High-flux high-ion-selectivity bionic nanofiltration membrane as well as preparation method and application thereof
By using HBc virus protein nanocage on polyethersulfone microporous membranes to prepare bionic polyesteramide separation layers, the problem that existing nanofiltration membranes cannot achieve high selectivity and high water flux at the same time, achieving high selectivity separation of monovalent and divalent ions and improving water flux.
Patent Information
- Application Number
- CN202510299948.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-13
- Publication Date
- 2025-06-13
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Existing ion-selective nanofiltration membranes cannot perform high-selective separation of monovalent and divalent anions and cations at the same time, and it is difficult to achieve a balance between water flux and selectivity.
A bionic polyesteramide separation layer was prepared on the polyethersulfone microporous membrane through interfacial polymerization to form a high-throughput high ion selective bionic nanofiltration membrane.
High selective separation of ions of different valence states is achieved, water flux is improved, and the film thickness and pore size can be adjusted, the process is gentle, the raw material cost is low, and it is green and environmentally friendly.
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Figure CN120132622A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of membrane separation, and in particular to a high-flux and high-ion-selective bionic nanofiltration membrane and a preparation method and application thereof. Background Art
[0002] The manufacture of efficient monovalent / divalent ion separation membranes is crucial for various industrial applications and has great economic benefits and social significance. The most advanced monovalent / divalent ion separation membranes are usually thin film composite materials, consisting of a porous substrate as a support layer and an ultrathin polyamide nanofilm as a selective layer. They are made by interfacial polymerization and achieve ion separation based on the synergistic effect of steric hindrance and Donnan exclusion. Most polyamide nanofiltration membranes have a single charge (negative or positive), and it is difficult to achieve high selectivity for monovalent / divalent positive and negative ions at the same time. The Cl of the currently reported ion-selective nanofiltration membranes is - / SO 4 2- and Na + / Mg 2+ The average selectivity values are all below 100.
[0003] Designing polyamide nanofiltration membranes with ion channels and adjusting the pore size and charge of polyamide nanofiltration membranes are considered to be effective strategies for the preparation of next-generation ion-selective separation membranes. A large number of new ion channels with ordered, uniform pore structures and adjustable functions have been used in the design of highly ion-selective nanofiltration membranes, including one-dimensional carbon nanotubes, layered two-dimensional graphene oxide nanosheets, metal organic frameworks, covalent organic frameworks, and porous organic cages. However, the stability and chemical compatibility of these structures in composites with scalable membrane materials are poor. In addition, ions need to overcome large energy barriers when passing through the channels, which will have a negative impact on ion permeability, and there is a problem that high flux and high ion selectivity cannot be taken into account at the same time.
[0004] Biological channels show great promise in designing high-flux membranes. Various biological channels, such as aquaporins, gramin A, and β-barrel protein channel families, have been used to prepare water separation membranes and achieve excellent permeability. However, due to the small pore contraction diameter and low structural stability of these biological channels, the use of biological channels in designing ion-selective nanofiltration membranes has not been reported, and the preparation of ion-selective separation membranes with adjustable membrane thickness and pore size remains a huge challenge. Summary of the invention
[0005] In view of this, the present application provides a high-flux and high-ion selectivity bionic nanofiltration membrane and its preparation method and application, aiming to effectively solve the problem in the prior art that ion-selective nanofiltration membranes cannot simultaneously perform high-selectivity separation of monovalent and divalent anions and cations, and that it is difficult to achieve a balance between water flux and selectivity.
[0006] This application provides a high-throughput and highly ion-selective bionic nanofiltration membrane, which includes a support layer and a separation layer prepared on the surface of the support layer. The support layer is a polyethersulfone microporous membrane, and the separation layer is a bionic polyester amide. The separation layer is prepared on the support layer by an interfacial polymerization reaction using an aqueous phase of m-phenylenediamine added with HBc virus protein nanocages and an organic phase of polyfunctional acyl chloride, where HBc is the hepatitis B virus core antibody.
