A method for preparing a composite bionic membrane with artificial water channels

Abstract

The present invention discloses a composite biomimetic membrane with artificial water channels, comprising: dissolving artificial water channel molecules in a first organic solution to obtain an artificial water channel organic solution; dissolving an aromatic multifunctional amine in water, then adding additives, adjusting the pH value of the solution, and ultrasonically degassing to obtain an aqueous phase liquid; dissolving an aromatic multifunctional acyl chloride in a hydrocarbon solvent to obtain a second organic solution; mixing the artificial water channel organic solution and the aqueous phase liquid in a preset ratio and ultrasonically treating them, soaking one side of a porous support layer in the mixed solution, coating the second organic solution, cleaning, and drying to obtain a composite biomimetic membrane with artificial water channels. The composite biomimetic membrane with artificial water channels is obtained by self-assembling the artificial water channel molecules into supramolecular aggregates to obtain an artificial water channel colloid solution of a specific size and concentration, and then controlling the artificial water channel colloid with a polyamide layer to encapsulate the artificial water channel colloid in a polyamide active layer.

Description

Technical Field

[0001] The invention relates to the technical field of separation membrane composite materials, in particular to a method for preparing a composite bionic membrane with artificial water channels. Background Art

[0002] Faced with the increasing severity of global water shortages and water pollution, water pollution control and wastewater reuse have become crucial solutions to address water shortage pressures. Membrane-based water treatment technology offers superior treatment quality and efficiency in a wide range of water treatment applications. Reverse osmosis (RO), with its core technology, offers excellent desalination performance and small molecule retention capabilities, making it widely used in a variety of applications, including desalination, wastewater treatment quality improvement and efficiency enhancement, and wastewater reuse.

[0003] After 30 years of extensive development and optimization, polyamide thin film composite membranes (PA-TFC) have demonstrated excellent performance. However, there has been no substantial breakthrough in the PA-TFC membrane materials and membrane separation performance based on interfacial polymerization for a long time. The PA-TFC membrane materials and preparation methods prepared by traditional interfacial polymerization have the following limitations: (1) The morphology and structure of the PA separation layer are rapidly formed during the diffusion-controlled interfacial polymerization process, accompanied by self-termination, which makes the reaction control complex, especially the membrane thickness is relatively difficult to control, and the membrane thickness is inversely proportional to the permeability; (2) There is a trade-off between the permeability and selectivity of RO membranes prepared by traditional interfacial polymerization methods, and the membrane permeability is low; (3) Membrane fouling has become an important factor limiting the application of RO technology. It is generally believed that the rough structure of the membrane induces membrane surface fouling. There are many factors that affect the membrane surface structure, and it is difficult to quantitatively adjust the morphology, structure and physicochemical properties of the active layer of the polyamide thin film composite membrane.

[0004] To this end, biomimetic technology provides a groundbreaking approach. The molecular properties of biological protein channels are very important for the future design of artificial systems that allow the regulation of pore function under ion gradients on both sides of lipid membranes. Water molecules are transported along the paths provided by aquaporins (AQPs) and quickly cross the cell membrane. Aquaporins have high permeability and ion retention rates, which give them great application potential. By adding membrane proteins expected to be used for desalination, the incorporation of AQP proteins into materials for RO membrane design was first considered for application. However, such applications are also affected by the high production cost of AQPs, low stability and harsh membrane preparation conditions. Summary of the Invention

[0005] The purpose of the embodiment of the present invention is to provide a method for preparing a composite biomimetic membrane with artificial water channels, by self-assembling artificial water channel molecules into supramolecular aggregates to obtain an artificial water channel colloid solution of specific size and concentration, and by regulating the polyamide layer, the artificial water channel colloid is wrapped in a polyamide active layer, thereby preparing a polyamide thin layer composite membrane with artificial water channels; only by uniformly mixing the solution, nanometer-sized artificial water channel supramolecular aggregates can be obtained; it has the advantages of simple process, convenient operation, and easy industrialization, and can be widely used in industrial production.

[0006] To solve the above technical problems, an embodiment of the present invention provides a method for preparing a composite biomimetic membrane having artificial water channels, comprising the following steps:

[0007] dissolving artificial water channel molecules having a mass concentration of a first preset ratio value in a first organic solution to obtain an artificial water channel organic solution;

[0008] dissolving an aromatic polyfunctional amine having a mass concentration of a second preset ratio value in water, adding an additive having a mass concentration of a third preset ratio value, and adjusting the pH value of the solution to a preset pH value to obtain an aqueous phase liquid;

[0009] dissolving an aromatic polyfunctional acyl chloride having a mass concentration of a fourth preset ratio in a hydrocarbon solvent to obtain a second organic solution;

[0010] The artificial water channel organic solution and the aqueous phase liquid are mixed in a preset ratio and ultrasonically treated. The porous support layer is soaked in the mixed solution and then coated with the second organic solution. After cleaning and drying, a composite bionic membrane with artificial water channels is obtained.

[0011] Furthermore, the artificial water channel molecule comprises: at least one compound of formula I, wherein

[0012]

[0013] wherein R represents a complex functional group comprising a hydroxyl group, a carboxyl group and / or an imidazole group, and the at least one compound of formula I exists in the form of a supramolecular aggregate;

[0014] The supramolecular aggregates are nano-scale microcrystals with an average diameter of less than 100 nm, and the crystals are in a quadruple layered phase.

[0015] Furthermore, the artificial water channel molecules include phenyl, urea and hydrophilic composite functional groups, which are hydrogen bonded through the urea groups and form tubular supramolecular aggregates through phenyl π-π stacking. The hydrophilic composite functional groups provide hydrogen bonding sites and transmission paths for water molecules in the supramolecular aggregate channels, and the phenyl groups twist and form an angle with the plane where the urea groups are located.

[0016] Furthermore, the first organic solution comprises: one or more of dimethyl sulfoxide, methanol, ethanol, ethylene glycol, acetonitrile, acetone and isopropanol, preferably methanol or ethanol.

[0017] Furthermore, the aromatic polyfunctional amine includes one or more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine and mesitylenetriamine, preferably m-phenylenediamine; and / or

[0018] The additives include: one or more of camphorsulfonic acid, N,N-dimethylformamide, dimethyl sulfoxide, acetone, ethyl acetate, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate and sodium dodecyl sulfate, preferably sodium dodecyl sulfate.

[0019] Furthermore, the aromatic multifunctional acyl chloride includes one or more of phthaloyl chloride, isophthaloyl chloride and trimesoyl chloride, preferably trimesoyl chloride.

[0020] Furthermore, the hydrocarbon solvent includes one or more of Isopar, n-pentane, n-hexane, n-heptane and n-octane, preferably n-hexane.

