CN113786731A - Preparation method of composite forward osmosis membrane based on ZIFs nano material modified supporting layer - Google Patents

Preparation method of composite forward osmosis membrane based on ZIFs nano material modified supporting layer Download PDF

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CN113786731A
CN113786731A CN202111068252.4A CN202111068252A CN113786731A CN 113786731 A CN113786731 A CN 113786731A CN 202111068252 A CN202111068252 A CN 202111068252A CN 113786731 A CN113786731 A CN 113786731A
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forward osmosis
osmosis membrane
zifs
composite forward
support layer
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薛立新
李士洋
马俊梅
林明杰
苌现
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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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
    • B01D61/002—Forward osmosis or direct osmosis
    • 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
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • 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
    • 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
    • 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

A preparation method of a composite forward osmosis membrane based on a ZIFs nano material modified supporting layer comprises the following steps: sequentially and respectively soaking the polymer support material in an aqueous solution of a metal precursor and an aqueous solution of a ligand, and then cleaning and drying to obtain a support layer material containing a ZIF group; sequentially and respectively contacting the support layer material containing the ZIF group with a water phase monomer solution and an organic phase monomer solution, and then carrying out heat treatment to obtain a composite forward osmosis membrane; the high-performance composite forward osmosis membrane prepared by the invention has certain mechanical strength, solvent resistance and good pollution resistance while ensuring high water flux and high salt rejection rate, and can be used in the fields of emergency water bags, aerospace, food concentration, pharmacy, green energy sources, plant protection boxes, seawater desalination, hard water softening, industrial wastewater and the like.

Description

Preparation method of composite forward osmosis membrane based on ZIFs nano material modified supporting layer
Technical Field
The invention relates to the technical field of membrane separation, in particular to a preparation method of a high-performance composite forward osmosis membrane based on a ZIFs nano-material modified supporting layer.
Background
The Forward Osmosis (FO) process is a process in which water automatically diffuses from a dope side with a high electrochemical potential to a draw solution side with a low electrochemical potential through a selectively permeable membrane by taking an osmotic pressure difference between the draw solution and the dope as a driving force, and does not require external pressure and energy. Therefore, compared with the traditional pressure-driven membrane separation process such as Reverse Osmosis (RO), the forward osmosis process has the advantages of low energy consumption, high water recovery rate, difficult membrane pollution, capability of operating at normal temperature and normal pressure and the like, has been successfully tried in the fields of food, pharmacy, energy sources and the like, particularly in the field of water purification and desalination, and shows potential application value.
However, the development of FO technology is greatly limited by the lack of efficient FO membrane materials. The membrane materials used in the FO process at present all have asymmetric structures and consist of a thin selective separation layer and a porous support layer, and both external concentration polarization and internal concentration polarization, especially internal concentration polarization, exist in the FO process, so that the actual water flux of the FO membrane is far smaller than the theoretical water flux. In general, external concentration polarization occurs at the interface between the membrane and the solution, which can be mitigated by increasing the flow rate and other hydrodynamics; the occurrence of internal concentration polarization is a specific phenomenon of the FO process, and solutes are accumulated or diluted in a membrane porous support layer in the FO process according to the orientation of the membrane to form concentrated and diluted internal concentration polarization, thereby greatly reducing the effective osmotic pressure difference at two sides of the membrane. Due to the generation of internal concentration polarization, solute is reversely diffused into stock solution while membrane flux is reduced, osmotic pressure on two sides of the membrane is reduced, and membrane flux is further reduced. The smaller the thickness of the supporting layer is, the higher the porosity is, the smaller the pore bending degree is, the better the hydrophilicity is, the smaller the structural parameters of the membrane are, and the smaller the internal concentration polarization is.
In recent years, much research has been focused on improving the support layer structure of the membrane. In the forward osmosis process, the porous support layer is used as a boundary layer of diffusion transfer and is influenced by the structure, so that the osmotic pressure difference on the active layer is reduced seriously, and the phenomenon of internal concentration polarization occurs. However, it has been found through research that different membrane structures such as finger-shaped pores, sponge-shaped pores, etc. can be obtained by changing the composition of the casting solution and the gel bath in the phase inversion method, thereby achieving the effects of reducing internal concentration polarization and improving the performance of the membrane. Researchers usually add nano materials into the supporting layer by a blending method to modify the structure and hydrophilicity of the supporting layer, so as to effectively improve the performance of the forward osmosis membrane. Increasing the roughness of the supporting layer structure and improving the hydrophilicity of the supporting layer structure are important methods for optimizing the structure of the forward osmosis membrane.
