CN102527250B - Hollow fibrous membrane and preparation method thereof - Google Patents
Hollow fibrous membrane and preparation method thereof Download PDFInfo
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- CN102527250B CN102527250B CN201110445560.4A CN201110445560A CN102527250B CN 102527250 B CN102527250 B CN 102527250B CN 201110445560 A CN201110445560 A CN 201110445560A CN 102527250 B CN102527250 B CN 102527250B
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Abstract
The invention discloses a hollow fibrous membrane and a preparation method thereof. A mixture containing polyvinylidene fluoride is used for preparing the hollow fibrous membrane, wherein the mixture is prepared by the components of polyvinylidene fluoride resins, organic liquid, inorganic fine powder, solvents and additives by mass percent. The preparation method comprises the following steps: speedily mixing all the components; melting, extruding and twice pelletizing; congruently melting and spinning; cooling; heating and drawing; extracting; and cleaning and soaking, thereby obtaining the membrane with a three-dimensional network. The porosity of pores on the membrane is 60%-90%; the pure water flux at 0.1Mpa and 25 DEG C is 1000-6000L/m2.h; the tensile failure strength is 4-10Mpa; the drawing elongation is 100-180%; and the anti-flatting strength is more than 0.8Mpa. The hollow fibrous membrane is excellent in pollution resistance and durability and is suitable for removing muddy matters from sewage under an excellent water environment as well as a wicked water environment.
Description
Technical field
The present invention relates to a kind of polyvinylidene fluoride hollow fiber membrane and manufacture method thereof.
Background technology
Middle hollow fiber membrane process is a kind of novel isolation technics, conventionally carries out at normal temperatures, without phase transformation, does not produce secondary pollution, is high-efficiency and energy-saving type isolation of purified technology.
Hollow-fibre membrane has been widely used in the separation of chemical process with refining; Field of Environment Protection is as purifying water process, zero discharge of industrial waste water system, and Chinese traditional medicine purification, food and drink field and remove bacterium, colloid, the suspension in running water, and fruit clarification of juice is with concentrated.
As membrane material, use various materials as cellulose, polyacrylonitrile, polyolefin and material modified.Cellulose acetate is the membrane material early developing, and acid-proof alkaline is poor, and the PH scope of application is only 4-9; The resistance to solvent of polyacrylonitrile, resistance to acids and bases are better than cellulose acetate, and the PH scope of application is 2-10.Wherein, polyvinylidene fluoride chemical stability is good, mechanical performance is high, anti-ultraviolet aging, resistance tocrocking permeation flux good, film are high, thereby is suitable as filter membrane, and it has a extensive future.
Traditional doughnut film manufacturing method adopts Wet technique preparation, by extruding by spinneret after resin and pore former and additive mixing, introduces in coagulating bath and solidifies, and by phase transfer, forms perforated membrane.But because technology is limit, prepared hollow-fibre membrane has finger-like pore and sponge structure, mechanical strength is poor, cannot meet the needs of more severe water treatment occasion.
Summary of the invention
The object of this invention is to provide a kind of hollow-fibre membrane and manufacture method thereof, with reference to thermally induced phase separation (TIPS), wet method, dry Wet technique, make described film there is intensive hole, high water permeation performance, durability, chemical resistance and excellent mechanical strength, be suitable for more severe water quality occasion.
The present invention adopts following technical scheme:
A kind of hollow-fibre membrane, it, is made through post processing by the mixture containing polyvinylidene fluoride after melt extruding, and this film has the hole of three-dimensional net structure, and porosity is 60%-90%, and 0.1Mpa, pure water flux is 1000-6000L/m 25 ℃ time
2h, tensile break strength is 4-10Mpa, tensile elongation is 100-180%, anti-collapse intensity > 0.8MPa.
The described mixture containing polyvinylidene fluoride is made up of the component of following mass percent:
The described mixture containing polyvinylidene fluoride is made up of the component of the optimum quality percentage of above-mentioned each component:
Described polyvinylidene fluoride resin is the mixture of different molecular weight poly (vinylidene fluoride).
Described organic liquid is benzoates, sebacic acid ester, the mixture of one or more in Phthalates.
Described inorganic fine powder is one or more the mixture in nano zine oxide, nano-calcium carbonate, nano silicon, organic clay, and the specific area of inorganic fine powder is 80-150m
2/ g, average grain diameter is less than 200nm.