[0021] Furthermore, the first preset ratio value is 0.01% to 10%, preferably 0.1% to 1.0%;

[0022] The second preset ratio is 0.25% to 8%, preferably 1.0% to 4.0%;

[0023] The third preset ratio is 0.025% to 0.8%, preferably 0.1% to 0.5%;

[0024] The fourth preset ratio is 0.05% to 0.25%, preferably 0.1% to 0.2%;

[0025] The preset pH value ranges from 10 to 12, preferably 10; and / or,

[0026] The numerical range of the preset ratio is 1:1 to 1:10, preferably 1:5.

[0027] Furthermore, the porous support layer is an ultrafiltration membrane with a molecular weight cut-off ranging from 10kD to 250kD, preferably 20kD to 50kD;

[0028] The ultrafiltration membrane is a polysulfone membrane, a polyethersulfone membrane, a polyacrylonitrile membrane or a polyvinylidene fluoride membrane produced on a non-woven fabric by a phase inversion method, preferably a polysulfone membrane or a polyethersulfone membrane.

[0029] Furthermore, the porous support layer is soaked in the mixed solution and then coated with the second organic solution, comprising:

[0030] removing excess of the mixed solution and / or the second organic solution from the surface of the porous supporting layer;

[0031] Among them, the removal method includes: rolling method and / or air blowing method;

[0032] The cleaning process includes: rinsing with n-hexane and / or soaking in deionized water; and / or, the drying temperature is 50° C. to 90° C., and the drying time is 5 minutes to 30 minutes.

[0033] The above technical solutions of the embodiments of the present invention have the following beneficial technical effects:

[0034] 1. By self-assembling artificial water channel molecules into supramolecular aggregates to obtain an artificial water channel colloid solution of specific size and concentration, and then regulating it through the polyamide layer, the artificial water channel colloid is wrapped in a polyamide active layer, thereby preparing a polyamide thin layer composite membrane with artificial water channels;

[0035] 2. Nanoscale artificial water channel supramolecular aggregates can be obtained by simply uniformly mixing the solutions. This method has the advantages of simple process, convenient operation, and easy industrialization, and can be widely used in industrial production.

[0036] 3. The polyamide thin-layer composite membrane with artificial water channels has high hydrophilicity, which can prevent organic pollution, and its membrane flux and desalination rate can be maintained at a high level for a long time. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a flow chart of a method for preparing a composite biomimetic membrane with artificial water channels provided by an embodiment of the present invention;

[0038] Figure 2 is an X-ray diffraction pattern of a quartet lamellar phase of the compound of formula I provided in an embodiment of the present invention;

[0039] Figure 3 is a scanning electron microscope image of the surface of a polyamide thin-layer composite membrane having artificial water channels provided by an embodiment of the present invention;

[0040] Figure 4 This is a transmission electron microscope image of a cross section of a polyamide thin-layer composite membrane with artificial water channels provided by an embodiment of the present invention. DETAILED DESCRIPTION

[0041] To make the objectives, technical solutions, and advantages of the present invention more clearly understood, the present invention will be further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings. It should be understood that these descriptions are merely exemplary and are not intended to limit the scope of the present invention. In addition, in the following description, descriptions of well-known structures and technologies are omitted to avoid unnecessary confusion of the concepts of the present invention.

[0042] Please refer to Figure 1 The embodiment of the present invention provides a method for preparing a composite biomimetic membrane having an artificial water channel, comprising the following steps:

[0043] Step S100 , dissolving artificial water channel molecules having a mass concentration of a first preset ratio value in a first organic solution to obtain an artificial water channel organic solution.

[0044] In step S200 , an aromatic polyfunctional amine having a mass concentration of a second preset ratio is dissolved in water, an additive having a mass concentration of a third preset ratio is added, the pH value of the solution is adjusted to a preset pH value, and ultrasonic degassing is performed to obtain an aqueous phase liquid.

[0045] In step S300 , an aromatic polyfunctional acyl chloride having a mass concentration of a fourth preset ratio is dissolved in a hydrocarbon solvent to obtain a second organic solution.

[0046] Step S400: mixing an artificial water channel organic solution and an aqueous phase liquid in a preset ratio, soaking one side of the porous support layer in the mixed solution and then coating it with a second organic solution, cleaning and drying the porous support layer to obtain a composite bionic membrane with artificial water channels.

[0047] In the above preparation method, step S100, step S200, and step S300 can be performed in any order or simultaneously, as long as the compound in each step is obtained for use in step S400. The numbering of the above steps is only for illustration and does not limit the specific order.

[0048] Specifically, the artificial water channel molecule includes: at least one compound of formula I, wherein

[0049]

[0050] Wherein, R represents a complex functional group comprising a hydroxyl group, a carboxyl group, and / or an imidazole group. At least one compound of Formula I exists in the form of a supramolecular aggregate, which is a nanoscale microcrystal with an average diameter of less than 100 nm, and the crystals are a quadruple lamellar phase. The artificial water channel molecules include phenyl, urea, and hydrophilic complex functional groups, connected by hydrogen bonds through the urea groups, and form tubular supramolecular aggregates through π-π stacking of the phenyl groups.

[0051] Hydroxyl, carboxyl, and imidazole groups provide hydrophilicity to the hydrophilic composite functional groups. The oxygen and nitrogen atoms within these groups are capable of polarization and hydrogen bonding with water, providing hydrogen bonding sites and transport pathways for water molecules within the supramolecular aggregate channels. The self-assembly of phenyl and urea groups, combined with the binding ability of the hydrophilic groups and water molecules, creates tubular water channels.

[0052] Specifically, the first organic solvent includes one or more of dimethyl sulfoxide, methanol, ethanol, ethylene glycol, acetonitrile, acetone, and isopropanol, preferably methanol or ethanol. By varying the composition of the first organic solvent, the viscosity and polarity of the solution can be controlled to regulate the morphology and size of the artificial water channel self-assembly crystals.

[0053] Specifically, the aromatic polyfunctional amine includes one or more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine and mesitylenetriamine, preferably m-phenylenediamine.

[0054] Specifically, the additive includes one or more of camphorsulfonic acid, N,N-dimethylformamide, dimethyl sulfoxide, acetone, ethyl acetate, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate, and sodium dodecyl sulfate, preferably sodium dodecyl sulfate. Camphorsulfonic acid, N,N-dimethylformamide, dimethyl sulfoxide, acetone, ethyl acetate, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate, and sodium dodecyl sulfate can provide a co-solvent interface between the two phases or increase the interfacial mass transfer rate, thereby promoting polyamide membrane formation, improving the doping efficiency of the artificial water channel, and reducing polyamide membrane defects. The increase in the diffusion rate of polyamide monomers at the interface between the two phases accelerates the reaction of polyamide and is conducive to the formation of a dense polyamide layer; the supramolecular aggregates of artificial water channels are suspended in the solution in the form of microcrystals, and the additives are conducive to the migration of artificial water channels at the phase interface, thereby improving the doping of artificial water channels in the polyamide active layer; artificial water channel microcrystals may agglomerate in the solution, and the large particles formed by the agglomeration are doped into the polyamide active layer, resulting in a decrease in the salt retention rate of the polyamide active layer. The additives can prevent the agglomeration of microcrystals, thereby improving the compatibility of artificial water channels with polyamide and enhancing the adaptability of the polyamide layer to microcrystal doping.