[0007] In one embodiment, the water flux of the bionic nanofiltration membrane is greater than 10 L / m 2 / h / bar; the separation factor of the bionic nanofiltration membrane for Cl - / SO 4 2- is greater than 400; the separation factor of the bionic nanofiltration membrane for Na + / Mg 2+ is greater than 70; the separation factor of the bionic nanofiltration membrane for Li + / Mg 2+ is greater than 60.
[0008] In one embodiment, the average diameter of the HBc virus protein nanocages is 28 - 33 nm.
[0009] This application also provides a preparation method of the high-throughput and highly ion-selective bionic nanofiltration membrane as described above, including the following steps:
[0010] S1: Disperse HBc virus protein nanocages and m-phenylenediamine in distilled water to obtain an aqueous phase reaction solution; dissolve the polyfunctional acyl chloride compound in an organic solvent to obtain an organic phase reaction solution;
[0011] S2: Infiltrate the surface of the polyethersulfone microporous membrane with the aqueous phase reaction solution for a preset time, and then remove the excess liquid on the surface of the polyethersulfone microporous membrane;
[0012] S3: Contact the organic phase reaction solution with the surface of the polyethersulfone microporous membrane coated with the aqueous phase reaction solution to carry out an interfacial polymerization reaction;
[0013] S4: After the interfacial polymerization reaction is terminated, a composite membrane is obtained, and the composite membrane is dried to obtain the bionic nanofiltration membrane.
[0014] In one embodiment, in step S1, the concentration of the HBc virus protein nanocages in the aqueous phase reaction solution is 0.01 - 0.1 w / v%, the concentration of m-phenylenediamine is 0.1 - 5 w / v%, and the concentration of the polyfunctional acyl chloride compound in the organic phase reaction solution is 0.1 - 5 w / v%.
[0015] In one embodiment, in the step S1, the organic solvent includes one or more of tetrahydrofuran, 1,4-dioxane, and n-hexane; the polyacyl chloride is trimesoyl chloride.
[0016] In one embodiment, in the step S2, the preset time is 1 to 10 min.
[0017] In one embodiment, in the step S3, the time of the interfacial polymerization reaction is 1 to 20 min, and the reaction temperature of the interfacial polymerization reaction is 15 to 30 °C.
[0018] In one embodiment, in the step S4, the drying temperature of the composite membrane is 40 to 60 °C, and the drying time of the composite membrane is 2 to 5 min.
[0019] The present application also provides an application of the high-flux and high-ion-selective bionic nanofiltration membrane as described above in the deep treatment of drinking water or industrial salt separation.
[0020] In summary, the present application provides a high-flux and high-ion-selective bionic nanofiltration membrane, a preparation method thereof, and an application. The high-flux and high-ion-selective bionic nanofiltration membrane includes a support layer and a separation layer prepared on the surface of the support layer. The support layer is a polyethersulfone microporous membrane, and the separation layer is a bionic poly(ester amide). The separation layer is prepared on the support layer by an interfacial polymerization reaction using an aqueous phase of m-phenylenediamine added with HBc virus protein nanocages and an organic phase of polyacyl chloride. The present application proposes a bionic nanofiltration membrane with high selectivity for different valence ions. Using HBc virus protein nanocages as ion channels helps to improve the water flux. Using a hydrophilic polyethersulfone microporous membrane as the support layer and a bionic poly(ester amide) with HBc virus protein nanocages as ion channels as the separation layer helps to achieve simultaneous high-selectivity separation of monovalent and divalent anions and cations. In addition, the present application uses a traditional interfacial polymerization method, which helps to synthesize a bionic nanofiltration membrane with controllable film thickness and pore size, has mild conditions, low raw material cost, and is green and environmentally friendly. Description of the Drawings
[0021] Figure 1 It is a process schematic diagram of the preparation method of the high-flux and high-ion-selective bionic nanofiltration membrane of the present application.