Described solvent is one or several the mixture in 1-METHYLPYRROLIDONE, dimethyl formamide, dimethylacetylamide, methyl alcohol, acetone, dimethyl sulfoxide (DMSO) or oxolane.
Described additive is one or more the mixture in antioxidant, stabilizing agent, ultra-violet absorber; Described antioxidant is one or more the mixture in 2,5-ditert-butylhydro quinone, BHT, gallate and butylated hydroxyarisol, polyethylene glycol; Described stabilizing agent is one or more the mixture in calcium-zinc composite stabilizing agent, antimony organic stabilizing agent; Described ultraviolet absorber is one or more the mixture in 2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-5-chlorinated benzotriazole, HMPA and UV-531.
A manufacture method for hollow-fibre membrane, it comprises following steps:
(1) take the component of following mass percent:
(2) mixed at high speed: adopt super mixer, closed blender or ploughshare blender mixing each component;
(3) melt extrude granulation: by conical double screw extruder, parallel double-screw extruder or single screw extrusion machine, gained mixture in (2) is melt extruded to granulation, the temperature of melt extruder is 190-280 ℃;
(4) melt extrude secondary granulation: by conical double screw extruder, parallel double-screw extruder or single screw extrusion machine, the grain of making in (3) is melt extruded, carry out secondary granulation, the temperature of melt extruder is 110-200 ℃;
(5) congruent melting spinning: carrying out melting inversion of phases by melt spinning tank, is to spray in the looping pit of 200-320 ℃ by temperature, and centre passes into air, forms hollow membrane silk;
(6) cooling: the hollow membrane silk traction obtaining in (5) is immersed and is equipped with in the bosh of cooling medium, cooling medium is the mixture of water or water and polar solvent, in blending agent, the mass content of solvent is less than 70%, and temperature is 20-80 ℃;
(7) add hot-stretch: cooled hollow-fibre membrane is introduced to the long heating bath of 1.5m, and heating-up temperature is 60-150 ℃,, recycling traction wheel carries out 1: 2-1: 4.5 ratios stretch, and are entangled on wire wrapping wheel;
(8) extract: organic liquid and solvent in the hollow-fibre membrane after stretching are extracted by polar solvent, and extraction temperature is 20-80 ℃, extract inorganic fine powder afterwards by acid solution or alkali lye, extraction temperature is 20-80 ℃;
(9) cleaning and dipping: the hollow-fibre membrane after extracting, immerse aftertreatment fluid as cleaned in clear water, cleaning temperature is 20-80 ℃, the time is 2-8 hour.
The described polar solvent that is used for extracting organic liquid and solvent is one or more the mixing polar solvent in alcohols or chlorinated hydrocarbon.
Beneficial effect of the present invention
Polyvinylidene fluoride intensity is high, and because its skeleton is hydrophobic, is therefore suitable for material for water treatment.Inorganic fine powder can improve the porosity of hollow-fibre membrane, forms the hole of three-dimensional net structure, and even aperture distribution.Three-dimensional net structure refers to that all three-dimensionals of film are all porose, and mutually connects between hole, if there is macropore to exist in film, film strength meeting variation, if continued presence can form leak source, if pore-size distribution is extremely inhomogeneous, can affect the rejection effect of film.The film that traditional film-forming method makes, be difficult to make the film with homogeneous three-dimensional net structure, pore-size distribution inequality mostly, and short texture, in film silk air purge and when shake process, once film galled spots or scuffing, just can cause breaking from impaired loci, make whole film silk even membrane module lose filter capacity.And when the film surface damage that the present invention makes, only can cause localized network to lose efficacy, but can not destroy the filter capacity in all the other network structure holes of film, just can not affect the filter capacity of membrane module yet.Hollow-fibre membrane of the present invention is guaranteeing, under the prerequisite of higher pure water flux, greatly to have improved the anti-fracture energy of film, makes it be more suitable for processing in the high turbidity water quality of the frequent air purge of needs and brushing.If tensile break strength is lower than 4Mpa, can often there is breakdown point in fiber, and be not suitable for severe water quality environment, and if higher than 10Mpa, the pure water flux of fiber can decline very large.The tensile break strength of hollow-fibre membrane provided by the present invention is 4-10MPa, also has higher mechanical strength in having high purity water flux, and porosity is 60%-90%, and 0.1Mpa, pure water flux is 1000-6000L/m 25 ℃ time
2h, tensile elongation is 100-180%, anti-collapse intensity > 0.8MPa.The hollow fiber film assembly being made by this kind of method, has excellent antipollution and durability, except being applicable to better water treatment, is applicable to too more severe water quality environment, for example, remove the muddy thing in sewage.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of hollow-fibre membrane inner surface of preparation in embodiment 1 in the present invention.
