Zeolite molecular sieve and polyamide pervaporation composite membrane as well as preparation method and application thereof

Abstract

The invention relates to the technical field of separation membranes, and provides a zeolite molecular sieve and polyamide pervaporation composite membrane as well as a preparation method and application thereof. The preparation method of the zeolite molecular sieve-coated polyamide pervaporation composite membrane comprises the following steps: immersing a porous base membrane into an amine monomer aqueous phase solution, taking out and drying, immersing into an acyl chloride monomer organic phase solution, taking out and heating to prepare the zeolite molecular sieve-coated polyamide pervaporation composite membrane, the amine monomer water-phase solution comprises polyvinyl alcohol (PVA) and a zeolite molecular sieve. The preparation method of the zeolite molecular sieve-polyamide pervaporation composite membrane 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 isopropanol and water.

Description

Technical Field

[0001] The present invention relates to the technical field of separation membranes, and more specifically to a zeolite molecular sieve@polyamide pervaporation composite membrane and a preparation method and application thereof. Background Art

[0002] Under the goal of "carbon peak and carbon neutrality", in order to achieve sustainable economic development and green transformation of the energy and chemical industry, new separation technologies are being actively developed at home and abroad. Compared with traditional separation technologies such as distillation, extraction, and absorption, membrane separation technology has the advantages of low energy consumption, high efficiency, and green environmental protection. At present, membrane separation technologies such as microfiltration, ultrafiltration, gas separation, reverse osmosis, and pervaporation have been widely used in the fields of chemical industry, energy, and medicine.

[0003] Pervaporation membrane separation technology is a process that uses the vapor pressure difference of each component as the driving force and relies on the difference in mass transfer rate of each component across the membrane to achieve the separation of the mixture. Pervaporation membrane dehydration technology is an efficient solvent separation and refining technology, especially suitable for the production of azeotropic systems, high boiling point 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 azeotropic distillation, and the operating cost is less than 50% of that of azeotropic distillation. It 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 require the addition of exogenous components, does not generate waste and pollutants, and has a 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 made of porous materials such as zeolite molecular sieves, which have regular pore structures and high porosity. They exhibit high permeability and selectivity based on the molecular sieve effect. However, they have the disadvantages of complex preparation process and high price. In order to solve the limitations of organic and inorganic membranes, combining polymer materials with porous materials to prepare mixed matrix membranes is an effective strategy to improve membrane performance (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. Interfacial polymerization method is a commonly used method for preparing commercial composite membranes, which has the advantages of simple operation, high film forming property, and easy industrial scale-up. At present, separation membranes prepared by interfacial polymerization method are mainly used in ultrafiltration membrane and nanofiltration membrane processes, and there are still limitations in the separation of liquid mixtures with small size differences. This is mainly because the polyamide separation layer prepared by interfacial polymerization method has insufficient density and membrane defects that affect the separation effect of the membrane. Secondly, the intrinsic chemical structure of the separation layer has limited hydrophilicity and poor adsorption selectivity for water / organic molecules. It has been reported that polyamide pervaporation composite membranes were prepared by interfacial polymerization (Desalination, 2019, 469, 114090; CN 115518525A; Journal of Membrane Science, 2013, 448, 34-43; Journal of Membrane Science, 2012, 405-406, 123-133). However, the separation performance of pure polyamide membranes is limited by the dissolution-diffusion model, and there is a trade-off effect in the separation performance. Membranes with high flux often have lower selectivity, and vice versa. In addition, the membrane performance can be improved by depositing porous materials on the substrate membrane by vacuum filtration and then preparing polyamide composite membranes by interfacial polymerization. However, it is difficult to accurately control the thickness of the deposited layer and the dispersion and uniformity of the porous material in the polyamide layer. Summary of the invention

[0006] The purpose of the present invention is to provide a zeolite molecular sieve @ polyamide pervaporation composite membrane and a preparation method thereof, to improve the dispersion and uniformity of the porous material in the polyamide layer, and to solve the technical problems of poor density and limited separation performance of the polyamide pervaporation membrane in the prior art.

[0007] To achieve the above object, the technical solution adopted by the present invention is:

[0008] In a first aspect, the present invention provides a method for preparing a zeolite molecular sieve @ polyamide pervaporation composite membrane, comprising: first immersing a porous base membrane in an aqueous phase solution of amine monomers, taking it out and drying it, then immersing it in an organic phase solution of acyl chloride monomers, taking it out and heating it to obtain the zeolite molecular sieve @ polyamide pervaporation composite membrane; the aqueous phase solution of amine monomers includes polyvinyl alcohol (PVA) and zeolite molecular sieve.

