CN108043227B - Preparation method of polyvinylidene fluoride nanofiltration membrane - Google Patents
Preparation method of polyvinylidene fluoride nanofiltration membrane Download PDFInfo
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- CN108043227B CN108043227B CN201711176289.2A CN201711176289A CN108043227B CN 108043227 B CN108043227 B CN 108043227B CN 201711176289 A CN201711176289 A CN 201711176289A CN 108043227 B CN108043227 B CN 108043227B
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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
- B01D61/027—Nanofiltration
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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
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
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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
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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
- B01D69/06—Flat membranes
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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
- B01D69/10—Supported membranes; Membrane supports
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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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
Abstract
A preparation method of a polyvinylidene fluoride nanofiltration membrane relates to the technical field of membrane separation. (1) Preparing a polyvinylidene fluoride ultrafiltration basement membrane by adopting a phase inversion method, mixing polyvinylidene fluoride, a solvent, an additive and a pore-forming agent, heating and uniformly stirring, standing and defoaming in vacuum, scraping the membrane by using a scraper and immersing the membrane into a coagulating bath to form a membrane or enabling a membrane casting solution to flow out of a spinneret plate to form a membrane in the coagulating bath; (2) preparing a polyvinylidene fluoride nanofiltration membrane by adopting an interfacial polymerization method, respectively immersing an ultrafiltration base membrane in a water-phase monomer solution and an oil-phase monomer solution, and performing heat treatment to obtain the nanofiltration membrane. The aqueous solution prepared from micromolecules or polymers containing amino, carboxyl, sulfonic group or hydroxyl functional group is used as the coagulating bath, the operation is simple, the defects on the functional separation layer are avoided, the binding force between the functional separation layer and the base membrane is improved, the prepared nanofiltration membrane has good separation performance, can stably run for a long time, and has wide application prospect in the fields of water treatment and the like.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a preparation method of a polyvinylidene fluoride nanofiltration membrane.
Background
The membrane separation technology has wide application in the field of separation and concentration of substances, can be operated at normal temperature, and has the advantages of energy conservation and environmental protection. The nanofiltration membrane technology is one of membrane separation technologies, and is a pressure driving membrane technology between an ultrafiltration membrane technology and a reverse osmosis technology. Nanofiltration membranes have membrane pore sizes on the nanometer scale and are most often charged, so that they can retain divalent or multivalent ions and higher molecular weight organics while allowing monovalent ions to pass through. Therefore, based on the unique performance of the nanofiltration membrane, the nanofiltration membrane is widely applied to wastewater treatment, food industry, chemical and pharmaceutical industry, drinking water industry and the like.
At present, commercial nanofiltration membrane series mainly comprise NF, NTR, UTC, MPT, SU and the like, and most commercial nanofiltration membranes are composite membranes. The composite membrane generally comprises a base membrane and a functional separation layer, and the preparation method generally comprises the steps of coating a polyamine aqueous phase solution on the surface of the base membrane, then coating an organic phase solution of polyacyl chloride, forming the functional separation layer on the surface of the base membrane through interfacial polymerization reaction of the aqueous phase solution and the organic phase solution, and then obtaining the nanofiltration membrane through certain post-treatment.
Polyvinylidene fluoride (PVDF) has good chemical stability and thermal stability, is an ideal film forming material, has obvious advantages compared with other film materials, and has wide application in the field of water treatment. However, the hydrophobic property is strong, and when the nanofiltration membrane is prepared by taking the nanofiltration membrane as a base membrane, on one hand, the aqueous phase solution is difficult to be uniformly distributed on the surface of the nanofiltration membrane, so that the formed functional separation layer has defects; on the other hand, the functional separation layer prepared by interfacial polymerization reaction has poor binding force with the polyvinylidene fluoride base membrane, so that the functional separation layer is easy to fall off from the surface of the base membrane, and the nanofiltration effect of the composite membrane is lost. Therefore, few commercial nanofiltration membranes taking the polyvinylidene fluoride ultrafiltration membrane as the base membrane are available on the market at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention mainly aims at solving the defects of the prior art, and provides the preparation method of the polyvinylidene fluoride-based nanofiltration membrane, which is simple to operate, avoids the defects on the functional separation layer, improves the binding force between the functional separation layer and the base membrane, and the nanofiltration membrane prepared by the method has good separation performance and can stably run for a long time.
