Preparation method of TA-modified aminated ZIF-90 polyamide reverse osmosis membrane

Abstract

The invention discloses a preparation method of a TA modified aminated ZIF-90 polyamide reverse osmosis membrane, which comprises the following steps: by taking a self-made polysulfone membrane as a base membrane, firstly soaking the base membrane in a water phase solution, then soaking the base membrane in an oil phase solution containing aminated ZIF-90, then treating the base membrane with a tannic acid (TA) / ethanol solution, and finally performing heat treatment to obtain the target polyamide reverse osmosis membrane. Aminated ZIF-90 is used for modifying a polyamide membrane, then TA is used for modifying a surface layer, and compared with an original membrane, the prepared membrane material is effectively improved in water flux and salt interception; after chlorine treatment, the attenuation rate of water flux and salt interception is smaller than that of the original membrane, which indicates that the chlorine resistance of the modified polyamide membrane is superior to that of the original membrane; meanwhile, the modified polyamide membrane has excellent anti-pollution performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of reverse osmosis, and particularly relates to a preparation method of a TA-modified amino-functionalized ZIF-90 polyamide reverse osmosis membrane. Background Art

[0002] In recent years, due to people's higher requirements for living standards, they pay more attention to the quality of drinking water. However, most of the water resources on the earth are seawater resources. Therefore, it is necessary to remove most of the ions in seawater and convert them into fresh water. The reverse osmosis membrane technology, as one of the most effective desalination methods, is widely used in the fields of seawater desalination, ultrapure water production, and industrial wastewater treatment and reuse. Its principle is: under the action of a pressure higher than the osmotic pressure of the solution, with the help of the selective retention of a semi-permeable membrane that only allows water to pass through and does not allow other substances to pass through, the solute and solvent in the solution are separated.

[0003] Polyamide has good stability and hydrophilicity, so it is often used to prepare the surface active layer of composite membranes. Compared with nanofiltration membranes, reverse osmosis membranes are required to work under high-pressure conditions. Therefore, commercially available reverse osmosis membranes mostly use aromatic polyamides with high cross-linking degrees. However, due to their high cross-linking degrees, the prepared reverse osmosis membranes show good selectivity but poor water flux.

[0004] Metal-organic frameworks (MOFs) are inorganic nanoparticles with regular pore structures developed in recent years and show great application prospects in membrane separation. The most successful example of the application of MOF in water treatment is the preparation of polyamide thin-film composite nanofilms (TFNs). By adding MOF inorganic nanoparticles to the polyamide layer, the synergistic optimization of flux and retention can be achieved. Zeolitic imidazolate frameworks (ZIFs) belong to a class of MOFs. ZIF-90 is a relatively novel porous material with complex and diverse nanopores; and it has a high porosity, a large specific surface area, and good chemical stability. These excellent properties enable it to effectively improve the water flux of reverse osmosis membranes. However, there is an agglomeration phenomenon of ZIF-90 after in-situ polymerization. Therefore, it is considered to use ethylenediamine to replace the aldehyde groups on ZIF-90 with amino groups to reduce the agglomeration phenomenon.

[0005] During the long-term water treatment process, reverse osmosis membranes are extremely vulnerable to various threats of pollution, mainly biological pollution. Therefore, using TA (tannic acid) to modify TFN membranes can increase the service life of the membranes and improve their chlorine resistance. Summary of the Invention

[0006] Aiming at the deficiencies existing in the prior art, the present invention provides a preparation method of a TA-modified amino-functionalized ZIF-90 polyamide reverse osmosis membrane.