[0022] Figure 2 It is a transmission electron microscope morphology diagram of HBc virus protein nanocages.
[0023] Figure 3 It is a self-assembly diagram of HBc virus protein nanocages.
[0024] Figure 4 It is a particle size distribution curve diagram of HBc virus protein nanocages.
[0025] Figure 5Scanning electron microscope morphology diagram of the high-throughput and highly ion-selective bionic nanofiltration membrane of Example 1.
[0026] Figure 6 Atomic force microscope image of the high-throughput and highly ion-selective bionic nanofiltration membrane of Example 1. Detailed implementation manners
[0027] In order to better understand the above objects, features, and advantages of the present invention, the technical solutions of the present invention will be further described below. It should be noted that, without conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other.
[0028] This application provides a high-throughput and highly ion-selective bionic nanofiltration membrane. The high-throughput and highly ion-selective bionic nanofiltration membrane includes a support layer and a separation layer prepared on the surface of the support layer. Among them, the support layer is a polyethersulfone microporous membrane, and the separation layer is a bionic polyester amide. The separation layer is prepared on the support layer by interfacial polymerization reaction using an aqueous phase of m-phenylenediamine added with HBc virus protein nanocages and an organic phase of polyacyl chloride, where HBc is hepatitis B virus core antibody.
[0029] In this application, please refer to Figure 2 and Figure 3 As shown, the ion channel added to the aqueous phase is selected from HBc virus protein nanocages. The HBc virus protein nanocage is spherical, and the surface of the nanocage is covered with pores. The diameter of the entire nanocage is about 30 nm. The polyethersulfone microporous membrane is, for example, a polyethersulfone microporous sheet, that is, the polyethersulfone microporous membrane is in a sheet structure. The water flux of this bionic nanofiltration membrane is greater than 10 L / m 2 / h / bar; the separation factor of the bionic nanofiltration membrane for Cl - / SO 4 2- is greater than 400; the separation factor of the bionic nanofiltration membrane for Na + / Mg 2+ is greater than 70; the separation factor of the bionic nanofiltration membrane for Li + / Mg 2+ is greater than 60.
[0030] In a preferred implementation manner, please refer to Figure 4 As shown, the average diameter of the HBc virus protein nanocage is 28 - 33 nm. Preferably, the average diameter of the HBc virus protein nanocage is 30 nm.
[0031] Please refer to Figure 1 , Figure 5 and Figure 6 As shown, this application also provides a preparation method of a high-throughput and highly ion-selective bionic nanofiltration membrane. The above-mentioned high-throughput and highly ion-selective bionic nanofiltration membrane can be prepared by this preparation method. The preparation method includes the following steps:
[0032] S1: Disperse the HBc virus protein nanocage and m-phenylenediamine in distilled water to obtain an aqueous reaction solution; dissolve the polyacyl chloride compound in an organic solvent to obtain an organic phase reaction solution.
[0033] S2: Immerse the aqueous reaction solution on the surface of the polyethersulfone microporous membrane for a preset time, and then remove the excess liquid on the surface of the polyethersulfone microporous membrane.
[0034] S3: Bring the organic phase reaction solution into contact with the surface of the polyethersulfone microporous membrane coated with the aqueous reaction solution to carry out an interfacial polymerization reaction.
[0035] S4: After the interfacial polymerization reaction is terminated, a composite membrane is obtained, and the composite membrane is dried to obtain a bionic nanofiltration membrane.
[0036] Optionally, in step S1, the concentration of the HBc virus protein nanocage in the aqueous reaction solution is 0.01 - 0.1 w / v%, and the concentration of m-phenylenediamine in the aqueous reaction solution is 0.1 - 5 w / v%.
[0037] Optionally, in step S1, the concentration of the polyacyl chloride compound in the organic phase reaction solution is 0.1 - 5 w / v%.
[0038] Optionally, in step S1, the organic solvent includes one or more of tetrahydrofuran, 1,4-dioxane, and n-hexane.
