Chlorine-resistant reverse osmosis membrane as well as synthesis method and application thereof

Abstract

The invention belongs to the technical field of membrane separation, and particularly relates to a chlorine-resistant reverse osmosis membrane as well as a synthesis method and application thereof. The chlorine-resistant reverse osmosis membrane provided by the invention comprises a supporting bottom membrane and a polyamide catalytic active layer compounded on the surface of one side of the supporting bottom membrane, the polyamide catalytic active layer is formed by carrying out interfacial polymerization reaction on a water phase solution and an oil phase solution and then carrying out active chlorine catalytic decomposition and active molecule modification; the water-phase solution contains amine monomers, and the oil-phase solution contains acyl chloride monomers. Molecules with active chlorine catalytic decomposition activity are fixed on the polyamide separation membrane, so that the separation membrane is endowed with the capability of directly decomposing active chlorine, and the chlorine resistance of the membrane material can be effectively improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of membrane separation, and in particular relates to a chlorine-resistant reverse osmosis membrane, a synthesis method thereof, and applications thereof. Background Art

[0002] Reverse osmosis membranes are a highly efficient separation technology widely used in seawater desalination, municipal water supply, industrial pure water production, wastewater treatment, and food and pharmaceutical industries. The operating principle of reverse osmosis membranes is based on the phenomenon of osmosis and the effects of applied pressure, achieving efficient separation of water and salt through a semipermeable membrane. Reverse osmosis involves applying an external pressure greater than the osmotic pressure of the solution, causing water molecules to reversely permeate the reverse osmosis membrane, flowing from the side with high solute concentration to the side with low solute concentration, thereby separating water from salt. In seawater desalination, reverse osmosis membranes can effectively remove salt and impurities from seawater, providing drinkable fresh water for coastal and arid areas. Furthermore, reverse osmosis membranes are widely used in deep tap water treatment, removing heavy metals, bacteria, viruses, and organic contaminants, thereby improving drinking water quality. Industrially, reverse osmosis membranes are widely used in the electronics, pharmaceutical, chemical, and power industries to provide ultrapure water to meet production needs.

[0003] However, in many water treatment applications, especially seawater desalination and municipal water treatment, reverse osmosis membranes face challenges from oxidants such as active chlorine. Seawater desalination and municipal water treatment often use chlorine or sodium hypochlorite for disinfection to kill bacteria and microorganisms, but traditional reverse osmosis membrane materials (such as polyamide) are extremely sensitive to chlorine and are easily oxidized and degraded by it, resulting in decreased membrane performance or even failure. Therefore, the development of chlorine-resistant reverse osmosis membranes has become one of the key directions of current research. The development of chlorine-resistant reverse osmosis membranes mainly focuses on improving the oxidation resistance of membrane materials, such as through chemical modification, surface coating or introduction of antioxidant groups to enhance the durability of the membrane. In addition, the improved stability of chlorine-resistant membranes can reduce the dependence on the dechlorination step in the pretreatment process, simplify the system process, reduce operating costs, and improve the overall water treatment efficiency. Therefore, the development of high-performance chlorine-resistant reverse osmosis membranes is of great significance for improving the stability of water treatment systems, extending membrane life and reducing operating costs. Summary of the Invention

[0004] In view of this, the object of the present invention is to provide a chlorine-resistant reverse osmosis membrane and its synthesis method and application. The chlorine-resistant reverse osmosis membrane provided by the present invention can withstand treatment with a certain concentration of active chlorine without a decrease in desalination performance.

[0005] The present invention provides a chlorine-resistant reverse osmosis membrane, comprising: a supporting base membrane, and a polyamide catalytic active layer composited on a single-side surface of the supporting base membrane; the polyamide catalytic active layer is formed by subjecting an aqueous solution and an oily solution to an interfacial polymerization reaction, followed by modification of active molecules by catalytic decomposition of active chlorine; the aqueous solution contains amine monomers, and the oily solution contains acyl chloride monomers.

[0006] Preferably, the amine monomer is one or more of m-phenylenediamine, piperazine, p-phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine and ethylenediamine.

[0007] Preferably, the acyl chloride monomer is one or more of trimesoyl chloride, terephthaloyl chloride and phthaloyl chloride.

[0008] Preferably, the active molecule catalyzed by active chlorine is one or more of vitamin B12, vitamin B12 hydrate, tetrakis(4-aminophenyl)porphyrin cobalt and tetrakis(4-aminophenyl)porphyrin cobalt hydrate; or, the aqueous phase solution further contains a thiol compound, the active molecule catalyzed by active chlorine is the product of reduction of a metal salt, and the metal salt is one or more of ferric nitrate, ferric nitrate hydrate, ferrous chloride, ferrous chloride hydrate, ferric chloride, ferric chloride hydrate, manganese chloride, manganese chloride hydrate, ammonium molybdate, manganese nitrate and manganese nitrate hydrate.

[0009] Preferably, the thiol compound is one or more of mercaptoethanol, cysteine, (3-mercaptopropyl)triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 2-mercaptoethylamine and dimercaptopropanol.

[0010] Preferably, the supporting base membrane is made of polysulfone, polyethersulfone or polyvinylidene fluoride.

[0011] Preferably, the average pore size of the chlorine-resistant reverse osmosis membrane is less than 0.6 nm, and the molecular weight cut-off is 80 to 200 Da.