[0007] The technical solution of the present invention is as follows:

[0008] A preparation method of a TA-modified amino-functionalized ZIF-90 polyamide reverse osmosis membrane, comprising the following steps:

[0009] (1) Wash the polysulfone resin (PSF) with pure water, dry it (80 °C, 24 h), and then dissolve it in N,N-dimethylacetamide (DMAc). Stir, sonicate, and let it stand for degassing to obtain a casting solution. Cast the casting solution on a clean and dry glass plate, scrape the film with a doctor blade, and then immerse it in deionized water for phase inversion to form a membrane, obtaining an ultrafiltration membrane support layer (stored in deionized water for later use);

[0010] Preferably, the mass fraction of the polysulfone resin in the casting solution is 15% - 20%;

[0011] Preferably, adjust the doctor blade to a thickness of 300 μm and scrape the film at a constant speed;

[0012] (2) Add the zinc nitrate solution to the imidazole-2-carbaldehyde solution, stir at 30 °C for 4 h, then add methanol, stir and let it stand, and then wash and dry by centrifugation with methanol to obtain ZIF-90;

[0013] The zinc nitrate solution is obtained by mixing zinc nitrate hexahydrate and N,N-dimethylacetamide. Preferably, the mass fraction of the zinc nitrate solution is 2% - 4%;

[0014] The imidazole-2-carbaldehyde solution is obtained by dissolving imidazole-2-carbaldehyde in N,N-dimethylacetamide. Preferably, the mass fraction of the imidazole-2-carbaldehyde solution is 7% - 10%;

[0015] (3) Dissolve the ZIF-90 obtained in step (2) in methanol, and then add the methanol solution of ZIF-90 to the methanol solution of ethylenediamine. Stir at 60 °C for 24 h, and then wash and dry by centrifugation with methanol and vacuum dry to obtain amino-functionalized ZIF-90;

[0016] Preferably, the ratio of ZIF-90 to ethylenediamine is 0.01 - 0.08 g: 0.1 - 0.5 mmol;

[0017] (4) Immerse the ultrafiltration membrane support layer obtained in step (1) in the aqueous solution, and then take it out to remove the excess aqueous solution on the surface;

[0018] The aqueous solution is composed of an aqueous monomer, (±)-camphor-10-sulfonic acid (CSA), triethylamine (TEA), and water; wherein, the mass fraction of the aqueous monomer is 2% - 4%, the mass fraction of (±)-camphor-10-sulfonic acid is 2% - 3%, and the mass fraction of triethylamine is 1% - 1.5%;

[0019] The aqueous monomer is selected from one or more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, and hexamethylenediamine;

[0020] Preferably, the soaking time of the ultrafiltration membrane support layer in the aqueous solution is 3 to 8 min;

[0021] (5) Immerse the membrane material treated in step (4) into the oil-phase solution containing the amidated ZIF-90 obtained in step (3) for interfacial polymerization, and then take it out to remove the excess oil-phase solution on the surface to obtain a mixed matrix membrane doped with amidated ZIF-90 nanoparticles;

[0022] The oil-phase solution consists of aromatic polyacyl chloride, amidated ZIF-90, and an organic solvent; wherein, the mass fraction of the aromatic polyacyl chloride is 0.1 to 0.3%, and the mass fraction of the amidated ZIF-90 is 0.1 to 0.5%;

[0023] The aromatic polyacyl chloride is selected from one or more of trimesoyl chloride, terephthaloyl chloride, and isophthaloyl chloride;

[0024] The organic solvent is selected from one or more of n-hexane, cyclohexane, n-heptane, and Isopar L isoparaffin;

[0025] Preferably, the soaking time of the membrane material in the oil-phase solution is 2 to 5 min;

[0026] (6) Immerse the membrane material obtained in step (5) in a tannic acid / ethanol solution, then take it out, perform heat treatment, and then wash it with hot water to obtain the TA-modified amidated ZIF-90 polyamide reverse osmosis membrane;

[0027] Preferably, in the tannic acid / ethanol solution, the mass fraction of tannic acid is 0.2 to 0.5%;

[0028] Preferably, the soaking time of the membrane material in the tannic acid / ethanol solution is 1 to 5 min;

[0029] Preferably, the temperature of the heat treatment is 50 to 80 °C, and the time is 10 to 30 min;

[0030] Preferably, the temperature of the hot water washing is 60 to 90 °C, and the time is 1 to 10 min.

