CN114917767A - Preparation method of efficient oil-water separation superfine nanofiber hydrophilic membrane - Google Patents

Preparation method of efficient oil-water separation superfine nanofiber hydrophilic membrane Download PDF

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CN114917767A
CN114917767A CN202210673583.9A CN202210673583A CN114917767A CN 114917767 A CN114917767 A CN 114917767A CN 202210673583 A CN202210673583 A CN 202210673583A CN 114917767 A CN114917767 A CN 114917767A
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pvdf
oil
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CN114917767B (en
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冯建永
许瑞祥
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QINGDAO YIMIN JIUZHOU CLEANING Co.,Ltd.
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Zhejiang Sci Tech University ZSTU
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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
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/02—Hydrophilization
    • 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
    • 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 preparation method of a high-efficiency oil-water separation superfine nanofiber hydrophilic membrane, which comprises the following steps: (1) polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP) and hydrophilic silicon dioxide (SiO) 2 ) Dissolving in N, N-Dimethylformamide (DMF) to prepare a spinning solution, and preparing the PVDF superfine hybrid nano-film through electrostatic spinning; (2) treating the PVDF superfine hybrid nano-film with absolute ethanol; (3) adding Catechol (CA) and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH560) into TrisHCl buffer solution to obtain a hydrophilic modified solution I; (4) putting the obtained membrane into a hydrophilic modification solution I for modification treatment; (5) taking out the membrane, adding Tannin (TA) into the treated hydrophilic modification solution I to obtain a hydrophilic modification solution II, and putting the membrane into the hydrophilic modification solution II to continue modification treatment; (6) taking out the film and then heating and drying;the polyvinylidene fluoride membrane prepared by the method has the advantages of excellent hydrophilic effect, small aperture and excellent underwater oleophobic property, and can be used in the fields of oil-water separation, water filtration and the like.

Description

Preparation method of efficient oil-water separation superfine nanofiber hydrophilic membrane
Technical Field
The invention belongs to the technical field of functional nano-film preparation, and particularly relates to a preparation method of a high-efficiency oil-water separation superfine nano-fiber hydrophilic film.
Background
The rapid development of the economic society generates a plurality of environmental pollution problems. Among them, oil pollution caused by industrial production discharge and oil leakage has serious harm to ecological environment and human health, and has become one of the most serious environmental problems. Significant advances have been made in a number of cleaning techniques directed to the enrichment and recovery of tiny oil droplets from wastewater, including adsorption, filtration, gravity separation, centrifugation, and flocculation. However, the technologies still have disadvantages such as low separation efficiency, secondary pollution, high cost and high energy consumption, which severely limits the practical application. In recent years, the preparation of novel materials with special wettability has attracted great research interest and is considered as a practical strategy for achieving efficient oil-water separation.
Frequent oil leakage accidents, increasing industrial oily wastewater and large amounts of discharged domestic oily wastewater make the problem of water resource pollution become increasingly serious. After the leakage accident, the oil floating on the sea surface is easy to diffuse to form a layer of airtight oil film, which hinders the reoxygenation of the water body, so that the ocean water body is anoxic, the growth of ocean plankton is influenced, and the ocean ecological balance is damaged. Oil is a relatively common contaminant in water resource systems, while water is also a contaminant in oil systems. The water in oil can make the oil go bad easily, and the water in fuel oil can greatly shorten the service life of power devices such as internal combustion locomotives, ships and the like and reduce the safety performance of the power devices. How to efficiently separate oil from water in oil-containing waste water and water-containing waste oil to obtain reusable pure water and high-purity oil products is one of the scientific problems in China and even in the world.
The high-efficiency and quick separation of the oil-water mixture is realized, and the method has important significance for protecting water environment and saving energy. The oil-water emulsion in the oily sewage is the most difficult to separate, and how to effectively treat the oil-water emulsion becomes one of the problems to be solved at present. Conventional separation methods are limited in their application because they are energy intensive or they cannot be effectively disposed of to meet environmental emission requirements. Compared with the traditional demulsification technology, the membrane demulsification technology has the advantages of higher separation efficiency, no need of adding chemical reagents, no phase change, higher economy and the like, so that the membrane demulsification technology has a good prospect, but also has the problems of serious membrane pollution, higher membrane preparation cost and the like. Meanwhile, the current microfiltration technology cannot meet the requirements of industrial application in terms of preparation process, application throughput, complexity of membrane operation and use cost, and the development of an oil-water emulsion separation membrane with high efficiency, high throughput, low energy consumption and low cost has important social and economic significance.