[0012] The present invention provides a method for synthesizing a chlorine-resistant reverse osmosis membrane, comprising the following steps:

[0013] a) contacting one side surface of the supporting base film with an aqueous solution containing an amine monomer to obtain a base film with the aqueous monomer attached thereto;

[0014] b) immersing the base membrane with the aqueous phase monomer attached thereto in an oil phase solution containing an acyl chloride monomer to perform an interfacial polymerization reaction to form a polyamide layer, thereby obtaining an unmodified polyamide separation membrane;

[0015] c) immersing the unmodified polyamide separation membrane in an active chlorine catalytic decomposition active molecule solution to form a polyamide catalytic active layer to obtain a chlorine-resistant reverse osmosis membrane;

[0016] In step c), the active chlorine catalytic decomposition active molecules in the active chlorine catalytic decomposition active molecule solution are one or more of vitamin B12, vitamin B12 hydrate, tetrakis(4-aminophenyl)porphyrin cobalt and tetrakis(4-aminophenyl)porphyrin cobalt hydrate.

[0017] The application also provides a method for synthesizing the chlorine-resistant reverse osmosis membrane, comprising the following steps:

[0018] a) contacting a single side surface of a supporting base membrane with an aqueous phase solution containing amine monomers and thiol compounds to obtain a base membrane with attached aqueous phase monomers;

[0019] b) immersing the base membrane with attached aqueous phase monomers in an oil phase solution containing acid chloride monomers to perform an interfacial polymerization reaction to form a polyamide layer, thereby obtaining an unmodified polyamide separation membrane;

[0020] c) immersing the unmodified polyamide separation membrane in a metal salt solution to obtain a polyamide separation membrane loaded with metal salts;

[0021] In step c), the metal salt in the metal salt solution is one or more of ferric nitrate, ferric nitrate hydrate, ferrous chloride, ferrous chloride hydrate, ferric chloride, ferric chloride hydrate, manganese chloride, manganese chloride hydrate, ammonium molybdate, manganese nitrate, and manganese nitrate hydrate;

[0022] d) immersing the polyamide separation membrane loaded with metal salts in a reducing agent solution to form a polyamide catalytically active layer through reduction, thereby obtaining a chlorine-resistant reverse osmosis membrane.

[0023] The application provides a water treatment method, wherein a separation membrane used in the water treatment process comprises the chlorine-resistant reverse osmosis membrane described in the above technical solution or the chlorine-resistant reverse osmosis membrane obtained through the synthesis method described in the above technical solution.

[0024] Compared with the prior art, the application provides a chlorine-resistant reverse osmosis membrane, which comprises a supporting base membrane and a polyamide catalytically active layer complexed on a single side surface of the supporting base membrane; the polyamide catalytically active layer is formed through interfacial polymerization reaction of an aqueous phase solution and an oil phase solution and then modified by an active chlorine catalytic decomposition active molecule; the aqueous phase solution contains amine monomers, and the oil phase solution contains acid chloride monomers. The application fixes a molecule with active chlorine catalytic decomposition activity on a polyamide separation membrane, thereby endowing the separation membrane with the ability to directly decompose active chlorine and effectively improving the chlorine resistance of the membrane material. Experimental results show that the chlorine-resistant reverse osmosis membrane provided by the application still has a sodium chloride rejection rate of more than 98% after being treated with 50 mg / L active chlorine for 2000 h.

[0025] More specifically, the technical solution provided by the application has at least the following beneficial effects:

[0026] 1. The chlorine-resistant reverse osmosis membrane provided by the application has excellent chlorine resistance and can effectively resist active chlorine treatment, thereby having a longer service life.

[0027] 2. The chlorine-resistant reverse osmosis membrane provided by the present invention proposes a new chlorine-resistant strategy for reverse osmosis membranes. By catalytically decomposing active chlorine molecules and loading them on the polyamide layer of the reverse osmosis membrane, the active chlorine can be directly decomposed to prevent it from contacting the oxidized polyamide layer.

[0028] 3. The synthesis method of the present invention is simple, the raw material cost is low, and it can be produced on a large scale. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are merely embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying any creative work.

[0030] Figure 1 It is a schematic structural diagram of a chlorine-resistant reverse osmosis membrane provided by an embodiment of the present invention.

[0031] Explanation of reference numerals: 1 is a supporting base membrane, 2 is a polyamide catalytic active layer. DETAILED DESCRIPTION

[0032] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0033] The present invention provides a chlorine-resistant reverse osmosis membrane, comprising: a supporting base membrane, and a polyamide catalytic active layer composited on a single-side surface of the supporting base membrane; the polyamide catalytic active layer is formed by subjecting an aqueous solution and an oily solution to an interfacial polymerization reaction, followed by modification of active molecules by catalytic decomposition of active chlorine; the aqueous solution contains amine monomers, and the oily solution contains acyl chloride monomers.

[0034] In the chlorine-resistant reverse osmosis membrane provided by the present invention, the material of the supporting base membrane includes but is not limited to polysulfone, polyethersulfone or polyvinylidene fluoride; the molecular weight cutoff of the supporting base membrane is preferably 20-200kDa, specifically 20kDa, 50kDa, 100kDa or 200kDa.

[0035] In the chlorine-resistant reverse osmosis membrane provided by the present invention, the amine monomer in the aqueous solution has at least two N-containing groups that can participate in the interfacial polymerization reaction, and the amine monomer is preferably one or more of m-phenylenediamine, piperazine, p-phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine and ethylenediamine; the content of the amine monomer in the aqueous solution is preferably 0.2-4wt%, specifically 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1 wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt% or 4wt%.

[0036] In the chlorine-resistant reverse osmosis membrane provided by the present invention, the aqueous phase solution is in contact with a single surface of the supporting base membrane. The contact temperature is preferably 10 to 40°C, specifically 10°C, 15°C, 20°C, 25°C (room temperature), 30°C, 35°C or 40°C; the contact time is preferably 10 to 300s, specifically 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 110s, 120s, 130s, 140s, 150s, 160s, 170s, 180s, 190s, 200s, 210s, 220s, 230s, 240s, 250s, 260s, 270s, 280s, 290s or 300s.