[0031] Compared with the prior art, the advantages of the present invention are as follows:

[0032] The present invention prepares a polyamide membrane with good anti-fouling property and excellent chlorine resistance. The TA-modified amidated ZIF-90 polyamide membrane prepared by the present invention can use TA as a sacrificial layer to protect the polyamide layer well to ensure normal interception. The pure polyamide layer has good interception effect, but poor water flux. Therefore, ZIF-90 is used to increase the water flux, and amidation is used to ensure that the ZIF-90 nanoparticles do not undergo agglomeration reaction.

[0033] Meanwhile, when the pure polyamide membrane is contaminated by organisms, treating it with chlorine-containing disinfectants will affect the original membrane. Through the improvement of the present invention, the impact of chlorine on the membrane material can be reduced, the service life of the membrane can be extended, and while maintaining long-term membrane retention, the membrane flux can be increased as much as possible. Description of the Drawings

[0034] Figure 1 : Anti-pollution performance of the polyamide membrane after adding BSA solution. Detailed Embodiments

[0035] The following will elaborate on the implementation of the present invention in detail in combination with specific embodiments. However, those skilled in the art should understand that the following embodiments are only intended to illustrate the present invention and should not be regarded as limiting the scope of the present invention. For those conditions not specified in the embodiments, they shall be carried out according to the conventional conditions or the conditions recommended by the manufacturer. For the reagents or instruments whose manufacturers are not indicated, they are all conventional products that can be purchased through the market.

[0036] Water flux and retention tests of the TFN membrane:

[0037] The water flux (F) is defined as: under a certain operating pressure, the volume of water passing through a unit membrane area per unit time, with the unit of L / m 2 / h;

[0038] The salt rejection rate (R) is defined as: under certain operating conditions, the difference between the salt concentration (C f ) in the feed liquid and the salt concentration (C p ) in the permeate, and then divided by the salt concentration in the feed liquid, that is, R = (1 - C C pf) × 100%.

[0039] Anti-pollution test:

[0040] Using bovine serum albumin (BSA) as a model substance, simulate the impact of protein contaminants in raw water on membrane fouling after long-term use. Study the impact of the anti-pollution performance of the polyamide composite membrane. By adjusting the pressure, the initial fluxes of all test membranes are controlled at the same value. The membrane is first pre-pressed with pure water. After pre-pressing for a period of time, the BSA solution is used as the contaminant to replace the pure water. After circulating for a period of time, deionized water is used for flux detection. From the start to the end of the anti-pollution experiment, calculate and measure the real-time water flux of the membrane, and evaluate the anti-pollution performance of the membrane with the relative flux ratio (FR) and flux recovery rate (FRR) as parameters.

[0041] Relative flux ratio (FR) of the membrane material: Jt —— the water flux of the membrane sheet at t h of operation; J0 —— the initial flux of the membrane sheet.

[0042] Flux recovery rate (FRR): Jc——Water flux through the membrane after being washed with pure water; J0——Initial flux of the membrane.

[0043] Chlorine resistance performance test: To explore the chlorine resistance performance of TA@A-ZIF-90 / polyamide reverse osmosis membrane, the membrane flux and rejection performance after being immersed in sodium hypochlorite solutions with different concentrations were measured. The general process was as follows: Immerse the membrane in the sodium hypochlorite solution with a concentration of 8000 ppm. After soaking for 1 h, wash it with pure water multiple times, then measure the salt rejection of the membrane with 10000 ppm high-salt water and compare it with the rejection of the original membrane, and measure the water flux of the membrane with pure water for comparison.

[0044] Examples 1-5:

[0045] Preparation of a TA-modified amino-functionalized ZIF-90 polyamide reverse osmosis membrane:

[0046] Wash the polysulfone resin (PSF) with pure water 3-4 times and place it in an oven at 80 °C for drying for 24 h; dissolve the dried polysulfone resin in N,N-dimethylacetamide (DMAc) to prepare a 18 wt% casting solution, stir for 12 h, ultrasonicate for 10 min, and let it stand for degassing for 12 h; then pour the casting solution onto a clean and dry glass plate, adjust the thickness of the blade to 300 μm, and scrape it evenly to form a film. After evaporation for 1 min, place the glass plate in deionized water for immersion phase inversion to form a membrane; immerse the prepared membrane in deionized water to ensure sufficient exchange of the solvent and non-solvent in the membrane, and store it for 24 hours for later use.