[0039] Optionally, in step S1, the polyacyl chloride is trimesoyl chloride.
[0040] Optionally, in step S2, the preset time for the aqueous reaction solution to immerse the surface of the polyethersulfone microporous membrane is 1 - 10 min. Preferably, the preset time is 5 min.
[0041] Optionally, in step S3, the time for the interfacial polymerization reaction is 1 - 20 min, and the reaction temperature for the interfacial polymerization reaction is 15 - 30 °C. Preferably, the time for the interfacial polymerization reaction is 4 min, and the reaction temperature for the interfacial polymerization reaction is 20 °C.
[0042] Optionally, in step S4, the composite membrane is dried in an oven, the drying temperature of the composite membrane is 40 - 60 °C, and the drying time of the composite membrane is 2 - 5 min. Preferably, the drying temperature of the composite membrane is 45 °C, and the drying time of the composite membrane is 3 min.
[0043] The following lists three specific examples of the preparation method of the high-throughput and high-ion-selective bionic nanofiltration membrane, and conducts a data comparison and analysis with Comparative Example 1.
[0044] Example 1
[0045] A high-throughput and highly ion-selective biomimetic nanofiltration membrane is prepared by the following method:
[0046] Prepare a deionized aqueous solution with an HBc virus protein nanocage content of 0.01 w / v% and a m-phenylenediamine content of 0.6 w / v%. The deionized water is the above-mentioned distilled water. After wetting the surface of the polyethersulfone microporous membrane with this deionized aqueous solution for 1 min, purge the membrane surface with nitrogen until no droplets remain; prepare a 1,4-dioxane organic phase solution with a trimesoyl chloride content of 0.5 w / v%. Contact the polyethersulfone microporous membrane treated in step 1 with the organic phase solution for 1 min. The interfacial polymerization reaction can be carried out in an oven at a temperature of 25 °C. After the reaction terminates, a composite membrane to be heat-treated is obtained; place the composite membrane to be heat-treated in an oven at 50 °C for 5 min, and then treat it with pure water to obtain a high-throughput and highly ion-selective biomimetic nanofiltration membrane.
[0047] Example 2
[0048] A high-throughput and highly ion-selective biomimetic nanofiltration membrane is prepared by the following method:
[0049] Prepare a deionized aqueous solution with an HBc virus protein nanocage content of 0.05 w / v% and a m-phenylenediamine content of 0.8 w / v%. The deionized water is the above-mentioned distilled water. After wetting the surface of the polyethersulfone microporous membrane with this deionized aqueous solution for 1 min, purge the membrane surface with nitrogen until no droplets remain; prepare a 1,4-dioxane organic phase solution with a trimesoyl chloride content of 0.8 w / v%. Contact the polyethersulfone microporous membrane treated in step 1 with the organic phase solution for 1 min. The interfacial polymerization reaction can be carried out in an oven at a temperature of 25 °C. After the reaction terminates, a composite membrane to be heat-treated is obtained; place the composite membrane to be heat-treated in an oven at 60 °C for 5 min, and then treat it with pure water to obtain a high-throughput and highly ion-selective biomimetic nanofiltration membrane.
[0050] Example 3
[0051] A high-throughput and highly ion-selective biomimetic nanofiltration membrane is prepared by the following method:
[0052] Prepare a deionized aqueous solution with an Hbc virus protein nanocage content of 0.08 w / v% and a m-phenylenediamine content of 1.5 w / v%. The deionized water is the above-mentioned distilled water. After wetting the surface of the polyethersulfone microporous membrane with this deionized aqueous solution for 1.5 min, purge the membrane surface with nitrogen until no droplets remain; prepare a 1,4-dioxane organic phase solution with a trimesoyl chloride content of 1.8 w / v%. Contact the polyethersulfone microporous membrane treated in step 1 with the organic phase solution for 1 min. The interfacial polymerization reaction can be carried out in an oven at a temperature of 25 °C. After the reaction is terminated, a composite membrane to be heat-treated is obtained; place the composite membrane to be heat-treated in an oven at 60 °C for 4 min, and then treat it with pure water to obtain a high-flux and high-ion-selective biomimetic nanofiltration membrane.