[0037] In the chlorine-resistant reverse osmosis membrane provided by the present invention, the acyl chloride monomer in the oil phase solution has at least two acyl chloride groups that can participate in the interfacial polymerization reaction, and the acyl chloride monomer is preferably one or more of trimesoyl chloride, terephthaloyl chloride and phthaloyl chloride; the content of the acyl chloride monomer in the oil phase solution is preferably 0.05-0.5wt%, specifically 0.05wt%, 0.07wt%, 0.1wt%, 0.12wt%, 0.15wt%, 0.17wt%, 0.2wt%, 0.23wt%, 0.25wt%, 0.27wt%, 0.3wt%, 0.32wt%, 0.35wt%, 0.37wt%, 0.4wt%, 0.42wt%, 0.45wt%, 0.47wt% or 0.5wt%.

[0038] In the chlorine-resistant reverse osmosis membrane provided by the present invention, the organic solvent in the oil phase solution includes, but is not limited to, one or more of n-hexane, isoparaffins and n-nonane.

[0039] In the chlorine-resistant reverse osmosis membrane provided by the present invention, the temperature for carrying out the interfacial polymerization reaction is preferably 10-40°C, specifically 10°C, 15°C, 20°C, 25°C (room temperature), 30°C, 35°C or 40°C; the time for carrying out the interfacial polymerization reaction is preferably 10-300s, specifically 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 110s, 120s, 130s, 140s, 150s, 160s, 170s, 180s, 190s, 200s, 210s, 220s, 230s, 240s, 250s, 260s, 270s, 280s, 290s or 300s.

[0040] In the chlorine-resistant reverse osmosis membrane provided by the present invention, the active chlorine catalytic decomposition active molecule is preferably one or more of vitamin B12, vitamin B12 hydrate, tetrakis(4-aminophenyl)porphyrin cobalt and tetrakis(4-aminophenyl)porphyrin cobalt hydrate; or, the active chlorine catalytic decomposition active molecule is preferably the product of reduction of a metal salt, and the metal salt is one or more of ferric nitrate, ferric nitrate hydrate, ferrous chloride, ferrous chloride hydrate, ferric chloride, ferric chloride hydrate, manganese chloride, manganese chloride hydrate, ammonium molybdate, manganese nitrate and manganese nitrate hydrate.

[0041] In the chlorine-resistant reverse osmosis membrane provided by the present invention, when the active chlorine catalytic decomposition active molecule is one or more of vitamin B12, vitamin B12 hydrate, tetrakis(4-aminophenyl)porphyrin cobalt and tetrakis(4-aminophenyl)porphyrin cobalt hydrate, the method of modifying the active chlorine catalytic decomposition active molecule is preferably to soak it in a solution of active chlorine catalytic decomposition active molecule. Wherein, the content of active chlorine catalytic decomposition active molecule in the active chlorine catalytic decomposition active molecule solution is preferably 10 to 100 mg / L, specifically 10 mg / L, 15 mg / L, 20 mg / L, 25 mg / L, 30 mg / L, 35 mg / L, 40 mg / L, 45 mg / L, 50 mg / L, 55 mg / L, 60 mg / L, 65 mg / L, 70 mg / L, 75 mg / L, 80 mg / L / L, 85mg / L, 90mg / L, 95mg / L or 100mg / L; the soaking temperature is preferably 10-40°C, specifically 10°C, 15°C, 20°C, 25°C (room temperature), 30°C, 35°C or 40°C; the soaking time is preferably 0.1-1h, specifically 0.1h, 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h.

[0042] In the chlorine-resistant reverse osmosis membrane provided by the present invention, when the active chlorine catalytically decomposes the active molecules into products after reduction of metal salts, the aqueous solution further contains a thiol compound. Wherein, the thiol compound is preferably one or more of mercaptoethanol, cysteine, (3-mercaptopropyl)triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 2-mercaptoethylamine and dimercaptopropanol; the content of the thiol compound in the aqueous solution is preferably 0.2 to 4 wt%, specifically 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt% %, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt% or 4wt%. In the present invention, by utilizing mercapto group to coordinate with metal, stable catalytic activity of the membrane material and extremely low risk of metal dissolution are guaranteed.

[0043] In the chlorine-resistant reverse osmosis membrane provided by the present invention, when the catalytic active molecules modified on the surface of the catalytic nanofiltration membrane are products of reduction of metal salts, the method of modifying the catalytic active molecules is preferably to soak them in a metal salt solution and a reducing agent solution in sequence. The content of the metal salt in the metal salt solution is preferably 0.01 to 1 mol / L, specifically 0.01 mol / L, 0.05 mol / L, 0.1 mol / L, 0.15 mol / L, 0.2 mol / L, 0.25 mol / L, 0.3 mol / L, 0.35 mol / L, 0.4 mol / L, 0.45 mol / L, 0.5 mol / L, 0.55 mol / L, 0.6 mol / L, 0.65 mol / L, 0.7 mol / L, 0.75 mol / L, 0.8 mol / L, 0.85mol / L, 0.9mol / L, 0.95mol / L or 1mol / L; the soaking temperature in the metal salt solution is preferably 10-40°C, specifically 10°C, 15°C, 20°C, 25°C (room temperature), 30°C, 35°C or 40°C; the soaking time in the metal salt solution is preferably 0.5-6h, specifically 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h; the reducing agent in the reducing agent solution is preferably is sodium borohydride and / or ascorbic acid; the content of the reducing agent in the reducing agent solution is preferably 0.01 to 0.5 mol / L, specifically 0.01 mol / L, 0.03 mol / L, 0.05 mol / L, 0.07 mol / L, 0.1 mol / L, 0.12 mol / L, 0.15 mol / L, 0.17 mol / L, 0.2 mol / L, 0.23 mol / L, 0.25 mol / L, 0.27 mol / L, 0.3 mol / L, 0.32 mol / L, 0.35 mol / L, 0.37mol / L, 0.4mol / L, 0.42mol / L, 0.45mol / L, 0.47mol / L or 0.5mol / L; the soaking temperature in the reducing agent solution is preferably 10-40°C, specifically 10°C, 15°C, 20°C, 25°C (room temperature), 30°C, 35°C or 40°C; the soaking time in the reducing agent solution is preferably 2-24h, specifically 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h.

