CN103230747A - Preparation method of composite film for water treatment - Google Patents
Preparation method of composite film for water treatment Download PDFInfo
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- CN103230747A CN103230747A CN2013101723893A CN201310172389A CN103230747A CN 103230747 A CN103230747 A CN 103230747A CN 2013101723893 A CN2013101723893 A CN 2013101723893A CN 201310172389 A CN201310172389 A CN 201310172389A CN 103230747 A CN103230747 A CN 103230747A
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Abstract
The invention provides a preparation method of a composite film for water treatment. The preparation method comprises the following steps of: (A) carrying out knifing, solidification and drying on a polyvinylidene fluoride solution to obtain a polyvinylidene fluoride film; (B) carrying out knifing and solidification on a polyvinyl alcohol solution on the surface of the polyvinylidene fluoride film to obtain a polyvinyl alcohol and polyvinylidene fluoride double-layer film; and (C) placing the polyvinyl alcohol and polyvinylidene fluoride double-layer film into a crosslinking liquid to crosslink, and drying to obtain a polyvinyl alcohol and polyvinylidene fluoride composite film. The polyvinylidene fluoride film with hydrophobicity is compounded and crosslinked with a polyvinyl alcohol film with hydrophilcity to obtain the composite film with amphipathy; and the composite film has the favorable hydrophobicity and chemical corrosion resistance of a hydrophobic film and the hydrophilcity and stain resistance of a hydrophilic film, and also has high film flux and impurity ion retention rate.
Description
Technical field
The invention belongs to the material technology field, be specifically related to the preparation method that composite membrane is used in a kind of water treatment.
Background technology
Macromolecule member material is widely used in fields such as water purified treatment, chemical industry, weaving owing to have efficient, simple and practical, energy-conservation, high added value, characteristics such as pollution-free.Chemical property and the membrane structure of macromolecule member material have determined separating effect.Macromolecule member material can be divided into hydrophilic membrane and hydrophobic membrane according to the film hydrophilicity and hydrophobicity.
At present, about the existing many reports of the preparation method of hydrophilic membrane and hydrophobic membrane.Hydrophilic film material comprise polyvinyl alcohol (PVA), cellulose family (App1.Biochem.Biotechnol, 2009,154:21), polyamide (membrane science and technology, 2004,24(3): 60) and polyacrylonitrile (applied chemistry, 14(5): 95,1997) etc.Wherein, PVA has highly hydrophilic, good stain resistance and film forming and becomes one of hydrophilic film material of extensive use, and its resistance to water and hear resistance are relatively poor, but by improving the water-resistance of film after the modification, mechanical strength and stability.Li Chunli etc. utilize the method for glutaraldehyde cross-linking to prepare polyvinyl alcohol film (Hebei University of Technology's journal, 34(6): 35,2005), concrete grammar is: with mass fraction be 10% polyvinyl alcohol film liquid mix with the glutaraldehyde cross-linking agent stir after, film liquid evenly is poured on an end of clean glass plate, spread to certain thickness with scraper, take out after glass plate being put into 45 ℃ the dry 2h of thermostatic drying chamber, at room temperature continue dry, treat the film bone dry after, can obtain the PVA film.Gold Zhe people wait utilize infra-red sepectrometry to the esterification of the crosslinked polyvinyl alcohol film of maleic acid carried out quantitative research (membrane science and technology, 23(4): 16).Concrete preparation method about polyvinyl alcohol film in the literary composition is: use the deionized water dissolve polyvinyl alcohol, add crosslinking agent maleic anhydride and an amount of concentrated sulfuric acid catalyst then, continue to stir, make crosslinking agent and catalyst be uniformly dispersed standing and defoaming, obtain mixed solution, with the on glass knifing of described mixed solution in cleaning, treat water evaporates after, take off and put into baking oven behind crosslinked certain hour under the set point of temperature, take out, making thickness is the crosslinked PVA film of maleic acid of 20～30 μ m.Though above-mentioned polyvinyl alcohol homogeneous membrane has higher separation, membrane flux is less.
The hydrophobic membrane material comprises Kynoar, polypropylene (S.Nago, etc.J.Membr.Sci., 116:01,1996; J.J.Kim, etc.J.Membr.Sci., 108:25,1995), polytetrafluoroethylene (PTFE) (U.S.Pat.3,962,153) etc.Wherein polytetrafluoroethylene (PTFE) and polypropylene are embarrassed soluble polymer, machinability is relatively poor, the process complexity, and Kynoar (PVDF) not only has excellent hydrophobic property and resistance to chemical corrosion, and can be dissolved in N, N-dimethylacetylamide (DMAc) is in the N-methyl pyrrolidone organic solvents such as (NMP).Because the above-mentioned plurality of advantages of PVDF, many documents and patent have prepared the higher microporous barrier of porosity with PVDF as membrane material.The dull and stereotyped PVDF microporous barrier pore diameter range that usefulness PVDF-DMAc-PEG systems such as Kong are prepared is (Sep.Puri.Technol.16:83,1999) between 0.24～1.0 μ m.This report prepares pvdf membrane by the method that immerses precipitation, and concrete grammar is: PVDF, DMAc and PEG are formed polymer solution, dissolved fully until polymer under 70 ℃ of conditions, last polymer solution at room temperature outgases.With polymer solution scraper with 0.23mm on glass plate, 20 ℃ of room temperatures, carry out knifing under the condition of humidity 65%.Scraped rear film and in air, exposed 30s, immersed in 20 ℃ of water coagulating baths with the glass plate of film coating then, wait divided thin film from after, film is shifted out coagulating bath, dry in air at room temperature and get final product.Kong Ying etc. are that solvent, lithium chloride are that micromolecule additive, ethanol-water solution are coagulating bath with the mixture of DMAc and acetone, make under proper condition and have concurrently spongy and PVDF flat plate porous film dactylotype, the average pore size of film is in 0.03～0.08 mu m range, porosity is up to 83～86% (water technologies, 18(3): 167,1992).The patent No. is that the Chinese patent of CN1050773C is solvent with DMAc, DMF etc., polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG) are additive, low mass molecule alcohol such as glycerine, ethylene glycol class or water are non-solvent, having prepared the aperture is 0.05～0.22 μ m, porosity reaches 80～90%, and water flux is 1 * 10
7～1.5 * 10
7L/m
2The PVDF hollow-fibre membrane of hPa.Human DMAc such as Li and PVP are respectively as solvent and additive, bathe as solidified inside as outside coagulating bath, water or ethanol with water, the PVDF hollow-fibre membrane of dry-wet spinning preparation, pore diameter range is 0.03～0.1 μ m (J.Membr.Sci.163:211,1999; J.Membr.Sci.150:75,1998).But the strong-hydrophobicity that the hydrophobic membrane of above-mentioned report has is easy to generate absorption to be polluted, making two of membrane flux and rejection mainly separate index descends, shorten the service life of film, restricted its application in aqueous phase systems such as biochemical pharmacy, food and drink and water body purification.
