CN114028947A - Reverse osmosis membrane modified by amino functionalized ZIFs nano material and preparation method thereof - Google Patents
Reverse osmosis membrane modified by amino functionalized ZIFs nano material and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a reverse osmosis membrane modified by amino functionalized ZIFs nano materials and a preparation method thereof, wherein the reverse osmosis membrane consists of a supporting layer, a polyamide layer and the amino functionalized ZIFs nano materials; the preparation process comprises the following steps: adding the synthesized amino functionalized ZIFs nano material into an oil phase, and forming a polyamide ultrathin skin layer added with the amino functionalized ZIFs nano material by an interfacial polymerization method; the invention relates to reverse osmosis modified by amino functionalized ZIFs nano materialThe water flux of the reverse osmosis membrane is up to 1.2Lm on average under the condition of ensuring that the salt rejection rate is 96 percent‑2h‑1bar‑1Compared with the reverse osmosis membrane prepared by adding common ZIFs nano materials, the prepared reverse osmosis membrane has higher flux and rejection rate, and the preparation method is simple, feasible and easy to operate, can be suitable for the fields of water softening, sewage treatment, seawater desalination, chemical material separation and the like, and has good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of reverse osmosis membranes, in particular to a reverse osmosis membrane modified by amino functionalized ZIFs nano materials and a preparation method thereof.
Background
The problems of the continuous increase of population and the shortage of water resources make global sustainable development face huge challenges. The membrane separation technology has the advantages of energy conservation, environmental protection and high efficiency, and becomes a mainstream process in the field of water treatment. Reverse Osmosis (RO) Reverse osmosis membrane is an artificial semipermeable membrane with certain characteristics and made by simulating a biological semipermeable membrane, and is a core component of Reverse osmosis technology. The principle of reverse osmosis is that under the action of the osmotic pressure higher than that of the solution, other substances are separated from water based on the fact that the substances cannot permeate a semipermeable membrane. The reverse osmosis membrane has a very small membrane pore size, and thus can effectively remove dissolved salts, colloids, microorganisms, organic substances, and the like in water. The system has the advantages of good water quality, low energy consumption, no pollution, simple process, simple and convenient operation and the like. Is widely applied in the fields of seawater desalination, softened water and industrial wastewater treatment.
Polyamide is a kind of high molecular material commonly used for preparing composite membrane skin, and has good stability, hydrophilicity, high temperature resistance, strong alkali resistance and organic solvent resistance. Currently, aromatic polyamide is used in commercial nanofiltration and reverse osmosis membranes, and the membranes are widely applied in industries worldwide, including water treatment, solution decolorization, drug concentration and purification, biochemical substance concentration and the like. The aromatic polyamide has high crosslinking degree and lower free volume, and the prepared reverse osmosis membrane shows good selectivity, but has lower water flux. It has been found that the addition of porous inorganic materials to polyamide materials to prepare novel organic-inorganic membranes can become an effective means for improving permeability, and the porous inorganic materials reported include silica, molecular sieves, carbon nanotubes and graphene, metal-organic framework materials, and the like.
The metal-organic framework material is a porous material newly discovered in recent years, has nanometer-sized pore channels or pores, is complex and diverse in pore channel types, and has high porosity, large specific surface area, small density, good chemical stability and controllable pore structure. The metal-organic framework material with the nanoscale pore channel shows excellent gas-liquid adsorption selectivity, so that the metal-organic framework material is developed into a gas separation membrane or pervaporation membrane material with excellent performance. In addition, the metal-organic framework material can improve the permeation flux and solvent resistance of the organic mixture separated by the reverse osmosis membrane.
How to solve the mutual restriction (Trade-Off) effect between the flux and the interception efficiency of the reverse osmosis membrane is a difficult problem which is continuously thought and researched by membrane technologists in recent years. According to the existing reports, the problems that the film is easy to generate defects and the like still exist in the modified film material added with the metal-organic framework material. According to the invention, the amino functionalized ZIFs nano material is directly added in the interface polymerization process, so that the interaction force of phase interfaces can be effectively regulated and controlled, the amino functionalized ZIFs nano material is doped in the PA active layer, interface gaps are avoided, a rapid transmission selective microscopic channel is accurately constructed, and the water flux can be increased to 2-3 times on the premise of not influencing the separation performance.