The invention provides a preparation method of a polyvinylidene fluoride nanofiltration membrane, which comprises the following steps:
(1) preparing a polyvinylidene fluoride ultrafiltration base membrane: mixing polyvinylidene fluoride, a solvent, an additive and a pore-foaming agent, heating to 50-90 ℃, uniformly stirring, standing and defoaming in a vacuum environment to prepare a membrane casting solution, scraping a membrane by using a scraper, immersing the membrane casting solution into a coagulating bath to form a membrane or allowing the membrane casting solution to flow out of a spinneret plate to the coagulating bath to form a membrane, wherein the prepared membrane is a polyvinylidene fluoride ultrafiltration basement membrane;
(2) preparing a polyvinylidene fluoride-based nanofiltration membrane: immersing the prepared polyvinylidene fluoride ultrafiltration base membrane in an aqueous phase monomer solution for 30 s-15 min, taking out, wiping off excessive water on the surface, immersing the polyvinylidene fluoride ultrafiltration base membrane in an organic solution of an oil phase monomer for 15 s-2 min, taking out, and carrying out heat treatment on the polyvinylidene fluoride ultrafiltration base membrane for 1 min-10 min at 30-120 ℃ to obtain the polyvinylidene fluoride base nanofiltration membrane.
Preferably, the solvent, the additive and the pore-forming agent are solvents, additives and pore-forming agents commonly used for preparing ultrafiltration membranes by a phase inversion method, wherein the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, acetone and tetrahydrofuran, and the additive and the pore-forming agent are one or more of lithium chloride, polyvinylpyrrolidone, polyethylene glycol and glycerol.
Further preferably, in the casting solution obtained in the step (1), the mass percentage concentration of polyvinylidene fluoride is 8-20%, the mass percentage concentration of the additive is 0.01-5%, and the mass percentage concentration of the pore-forming agent is 0.01-5%.
Preferably, the coagulation bath is an aqueous solution of a compound containing amino, carboxyl, sulfonic acid or hydroxyl functional groups, and the mass percentage concentration of the compound is in the range of 0.01-5%. The compound containing amino, carboxyl, sulfonic group or hydroxyl functional group can be one or more of m-phenylenediamine, piperazine, polyvinyl alcohol, polyglutamic acid, melamine, sulfonated polyether sulfone, sulfonated polysulfone, o-phenylenediamine, dimethyl m-phenylenediamine, 1, 4-cyclohexanediamine, N-dimethylcyclohexanediamine, triethanolamine, polyethyleneimine (newly added substances) and the like.
Preferably, the aqueous phase monomer is one or more of piperazine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, pyromellitic triamine, N-dimethyl m-phenylenediamine, 1, 4-cyclohexanediamine, N-dimethyl cyclohexanediamine, triethanolamine, polyethyleneimine and the like, and the concentration range of the aqueous phase monomer solution is 0.05-5% by mass percent.
Preferably, an additive or a catalyst can be further added into the aqueous phase monomer solution, the added additive or catalyst is one or more of sodium dodecyl sulfate, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and triethylamine, and the mass percentage concentration range of the added additive or catalyst is 0-0.5%.
Preferably, the solute of the oil phase monomer organic solution is one or more of trimesoyl chloride, 1,3, 5-cyclohexane trimethyl chloride, biphenyl triacyl chloride, 5-benzoyl-isophthalic acid chloride, terephthaloyl chloride and phthaloyl chloride, the solvent is one or more of n-hexane and n-heptane, and the concentration of the oil phase monomer solution is 0.05-2%.
Preferably, the polyvinylidene fluoride ultrafiltration base membrane can be a flat membrane or a fiber membrane, and when the polyvinylidene fluoride ultrafiltration base membrane is the flat membrane, a scraper is used for scraping the membrane and immersing the membrane into a coagulating bath to form the membrane; and when the polyvinylidene fluoride ultrafiltration base membrane is a fiber membrane, the membrane casting solution flows out of the spinneret plate to a coagulating bath for membrane formation.
Preferably, the aqueous solution prepared by micromolecules or polymers containing amino, carboxyl, sulfonic group or hydroxyl functional group is used as the coagulating bath, so that the binding force between the functional separation layer of the nanofiltration membrane and the polyvinylidene fluoride ultrafiltration base membrane is greatly improved, the defects on the functional separation layer are avoided, and the long-term running stability of the prepared nanofiltration membrane is ensured.
Preferably, the polyvinylidene fluoride ultrafiltration membrane can be provided with other support layers or not, the support layer can be made of non-woven fabrics, woven tubes or tows, and the structure of the support layer can be one or more of polyester, nylon, polypropylene, polyhexamethylene adipamide, polyethylene terephthalate, poly-m-phenylene isophthalamide, poly-terephthaloyl, p-phenylenediamine, polyvinyl chloride, polyacrylonitrile, polyamide, polyurethane and polyvinyl formal.