[0044] In the chlorine-resistant reverse osmosis membrane provided by the present invention, the average membrane pore size of the chlorine-resistant reverse osmosis membrane is preferably less than 0.6 nm; and the molecular weight cut-off of the chlorine-resistant reverse osmosis membrane is preferably 80 to 200 Da.

[0045] The present invention also provides a method for synthesizing a chlorine-resistant reverse osmosis membrane, which is characterized by comprising the following steps:

[0046] a) contacting one side surface of the supporting base film with an aqueous solution containing an amine monomer to obtain a base film with the aqueous monomer attached thereto;

[0047] b) immersing the base membrane with the aqueous phase monomer attached thereto in an oil phase solution containing an acyl chloride monomer to perform an interfacial polymerization reaction to form a polyamide layer, thereby obtaining an unmodified polyamide separation membrane;

[0048] c) immersing the unmodified polyamide separation membrane in an active chlorine catalytic decomposition active molecule solution to form a polyamide catalytic active layer to obtain a chlorine-resistant reverse osmosis membrane;

[0049] In step c), the active chlorine catalytic decomposition active molecules in the active chlorine catalytic decomposition active molecule solution are one or more of vitamin B12, vitamin B12 hydrate, tetrakis(4-aminophenyl)porphyrin cobalt and tetrakis(4-aminophenyl)porphyrin cobalt hydrate.

[0050] In the above-mentioned synthesis method provided by the present invention, in step a), the material of the supporting base membrane includes but is not limited to polysulfone, polyethersulfone or polyvinylidene fluoride.

[0051] In the above-mentioned synthesis method provided by the present invention, in step a), the aqueous phase solution contains amine monomers and water.

[0052] In the above-mentioned synthesis method provided by the present invention, in step a), the amine monomer in the aqueous solution has at least two N-containing groups that can participate in the interfacial polymerization reaction, and the amine monomer is preferably one or more of m-phenylenediamine, piperazine, p-phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine and ethylenediamine; the content of the amine monomer in the aqueous solution is preferably 0.2-4wt%, specifically 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt% or 4wt%.

[0053] In the above-mentioned synthesis method provided by the present invention, in step a), the contact temperature is preferably 10-40°C, specifically 10°C, 15°C, 20°C, 25°C (room temperature), 30°C, 35°C or 40°C; the contact time is preferably 10-300s, specifically 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 110s, 120s, 130s, 140s, 150s, 160s, 170s, 180s, 190s, 200s, 210s, 220s, 230s, 240s, 250s, 260s, 270s, 280s, 290s or 300s.

[0054] In the above-mentioned synthesis method provided by the present invention, in step b), the oil phase solution contains acyl chloride monomers and an organic solvent.

[0055] In the above-mentioned synthesis method provided by the present invention, in step b), the acyl chloride monomer in the oil phase solution has at least two acyl chloride groups that can participate in the interfacial polymerization reaction, and the acyl chloride monomer is preferably one or more of trimesoyl chloride, terephthaloyl chloride and phthaloyl chloride; the content of the acyl chloride monomer in the oil phase solution is preferably 0.05-0.5wt%, specifically 0.05wt%, 0.07wt%, 0.1wt%, 0.12wt%, 0.15wt%, 0.17wt%, 0.2wt%, 0.23wt%, 0.25wt%, 0.27wt%, 0.3wt%, 0.32wt%, 0.35wt%, 0.37wt%, 0.4wt%, 0.42wt%, 0.45wt%, 0.47wt% or 0.5wt%.

[0056] In the above-mentioned synthesis method provided by the present invention, in step b), the organic solvent in the oil phase solution includes but is not limited to one or more of n-hexane, isoparaffins and n-nonane.

[0057] In the above-mentioned synthesis method provided by the present invention, in step b), the temperature for carrying out the interfacial polymerization reaction is preferably 10-40°C, specifically 10°C, 15°C, 20°C, 25°C (room temperature), 30°C, 35°C or 40°C; the time for carrying out the interfacial polymerization reaction is preferably 10-300s, specifically 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 110s, 120s, 130s, 140s, 150s, 160s, 170s, 180s, 190s, 200s, 210s, 220s, 230s, 240s, 250s, 260s, 270s, 280s, 290s or 300s.

[0058] In the above-mentioned synthesis method provided by the present invention, in step c), the active chlorine catalytic decomposition active molecule solution contains active chlorine catalytic decomposition active molecules and water.