Disclosure of Invention
In order to overcome the defects of the existing reverse osmosis membrane, the invention provides a reverse osmosis membrane modified by amino functionalized ZIFs nano materials and a preparation method thereof.
The reverse osmosis membrane is composed of an ultrafiltration membrane supporting layer, a polyamide layer and amino functionalized ZIFs nano materials distributed in the polyamide layer. The preparation process comprises the following steps: adding the amino functionalized ZIFs nano material into an oil phase, and forming a polyamide ultrathin skin layer added with the amino functionalized ZIFs nano material by using an interfacial polymerization method.
The reverse osmosis membrane prepared by the invention has high flux and high interception performance, the preparation method is simple and feasible, the cost is low, and the reverse osmosis membrane can be applied to the fields of water softening, sewage treatment, seawater desalination, chemical material separation and the like and has good industrial application prospect.
The technical scheme of the invention is as follows:
a reverse osmosis membrane modified by amino functionalized ZIFs nanomaterials comprising: the composite membrane comprises an ultrafiltration membrane supporting layer, a polyamide layer and amino functionalized ZIFs nano-materials distributed in the polyamide layer;
the ultrafiltration membrane supporting layer can be prepared from one or more of polysulfone, polyethersulfone, polyether ketone, polyarylsulfone, polyacrylonitrile and polyvinylidene fluoride;
the polyamide layer is prepared by interfacial polymerization of a water-phase amine monomer and an oil-phase acyl chloride monomer;
the amino functionalized ZIFs nano material comprises but is not limited to ZIF-7-NH2、ZIF-8-NH2、ZIF-9-NH2、ZIF-11-NH2One or more combinations of iso-amino functionalized ZIFs; the particle size of the amino functionalized ZIFs nano material is 10-500 nm.
A preparation method of a reverse osmosis membrane modified by amino functionalized ZIFs nano materials comprises the following steps:
(1) synthesis of amino functionalized ZIFs nano material
Mixing a metal precursor solution and a ligand solution, stirring and reacting for 2-15 h at room temperature (20-30 ℃), then centrifuging and collecting nano-scale solid particles, cleaning (using methanol), and drying in vacuum (50-80 ℃, 6-12 h) to obtain an amino functionalized ZIFs nano-material;
the concentration of the metal precursor solution is 0.05-1 mol/L, the solvent is DMF (N, N-2 methyl formamide), and the metal precursor is selected from one or more of zinc oxide, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate and the like;
the concentration of the ligand solution is 0.05-1 mol/L, the solvent is methanol, and the ligand is aminoimidazole or a mixture containing no aminoimidazole and aminoimidazole; the non-aminoimidazole is selected from one or more of benzimidazole, 2-methylbenzimidazole, 1,2, 4-triazole, tetrazole and the like; the amino imidazole is selected from one or more of 2-aminobenzimidazole, 3, 5-diamino-1, 2, 4-triazole, 3-amino-1, 2, 4-triazole, 5-amino tetrazole and the like;
the volume ratio of the metal precursor solution to the ligand solution is 1: 1;
(2) preparation of film-forming solution
Dissolving an amine monomer in deionized water at room temperature to prepare a water phase solution, dissolving an acyl chloride monomer in an organic solvent, adding the amino functionalized ZIFs nano material obtained in the step (1), and performing ultrasonic dispersion uniformly to obtain an oil phase solution for later use;
in the aqueous phase solution, the mass fraction of the amine monomer is 0.001-5% (preferably 1-3%), and the amine monomer includes but is not limited to one or more of piperazine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, ethylenediamine, hexamethylenediamine, 1, 4-butanediamine, 4-diaminodiphenyl ether, 4-diaminodiphenylmethane, o-biphenylmethylamine, 1, 2-propanediamine, 1, 3-propanediamine, 2, 4-diaminotoluene, 1, 2-cyclohexanediamine, 4, 5-dichloroo-phenylenediamine, diethylenetriamine, trimesamine and derivatives thereof;