The electrostatic spinning polyvinylidene fluoride (PVDF) nanofiber porous membrane has the advantages of high porosity, uniform pore size distribution, good pore connectivity, good structure adjustability and the like, is widely applied to solving the environmental problems and filtering water quality, is expected to prepare an oil-water separation membrane which has high efficiency and high flux and can be produced in a large scale at low cost by combining a corresponding modification treatment technology, and has wide application prospect in the aspect of oil-water emulsion separation. However, polyvinylidene fluoride does not have a hydrophilic group, and the polyvinylidene fluoride nano-film shows strong hydrophobicity, so that the polyvinylidene fluoride nano-film is hindered in the fields of oil-water separation, water filtration and the like which require that products have hydrophilic performance. Therefore, how to develop a polyvinylidene fluoride hydrophilic membrane with good hydrophilicity and strong oil stain resistance becomes a research hotspot of polyvinylidene fluoride nano-membrane modification.
Disclosure of Invention
The invention aims to provide a preparation method of a high-efficiency oil-water separation superfine nanofiber hydrophilic membrane, aiming at the defects of the prior art, and the polyvinylidene fluoride hydrophilic membrane prepared by the method has excellent oil-water separation efficiency.
The technical scheme adopted by the invention is as follows:
firstly, polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP) and hydrophilic silicon dioxide (SiO) are prepared 2 ) The hybrid nano-fiber membrane is treated by ethanol, so that the fiber can be bent and wound to reduce the aperture, the PVDF hybrid membrane is obtained, then a first modified solution of Catechol (CA) and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH560) is prepared, and the PVDF hybrid membrane is wetted and then put into the modified solutionIn the first aqueous solution, heating in a vacuum oven to dehydrate and condense KH560, and allowing an epoxy group in the KH560 to perform a ring-opening reaction with a phenolic hydroxyl group of CA, then adding Tannic Acid (TA) into the first modified solution after treatment, heating in the oven to oxidize the phenolic hydroxyl group of TA into a quinoid form, and forming a strong hydrogen bonding effect between the quinone oxide of TA and the KH560 of dehydration and condensation, so as to endow the polyvinylidene fluoride nano-membrane with excellent hydrophilicity and enable the polyvinylidene fluoride nano-membrane to have smaller pores.
The technical scheme adopted by the invention is as follows:
a preparation method of a superfine nanofiber hydrophilic membrane for efficient oil-water separation comprises the following steps:
(1) polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP) and hydrophilic silicon dioxide (SiO) 2 ) Dissolving the mixture in N, N-Dimethylformamide (DMF), heating and stirring for 6-7h, then stirring without heating for 16-18h to obtain a spinning solution, and preparing the PVDF superfine (the fiber diameter is less than 100nm) hybrid nano-film by electrostatic spinning;
(2) treating the PVDF superfine hybrid nano-film in absolute ethyl alcohol for 30-40min, and then putting the treated PVDF superfine hybrid nano-film in deionized water to obtain a PVDF hybrid film; PVP can be completely dissolved within the treatment time range, the treatment time of absolute ethyl alcohol is too short, PVP cannot be completely dissolved, the treatment time of ethyl alcohol is too long, the preparation efficiency is not facilitated, fibers in the PVDF hybrid membrane are bent and wound with one another after the treatment, and pores are reduced.
(3) Placing a certain amount of Catechol (CA) and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH560) in a TrisHCl buffer solution with the pH value of 8.5-pH value of 9, and stirring for 5-10min to prepare a hydrophilic modified solution I;
(4) putting the PVDF hybrid membrane into the hydrophilic modification solution I, and putting the PVDF hybrid membrane into a vacuum oven to be heated for 6 hours at the temperature of 35-40 ℃;
(5) taking out the membrane, adding Tannic Acid (TA) into the hydrophilic modification solution I treated in the step (4), stirring for 7-9min to obtain a hydrophilic modification solution II, and then putting the membrane into the hydrophilic modification solution II to heat for 6h at 35-40 ℃ in an oven;
(6) and taking out the membrane, putting the membrane into deionized water, taking out the membrane, and then putting the membrane into an oven to be heated and dried at 35-40 ℃ to obtain the high oil-water separation superfine nanofiber hydrophilic membrane.