Metal-organic frameworks (MOFs), in turn, are novel porous materials constructed by interconnecting metal building blocks with organic ligands, in particular Zeolitic Imidazolate Frameworks (ZIFs), which have attracted interest as potential membrane materials. ZIFs consisting of zinc or cobalt metal and an imidazolyl linking group have high thermal and chemical stability, and have a zeolite-like topology and uniform pore size. ZIFs are extensively studied MOF membranes due to their high thermal stability (up to 550 ℃), high chemical resistance in various solvents, and lower synthesis temperature than any other MOF.
Based on the limitations of the structure and performance of the traditional forward osmosis membrane, the research and development of a new forward osmosis membrane is a necessary trend. In recent years, with the continuous progress of nano material preparation technology, reports of adding nano materials into the traditional forward osmosis membrane are increased continuously, a feasible way is provided for improving the structure and performance of the traditional forward osmosis membrane, the roughness of the supporting layer can be modified by adding nano particles, a unique water channel is provided, the porosity of the osmosis membrane is increased, and the selective permeability of the FO membrane is improved. But there are some disadvantages and problems to be further solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a high-performance composite forward osmosis membrane by modifying a supporting layer structure through a metal-organic framework (MOF) material. The invention mainly solves the problem that the existing forward osmosis membrane cannot simultaneously have high water flux and high salt rejection rate, and prepares a novel forward osmosis membrane by growing a zeolite imidazolium salt framework (ZIF) material on a support layer material and covering a polyaromatic amide compact separation layer by interfacial polymerization.
The high-performance composite forward osmosis membrane provided by the invention has certain mechanical strength, solvent resistance and good pollution resistance while ensuring high water flux and high salt rejection rate, and can be used in the fields of emergency water bags, aerospace, food concentration, pharmacy, green energy, plant protection boxes, seawater desalination, hard water softening, industrial wastewater and the like.
The technical scheme of the invention is as follows:
a preparation method of a composite forward osmosis membrane based on a ZIFs nano material modified supporting layer comprises the following steps:
(1) sequentially and respectively soaking the polymer support material in an aqueous solution of a metal precursor and an aqueous solution of a ligand, and then cleaning and drying to obtain a support layer material containing a ZIF group;
the polymer support material is selected from fiber non-woven fabrics or textile materials consisting of one or more of polymers such as polyester, polyolefin, nylon and the like, and the thickness of the polymer support material is 30-300 micrometers;
the concentration of the aqueous solution of the metal precursor is 0.01-10 wt%; the metal precursor is selected from one or more of zinc oxide, zinc nitrate, zinc chloride, zinc sulfate and zinc acetate; soaking in the aqueous solution of the metal precursor for 0.01-24 h;
the concentration of the aqueous solution of the ligand is 0.01-7 wt%; the ligand is selected from benzimidazole, 2-methylimidazole or imidazole-2-formaldehyde; soaking in the aqueous solution of the ligand for 0.01-24 h;
the drying temperature is 10-80 ℃, and the drying time is 0.1-24 h;
(2) sequentially and respectively contacting the support layer material containing the ZIF group obtained in the step (1) with a water phase monomer solution and an organic phase monomer solution, and then carrying out heat treatment to obtain a composite forward osmosis membrane;
the concentration of the aqueous phase monomer solution is 0.001-5 wt%, the solvent is deionized water, and the aqueous phase monomer is selected from any one of m-phenylenediamine, o-phenylenediamine, diethylenetriamine, triethylene tetramine and piperazine, or the mass ratio of any two is 1: 1-5 of a mixture; the time for contacting the aqueous monomer solution is 1-30 min;
the concentration of the organic phase monomer solution is 0.001-5 wt%, the solvent is one or more of n-hexane, n-heptane, n-octane, n-dodecane, isododecane and isohexadecane, the organic phase monomer is selected from one of trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride and polybasic sulfonyl, or the mass ratio of any two is 1: 1-5 of a mixture; the time for contacting the organic phase monomer solution is 1-15 min;
the temperature of the heat treatment is 10-80 ℃, and the time is 0.1-24 h.