[0047] Dissolve 1.92 g of imidazole-2-carboxaldehyde in 25 mL of N,N-dimethylacetamide, heat and dissolve it at 80 °C, cool it to room temperature, then add a 25 mL N,N-dimethylacetamide mixed solution containing 0.59 g of zinc nitrate hexahydrate, stir at 30 °C for 4 h, then add 5 mL of methanol and stir for 5 min, let it stand for 30 min, and wash and centrifuge it with methanol 5 times and dry it.

[0048] Take 0.05 g of ZIF-90 and dissolve it in 15 mL of methanol, dissolve it in a 10 mL methanol solution containing 0.012 g of ethylenediamine, heat and stir at 60 °C for 24 h, then wash and centrifuge it with methanol 3 times, and store it in vacuum drying at 60 °C.

[0049] Immerse the ultrafiltration membrane in 2 wt% m-phenylenediamine, 2.6 wt% CSA, and 1.1 wt% TEA for 5 min. After taking it out, remove the excess aqueous solution on the surface of the ultrafiltration membrane and let it dry.

[0050] Then immerse the ultrafiltration membrane in a hexane solution containing 0.1 wt% of trimesoyl chloride and the amino-functionalized ZIF-90 in the ratio shown in Table 1 for reaction for 5 min, and then remove the excess oil-phase solution on the surface of the ultrafiltration membrane.

[0051] After the reaction, the polyamide membrane was immersed in a 0.4 wt.% TA / ethanol solution for 2 min and then taken out.

[0052] The membrane was then placed in an oven at 60 °C for 10 min, taken out, and after cooling to room temperature, stored in pure water.

[0053] The obtained membrane was analyzed and tested:

[0054] The prepared reverse osmosis membrane was installed in a membrane performance test device. Experimental conditions: 25 °C, 1.5 MPa, pre-pressurized for 0.5 h, 10000 ppm NaCl salt solution.

[0055] Table 1

[0056]

[0057]

[0058] Examples 6 - 9:

[0059] Preparation of a TA-modified amino-functionalized ZIF-90 polyamide reverse osmosis membrane:

[0060] The polysulfone resin (PSF) was washed 3 - 4 times with pure water and placed in an oven at 80 °C for drying for 24 h; the dried polysulfone resin was dissolved in N,N-dimethylacetamide (DMAc) to prepare an 18 wt% casting solution, stirred for 12 h, sonicated for 10 min, and left to stand for defoaming for 12 h; then the casting solution was cast on a clean and dry glass plate, the blade was adjusted to a thickness of 300 μm, and it was evenly scraped to form a film. After evaporation for 1 min, the glass plate was placed in deionized water for immersion phase inversion to form a membrane; the prepared membrane was immersed in deionized water to ensure sufficient exchange of the solvent and non-solvent inside the membrane and stored for 24 h for use.

[0061] 1.92 g of imidazole-2-carbaldehyde was dissolved in 25 mL of N,N-dimethylacetamide, heated and dissolved at 80 °C, cooled to room temperature, and then a 25 mL mixed solution of 0.59 g of zinc nitrate hexahydrate in N,N-dimethylacetamide was added. It was stirred at 30 °C for 4 h, then 5 mL of methanol was added and stirred for 5 min, left to stand for 30 min, and centrifugally washed 5 times with methanol and dried.

[0062] 0.05 g of ZIF-90 was dissolved in 15 mL of methanol, dissolved in a 10 mL methanol solution of 0.012 g of ethylenediamine, heated and stirred at 60 °C for 24 h, then washed and centrifuged 3 times with methanol, and vacuum dried and stored at 60 °C.