In the above technical solution, further, the concentration of PVDF obtained in the step (1) is 1-10 wt%, the concentration of PVP is 1-15 wt%, and hydrophilic SiO is 2 The concentration is 0.1-1 wt%. Therefore, a low-viscosity solution is prepared, so that the preparation of the superfine nano fibers is facilitated, the submicron fibers can be prepared when the viscosity is out of the range, and the fibers cannot be prepared when the viscosity is below the range.
Further, the concentration of CA in the hydrophilic modification solution I in the step (3) is 0.1-2 g/L.
Further, the concentration of KH560 in the hydrophilic modification solution I in the step (3) is 1-10 g/L.
Further, the concentration of the TrisHCl buffer solution in the hydrophilic modification solution I in the step (3) is 5-20 mmol/L. Further, the concentration of TA in the hydrophilic modification solution II in the step (5) is 0.1-2 g/L.
The above preferred ranges can ensure better modification in the method of the present invention, and below these ranges, the modification effect is not good, while when the CA concentration, KH560 concentration, TrisHCl buffer solution concentration, and TA concentration are higher, the pores of the prepared membrane are easily blocked, which is not beneficial to application.
Due to the adoption of the technical scheme, the method has the following beneficial effects:
the invention utilizes PVP and hydrophilic SiO 2 On the one hand, the conductivity of a PVDF solution can be effectively increased, the fiber diameter is smaller, the pore diameter is smaller, PVP can be dissolved by an organic solvent ethanol, the pore is further reduced, KH560 can be subjected to dehydration condensation by heating a silane coupling agent KH560 and catechol CA in vacuum, an epoxy group in the KH560 can perform ring-opening reaction with a phenolic hydroxyl group of CA, TA is added for reheating, the phenolic hydroxyl group of TA is oxidized into a quinoid form, and strong hydrogen bond action can be formed between quinone oxide of TA and the KH560 subjected to dehydration condensation, so that the polyvinylidene fluoride nano-membrane is endowed with excellent hydrophilicity and has smaller pores. The hydrophilic membrane prepared by the method has a good hydrophilic effect and excellent oil-water separation efficiency.
Drawings
The invention will be further described with reference to the accompanying drawings in which:
FIG. 1 is a scanning electron microscope image of the polyvinylidene fluoride hybrid nano-film obtained in step (1) of example 1;
FIG. 2 is a scanning electron microscope image of the polyvinylidene fluoride nano-film treated with ethanol obtained in step (2) of example 1.
FIG. 3 is the scanning electron microscope image of the modified polyvinylidene fluoride nano-film obtained finally in example 1.
Detailed Description
The invention is further illustrated by the following examples:
in the following examples, reagents, materials and devices used were each commercially available or prepared by a conventional method, unless otherwise specified.
Example 1
(1) Mixing 6 wt% polyvinylidene fluoride (PVDF), 4 wt% polyvinylpyrrolidone (PVP), 0.5 wt% hydrophilic Silica (SiO) 2 ) Dissolving the PVDF nano-film in N, N-Dimethylformamide (DMF), heating and stirring for 6 hours firstly, then not heating and stirring for 18 hours to obtain a spinning solution, and preparing the PVDF superfine hybrid nano-film through electrostatic spinning;
(2) treating the PVDF superfine hybrid nano-film in absolute ethyl alcohol for 30min, and then putting the treated PVDF superfine hybrid nano-film in deionized water;
(3) placing a certain amount of 0.4g/L Catechol (CA) and 2g/L gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH560) in TrisHCl buffer solution with the pH value of 8.5, and stirring for 10min to prepare a hydrophilic modification solution I;
(4) putting the fiber membrane obtained after the treatment in the step (2) into the hydrophilic modification solution I, and putting the fiber membrane into a vacuum oven to heat for 6 hours at the temperature of 40 ℃;
(5) taking out the membrane, adding 0.4g/L Tannic Acid (TA) into the hydrophilic modification solution I, stirring for 9min to prepare a hydrophilic modification solution II, then putting the membrane into the hydrophilic modification solution II, and heating for 6h at 40 ℃ in an oven;
(6) and (3) putting the membrane into deionized water, taking out the membrane, and then putting the membrane into an oven to be heated and dried at 40 ℃ to obtain the superfine nanofiber hydrophilic membrane.