[0053] Comparative Example 1
[0054] Prepare a deionized aqueous solution with a m-phenylenediamine content of 1.5 w / v%. The deionized water is the above-mentioned distilled water. After wetting the surface of the polyethersulfone microporous membrane with this deionized aqueous solution for 1.5 min, purge the membrane surface with nitrogen until no droplets remain; prepare a 1,4-dioxane organic phase solution with a trimesoyl chloride content of 1.8 w / v%. Contact the polyethersulfone microporous membrane treated in step 1 with the organic phase solution for 1 min to carry out an interfacial polymerization reaction. After the reaction is terminated, a composite membrane to be heat-treated is obtained; place the composite membrane to be heat-treated in an oven at 60 °C for 4 min, and then treat it with pure water to obtain a nanofiltration membrane.
[0055] Perform performance tests on the nanofiltration membranes prepared in Examples 1-3 and Comparative Example 1.
[0056] The detection method is as follows: Use a cross-flow filtration membrane cell device. Pre-pressurize at an operating pressure of 5 bar and a temperature of 20 °C for 30 minutes. After the membrane performance is basically stable, test the water flux and salt rejection performance of the prepared membrane at a pressure of 4 bar. The feed solutions are NaCl, LiCl, MgCl 2 , and Na 2 SO 4 , and their concentrations are all 1000 ppm.
[0057] In this application, the separation performance (water flux, separation factor) of the high-flux and high-ion-selective biomimetic nanofiltration membranes obtained in Examples 1-3 is compared with the result data of the nanofiltration membrane in Comparative Example 1. The resulting water flux and separation factor result data are shown in Table 1.
[0058] Table 1
[0059]
[0060] As can be seen from Table 1, the bionic nanofiltration membrane in Example 1 is 3.3 times the water flux of the nanofiltration membrane in Comparative Example 1, and the bionic nanofiltration membrane in Example 1 is the Cl - / SO 4 2- separation factor of the nanofiltration membrane in Comparative Example 1 by 41 times, and the bionic nanofiltration membrane in Example 1 is the Na + / Mg 2+ separation factor of the nanofiltration membrane in Comparative Example 1 by 14.8 times, and the bionic nanofiltration membrane in Example 1 is the Li + / Mg 2+ separation factor of the nanofiltration membrane in Comparative Example 1 by 14.4 times.
[0061] It can be seen therefrom that the bionic nanofiltration membrane prepared by adding HBc virus protein nanocages exhibits excellent performance in both water flux and salt ion rejection rate.
[0062] The present application also provides an application of the high-flux and high-ion-selective bionic nanofiltration membrane as described above in the deep treatment of drinking water or industrial salt separation.
[0063] In summary, the present application provides a high-flux and high-ion-selective bionic nanofiltration membrane, a preparation method thereof, and an application. The high-flux and high-ion-selective bionic nanofiltration membrane includes a support layer and a separation layer prepared on the surface of the support layer. The support layer is a polyethersulfone microporous membrane, and the separation layer is a bionic polyester amide. The separation layer is prepared on the support layer by an interfacial polymerization reaction using an aqueous phase of m-phenylenediamine added with HBc virus protein nanocages and an organic phase of polyfunctional acyl chloride. The present application proposes a bionic nanofiltration membrane with high selectivity for different valence ions. Using HBc virus protein nanocages as ion channels helps to improve the water flux. Using a hydrophilic polyethersulfone microporous membrane as the support layer and a bionic polyester amide with HBc virus protein nanocages as ion channels as the separation layer helps to achieve simultaneous high-selectivity separation of monovalent and divalent anions and cations. In addition, the present application uses a traditional interfacial polymerization method, which helps to synthesize a bionic nanofiltration membrane with controllable film thickness and pore size, mild conditions, low raw material cost, and environmental friendliness.