[0055] Specifically, the aromatic multifunctional acyl chloride includes one or more of phthaloyl chloride, isophthaloyl chloride and trimesoyl chloride, preferably trimesoyl chloride.

[0056] Metaphenylenediamine, paraphenylenediamine, o-phenylenediamine, iso-phenylenediamine, trimesoyl chloride, phthaloyl chloride, and isophthaloyl chloride are all monomers of aromatic polyamide thin layer composite membranes. The water permeability or salt rejection rate of the membrane can be improved by changing the type of monomers.

[0057] Specifically, the hydrocarbon solvent includes one or more of Isopar, n-pentane, n-hexane, n-heptane, and n-octane, with n-hexane being preferred. Isopar, n-pentane, n-hexane, n-heptane, and n-octane have different viscosities. Using a high-viscosity solvent results in a smoother film surface, while using a low-viscosity solvent results in a rougher film surface.

[0058] Based on the specific implementation of the above-mentioned various compounds, the numerical range of the first preset ratio value in step S100 is 0.01% to 10%, preferably 0.1% to 1.0%; the numerical range of the second preset ratio value in step S200 is 0.25% to 8%, preferably 1.0% to 4.0%; the numerical range of the third preset ratio value in step S200 is 0.025% to 0.8%, preferably 0.1% to 0.5%; the numerical range of the preset pH value in step S200 is 10 to 12, preferably 10; the fourth preset ratio value in step S300 is 0.05% to 0.25%, preferably 0.1% to 0.2%; and / or the numerical range of the preset ratio value in step S400 is 1:1 to 1:10, preferably 1:5. The ratio of water to ethanol can control the crystallization behavior of the artificial water channel. Increasing the water ratio is conducive to the formation of larger crystals, but too much water will result in poor dispersibility of the artificial water channel crystal particles.

[0059] Specifically, the porous support layer is an ultrafiltration membrane with a molecular weight cut-off in the range of 10 kD to 250 kD, preferably 20 kD to 50 kD. Optionally, the ultrafiltration membrane is a polysulfone membrane, polyethersulfone membrane, polyacrylonitrile membrane, or polyvinylidene fluoride membrane produced on a non-woven fabric by a phase inversion method, preferably a polysulfone membrane or a polyethersulfone membrane.

[0060] Specifically, in step S400, after one side of the porous support layer is immersed in the mixed solution, the excess mixed solution on the surface of the porous support layer is removed, and then the second organic solution is coated; similarly, after the excess second organic solution on the surface is removed, cleaning and drying operations are performed.

[0061] Optionally, in step S400, the method for removing excess mixed solution and / or second organic solution on the surface of the porous support layer includes: rolling method and / or air blowing method; the cleaning process includes: n-hexane rinsing and / or deionized water soaking; and / or, the drying temperature is 50°C to 90°C, and the drying time is 5min to 30min.

[0062] Below, a comparative example and several examples are used to further illustrate the preparation method of the composite biomimetic membrane with artificial water channels in the present invention:

[0063] Comparative Example

[0064] 1. Prepare aqueous phase

[0065] Add 20 g of m-phenylenediamine into 1 L of water, and after it is completely dissolved, adjust the pH value of the solution to 10 with triethylamine, and degas by ultrasonication for 1 min to obtain an aqueous phase liquid.

[0066] 2. Prepare organic solution

[0067] 1 g of trimesoyl chloride was added to 1 L of n-hexane and completely dissolved to obtain an organic solution.

[0068] 3. Preparation of polyamide thin layer composite membrane:

[0069] A 20 kDa molecular weight cutoff polysulfone membrane-nonwoven fabric was placed on a metal plate with the polysulfone side facing outward. The membrane was moistened with aqueous solution A for 2 minutes. Excess mixed solution was removed with a rubber roller. Organic solution A was then applied to the same surface for 1 minute to initiate interfacial polymerization, completing the preparation of a polyamide thin-layer composite membrane. The membrane surface was cleaned with n-hexane and dried in a 60°C oven for 5 minutes. The resulting polyamide thin-layer composite membrane was then stored in deionized water.

[0070] Example 1

[0071] 1. Prepare artificial water channel organic solution

[0072] 2.5 g of artificial water channel molecules were added to 1 L of ethanol and completely dissolved to obtain an artificial water channel organic solution.

[0073] The first organic solution in the above steps is an ethanol solution.

[0074] 2. Prepare aqueous phase liquid

[0075] Add 20 g of m-phenylenediamine to 1 L of water. After it is completely dissolved, add 2 g of sodium dodecyl sulfate. After it is completely dissolved, adjust the pH value of the solution to 10 with NaOH. Degas by ultrasonication for 1 minute to obtain an aqueous phase liquid.

[0076] In the above steps, the aromatic multifunctional amine is m-phenylenediamine, the additive is sodium lauryl sulfate, and NaOH is used to adjust the pH value of the solution.

[0077] 3. Prepare organic solution

[0078] 1 g of trimesoyl chloride was added to 1 L of n-hexane and completely dissolved to obtain a second organic solution.

[0079] In the above steps, the aromatic multifunctional acyl chloride is trimesoyl chloride, and the hydrocarbon solvent is n-hexane.

[0080] 4. Preparation of a thin polyamide composite membrane with artificial water channels: Add the artificial water channel organic solution A to the aqueous phase at a ratio of 1:5 to obtain a mixed solution. Place a 20 kDa molecular weight cutoff polysulfone membrane-nonwoven fabric membrane on a metal plate with the polysulfone side facing outward. Wet the membrane with the mixed solution for 2 minutes. Remove the excess mixed solution with a rubber roller, then apply a second organic solution to the same surface for 1 minute to induce interfacial polymerization, completing the preparation of the thin polyamide composite membrane with artificial water channels. Clean the membrane surface with n-hexane and dry it in a 60°C oven for 5 minutes to obtain a biomimetic composite membrane with artificial water channels. Store in deionized water.

[0081] Example 2

[0082] 1. Prepare artificial water channel organic solution

[0083] 2.5 g of artificial water channel molecules were added to 1 L of methanol and completely dissolved to obtain an artificial water channel organic solution.

