CN106474943A - Hollow fiber ultrafiltration membrane - Google Patents
Hollow fiber ultrafiltration membrane Download PDFInfo
- Publication number
- CN106474943A CN106474943A CN201510542674.9A CN201510542674A CN106474943A CN 106474943 A CN106474943 A CN 106474943A CN 201510542674 A CN201510542674 A CN 201510542674A CN 106474943 A CN106474943 A CN 106474943A
- Authority
- CN
- China
- Prior art keywords
- hollow fiber
- ultrafiltration membrane
- fiber ultrafiltration
- coagulation bath
- casting solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a kind of hollow fiber ultrafiltration membrane, including exodermiss, endodermiss first internal layer adjacent with exodermiss and second internal layer adjacent with endodermiss.The hollow fiber ultrafiltration film of the present invention has the advantages that film-strength is high, membrane aperture is less, pore-size distribution is narrower, membrane flux is high.This hollow fiber ultrafiltration membrane product can effectively remove the pollutant such as colloid in waste water, float, microorganism during actual advanced treatment of wastewater and reuse.
Description
Technical field
The present invention relates to ultrafiltration membrane technique field, particularly to a kind of hollow fiber ultrafiltration membrane.
Background technology
Membrane separation technique, with respect to traditional separation, purification, filtering technique have high separating efficiency, energy-conservation,
A series of superioritys such as easy to operate and environmentally friendly, obtain the most attention of countries in the world.External 20 generation
Discipline has just just had started to the research to microfiltration and ultrafilter membrane, to the sixties, the cellulose acetate of the early development that continues
After filter membrane, develop many new varieties, such as polysulfones, polyester, Nomex, politef etc., generation again
The market sales revenue of boundary's seperation film reaches multi-billion dollar.In energy shortage, shortage of resources, ecological environment is increasingly disliked
Change today, scientific and technological circle, industrial circle and national governments all membrane process be considered as 21 century industrial technology transformation with
One needed for industry technology upgrade particularly important and the new technique on basis, the energy and chemical industry, desalinization,
Waste water (gas) process and other field of Environment Protection etc. are widely used.
Ultrafilter membrane is one of principal mode of seperation film, and its operation operating pressure is relatively low, only 50-200kPa,
And treatment effect is stable, less by the interference of the change of water quality (referring mainly to the change of turbidity) of raw water, can remove
In water, the float of the overwhelming majority, colloidal impurity, antibacterial and viral sporangiocyst etc., lead in water process etc. from after come out
Domain is increasingly widely applied.Material currently used for preparation and production ultrafilter membrane mainly includes machine polymerization
Thing material and inorganic material.Organic polymer material generally prepares ultrafilter membrane by phase inversion, conventional material
Material includes：Polyacrylonitrile (polyacrylonitrile), polysulfones (polysulfone), cellulose (cellulose), polyethers
Sulfone (polyethersulfone), SPSF (sulfonated polysulfone), polyimides (polyimide), poly-
Etherimide (polyetherimide), polyvinylidene fluoride (polyvinylidene fluoride), polyether-ketone (peek)
Deng due to the restriction of material body performance, preparation method and yield, the ultrafiltration membrane material commonly used at present has：Vinegar
Acid cellulose, polyamide, polypropylene, polyacrylonitrile, polyolefin, polyether sulfone, polysulfones, polyimides, poly-
Carbonic ester, PVDF etc..Relatively common in the market is PVDF, poly- (ether) sulfone and polyacrylonitrile 3
Kind.
China's economy is fast-developing through decades, and water resource is very nervous, and petrochemical industry is that China is industrial
Water rich and influential family (water withdrawal account for the whole nation industry water intaking total amount 5%), be also the larger industry of quantity of wastewater effluent it
One, with the shortage of water resource, the development of industry will be had a strong impact on, and be possible to bring a series of social problems.
Therefore, by abundant for petrifaction sewage reuse, not only can with effectively solving shortage of water resources and environmental protection capacity restriction problem,
And preferable economic benefit can be created for enterprise and bring significant social benefit and environmental benefit.