Fig. 2 is the electron scanning micrograph of doughnut film outer surface of preparation in embodiment 4 in the present invention.
The specific embodiment
The organic liquid that the present invention uses refers to that boiling point is not less than the liquid of 150 ℃, preferably incompatible with polyvinylidene fluoride at lower than 100 ℃, and under melt temperature the organic liquid compatible with it.
Described organic liquid is repefral, diethyl phthalate, dibatyl phithalate, dioctyl phthalate, didecyl phthalate and phosphate etc.Wherein preferred didecyl phthalate and dibutyl phthalate, and their mixture, but the present invention is not restricted to this.Didecyl phthalate is a common name, comprising phthalic acid two 2-ethylhexyls.
Described stabilizing agent is calcium-zinc composite stabilizing agent, antimony organic stabilizing agent etc., preferably the mixture of one or more in zinc stearate, calcium stearate, ferric stearate.
Further explain technical scheme of the present invention with specific embodiment below, but protection scope of the present invention is not limited to this.
Embodiment 1:
Mixture (mass percent) composed of the following components containing polyvinylidene fluoride: (average particulate diameter is 100nm to 20% nano silicon, and specific area is 120m
2/ g), 0.1% butylhydroxy anisole, 5% dibutyl phthalate, 10% didecyl phthalate, 19.9% dimethylacetylamide and 45% polyvinylidene fluoride, in super mixer, mix, last mixture further carries out melting mixing granulation later by Φ 35 parallel double-screw extruders, again, by Φ 35 parallel double-screw extruders, in the time of 190 ℃, carry out mixing and secondary granulation.Be fused into liquid state by the melt spinning tank of 220 ℃ again, after 20h congruent melting, made liquid homogenization, by extruding in the looping pit with 1.05mm internal diameter and 2.00mm external diameter of 260 ℃.Doughnut after extruding leads to the heating bath of another 80 ℃ of space temperatures from 40 ℃ of pure water cooling baths with the speed of 20m/min, the long 1.5m of heating bath, be stretched to wire wrapping wheel with the speed of 30m/min again, cut hollow-fibre membrane from wire wrapping wheel, immerse 95% ethanolic solution, extract organic liquid through machinery concussion, repeat three grooves, every groove one hour, clean with pure water subsequently, move in 10% sodium hydroxide solution of 40 ℃, shake through machinery, stripping inorganic fine powder, repeat three grooves, every groove half an hour, finally use 70 ℃ of warm water cleaning and dipping, repeat five grooves, every groove half an hour.Enter in constant temperature and humidity and dry subsequently.The external diameter of the hollow-fibre membrane making is 1.85mm, and internal diameter is 0.75mm, and porosity is 85%, 0.1Mpa, pure water flux is 1750L/m 25 ℃ time
2h, tensile break strength is 6MPa, tensile elongation is 120%, anti-collapse intensity > 0.8MPa.
The electron scanning micrograph of the polyvinylidene fluoride hollow fiber membrane making in this example is shown in Fig. 1, and the porosity forming on visible doughnut membranous wall is higher.
Embodiment 2:
Mixture (mass percent) composed of the following components containing polyvinylidene fluoride: (average particulate diameter is 95nm to 15% active nano-calcium carbonate, and specific area is 110m
2/ g), 0.5% zinc stearate, 25% dibutyl phthalate, 5% didecyl phthalate, 15% dimethyl formamide and 39.5% polyvinylidene fluoride, in closed blender, mix, last mixture further carries out melting mixing granulation later by Φ 51 conical double screw extruders, again by Φ 35 parallel double-screw extruders, in the time of 180 ℃, carry out mixingly, extrude granulation again by having in six circular holes of 5mm external diameter.Dropped into and in high temperature spinning box, carried out further congruent melting, temperature is 253 ℃, after melting inversion of phases 22h, from the looping pit with 1.20mm internal diameter and 2.20mm external diameter of 260 ℃, spray, from 40 ℃ of pure water cooling baths, lead to the heating bath of another 80 ℃ of space temperatures with the speed of 20m/min, speed with 30m/min is stretched to wire wrapping wheel, cut hollow-fibre membrane from wire wrapping wheel, immerse 95% ethanolic solution, extract organic liquid through machinery concussion, repeat three grooves, every groove one hour, clean with pure water subsequently, move in 40 ℃ of 10% hydrochloric acid solution, shake through machinery, stripping inorganic fine powder, repeat three grooves, every groove half an hour, finally use 70 ℃ of warm water cleaning and dipping, repeat five grooves, every groove half an hour.Enter in constant temperature and humidity and dry subsequently.