Therefore, the homogeneous membrane of single property often can not meet the demands in actual applications fully, and this impels people to study composite membrane, makes it have the excellent properties of multiple film concurrently.At present, existing hydrophily has hydrophobic composite membrane report again seldom.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide the preparation method of a kind of water treatment with composite membrane, adopts the prepared water treatment of the present invention to have good membrane flux and foreign ion rejection with composite membrane.
The invention provides a kind of water treatment preparation method of composite membrane, may further comprise the steps:
A) Kynoar solution is carried out obtaining polyvinylidene difluoride film after knifing, curing molding, the drying;
B) poly-vinyl alcohol solution is carried out knifing on described polyvinylidene difluoride film surface, curing molding obtains polyvinyl alcohol-Kynoar duplicature;
C) with that described polyvinyl alcohol-the Kynoar duplicature places crosslinked fluid to carry out is crosslinked, after the drying, obtain the water treatment composite membrane.
Preferably, the thickness of described polyvinylidene difluoride film is 0.2～1.5mm, and the thickness of described polyvinyl alcohol-Kynoar duplicature is 0.4～3mm.
Preferably, described Kynoar solution is prepared as follows:
Kynoar, organic solvent and additive are mixed, and deaeration obtains Kynoar solution;
Described organic solvent is N, N-dimethylacetylamide, N, dinethylformamide, N-methyl pyrrolidone or dimethyl sulfoxide (DMSO);
Described additive is polyethylene glycol or lithium chloride.
Preferably, the temperature of described deaeration is 45～55 ℃, and the time is 12～72h.
Preferably, described poly-vinyl alcohol solution is prepared as follows:
Polyvinyl alcohol is mixed with water, heating, cooling can obtain poly-vinyl alcohol solution.
Preferably, the temperature of described heating is 90～100 ℃, and the time of described heating is 2～3h, and the temperature of described cooling is 25～35 ℃.
Preferably, described crosslinked fluid is prepared as follows:
Glutaraldehyde water solution, absolute ethyl alcohol are mixed, obtain mixed solution; Add mass fraction in the described mixed solution and be 37% concentrated hydrochloric acid, mix, can obtain crosslinked fluid.
Preferably, steps A) coagulating bath of curing molding is the water coagulating bath described in, and the time of described curing molding is 2～24h.
Preferably, step B) temperature of curing molding is 30～50 ℃ described in, and the time is 6～24h.
Preferably, described crosslinked temperature is 35～45 ℃, and the time is 1～10h.
Compared with prior art, the invention provides a kind of water treatment with the preparation method of composite membrane, may further comprise the steps: A) Kynoar solution is carried out obtaining polyvinylidene difluoride film after knifing, curing molding, the drying; B) poly-vinyl alcohol solution is carried out knifing on described polyvinylidene difluoride film surface, curing molding obtains polyvinyl alcohol-Kynoar duplicature; C) with that described polyvinyl alcohol-the Kynoar duplicature places crosslinked fluid to carry out is crosslinked, after the drying, obtain polyvinyl alcohol-poly-vinylidene-fluoride composite film.The present invention will have the polyvinylidene difluoride film of hydrophobic property and the polyvinyl alcohol film of possess hydrophilic property matter carries out composite crosslinking, obtain having amphipathic composite membrane, described composite membrane had both had hydrophobic membrane excellent hydrophobic property and resistance to chemical corrosion, have hydrophily and the stain resistance of hydrophilic membrane again, and have good membrane flux and to the rejection of foreign ion.
The result shows, when water treatment provided by the present invention is applied to pure aquatic system with composite membrane, is 25 ℃ in temperature, and under the condition of 0.1MPa, the membrane flux of water is 5～60Kgm
-2H
-1, rejection is 95%～99%, porosity is 65%～85%; When described water treatment is applied to have the mixed system of different kinds of ions with composite membrane, be 40 ℃ in temperature, under the condition of 0.4MPa, the membrane flux of water is 0.1～3Kgm
-2H
-1, rejection is 50%～90%, porosity is 25%～60%.
The specific embodiment
The invention provides a kind of water treatment preparation method of composite membrane, may further comprise the steps:
A) Kynoar solution is carried out obtaining polyvinylidene difluoride film after knifing, curing molding, the drying;
B) poly-vinyl alcohol solution is carried out knifing on described polyvinylidene difluoride film surface, curing molding obtains polyvinyl alcohol-Kynoar duplicature;
C) with that described polyvinyl alcohol-the Kynoar duplicature places crosslinked fluid to carry out is crosslinked, after the drying, obtain polyvinyl alcohol-poly-vinylidene-fluoride composite film.
The present invention at first carries out Kynoar solution to obtain polyvinylidene difluoride film after knifing, curing molding, the drying.
In the present invention, described Kynoar solution preferably is prepared as follows:
Kynoar, organic solvent and additive are mixed, and deaeration obtains Kynoar solution.
The present invention is to the mixing of described Kynoar, organic solvent and additive, the mode of deaeration there is no particular restriction, concrete grammar is: Kynoar is dissolved in the organic solvent, be mixed with mixed solution, in described mixed solution, add additive, stir, place the baking oven standing and defoaming after, can obtain Kynoar solution.