In petrifaction sewage, pollutant kind is various, water quality is relative complex and is easily subject to the fluctuation of front-end process to lead
Cause water treatment difficulty big, need the major pollutants feature according to waste water for sewage embrane method reuse technology
Required with water with target water quality, on the one hand need to select be more suitable for complex system, there is specific membrane structure
Ultrafilter membrane product is as the pretreating process of reverse osmosis units；On the other hand it is also required to select suitable sewage disposal
Reuse technology parameter.
Now widely used polyolefin ultrafilter membrane product, the outstanding problem existing mainly includes：(1) single-skin drum
Layer, section show as finger-like or spongy or finger-like-spongiosiss although can respectively as intrinsic pressure or
External-compression type ultrafiltration technology uses, but during backwash process, the ultrafilter membrane of single-skin drum Rotating fields is easy to lead in backwash
Process forms irreversible pollution, as depicted in figs. 1 and 2；(2) porosity is low, pore-size distribution width, logical
Amount low it is difficult to meet the requirement of large-scale engineering applications, especially in the wastewater treatment process of petrochemical field,
Sewage complicated component, pollutant kind is many, and sewage species are different, and its performance difference is bigger, for embrane method reuse
Need for technology the major pollutants feature according to waste water and target water quality to require preparation to have with water specific
The ultrafilter membrane product of structure, meets simultaneously and selects that performance is good, membrane aperture is little and the ultrafiltration of pore-size distribution relative narrower
Film product.
Content of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of new hollow fiber ultrafiltration membrane.The present invention
Described hollow fiber ultrafiltration membrane, including exodermiss, endodermiss first internal layer adjacent with exodermiss and with
The second adjacent internal layer of endodermiss.The hollow fiber ultrafiltration film of the present invention has that film-strength is high, membrane aperture is less, aperture
The high feature of narrow distribution, membrane flux, has separation accuracy height simultaneously, easily forms surface contamination, easy cleaning etc.
Advantage.
The preferred implementation of the hollow fiber ultrafiltration membrane according to the present invention, with exodermiss as starting point or face,
Endodermiss are that on terminal or the direction in face, the aperture of described first internal layer is gradually increased, i.e. fine along described hollow
The radial direction of the section of dimension ultrafilter membrane, the aperture of described first internal layer is gradually reduced.
The preferred implementation of the hollow fiber ultrafiltration membrane according to the present invention, with endodermiss as starting point or face,
Exodermiss are that on terminal or the direction in face, the aperture of described second internal layer is gradually increased, i.e. fine in described hollow
In the radial direction, the aperture of described second internal layer is gradually increased the section of dimension ultrafilter membrane.
The preferred implementation of the hollow fiber ultrafiltration membrane according to the present invention, its section is spongiosiss.
According to a preferred embodiment of the invention, the pore size of outer surface (i.e. the surface of exodermiss) is
10-18nm, preferably 12-16nm.
According to the preferred embodiment of the present invention, the pore size of inner surface (i.e. the surface of endodermiss) is 6-14nm,
It is preferably 8-12nm.
According to the preferred embodiment of the present invention, the thickness of the first internal layer is 1.0-6.5 μm, preferably 2.2-4.5 μm.
According to the preferred embodiment of the present invention, the thickness of the second internal layer is 0.7-5.6 μm, preferably 1.4-4.2 μm.
According to the preferred embodiment of the present invention, the porosity of described hollow fiber ultrafiltration membrane is 70-90%, preferably
75-85%.
According to the preferred embodiment of the present invention, the elongation at break 100-220% of described hollow fiber ultrafiltration membrane,
It is preferably 150-200%.
According to the preferred embodiment of the present invention, fracture strength 2.3-3.5MPa of described hollow fiber ultrafiltration membrane,
It is preferably 2.5-3.2MPa.
According to the preferred embodiment of the present invention, described hollow fiber ultrafiltration membrane is steady under 25 DEG C, 0.1MPa
Determining pure water flux size is 480-1000LMH, preferably 500-800LMH.
According to the preferred embodiment of the present invention, the contact angle size of described hollow fiber ultrafiltration membrane is 55-60 degree,
It is preferably 56-58 degree.