[0009] The present invention provides a method for preparing a zeolite molecular sieve@polyamide pervaporation composite membrane. A porous base membrane is used as a substrate, and a separation layer with high permeability selectivity is prepared by one-step interfacial polymerization. Adding PVA to an amine monomer aqueous solution can adjust the diffusion rate of the amine monomer; and can adjust the viscosity of the amine monomer aqueous solution, thereby improving the dispersibility and uniformity of the zeolite molecular sieve in the amine monomer aqueous solution, so that the zeolite molecular sieve can be evenly dispersed in the polyamide membrane, which can effectively reduce the defect density of the polyamide membrane and solve the problem of poor membrane compactness. In addition, the regular pores of the zeolite molecular sieve can improve the selective screening performance of the target (such as water / isopropanol), so that the separation effect of the membrane is better.

[0010] In the present invention, PVA can be selected from products of common brands and grades, for example, at least one of PVA 17-88, PVA 17-92, and PVA 17-99 can be selected.

[0011] According to some embodiments of the present invention, the concentration of the polyvinyl alcohol in the aqueous solution of the amine monomer 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, 0.15% w / v, etc.

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

[0013] According to some embodiments of the present invention, the concentration of the zeolite molecular sieve in the aqueous phase solution of the amine monomer is 0.01 to 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, 1.0% w / v, etc.

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

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

[0016] In the present invention, zeolite molecular sieve is used as a porous filler, and its specific type will affect the performance of the prepared zeolite molecular sieve@polyamide pervaporation composite membrane to a certain 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 help to improve the film forming property and compactness integrity of the composite membrane.

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

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

[0019] According to some embodiments of the present invention, the acyl chloride monomer includes at least one of trimesoyl chloride (TMC), terephthaloyl chloride, phthaloyl chloride, isophthaloyl chloride, and biphenyltetrachlorochloride, preferably trimesoyl chloride (TMC).

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

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

[0022] According to some embodiments of the present invention, the porous base membrane comprises a flat membrane or a tubular membrane.

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

[0024] According to some embodiments of the present invention, the porous base membrane is immersed in the aqueous amine monomer solution for 90 to 900 seconds, preferably 600 to 800 seconds.

[0025] According to some embodiments of the present invention, the porous base membrane is immersed in the organic phase solution of the acyl chloride monomer for 30 to 240 seconds, preferably 120 to 200 seconds.

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

[0027] In a second aspect, the present invention provides a zeolite molecular sieve@polyamide pervaporation composite membrane, which is prepared by the preparation method described in the first aspect.

[0028] According to some embodiments of the present invention, the zeolite molecular sieve@polyamide pervaporation composite membrane includes a porous base membrane layer and a zeolite molecular sieve@polyamide layer.

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

[0030] In a third aspect, the present invention provides the use of the zeolite molecular sieve@polyamide pervaporation composite membrane described in the second aspect in the field of pervaporation, especially in the dehydration of alcohols, acids, ketones and esters.

[0031] The beneficial effects of the present invention are at least:

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

[0033] Figure 1 This is a SEM image of the zeolite molecular sieve@polyamide pervaporation composite membrane of Example 1 of the present invention;

[0034] Figure 2 This is a SEM image of the zeolite molecular sieve nanosheets of Example 1 of the present invention. DETAILED DESCRIPTION

[0035] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain this patent in detail and do not limit the scope of protection of the present invention in any way.

[0036] Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by those skilled in the art to which the present invention 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, etc., can all be purchased on the market or can be obtained by existing methods; the reagent amounts, unless otherwise specified, are the reagent amounts used in conventional experimental operations; the experimental methods, unless otherwise specified, are all conventional methods.

[0037] In each embodiment and comparative example of the present invention, the evaluation method of the pervaporation separation performance is as follows:

[0038] The prepared separation membrane was sealed in a pervaporation membrane pool, the feed liquid temperature was controlled at 60°C, and the permeation side pressure was maintained below 100Pa. Before the test began, the device was pre-operated for more than 60 minutes to allow the system to reach a balanced state, and the permeation side was cooled and collected by immersing the cold trap in liquid nitrogen. The feed liquid concentration on the feed side and the permeation side were determined by gas chromatography. The test was carried out with an isopropanol aqueous solution (isopropanol / water = 90wt%: 10wt%).

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

[0040]

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

[0042]

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

[0044] In the various embodiments and comparative examples of the present invention, the PVA used is PVA 17-99 produced by Shanghai MacLean Biochemical Technology Co., Ltd.

[0045] Example 1

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

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

[0048] (3) Interfacial polymerization reaction: The microporous PVDF / non-woven fabric support layer was immersed in an aqueous solution of amine monomers for 600 seconds, then taken out, allowed to stand in the air to remove excess surface solution, and then immersed in an organic solution of acyl chloride monomers for interfacial polymerization reaction. The reaction time was 180 seconds.