Wherein, described temperature of oven is the temperature of deaeration, is preferably 45～55 ℃, more preferably 48～52 ℃; The time of described deaeration is preferably 12～72h, more preferably 24～60h.Described organic solvent is preferably N, N-dimethylacetylamide, N, dinethylformamide, N-methyl pyrrolidone or dimethyl sulfoxide (DMSO), N more preferably, N-dimethylacetylamide or N, dinethylformamide; Described additive is preferably polyethylene glycol or lithium chloride, more preferably PEG-400, PEG-600, PEG-1000, PEG-2000, PEG-6000, PEG-10000, PEG-20000 or lithium chloride.The mass concentration of Kynoar is preferably 10wt%～30wt% in the mixed solution, more preferably 15wt%～25wt%; The mass ratio of described additive and Kynoar is preferably (0.03～0.2): 1, more preferably (0.05～0.15): 1.
After the Kynoar solution that configures carried out knifing, curing molding, drying, obtain polyvinylidene difluoride film.
The present invention there is no particular restriction to the mode of described knifing, and concrete grammar is: in thermostatic chamber, with scraper Kynoar solution is carried out knifing at glass plate, leave standstill, obtain the polyvinylidene difluoride film of uncured moulding.Wherein, the temperature of described thermostatic chamber is preferably 30～50 ℃, more preferably 35～45 ℃.
The polyvinylidene difluoride film of described uncured moulding is placed coagulating bath, and curing molding obtains the polyvinylidene difluoride film of curing molding.The present invention there is no particular restriction to the kind of described coagulating bath, the solution of the polyvinylidene difluoride film curing molding of uncured moulding can be got final product, and the present invention preferably adopts the water coagulating bath.The time of described curing molding is preferably 2～24h, more preferably 5～20h.
With the polyvinylidene difluoride film washing of described curing molding, drying can obtain polyvinylidene difluoride film.The cleaning solution of described washing is preferably water.The present invention there is no particular restriction to the mode of described drying, and drying mode well known to those skilled in the art gets final product, and the present invention preferably adopts nitrogen to dry up.
The thickness of the polyvinylidene difluoride film that scraper used in the present invention scrapes is accurately controlled, and the thickness of described polyvinylidene difluoride film is preferably 0.2～1.5mm, more preferably 0.5～1.2mm.
After obtaining polyvinylidene difluoride film, poly-vinyl alcohol solution is carried out knifing on described polyvinylidene difluoride film surface, curing molding obtains polyvinyl alcohol-Kynoar duplicature.
In the present invention, described poly-vinyl alcohol solution is prepared as follows:
Polyvinyl alcohol is mixed with water, heating, cooling can obtain poly-vinyl alcohol solution.
The present invention mixes polyvinyl alcohol with water, obtain mixed solution, and in the described mixed solution, the mass concentration of polyvinyl alcohol is preferably 1wt%～5wt%, more preferably 2wt%～4wt%.The present invention there is no particular restriction to the source of described polyvinyl alcohol, general commercially available getting final product, and preferably adopting the trade mark is the polyvinyl alcohol of 17-99.With described mixed solution heating, the present invention there is no particular restriction to the mode of described heating, preferred employing water-bath heating, described mixed solution heats while stirring, the temperature of described heating is preferably 90～98 ℃, more preferably 93～96 ℃, the time of described heating is preferably 2～3h, more preferably 2～2.5h.After heating finished, with the mixed solution cooling, the temperature of described cooling was preferably 25～35 ℃, more preferably 28～33 ℃.
The poly-vinyl alcohol solution that obtains is carried out knifing on described polyvinylidene difluoride film surface, concrete grammar is: described polyvinylidene difluoride film is placed clean glass pane surface, guaranteeing does not have bubble between described polyvinylidene difluoride film and the glass plate, with scraper poly-vinyl alcohol solution is carried out knifing on described polyvinylidene difluoride film surface, leave standstill, obtain the polyvinyl alcohol-Kynoar duplicature of uncured moulding.
Polyvinyl alcohol-Kynoar duplicature curing molding with described uncured moulding, the method of curing molding is: the polyvinyl alcohol-Kynoar duplicature of described uncured moulding is left standstill in thermostatic chamber, can obtain polyvinyl alcohol-Kynoar duplicature.The temperature of described curing molding is preferably 30～50 ℃, more preferably 35～45 ℃.The time of described curing molding is preferably 6～24h, more preferably 10～20h.
Wherein, described polyvinyl alcohol-Kynoar duplicature comprises polyvinyl alcohol film and polyvinylidene difluoride film.The thickness of the polyvinyl alcohol film that scraper used in the present invention scrapes is accurately controlled, and the thickness of described polyvinyl alcohol film is preferably 0.2～1.5mm, more preferably 0.5～1.2mm; The thickness of described polyvinyl alcohol-Kynoar duplicature is preferably 0.4～3mm, more preferably 0.5～2.5mm.
With that described polyvinyl alcohol-the Kynoar duplicature places crosslinked fluid to carry out is crosslinked, after the drying, obtain the water treatment composite membrane.
In the present invention, described crosslinked fluid is prepared as follows:
Glutaraldehyde water solution, absolute ethyl alcohol are mixed, obtain mixed solution; Add mass fraction in the described mixed solution and be 37% concentrated hydrochloric acid, mix, can obtain crosslinked fluid.
Described glutaraldehyde water solution is preferably the glutaraldehyde solution that mass concentration is 50wt%.In the described mixed solution, the volumetric concentration of glutaraldehyde is preferably 2.5%～7.5%, and more preferably 4%～7%.Wherein, described mass fraction is that 37% concentrated hydrochloric acid is catalyst, and described mass fraction is that 37% concentrated hydrochloric acid and the volume ratio of mixed solution are preferably (0.10～0.20): 100, more preferably (0.12～0.18): 100.The present invention is that the source of 37% concentrated hydrochloric acid there is no particular restriction to described glutaraldehyde, absolute ethyl alcohol and mass fraction, general commercially available getting final product.The maintenance crosslinked fluid is constant temperature, and wherein, the temperature of constant temperature is preferably 35～45 ℃, more preferably 38～42 ℃.