According to the preferred embodiment of the present invention, the material of main part of described hollow fiber ultrafiltration membrane be selected from polyacrylonitrile,
Polysulfones, cellulose, polyether sulfone (PES), SPSF, polyimides, Polyetherimide, Kynoar (PVDF)
With at least one in polyether-ketone, preferably cellulose acetate, polyamide, polypropylene, polyacrylonitrile, polyolefin,
At least one in polyether sulfone, polysulfones, polyimides, Merlon and PVDF, more preferably Kynoar
(PVDF), at least one in polysulfones ether (PES) and polyacrylonitrile.
According to the preferred embodiment of the present invention, described hollow fiber ultrafiltration membrane is prepared by phase inversion.
Therefore, present invention also offers a kind of preparation method of above-mentioned hollow fiber ultrafiltration membrane.Described preparation method
Comprise the following steps：
Step S1, prepares casting solution, wherein, described casting solution includes polymer, porogen and solvent；
Step S2, prepares the first coagulation bath, the second coagulation bath and the 3rd coagulation bath, wherein, the first coagulation bath
In comprise 2,2'-ethylenedioxybis(ethanol). and diethylene glycol, comprise glycerol or 2,2'-ethylenedioxybis(ethanol). in second coagulation bath, the third coagulation bath be water；
Step S3, prepares core liquid；
Casting solution and core liquid are extruded by device for spinning, are obtained the doughnut of nascent state by step S4；
Step S5, the doughnut of described nascent state is immersed described first coagulation bath, described second gel successively
Bath and described 3rd coagulation bath, obtain hollow fiber ultrafiltration membrane of the present invention.
According to the preferred embodiment of the present invention, described in step S3, core liquid includes solvent and porogen.Some
In embodiment, described core liquid comprises solvent 30-45wt% and porogen 15-30wt%, balance of water.
According to the preferred embodiment of the present invention, in described core liquid, comprise solvent 30-45wt%, organic porogen
10-20wt% and inorganic salt porogen 5-10wt%.Its process for preparation may include：By solvent, organic porogen,
Inorganic salt porogen and deionized water are dissolved in deionized water according to mass ratio respectively, and add core liquid to react
Kettle, by core liquid kettle temperature control between 60-90 DEG C, core liquid is through standing, taking off for the heating of startup core liquid reactor
Bubble is stand-by after processing.Preferably, described organic porogen is PEG200 or PEG400 or PEG600；Described
Inorganic salt porogen is aluminum trichloride (anhydrous) or sodium chloride.
According to the present invention, described solvent can be dimethylformamide, dimethyl acetylamide, dimethyl sulfoxide,
N-Methyl pyrrolidone, triethyl phosphate, trimethyl phosphate, hexamethyl ammonium phosphate, tetramethylurea, tetrahydrochysene furan
Mutter and acetone in any one or more.Described solvent be preferably dimethylformamide, dimethyl acetylamide,
Dimethyl sulfoxide or its mixture.In the present invention, water used is preferably deionized water.
Preparation in accordance with the present invention, described porogen includes organic porogen and/or inorganic salt porogen.Institute
State inorganic salt porogen can be aluminum chloride, sodium chloride, lithium chloride, calcium chloride, lithium nitrate, calcium nitrate,
At least one in magnesium chloride and zinc chloride.Described organic additive can be Polyethylene Glycol (PEG) series, second
Glycol methyl ether, ethylene glycol, ethyl acetate, polymaleic anhydride, Hexalin, glycerol, triethyl phosphate,
At least one in tributyl phosphate, polyvinyl pyrrolidone, polyacrylic acid and polyacrylamide.For poly-
The porogen of ethylene glycol series, PEG200, PEG400 or PEG600 are preferred.
According to the preferred embodiment of the present invention, in step sl, described polymer include main polymer and
Hydrophilic polymer.Preferably, described main polymer be selected from polyacrylonitrile, polysulfones, cellulose, polyether sulfone,
In SPSF, polyimides, Polyetherimide, polyvinylidene fluoride (PVDF) and polyether-ketone at least
At least one in one kind, preferably polyvinylidene fluoride, polyether sulfone and polyacrylonitrile, its weight average molecular weight is preferred
For 1,000,000-150 ten thousand.Preferably, described hydrophilic polymer is selected from Polyethylene Glycol and Polyvinylpyrrolidone
At least one, the preferably at least one in PEG20000, PVPk30 and PVPk90.