The composite forward osmosis membrane prepared by the invention comprises: the composite film comprises a polymer supporting layer, a ZIFs nano material layer and a compact polyaramide separating layer, wherein the ZIFs nano material layer is positioned between the polymer supporting layer and the compact polyaramide separating layer;
the ZIFs nano material layer uniformly grows and covers the polymer supporting layer, and ZIFs nano materials with different shapes and sizes on the surface are filled on the surface of the polymer supporting layer and at the defect positions; the ZIFs nano material layer comprises one or more of ZIFs materials such as ZIF-5, ZIF-7, ZIF-8, ZIF-67, ZIF-90 and ZIF-L;
the compact separation layer of the polyaromatic amide is formed by interfacial polymerization of aromatic amine with more than one functional group and aromatic acyl chloride with more than one functional group.
The composite forward osmosis membrane prepared by the invention can be a flat membrane, a hollow fiber homogeneous membrane, a hollow composite membrane or a tubular membrane.
The invention has the beneficial effects that:
1. the nano particles can be uniformly dispersed at the bottom, the middle and the surface of the supporting layer of the forward osmosis membrane by an in-situ growth method, so that the surface roughness of the membrane can be increased, the surface area of the separation layer is increased, and the water flux is improved.
2. Because the metal particles can be complexed with the aqueous monomer, the problem of interfacial compatibility between inorganic and organic materials is overcome.
3. The ZIFs nano particle modification effectively improves the water flux of the polyamide composite membrane, the retention rate is not reduced, and the selective permeability of the separation membrane is obviously improved.
The high-performance composite forward osmosis membrane based on the ZIFs modified supporting layer ensures that the back mixing of the salt thereof is 0.3 mol/(m)2H) the water flux of the forward osmosis membrane is up to 86.1L/(m) on average2H), due to the existence of the ZIFs nanometer material layer, the supporting layer structure is improved, high water flux and high salt rejection rate are ensured, and certain pressure resistance of the forward osmosis membrane is provided.
Drawings
Fig. 1 is an electron microscope image of ZIFs-based support layers prepared from a blank nonwoven fabric (left), example 2 (right, bottom right), and example 12 (bottom left).
FIG. 2 is an X-ray powder diffraction pattern of a support layer modified based on ZIF-8 nanomaterial prepared in example 2 and pure phase ZIF-8 nanocrystals.
FIG. 3 is a graph of water flux versus salt back-mixing data for control forward osmosis membranes made from a blank nonwoven fabric and forward osmosis membranes made from examples 2, 8, 12, and 15.
FIG. 4 is a graph comparing the pressure resistance against sodium sulfate rejection for a control forward osmosis membrane prepared from a blank nonwoven fabric and reverse osmosis mode prepared from example 2, example 8, example 12 and example 15.
Detailed Description
The invention is further described below by means of specific examples, without the scope of protection of the invention being limited thereto.
Example 1:
the preparation method of the high-performance composite forward osmosis membrane based on the ZIFs nano material modified supporting layer comprises the following specific steps:
step (1): soaking a 14 cm-by-14 cm polyethylene terephthalate (PET) non-woven fabric support layer in 0.02 wt% zinc nitrate hexahydrate aqueous solution for 0.5 h;
step (2): taking out, continuously soaking the support layer in 0.026 wt% 2-methylimidazole water solution for 5h, taking out, cleaning, and performing heat treatment at 60 ℃ for 15min to obtain a ZIF-based support layer material;
and (3): dissolving m-phenylenediamine in deionized water to prepare a 2% by mass m-phenylenediamine aqueous solution as a water phase;
and (4): dissolving trimesoyl chloride in n-hexane to prepare a trimesoyl n-hexane solution with the mass fraction of 0.1 percent as an organic phase;
and (5): uniformly coating the m-phenylenediamine aqueous solution on the ZIFs-based support layer material prepared in the step (2), fixing for 4min, and then pouring off the excessive m-phenylenediamine aqueous solution on the surface;
and (6): uniformly coating the organic phase solution prepared in the step (4) on the ZIFs-based supporting layer material treated in the step (5) for interfacial polymerization for 4 minutes, and removing redundant solution; and then carrying out heat treatment at 60 ℃ for 15 minutes, then washing the surface of the membrane with deionized water, and drying (60 ℃ for 0.25h) to obtain the high-performance composite forward osmosis membrane based on the ZIFs nano material modified support layer.