With that described polyvinyl alcohol-the Kynoar duplicature places crosslinked fluid to carry out is crosslinked, obtain polyvinyl alcohol-Kynoar cross linking membrane.Wherein, described crosslinked temperature is preferably 35～45 ℃, more preferably 38～42 ℃; The described crosslinked time is preferably 1～10h, more preferably 3～7h.
With described polyvinyl alcohol-Kynoar cross linking membrane washing, after the drying, can obtain the water treatment composite membrane.Wherein, the used cleaning solution of described washing is preferably water, and the present invention there is no particular restriction to the mode of described drying, preferably adopts nitrogen to dry up.Described water treatment is preferably 0.4～3mm with the thickness of composite membrane, more preferably 0.5～2.5mm.
The present invention will have the polyvinylidene difluoride film of hydrophobic property and the polyvinyl alcohol film of possess hydrophilic property matter carries out composite crosslinking, obtain having amphipathic composite membrane, described composite membrane had both had hydrophobic membrane excellent hydrophobic property and resistance to chemical corrosion, have hydrophily and the stain resistance of hydrophilic membrane again, and have good membrane flux and to the rejection of foreign ion.
The result shows, when water treatment provided by the present invention is applied to pure aquatic system with composite membrane, is 25 ℃ in temperature, and under the condition of 0.1MPa, the membrane flux of water is 5～60KGm
-2H
-1, rejection is 95%～99%, porosity is 65%～85%; When described water treatment is applied to have the mixed system of different kinds of ions with composite membrane, be 40 ℃ in temperature, under the condition of 0.4MPa, the membrane flux of water is 0.1～3Kgm
-2H
-1, rejection is 50%～90%, porosity is 25%～60%.
In order further to understand the present invention, below in conjunction with embodiment the preparation method of water treatment provided by the invention with composite membrane described, protection scope of the present invention is not limited by the following examples.
Embodiment 1
The trade mark that Shanghai Sanaifu New Material Co., Ltd is produced is that the Kynoar preparation mass concentration of FR904 is 10% solution, wherein, N, the N-dimethylacetylamide is solvent, add that to account for the Kynoar mass percent be that 3% PEG-400 stirs, after leaving standstill the 12h deaeration in 50 ℃ of baking ovens, obtain Kynoar solution.
In 30 ℃ of thermostatic chambers, accurately controlled scraper is at clean glass pane surface knifing with thickness with described Kynoar solution, and the thickness of film is 1.5mm, after leaving standstill 15min, immerse the water coagulating bath immediately, keep the 2h curing molding, obtain the polyvinylidene difluoride film of curing molding.With the polyvinylidene difluoride film of described curing molding with the clear water flushing after, nitrogen dries up and can obtain polyvinylidene difluoride film.
The preparation mass concentration is the aqueous solution of 1% polyvinyl alcohol, places water-bath, and warming while stirring is until 95 ℃.After keeping 2h under this temperature, stop heating, cooling during to 30 ℃, obtains poly-vinyl alcohol solution while stirring.
In 35 ℃ of thermostatic chambers, the polyvinylidene difluoride film of above-mentioned preparation is divided glass pane surface in cleaning, guarantee between film and the glass plate without any bubble.With thickness accurately controlled scraper with the casting solution for preparing previously directly at polyvinylidene difluoride film surface knifing, scraping film thickness is 0.2mm, leaves standstill the 6h solidified forming in thermostatic chamber, obtains polyvinyl alcohol-Kynoar duplicature.
Be 50% glutaraldehyde water solution with the 10mL mass concentration, after the 190mL absolute ethyl alcohol mixes, add the 0.24mL mass concentration and be 37% concentrated hydrochloric acid, mix, obtain crosslinked fluid.
Crosslinked fluid is placed 40 ℃ of following constant temperature.Above-mentioned polyvinyl alcohol-Kynoar duplicature is uncovered, be soaked in the crosslinked fluid under 40 ℃ cross-linking reaction 1h.Take out after finishing, big water gaging washes, and dries up with nitrogen and can obtain polyvinyl alcohol-poly-vinylidene-fluoride composite film, be i.e. the water treatment composite membrane.
When the water treatment of above-mentioned preparation is applied to pure aquatic system with composite membrane, be 25 ℃ in temperature, under the condition of 0.1MPa, the membrane flux of measuring pure water is 60Kgm
-2H
-1, rejection is 95%, porosity is 85%;
The mixed system that described water treatment is applied to have different kinds of ions with composite membrane wherein, contains the KCl of NaCl, the 0.064mol/L of 0.16mol/L, the NH of 0.045mol/L in the described mixed system with different kinds of ions
4The MgSO of Cl, 0.021mol/L
4NaH with 0.032mol/L
2PO
4, be 40 ℃ in temperature, under the condition of 0.4MPa, the membrane flux of water is 3Kgm
-2H
-1, rejection is 50%, porosity is 60%.
Embodiment 2
The trade mark that Shanghai Sanaifu New Material Co., Ltd is produced is that the Kynoar preparation mass concentration of FR904 is 20% solution, wherein, N, the N-dimethylacetylamide is solvent, add that to account for the Kynoar mass percent be that 10% PEG-20000 stirs, after leaving standstill the 36h deaeration in 50 ℃ of baking ovens, obtain Kynoar solution.
In 50 ℃ of thermostatic chambers, accurately controlled scraper is at clean glass pane surface knifing with thickness with described Kynoar solution, and the thickness of film is 1mm, after leaving standstill 10min, immerse the water coagulating bath immediately, keep the 12h curing molding, obtain the polyvinylidene difluoride film of curing molding.With the polyvinylidene difluoride film of described curing molding with the clear water flushing after, nitrogen dries up and can obtain polyvinylidene difluoride film.