According to the preferred embodiment of the present invention, in described step S1, the process for preparation of casting solution includes：?
Under the conditions of heating (95-120 DEG C), according to inorganic salt porogen, organic additive, hydrophilic polymer, master
The order of body polymer successively each material is dissolved in solvent.Preferably, often plus start after a kind of material stirring will
Added material with plus after material stirring 10-30 minute, a kind of material under adding.
According to the preferred embodiment of the present invention, described first coagulation bath is the aqueous solution of 2,2'-ethylenedioxybis(ethanol). and diethylene glycol；
Preferably, the concentration of 2,2'-ethylenedioxybis(ethanol). is 20-30wt%, preferably 22-28wt%, and the concentration of diethylene glycol is 10-20
Wt%, preferably 12-18wt%.
According to the preferred embodiment of the present invention, described second coagulation bath is the aqueous solution of 2,2'-ethylenedioxybis(ethanol). or glycerol, excellent
Selection of land, in the second coagulation bath, the concentration of 2,2'-ethylenedioxybis(ethanol). or glycerol is 10-15wt%.
According to the preferred embodiment of the present invention, before step S 4, casting solution need to be filtered and aerofluxuss
Bubble.
According to the preferred embodiment of the present invention, in step S4, the temperature setting of the first coagulation bath is 90-110
DEG C, the temperature setting of the second coagulation bath is 60-80 DEG C, and the temperature setting of the 3rd coagulation bath is 50-70 DEG C.
According to the preferred embodiment of the present invention, in step S5, the doughnut of nascent state is in the first coagulation bath
In gel time be 10-60sec, preferably 15-45sec；Gel time in the second coagulation bath is
60-300sec, preferably 120-240sec；Gel time in the 3rd coagulation bath is 300-420sec, preferably
For 360-400sec.
According to the preferred embodiment of the present invention, in step S5, the doughnut of nascent state coagulates in immersion first
One section of air dry-spinning path is first passed through before glue bath.Preferably, length 2-10 centimetre of described air dry-spinning path, excellent
Elect 4-6 centimetre as.
According to the preferred embodiment of the present invention, described casting solution comprises 14-20wt%, preferred 18-20wt%
Main polymer.
According to the preferred embodiment of the present invention, described casting solution comprise 2-10wt%, preferred 4-8wt% hydrophilic
Property polymer.
According to the preferred embodiment of the present invention, described casting solution comprises 56-72wt%, preferred 66-70wt%
Solvent.
According to the preferred embodiment of the present invention, described casting solution comprise 3-10wt%, preferred 5-8wt% organic
Porogen.
According to the preferred embodiment of the present invention, described casting solution comprise 1-5wt%, preferred 2-3wt% inorganic
Salt porogen.
According to some specific embodiments, described preparation method includes：
Step 1：By main polymer concentration be 14-20wt%, hydrophilic polymer concentration be 2-10wt%, molten
The concentration of agent is 66-72wt%, organic porogen mass concentration is 3-10wt% and inorganic salt pore-foaming agent concentration is
Above-mentioned each material of 1-5wt% is according to certain quality weighing；
Wherein：Polymer in step 1 is polyvinylidene fluoride (PVDF) or (polyether sulfone) PES, and it is heavy
Average molecular weight is 1,000,000-150 ten thousand；Hydrophilic polymer is PEG 20000 or PVPk30 or PVPk90；
Organic porogen is PEG200 or PEG400 or PEG600；Inorganic salt porogen is aluminum trichloride (anhydrous)；
Step 2：By each material weighing in step 1 successively according to solvent, inorganic salt porogen, organic pore
Agent, hydrophilic polymer additive and main polymer are added in casting solution reactor；
Step 3：Solvent in step 2 is added the heating unit starting casting solution reactor after reactor,
Casting solution temperature of reaction kettle is heated to 95-120 DEG C, during solvent is heated, successively by leftover materials
Add reactor, need often plus after a kind of material to start and stir added material and above added material stirring 20min
Stop a kind of material under stirring is added afterwards；
Step 4：Will be molten under conditions of 130-150 rev/min for the casting solution reactor completing each material in step 1
Solution 25-36h, obtains homogeneous casting film liquid system after vacuum, standing and defoaming 36-48h.
