Green preparation method of hydrophilic zsm-5 zeolite membrane and application thereof

Abstract

The application discloses a kind of green preparation methods of hydrophilic ZSM-5 zeolite membrane and its application, belong to inorganic membrane separation technical field.The application includes the following steps: S1, precoat ZSM-5 seed on the surface of porous carrier;S2, silicon source, aluminum source, alkali source, deionized water and isopropyl alcohol are mixed, and stirring is obtained even organic ammonium template-free synthesis liquid;S3, the porous carrier of precoat seed is placed in the synthesis liquid, and hydrothermal crystallization reaction is carried out;S4, after reaction, membrane body is taken out, and washed to neutral with deionized water, after drying, calcination treatment, obtain hydrophilic ZSM-5 zeolite membrane.The application avoids the high cost and environmental pollution problem caused by organic ammonium template from root, and the prepared zeolite membrane shows excellent separation performance in pervaporation dehydration of ethanol, isopropyl alcohol, acetone and other various organic solvent-water systems, and has good industrial application prospect.

Description

Technical Field

[0001] This invention belongs to the field of inorganic membrane separation technology, specifically relating to a green preparation method of hydrophilic ZSM-5 zeolite membrane and its application. Background Technology

[0002] Dehydration of organic solvents is a core separation process in chemical, pharmaceutical, and water treatment industries. Compared with traditional separation technologies such as distillation and adsorption, zeolite membrane separation technology has outstanding advantages such as low energy consumption, high separation efficiency, easy coupling with reaction processes, and no secondary pollution, and has extremely wide application demand in the field of energy conservation and emission reduction in industrial production.

[0003] ZSM-5 zeolite membrane is currently the most promising inorganic separation membrane material in the field of pervaporation dehydration. It has a uniform MFI topological structure with micropores (pore size of about 0.55 nm), excellent hydrothermal and chemical stability, and tunable hydrophilicity and hydrophobicity. It can achieve efficient separation of water molecules from most organic solvent molecules through size sieving effect. At the same time, it has anti-swelling ability that organic membranes cannot match, making it one of the inorganic membrane materials with the greatest industrial potential in the field of organic solvent dehydration.

[0004] The traditional synthesis of ZSM-5 zeolite membranes typically requires the addition of organic ammonium templates such as tetrapropylammonium hydroxide to guide the formation of the MFI topology. However, the use of organic ammonium templates introduces unavoidable drawbacks to industrial production: firstly, the high cost of organic ammonium templates significantly increases the preparation cost of membrane materials, hindering industrial scale-up and promotion; secondly, the synthesis process generates a large amount of production wastewater containing high concentrations of organic ammonium, which is difficult and costly to treat, greatly increasing the environmental burden; and thirdly, the organic ammonium templates must be removed from the membrane layer through high-temperature calcination, which generates harmful waste gases such as nitrogen oxides, causing air pollution. Therefore, developing a technology for synthesizing low-defect, high-performance hydrophilic ZSM-5 zeolite membranes without organic ammonium templates has significant scientific research value and industrial implications.

[0005] Existing technologies have reported some methods for preparing ZSM-5 zeolite films in template-free systems, mainly by controlling the silicon-aluminum ratio of the synthesis solution or by pre-coating seed crystals to achieve film preparation. However, these methods still have insurmountable technical bottlenecks: in template-free systems, the nucleation and growth process of zeolite grains is difficult to control precisely, and problems such as the generation of impurities and disordered grain growth are very likely to occur. Ultimately, this leads to a large number of grain boundary defects and pinhole defects in the film, making it impossible to prepare a continuous, dense, high-performance film, which is difficult to meet the application requirements of industrial organic solvent dehydration. Summary of the Invention

[0006] This invention provides a green preparation method for hydrophilic ZSM-5 zeolite membranes and their applications, aiming to overcome the shortcomings of existing ZSM-5 zeolite membrane preparation processes, such as reliance on high-cost, high-pollution organic ammonium template agents, difficulty in controlling the crystallization process in template-free systems, easy generation of impurities and grain boundary defects in the membrane layer, and poor separation performance.