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

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

[0051] Example 2

[0052] (1) preparing an aqueous amine monomer solution for the interfacial polymerization process: the amine monomer is m-phenylenediamine (MPD), and the MPD concentration is 2.5% w / v; PVA and zeolite molecular sieve nanosheets MCM-22 are added to the aqueous amine monomer solution, and the PVA concentration is 0.12% w / v, and the zeolite molecular sieve nanosheet concentration is 0.3% w / v;

[0053] (2) preparing an organic phase solution of acyl chloride monomers for interfacial polymerization: the acyl chloride monomer is trimesoyl chloride (TMC), the solvent is n-hexane, and the TMC concentration is 0.2% w / v;

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

[0055] (4) Interfacial polymerization heat treatment and post-treatment: The film was taken out from the organic phase solution of the acyl chloride monomer, and then placed in an oven for heating at 70°C for 7 min. It was then rinsed 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 isopropanol / water (mass ratio 90:10) mixed solution. At a temperature of 60°C, the flux and separation factor were 2.10 kg m -2 h -1and 225.

[0057] Example 3

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

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

[0060] (3) Interfacial polymerization reaction: The microporous polyacrylonitrile (PAN) / non-woven fabric support layer was immersed in an aqueous solution of amine monomers for 600 seconds, allowed to stand in air to remove excess surface solution, and then immersed in an organic solution of acyl chloride monomers for interfacial polymerization reaction for 180 seconds;

[0061] (4) Interfacial polymerization heat treatment and post-treatment: The film was taken out from the organic phase solution of the acyl chloride monomer, and then placed in an oven for heating at 80°C for 6 min. It was then rinsed with methanol and finally immersed in deionized water to obtain a zeolite molecular sieve@polyamide pervaporation composite membrane.

[0062] The zeolite molecular sieve@polyamide pervaporation composite membrane prepared in this example was used for pervaporation dehydration test of isopropanol / water (mass ratio 90:10) mixed solution. At a temperature of 60°C, the flux and separation factor were 2.0 kg m -2 h -1 and 210.

[0063] Example 4

[0064] (1) preparing an aqueous amine monomer solution for the interfacial polymerization process: the amine monomer is m-phenylenediamine (MPD), and the MPD concentration is 2.2% w / v; PVA and zeolite molecular sieve nanosheets MCM-22 are added to the aqueous amine monomer solution, and the PVA concentration is 0.11% w / v, and the zeolite molecular sieve nanosheet concentration is 0.2% w / v;

[0065] (2) preparing an organic phase solution of acyl chloride monomers for interfacial polymerization: the acyl chloride monomer is trimesoyl chloride (TMC), the solvent is n-hexane, and the TMC concentration is 0.2% w / v;

[0066] (3) Interfacial polymerization reaction: The microporous alumina ceramic membrane was immersed in an aqueous solution of amine monomers for 600 seconds, allowed to stand in air to remove excess surface solution, and then immersed in an organic solution of acyl chloride monomers for interfacial polymerization reaction for 200 seconds;

[0067] (4) Interfacial polymerization heat treatment and post-treatment: The film was taken out from the organic phase solution of the acyl chloride monomer, and then placed in an oven for heating at 70°C for 5 min. It was then rinsed with methanol and finally immersed in deionized water to obtain a zeolite molecular sieve@polyamide pervaporation composite membrane.

[0068] The zeolite molecular sieve@polyamide pervaporation composite membrane prepared in this example was used for pervaporation dehydration test of isopropanol / water (mass ratio 90:10) mixed solution. At a temperature of 60°C, the flux and separation factor were 2.3 kg m -2 h -1 and 178.

[0069] Example 5

[0070] The preparation method of zeolite molecular sieve@polyamide pervaporation composite membrane is similar to that of Example 1, except that the zeolite molecular sieve nanosheets MCM-22 are replaced by zeolite molecular sieve nanosheets ZSM-35.

[0071] The zeolite molecular sieve@polyamide pervaporation composite membrane prepared in this example was used for pervaporation dehydration test of isopropanol / water (mass ratio 90:10) mixed solution. At a temperature of 60°C, the flux and separation factor were 2.1 kg m -2 h -1 and 206.

[0072] Example 6

[0073] The preparation method of zeolite molecular sieve@polyamide pervaporation composite membrane is similar to that of Example 1, except that the zeolite molecular sieve nanosheets MCM-22 are replaced by ZSM-5 molecular sieve.

[0074] The zeolite molecular sieve@polyamide pervaporation composite membrane prepared in this example was used for pervaporation dehydration test of isopropanol / water (mass ratio 90:10) mixed solution. At a temperature of 60°C, the flux and separation factor were 2.4 kg m -2 h -1 and 145.

[0075] Example 7

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

[0077] The zeolite molecular sieve@polyamide pervaporation composite membrane prepared in this example was used for pervaporation dehydration test of isopropanol / water (mass ratio 90:10) mixed solution. At a temperature of 60°C, the flux and separation factor were 2.3 kg m -2 h -1 and 138.