The invention has the following advantages and beneficial effects: the invention provides a preparation method of a polyvinylidene fluoride-based nanofiltration membrane, which is simple to operate and can avoid the defects of a prepared functional separation layer.
Detailed Description
The present invention will be further described with reference to specific examples.
The invention provides a preparation method of a polyvinylidene fluoride nanofiltration membrane, which comprises the following steps:
(1) preparing a polyvinylidene fluoride ultrafiltration base membrane: mixing polyvinylidene fluoride, a solvent, an additive and a pore-forming agent, heating to 50-90 ℃, uniformly stirring, standing and defoaming in a vacuum environment to prepare a membrane casting solution, scraping a membrane on a planar support by using a scraper, and immersing the membrane into a coagulating bath to form a membrane or flowing out of a spinneret plate to form a membrane in the coagulating bath, wherein the prepared membrane is a polyvinylidene fluoride ultrafiltration basement membrane;
(2) preparing a polyvinylidene fluoride-based nanofiltration membrane: immersing the prepared polyvinylidene fluoride ultrafiltration base membrane in an aqueous phase monomer solution for 30 s-15 min, taking out, wiping off excessive water on the surface of the polyvinylidene fluoride ultrafiltration base membrane, immersing the polyvinylidene fluoride ultrafiltration base membrane in an oil phase monomer solution for 15 s-2 min, taking out, and carrying out heat treatment on the polyvinylidene fluoride ultrafiltration base membrane at the temperature of 30-120 ℃ for 1 min-10 min to obtain the polyvinylidene fluoride base nanofiltration membrane.
As a preferable mode of the above embodiment, the solvent, the additive and the porogen are solvents, additives and porogens commonly used in the preparation of ultrafiltration membranes by a phase inversion method, wherein the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, acetone and tetrahydrofuran, and the additive and the porogens are one or more of lithium chloride, polyvinylpyrrolidone, polyethylene glycol and glycerol.
In a preferred embodiment of the above embodiment, the coagulation bath is an aqueous solution prepared from a small molecule or polymer containing an amino group, a carboxyl group, a sulfonic acid group or a hydroxyl functional group, and the concentration of the aqueous solution is in the range of 0.01% to 5%.
In a preferred embodiment of the above embodiment, the aqueous monomer is one or more of piperazine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, sym-benzenetriamine, N-dimethyl m-phenylenediamine, 1, 4-cyclohexanediamine, N-dimethyl cyclohexanediamine, triethanolamine, and polyethyleneimine, and the concentration of the monomer in the aqueous monomer solution is in the range of 0.05% to 5%.
As a preferable mode of the above embodiment, an additive or a catalyst may be added to the aqueous monomer solution, the additive or the catalyst is generally one or more of sodium dodecyl sulfate, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and triethylamine, and the concentration of the additive or the catalyst is 0 to 0.5%.
In a preferred embodiment of the above embodiment, the solute of the oil phase monomer solution is one or more of trimesoyl chloride, 1,3, 5-cyclohexanetriyl chloride, biphenyltriacyl chloride, 5-oxoformyl-isophthaloyl chloride, terephthaloyl chloride and phthaloyl chloride, the solvent is one or more of n-hexane and n-heptane, and the concentration of the oil phase monomer solution is 0.05% to 2%.
As a preferable mode of the above embodiment, the polyvinylidene fluoride ultrafiltration membrane may be a flat membrane or a fiber membrane, and when the polyvinylidene fluoride ultrafiltration membrane is a flat membrane, the polyvinylidene fluoride ultrafiltration membrane is scraped by a scraper and immersed in a coagulation bath to form a membrane; and when the polyvinylidene fluoride ultrafiltration base membrane is a fiber membrane, the membrane casting solution flows out of the spinneret plate to a coagulating bath for membrane formation.
As a preferred mode of the above embodiment, an aqueous solution prepared from a small molecule or a polymer containing amino, carboxyl, sulfonic group or hydroxyl functional group is used as a coagulation bath, so that the binding force between the functional separation layer of the nanofiltration membrane and the polyvinylidene fluoride ultrafiltration substrate is greatly improved, defects on the functional separation layer are avoided, and the long-term operation stability of the prepared nanofiltration membrane is ensured.
As a preferable mode of the above embodiment, the polyvinylidene fluoride ultrafiltration membrane may have other support layers or no other support layers, the support layer material may be non-woven fabric, woven tube or filament bundle, and the structure of the support layer material may be one or more of polyester, nylon, polypropylene, polyhexamethylene adipamide, polyethylene terephthalate, poly-m-phenylene isophthalamide, poly-terephthaloyl, p-phenylenediamine, polyvinyl chloride, polyacrylonitrile, polyamide, polyurethane and polyvinyl formal.