The high-performance composite forward osmosis membrane prepared in the embodiment is loaded into a membrane performance evaluation device, and then membrane flux 73.02L/(m) is measured by taking 1mol/L sodium chloride aqueous solution as an extraction solution and deionized water as a stock solution2H), salt rejection 98.96%.
Examples 2 to 4:
examples 2 to 4 the same procedure as in example 1 was repeated, except that the zinc nitrate hexahydrate in step (1) of example 1 was replaced with zinc chloride (example 2), zinc acetate (example 3), zinc sulfate (example 4); after the zinc source is replaced, the ZIF-8 particles on the supporting layer are found to have no other abnormity obviously, and have no obvious difference on the forward permeability of the membrane, thereby proving the feasibility of changing the zinc source.
Prepared by the present exampleThe high-performance composite forward osmosis membrane is placed in a membrane performance evaluation device, then 1mol/L sodium chloride aqueous solution is used as an extraction solution, deionized water is used as a stock solution, and the membrane flux is measured to be 68.31L/(m)2.h)，67.52L/(m2.h)、65.45L/(m2H) salt retention was 98.57%, 98.91%, 97.36% respectively.
Examples 5 to 6:
examples 5 to 6 the same procedure as in example 1 except for changing 2-methylimidazole in step (2) of example 1 to benzimidazole (example 5), imidazole-2-carbaldehyde (example 6); after the ligand is replaced, different zeolite imidazole framework materials, such as ZIF-7 in example 5, ZIF-90 in example 6 and the like, are grown on the supporting layer, and the forward osmosis membrane with the nano material modified supporting layer prepared after the ligand is replaced has obvious difference compared with the forward osmosis membrane without the modified supporting layer material, and has excellent modification effect on selective permeability.
The high-performance composite forward osmosis membrane prepared in the embodiment is loaded into a membrane performance evaluation device, and then the water fluxes of the two membrane membranes are respectively 64.42L/(m) by taking 1mol/L sodium chloride aqueous solution as an extraction solution and deionized water as a stock solution2.h)、61.23L/(m2H), the salt retention was 98.62%, 98.95%, respectively.
Examples 7 to 10:
examples 7 to 10 are the same as in example 1 except that the time for immersing the nonwoven fabric in the step (1) of example 1 in the zinc ion solution was changed to 10min (example 7), 3h (example 8), 12h (example 9) and 24h (example 10), and the growth conditions of the zeolitic imidazole framework material in the support layer were slightly different after different growth times, and at 3h, the content of ZIFs in the support layer was completely covered on the support layer, and the forward osmosis performance of the membrane was slightly affected.
The high-performance composite forward osmosis membrane prepared in the embodiment is loaded into a membrane performance evaluation device, and then 1mol/L sodium chloride aqueous solution is used as an extraction solution, and deionized water is usedThe water flux of the four membrane membranes is measured to be 75.36L/(m) respectively as stock solution2.h)、74.12L/(m2.h)、71.35L/(m2.h)、68.64L/(m2H) salt retention was 97.69%, 97.33%, 97.58%, 98.37%, respectively.
Examples 11 to 13:
examples 11 to 13 were the same as in example 1, except that the temperature of immersing the step (2) of example 1 in the imidazole solution was adjusted to 10 ℃ (example 11), 50 ℃ (example 12), and 70 ℃ (example 13), the reaction temperature was changed, and the growth rate of ZIFs nanomaterial in the support layer was controlled, and we found that the faster the nanoparticles grow in the support layer with increasing temperature, the faster the reaction is at 50 ℃, and the excellent forward osmosis performance is obtained.