The preparation mass concentration is the aqueous solution of 1% polyvinyl alcohol, places water-bath, and warming while stirring is until 95 ℃.Keep 2h under this temperature, stop heating, cooling during to 30 ℃, obtains poly-vinyl alcohol solution while stirring.
In 35 ℃ of thermostatic chambers, the polyvinylidene difluoride film of above-mentioned preparation is divided glass pane surface in cleaning, guarantee between film and the glass plate without any bubble.With thickness accurately controlled scraper with the casting solution for preparing previously directly at polyvinylidene difluoride film surface knifing, thickness is 0.5mm, leaves standstill the 6h solidified forming in thermostatic chamber, obtains polyvinyl alcohol-Kynoar duplicature.
Be 50% glutaraldehyde water solution with the 10mL mass concentration, after the 190mL absolute ethyl alcohol mixes, add the 0.24mL mass concentration and be 37% concentrated hydrochloric acid, mix, obtain crosslinked fluid.
Crosslinked fluid is placed 40 ℃ of following constant temperature.Polyvinyl alcohol-Kynoar the duplicature of above-mentioned curing is uncovered, be soaked in the crosslinked fluid under 40 ℃ cross-linking reaction 3h.Take out after finishing, big water gaging washes, and dries up with nitrogen and can obtain polyvinyl alcohol-poly-vinylidene-fluoride composite film, be i.e. the water treatment composite membrane.
Crosslinked fluid is placed 40 ℃ of following constant temperature.Above-mentioned polyvinyl alcohol-Kynoar duplicature is uncovered, be soaked in the crosslinked fluid under 40 ℃ cross-linking reaction 1h.Take out after finishing, big water gaging washes, and dries up with nitrogen and can obtain polyvinyl alcohol-poly-vinylidene-fluoride composite film, be i.e. the water treatment composite membrane.
When the water treatment of above-mentioned preparation is applied to pure aquatic system with composite membrane, be 25 ℃ in temperature, under the condition of 0.1MPa, the membrane flux of measuring pure water is 49Kgm
-2H
-1, rejection is 96%, porosity is 81%;
The mixed system that described water treatment is applied to have different kinds of ions with composite membrane wherein, contains the KCl of NaCl, the 0.064mol/L of 0.16mol/L, the NH of 0.045mol/L in the described mixed system with different kinds of ions
4The MgSO of Cl, 0.021mol/L
4NaH with 0.032mol/L
2PO
4, be 40 ℃ in temperature, under the condition of 0.4MPa, the membrane flux of water is 2.6Kgm
-2H
-1, rejection is 53%, porosity is 83%.
Embodiment 3:
The trade mark that Shanghai Sanaifu New Material Co., Ltd is produced is that the Kynoar preparation mass concentration of FR904 is 30% solution, wherein, N, the N-dimethylacetylamide is solvent, add that to account for the Kynoar mass percent be that 20% PEG-6000 stirs, after leaving standstill the 72h deaeration in 50 ℃ of baking ovens, obtain Kynoar solution.
In 50 ℃ of thermostatic chambers, accurately controlled scraper is at clean glass pane surface knifing with thickness with described Kynoar solution, and the thickness of film is 0.2mm, after leaving standstill 1min, immerse the water coagulating bath immediately, keep the 24h curing molding, obtain the polyvinylidene difluoride film of curing molding.With the polyvinylidene difluoride film of described curing molding with the clear water flushing after, nitrogen dries up and can obtain polyvinylidene difluoride film.
The preparation mass concentration is the aqueous solution of 3% polyvinyl alcohol, places water-bath, and warming while stirring is until 95 ℃.Keep 2h under this temperature, stop heating, cooling during to 30 ℃, obtains poly-vinyl alcohol solution while stirring.
In 35 ℃ of thermostatic chambers, the polyvinylidene difluoride film of above-mentioned preparation is divided glass pane surface in cleaning, guarantee between film and the glass plate without any bubble.With thickness accurately controlled scraper with the casting solution for preparing previously directly at polyvinylidene difluoride film surface knifing, thickness is 0.5mm, leaves standstill the 12h solidified forming in thermostatic chamber, obtains polyvinyl alcohol-Kynoar duplicature.
Be 50% glutaraldehyde water solution with the 20mL mass concentration, after the 180mL absolute ethyl alcohol mixes, add the 0.24mL mass concentration and be 37% concentrated hydrochloric acid, mix, obtain crosslinked fluid.
Crosslinked fluid is placed 40 ℃ of following constant temperature.Polyvinyl alcohol-Kynoar the duplicature of above-mentioned curing is uncovered, be soaked in the crosslinked fluid under 40 ℃ cross-linking reaction 3h.Take out after finishing, big water gaging washes, and dries up with nitrogen and can obtain polyvinyl alcohol-poly-vinylidene-fluoride composite film, be i.e. the water treatment composite membrane.
When the water treatment of above-mentioned preparation is applied to pure aquatic system with composite membrane, be 25 ℃ in temperature, under the condition of 0.1MPa, the membrane flux of measuring pure water is 26Kgm
-2H
-1, rejection is 96%, porosity is 73%;
The mixed system that described water treatment is applied to have different kinds of ions with composite membrane wherein, contains the KCl of NaCl, the 0.064mol/L of 0.16mol/L, the NH of 0.045mol/L in the described mixed system with different kinds of ions
4The MgSO of Cl, 0.021mol/L
4NaH with 0.032mol/L
2PO
4, be 40 ℃ in temperature, under the condition of 0.4MPa, the membrane flux of water is 0.51Kgm
-2H
-1, rejection is 68%, porosity is 39%.
Embodiment 4:
The trade mark that Shanghai Sanaifu New Material Co., Ltd is produced is that the Kynoar preparation mass concentration of FR904 is 15% solution, wherein, N, the N-dimethylacetylamide is solvent, add that to account for the Kynoar mass percent be that 25% PEG-1000 stirs, after leaving standstill the 24h deaeration in 50 ℃ of baking ovens, obtain Kynoar solution.