[0007] To achieve the above-mentioned objectives, the present invention adopts the following technical solution: The core technical solution of this invention is a green preparation method for hydrophilic ZSM-5 zeolite membranes, comprising the following steps: S1. Pre-coat ZSM-5 seed crystals onto the surface of the porous carrier; S2. Mix the silicon source, aluminum source, alkali source, deionized water and isopropanol, and stir to obtain a uniform synthesis solution without organic ammonium template agent; S3. Place the porous carrier with pre-coated seed crystals in the synthesis solution to carry out a hydrothermal crystallization reaction; S4. After the reaction is complete, the membrane is removed, washed with deionized water until neutral, and then dried and calcined to obtain the hydrophilic ZSM-5 zeolite membrane.

[0008] Furthermore, in a preferred embodiment of the present invention, the ZSM-5 seed crystals and the porous support are specified: the particle size of the ZSM-5 seed crystals is 10 nm to 1 μm; the porous support is any one of a porous alumina support, a porous silicon carbide support, or a porous stainless steel support. This specification ensures that the seed layer forms a uniform film on the support surface, providing stable nucleation sites for subsequent directional grain growth, while also adapting to the support requirements of different industrial applications.

[0009] Furthermore, in a preferred embodiment of the present invention, the types of raw materials for the synthesis liquid are limited: the silicon source is one or more of sodium silicate, colloidal silica, and tetraethyl orthosilicate; the aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum hydroxide, and aluminum isopropoxide; and the alkali source is one or more of lithium hydroxide, sodium hydroxide, and potassium hydroxide. This limitation covers all alternative raw materials that can achieve the technical effects of the present invention, significantly improving the raw material adaptability and industrial feasibility of the process.

[0010] Furthermore, in a preferred embodiment of the present invention, the component ratio of the synthesis solution is defined as follows: in the synthesis solution, the silicon source, aluminum source, and alkali source are all in oxide form, and the molar ratio of each component is SiO2:Al2O3:M2O:IPA:H2O=1:(0.01~0.1):(0.01~0.50):(0.1~5.0):(10~90); wherein, M is an alkali metal element in the alkali source, and IPA is isopropanol. This ratio range ensures the stability of the synthesis solution system and provides an optimal reaction environment for isopropanol-controlled nucleation growth, achieving dense growth of the film.

[0011] Furthermore, in a preferred embodiment of the present invention, the hydrothermal crystallization reaction conditions are specified as follows: the temperature of the hydrothermal crystallization reaction is 100℃~200℃, and the reaction time is 10h~100h. This range of conditions allows for precise control of the grain growth rate and crystallinity, avoiding film defects caused by excessively rapid grain growth, while ensuring synthesis efficiency.

[0012] Furthermore, in a preferred embodiment of the present invention, the calcination conditions are specified as follows: the calcination temperature is 300℃~600℃, and the calcination time is 5h~100h. These conditions can thoroughly remove residual moisture and organic impurities from the film layer, while eliminating internal stress within the film layer, avoiding crack defects during the calcination process, and improving the mechanical stability of the film layer.

[0013] Furthermore, in a preferred embodiment of the present invention, the roasting atmosphere is defined as follows: the roasting atmosphere is any one of pure oxygen, air, or diluted oxygen. This limitation is adaptable to different industrial roasting equipment while ensuring the complete removal of impurities.

[0014] Furthermore, in a preferred embodiment of the present invention, the properties of the obtained zeolite membrane are defined as follows: the silicon-aluminum molar ratio of the obtained hydrophilic ZSM-5 zeolite membrane is 5 to 50. This silicon-aluminum ratio range ensures that the membrane has excellent hydrophilicity and water preferential permeability selectivity, adapting to the dehydration requirements of different organic solvent systems.

[0015] Based on the above preparation method, the present invention also provides an application of the hydrophilic ZSM-5 zeolite membrane, wherein the hydrophilic ZSM-5 zeolite membrane prepared by the above preparation method is used for pervaporation dehydration of organic solvent systems.

[0016] Furthermore, in the preferred embodiment of the present invention, the application scenario is limited as follows: the organic solvent system is any one of ethanol-water system, isopropanol-water system, and acetone-water system; the operating temperature of the pervaporation dehydration is 30℃~90℃, and the mass fraction of water in the organic solvent system is 1%~30%.

[0017] Compared with the prior art, the present invention has the following outstanding advantages: Green and environmentally friendly, low cost: The preparation method of this invention does not use any organic ammonium template agent, thus avoiding the problems caused by organic ammonium template agents, such as high raw material costs, difficulty in treating ammonium-containing waste liquid, and nitrogen oxide waste gas pollution generated during the calcination process. It reduces the raw material cost of membrane materials by more than 60%, and completely eliminates wastewater and waste gas pollution related to organic ammonium. This significantly reduces the environmental pressure and overall cost of industrial production, making it more suitable for large-scale industrial scale-up and promotion.