[0063] The ultrafiltration membrane was immersed in 2 wt% m-phenylenediamine, 2.6 wt% CSA, and 1.1 wt% TEA for 5 min. After taking it out, the excess aqueous solution on the surface of the ultrafiltration membrane was removed and air-dried.

[0064] Afterwards, the ultrafiltration membrane was immersed in a n-hexane solution containing 0.1 wt% of trimesoyl chloride and 0.15 wt% of amino-functionalized ZIF-90 for reaction for 5 min, and then the excess oil-phase solution on the surface of the ultrafiltration membrane was removed.

[0065] The membrane was immersed in TA / ethanol in the ratio shown in Table 2 for 1 min, then placed in an oven at 60 °C for reaction for 10 min, taken out, and after cooling to room temperature, stored in pure water.

[0066] The obtained membrane was analyzed and tested:

[0067] The prepared reverse osmosis membrane was installed in a membrane performance testing device, and the experimental conditions were: 25 °C, 1.5 MPa, pre-pressurized for 0.5 h, 10000 ppm NaCl salt solution.

[0068] Table 2

[0069]

[0070] Comparative Example 1:

[0071] Preparation of an amino-functionalized ZIF-90 polyamide reverse osmosis membrane:

[0072] The polysulfone resin (PSF) was washed 3 - 4 times with pure water and placed in an oven at 80 °C for drying for 24 h; the dried polysulfone resin was dissolved in N,N-dimethylacetamide (DMAc) to prepare an 18 wt% casting solution, stirred for 12 h, sonicated for 10 min, and left to stand for degassing for 12 h; then the casting solution was cast on a clean and dry glass plate, the blade was adjusted to a thickness of 300 μm, and it was evenly scraped to form a film. After evaporation for 1 min, the glass plate was placed in deionized water for immersion phase inversion to form a membrane; the obtained membrane was immersed in a large amount of deionized water to ensure sufficient exchange of the solvent and non-solvent inside the membrane, and stored for 24 h for use.

[0073] 1.92 g of imidazole-2-carboxaldehyde was dissolved in 25 mL of N,N-dimethylacetamide, heated and dissolved at 80 °C, cooled to room temperature, and then a 25 mL N,N-dimethylacetamide mixed solution containing 0.59 g of zinc nitrate hexahydrate was added, stirred at 30 °C for 4 h, then 5 mL of methanol was added and stirred for 5 min, left to stand for 30 min, and centrifugally washed 5 times with methanol and dried.

[0074] 0.05 g of ZIF-90 was dissolved in 15 mL of methanol, dissolved in a 10 mL methanol solution containing 0.012 g of ethylenediamine, heated and stirred at 60 °C for 24 h, then washed and centrifuged 3 times with methanol, and vacuum dried and stored at 60 °C.

[0075] Immerse the ultrafiltration membrane in a solution containing 2 wt% m-phenylenediamine, 2.6 wt% CSA, and 1.1 wt% TEA for 5 minutes. After taking it out, remove the excess aqueous solution on the surface of the ultrafiltration membrane and let it dry.

[0076] Then immerse the ultrafiltration membrane in a hexane solution containing 0.1 wt% trimesoyl chloride and 0.15 wt% aminated ZIF-90 for reaction for 5 minutes, and then remove the excess oil-phase solution on the surface of the ultrafiltration membrane.

[0077] Place the membrane in an oven at 60 °C for reaction for 10 minutes, take it out, and after cooling to room temperature, store it in pure water.

[0078] Analyze and test the membrane obtained in Comparative Example 1:

[0079] Install the reverse osmosis membrane prepared in this example into a membrane performance test device. Experimental conditions: 25 °C, 1.5 MPa, pre-pressurize for 0.5 h, 10000 ppm NaCl salt solution.