The following examples film performance tests were conducted at room temperature.
Example 1
Weighing 17g of polyvinylidene fluoride, 1g of lithium chloride, 3g of polyvinylpyrrolidone and 79g of N, N-dimethylacetamide, mixing, heating to 80 ℃, uniformly stirring, standing and defoaming in a vacuum environment to prepare a membrane casting solution, scraping a membrane on a glass plate by using a scraper, and immersing the glass plate into a coagulating bath with the piperazine content of 2% to form a membrane, thereby preparing a polyvinylidene fluoride ultrafiltration basement membrane; immersing the prepared polyvinylidene fluoride ultrafiltration base membrane in 0.5% piperazine water solution (additive triethylamine content is 0.01%) for 10min, taking out, wiping off excessive water on the membrane surface, immersing the membrane in 0.1% trimesoyl chloride n-hexane solution for 1min, taking out, and placing in a 50 ℃ oven for 2min to obtain the polyvinylidene fluoride nanofiltration membrane. The nanofiltration membrane is applied to 1g/L MgSO4The rejection rate of the composite membrane is 78 percent, the rejection rate of the composite membrane for 1g/L NaCl is 23 percent, the composite membrane has a good separation effect on monovalent ions and divalent ions, the rejection and separation performance of the composite membrane is not reduced after the composite membrane continuously runs for 48 hours, and the composite membrane has good stability.
Example 2
Weighing 16g of polyvinylidene fluoride, 1.5g of lithium chloride, 2.5g of polyvinylpyrrolidone and 80g of N, N-dimethylacetamide, mixing, heating to 85 ℃, uniformly stirring, standing and defoaming in a vacuum environment to prepare a membrane casting solution, scraping a membrane on a glass plate by using a scraper, and immersing the glass plate into a coagulating bath with the content of m-phenylenediamine of 1.5% to form a membrane, thus preparing a polyvinylidene fluoride ultrafiltration basement membrane; will be prepared intoImmersing the prepared polyvinylidene fluoride ultrafiltration basal membrane in a m-phenylenediamine aqueous solution with the concentration of 1% for 10min (the contents of additives of sodium dodecyl sulfate and sodium carbonate are 0.5% and 0.05% respectively), taking out, wiping off excessive water on the surface of the membrane, immersing the membrane in a n-hexane solution of trimesoyl chloride with the concentration of 0.2% for 1min, taking out, and placing in a 60 ℃ drying oven for 3min to prepare the polyvinylidene fluoride nanofiltration membrane. The nanofiltration membrane is applied to 1g/L MgSO4The rejection rate of the composite membrane is 90 percent, the rejection rate of the composite membrane for 1g/L NaCl is 35 percent, the composite membrane has a good separation effect on monovalent ions and divalent ions, the rejection and separation performance of the composite membrane is not reduced after the composite membrane continuously runs for 48 hours, and the composite membrane has good stability.
Example 3
Weighing 660g of polyvinylidene fluoride, 50g of lithium chloride, 130g of polyvinylpyrrolidone and 3160g of N, N-dimethylacetamide, mixing, heating to 85 ℃, uniformly stirring, standing and defoaming in a vacuum environment, and thus obtaining the casting solution. Then, the casting solution flows out through a spinneret plate to a coagulating bath with 1.5% of melamine content for film formation, and a polyvinylidene fluoride ultrafiltration base film is prepared; immersing the prepared polyvinylidene fluoride ultrafiltration base membrane in 0.2% piperazine water solution (additive triethylamine content is 0.02%) for 10min, taking out, wiping off excessive water on the membrane surface, immersing the membrane in 0.1% trimesoyl chloride n-hexane solution for 1min, taking out, and placing in a 60 ℃ oven for 5min to obtain the polyvinylidene fluoride nanofiltration membrane. The nanofiltration membrane is applied to 1g/L MgSO4The rejection rate of the composite membrane is 85 percent, the rejection rate of the composite membrane for 1g/L NaCl is 30 percent, the composite membrane has better separation effect on monovalent ions and divalent ions, the rejection and separation performance of the composite membrane is not reduced after the composite membrane continuously runs for 96 hours, and the composite membrane has better stability.