[0018] Excellent membrane quality and outstanding separation performance: This invention overcomes the technical bottleneck of difficult-to-control zeolite membrane crystallization process in template-free systems. By adding isopropanol as a structure-directing regulator in the synthesis solution, the heterogeneous nucleation and directional growth process of zeolite grains on the seed layer surface is precisely controlled, effectively suppressing the formation of impurity crystals and the generation of grain boundary and pinhole defects. A continuous, dense, and defect-free hydrophilic ZSM-5 zeolite membrane can be prepared in a template-free system. The resulting membrane exhibits excellent hydrophilicity, extremely high permeation flux, and separation selectivity. In pervaporation dehydration of various organic solvent-water systems, the separation factor can reach up to 8725, far exceeding the separation performance of ZSM-5 zeolite membranes prepared by existing template-free technologies, achieving the performance level of membranes synthesized using organic template systems.

[0019] The process is highly controllable and has a wide range of applications: The preparation process parameters of this invention have a wide window and strong adaptability to raw material types, carrier materials, crystallization and calcination conditions. By adjusting the synthesis solution ratio and process parameters, the silicon-aluminum ratio, thickness and separation performance of the membrane can be flexibly controlled to meet the application requirements of different organic solvent dehydration scenarios. At the same time, the process steps are simple and do not require complex equipment modifications. It can be directly adapted to existing zeolite membrane industrial production lines and has a very strong prospect for industrial application. Detailed Implementation

[0020] The present invention will be further described in detail below with reference to embodiments. It should be noted that the following embodiments are merely preferred embodiments of the present invention, used to explain the technical solutions of the present invention, and not to limit the scope of protection of the present invention. Any non-creative modifications and substitutions made based on the core concept of the present invention fall within the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are also within the scope of protection of the present invention.

[0021] Unless otherwise specified, the raw materials used in the following examples are all commercially available analytical grade reagents, the porous carriers used are all commercially available industrial grade products, and the testing equipment used are all standard industry equipment.

[0022] Performance testing methods The separation performance of the membranes prepared in each embodiment and comparative example was tested using a laboratory-made pervaporation apparatus. During the test, the effective separation area of ​​the membrane was 12.56 cm². 2 On the permeate side, a vacuum pump was used to maintain a vacuum level of less than 100 Pa. The permeate was collected using a liquid nitrogen cold trap. Gas chromatography was used to analyze the composition of the permeate and feed solution, and the permeate flux and separation factor were calculated. The permeate flux is the mass of permeate passing through a unit membrane area per unit time, expressed in kg·m³. -2 ·h -1The separation factor is the mass ratio of water and organic solvent in the feed solution to that in the permeate, and is used to characterize the separation selectivity of the membrane.

[0023] Basic Implementation This embodiment corresponds to the core technical solution of the present invention and provides a green preparation method for hydrophilic ZSM-5 zeolite membranes. The specific steps are as follows: S1. A porous α-alumina ceramic tube was selected as a porous carrier. ZSM-5 seed crystals were pre-coated on its surface by impregnation method. After drying at room temperature, the carrier with pre-coated seed crystals was obtained. S2. Mix silicon source, aluminum source, alkali source, deionized water and isopropanol, and stir at room temperature for 2 hours to obtain a uniform and transparent synthesis solution without organic ammonium template agent. S3. The carrier with pre-coated seed crystals is placed vertically into a polytetrafluoroethylene-lined stainless steel high-pressure reactor containing the synthesis liquid, and then sealed for hydrothermal crystallization reaction. S4. After the reaction is complete, the membrane is naturally cooled to room temperature. The membrane is then removed and repeatedly washed with deionized water until the washing solution is neutral. It is then dried in a 100°C oven for 12 hours and then calcined in a muffle furnace. After naturally cooling to room temperature, the hydrophilic ZSM-5 zeolite membrane is obtained.