[0084] 2. Prepare aqueous phase liquid

[0085] Add 2.5 g of p-phenylenediamine to 1 L of water, and add 2 ml of dimethyl sulfoxide after it is completely dissolved. After it is completely dissolved, adjust the pH value of the solution to 10 with triethylamine, and degas by ultrasonication for 1 minute to obtain an aqueous phase liquid.

[0086] 3. Prepare organic solution

[0087] 0.5 g of trimesoyl chloride was added to 1 L of n-heptane and completely dissolved to obtain a second organic solution.

[0088] 4. Preparation of polyamide thin layer composite membrane with artificial water channels

[0089] The artificial water channel organic solution was added to the aqueous phase at a ratio of 1:5 to obtain a mixed solution. A polysulfone membrane-nonwoven fabric with a molecular weight cutoff of 20 kDa was placed on a metal plate with the polysulfone side facing outward. The membrane was moistened with the mixed solution for 2 minutes. Excess mixed solution was removed with a rubber roller, and then a second organic solution was applied to the same surface for 1 minute to induce interfacial polymerization, completing the preparation of a thin polyamide composite membrane with artificial water channels. The membrane surface was cleaned with n-hexane and dried in a 60°C oven for 5 minutes to obtain a composite biomimetic membrane with artificial water channels. The membrane was then stored in deionized water.

[0090] Example 3

[0091] 1. Prepare artificial water channel organic solution

[0092] 2.5 g of artificial water channel molecules were added to 1 L of a methanol / isopropanol (1 / 1) mixed solution and dissolved completely to obtain an artificial water channel organic solution.

[0093] 2. Prepare aqueous phase liquid

[0094] Add 10 g of p-phenylenediamine to 1 L of water, and add 5 ml of acetone after it is completely dissolved. After it is completely dissolved, adjust the pH value of the solution to 12 with triethylamine, and degas by ultrasonication for 1 minute to obtain an aqueous phase liquid.

[0095] 3. Prepare organic solution

[0096] 1 g of trimesoyl chloride was added to 1 L of n-hexane and completely dissolved to obtain a second organic solution.

[0097] 4. Preparation of polyamide thin layer composite membrane with artificial water channels

[0098] The artificial water channel organic solution was added to the aqueous phase at a ratio of 1:5 to obtain a mixed solution. A polysulfone membrane-nonwoven fabric with a molecular weight cutoff of 20 kDa was placed on a metal plate with the polysulfone side facing outward. The membrane was moistened with the mixed solution for 2 minutes. Excess mixed solution was removed with a rubber roller, and then a second organic solution was applied to the same surface for 1 minute to induce interfacial polymerization, completing the preparation of a thin polyamide composite membrane with artificial water channels. The membrane surface was cleaned with n-hexane and dried in a 60°C oven for 10 minutes to obtain a biomimetic composite membrane with artificial water channels. The membrane was then stored in deionized water.

[0099] Example 4

[0100] 1. Prepare artificial water channel organic solution

[0101] 2.5 g of artificial water channel molecules were added to 1 L of isopropanol and completely dissolved to obtain an artificial water channel organic solution.

[0102] 2. Prepare aqueous phase liquid

[0103] Add 20 g of m-phenylenediamine to 1 L of water, and add 2 ml of ethyl acetate after it is completely dissolved. After it is completely dissolved, adjust the pH value of the solution to 10 with NaOH, and degas by ultrasonication for 1 minute to obtain an aqueous phase liquid.

[0104] 3. Prepare organic solution

[0105] 1 g of phthaloyl chloride was added to 1 L of Isopar and completely dissolved to obtain a second organic solution.

[0106] 4. Preparation of polyamide thin layer composite membrane with artificial water channels

[0107] The organic solution of artificial water channels was added to the aqueous phase at a ratio of 1:5 to obtain a mixed solution. A polysulfone membrane-nonwoven fabric with a molecular weight cutoff of 20 kDa was placed on a metal plate with the polysulfone side facing outward. The membrane was moistened with the mixed solution for 2 minutes. Excess mixed solution was removed with a rubber roller, and then a second organic solution was applied to the same surface for 1 minute to induce interfacial polymerization, completing the preparation of a thin polyamide composite membrane with artificial water channels. The membrane surface was cleaned with n-hexane and dried in an 80°C oven for 5 minutes to obtain a composite biomimetic membrane with artificial water channels. The membrane was then stored in deionized water.

[0108] Example 5

[0109] 1. Prepare artificial water channel organic solution

[0110] 2.5 g of artificial water channel molecules were added to 1 L of ethylene glycol and completely dissolved to obtain an artificial water channel organic solution.

[0111] 2. Prepare aqueous phase liquid

[0112] Add 20 g of m-phenylenediamine to 1 L of water. After it is completely dissolved, add 2 g of sodium dodecylbenzenesulfonate. After it is completely dissolved, adjust the pH value of the solution to 11 with NaOH. Degas by ultrasonication for 1 minute to obtain an aqueous phase liquid.

[0113] 3. Prepare organic solution

[0114] 1 g of isophthaloyl dichloride was added to 1 L of n-hexane and completely dissolved to obtain a second organic solution.

[0115] 4. Preparation of polyamide thin layer composite membrane with artificial water channels

[0116] The artificial water channel organic solution was added to the aqueous phase at a ratio of 1:5 to obtain a mixed solution. A polysulfone membrane-nonwoven fabric with a molecular weight cutoff of 50 kDa was placed on a metal plate with the polysulfone side facing outward. The membrane was moistened with the mixed solution for 2 minutes, purged with nitrogen to remove excess mixed solution, and then a second organic solution was applied to the same surface for 1 minute to induce interfacial polymerization, completing the preparation of a thin polyamide composite membrane with artificial water channels. The membrane surface was cleaned with n-hexane and dried in a 60°C oven for 5 minutes to obtain a composite biomimetic membrane with artificial water channels. The membrane was then stored in deionized water.

[0117] Example 6

[0118] 1. Prepare artificial water channel organic solution

[0119] 0.1 g of artificial water channel molecules were added to 1 L of ethanol / isopropanol (1 / 1) mixed solution and dissolved completely to obtain an artificial water channel organic solution.

[0120] 2. Prepare aqueous phase liquid

[0121] 40 g of o-phenylenediamine was added to 1 L of water. After it was completely dissolved, 5 g of camphorsulfonic acid was added. After it was completely dissolved, the pH value of the solution was adjusted to 10 with NaOH. The solution was degassed by ultrasonication for 1 min to obtain an aqueous phase liquid.

[0122] 3. Prepare organic solution

[0123] 0.5 g of trimesoyl chloride and 0.5 g of phthaloyl chloride were added to 1 L of n-hexane and completely dissolved to obtain a second organic solution.