The high-performance composite forward osmosis membrane prepared in the embodiment is loaded into a membrane performance evaluation device, and then water fluxes of the three membrane membranes are respectively 107.55L/(m) by taking 1mol/L sodium chloride aqueous solution as an extraction solution and deionized water as a stock solution2.h)、96..65L/(m2.h)、10.46L/(m2H) salt retention was 96.17%, 96.82%, 96.16%, respectively.
Example 14:
example 14 the same as example 1 except that piperazine was used instead of the aqueous phase monomer and the organic phase monomer was not used in the interfacial polymerization in step (3) of example 1, the forward osmosis membrane prepared thereby had better pressure resistance.
The high-performance composite forward osmosis membrane prepared in the embodiment is loaded into a membrane performance evaluation device, and then a 1mol/L sodium chloride aqueous solution is used as an extraction solution, deionized water is used as a stock solution, so that the membrane flux is measured to be 93.88L/(m2H), salt rejection 96.45%.
Examples 15 to 17:
examples 15 to 17 were prepared in the same manner as in example 1 except that the concentrations of the aqueous phase monomers in step (3) of example 1 were adjusted to 0.5% (example 15), 1% (example 16) and 5% (example 17), and the polyamide layer formed by interfacial polymerization was more compact, thicker and more pressure resistant by changing the concentrations of the aqueous phase monomers.
This implementationThe high-performance composite forward osmosis membrane prepared in the example is put into a membrane performance evaluation device, and then water fluxes of the three membrane membranes are respectively 65.02L/(m) by taking 1mol/L sodium chloride aqueous solution as an extraction solution and deionized water as a stock solution2.h)、56.92L/(m2.h)、68.06L/(m2H) salt retention of 99.26%, 99.34%, 99.16%, respectively.
Examples 18 to 20:
examples 18 to 20 were the same as in example 1 except that the organic phase monomer concentration was adjusted to 0.05% (example 18), 0.3% (example 19) and 0.5% (example 20).
The high-performance composite forward osmosis membrane prepared in the embodiment is loaded into a membrane performance evaluation device, and then water fluxes of the three membrane membranes are respectively 73.02L/(m) by taking 1mol/L sodium chloride aqueous solution as an extraction solution and deionized water as a stock solution2.h)、64.33L/(m2.h)、65.02L/(m2H), the salt retention was 97.84%, 98.64%, 98.23%, respectively.
Comparative example 1:
step (1): dissolving m-phenylenediamine with the mass percentage of 2% in deionized water to prepare a m-phenylenediamine aqueous solution as a water phase;
step (2): dissolving 0.1% by mass of trimesoyl chloride in n-hexane to prepare a trimesoyl n-hexane solution as an organic phase;
and (3): uniformly coating the m-phenylenediamine aqueous solution on a blank support layer material, fixing for 4min, and then removing the redundant m-phenylenediamine aqueous solution;
and (4): uniformly coating the organic phase solution prepared in the step (2) on the blank supporting layer material treated in the step (3) for interfacial polymerization for 4 minutes, and removing redundant solution; then heat-treating for 15 minutes at 60 ℃, rinsing and drying to obtain the blank control forward osmosis membrane.
The composite forward osmosis membrane prepared by the comparative example is loaded into a membrane performance evaluation device, and then the membrane water flux is measured to be 22.16L/(m) by taking 1mol/L sodium chloride aqueous solution as an extraction solution and deionized water as a stock solution2H), the salt rejection was 98.2%.
According to the high-performance composite forward osmosis membrane based on the ZIFs nanomaterial modified supporting layer, a novel porous bottom layer is prepared by growing the ZIFs nanomaterial in situ in the supporting layer, high water flux and high salt rejection rate are guaranteed, the water flux is increased by 3-5 times compared with a comparative example, the salt rejection rate can still keep the same level, and the pressure resistance value is increased by 5-10 times compared with the comparative example in a reverse osmosis mode. Meanwhile, the paint has high mechanical strength, solvent resistance and pollution resistance, and can be used in the fields of emergency water bags, aerospace, food concentration, pharmacy, green energy sources, plant protection boxes, seawater desalination, hard water softening, industrial wastewater and the like.