[0059] In the above-mentioned synthesis method provided by the present invention, in step c), the content of active chlorine catalytic decomposition active molecules in the active chlorine catalytic decomposition active molecule solution is preferably 10-100 mg / L, specifically 10 mg / L, 15 mg / L, 20 mg / L, 25 mg / L, 30 mg / L, 35 mg / L, 40 mg / L, 45 mg / L, 50 mg / L, 55 mg / L, 60 mg / L, 65 mg / L, 70 mg / L, 75 mg / L, 80 mg / L, 85 mg / L, 90 mg / L, 95 mg / L or 100 mg / L.

[0060] In the above-mentioned synthesis method provided by the present invention, in step c), the soaking temperature is preferably 10-40°C, specifically 10°C, 15°C, 20°C, 25°C (room temperature), 30°C, 35°C or 40°C; the soaking time is preferably 0.1-1h, specifically 0.1h, 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h.

[0061] The present invention also provides a method for synthesizing a chlorine-resistant reverse osmosis membrane, comprising the following steps:

[0062] a) contacting one side surface of the supporting base film with an aqueous solution containing an amine monomer and a thiol compound to obtain a base film with the aqueous monomer attached thereto;

[0063] b) immersing the base membrane with the aqueous phase monomer attached thereto in an oil phase solution containing an acyl chloride monomer to perform an interfacial polymerization reaction to form a polyamide layer, thereby obtaining an unmodified polyamide separation membrane;

[0064] c) soaking the unmodified polyamide separation membrane in a metal salt solution to obtain a metal salt-loaded polyamide separation membrane;

[0065] In step c), the metal salt in the metal salt solution is one or more of ferric nitrate, ferric nitrate hydrate, ferrous chloride, ferrous chloride hydrate, ferric chloride, ferric chloride hydrate, manganese chloride, manganese chloride hydrate, ammonium molybdate, manganese nitrate and manganese nitrate hydrate;

[0066] d) soaking the metal salt-loaded polyamide separation membrane in a reducing agent solution to form a polyamide catalytic active layer through reduction, thereby obtaining a chlorine-resistant reverse osmosis membrane.

[0067] In the above-mentioned synthesis method provided by the present invention, in step a), the material of the supporting base membrane includes but is not limited to polysulfone, polyethersulfone or polyvinylidene fluoride.

[0068] In the above-mentioned synthesis method provided by the present invention, in step a), the aqueous phase solution contains amine monomers and water.

[0069] In the above-mentioned synthesis method provided by the present invention, in step a), the amine monomer in the aqueous solution has at least two N-containing groups that can participate in the interfacial polymerization reaction, and the amine monomer is preferably one or more of m-phenylenediamine, piperazine, p-phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine and ethylenediamine; the content of the amine monomer in the aqueous solution is preferably 0.2-4wt%, specifically 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt% or 4wt%.

[0070] In the above-mentioned synthesis method provided by the present invention, in step a), the thiol compound in the aqueous phase solution is preferably one or more of mercaptoethanol, cysteine, (3-mercaptopropyl)triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 2-mercaptoethylamine and dimercaprol; the content of the thiol compound in the aqueous phase solution is preferably 0.2-4wt%, specifically 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1 .1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt% or 4wt%.

[0071] In the above-mentioned synthesis method provided by the present invention, in step a), the contact temperature is preferably 10-40°C, specifically 10°C, 15°C, 20°C, 25°C (room temperature), 30°C, 35°C or 40°C; the contact time is preferably 10-300s, specifically 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 110s, 120s, 130s, 140s, 150s, 160s, 170s, 180s, 190s, 200s, 210s, 220s, 230s, 240s, 250s, 260s, 270s, 280s, 290s or 300s.

[0072] In the above-mentioned synthesis method provided by the present invention, in step b), the oil phase solution contains acyl chloride monomers and an organic solvent.

[0073] In the above-mentioned synthesis method provided by the present invention, in step b), the acyl chloride monomer in the oil phase solution has at least two acyl chloride groups that can participate in the interfacial polymerization reaction, and the acyl chloride monomer is preferably one or more of trimesoyl chloride, terephthaloyl chloride and phthaloyl chloride; the content of the acyl chloride monomer in the oil phase solution is preferably 0.05-0.5wt%, specifically 0.05wt%, 0.07wt%, 0.1wt%, 0.12wt%, 0.15wt%, 0.17wt%, 0.2wt%, 0.23wt%, 0.25wt%, 0.27wt%, 0.3wt%, 0.32wt%, 0.35wt%, 0.37wt%, 0.4wt%, 0.42wt%, 0.45wt%, 0.47wt% or 0.5wt%.

[0074] In the above-mentioned synthesis method provided by the present invention, in step b), the organic solvent in the oil phase solution includes but is not limited to one or more of n-hexane, isoparaffins and n-nonane.

[0075] In the above-mentioned synthesis method provided by the present invention, in step b), the temperature for carrying out the interfacial polymerization reaction is preferably 10-40°C, specifically 10°C, 15°C, 20°C, 25°C (room temperature), 30°C, 35°C or 40°C; the time for carrying out the interfacial polymerization reaction is preferably 10-300s, specifically 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 110s, 120s, 130s, 140s, 150s, 160s, 170s, 180s, 190s, 200s, 210s, 220s, 230s, 240s, 250s, 260s, 270s, 280s, 290s or 300s.

[0076] In the above synthesis method provided by the present invention, in step c), the metal salt solution contains metal salt and water.

[0077] In the above-mentioned synthesis method provided by the present invention, in step c), the content of the metal salt in the metal salt solution is preferably 0.01 to 1 mol / L, specifically 0.01 mol / L, 0.05 mol / L, 0.1 mol / L, 0.15 mol / L, 0.2 mol / L, 0.25 mol / L, 0.3 mol / L, 0.35 mol / L, 0.4 mol / L, 0.45 mol / L, 0.5 mol / L, 0.55 mol / L, 0.6 mol / L, 0.65 mol / L, 0.7 mol / L, 0.75 mol / L, 0.8 mol / L, 0.85 mol / L, 0.9 mol / L, 0.95 mol / L or 1 mol / L.