The external diameter of the hollow-fibre membrane making is 1.60mm, and internal diameter is 0.85mm, and porosity is 88%, 0.1Mpa, pure water flux is 3600L/m 25 ℃ time
2h, tensile break strength is 7MPa, tensile elongation is 110%, anti-collapse intensity > 0.8MPa.
Embodiment 3:
Mixture (mass percent) composed of the following components containing polyvinylidene fluoride: (average particulate diameter is 99nm to 25% nano zine oxide, and specific area is 125m
2/ g), 0.3%2-hydroxyl-4-oxy-octyl benzophenone, 20% dibutyl phthalate, 19.7% didecyl phthalate, 5% methyl alcohol and 30% polyvinylidene fluoride, in ploughshare blender, mix, last mixture further carries out melting mixing granulation later by Φ 51 conical double screw extruders, again by Φ 35 parallel double-screw extruders, in the time of 260 ℃, carry out mixingly, extrude granulation again by having in six circular holes of 5mm external diameter.Dropped into and in melt spinning tank, carried out further congruent melting, temperature is 200 ℃, after melting inversion of phases 24h, from the looping pit with 1.05mm internal diameter and 2.00mm external diameter of 260 ℃, spray, from 40 ℃ of pure water cooling baths, lead to the heating bath of another 80 ℃ of space temperatures with the speed of 20m/min, speed with 30m/min is stretched to wire wrapping wheel, cut hollow-fibre membrane from wire wrapping wheel, immerse 95% ethanolic solution, extract organic liquid through machinery concussion, repeat three grooves, every groove one hour, clean with pure water subsequently, move in 10% hydrochloric acid solution, shake through machinery, stripping inorganic fine powder, repeat three grooves, every groove half an hour, finally use 70 ℃ of warm water cleaning and dipping, repeat five grooves, every groove half an hour.Enter in constant temperature and humidity and dry subsequently.
The external diameter of the hollow-fibre membrane making is 1.45mm, and internal diameter is 0.75mm, and porosity is 86%, 0.1Mpa, pure water flux is 3300L/m 25 ℃ time
2h, tensile break strength is 5.5MPa, tensile elongation is 114%, anti-collapse intensity > 0.8MPa.
Embodiment 4:
Adopt the formula rate of example 1 and the method for making of example 2, difference is that it is heat treatment four hours between the heating of 80 ℃ that the film silk after cleaning and dipping is put into space temperature, and acid soak changes dipping by lye into, and in film, silica residual quantity is 1%.
The electron scanning micrograph that is illustrated in figure 2 the polyvinylidene fluoride hollow fiber membrane outer surface making, from the image of film, film has three-dimensional net structure, macropore be can't see in the inside of film, aperture homogeneous, with bubble point method measure maximum diameter of hole be 0.3um, porosity is 80%.The external diameter of hollow-fibre membrane is 1.60 millimeters, and internal diameter is 0.85 millimeter, and 0.1Mpa, pure water flux is 5500L/m 25 ℃ time
2h, tensile break strength is 8MPa, tensile elongation is 150%, anti-collapse intensity > 0.8MPa.
Embodiment 5:
18% active nano-ZnO, 2% active diatom soil, 0.2% HMPA, 20% dibutyl phthalate, 4.8% didecyl phthalate, 5% dimethylacetylamide and 45% polyvinylidene fluoride, under the method for making of embodiment 2, it is 220 ℃ that technological parameter removes melting temperature, the looping pit spinning head temperature with 1.20mm internal diameter and 2.2mm external diameter is outside 255 ℃, and all the other parameters are all constant.
The external diameter of the hollow-fibre membrane making is 1.80mm, and internal diameter is 0.95mm, and porosity is 73%, 0.1Mpa, pure water flux is 1900L/m 25 ℃ time
2h, tensile break strength is 9MPa, tensile elongation is 150%, anti-collapse intensity > 0.8MPa.