in the oil phase solution, the mass fraction of acyl chloride monomers is 0.001-5% (preferably 0.1-0.5%), the mass fraction of amino functionalized ZIFs nano materials is 0.001-5% (preferably 0.03-1%), the organic solvent is selected from one or more of alkanes such as n-hexane, n-heptane, n-octane, n-dodecane, isododecane, isohexadecane and the like, and the acyl chloride monomers include but are not limited to one or more of isophthaloyl chloride, terephthaloyl chloride, phthaloyl chloride, trimesoyl chloride, multi-element aromatic sulfonyl chloride and derivatives thereof;
(3) preparation of polyamide layer by interfacial polymerization
Immersing an ultrafiltration membrane supporting layer in an aqueous phase solution for 1-15 min (preferably 3-5 min) at room temperature, taking out the ultrafiltration membrane supporting layer to remove the excessive aqueous phase solution on the surface of the membrane, immersing the ultrafiltration membrane supporting layer in an oil phase solution for 20 s-8 min (preferably 30 s-2 min) to generate an interfacial polymerization reaction, taking out the ultrafiltration membrane supporting layer and airing the ultrafiltration membrane supporting layer in the air, and forming a polyamide layer added with amino functionalized ZIFs nano materials on the surface of the ultrafiltration membrane supporting layer;
(4) post-treatment
And (3) carrying out heat treatment on the membrane for 5-30 min (preferably 10-20 min) at 40-80 ℃ (preferably 50-70 ℃), so as to obtain the reverse osmosis membrane modified by the amino functionalized ZIFs nano material.
The types of the reverse osmosis membrane modified by the amino functionalized ZIFs nano material comprise a flat membrane, a hollow fiber homogeneous membrane or a hollow composite membrane and a tubular membrane.
The invention has the advantages that:
1) through directly adding amino functionalized ZIFs materials in the interface polymerization process, the ZIFs nano materials are doped in the polyamide active layer, the interaction force of a phase interface can be effectively regulated and controlled, interface gaps are avoided, a rapid transmission selectivity micro channel is accurately constructed, the surface roughness of the membrane is increased, the surface area of a separation layer is increased, and therefore the water flux is improved.
2) Because the amino group can react with the acyl chloride group, the amino functionalized ZIFs can be fixed in and on the polyamide layer, and meanwhile, the amino group has hydrophilicity, so that the flux of the reverse osmosis membrane modified by the amino functionalized ZIF nano material can be higher.
3) The reverse osmosis membrane modified by amino functionalized ZIFs nano material ensures that the salt rejection rate is 96 percent, and the water flux of the reverse osmosis membrane is as high as 1.2Lm on average-2h-1bar-1Compared with the reverse osmosis membrane prepared by adding common ZIFs nano materials, the prepared reverse osmosis membrane has higher flux and rejection rate, and the preparation method is simple, feasible and easy to operate, can be suitable for the fields of water softening, sewage treatment, seawater desalination, chemical material separation and the like, and has good industrial application prospect.
Drawings
FIG. 1 is a flow chart of a process for preparing a reverse osmosis membrane modified by amino functionalized ZIFs nanomaterials.
FIG. 2 is an electron microscope image of a modified polyamide layer prepared from a blank film (top left), example 1 (top right), example 3 (bottom left) and example 4 (bottom right); the reverse osmosis membrane blank at the upper left of fig. 2 is also comparative example 1, and only the polyamide layer can be seen in an electron micrograph; in the figures of examples 1,3 and 4, the amino functionalized ZIFs nanoparticles were clearly seen on the polyamide layer, and the particle size was 30 to 100 nm.
FIG. 3 is a graph of water flux versus salt rejection data for a blank reverse osmosis membrane (comparative example 1), a ZIF-7 reverse osmosis membrane (comparative example 2), and reverse osmosis membranes prepared according to examples 1-4.