Step 5：2,2'-ethylenedioxybis(ethanol). and diethylene glycol are fully dissolved in deionized water, obtaining 2,2'-ethylenedioxybis(ethanol). concentration is 28wt%
It is the gel of 12wt% with diethylene glycol concentration, and the gel that this is formed is as the first coagulation bath, and by the
The temperature of one coagulation bath rises to 95 DEG C；The aqueous solution that 2,2'-ethylenedioxybis(ethanol). concentration is 13wt% is solidifying as the second coagulation bath
Colloid, and adjust 65 DEG C of the temperature of the second coagulation bath；Deionized water is as the 3rd coagulation bath, and adjusts the 3rd
The temperature of coagulation bath is 55 DEG C；Wherein, gel time in the first coagulation bath for the doughnut of nascent state is
10-60sec, preferably 15-45sec；Gel time in the second coagulation bath is 60-300sec, preferably
120-240sec；Gel time in the 3rd coagulation bath is 300-420sec, preferably 360-400sec.
Step 6：By solvent, organic porogen, inorganic salt porogen and deionized water respectively according to 30-45%,
The mass ratio of 10-20% and 5-10% is dissolved in deionized water, and adds core liquid reactor, starts core liquid anti-
Answer the heating of kettle by core liquid kettle temperature control between 60-90 DEG C, core liquid is stand-by after processing through standing, deaeration；
Wherein organic molecule additive is PEG200 or PEG400 or PEG600；Inorganic salt is aluminum trichloride (anhydrous)
Or sodium chloride；
Step 7：Homogeneous casting solution in step 4 is entered under the nitrogen pressure of 0.4-0.8MPa preheating temperature
For entering the entrance of spinning pump after 80-100 DEG C of filter, through metering spinning pump by pipeline and initial casting film
Bubble in liquid is discharged, and when not containing bubble in the casting solution flowing out connects preprepared spinning head；
Step 8：Open casting solution reactor pipe valve and start spinning pump, by above-mentioned casting solution through dosing pump
It is delivered to the annular space of spinning head, after the outflow of spinning head annular space, the core being exhausted liquid pipe is connected with casting solution
Core liquid entrance to spinning head.
Step 9：The doughnut of nascent state is sequentially entered after the air dry-spinning path of 2-10cm the first coagulation bath,
Second coagulation bath, the 3rd coagulation bath, finally under conditions of the windup rate of 20-30m/min, the present invention is made
The standby hollow fiber ultrafiltration membrane with topological structure, then through again washing and dry film preparation after can be made into curtain,
Pressure type membrane module.
Not only can be obtained using above-mentioned preparation method there are double cortex constructions, section be topological structure hollow fine
Dimension ultrafilter membrane, and the hollow fiber ultrafiltration membrane product of this structure has that film-strength is high, membrane aperture is less, aperture
The higher feature of narrow distribution, membrane flux.
According to specific embodiment, following spy is had by the hollow fiber ultrafiltration membrane that said method preparation method obtains
Levy：
(1) there are double cortex constructions, i.e. exodermiss and endodermiss, section is spongiosiss, wherein appearance
Face pore size is 10-18nm, and inner surface pore size is 6-14nm；
(2) it is 1.0-6.5um with the thickness of the first exodermiss adjacent internal layer；With endodermiss adjacent
The thickness of one internal layer is 0.7-5.6um；
(3) porosity of hollow fiber ultrafiltration membrane product is 70-85%；
(4) the contact angle size of hollow fiber ultrafiltration membrane product is 55-60 °, elongation at break 100-220%,
Fracture strength 2.3-3.5MPa, 25 DEG C, the stable pure water flux size under 0.1MPa be 280-1000LMH.
There is the first internal layer and second internal layer of topological structure according to the hollow fiber ultrafiltration membrane of the present invention, that is, by
The fine and close interior exodermiss of fibre ultrafiltration film are starting point dough-making powder, by the point dough-making powder of this compacted zone successively to section
Extend geometry shape spatial network or alveolate texture, during extension membrane aperture be gradually increased, porosity gradually
The increased seriality structure with sharp interface.