Claims (10)

1. A preparation method of a composite forward osmosis membrane based on a ZIFs nano material modified supporting layer is characterized by comprising the following steps:
(1) sequentially and respectively soaking the polymer support material in an aqueous solution of a metal precursor and an aqueous solution of a ligand, and then cleaning and drying to obtain a support layer material containing a ZIF group;
the metal precursor is selected from one or more of zinc oxide, zinc nitrate, zinc chloride, zinc sulfate and zinc acetate;
the ligand is selected from benzimidazole, 2-methylimidazole or imidazole-2-formaldehyde;
the drying temperature is 10-80 ℃, and the drying time is 0.1-24 h;
(2) sequentially and respectively contacting the support layer material containing the ZIF group obtained in the step (1) with a water phase monomer solution and an organic phase monomer solution, and then carrying out heat treatment to obtain a composite forward osmosis membrane;
the water phase monomer is selected from any one of m-phenylenediamine, o-phenylenediamine, diethylenetriamine, triethylene tetramine and piperazine, or the mass ratio of any two is 1: 1-5 of a mixture;
the organic phase monomer is selected from any one of trimesoyl chloride, isophthaloyl dichloride, terephthaloyl dichloride and polybasic sulfonyl, or the mass ratio of any two is 1: 1-5 of a mixture;
the temperature of the heat treatment is 10-80 ℃, and the time is 0.1-24 h.
2. The method for preparing a composite forward osmosis membrane based on a ZIFs nanomaterial modified support layer as claimed in claim 1, wherein in the step (1), the polymer support material is selected from a fiber non-woven fabric or a textile material consisting of one or more of polyester, polyolefin and nylon, and the thickness of the polymer support material is 30-300 μm.
3. The method for preparing a composite forward osmosis membrane based on a ZIFs nanomaterial modified support layer as claimed in claim 1, wherein in the step (1), the concentration of the aqueous solution of the metal precursor is 0.01-10 wt%.
4. The preparation method of the composite forward osmosis membrane based on the ZIFs nanomaterial modified support layer as claimed in claim 1, wherein in the step (1), the soaking time in the aqueous solution of the metal precursor is 0.01-24 h.
5. The method for preparing a composite forward osmosis membrane based on a ZIFs nanomaterial modified support layer as claimed in claim 1, wherein in the step (1), the concentration of the aqueous solution of the ligand is 0.01-7 wt%.
6. The preparation method of the composite forward osmosis membrane based on the ZIFs nanomaterial modified support layer as claimed in claim 1, wherein in the step (1), the soaking time in the ligand aqueous solution is 0.01-24 h.
7. The method for preparing a composite forward osmosis membrane based on a ZIFs nanomaterial modified support layer as claimed in claim 1, wherein in the step (2), the concentration of the aqueous phase monomer solution is 0.001-5 wt%, and the solvent is deionized water.
8. The preparation method of the composite forward osmosis membrane based on the ZIFs nanomaterial modified support layer as claimed in claim 1, wherein in the step (2), the time for contacting the aqueous monomer solution is 1-30 min.
9. The method for preparing a composite forward osmosis membrane based on a ZIFs nanomaterial modified supporting layer according to claim 1, wherein in the step (2), the concentration of the organic phase monomer solution is 0.001-5 wt%, and the solvent is one or more of n-hexane, n-heptane, n-octane, n-dodecane, isododecane, and isohexadecane.
10. The preparation method of the composite forward osmosis membrane based on the ZIFs nanomaterial modified support layer as claimed in claim 1, wherein in the step (2), the time for contacting the organic phase monomer solution is 1-15 min.
CN202111068252.4A 2021-09-13 2021-09-13 Preparation method of composite forward osmosis membrane based on ZIFs nano material modified supporting layer Pending CN113786731A (en)

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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
CN114887504A (en) * 2022-06-21 2022-08-12 济南大学 Flat plate type mixed matrix forward osmosis membrane based on ZIF-67 and preparation method thereof
CN114904404A (en) * 2022-06-20 2022-08-16 济南大学 Mixed matrix forward osmosis membrane based on MOF-808(Zr) and preparation method thereof
CN115193256A (en) * 2022-08-08 2022-10-18 浙江工业大学 PE-based ZIFs/PA secondary sealed composite forward osmosis membrane and preparation method thereof
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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