In 40 ℃ of thermostatic chambers, accurately controlled scraper is at clean glass pane surface knifing with thickness with described Kynoar solution, and the thickness of film is 0.6mm, after leaving standstill 5min, immerse the water coagulating bath immediately, keep the 6h curing molding, obtain the polyvinylidene difluoride film of curing molding.With the polyvinylidene difluoride film of described curing molding with the clear water flushing after, nitrogen dries up and can obtain polyvinylidene difluoride film.
The preparation mass concentration is the aqueous solution of 3% polyvinyl alcohol, places water-bath, and warming while stirring is until 95 ℃.Keep 2h under this temperature, stop heating, cooling during to 30 ℃, obtains poly-vinyl alcohol solution while stirring.
In 35 ℃ of thermostatic chambers, the polyvinylidene difluoride film of above-mentioned preparation is divided glass pane surface in cleaning, guarantee between film and the glass plate without any bubble.With thickness accurately controlled scraper with the casting solution for preparing previously directly at polyvinylidene difluoride film surface knifing, thickness is 0.8mm, leaves standstill the 12h solidified forming in thermostatic chamber, obtains polyvinyl alcohol-Kynoar duplicature.
Be 50% glutaraldehyde water solution with the 30mL mass concentration, after the 170mL absolute ethyl alcohol mixes, add the 0.24mL mass concentration and be 37% concentrated hydrochloric acid, mix, obtain crosslinked fluid.
Crosslinked fluid is placed 40 ℃ of following constant temperature.Polyvinyl alcohol-Kynoar the duplicature of above-mentioned curing is uncovered, be soaked in the crosslinked fluid under 40 ℃ cross-linking reaction 5h.Take out after finishing, big water gaging washes, and dries up with nitrogen and can obtain polyvinyl alcohol-poly-vinylidene-fluoride composite film, be i.e. the water treatment composite membrane.
When the water treatment of above-mentioned preparation is applied to pure aquatic system with composite membrane, be 25 ℃ in temperature, under the condition of 0.1MPa, the membrane flux of measuring pure water is 32Kgm
-2H
-1, rejection is 97%, porosity is 76%;
The mixed system that described water treatment is applied to have different kinds of ions with composite membrane wherein, contains the KCl of NaCl, the 0.064mol/L of 0.16mol/L, the NH of 0.045mol/L in the described mixed system with different kinds of ions
4The MgSO of Cl, 0.021mol/L
4NaH with 0.032mol/L
2PO
4, be 40 ℃ in temperature, under the condition of 0.4MPa, the membrane flux of water is 1.6Kgm
-2H
-1, rejection is 73%, porosity is 45%.
Embodiment 5:
The trade mark that Shanghai Sanaifu New Material Co., Ltd is produced is that the Kynoar preparation mass concentration of FR904 is 25% solution, wherein, N, the N-dimethylacetylamide is solvent, add that to account for the Kynoar mass percent be that 15% lithium chloride stirs, after leaving standstill the 48h deaeration in 50 ℃ of baking ovens, obtain Kynoar solution.
In 50 ℃ of thermostatic chambers, accurately controlled scraper is at clean glass pane surface knifing with thickness with described Kynoar solution, and the thickness of film is 0.45mm, after leaving standstill 6min, immerse the water coagulating bath immediately, keep the 10h curing molding, obtain the polyvinylidene difluoride film of curing molding.With the polyvinylidene difluoride film of described curing molding with the clear water flushing after, nitrogen dries up and can obtain polyvinylidene difluoride film.
The preparation mass concentration is the aqueous solution of 5% polyvinyl alcohol, places water-bath, and warming while stirring is until 95 ℃.Keep 2h under this temperature, stop heating, cooling during to 30 ℃, obtains poly-vinyl alcohol solution while stirring.
In 35 ℃ of thermostatic chambers, the polyvinylidene difluoride film of above-mentioned preparation is divided glass pane surface in cleaning, guarantee between film and the glass plate without any bubble.With thickness accurately controlled scraper with the casting solution for preparing previously directly at polyvinylidene difluoride film surface knifing, thickness is 0.8mm, leaves standstill the 15h solidified forming in thermostatic chamber, obtains polyvinyl alcohol-Kynoar duplicature.
Be 50% glutaraldehyde water solution with the 10mL mass concentration, after the 190mL absolute ethyl alcohol mixes, add the 0.24mL mass concentration and be 37% concentrated hydrochloric acid, mix, obtain crosslinked fluid.
Crosslinked fluid is placed 40 ℃ of following constant temperature.Polyvinyl alcohol-Kynoar the duplicature of above-mentioned curing is uncovered, be soaked in the crosslinked fluid under 40 ℃ cross-linking reaction 7h.Take out after finishing, big water gaging washes, and dries up with nitrogen and can obtain polyvinyl alcohol-poly-vinylidene-fluoride composite film, be i.e. the water treatment composite membrane.
When the water treatment of above-mentioned preparation is applied to pure aquatic system with composite membrane, be 25 ℃ in temperature, under the condition of 0.1MPa, the membrane flux of measuring pure water is 22Kgm
-2H
-1, rejection is 97%, porosity is 71%;
The mixed system that described water treatment is applied to have different kinds of ions with composite membrane wherein, contains the KCl of NaCl, the 0.064mol/L of 0.16mol/L, the NH of 0.045mol/L in the described mixed system with different kinds of ions
4The MgSO of Cl, 0.021mol/L
4NaH with 0.032mol/L
2PO
4, be 40 ℃ in temperature, under the condition of 0.4MPa, the membrane flux of water is 0.43Kgm
-2H
-1, rejection is 78%, porosity is 35%.
Embodiment 6:
The trade mark that Shanghai Sanaifu New Material Co., Ltd is produced is that the Kynoar preparation mass concentration of FR904 is 25% solution, wherein, N, the N-dimethylacetylamide is solvent, add that to account for the Kynoar mass percent be that 8% PEG-2000 stirs, after leaving standstill the 60h deaeration in 50 ℃ of baking ovens, obtain Kynoar solution.