This hollow fiber ultrafiltration membrane product can be by waste water during actual advanced treatment of wastewater and reuse
Colloid, float, microorganism etc. effectively remove, easily form both surface filtration during filtering, prevent
Deep layer pollutes, and the film properties after being conducive to polluting recover, and effectively extend the Chemical cleaning cycle, high membrane flux
Power consumption and the operation expense in running can effectively be reduced.
Brief description
Fig. 1 shows the SEM structure of the section, nearly section and surface of A brand ultrafilter membrane commodity.
Fig. 2 shows section, nearly section and the surface SEM structure of B brand ultrafilter membrane commodity.
Fig. 3 show comparative example under the conditions of section, nearly section and surface SEM structure.
Fig. 4 is the electromicroscopic photograph of the partial cross-section of hollow fiber ultrafiltration membrane product of the present invention.
Fig. 5 is the hollow fiber ultrafiltration membrane product of the present invention close to exodermiss partial cross-section electromicroscopic photograph.
Fig. 6 is the hollow fiber ultrafiltration membrane product of the present invention close to endodermiss partial cross-section electromicroscopic photograph.
Fig. 7 is the electromicroscopic photograph of the outer surface of hollow fiber ultrafiltration membrane product of the present invention.
Fig. 8 is the electromicroscopic photograph of the inner surface of hollow fiber ultrafiltration membrane product of the present invention.
Specific embodiment
Embodiment 1
The preparation of casting solution：Weigh dimethyl acetylamide (DMAc) 70kg, anhydrous Lithium chloride 1kg, poly- second
Glycol (PEG600) 5kg, polyvinyl pyrrolidone (K90) 10kg, PVDF 14kg, are added sequentially to
In the casting solution reactor of 150L, and after being sufficiently stirred for 20min in reactor when adding materials, then under adding
A kind of material, casting solution temperature of reaction kettle is heated to 95 DEG C, by above-mentioned casting film liquid system at 130 revs/min
Under the conditions of dissolve 25h, obtain homogeneous casting film liquid system after vacuum, standing and defoaming 36h.
The preparation of gel in coagulation bath：2,2'-ethylenedioxybis(ethanol). and diethylene glycol are fully dissolved in deionized water, obtain three
Glycol concentration 28wt% and the gel of diethylene glycol concentration 12wt%, and the gel that this is formed coagulates as first
Glue is bathed, and the temperature of the first coagulation bath is risen to 95 DEG C；The 2,2'-ethylenedioxybis(ethanol). aqueous solution that mass content is 13% as
The gel of the second coagulation bath, and adjust 65 DEG C of the temperature of the second coagulation bath；Deionized water is as the 3rd gel
Bath, and the temperature of regulation the 3rd coagulation bath is 55 DEG C.
The preparation of core liquid：DMAc, PEG400 and sodium chloride are dissolved in deionized water, wherein, diformazan
The mass content of yl acetamide, PEG400 and sodium chloride is respectively 45wt%, 10wt% and 5wt%, and adds
Core liquid reactor, starts the stirring of core liquid reactor and heats core liquid kettle temperature control at 90 DEG C, treat above-mentioned molten
Liquid stirring and dissolving simultaneously forms uniform solution completely, stand-by after processing through standing, deaeration.
The preparation of hollow fiber ultrafiltration membrane：The casting solution of above-mentioned preparation is entered under the nitrogen pressure of 0.4MPa
Preheating temperature is to enter the entrance of spinning pump after 80 DEG C of filter, through metering spinning pump by pipeline and initial
Bubble in casting solution is discharged, when not containing bubble in the casting solution flowing out by preprepared spinning head even
Connect.
Open casting solution reactor pipe valve and start spinning pump, above-mentioned casting solution is delivered to spray through dosing pump
The core being exhausted liquid pipe is connected to spinning head with casting solution after the outflow of spinning head annular space by the annular space of silk head
Core liquid entrance.
The doughnut of nascent state is sequentially entered after the air dry-spinning path of 2cm the first coagulation bath, the second gel
Bath, the 3rd coagulation bath, the doughnut of the nascent state gel time in the first coagulation bath is 10sec；?