[0124] 4. Preparation of polyamide thin layer composite membrane with artificial water channels

[0125] The organic solution of artificial water channels was added to the aqueous phase at a 1:1 ratio to form a mixed solution. A polyethersulfone membrane-nonwoven fabric with a molecular weight cutoff of 10 kDa was placed on a metal plate with the polyethersulfone side facing outward. The membrane was moistened with the mixed solution for 2 minutes, then purged with nitrogen to remove excess mixed solution. A second organic solution was then applied to the same surface for 1 minute to initiate interfacial polymerization, completing the preparation of a thin polyamide composite membrane with artificial water channels. The membrane surface was cleaned with n-hexane and dried in a 50°C oven for 30 minutes to obtain a biomimetic composite membrane with artificial water channels. The membrane was then stored in deionized water.

[0126] Example 7

[0127] 1. Prepare artificial water channel organic solution

[0128] 10 g of artificial water channel molecules were added to 1 L of ethanol / ethylene glycol (1 / 1) mixed solution and dissolved completely to obtain an artificial water channel organic solution.

[0129] 2. Prepare aqueous phase liquid

[0130] 80 g of phenyltriamine was added to 1 L of water. After it was completely dissolved, 1 ml of N,N-dimethylformamide was added. After it was completely dissolved, the pH value of the solution was adjusted to 11 with NaOH. The solution was degassed by ultrasonication for 1 min to obtain an aqueous phase liquid.

[0131] 3. Prepare organic solution

[0132] 0.5 g of trimesoyl chloride and 0.5 g of isophthaloyl chloride were added to 1 L of n-hexane and completely dissolved to obtain a second organic solution.

[0133] 4. Preparation of polyamide thin layer composite membrane with artificial water channels

[0134] The artificial water channel organic solution was added to the aqueous phase at a 1:1 ratio to form a mixed solution. A 50 kDa molecular weight cut-off polyacrylonitrile membrane-nonwoven fabric was placed on a metal plate with the polyacrylonitrile side facing outward. The membrane was moistened with the mixed solution for 2 minutes, purged with nitrogen to remove excess mixed solution, and then a second organic solution was applied to the same surface for 1 minute to initiate interfacial polymerization, completing the preparation of a thin polyamide composite membrane with artificial water channels. The membrane surface was cleaned with n-hexane and dried in a 60°C oven for 20 minutes to obtain a biomimetic composite membrane with artificial water channels. The membrane was then stored in deionized water.

[0135] Example 8

[0136] 1. Prepare artificial water channel organic solution

[0137] 20 g of artificial water channel molecules were added to 1 L of dimethyl sulfoxide and dissolved completely to obtain an artificial water channel organic solution.

[0138] 2. Prepare aqueous phase liquid

[0139] Add 10 g of m-phenylenediamine and 10 g of p-phenylenediamine to 1 L of water. After they are completely dissolved, add 0.25 g of sodium dodecylbenzenesulfonate. After they are completely dissolved, adjust the pH value of the solution to 11 with NaOH. Degas by ultrasonication for 1 minute to obtain an aqueous phase liquid.

[0140] 3. Prepare organic solution

[0141] 2 g of trimesoyl chloride was added to 1 L of n-pentane and completely dissolved to obtain a second organic solution.

[0142] 4. Preparation of polyamide thin layer composite membrane with artificial water channels

[0143] The artificial water channel organic solution was added to the aqueous phase at a ratio of 1:5 to obtain a mixed solution. A polyacrylonitrile membrane-nonwoven fabric with a molecular weight cutoff of 100 kDa was placed on a metal plate with the polyacrylonitrile side facing outward. The membrane was moistened with the mixed solution for 2 minutes, purged with nitrogen to remove excess mixed solution, and then a second organic solution was applied to the same surface for 1 minute to undergo interfacial polymerization, completing the preparation of a thin polyamide composite membrane with artificial water channels. The membrane surface was cleaned with n-hexane and dried in a 70°C oven for 15 minutes to obtain a biomimetic composite membrane with artificial water channels. The membrane was then stored in deionized water.

[0144] Example 9

[0145] 1. Prepare artificial water channel organic solution

[0146] 50 g of artificial water channel molecules were added to 1 L of a methanol / acetonitrile (1 / 1) mixed solution and dissolved completely to obtain an artificial water channel organic solution.

[0147] 2. Prepare aqueous phase liquid

[0148] Add 10 g of m-phenylenediamine and 10 g of o-phenylenediamine to 1 L of water. After they are completely dissolved, add 2 g of sodium dodecylbenzenesulfonate and 2 ml of acetone. After they are completely dissolved, adjust the pH value of the solution to 12 with NaOH. Degas by ultrasonication for 1 minute to obtain an aqueous phase liquid.

[0149] 3. Prepare organic solution

[0150] 2 g of trimesoyl chloride was added to 1 L of n-heptane and completely dissolved to obtain a second organic solution.

[0151] 4. Preparation of polyamide thin layer composite membrane with artificial water channels

[0152] The artificial water channel organic solution was added to the aqueous phase at a ratio of 1:5 to obtain a mixed solution. A polyvinylidene fluoride (PVDF)-nonwoven membrane with a molecular weight cutoff of 100 kDa was placed on a metal plate with the PVDF side facing outward. The membrane was moistened with the mixed solution for 2 minutes, purged with nitrogen to remove excess mixed solution, and then a second organic solution was applied to the same surface for 1 minute to induce interfacial polymerization, completing the preparation of a thin polyamide composite membrane with artificial water channels. The membrane surface was cleaned with n-hexane and dried in an 80°C oven for 10 minutes to obtain a composite biomimetic membrane with artificial water channels. The membrane was then stored in deionized water.

[0153] Example 10

[0154] 1. Prepare artificial water channel organic solution

[0155] 100 g of artificial water channel molecules were added to 1 L of ethanol / acetone (1 / 1) mixed solution and dissolved completely to obtain an artificial water channel organic solution.

[0156] 2. Prepare aqueous phase liquid

[0157] Add 10 g of m-phenylenediamine and 10 g of s-phenyltriamine to 1 L of water. After they are completely dissolved, add 2 g of camphorsulfonic acid and 2 ml of acetone. After they are completely dissolved, adjust the pH value of the solution to 12 with NaOH. Degas by ultrasonication for 1 minute to obtain an aqueous phase liquid.

[0158] 3. Prepare organic solution

[0159] 2.5 g of trimesoyl chloride was added to 1 L of n-octane and completely dissolved to obtain a second organic solution.

[0160] 4. Preparation of polyamide thin layer composite membrane with artificial water channels

[0161] The artificial water channel organic solution was added to the aqueous phase at a ratio of 1:10 to obtain a mixed solution. A polyvinylidene fluoride (PVDF)-nonwoven membrane with a molecular weight cutoff of 250 kDa was placed on a metal plate with the PVDF side facing outward. The membrane was moistened with the mixed solution for 2 minutes, purged with nitrogen to remove excess mixed solution, and then a second organic solution was applied to the same surface for 1 minute to initiate interfacial polymerization, completing the preparation of a thin polyamide composite membrane with artificial water channels. The membrane surface was cleaned with n-hexane and dried in a 90°C oven for 5 minutes to obtain a composite biomimetic membrane with artificial water channels. The membrane was then stored in deionized water.