[0078] In the above-mentioned synthesis method provided by the present invention, in step c), the soaking temperature is preferably 10-40°C, specifically 10°C, 15°C, 20°C, 25°C (room temperature), 30°C, 35°C or 40°C; the soaking time is preferably 0.5-6h, specifically 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h.

[0079] In the above-mentioned synthesis method provided by the present invention, in step d), the reducing agent solution contains a reducing agent and water.

[0080] In the above-mentioned synthesis method provided by the present invention, in step d), the reducing agent in the reducing agent solution is preferably sodium borohydride and / or ascorbic acid; the content of the reducing agent in the reducing agent solution is preferably 0.01-0.5 mol / L, specifically 0.01 mol / L, 0.03 mol / L, 0.05 mol / L, 0.07 mol / L, 0.1 mol / L, 0.12 mol / L, 0.15 mol / L, 0.17 mol / L, 0.2 mol / L, 0.23 mol / L, 0.25 mol / L, 0.27 mol / L, 0.3 mol / L, 0.32 mol / L, 0.35 mol / L, 0.37 mol / L, 0.4 mol / L, 0.42 mol / L, 0.45 mol / L, 0.47 mol / L or 0.5 mol / L.

[0081] In the above-mentioned synthesis method provided by the present invention, in step d), the soaking temperature is preferably 10-40°C, specifically 10°C, 15°C, 20°C, 25°C (room temperature), 30°C, 35°C or 40°C; the soaking time is preferably 2-24h, specifically 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h.

[0082] The present invention also provides a water treatment method, wherein the separation membrane used in the water treatment process comprises the chlorine-resistant reverse osmosis membrane described in the above technical solution or the chlorine-resistant reverse osmosis membrane prepared by the synthesis method described in the above technical solution.

[0083] For the purpose of greater clarity, the present invention is described in detail with reference to the following examples and comparative examples.

[0084] Example 1

[0085] A chlorine-resistant reverse osmosis membrane having a structure such as Figure 1 As shown, it includes: a supporting base membrane 1, and a polyamide catalytic active layer 2 composited on a single side surface of the supporting base membrane 1; the polyamide catalytic active layer 2 is formed by interfacial polymerization reaction between an aqueous solution and an oily solution, and then modified with active chlorine catalytic decomposition active molecules.

[0086] The synthesis method of the above-mentioned chlorine-resistant reverse osmosis membrane is as follows:

[0087] Step 1: dissolving an amine monomer (m-phenylenediamine) in water to obtain an aqueous solution; wherein the content of the amine monomer in the aqueous solution is 3 wt %;

[0088] Step 2: dissolving an acyl chloride monomer (trimellitoyl chloride) in an organic phase solvent (n-hexane) to obtain an oil phase solution; wherein the content of the acyl chloride monomer in the oil phase solution is 0.15 wt %;

[0089] Step 3: contacting the aqueous phase solution with one side of a supporting base membrane (material: polysulfone, molecular weight cut-off: 100 kDa) to obtain a base membrane with attached aqueous phase monomers; wherein the contact temperature is room temperature and the contact time is 120 seconds;

[0090] Step 4: immersing the base membrane with the aqueous phase monomer attached in the oil phase solution to perform interfacial polymerization reaction to form a polyamide layer, thereby obtaining an unmodified polyamide separation membrane; wherein the interfacial polymerization reaction temperature is room temperature and the time is 100 seconds;

[0091] Step 5: dissolving an active chlorine catalytic decomposition active molecule (tetrakis(4-aminophenyl)porphyrin cobalt) in water to obtain an active chlorine catalytic decomposition active molecule solution; wherein the content of the active chlorine catalytic decomposition active molecule in the water is 100 mg / L;

[0092] Step 6: soaking the unmodified polyamide separation membrane obtained in step 4 in the active chlorine catalytic decomposition active molecule solution obtained in step 5 to form a polyamide catalytic active layer, thereby obtaining a chlorine-resistant reverse osmosis membrane; wherein the soaking temperature is room temperature, and the soaking time is 0.1 h.

[0093] Example 2

[0094] With reference to Example 1, the difference is that the active chlorine catalytic decomposition active molecule used in step 5 is vitamin B12.

[0095] Example 3

[0096] A chlorine-resistant reverse osmosis membrane has a structure as shown in Figure 1 The chlorine-resistant reverse osmosis membrane comprises a support base film 1 and a polyamide catalytic active layer 2 combined on one side of the support base film 1. The polyamide catalytic active layer 2 is formed by interfacial polymerization of an aqueous phase solution and an oil phase solution, followed by loading of a metal salt and reduction by a reducing agent.

[0097] The synthesis method of the chlorine-resistant reverse osmosis membrane is as follows:

[0098] Step 1: dissolving an amine monomer (m-phenylenediamine) and a mercapto compound (cysteine) in water to obtain an aqueous phase solution; wherein the content of the amine monomer in the aqueous phase is 1.5 wt%, and the content of the mercapto compound in the aqueous phase is 3 wt%.

[0099] Step 2: dissolving an acyl chloride monomer (trimesoyl chloride) in an organic phase solvent (n-hexane) to obtain an oil phase solution; wherein the content of the acyl chloride monomer in the oil phase solution is 0.15 wt%.

[0100] Step 3: contacting the aqueous phase solution with one side of a support base film (material: polysulfone, molecular weight cut-off: 100 kDa) to obtain a base film with attached aqueous phase monomers; wherein the contacting temperature is room temperature, and the contacting time is 120 s.