Gel time in two coagulation baths is 60sec；Gel time in the 3rd coagulation bath is 360sec, finally exists
The hollow fiber ultrafiltration membrane of the present invention is obtained under conditions of the windup rate of 20m/min.
This hollow fiber ultrafiltration membrane product has following structure and performance technologies feature：
(1) double cortex constructions, section is spongiosiss, and the pore size of its outer surface is 18nm, interior
The pore size on surface is 14nm；
(2) thickness of first internal layer adjacent with outer surface is 1.0um；Second internal layer adjacent with inner surface
Thickness is 0.7um；
(3) porosity of hollow fiber ultrafiltration membrane product is 85%；
(4) the contact angle size of hollow fiber ultrafiltration membrane product is 55 °, elongation at break 100%, and fracture is strong
Degree 2.3MPa, 25 DEG C, the stable pure water flux size under 0.1MPa be 1000LMH.
Embodiment 2
The preparation of casting solution：Weigh dimethyl acetylamide (DMAc) 66kg, aluminum trichloride (anhydrous) 2kg, gather
Ethylene glycol (PEG400) 10kg, polyvinyl pyrrolidone (K30) 8kg, PES polymer 14kg, according to
In the secondary casting solution reactor being added to 150L, and after being sufficiently stirred for 20min in reactor when adding materials,
A kind of material under adding again, casting solution temperature of reaction kettle is heated to 100 DEG C, by above-mentioned casting film liquid system 130
Dissolve 30h under conditions of rev/min, obtain homogeneous casting film liquid system after vacuum, standing and defoaming 40h.
The preparation of gel in coagulation bath：2,2'-ethylenedioxybis(ethanol). and diethylene glycol are fully dissolved in deionized water, obtain three
Glycol concentration 28wt% and the gel of diethylene glycol concentration 12wt%, and the gel that this is formed coagulates as first
Glue is bathed, and the temperature of the first coagulation bath is risen to 95 DEG C；The aqueous solution that 2,2'-ethylenedioxybis(ethanol). concentration is 13wt% is as the
The gel of two coagulation baths, and adjust 65 DEG C of the temperature of the second coagulation bath；Deionized water as the 3rd coagulation bath,
And the temperature of regulation the 3rd coagulation bath is 55 DEG C.
The preparation of core liquid：DMAc, PEG200 and sodium chloride are dissolved in deionized water, wherein, diformazan
The mass content of yl acetamide, PEG200 and sodium chloride is respectively 40wt%, 13wt% and 7wt%, and adds
Core liquid reactor, starts the stirring of core liquid reactor and heats core liquid kettle temperature control at 85 DEG C, treat above-mentioned molten
Liquid stirring and dissolving simultaneously forms uniform solution completely, stand-by after processing through standing, deaeration.
The preparation of hollow fiber ultrafiltration membrane：The casting solution of above-mentioned preparation is entered under the nitrogen pressure of 0.5MPa
Preheating temperature is to enter the entrance of spinning pump after 85 DEG C of filter, through metering spinning pump by pipeline and initial
Bubble in casting solution is discharged, when not containing bubble in the casting solution flowing out by preprepared spinning head even
Connect.
Open casting solution reactor pipe valve and start spinning pump, above-mentioned casting solution is delivered to spray through dosing pump
The core being exhausted liquid pipe is connected to spinning head with casting solution after the outflow of spinning head annular space by the annular space of silk head
Core liquid entrance.
The doughnut of nascent state is sequentially entered after the air dry-spinning path of 4cm the first coagulation bath, the second gel
Bath, the 3rd coagulation bath, the doughnut of the nascent state gel time in the first coagulation bath is 15sec；?
Gel time in two coagulation baths is 120sec；Gel time in the 3rd coagulation bath is 300sec, finally exists
The hollow fiber ultrafiltration membrane of the present invention is obtained under conditions of the windup rate of 23m/min.This hollow fiber ultrafiltration membrane
Product has following structure and performance technologies feature：
(1) double cortex constructions, section is spongiosiss, and the pore size of its outer surface is 16nm, interior
The pore size on surface is 12nm；
(2) thickness of first internal layer adjacent with outer surface is respectively 2.2um；In second adjacent with inner surface
The thickness of layer is respectively 1.4um；
(3) porosity of hollow fiber ultrafiltration membrane product is 75%；
(4) the contact angle size of hollow fiber ultrafiltration membrane product is 58 °, elongation at break 150%, and fracture is strong
Degree 2.5MPa, 25 DEG C, the stable pure water flux size under 0.1MPa be 800LMH.