[0024] Optimized Example 1 The specific steps are as follows: S1. Select a porous silicon carbide ceramic tube as a porous carrier, immerse it in 1wt% ZSM-5 seed suspension (seed particle size is 10nm) for 30s, remove it and blow off the excess suspension on the surface with nitrogen, air dry at room temperature and repeat the immersion twice to obtain a carrier with pre-coated seed. S2. Colloidal silica, aluminum nitrate, sodium hydroxide, deionized water and isopropanol were added sequentially to a container and stirred at 300 rpm for 3 hours at room temperature to obtain a homogeneous synthesis solution without organic ammonium template agent. The molar ratio of each component in the synthesis solution, based on oxides, was SiO2:Al2O3:M2O:IPA:H2O=1:0.02:0.15:2:50. S3. Place the pre-coated seed carrier vertically into a stainless steel high-pressure reactor containing the synthesis liquid, seal it, and place it in an oven at 160°C for hydrothermal crystallization reaction for 48 hours. S4. After the reaction is complete, the membrane is naturally cooled to room temperature. The membrane is then removed and repeatedly washed with deionized water until the washing solution is neutral. It is then dried overnight in a 100°C oven. Subsequently, it is placed in a muffle furnace and calcined at 500°C for 6 hours in an air atmosphere. After naturally cooling to room temperature, a hydrophilic ZSM-5 zeolite membrane with a silicon-aluminum molar ratio of 25 is obtained.

[0025] Performance testing showed that the membrane prepared in this embodiment exhibited a pervaporation flux of 2.1 kg·m³ in a pervaporation dehydration test of a 10 wt% water-90 wt% ethanol system at 75°C. -2 ·h -1 The separation factor is 5564.

[0026] Optimized Example 2 Except for step S1, where the ZSM-5 seed crystals have a particle size of 1 μm and the porous carrier is a porous stainless steel tube, the rest of the steps in this embodiment are exactly the same as in optimized embodiment 1. The resulting hydrophilic ZSM-5 zeolite membrane has a silicon-to-aluminum molar ratio of 25.

[0027] Performance testing showed that the membrane prepared in this embodiment exhibited a pervaporation flux of 2.3 kg·m³ in a pervaporation dehydration test of a 10 wt% water-90 wt% isopropanol system at 90°C. -2 ·h -1 The separation factor is 4860.

[0028] Optimized Example 3 In this embodiment, except for step S2 where the silicon source is sodium silicate, the aluminum source is sodium aluminate, and the alkali source is potassium hydroxide, the remaining steps are exactly the same as in optimized embodiment 1. The molar ratio of each component in the synthesis solution, calculated as oxides, is SiO2:Al2O3:M2O:IPA:H2O = 1:0.02:0.15:2:50. The resulting hydrophilic ZSM-5 zeolite membrane has a silicon-to-aluminum molar ratio of 25.

[0029] Performance testing showed that the membrane prepared in this embodiment exhibited a pervaporation flux of 3.6 kg·m³ in a pervaporation dehydration test of a 30 wt% water-70 wt% acetone system at 75°C. -2 ·h -1 The separation factor is 7640.

[0030] Optimized Example 4 This embodiment corresponds to the lower limit of the molar ratio. Except for step S2, where the molar ratio of each component in the synthesis solution is SiO2:Al2O3:M2O:IPA:H2O = 1:0.01:0.01:0.1:10 (based on oxides), the remaining steps are exactly the same as in optimized embodiment 1. The resulting hydrophilic ZSM-5 zeolite membrane has a silicon-aluminum molar ratio of 50.

[0031] Performance testing showed that the membrane prepared in this embodiment exhibited a pervaporation flux of 1.9 kg·m³ in a pervaporation dehydration test of a 10 wt% water-90 wt% ethanol system at 75°C. -2 ·h -1 The separation factor is 4217.

[0032] Optimized Example 5 This embodiment corresponds to the upper limit of the molar ratio. Except for step S2, where the molar ratio of each component in the synthesis solution is SiO2:Al2O3:M2O:IPA:H2O = 1:0.1:0.50:5.0:90 (based on oxides), the remaining steps are exactly the same as in optimized embodiment 1. The resulting hydrophilic ZSM-5 zeolite membrane has a silicon-aluminum molar ratio of 5.

[0033] Performance testing showed that the membrane prepared in this embodiment exhibited a pervaporation flux of 2.4 kg·m³ in a pervaporation dehydration test of a 10 wt% water-90 wt% ethanol system at 75°C. -2 ·h -1 The separation factor is 3892.

[0034] Optimized Example 6 In this embodiment, the crystallization condition is at the lower limit. Except for step S3, where the temperature of the hydrothermal crystallization reaction is 100°C and the reaction time is 100h, the other steps are exactly the same as in optimized embodiment 1.