[0162] Example 11

[0163] 1. Prepare artificial water channel organic solution

[0164] 0.1 g of artificial water channel molecules were added to 1 L of ethanol and completely dissolved to obtain an artificial water channel organic solution.

[0165] The first organic solution in the above steps is an ethanol solution.

[0166] 2. Prepare aqueous phase liquid

[0167] Add 20 g of m-phenylenediamine to 1 L of water. After it is completely dissolved, add 0.25 g of sodium dodecyl sulfate. After it is completely dissolved, adjust the pH value of the solution to 10 with NaOH. Degas by ultrasonication for 1 minute to obtain an aqueous phase liquid.

[0168] In the above steps, the aromatic multifunctional amine is m-phenylenediamine, the additive is sodium lauryl sulfate, and NaOH is used to adjust the pH value of the solution.

[0169] 3. Prepare organic solution

[0170] 1 g of trimesoyl chloride was added to 1 L of n-hexane and completely dissolved to obtain a second organic solution.

[0171] In the above steps, the aromatic multifunctional acyl chloride is trimesoyl chloride, and the hydrocarbon solvent is n-hexane.

[0172] 4. Preparation of a thin polyamide composite membrane with artificial water channels: Add the artificial water channel organic solution A to the aqueous phase at a ratio of 1:5 to obtain a mixed solution. Place a 20 kDa molecular weight cutoff polysulfone membrane-nonwoven fabric membrane on a metal plate with the polysulfone side facing outward. Wet the membrane with the mixed solution for 2 minutes. Remove the excess mixed solution with a rubber roller, then apply a second organic solution to the same surface for 1 minute to induce interfacial polymerization, completing the preparation of the thin polyamide composite membrane with artificial water channels. Clean the membrane surface with n-hexane and dry it in a 60°C oven for 5 minutes to obtain a biomimetic composite membrane with artificial water channels. Store in deionized water.

[0173] Example 12

[0174] 1. Prepare artificial water channel organic solution

[0175] 10 g of artificial water channel molecules were added to 1 L of ethanol and completely dissolved to obtain an artificial water channel organic solution.

[0176] The first organic solution in the above steps is an ethanol solution.

[0177] 2. Prepare aqueous phase liquid

[0178] Add 20 g of m-phenylenediamine to 1 L of water. After it is completely dissolved, add 0.25 g of sodium dodecyl sulfate. After it is completely dissolved, adjust the pH value of the solution to 10 with NaOH. Degas by ultrasonication for 1 minute to obtain an aqueous phase liquid.

[0179] In the above steps, the aromatic multifunctional amine is m-phenylenediamine, the additive is sodium lauryl sulfate, and NaOH is used to adjust the pH value of the solution.

[0180] 3. Prepare organic solution

[0181] 1 g of trimesoyl chloride was added to 1 L of n-hexane and completely dissolved to obtain a second organic solution.

[0182] In the above steps, the aromatic multifunctional acyl chloride is trimesoyl chloride, and the hydrocarbon solvent is n-hexane.

[0183] 4. Preparation of a thin polyamide composite membrane with artificial water channels: Add the artificial water channel organic solution A to the aqueous phase at a ratio of 1:5 to obtain a mixed solution. Place a 20 kDa molecular weight cutoff polysulfone membrane-nonwoven fabric membrane on a metal plate with the polysulfone side facing outward. Wet the membrane with the mixed solution for 2 minutes. Remove the excess mixed solution with a rubber roller, then apply a second organic solution to the same surface for 1 minute to induce interfacial polymerization, completing the preparation of the thin polyamide composite membrane with artificial water channels. Clean the membrane surface with n-hexane and dry it in a 60°C oven for 5 minutes to obtain a biomimetic composite membrane with artificial water channels. Store in deionized water.

[0184] Example 13

[0185] 1. Prepare artificial water channel organic solution

[0186] 100 g of artificial water channel molecules were added to 1 L of ethanol and completely dissolved to obtain an artificial water channel organic solution.

[0187] The first organic solution in the above steps is an ethanol solution.

[0188] 2. Prepare aqueous phase liquid

[0189] Add 20 g of m-phenylenediamine to 1 L of water. After it is completely dissolved, add 0.25 g of sodium dodecyl sulfate. After it is completely dissolved, adjust the pH value of the solution to 10 with NaOH. Degas by ultrasonication for 1 minute to obtain an aqueous phase liquid.

[0190] In the above steps, the aromatic multifunctional amine is m-phenylenediamine, the additive is sodium lauryl sulfate, and NaOH is used to adjust the pH value of the solution.

[0191] 3. Prepare organic solution

[0192] 1 g of trimesoyl chloride was added to 1 L of n-hexane and completely dissolved to obtain a second organic solution.

[0193] In the above steps, the aromatic multifunctional acyl chloride is trimesoyl chloride, and the hydrocarbon solvent is n-hexane.

[0194] 4. Preparation of a thin polyamide composite membrane with artificial water channels: Add the artificial water channel organic solution A to the aqueous phase at a ratio of 1:5 to obtain a mixed solution. Place a 20 kDa molecular weight cutoff polysulfone membrane-nonwoven fabric membrane on a metal plate with the polysulfone side facing outward. Wet the membrane with the mixed solution for 2 minutes. Remove the excess mixed solution with a rubber roller, then apply a second organic solution to the same surface for 1 minute to induce interfacial polymerization, completing the preparation of the thin polyamide composite membrane with artificial water channels. Clean the membrane surface with n-hexane and dry it in a 60°C oven for 5 minutes to obtain a biomimetic composite membrane with artificial water channels. Store in deionized water.

[0195] Example 14

[0196] 1. Prepare artificial water channel organic solution

[0197] 10 g of artificial water channel molecules were added to 1 L of ethanol and completely dissolved to obtain an artificial water channel organic solution.

[0198] The first organic solution in the above steps is an ethanol solution.

[0199] 2. Prepare aqueous phase liquid

[0200] Add 20 g of m-phenylenediamine to 1 L of water. After it is completely dissolved, add 8 g of sodium dodecyl sulfate. After it is completely dissolved, adjust the pH value of the solution to 10 with NaOH. Degas by ultrasonication for 1 minute to obtain an aqueous phase liquid.

[0201] In the above steps, the aromatic multifunctional amine is m-phenylenediamine, the additive is sodium lauryl sulfate, and NaOH is used to adjust the pH value of the solution.