Detailed Description
The invention is further described below by means of specific examples, without the scope of protection of the invention being limited thereto.
The preparation environment for all initial reverse osmosis membranes in the examples was: the temperature is 25 ℃, the humidity is 40%, and the pressure is normal.
The polysulfone ultrafiltration membrane support layer used in the examples was purchased from the Hangzhou Water treatment center.
Example 1:
preparing the high-performance composite reverse osmosis membrane modified by amino functionalized ZIFs nano materials. The preparation method comprises the following specific steps:
(1) adding 5mmol of Zn (NO)3)2·6H2Dissolving O in 50ml DMF to prepare Zn2+A solution; dissolving 9mmol of benzimidazole and 1mmol of 2-aminobenzimidazole in 50ml of methanol to prepare an imidazole solution; the imidazole solution was poured rapidly into Zn at room temperature2+The solution was stirred for 6h to obtain a white amino-functionalized ZIF dispersion. Centrifuging at high speed to collect the obtained nanoscale amino functionalized ZIF particles, washing with methanol to obtain pure amino functionalized ZIF, and vacuum drying to obtain solid powder ZIF-7-NH2(10)；
(2) Immersing an ultrafiltration membrane supporting layer in 0.2 wt% MPD (m-phenylenediamine) solution for 4min, forming a water phase liquid layer on the surface of the ultrafiltration membrane supporting layer, taking out the ultrafiltration membrane supporting layer, airing the excessive water phase solution on the surface of the ultrafiltration membrane, and immersing the ultrafiltration membrane supporting layer in 0.1 wt% TMC (trimesoyl chloride) and 0.2 wt% ZIF-7-NH2(10) And (3) carrying out interfacial polymerization reaction in a normal hexane solution for 1min, taking out, airing in the air, then carrying out heat treatment at 60 ℃ for 15min, and drying to obtain the reverse osmosis membrane modified by the amino functionalized ZIFs nano material.
Analytical testing of the reverse osmosis membranes obtained in example 1:
the reverse osmosis membrane prepared in the embodiment is loaded into a membrane performance evaluation device, and the experimental conditions are as follows: pre-pressing NaCl salt solution of 32g/L for 1h at normal temperature and 5.5 MPa; the experimental results are as follows: water flux: 1.26Lm-2h-1bar-1NaCl rejection: 96.67 percent.
Example 2:
example 2 the same procedure as in example 1 was repeated except for changing 9mmol of benzimidazole and 1mmol of 2-aminobenzimidazole to 7mmol of benzimidazole and 3mmol of 2-aminobenzimidazole in step (1) of example 1;
the membrane performance test method is the same as that of example 1, and the experimental result is as follows: water flux: 1.13Lm-2h-1bar-1NaCl rejection: 96.06 percent.
Example 3:
example 3 the same procedure as in example 1 except for changing 9mmol of benzimidazole and 1mmol of 2-aminobenzimidazole to 5mmol of benzimidazole and 5mmol of 2-aminobenzimidazole in step (1) of example 1;
the membrane performance test method is the same as that of example 1, and the experimental result is as follows: water flux: 1.28Lm-2h-1bar-1NaCl rejection: 98.35 percent.
Example 4:
example 4 the same procedure as in example 1 except for changing 9mmol of benzimidazole and 1mmol of 2-aminobenzimidazole to 3mmol of benzimidazole and 7mmol of 2-aminobenzimidazole in step (1) of example 1;
the membrane performance test method is the same as that of example 1, and the experimental result is as follows: water flux: 1.3Lm-2h-1bar-1NaCl rejection: 96.91 percent.
Example 5:
example 5 the same procedure as in example 1 except for changing 9mmol of benzimidazole and 1mmol of 2-aminobenzimidazole to 10mmol of 2-aminobenzimidazole in step (1) of example 1;
the membrane performance test method is the same as that of example 1, and the experimental result is as follows: water flux: 1.26Lm-2h-1bar-1NaCl rejection: 96.55 percent.