[0035] Performance testing showed that the membrane prepared in this embodiment exhibited a pervaporation flux of 1.7 kg·m³ in a pervaporation dehydration test of a 10 wt% water-90 wt% ethanol system at 75°C. -2 ·h -1 The separation factor is 4526.

[0036] Optimized Example 7 This embodiment corresponds to the upper limit of the crystallization conditions. Except for step S3, where the temperature of the hydrothermal crystallization reaction is 200°C and the reaction time is 10h, the other steps are exactly the same as those in optimized embodiment 1.

[0037] Performance testing showed that the membrane prepared in this embodiment exhibited a pervaporation flux of 1.8 kg·m³ in a pervaporation dehydration test of a 30 wt% water-70 wt% ethanol system at 30°C. -2 ·h -1 The separation factor is 2384.

[0038] Optimized Example 8 This embodiment corresponds to the lower limit of the calcination conditions. Except for step S4, where the calcination temperature is 300°C, the calcination time is 100h, and the calcination atmosphere is pure oxygen, the other steps are exactly the same as those in optimized embodiment 1.

[0039] Performance testing showed that the membrane prepared in this embodiment exhibited a pervaporation flux of 2.0 kg·m³ in a pervaporation dehydration test of a 10 wt% water-90 wt% ethanol system at 75°C. -2 ·h -1 The separation factor is 5108.

[0040] Optimized Example 9 This embodiment corresponds to the upper limit of the calcination conditions. Except for step S4, where the calcination temperature is 600℃, the calcination time is 5h, and the calcination atmosphere is a diluted oxygen atmosphere with a volume fraction of 5% oxygen-nitrogen mixture, the other steps are exactly the same as in optimized embodiment 1.

[0041] Performance testing showed that the membrane prepared in this embodiment exhibited a pervaporation flux of 2.2 kg·m³ in a pervaporation dehydration test of a 10 wt% water-90 wt% ethanol system at 75°C. -2 ·h -1 The separation factor is 5327.

[0042] Preferred Implementation This embodiment represents the optimal overall performance implementation, and the specific steps are as follows: S1. A porous α-alumina ceramic tube with an outer diameter of 12 mm and an average pore size of 0.2 μm is selected as a porous carrier. It is immersed in 1 wt% ZSM-5 seed suspension (seed particle size is 100 nm) for 30 s. After removal, the excess suspension on the surface is blown off with clean nitrogen gas and air-dried at room temperature. The immersion operation is repeated 3 times to ensure that a uniform and continuous seed layer is formed on the surface of the carrier, thus obtaining a carrier with pre-coated seeds. S2. Colloidal silica, aluminum nitrate, sodium hydroxide, deionized water and isopropanol were added sequentially to a container and stirred at 300 rpm for 3 hours at room temperature to obtain a uniform and transparent synthetic solution without organic ammonium template agent. The molar ratio of each component in the synthetic solution, in oxide form, was SiO2:Al2O3:M2O:IPA:H2O=1:0.03:0.15:3:40. S3. Place the carrier with pre-coated seed crystals vertically into a stainless steel high-pressure reactor lined with polytetrafluoroethylene containing the synthesis liquid. After sealing, place it in a programmable oven, heat it to 160°C and keep it at that temperature for 48 hours for hydrothermal crystallization. S4. After the reaction is complete, close the oven and allow the reactor to cool naturally to room temperature. Remove the membrane and wash it repeatedly with deionized water until the pH of the washing solution is neutral. Place it in a 100°C forced-air drying oven and dry for 12 hours. Then place it in a muffle furnace and heat it to 500°C at a rate of 2°C / min in air atmosphere. Hold it at that temperature for 6 hours and then cool it to room temperature at a rate of 2°C / min to obtain a hydrophilic ZSM-5 zeolite membrane with a silicon-aluminum molar ratio of 16.7.

[0043] Performance testing showed that the membrane prepared in this embodiment exhibited a pervaporation flux of 2.5 kg·m³ in a pervaporation dehydration test of a 10 wt% water-90 wt% isopropanol system at 75°C. -2 ·h -1 With a separation factor of 8725, its overall separation performance reaches the industry-leading level.

[0044] Comparative Example This comparative example is an implementation scheme of the existing template-free technology. Except for the fact that isopropanol is not added to the synthesis solution in step S2, the other steps are exactly the same as those in optimized example 1.