Through testing, the water contact angle of the prepared polyvinylidene fluoride nano-film is 21.9 degrees (0s test); two 5 x 5cm hydrophilically finished polyvinylidene fluoride nano-films are taken and sequentially subjected to separation tests of a sunflower oil-water emulsion, a kerosene oil-water emulsion, a cyclohexane oil-water emulsion and a n-hexadecane oil-water emulsion, and the oil-water separation efficiency of the polyvinylidene fluoride nano-films is more than 99%, which indicates that the polyvinylidene fluoride nano-films still have good hydrophilicity and oil-water separation performance.
In addition, the electrospun PVDF nano-film obtained by only carrying out the steps (1) to (4) in the example 1 is tested, the water contact angle is 49.2 degrees, and then the oil-water emulsion of sunflower oil, the oil-water emulsion of kerosene, the oil-water emulsion of cyclohexane and the oil-water emulsion of n-hexadecane are sequentially carried out for separation tests, and the oil-water separation efficiency of the polyvinylidene fluoride nano-film is about 95 percent;
the electrospun PVDF nano-film obtained by only performing the steps (1) and (2) in the embodiment 1 is tested, the water contact angle is about 85 degrees, and then the separation tests of sunflower oil-water emulsion, kerosene oil-water emulsion, cyclohexane oil-water emulsion and n-hexadecane oil-water emulsion are sequentially performed, so that the oil-water separation efficiency of the polyvinylidene fluoride nano-film is only about 70 percent;
the electrospun PVDF nano-film obtained by only carrying out the steps (1), (2) and (5) in the embodiment 1 is tested, the water contact angle is about 40 degrees, and then the separation tests of sunflower oil-water emulsion, kerosene oil-water emulsion, cyclohexane oil-water emulsion and n-hexadecane oil-water emulsion are carried out in sequence, so that the oil-water separation efficiency of the polyvinylidene fluoride nano-film is only about 97 percent;
changing the condition of the step (4) in the embodiment 1 into aerobic heating, testing the obtained electrospun PVDF nano-film, wherein the water contact angle is about 45 degrees, and then sequentially carrying out separation tests on sunflower oil-water emulsion, kerosene oil-water emulsion, cyclohexane oil-water emulsion and n-hexadecane oil-water emulsion, wherein the oil-water separation efficiency of the polyvinylidene fluoride nano-film is only about 96 percent;
step (4) in example 1 is omitted, step (5) is directly performed after step (3), the obtained electrospun PVDF nano-film is tested, the water contact angle is about 35 degrees, then the separation test of sunflower oil-water emulsion, kerosene oil-water emulsion, cyclohexane oil-water emulsion and n-hexadecane oil-water emulsion is sequentially performed, and the oil-water separation efficiency of the polyvinylidene fluoride nano-film is about 97%;
example 2
(1) Mixing 7 wt% polyvinylidene fluoride (PVDF), 3 wt% polyvinylpyrrolidone (PVP), 0.7 wt% hydrophilic Silica (SiO) 2 ) Dissolving the PVDF nano-film in N, N-Dimethylformamide (DMF), heating and stirring for 7 hours firstly, then not heating and stirring for 17 hours to obtain a spinning solution, and preparing the PVDF superfine hybrid nano-film through electrostatic spinning;
(2) treating the PVDF superfine hybrid nano-film in absolute ethyl alcohol for 33min, and then putting the PVDF superfine hybrid nano-film in deionized water to form bent dendritic fibers;
(3) placing a certain amount of 0.5g/L Catechol (CA) and 4g/L gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH560) in TrisHCl buffer solution with pH of 8.5, stirring for 10min to obtain hydrophilic modification solution I;
(4) putting the membrane obtained by the treatment in the step (2) into the hydrophilic modification solution I, and putting the membrane into a vacuum oven to heat for 6 hours at the temperature of 36 ℃;
(5) taking out the membrane, adding 0.5g/L Tannic Acid (TA) into the hydrophilic modification solution I, stirring for 10min to prepare a hydrophilic modification solution II, and then putting the membrane into the hydrophilic modification solution II to heat in an oven at 40 ℃ for 6 h;
(6) and (3) putting the membrane into deionized water, taking out the membrane, and then putting the membrane into an oven to be heated and dried at 40 ℃ to obtain the bionic dendritic polyvinylidene fluoride hydrophilic membrane.