In 50 ℃ of thermostatic chambers, accurately controlled scraper is at clean glass pane surface knifing with thickness with described Kynoar solution, and the thickness of film is 0.9mm, after leaving standstill 12min, immerse the water coagulating bath immediately, keep the 24h curing molding, obtain the polyvinylidene difluoride film of curing molding.With the polyvinylidene difluoride film of described curing molding with the clear water flushing after, nitrogen dries up and can obtain polyvinylidene difluoride film.
The preparation mass concentration is the aqueous solution of 5% polyvinyl alcohol, places water-bath, and warming while stirring is until 95 ℃.Keep 2h under this temperature, stop heating, cooling during to 30 ℃, obtains poly-vinyl alcohol solution while stirring.
In 35 ℃ of thermostatic chambers, the polyvinylidene difluoride film of above-mentioned preparation is divided glass pane surface in cleaning, guarantee between film and the glass plate without any bubble.With thickness accurately controlled scraper with the casting solution for preparing previously directly at polyvinylidene difluoride film surface knifing, thickness is 1.0mm, leaves standstill the 20h solidified forming in thermostatic chamber, obtains polyvinyl alcohol-Kynoar duplicature.
Be 50% glutaraldehyde water solution with the 20mL mass concentration, after the 180mL absolute ethyl alcohol mixes, add the 0.24mL mass concentration and be 37% concentrated hydrochloric acid, mix, obtain crosslinked fluid.
Crosslinked fluid is placed 40 ℃ of following constant temperature.The duplicature of aforementioned curing is uncovered, be soaked in the crosslinked fluid under 40 ℃ cross-linking reaction 8h.Take out after finishing, big water gaging washes, and dries up with nitrogen and can obtain polyvinyl alcohol-poly-vinylidene-fluoride composite film, be i.e. the water treatment composite membrane.
When the water treatment of above-mentioned preparation is applied to pure aquatic system with composite membrane, be 25 ℃ in temperature, under the condition of 0.1MPa, the membrane flux of measuring pure water is 10Kgm
-2H
-1, rejection is 98%, porosity is 65%;
The mixed system that described water treatment is applied to have different kinds of ions with composite membrane wherein, contains the KCl of NaCl, the 0.064mol/L of 0.16mol/L, the NH of 0.045mol/L in the described mixed system with different kinds of ions
4The MgSO of Cl, 0.021mol/L
4NaH with 0.032mol/L
2PO
4, be 40 ℃ in temperature, under the condition of 0.4MPa, the membrane flux of water is 0.2Kgm
-2H
-1, rejection is 86%, porosity is 25%.
Embodiment 7:
The trade mark that Shanghai Sanaifu New Material Co., Ltd is produced is that the Kynoar preparation mass concentration of FR904 is 20% solution, wherein, N, the N-dimethylacetylamide is solvent, add that to account for the Kynoar mass percent be that 20% lithium chloride stirs, after leaving standstill the 72h deaeration in 50 ℃ of baking ovens, obtain Kynoar solution.
In 50 ℃ of thermostatic chambers, accurately controlled scraper is at clean glass pane surface knifing with thickness with described Kynoar solution, and the thickness of film is 0.8mm, after leaving standstill 5min, immerse the water coagulating bath immediately, keep the 20h curing molding, obtain the polyvinylidene difluoride film of curing molding.With the polyvinylidene difluoride film of described curing molding with the clear water flushing after, nitrogen dries up and can obtain polyvinylidene difluoride film.
The preparation mass concentration is the aqueous solution of 5% polyvinyl alcohol, places water-bath, and warming while stirring is until 95 ℃.Keep 2h under this temperature, stop heating, cooling during to 30 ℃, obtains poly-vinyl alcohol solution while stirring.
In 35 ℃ of thermostatic chambers, the polyvinylidene difluoride film of above-mentioned preparation is divided glass pane surface in cleaning, guarantee between film and the glass plate without any bubble.With thickness accurately controlled scraper with the casting solution for preparing previously directly at polyvinylidene difluoride film surface knifing, thickness is 1.5mm, leaves standstill the 24h solidified forming in thermostatic chamber, obtains polyvinyl alcohol-Kynoar duplicature.
Be 50% glutaraldehyde water solution with the 30mL mass concentration, after the 170mL absolute ethyl alcohol mixes, add the 0.24mL mass concentration and be 37% concentrated hydrochloric acid, mix, obtain crosslinked fluid.
Crosslinked fluid is placed 40 ℃ of following constant temperature.Polyvinyl alcohol-Kynoar the duplicature of above-mentioned curing is uncovered, be soaked in the crosslinked fluid under 40 ℃ cross-linking reaction 10h.Take out after finishing, big water gaging washes, and dries up with nitrogen and can obtain polyvinyl alcohol-poly-vinylidene-fluoride composite film, be i.e. the water treatment composite membrane.
When the water treatment of above-mentioned preparation is applied to pure aquatic system with composite membrane, be 25 ℃ in temperature, under the condition of 0.1MPa, the membrane flux of measuring pure water is 5Kgm
-2H
-1, rejection is 99%, porosity is 60%;
The mixed system that described water treatment is applied to have different kinds of ions with composite membrane wherein, contains the KCl of NaCl, the 0.064mol/L of 0.16mol/L, the NH of 0.045mol/L in the described mixed system with different kinds of ions
4The MgSO of Cl, 0.021mol/L
4NaH with 0.032mol/L
2PO
4, be 40 ℃ in temperature, under the condition of 0.4MPa, the membrane flux of water is 0.1Kgm
-2H
-1, rejection is 90%, porosity is 20%.
Comparative Examples 1
Use the deionized water dissolve polyvinyl alcohol, it is 6.5% poly-vinyl alcohol solution by amount ratio configuration quality mark, after the poly-vinyl alcohol solution dissolving, add crosslinking agent maleic anhydride and an amount of concentrated sulfuric acid catalyst, continue to stir 1h, crosslinking agent and catalyst are uniformly dispersed, and standing and defoaming obtains poly-vinyl alcohol solution;
With described poly-vinyl alcohol solution knifing on the glass plate of cleaning, treat water evaporates after, take off the crosslinked 12h of the baking oven of putting into 50 ℃, take out, obtaining thickness is the crosslinked PVA film of maleic acid of 20～30 μ m.