[0202] 3. Prepare organic solution

[0203] 1 g of trimesoyl chloride was added to 1 L of n-hexane and completely dissolved to obtain a second organic solution.

[0204] In the above steps, the aromatic multifunctional acyl chloride is trimesoyl chloride, and the hydrocarbon solvent is n-hexane.

[0205] 4. Preparation of a thin polyamide composite membrane with artificial water channels: Add the artificial water channel organic solution A to the aqueous phase at a ratio of 1:5 to obtain a mixed solution. Place a 20 kDa molecular weight cutoff polysulfone membrane-nonwoven fabric membrane on a metal plate with the polysulfone side facing outward. Wet the membrane with the mixed solution for 2 minutes. Remove the excess mixed solution with a rubber roller, then apply a second organic solution to the same surface for 1 minute to induce interfacial polymerization, completing the preparation of the thin polyamide composite membrane with artificial water channels. Clean the membrane surface with n-hexane and dry it in a 60°C oven for 5 minutes to obtain a biomimetic composite membrane with artificial water channels. Store in deionized water.

[0206] Example 15

[0207] 1. Prepare artificial water channel organic solution

[0208] 100 g of artificial water channel molecules were added to 1 L of ethanol and completely dissolved to obtain an artificial water channel organic solution.

[0209] The first organic solution in the above steps is an ethanol solution.

[0210] 2. Prepare aqueous phase liquid

[0211] Add 20 g of m-phenylenediamine to 1 L of water. After it is completely dissolved, add 8 g of sodium dodecyl sulfate. After it is completely dissolved, adjust the pH value of the solution to 10 with NaOH. Degas by ultrasonication for 1 minute to obtain an aqueous phase liquid.

[0212] In the above steps, the aromatic multifunctional amine is m-phenylenediamine, the additive is sodium lauryl sulfate, and NaOH is used to adjust the pH value of the solution.

[0213] 3. Prepare organic solution

[0214] 1 g of trimesoyl chloride was added to 1 L of n-hexane and completely dissolved to obtain a second organic solution.

[0215] In the above steps, the aromatic multifunctional acyl chloride is trimesoyl chloride, and the hydrocarbon solvent is n-hexane.

[0216] 4. Preparation of a thin polyamide composite membrane with artificial water channels: Add the artificial water channel organic solution A to the aqueous phase at a ratio of 1:5 to obtain a mixed solution. Place a 20 kDa molecular weight cutoff polysulfone membrane-nonwoven fabric membrane on a metal plate with the polysulfone side facing outward. Wet the membrane with the mixed solution for 2 minutes. Remove the excess mixed solution with a rubber roller, then apply a second organic solution to the same surface for 1 minute to induce interfacial polymerization, completing the preparation of the thin polyamide composite membrane with artificial water channels. Clean the membrane surface with n-hexane and dry it in a 60°C oven for 5 minutes to obtain a biomimetic composite membrane with artificial water channels. Store in deionized water.

[0217] The prepared membranes were subjected to reverse osmosis testing using a cross-flow filtration system, including measurements of permeate flow rate and solute retention. The cross-flow filtration system includes a centrifugal piston pump, pressure controlled by a bypass valve and back-pressure regulator, flow controlled by a floating disc rotor flowmeter, and temperature controlled by a recirculating chiller. The feed solution circulates between the feed tank, stainless steel disc, and membrane press tank. The permeate, under pressure, enters the effluent tank from the membrane press tank.

[0218] The membrane's water permeability (A), water flux, and solute retention were measured as follows: After placing the membrane sample in a pressurized membrane cell, the sample was compacted at 20 bar for 2 hours. The pressure was then reduced to 16 bar. The water flux, Jw, was calculated by dividing the permeate volume obtained at equilibrium by the membrane's surface area. The membrane's water permeability was calculated using the formula: A = Jw / ΔP. After equilibrium, the conductivity of the permeate outlet and inlet water was measured every 30 minutes to calculate the solute concentration and solute retention. The membrane performance data obtained from the tests is shown in Table 1.

[0219] Table 1 Performance of the reverse osmosis membranes prepared in Examples 1-15 and Comparative Example 1

[0220]

[0221] By comparing the examples, it can be found that the addition of artificial water channels significantly improves the water permeability coefficient of the polyamide membrane, and the preferred addition concentration of artificial water channels is 0.1% to 1.0%. When the concentration of artificial water channels is too low, the improvement on the polyamide composite membrane is small; when the concentration of artificial water channels is too high, the microcrystals agglomerate into large particles, causing doping, which destroys the integrity of the polyamide layer and leads to a significantly lower salt retention rate. The appropriate use of additives can alleviate the damage of microcrystal agglomeration to the polyamide layer and improve the compatibility of artificial water channels with the polyamide layer, but excessive use of additives will affect the water permeability coefficient of the polyamide membrane. The artificial water channel biomimetic membrane improves the water permeability of the polyamide membrane through the artificial water channel supramolecular aggregates, and improves the compatibility of artificial water channels and polyamide membrane through additives, while improving the water permeability coefficient and salt retention rate of the membrane.

[0222] like Figure 2 The figure shows the X-ray diffraction pattern of the quartet layered phase of the compound of formula I provided in an embodiment of the present invention. The peaks are concentrated and there are fewer impurity peaks, indicating that the artificial water channels are of high purity and the nano-scale microcrystals have high crystallinity.

[0223] like Figure 3 Shown is a scanning electron microscope image of the surface of a polyamide thin-layer composite membrane with artificial water channels provided by an embodiment of the present invention. The membrane surface is smooth and neat, indicating that the doping of artificial water channel microcrystals does not cause membrane defects.

[0224] like Figure 4 Shown is a transmission electron microscope image of a cross section of a polyamide thin layer composite membrane with artificial water channels provided by an embodiment of the present invention, in which doped artificial water channel microcrystals in the polyamide layer can be clearly observed.

[0225] The embodiment of the present invention is intended to protect a method for preparing a composite biomimetic membrane with artificial water channels, comprising the following steps: dissolving artificial water channel molecules with a mass concentration of a first preset ratio value in a first organic solution to obtain an artificial water channel organic solution; dissolving an aromatic multifunctional amine with a mass concentration of a second preset ratio value in water, adding an additive with a mass concentration of a third preset ratio value, adjusting the pH value of the solution to a preset pH value, and performing ultrasonic degassing to obtain an aqueous phase liquid; dissolving an aromatic multifunctional acyl chloride with a mass concentration of a fourth preset ratio value in a hydrocarbon solvent to obtain a second organic solution; mixing the artificial water channel organic solution and the aqueous phase liquid at a preset ratio, coating one side of the porous support layer with the second organic solution after soaking in the mixed solution, and obtaining a composite biomimetic membrane with artificial water channels after cleaning and drying. The above technical solution has the following effects:

[0226] 1. The present invention obtains an artificial water channel colloid solution of specific size and concentration by self-assembling artificial water channel molecules into supramolecular aggregates. The artificial water channel colloid is then encapsulated in a polyamide active layer through polyamide layer regulation to produce a polyamide thin-layer composite membrane with artificial water channels.