Comparative example 1:
step (1): immersing an ultrafiltration membrane supporting layer in 0.2 wt% MPD solution for 4min, forming an aqueous phase liquid layer on the surface of the ultrafiltration membrane supporting layer, and removing the excessive aqueous phase solution on the surface of the ultrafiltration membrane supporting layer after taking out;
step (2): and immersing the ultrafiltration membrane supporting layer in a 0.1 wt% TMC n-hexane solution for 1min to perform interfacial polymerization reaction, taking out and airing in the air, then performing heat treatment at 60 ℃ for 15min, and drying to obtain the blank reverse osmosis membrane.
The membrane performance test method is the same as that of example 1, and the experimental result is as follows: water flux: 0.68Lm-2h-1bar-1NaCl rejection: 95.95 percent.
Comparative example 2:
comparative example 2 the same procedure as in example 1 except for changing 9mmol of benzimidazole and 1mmol of 2-aminobenzimidazole to 10mmol of benzimidazole in step (1) of example 1;
the membrane performance test method is the same as that of example 1, and the experimental result is as follows: water flux: 0.6Lm-2h-1bar-1NaCl rejection: 96.18 percent.
According to the reverse osmosis membrane modified by the amino functionalized ZIFs nano material, the amino functionalized ZIFs nano material is added into an oil phase, and an interface polymerization method is used for forming the polyamide ultrathin skin layer added with the amino functionalized ZIFs nano material, so that high water flux and high salt rejection rate are ensured, compared with a comparative example, the water flux is increased by 2 times, and the salt rejection rate is also improved. Meanwhile, the preparation method is simple and feasible, easy to operate and low in cost, can be applied to the fields of water softening, sewage treatment, seawater desalination, chemical material separation and the like, and has a good industrial application prospect.
Claims (10)
1. A reverse osmosis membrane modified by amino functionalized ZIFs nanomaterials, comprising: the composite membrane comprises an ultrafiltration membrane supporting layer, a polyamide layer and amino functionalized ZIFs nano-materials distributed in the polyamide layer;
the ultrafiltration membrane supporting layer is made of one or more of polysulfone, polyethersulfone, polyether ketone, polyarylsulfone, polyacrylonitrile and polyvinylidene fluoride;
the polyamide layer is prepared by interfacial polymerization of a water-phase amine monomer and an oil-phase acyl chloride monomer;
the amino functionalized ZIFThe s nano material is ZIF-7-NH2、ZIF-8-NH2、ZIF-9-NH2、ZIF-11-NH2One or more of the above.
2. A preparation method of a reverse osmosis membrane modified by amino functionalized ZIFs nano materials is characterized by comprising the following steps:
(1) synthesis of amino functionalized ZIFs nano material
Mixing the metal precursor solution and the ligand solution, stirring and reacting for 2-15 h at room temperature, then centrifugally collecting nano-scale solid particles, cleaning, and drying in vacuum to obtain an amino functionalized ZIFs nano-material;
the metal precursor is selected from one or more of zinc oxide, zinc nitrate, zinc chloride, zinc sulfate and zinc acetate;
the ligand is aminoimidazole or a mixture without aminoimidazole and aminoimidazole; the non-aminoimidazole is selected from one or more of benzimidazole, 2-methylbenzimidazole, 1,2, 4-triazole and tetrazole; the amino imidazole is selected from one or more of 2-aminobenzimidazole, 3, 5-diamino-1, 2, 4-triazole, 3-amino-1, 2, 4-triazole and 5-amino tetrazole;
(2) preparation of film-forming solution
Dissolving an amine monomer in deionized water at room temperature to prepare a water phase solution, dissolving an acyl chloride monomer in an organic solvent, adding the amino functionalized ZIFs nano material obtained in the step (1), and performing ultrasonic dispersion uniformly to obtain an oil phase solution for later use;
(3) preparation of polyamide layer by interfacial polymerization
Immersing an ultrafiltration membrane supporting layer in an aqueous phase solution for 1-15 min at room temperature, taking out the aqueous phase solution to remove the excess amount of the membrane surface, immersing the ultrafiltration membrane supporting layer in an oil phase solution for 20 s-8 min to generate an interfacial polymerization reaction, taking out the ultrafiltration membrane supporting layer and drying in the air, and forming a polyamide layer added with amino functionalized ZIFs nano materials on the surface of the ultrafiltration membrane supporting layer;
(4) post-treatment
And (3) carrying out heat treatment on the membrane at the temperature of 40-80 ℃ for 5-30 min to obtain the reverse osmosis membrane modified by the amino functionalized ZIFs nano material.