[0080] Comparative Example 2:

[0081] Preparation of a polyamide reverse osmosis membrane:

[0082] Wash the polysulfone resin (PSF) with pure water 3 - 4 times, and place it in an oven at 80 °C to dry for 24 h; take the dried polysulfone resin and dissolve it in N,N-dimethylacetamide (DMAc) to prepare an 18 wt% casting solution, stir for 12 h, ultrasonicate for 10 min, and let it stand for degassing for 12 h; then pour the casting solution onto a clean and dry glass plate, adjust the thickness of the blade to 300 μm, and scrape it evenly to form a film. After evaporation for 1 min, place the glass plate in deionized water for immersion phase inversion to form a film; immerse the prepared film in a large amount of deionized water to ensure sufficient exchange of the solvent and non-solvent inside the film, and store it for 24 hours for use.

[0083] Immerse the ultrafiltration membrane in a solution containing 2 wt% m-phenylenediamine, 2.6 wt% CSA, and 1.1 wt% TEA for 5 minutes. After taking it out, remove the excess aqueous solution on the surface of the ultrafiltration membrane and let it dry.

[0084] Then immerse the ultrafiltration membrane in a hexane solution containing 0.1 wt% trimesoyl chloride for reaction for 5 minutes, and then remove the excess oil-phase solution on the surface of the ultrafiltration membrane.

[0085] Place the membrane in an oven at 60 °C for reaction for 10 minutes, take it out, and after cooling to room temperature, store it in pure water.

[0086] Analyze and test the membrane obtained in Comparative Example 2:

[0087] The reverse osmosis membrane prepared in this example was installed in a membrane performance testing device. Experimental conditions: 25°C, 1.5 MPa, pre-pressurized for 0.5 h, 10,000 ppm NaCl salt solution.

[0088] Performance test results:

[0089] Table 3 Initial fluxes and salt rejection rates of polyamide reverse osmosis membranes prepared in examples and comparative examples

[0090]

[0091] Table 4 Surface chlorine resistance performance data of polyamide reverse osmosis membranes prepared in examples and comparative examples

[0092]

[0093] Taking into comprehensive consideration the water flux, salt rejection rate, and performance after chlorination of the membrane, the conditions of the membrane selected in Example 3 are particularly preferred implementation conditions, and both the water flux and salt rejection are at a relatively high level. After comparing the chlorination performance, it was found that the concentration of TA / ethanol selected should be near that of Example 7 for better performance. The above results indicate that the introduction of amino-functionalized ZIF-90 and surface TA modification to the polyamide composite reverse osmosis membrane significantly improves the water flux, rejection rate, and chlorine resistance of the membrane.

[0094] The reverse osmosis membrane prepared in Example 3 was installed in a membrane performance testing device. Experimental conditions: 25°C, 1.5 MPa, pre-pressurized for 0.5 h, 10,000 ppm NaCl salt solution, 150 ppm BSA solution.

[0095] As Figure 1 shown, the water flux measured during BSA fouling was from 0 to 240 min, and the water flux measured after cleaning with pure water was from 240 to 300 min. The flux ratio of the TA@A-ZIF-90 membrane remained at 85% after being fouled by the BSA solution, and the flux recovery rate after cleaning with pure water was 94%, both of which were much higher than those of the A-ZIF-90 membrane and the TFC membrane. This shows that the modified membrane has excellent anti-fouling performance.