Through testing, the water contact angle of the prepared hydrophilic polyvinylidene fluoride nano-film is 21.6 degrees (0s test); two 5 x 5cm hydrophilically finished polyvinylidene fluoride nano-films are taken and sequentially subjected to separation tests of a sunflower oil-water emulsion, a kerosene oil-water emulsion, a cyclohexane oil-water emulsion and a n-hexadecane oil-water emulsion, and the oil-water separation efficiency of the polyvinylidene fluoride nano-films is more than 99%, which indicates that the polyvinylidene fluoride nano-films still have good hydrophilicity and oil-water separation performance.
Example 3
(1) 6 wt% of polyvinylidene fluoride (PVDF), 5 wt% of polyvinylpyrrolidone (PVP), 0.8 wt% of hydrophilic silicon dioxide (SiO) 2 ) Dissolving in N, N-Dimethylformamide (DMF), heating and stirring for 6 hr, and then heatingStirring for 18h to obtain a spinning solution, and preparing the PVDF superfine hybrid nano-film through electrostatic spinning;
(2) treating the PVDF superfine hybrid nano-film in absolute ethyl alcohol for 34min, and then putting the PVDF superfine hybrid nano-film in deionized water to form bent dendritic fibers;
(3) placing a certain amount of 0.4g/L Catechol (CA) and 2g/L gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH560) in TrisHCl buffer solution with pH9, and stirring for 10min to obtain hydrophilic modification solution I;
(4) putting the membrane obtained in the step (2) into the hydrophilic modification solution I, and putting the membrane into a vacuum oven to heat for 6 hours at the temperature of 40 ℃;
(5) taking out the membrane, adding 0.4g/L Tannic Acid (TA) into the first hydrophilic modification solution, stirring for 8min to prepare a second hydrophilic modification solution, and then putting the membrane into the second hydrophilic modification solution to heat for 6h at 40 ℃ in an oven;
(6) and (3) putting the membrane into deionized water, taking out the membrane, and then putting the membrane into an oven to be heated and dried at 35 ℃ to obtain the bionic dendritic polyvinylidene fluoride hydrophilic membrane.
Through testing, the water contact angle of the prepared hydrophilic polyvinylidene fluoride nano-film is 21.9 degrees (0s test); two 5 x 5cm hydrophilically finished polyvinylidene fluoride nano-films are taken and sequentially subjected to separation tests of a sunflower oil-water emulsion, a kerosene oil-water emulsion, a cyclohexane oil-water emulsion and a n-hexadecane oil-water emulsion, and the oil-water separation efficiency of the polyvinylidene fluoride nano-films is more than 99%, which indicates that the polyvinylidene fluoride nano-films still have good hydrophilicity and oil-water separation performance.
Example 4
(1) Mixing 6 wt% polyvinylidene fluoride (PVDF), 6 wt% polyvinylpyrrolidone (PVP), 0.3 wt% hydrophilic Silica (SiO) 2 ) Dissolving the PVDF nano-film in N, N-Dimethylformamide (DMF), heating and stirring for 6 hours firstly, then not heating and stirring for 18 hours to obtain a spinning solution, and preparing the PVDF superfine hybrid nano-film through electrostatic spinning;
(2) treating the PVDF superfine hybrid nano-film in absolute ethyl alcohol for 32min, and then putting the PVDF superfine hybrid nano-film in deionized water to form bent dendritic fibers;
(3) placing a certain amount of 0.3g/L Catechol (CA) and 4g/L gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH560) in TrisHCl buffer solution with pH of 8.5, stirring for 10min, and preparing into a hydrophilic modification solution I;
(4) putting the membrane obtained in the step (2) into the hydrophilic modification solution I, and putting the membrane into a vacuum oven to heat for 6 hours at the temperature of 40 ℃;
(5) taking out the membrane, adding 0.5g/L Tannic Acid (TA) into the hydrophilic modification solution I, stirring for 9min to prepare a hydrophilic modification solution II, then putting the membrane into the hydrophilic modification solution II, and heating for 6h at 40 ℃ in an oven;
(6) and (3) putting the membrane in deionized water, taking out, and then putting the membrane in an oven for heating and drying at 40 ℃ to obtain the bionic dendritic polyvinylidene fluoride hydrophilic membrane.