Claims (7)
1. The preparation method of the polyvinylidene fluoride nanofiltration membrane is characterized by comprising the following steps:
(1) preparing a polyvinylidene fluoride ultrafiltration base membrane: mixing polyvinylidene fluoride, a solvent, an additive and a pore-foaming agent, heating to 50-90 ℃, uniformly stirring, standing and defoaming in a vacuum environment to prepare a membrane casting solution, scraping a membrane by using a scraper, immersing the membrane casting solution into a coagulating bath to form a membrane or allowing the membrane casting solution to flow out of a spinneret plate to the coagulating bath to form a membrane, wherein the prepared membrane is a polyvinylidene fluoride ultrafiltration basement membrane;
(2) preparing a polyvinylidene fluoride-based nanofiltration membrane: immersing the prepared polyvinylidene fluoride ultrafiltration base membrane in an aqueous phase monomer solution for 30 s-15 min, taking out, wiping off excessive water on the surface of the polyvinylidene fluoride ultrafiltration base membrane, immersing the polyvinylidene fluoride ultrafiltration base membrane in an organic solution of an oil phase monomer for 15 s-2 min, taking out, and carrying out heat treatment on the polyvinylidene fluoride ultrafiltration base membrane at the temperature of 30-120 ℃ for 1 min-10 min to obtain a polyvinylidene fluoride base nanofiltration membrane;
the coagulating bath is an aqueous solution of a compound containing amino, carboxyl, sulfonic acid or hydroxyl functional groups;
the mass percentage concentration range of the coagulating bath is 0.01% -5%;
the compound containing amino, carboxyl, sulfonic group or hydroxyl functional group is one or more of m-phenylenediamine, piperazine, polyvinyl alcohol, polyglutamic acid, melamine, sulfonated polyether sulfone, sulfonated polysulfone, o-phenylenediamine, dimethyl m-phenylenediamine, 1, 4-cyclohexanediamine, N-dimethylcyclohexanediamine, triethanolamine and polyethyleneimine.
2. The preparation method of a polyvinylidene fluoride nanofiltration membrane according to claim 1, wherein the solvent in step (1) is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, acetone, and tetrahydrofuran, and the additive and pore-forming agent are one or more of lithium chloride, polyvinylpyrrolidone, polyethylene glycol, and glycerol; in the casting solution of the step (1), the mass percent concentration of polyvinylidene fluoride is 8-20%, the mass percent concentration of additive is 0.01-5%, and the mass percent concentration of pore-forming agent is 0.01-5%.
3. The preparation method of a polyvinylidene fluoride nanofiltration membrane according to claim 1, wherein the aqueous phase monomer is one or more of piperazine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, trimesamine, N-dimethyl m-phenylenediamine, 1, 4-cyclohexanediamine, N-dimethylcyclohexanediamine, triethanolamine and polyethyleneimine, and the concentration of the aqueous phase monomer solution is 0.05% to 5% by mass.
4. The preparation method of a polyvinylidene fluoride nanofiltration membrane according to claim 1, wherein an additive or a catalyst is further added to the aqueous phase monomer solution, the additive or the catalyst is one or more of sodium dodecyl sulfate, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and triethylamine, and the concentration of the additive or the catalyst is 0-0.5% by mass.
5. The preparation method of a polyvinylidene fluoride nanofiltration membrane according to claim 1, wherein the solute of the oil phase monomer organic solution is one or more of trimesoyl chloride, 1,3, 5-cyclohexanetriyl chloride, biphenyltriacyl chloride, 5-oxoformyl-isophthaloyl chloride, terephthaloyl chloride and phthaloyl chloride, the solvent is one or more of n-hexane and n-heptane, and the concentration of the oil phase monomer solution is 0.05-2%.
6. The method for preparing a polyvinylidene fluoride nanofiltration membrane according to claim 1, wherein the polyvinylidene fluoride ultrafiltration base membrane is a flat membrane or a fiber membrane, and when the polyvinylidene fluoride ultrafiltration base membrane is a flat membrane, a scraper is used for scraping the membrane and immersing the membrane into a coagulation bath to form a membrane; and when the polyvinylidene fluoride ultrafiltration base membrane is a fiber membrane, the membrane casting solution flows out of the spinneret plate to a coagulating bath for membrane formation.
7. A method for preparing a polyvinylidene fluoride nanofiltration membrane according to claim 1, wherein the polyvinylidene fluoride ultrafiltration membrane has other support layers or does not have other support layers, the support layer is made of non-woven fabrics, woven tubes or tows, and the support layer is made of one or more of polyester, nylon, polypropylene, polyhexamethylene adipamide, polyethylene terephthalate, poly-m-phenylene isophthalamide, poly-phenylene terephthalamide, poly-vinyl chloride, polyacrylonitrile, polyamide, polyurethane and polyvinyl formal.
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