[0101] Step 4: soaking the base film with attached aqueous phase monomers in the oil phase solution to form a polyamide layer by interfacial polymerization, thereby obtaining an unmodified polyamide separation membrane; wherein the interfacial polymerization temperature is room temperature, and the interfacial polymerization time is 100 s.

[0102] Step 5: dissolving a metal salt (ferric nitrate) in water to obtain a metal salt solution; wherein the content of the metal salt in water is 0.1 mol / L.

[0103] Step 6: soaking the unmodified polyamide separation membrane obtained in step 4 in the metal salt solution obtained in step 5 to obtain a polyamide separation membrane loaded with a metal salt; wherein the soaking temperature is room temperature, and the soaking time is 1 h.

[0104] Step 7: dissolving a reducing agent (ascorbic acid) in water to obtain a reducing agent solution; wherein the content of the reducing agent in the water is 0.1 mol / L;

[0105] Step 8: Soak the metal salt-loaded polyamide separation membrane obtained in step 6 in the reducing agent solution of step 7 to form a polyamide catalytic active layer through reduction, thereby obtaining a chlorine-resistant reverse osmosis membrane; wherein the soaking temperature is room temperature and the soaking time is 12 hours.

[0106] Example 4

[0107] Refer to Example 3, the only difference is that the metal salt used in step 5 is ammonium molybdate.

[0108] Example 5

[0109] Refer to Example 1, the only difference is that the material of the supporting base membrane used in step 3 is polyethersulfone.

[0110] Example 6

[0111] Refer to Example 1, the only difference is that the material of the supporting base membrane used in step 3 is polyvinylidene fluoride, and the molecular weight cut-off is 100 kDa.

[0112] Example 7

[0113] Refer to Example 1, the only difference is that the amine monomer used in step 1 is piperazine.

[0114] Example 8

[0115] Refer to Example 1, the only difference is that the amine monomer used in step 1 is triethylenetetramine.

[0116] Example 9

[0117] Refer to Example 1, the only difference is that the acyl chloride monomer used in step 2 is terephthaloyl chloride.

[0118] Comparative Example 1

[0119] A polyamide separation membrane comprises: a supporting base membrane and a polyamide layer composited on one side surface of the supporting base membrane; the polyamide catalytic layer is formed by interfacial polymerization reaction between an aqueous solution and an oily solution.

[0120] The synthesis method of the above-mentioned polyamide separation membrane is as follows:

[0121] Step 1: dissolving an amine monomer (m-phenylenediamine) in water to obtain an aqueous solution; wherein the content of the amine monomer in the aqueous solution is 3 wt %;

[0122] Step 2: dissolving an acyl chloride monomer (trimellitoyl chloride) in an organic phase solvent (n-hexane) to obtain an oil phase solution; wherein the content of the acyl chloride monomer in the oil phase solution is 0.15 wt %;

[0123] Step 3: contacting the aqueous phase solution with one side of a supporting base membrane (material: polysulfone, molecular weight cut-off: 100 kDa) to obtain a base membrane with attached aqueous phase monomers; wherein the contact temperature is room temperature and the contact time is 120 seconds;

[0124] Step 4: Immerse the base membrane with the attached aqueous phase monomer in the oil phase solution to perform interfacial polymerization to form a polyamide layer, thereby obtaining a polyamide separation membrane; wherein the interfacial polymerization reaction is performed at room temperature for 100 seconds.

[0125] Performance evaluation

[0126] (1) Average membrane pore size and molecular weight cut-off

[0127] The membrane materials prepared in the above examples and comparative examples were tested for average membrane pore size and molecular weight cut-off, and the results are shown in the following table:

[0128]

[0129]

[0130] (2) Water flux and salt interception performance test

[0131] The water flux and salt rejection performance of the membrane materials prepared in the above embodiments and comparative examples were tested using a cross-flow reverse osmosis test apparatus. The specific test method was as follows: the membrane material was first compacted with deionized water until the flux was stable; a salt solution containing 2 g / L sodium chloride was prepared as the feed solution, and the pH was adjusted to 7.0±0.1; the feed solution was thoroughly mixed for 1 hour without applying pressure; after equilibrium, in the circulation mode, the system pressure was adjusted to 20 bar at 25°C and a flow rate of 60 LPH, and the water flux and salt rejection rate were tested after equilibration for 1 hour.

[0132] The test results of Examples 1 to 9 and Comparative Example 1 are shown in the following table:

[0133] Water flux (LMH / Bar) Retention (%) Example 1 1.12 98.5 Example 2 1.32 99.0 Example 3 1.22 98.5 Example 4 1.08 98.4 Example 5 1.17 99.2 Example 6 1.07 98.9 Example 7 1.11 99.4 Example 8 0.99 98.7 Example 9 1.15 98.1 Comparative Example 1 1.10 99.1

[0134] (3) Chlorine resistance test

[0135] The chlorine resistance of the membrane materials prepared in the above examples and comparative examples was tested using a cross-flow reverse osmosis test apparatus. The specific test method was as follows: the membrane material was first compacted with deionized water until the flux was stable; a 50 mg / L sodium hypochlorite solution was prepared as the feed solution; after equilibration, the system pressure was adjusted to 20 bar at 25°C and a flow rate of 60 LPH in the circulation mode, and the system was operated continuously, replaced every 12 hours, and operated continuously for 2000 hours. A salt solution containing 2 g / L sodium chloride was prepared as the feed solution, and the pH was adjusted to 7.0±0.1; the feed solution was thoroughly mixed for 1 hour without applying pressure; after equilibration, the system pressure was adjusted to 20 bar at 25°C and a flow rate of 60 LPH in the circulation mode, and the water flux and salt rejection were tested after equilibration for 1 hour.