[0078] Example 8

[0079] The preparation method of zeolite molecular sieve@polyamide pervaporation composite membrane is similar to that of 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 was used for pervaporation dehydration test of isopropanol / water (mass ratio 90:10) mixed solution. At a temperature of 60°C, the flux and separation factor were 2.3 kg m -2 h -1 and 183.

[0081] Example 9

[0082] The preparation method of zeolite molecular sieve@polyamide pervaporation composite membrane is similar to that of 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 was used for pervaporation dehydration test of isopropanol / water (mass ratio 90:10) mixed solution. At a temperature of 60°C, the flux and separation factor were 2.5 kg m -2 h -1 and 196.

[0084] Example 10

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

[0086] The zeolite molecular sieve@polyamide pervaporation composite membrane prepared in this example was used for pervaporation dehydration test of isopropanol / water (mass ratio 90:10) mixed solution. At a temperature of 60°C, the flux and separation factor were 2.5 kg m -2 h -1 and 142.

[0087] Embodiment 11

[0088] The preparation method of the polyamide pervaporation membrane is similar to that of Example 1, except that the concentration of the zeolite molecular sieve nanosheets is 1.0% w / v.

[0089] The zeolite molecular sieve@polyamide pervaporation composite membrane prepared in this example was used for pervaporation dehydration test of isopropanol / water (mass ratio 90:10) mixed solution. At a temperature of 60°C, the flux and separation factor were 2.8 kg m -2 h -1 and 173.

[0090] Comparative Example 1

[0091] The preparation method of the polyamide pervaporation composite membrane is similar to that of Example 1, except that no PVA and zeolite molecular sieve nanosheets are added.

[0092] The polyamide pervaporation composite membrane prepared in this example was used for the pervaporation dehydration test of a mixed solution of isopropanol / water (mass ratio 90:10). At a temperature of 60°C, the flux and separation factor were 2.5 kg m -2 h -1 and 130.

[0093] Comparative Example 2

[0094] The preparation method of zeolite molecular sieve@polyamide pervaporation composite membrane is similar to that of Example 1, except that no PVA is added.

[0095] The zeolite molecular sieve@polyamide pervaporation composite membrane prepared in this example was used for pervaporation dehydration test of isopropanol / water (mass ratio 90:10) mixed solution. At a temperature of 60°C, the flux and separation factor were 2.3 kg m -2 h -1 and 160.

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

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, taken out and dried, and then immersed in an organic solution of acyl chloride monomers, taken out and heated to obtain the zeolite molecular sieve@polyamide pervaporation composite membrane; the aqueous solution of amine monomers includes polyvinyl alcohol and zeolite molecular sieve.

2. The preparation method according to claim 1, characterized in that: The concentration of the polyvinyl alcohol in the aqueous amine monomer solution is 0.05 to 0.15% w / v, preferably 0.10 to 0.15% w / v; And / or, the concentration of the zeolite molecular sieve in the aqueous amine monomer solution is 0.01-1.0% w / v, preferably 0.2-0.3% w / v.

3. The preparation method according to claim 1 or 2, characterized in that: The zeolite molecular sieve includes at least one of MCM-22 and ZSM-35.

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

5. The preparation method according to any one of claims 1 to 4, characterized in that: The acyl chloride monomer includes at least one of trimesoyl chloride, terephthaloyl chloride, phthaloyl chloride, isophthaloyl chloride, and biphenyltetrachlorochloride; and / or, the solvent in the organic phase solution of the acyl chloride monomer comprises at least one of n-hexane, n-heptane and cyclohexane; And / or, 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.

6. The preparation method according to any one of claims 1 to 5, characterized in that: The porous base membrane includes a flat membrane or a tubular membrane; And / or, the porous base membrane includes any one of polyvinylidene fluoride / non-woven fabric, polyacrylonitrile / non-woven fabric, polyether sulfone / non-woven fabric, and alumina ceramic membrane.

7. The preparation method according to any one of claims 1 to 6, characterized in that: The porous base membrane is immersed in the aqueous amine monomer solution for 90 to 900 seconds, preferably 600 to 800 seconds; And / or, the porous base membrane is immersed in the organic phase solution of the acyl chloride monomer for 30 to 240 seconds, preferably 120 to 200 seconds.

8. The preparation method according to any one of claims 1 to 7, characterized in that: The heating temperature is 50-90° C., preferably 70-85° C.; the heating time is 5-10 min, preferably 5-7 min.

9. A zeolite molecular sieve@polyamide pervaporation composite membrane prepared by the preparation method according to any one of claims 1 to 8.

10. Application of the zeolite molecular sieve@polyamide pervaporation composite membrane according to claim 9 in the field of pervaporation, especially in the dehydration of alcohols, acids, ketones and esters.

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