[0064] The above are specific embodiments of the present invention, so that those skilled in the art can understand or implement the present invention. The principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments described herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A high-flux, high-ion-selectivity bionic nanofiltration membrane, characterized in that: The invention comprises a support layer and a separation layer prepared on the surface of the support layer, wherein the support layer is a polyethersulfone microporous membrane, the separation layer is a bionic polyester amide, and the separation layer is prepared on the support layer by an interfacial polymerization reaction using an aqueous phase of m-phenylenediamine added with HBc virus protein nanocages and an organic phase of a polyacid chloride, wherein HBc is a core antibody of the hepatitis B virus.
2. The high-flux, high-ion-selective biomimetic nanofiltration membrane according to claim 1, characterized in that: The water flux of the bionic nanofiltration membrane is greater than 10L / m 2 / h / bar; the bionic nanofiltration membrane has a great influence on Cl - / SO4 2- The separation factor is greater than 400; the bionic nanofiltration membrane has a + / Mg 2+ The separation factor of the bionic nanofiltration membrane is greater than 70; + / Mg 2+ The separation factor is greater than 60.
3. The high-flux, high-ion-selective biomimetic nanofiltration membrane according to claim 1, characterized in that: The average diameter of the HBc virus protein nanocage is 28-33 nm.
4. A method for preparing a high-flux, high-ion-selective bionic nanofiltration membrane as claimed in any one of claims 1 to 3, characterized in that: The following steps are involved: S1: dispersing HBc virus protein nanocages and m-phenylenediamine in distilled water to obtain an aqueous phase reaction solution; dissolving a polyacyl chloride compound in an organic solvent to obtain an organic phase reaction solution; S2: soaking the surface of the polyethersulfone microporous membrane with the aqueous reaction liquid for a preset time, and then removing excess liquid on the surface of the polyethersulfone microporous membrane; S3: contacting the organic phase reaction solution with the surface of the polyethersulfone microporous membrane impregnated with the aqueous phase reaction solution to perform an interfacial polymerization reaction; S4: After the interfacial polymerization reaction is terminated, a composite membrane is obtained, and the composite membrane is dried to obtain the bionic nanofiltration membrane.
5. The method for preparing a high-flux and high-ion-selective bionic nanofiltration membrane according to claim 4, characterized in that: In step S1, the concentration of the HBc virus protein nanocages in the aqueous phase reaction solution is 0.01-0.1 w / v%, the concentration of the m-phenylenediamine is 0.1-5 w / v%, and the concentration of the polyacyl chloride compound in the organic phase reaction solution is 0.1-5 w / v%.
6. The method for preparing a high-flux, high-ion-selective biomimetic nanofiltration membrane according to claim 4, characterized in that: In the step S1, the organic solvent includes one or more of tetrahydrofuran, 1,4-dioxane and n-hexane; and the polyacyl chloride is trimesoyl chloride.
7. The method for preparing a high-flux and high-ion-selective bionic nanofiltration membrane according to claim 4, characterized in that: In the step S2, the preset time is 1 to 10 minutes.
8. The method for preparing a high-flux and high-ion-selective bionic nanofiltration membrane according to claim 4, characterized in that: In the step S3, the time of the interfacial polymerization reaction is 1 to 20 minutes, and the reaction temperature of the interfacial polymerization reaction is 15 to 30°C.
9. The method for preparing a high-flux and high-ion-selective biomimetic nanofiltration membrane according to claim 4, characterized in that: In the step S4, the composite film is dried at a temperature of 40 to 60° C. and for a drying time of 2 to 5 minutes.
10. Use of the high-flux, high-ion-selective bionic nanofiltration membrane according to any one of claims 1 to 9 in deep treatment of drinking water or industrial salt separation.