[0136] The test results of Examples 1 to 9 and Comparative Example 1 are shown in the following table:

[0137] Water flux (LMH / Bar) Retention (%) Example 1 0.98 99.0 Example 2 0.96 98.3 Example 3 1.01 98.7 Example 4 0.99 99.2 Example 5 1.04 98.9 Example 6 0.89 98.1 Example 7 0.95 98.3 Example 8 0.98 98.0 Example 9 1.03 99.0 Comparative Example 1 2.05 56.3

[0138] As can be seen from the table above, the chlorine-resistant reverse osmosis membrane still maintained an extremely high sodium chloride rejection rate after continuous treatment with 50 mg / L active chlorine for 2000 hours, while the rejection rate of the reverse osmosis membrane used as the control dropped to 56.3% and the flux increased to 2LMH, indicating that it had been destroyed by the active chlorine.

[0139] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A chlorine-resistant reverse osmosis membrane, characterized in that include: A supporting base membrane, and a polyamide catalytic active layer composited on a single side surface of the supporting base membrane; The polyamide catalytic active layer is formed by interfacial polymerization of an aqueous solution and an oily solution, followed by active chlorine catalytic decomposition of active molecules; the aqueous solution contains amine monomers, and the oily solution contains acyl chloride monomers.

2. The chlorine-resistant reverse osmosis membrane according to claim 1, characterized in that The amine monomer is one or more of m-phenylenediamine, piperazine, p-phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine and ethylenediamine.

3. The chlorine-resistant reverse osmosis membrane according to claim 1, characterized in that The acyl chloride monomer is one or more of trimesoyl chloride, terephthaloyl chloride and phthaloyl chloride.

4. The chlorine-resistant reverse osmosis membrane according to claim 1, characterized in that The active molecule catalyzed by active chlorine is one or more of vitamin B12, vitamin B12 hydrate, tetrakis(4-aminophenyl)porphyrin cobalt and tetrakis(4-aminophenyl)porphyrin cobalt hydrate; or, the aqueous phase solution further contains a thiol compound, the active molecule catalyzed by active chlorine is a product of reduction of a metal salt, and the metal salt is one or more of ferric nitrate, ferric nitrate hydrate, ferrous chloride, ferrous chloride hydrate, ferric chloride, ferric chloride hydrate, manganese chloride, manganese chloride hydrate, ammonium molybdate, manganese nitrate and manganese nitrate hydrate.

5. The chlorine-resistant reverse osmosis membrane according to claim 4, characterized in that The thiol compound is one or more of mercaptoethanol, cysteine, (3-mercaptopropyl)triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 2-mercaptoethylamine and dimercaptopropanol.

6. The chlorine-resistant reverse osmosis membrane according to claim 1, characterized in that The material of the supporting base membrane is polysulfone, polyethersulfone or polyvinylidene fluoride.

7. The chlorine-resistant reverse osmosis membrane according to claim 1, characterized in that The average pore size of the chlorine-resistant reverse osmosis membrane is less than 0.6 nm, and the molecular weight cut-off is 80 to 200 Da.

8. A method for synthesizing a chlorine-resistant reverse osmosis membrane, characterized in that: The following steps are involved: a) contacting one side surface of the supporting base film with an aqueous solution containing an amine monomer to obtain a base film with the aqueous monomer attached thereto; b) immersing the base membrane with the aqueous phase monomer attached thereto in an oil phase solution containing an acyl chloride monomer to perform an interfacial polymerization reaction to form a polyamide layer, thereby obtaining an unmodified polyamide separation membrane; c) immersing the unmodified polyamide separation membrane in an active chlorine catalytic decomposition active molecule solution to form a polyamide catalytic active layer to obtain a chlorine-resistant reverse osmosis membrane; In step c), the active chlorine catalytic decomposition active molecules in the active chlorine catalytic decomposition active molecule solution are one or more of vitamin B12, vitamin B12 hydrate, tetrakis(4-aminophenyl)porphyrin cobalt and tetrakis(4-aminophenyl)porphyrin cobalt hydrate.

9. A method for synthesizing a chlorine-resistant reverse osmosis membrane, characterized in that: The following steps are involved: a) contacting one side surface of the supporting base film with an aqueous solution containing an amine monomer and a thiol compound to obtain a base film with the aqueous monomer attached thereto; b) immersing the base membrane with the aqueous phase monomer attached thereto in an oil phase solution containing an acyl chloride monomer to perform an interfacial polymerization reaction to form a polyamide layer, thereby obtaining an unmodified polyamide separation membrane; c) soaking the unmodified polyamide separation membrane in a metal salt solution to obtain a metal salt-loaded polyamide separation membrane; In step c), the metal salt in the metal salt solution is one or more of ferric nitrate, ferric nitrate hydrate, ferrous chloride, ferrous chloride hydrate, ferric chloride, ferric chloride hydrate, manganese chloride, manganese chloride hydrate, ammonium molybdate, manganese nitrate and manganese nitrate hydrate; d) soaking the metal salt-loaded polyamide separation membrane in a reducing agent solution to form a polyamide catalytic active layer through reduction, thereby obtaining a chlorine-resistant reverse osmosis membrane.

10. A water treatment method, characterized in that: The separation membrane used in the water treatment process includes the chlorine-resistant reverse osmosis membrane according to any one of claims 1 to 7 or the chlorine-resistant reverse osmosis membrane prepared by the synthesis method according to any one of claims 8 to 9.

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