Embodiment 6:
The hollow-fibre membrane that adopts the formula of example 5 and the method for making of example 1 to make, difference is that dipping by lye changes acid soak into.Film surface average pore size is 0.11 μ m, and porosity is 77%, and film surface contact angle is 92%.
Claims (9)
1. a hollow-fibre membrane, it is characterized in that its by containing the mixture of polyvinylidene fluoride through melt extruding, then make through post processing, this film has the hole of three-dimensional net structure, porosity is 60%～90%, 0.1MPa, pure water flux is 1000～6000L/m 25 ℃ time
2h, tensile break strength is 4～10MPa, tensile elongation is 100～180%, anti-collapse intensity > 0.8MPa, is made up of the component of following mass percent containing the mixture of polyvinylidene fluoride: polyvinylidene fluoride resin 20～50%, organic liquid 5～60%, inorganic fine powder 10～30%, solvent 1～30%, additive 0.1～5%, the manufacture method of hollow-fibre membrane comprises following steps:
(1) take the component of described mass percent: polyvinylidene fluoride resin, organic liquid, inorganic fine powder, solvent and additive;
(2) mixed at high speed: adopt super mixer, closed blender or ploughshare blender mixing each component;
(3) melt extrude granulation: by conical double screw extruder, parallel double-screw extruder or single screw extrusion machine, gained mixture in (2) is melt extruded to granulation, the temperature of melt extruder is 190～280 ℃;
(4) melt extrude secondary granulation: by conical double screw extruder, parallel double-screw extruder or single screw extrusion machine, the grain of making in (3) is melt extruded, carry out secondary granulation, the temperature of melting extruder is 110～200 ℃;
(5) congruent melting spinning, carries out melting inversion of phases by melt spinning tank, is to spray in the looping pit of 200～320 ℃ by temperature, and centre passes into air, forms hollow membrane silk;
(6) cooling: the hollow membrane silk traction obtaining in (5) is immersed and is equipped with in the bosh of cooling medium, cooling medium is the mixture of water or water and polar solvent, in blending agent, the mass content of solvent is less than 70%, and temperature is 20～80 ℃;
(7) add hot-stretch: cooled hollow-fibre membrane is introduced to the long heating bath of 1.5m, and heating-up temperature is 60～150 ℃, recycling traction wheel carries out 1: 2～1: 4.5 ratio and stretches, and is entangled on wire wrapping wheel;
(8) extract: organic liquid and solvent in the hollow-fibre membrane after stretching are extracted by polar solvent, and extracting temperature is 20～80 ℃, extract inorganic fine powder afterwards by acid solution or alkali lye, extracting temperature is 20～80 ℃;
(9) cleaning and dipping: the hollow-fibre membrane after extracting, immerse in aftertreatment fluid and clean, cleaning temperature is 20～80 ℃, the time is 2～8 hours.
2. a kind of hollow-fibre membrane according to claim 1, the mixture containing polyvinylidene fluoride described in it is characterized in that is made up of the component of following preferred mass percentage:
3. hollow-fibre membrane according to claim 1 and 2, is characterized in that described polyvinylidene fluoride resin is the mixture of different molecular weight poly (vinylidene fluoride).
4. hollow-fibre membrane according to claim 1 and 2, is characterized in that described organic liquid is benzoates, sebacic acid ester, the mixture of one or more in Phthalates.
5. hollow-fibre membrane according to claim 1 and 2, is characterized in that described inorganic fine powder is one or more the mixture in nano zine oxide, nano-calcium carbonate, nano silicon, organic clay, and the specific area of inorganic fine powder is 80～150m
2/ g, average grain diameter is less than 200nm.
6. hollow-fibre membrane according to claim 1 and 2, is characterized in that described solvent is one or several the mixture in 1-METHYLPYRROLIDONE, dimethyl formamide, dimethylacetylamide, methyl alcohol, acetone, dimethyl sulfoxide (DMSO) or oxolane.
7. hollow-fibre membrane according to claim 1 and 2, is characterized in that described additive is one or more the mixture in antioxidant, stabilizing agent, ultra-violet absorber.