Through testing, the water contact angle of the prepared hydrophilic polyvinylidene fluoride nano-film is 22.3 degrees (0s test); two 5 x 5cm hydrophilically finished polyvinylidene fluoride nano-films are taken and sequentially subjected to separation tests of a sunflower oil-water emulsion, a kerosene oil-water emulsion, a cyclohexane oil-water emulsion and a n-hexadecane oil-water emulsion, and the oil-water separation efficiency of the polyvinylidene fluoride nano-films is more than 99%, which indicates that the polyvinylidene fluoride nano-films still have good hydrophilicity and oil-water separation performance.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple change, equivalent replacement or modification made based on the present invention to solve the substantially same technical problems and achieve the substantially same technical effects all fall within the protection scope of the present invention.

Claims (6)

1. A preparation method of a superfine nanofiber hydrophilic membrane for efficient oil-water separation is characterized by comprising the following steps: the method comprises the following steps:
(1) polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP) and hydrophilic silicon dioxide (SiO) 2 ) Dissolving in N, N-Dimethylformamide (DMF), heating and stirring for 6-7h, then not heating and stirring for 16-18h to obtain a spinning solution, and preparing the PVDF superfine hybrid nano-film through electrostatic spinning, wherein the fiber diameter is not more than 100 nm;
(2) treating the PVDF superfine hybrid nano-film in absolute ethyl alcohol for 30-40min, and then putting the PVDF superfine hybrid nano-film in deionized water to obtain a PVDF hybrid film with bent fibers and intertwined with each other;
(3) adding Catechol (CA) and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH560) into TrisHCl buffer solution with pH of 8.5-9, and stirring for 5-10min to prepare hydrophilic modified solution I;
(4) putting the PVDF hybrid membrane into the hydrophilic modification solution I, and putting the PVDF hybrid membrane into a vacuum oven to be heated for 6 hours at the temperature of 35-40 ℃;
(5) taking out the membrane, adding Tannic Acid (TA) into the hydrophilic modification solution I treated in the step (4), stirring for 7-9min to prepare a hydrophilic modification solution II, and then putting the membrane into the hydrophilic modification solution II to heat for 6h at 35-40 ℃ in an oven;
(6) and taking out the membrane, putting the membrane into deionized water, taking out the membrane, and then putting the membrane into an oven to be heated and dried at 35-40 ℃ to obtain the high-efficiency oil-water separation superfine nanofiber hydrophilic membrane.
2. The preparation method of the efficient oil-water separation ultrafine nanofiber hydrophilic membrane as claimed in claim 1, wherein the concentration of PVDF obtained in the step (1) is 1-10 wt%, the concentration of PVP is 1-15 wt%, and the concentration of hydrophilic SiO is 1-15 wt% 2 The concentration is 0.01-0.1 wt%.
3. The method for preparing the superfine nanofiber hydrophilic membrane for high-efficiency oil-water separation as claimed in claim L, wherein the concentration of CA in the hydrophilic modification solution I in the step (3) is 0.1-2 g/L.
4. The preparation method of the hydrophilic membrane for the ultra-fine nano-fibers with high efficiency oil-water separation as claimed in claim L, wherein the concentration of KH560 in the hydrophilic modification solution I in the step (3) is 1-10 g/L.
5. The method for preparing the superfine nanofiber hydrophilic membrane for efficient oil-water separation as claimed in claim I, wherein the concentration of TrisHCl in the first hydrophilic modification solution in the step (3) is 5-20 mmol.
6. The preparation method of the efficient oil-water separation ultrafine nanofiber hydrophilic membrane as claimed in claim 1, wherein the concentration of TA in the hydrophilic modification solution II in the step (5) is 0.1-2 g/L.
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