[0045] Performance testing showed that the membrane prepared in this comparative example exhibited severe leakage and no effective separation performance in the pervaporation dehydration test of a 10wt% water-90wt% ethanol system at 75℃. This demonstrates that the addition of isopropanol is the core key to achieving the preparation of high-performance dense zeolite membranes in a template-free system.

[0046] Application Examples This application example uses the hydrophilic ZSM-5 zeolite membrane prepared in the optimal embodiment, and performs pervaporation dehydration tests in different organic solvent systems. The test results are as follows: The permeation flux of a 5wt% water-95wt% ethanol system at 75℃ is 1.8 kg·m³. -2 ·h -1 Separation factor 9852; The osmotic flux of a 10wt% water-90wt% isopropanol system at 90℃ is 3.2 kg·m³. -2 ·h -1 Separation factor 7631; 20wt% water-80wt% acetone system at 50℃: osmotic flux 2.9 kg·m -2 ·h -1 Separation factor 6528.

[0047] Test results demonstrate that the hydrophilic ZSM-5 zeolite membrane prepared by this invention exhibits excellent pervaporation dehydration performance in various organic solvent systems, over a wide temperature range, and within a wide water content range, thus meeting the organic solvent dehydration requirements of different industrial scenarios.

[0048] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A green preparation method for a hydrophilic ZSM-5 zeolite membrane, characterized in that, Includes the following steps: S1. Pre-coat ZSM-5 seed crystals onto the surface of the porous carrier; S2. Mix the silicon source, aluminum source, alkali source, deionized water and isopropanol, and stir to obtain a uniform synthesis solution without organic ammonium template agent; S3. Place the porous carrier with pre-coated seed crystals in the synthesis solution to carry out a hydrothermal crystallization reaction; S4. After the reaction is complete, the membrane is removed, washed with deionized water until neutral, and then dried and calcined to obtain the hydrophilic ZSM-5 zeolite membrane.

2. The green preparation method of the hydrophilic ZSM-5 zeolite membrane according to claim 1, characterized in that, In step S1, the ZSM-5 seed crystals have a particle size of 10 nm to 1 μm; the porous support is any one of porous alumina support, porous silicon carbide support, or porous stainless steel support.

3. The green preparation method of the hydrophilic ZSM-5 zeolite membrane according to claim 1, characterized in that, In step S2, the silicon source is one or more of sodium silicate, colloidal silica, and tetraethyl orthosilicate; the aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum hydroxide, and aluminum isopropoxide; and the alkali source is one or more of lithium hydroxide, sodium hydroxide, and potassium hydroxide.

4. The green preparation method of the hydrophilic ZSM-5 zeolite membrane according to claim 1, characterized in that, In step S2, the silicon source, aluminum source, and alkali source in the synthesis solution are all in oxide form, and the molar ratio of each component is SiO2:Al2O3:M2O:IPA:H2O=1:(0.01~0.1):(0.01~0.50):(0.1~5.0):(10~90); where M is the alkali metal element in the alkali source, and IPA is isopropanol.

5. The green preparation method of the hydrophilic ZSM-5 zeolite membrane according to claim 1, characterized in that, In step S3, the temperature of the hydrothermal crystallization reaction is 100℃~200℃, and the reaction time is 10h~100h.

6. The green preparation method of the hydrophilic ZSM-5 zeolite membrane according to claim 1, characterized in that, In step S4, the calcination temperature is 300℃~600℃, and the calcination time is 5h~100h.

7. The green preparation method of the hydrophilic ZSM-5 zeolite membrane according to claim 6, characterized in that, In step S4, the calcination atmosphere is any one of pure oxygen atmosphere, air atmosphere, or diluted oxygen atmosphere.

8. The green preparation method of the hydrophilic ZSM-5 zeolite membrane according to claim 1, characterized in that, The resulting hydrophilic ZSM-5 zeolite membrane has a silicon-to-aluminum molar ratio of 5 to 50.

9. An application of a hydrophilic ZSM-5 zeolite membrane, characterized in that, The hydrophilic ZSM-5 zeolite membrane prepared by the green preparation method of the hydrophilic ZSM-5 zeolite membrane according to any one of claims 1 to 8 is used for pervaporation dehydration of organic solvent systems.

10. The application of the hydrophilic ZSM-5 zeolite membrane according to claim 9, characterized in that, The organic solvent system is any one of ethanol-water system, isopropanol-water system, and acetone-water system; the pervaporation dehydration operation temperature is 30℃~90℃, and the water mass fraction of the organic solvent system is 1%~30%.