8. manufacture a method for hollow-fibre membrane as claimed in claim 1, it is characterized in that it comprises following steps:
(1) take the component of following mass percent:
(2) mixed at high speed: adopt super mixer, closed blender or ploughshare blender mixing each component;
(3) melt extrude granulation: by conical double screw extruder, parallel double-screw extruder or single screw extrusion machine, gained mixture in (2) is melt extruded to granulation, the temperature of melt extruder is 190～280 ℃;
(4) melt extrude secondary granulation: by conical double screw extruder, parallel double-screw extruder or single screw extrusion machine, the grain of making in (3) is melt extruded, carry out secondary granulation, the temperature of melting extruder is 110～200 ℃ of temperature;
(5) congruent melting spinning, carries out melting inversion of phases by melt spinning tank, is to spray in the looping pit of 200～320 ℃ by temperature, and centre passes into air, forms hollow membrane silk;
(6) cooling: the hollow membrane silk traction obtaining in (5) is immersed and is equipped with in the bosh of cooling medium, cooling medium is the mixture of water or water and polar solvent, in blending agent, the mass content of solvent is less than 70%, and temperature is 20～80 ℃;
(7) add hot-stretch: cooled hollow-fibre membrane is introduced to the long heating bath of 1.5m, and heating-up temperature is 60～150 ℃, recycling traction wheel carries out 1: 2～1: 4.5 ratio and stretches, and is entangled on wire wrapping wheel;
(8) extract: organic liquid and solvent in the hollow-fibre membrane after stretching are extracted by polar solvent, and extracting temperature is 20～80 ℃, extract inorganic fine powder afterwards by acid solution or alkali lye, extracting temperature is 20～80 ℃;
(9) cleaning and dipping: the hollow-fibre membrane after extracting, immerse in aftertreatment fluid and clean, cleaning temperature is 20～80 ℃, the time is 2～8 hours.
9. the manufacture method of a kind of hollow-fibre membrane according to claim 8, is characterized in that it is one or more the mixing polar solvent in alcohols or chlorinated hydrocarbon that the polar solvent of organic liquid and solvent is extracted in described being used for.
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| CN106110902A (en) * | 2016-07-26 | 2016-11-16 | 华中农业大学 | The Kynoar antibacterial film of nanometer doped zinc oxide and preparation method |
| JP7185448B2 (en) * | 2017-09-01 | 2022-12-07 | 旭化成株式会社 | Porous hollow fiber membrane, manufacturing method thereof, and filtration method |
| JP7219032B2 (en) * | 2017-09-01 | 2023-02-07 | 旭化成株式会社 | Method for producing porous hollow fiber membrane including separation layer, porous hollow fiber membrane, and filtration method |
| US11110402B2 (en) | 2017-09-01 | 2021-09-07 | Asahi Kasei Kabushik Kasha | Porous hollow fiber membrane, method for producing porous hollow fiber membrane and filtration method |
| WO2019049857A1 (en) * | 2017-09-07 | 2019-03-14 | 旭化成株式会社 | Filtration method using porous membrane |
| JP6839766B2 (en) * | 2017-09-07 | 2021-03-10 | 旭化成株式会社 | Filtration method using a porous membrane |
| CN110975642A (en) * | 2019-12-31 | 2020-04-10 | 江苏美能膜材料科技有限公司 | High-strength hollow fiber membrane for filtering beverage and wine, membrane component and preparation process of membrane |
| CN111644074B (en) * | 2020-07-17 | 2022-12-30 | 安徽森诺膜技术有限公司 | Polyvinylidene fluoride hollow fiber membrane and preparation method thereof |
| CN114471201B (en) * | 2022-03-23 | 2022-12-23 | 烟台大学 | Polyether-ether-ketone hollow fiber membrane, preparation method thereof and membrane absorption application |
| CN116272433B (en) * | 2023-04-28 | 2023-08-18 | 常州工程职业技术学院 | Modified polyvinylidene fluoride water treatment film and preparation method thereof |
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| CN1980729A (en) * | 2004-07-07 | 2007-06-13 | 株式会社吴羽 | Porous vinylidene fluoride resin membrane for water treatment and process for producing the same |
| CN101227967A (en) * | 2005-07-20 | 2008-07-23 | 株式会社吴羽 | Porous hollow-yarn membrane of vinylidene fluoride resin |
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| CN1980729A (en) * | 2004-07-07 | 2007-06-13 | 株式会社吴羽 | Porous vinylidene fluoride resin membrane for water treatment and process for producing the same |
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| CN102029114A (en) * | 2010-11-22 | 2011-04-27 | 杭州卫士环保科技有限公司 | Hydrophilic hollow fiber membrane and preparation method thereof |
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