When measuring the crosslinked PVA film of described maleic acid and being applied to pure aquatic system, be 25 ℃ in temperature, under the condition of 0.1MPa, the membrane flux of measuring pure water is 0.15～0.2Kg/m
2H.
Comparative Examples 2
Under 30 ℃, be dissolved in 20g Kynoar, 12g lithium chloride, 40mL acetone in the 160mL dimethylacetylamide, after filtration, after the degassing, at 30 ℃ of films of painting 0.3mm down uniformly at glass plate, after controlling certain volatilization time, immerse film forming in the coagulating bath, after the drying, obtain polyvinylidene difluoride film.
The porosity of measuring described Kynoar is 85%, and the membrane flux when being used for pure water is 3.5Kg/ (m
2H).
The result shows, when water treatment provided by the present invention is applied to pure aquatic system with composite membrane, is 25 ℃ in temperature, and under the condition of 0.1MPa, the membrane flux of water is 5～60Kgm
-2H
-1, rejection is 95%～99%, porosity is 65%～85%; When described water treatment is applied to have the mixed system of different kinds of ions with composite membrane, be 40 ℃ in temperature, under the condition of 0.4MPa, the membrane flux of water is 0.1～3Kgm
-2H
-1, rejection is 50%～90%, porosity is 25%～60%.
The above only is preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a water treatment may further comprise the steps with the preparation method of composite membrane:
A) Kynoar solution is carried out obtaining polyvinylidene difluoride film after knifing, curing molding, the drying;
B) poly-vinyl alcohol solution is carried out knifing on described polyvinylidene difluoride film surface, curing molding obtains polyvinyl alcohol-Kynoar duplicature;
C) with that described polyvinyl alcohol-the Kynoar duplicature places crosslinked fluid to carry out is crosslinked, after the drying, obtain the water treatment composite membrane.
2. preparation method according to claim 1 is characterized in that, the thickness of described polyvinylidene difluoride film is 0.2～1.5mm, and the thickness of described polyvinyl alcohol-Kynoar duplicature is 0.4～3mm.
3. preparation method according to claim 1 is characterized in that, described Kynoar solution is prepared as follows:
Kynoar, organic solvent and additive are mixed, and deaeration obtains Kynoar solution;
Described organic solvent is N, N-dimethylacetylamide, N, dinethylformamide, N-methyl pyrrolidone or dimethyl sulfoxide (DMSO);
Described additive is polyethylene glycol or lithium chloride.
4. preparation method according to claim 3 is characterized in that, the temperature of described deaeration is 45～55 ℃, and the time is 12～72h.
5. preparation method according to claim 1 is characterized in that, described poly-vinyl alcohol solution is prepared as follows:
Polyvinyl alcohol is mixed with water, heating, cooling can obtain poly-vinyl alcohol solution.
6. preparation method according to claim 5 is characterized in that, the temperature of described heating is 90～100 ℃, and the time of described heating is 2～3h, and the temperature of described cooling is 25～35 ℃.
7. preparation method according to claim 1 is characterized in that, described crosslinked fluid is prepared as follows:
Glutaraldehyde water solution, absolute ethyl alcohol are mixed, obtain mixed solution; Add mass fraction in the described mixed solution and be 37% concentrated hydrochloric acid, mix, can obtain crosslinked fluid.
8. preparation method according to claim 1 is characterized in that, steps A) described in the coagulating bath of curing molding be the water coagulating bath, the time of described curing molding is 2～24h.
9. preparation method according to claim 1 is characterized in that, step B) described in the temperature of curing molding be 30～50 ℃, the time is 6～24h.
10. preparation method according to claim 1 is characterized in that, described crosslinked temperature is 35～45 ℃, and the time is 1～10h.
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| CN104607063A (en) * | 2014-08-18 | 2015-05-13 | 济南大学 | PVDF permanently hydrophilic ultrafiltration membrane and modification method thereof |
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| CN112295405A (en) * | 2019-07-30 | 2021-02-02 | 上海恩捷新材料科技有限公司 | High-flux high-pollution-resistance polyethylene ultrafiltration membrane and preparation method thereof |
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| CN104607063A (en) * | 2014-08-18 | 2015-05-13 | 济南大学 | PVDF permanently hydrophilic ultrafiltration membrane and modification method thereof |
| CN104607063B (en) * | 2014-08-18 | 2017-02-01 | 济南大学 | PVDF permanently hydrophilic ultrafiltration membrane and modification method thereof |
| CN109012234A (en) * | 2018-08-03 | 2018-12-18 | 常州大学 | The organic/inorganic composite film and preparation method thereof of passive type regulating and controlling humidity |
| CN112295405A (en) * | 2019-07-30 | 2021-02-02 | 上海恩捷新材料科技有限公司 | High-flux high-pollution-resistance polyethylene ultrafiltration membrane and preparation method thereof |
| CN112295405B (en) * | 2019-07-30 | 2022-06-10 | 上海恩捷新材料科技有限公司 | High-flux high-pollution-resistance polyethylene ultrafiltration membrane and preparation method thereof |
| CN112952167A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Application of acid-base cross-linked ion-conducting membrane in flow battery |
| CN115105862A (en) * | 2022-06-10 | 2022-09-27 | 北京航天试验技术研究所 | Permeable membrane, application of permeable membrane in dehydration method of cyclopropane aerospace fuel, dehydration method, dehydration system and fuel |
| CN115105862B (en) * | 2022-06-10 | 2024-03-26 | 北京航天试验技术研究所 | Permeable membrane and application thereof in dehydration method, dehydration system and fuel of cyclopropane-based aerospace fuel |
| CN116216824A (en) * | 2023-03-08 | 2023-06-06 | 成都理工大学 | Hydrogel type interface photo-thermal evaporator and preparation and application methods thereof |
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