Claims

1. A method for preparing a TA-modified amino ZIF-90 polyamide reverse osmosis membrane, characterized in that: The steps include: (1) washing a polysulfone resin with pure water, drying it, dissolving it in N,N-dimethylacetamide, stirring, ultrasonicating, and standing to degas, to obtain a casting solution; casting the casting solution on a clean and dry glass plate, scraping the film with a scraper, and then immersing it in deionized water to perform phase conversion to form a film, thereby obtaining an ultrafiltration membrane support layer; (2) adding zinc nitrate solution to imidazole-2-carboxaldehyde solution, stirring at 30° C. for 4 h, then adding methanol, stirring, standing, then centrifuging and washing with methanol, and drying to obtain ZIF-90; The zinc nitrate solution is prepared by mixing zinc nitrate hexahydrate and N,N-dimethylacetamide; Imidazole-2-carboxaldehyde solution is obtained by dissolving imidazole-2-carboxaldehyde in N,N-dimethylacetamide; (3) dissolving the ZIF-90 obtained in step (2) in methanol, then adding the methanol solution of ZIF-90 to the methanol solution of ethylenediamine, stirring at 60° C. for 24 h, then centrifuging and washing with methanol, and vacuum drying to obtain amino ZIF-90; (4) immersing the ultrafiltration membrane support layer obtained in step (1) into an aqueous solution, and then removing excess aqueous solution from the surface; The aqueous phase solution is composed of aqueous phase monomer, (±)-camphor-10-sulfonic acid, triethylamine and water; The aqueous phase monomer is selected from one or more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine and hexamethylenediamine; (5) immersing the membrane material treated in step (4) into an oil phase solution containing the amino ZIF-90 obtained in step (3) to perform interfacial polymerization, and then removing excess oil phase solution on the surface to obtain a mixed matrix membrane doped with amino ZIF-90 nanoparticles; The oil phase solution is composed of aromatic polyacyl chloride, amino ZIF-90 and organic solvent; The aromatic polyacyl chloride is selected from one or more of trimesoyl chloride, terephthaloyl chloride and isophthaloyl chloride; The organic solvent is selected from one or more of n-hexane, cyclohexane, n-heptane, and Isopar L isoparaffin; (6) soaking the membrane material obtained in step (5) in a tannic acid / ethanol solution, then taking it out, heat treating it, and then washing it with hot water to obtain the TA-modified amino ZIF-90 polyamide reverse osmosis membrane; The heat treatment temperature is 50-80°C and the time is 10-30 minutes.

2. The method for preparing the TA-modified amino ZIF-90 polyamide reverse osmosis membrane according to claim 1, characterized in that: The mass fraction of the polysulfone resin in the casting solution of step (1) is 15% to 20%.

3. The method for preparing the TA-modified amino ZIF-90 polyamide reverse osmosis membrane according to claim 1, characterized in that: In step (1), the scraper is adjusted to a thickness of 300 μm and the film is scraped at a constant speed.

4. The method for preparing the TA-modified amino ZIF-90 polyamide reverse osmosis membrane according to claim 1, characterized in that: In step (2), the mass fraction of the zinc nitrate solution is 2-4%, and the mass fraction of the imidazole-2-carboxaldehyde solution is 7-10%.

5. The method for preparing the TA-modified amino ZIF-90 polyamide reverse osmosis membrane according to claim 1, characterized in that: In step (3), the ratio of ZIF-90 to ethylenediamine is 0.01-0.08 g: 0.1-0.5 mmol.

6. The method for preparing the TA-modified amino ZIF-90 polyamide reverse osmosis membrane according to claim 1, characterized in that: In the aqueous phase solution of step (4), the mass fraction of aqueous phase monomer is 2-4%, the mass fraction of (±)-camphor-10-sulfonic acid is 2-3%, and the mass fraction of triethylamine is 1-1.5%.

7. The method for preparing the TA-modified amino ZIF-90 polyamide reverse osmosis membrane according to claim 1, characterized in that: In step (4), the ultrafiltration membrane support layer is immersed in the aqueous solution for 3 to 8 minutes.

8. The method for preparing the TA-modified amino ZIF-90 polyamide reverse osmosis membrane according to claim 1, characterized in that: In the oil phase solution of step (5), the mass fraction of the aromatic polyacyl chloride is 0.1-0.3%, and the mass fraction of the amino ZIF-90 is 0.1-0.5%.

9. The method for preparing the TA-modified amino ZIF-90 polyamide reverse osmosis membrane according to claim 1, characterized in that: In step (5), the membrane material is immersed in the oil phase solution for 2 to 5 minutes.

10. The method for preparing the TA-modified amino ZIF-90 polyamide reverse osmosis membrane according to claim 1, characterized in that: In step (6), the mass fraction of tannic acid in the tannic acid / ethanol solution is 0.2 to 0.5%; and the immersion time of the membrane material in the tannic acid / ethanol solution is 1 to 5 minutes.

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