.

5. The preparation method according to any one of claims 1-3, characterized in that, Amine monomers include at least one of m-phenylenediamine, piperazine, ethylenediamine, and polyimide; And / or, the concentration of amine monomers in the aqueous solution of amine monomers is 2-3% w / v.

6. The preparation method according to any one of claims 1-3, characterized in that, Acyl chloride monomers include at least one of pyromellitic trichloroethylene chloride, terephthaloyl chloride, phthaloyl chloride, isophthaloyl chloride, and biphenyl tetrachloroethylene chloride; And / or, the solvent in the organic phase solution of the acyl chloride monomer includes at least one of n-hexane, n-heptane, and cyclohexane; And / or, the concentration of acyl chloride monomer in the acyl chloride monomer organic phase solution is 0.15–0.2 % w / v.

7. The preparation method according to any one of claims 1-3, characterized in that, The porous base membrane includes a flat sheet membrane or a tubular membrane; And / or, the porous base membrane includes any one of polyvinylidene fluoride / nonwoven fabric, polyacrylonitrile / nonwoven fabric, polyethersulfone / nonwoven fabric, and alumina ceramic membrane.

8. The preparation method according to any one of claims 1-3, characterized in that, The porous base membrane is immersed in the aqueous solution of amine monomers for 90–900 s; And / or, the porous base membrane is immersed in the organic phase solution of acyl chloride monomer for 30 to 240 s.

9. The preparation method according to any one of claims 1-3, characterized in that, The porous base membrane is immersed in the aqueous solution of amine monomers for 600–800 s; And / or, the porous base membrane is immersed in the organic phase solution of acyl chloride monomer for 120 to 200 s.

10. The preparation method according to any one of claims 1-3, characterized in that, The heating temperature is 50-90℃; the heating time is 5-10 min.

11. The preparation method according to any one of claims 1-3, characterized in that, The heating temperature is 70-85℃; the heating time is 5-7 minutes.

12. A zeolite molecular sieve@polyamide pervaporation composite membrane, prepared by the preparation method described in any one of claims 1-11.

13. The application of the zeolite molecular sieve@polyamide pervaporation composite membrane according to claim 12 in the field of pervaporation.

14. The application according to claim 13, characterized in that, The application is in the dehydration of alcohols, acids, ketones, and esters.

Images