3. The method for preparing a reverse osmosis membrane modified by amino functionalized ZIFs nano materials according to claim 2, wherein in the step (1), the concentration of the metal precursor solution is 0.05-1 mol/L, and the solvent is DMF.
4. The method for preparing a reverse osmosis membrane modified by amino functionalized ZIFs nano materials according to claim 2, wherein in the step (1), the concentration of the ligand solution is 0.05-1 mol/L, and the solvent is methanol.
5. The method for preparing a reverse osmosis membrane modified by amino functionalized ZIFs nanomaterials of claim 2, wherein in step (1), the volume ratio of the metal precursor solution to the ligand solution is 1: 1.
6. the preparation method of the reverse osmosis membrane modified by the amino functionalized ZIFs nano material as claimed in claim 2, wherein in the step (2), the mass fraction of the amine monomer in the aqueous phase solution is 0.001-5%.
7. The method of claim 2, wherein in the step (2), the amine-based monomer is selected from one or more of piperazine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, ethylenediamine, hexamethylenediamine, 1, 4-butanediamine, 4-diaminodiphenyl ether, 4-diaminodiphenylmethane, o-biphenylmethylamine, 1, 2-propanediamine, 1, 3-propanediamine, 2, 4-diaminotoluene, 1, 2-cyclohexanediamine, 4, 5-dichlorophthalenediamine, diethylenetriamine, trimesamine, and derivatives thereof.
8. The preparation method of the reverse osmosis membrane modified by the amino functionalized ZIFs nano material, according to the claim 2, wherein in the step (2), the mass fraction of the acyl chloride monomer is 0.001-5%, and the mass fraction of the amino functionalized ZIFs nano material is 0.001-5%.
9. The method for preparing a reverse osmosis membrane modified by amino functionalized ZIFs nanomaterials of claim 2, wherein in step (2), the organic solvent is selected from one or more alkanes such as n-hexane, n-heptane, n-octane, n-dodecane, isododecane, isohexadecane, etc.
10. The method for preparing a reverse osmosis membrane modified by amino functionalized ZIFs nanomaterials of claim 2, wherein in step (2), the acyl chloride monomer is selected from one or more of isophthaloyl dichloride, terephthaloyl dichloride, phthaloyl dichloride, trimesoyl dichloride, poly aromatic sulfonyl chloride, and derivatives thereof.
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| CN114642975A (en) * | 2020-12-18 | 2022-06-21 | 中国石油化工股份有限公司 | Metal-organic framework mixed matrix membrane and preparation method and application thereof |
| CN114699915A (en) * | 2022-04-25 | 2022-07-05 | 浙江工业大学 | ZIFs/PA mixed matrix forward osmosis membrane and preparation method thereof |
| CN114832641A (en) * | 2022-05-30 | 2022-08-02 | 浙江工业大学 | Method for preparing polyamide mixed matrix total heat exchange membrane by using interfacial polymerization technology and introducing ZIFs |
| CN115006994A (en) * | 2022-05-11 | 2022-09-06 | 武汉工程大学 | Preparation method of high-hydrophilicity composite membrane for alcohol dehydration |
| CN115282782A (en) * | 2022-06-27 | 2022-11-04 | 浙江工业大学 | Total heat exchange membrane doped with functionalized ZIF-7 nanoparticles and preparation method thereof |
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