[0227] 2. The present invention can obtain nanoscale artificial water channel supramolecular aggregates by simply uniformly mixing the solutions. It has the advantages of simple process, convenient operation, and easy industrialization, and can be widely used in industrial production.

[0228] 3. The polyamide thin-layer composite membrane with artificial water channels in the present invention has high hydrophilicity, can prevent organic pollution, and its membrane flux and desalination rate can be maintained at a high level for a long time.

[0229] It should be understood that the above-described specific embodiments of the present invention are merely illustrative or illustrative of the principles of the present invention and do not constitute limitations of the present invention. Therefore, any modifications, equivalent substitutions, improvements, etc. made without departing from the spirit and scope of the present invention should be included within the scope of protection of the present invention. In addition, the appended claims are intended to cover all variations and modifications that fall within the scope and metes and bounds of the appended claims, or equivalents thereof.

Claims

1. A method for preparing a composite biomimetic membrane with artificial water channels, characterized in that: The steps include: Dissolving artificial water channel molecules having a mass concentration of a first preset ratio in a first organic solution to obtain an artificial water channel organic solution; the artificial water channel molecules include: at least one compound of formula I, Formula I wherein R represents a complex functional group comprising a hydroxyl group, a carboxyl group and / or an imidazole group, and the at least one compound of formula I exists in the form of a supramolecular aggregate; the supramolecular aggregate is a nanoscale microcrystal with an average diameter of less than 100 nm, and the crystal is a quadruple layered phase; dissolving an aromatic polyfunctional amine having a mass concentration of a second preset ratio value in water, adding an additive having a mass concentration of a third preset ratio value, adjusting the pH value of the solution to a preset pH value, and performing ultrasonic degassing to obtain an aqueous phase liquid; dissolving an aromatic polyfunctional acyl chloride having a mass concentration of a fourth preset ratio in a hydrocarbon solvent to obtain a second organic solution; The artificial water channel organic solution and the aqueous phase liquid are mixed in a preset ratio, one side of the porous support layer is soaked in the mixed solution and then coated with the second organic solution, and then cleaned and dried to obtain a composite bionic membrane with artificial water channels.

2. The method for preparing a composite biomimetic membrane having an artificial water channel according to claim 1, wherein: The artificial water channel molecule includes a phenyl group, a urea group, and a hydrophilic composite functional group, which are connected by hydrogen bonds through the urea group and form a tubular supramolecular aggregate through π-π stacking of the phenyl groups. The hydrophilic composite functional group provides hydrogen bonding sites and transmission paths for water molecules in the supramolecular aggregate channel, and the phenyl group twists and forms an angle with the plane where the urea group is located.

3. The method for preparing a composite biomimetic membrane having an artificial water channel according to claim 2, wherein: The first organic solution includes one or more of dimethyl sulfoxide, methanol, ethanol, ethylene glycol, acetonitrile, acetone and isopropanol.

4. The method for preparing a composite biomimetic membrane having an artificial water channel according to claim 3, characterized in that: The first organic solution is methanol or ethanol.

5. The method for preparing a composite biomimetic membrane having an artificial water channel according to claim 3, wherein: The aromatic multifunctional amine includes one or more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine and mesitylenetriamine; and / or, The additives include one or more of camphorsulfonic acid, N,N-dimethylformamide, dimethyl sulfoxide, acetone, ethyl acetate, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate and sodium dodecyl sulfate.

6. The method for preparing a composite biomimetic membrane having an artificial water channel according to claim 5, characterized in that: The aromatic multifunctional amine is m-phenylenediamine, and / or the additive is sodium lauryl sulfate.

7. The method for preparing a composite biomimetic membrane having an artificial water channel according to claim 5, characterized in that: The aromatic multifunctional acyl chloride includes one or more of phthaloyl chloride, isophthaloyl chloride and trimesoyl chloride.

8. The method for preparing a composite biomimetic membrane having an artificial water channel according to claim 7, characterized in that: The aromatic multifunctional acyl chloride is trimesoyl chloride.

9. The method for preparing a composite biomimetic membrane having an artificial water channel according to claim 7, characterized in that: The hydrocarbon solvent includes one or more of Isopar, n-pentane, n-hexane, n-heptane and n-octane.

10. The method for preparing a composite biomimetic membrane having an artificial water channel according to claim 7, characterized in that: The hydrocarbon solvent is n-hexane.

11. The method for preparing a composite biomimetic membrane having an artificial water channel according to any one of claims 1 to 10, characterized in that: The first preset ratio value is 0.01% to 10%; The second preset ratio is 0.25% to 8%; The third preset ratio is 0.025% to 0.8%; The fourth preset ratio value is 0.05% to 0.25%; The preset pH value range is 10 to 12; and / or, The numerical range of the preset ratio is 1:1 to 1:

10.

12. The method for preparing a composite biomimetic membrane having an artificial water channel according to claim 11, characterized in that: The first preset ratio value is 0.1% to 1.0%; The second preset ratio value is 1.0% to 4.0%; The third preset ratio is 0.1% to 0.5%; The fourth preset ratio is 0.1% to 0.2%; The preset pH value range is 10; and / or, The numerical range of the preset ratio is 1:

5.

13. The method for preparing a composite biomimetic membrane having an artificial water channel according to claim 11, characterized in that: The porous support layer is an ultrafiltration membrane with a molecular weight cut-off ranging from 10kD to 250kD; The ultrafiltration membrane is a polysulfone membrane, a polyethersulfone membrane, a polyacrylonitrile membrane or a polyvinylidene fluoride membrane generated on a non-woven fabric by a phase inversion method.

14. The method for preparing a composite biomimetic membrane having an artificial water channel according to claim 13, wherein: The porous support layer is an ultrafiltration membrane with a molecular weight cut-off in the range of 20kD to 50kD; The ultrafiltration membrane is a polysulfone membrane or a polyethersulfone membrane generated on a non-woven fabric by a phase inversion method.

15. The method for preparing a composite biomimetic membrane having an artificial water channel according to any one of claims 1 to 10, characterized in that: The second organic solution is coated on one side of the porous support layer after being soaked in the mixed solution, comprising: removing excess of the mixed solution and / or the second organic solution from the surface of the porous supporting layer; Among them, the removal method includes: rolling method and / or air blowing method; The cleaning process includes: washing with n-hexane and / or soaking in deionized water; and / or, The drying temperature is 50° C. to 90° C., and the drying time is 5 min to 30 min.

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