Embodiment 3
The preparation of casting solution：Weigh N-methyl ketopyrrolidine (NMP) 56kg, aluminum trichloride (anhydrous) 2kg, gather
Ethylene glycol (PEG600) 8kg, polyvinyl pyrrolidone (K90) 6kg, PVDF polymer 18kg, according to
In the secondary casting solution reactor being added to 150L, and after being sufficiently stirred for 20min in reactor when adding materials,
A kind of material under adding again, casting solution temperature of reaction kettle is heated to 110 DEG C, by above-mentioned casting film liquid system 130
Dissolve 34h under conditions of rev/min, obtain homogeneous casting film liquid system after vacuum, standing and defoaming 42h.
The preparation of gel in coagulation bath：2,2'-ethylenedioxybis(ethanol). and diethylene glycol are fully dissolved in deionized water, obtain three
Glycol concentration 28wt% and the gel of diethylene glycol concentration 12wt%, and the gel that this is formed coagulates as first
Glue is bathed, and the temperature of the first coagulation bath is risen to 95 DEG C；The aqueous solution that 2,2'-ethylenedioxybis(ethanol). concentration is 13wt% is as the
The gel of two coagulation baths, and adjust 65 DEG C of the temperature of the second coagulation bath；Deionized water as the 3rd coagulation bath,
And the temperature of regulation the 3rd coagulation bath is 55 DEG C.
The preparation of core liquid：DMAc, PEG600 and sodium chloride are dissolved in deionized water, wherein, diformazan
The mass content of yl acetamide, PEG600 and sodium chloride is respectively 35wt%, 16wt% and 9wt%, and adds
Core liquid reactor, starts the stirring of core liquid reactor and heats core liquid kettle temperature control at 80 DEG C, treat above-mentioned molten
Liquid stirring and dissolving simultaneously forms uniform solution completely, stand-by after processing through standing, deaeration.
The preparation of hollow fiber ultrafiltration membrane：The casting solution of above-mentioned preparation is entered under the nitrogen pressure of 0.6MPa
Preheating temperature is to enter the entrance of spinning pump after 90 DEG C of filter, through metering spinning pump by pipeline and initial
Bubble in casting solution is discharged, when not containing bubble in the casting solution flowing out by preprepared spinning head even
Connect.
Open casting solution reactor pipe valve and start spinning pump, above-mentioned casting solution is delivered to spray through dosing pump
The core being exhausted liquid pipe is connected to spinning head with casting solution after the outflow of spinning head annular space by the annular space of silk head
Core liquid entrance.
The doughnut of nascent state is sequentially entered after the air dry-spinning path of 6cm the first coagulation bath, the second gel
Bath, the 3rd coagulation bath, the doughnut of the nascent state gel time in the first coagulation bath is 45sec；?
Gel time in two coagulation baths is 300sec；Gel time in the 3rd coagulation bath is 400sec, finally exists
The hollow fiber ultrafiltration membrane of the present invention is obtained under conditions of the windup rate of 25m/min.
This hollow fiber ultrafiltration membrane product has following structure and performance technologies feature：
(1) double cortex constructions, section is spongiosiss, and wherein outer surface pore size is 14nm, interior table
Face pore size is 10nm；
(2) thickness of first internal layer adjacent with outer surface is 3.0um；Second internal layer adjacent with inner surface
Thickness is 2.6um；
(3) porosity of hollow fiber ultrafiltration membrane product is 80%；
(4) the contact angle size of hollow fiber ultrafiltration membrane product is 56 °, elongation at break 180%, and fracture is strong
Degree 2.8MPa, 25 DEG C, the stable pure water flux size under 0.1MPa be 600LMH.
Embodiment 4
The preparation of casting solution：Weigh N-methyl ketopyrrolidine (NMP) 68kg, anhydrous tri-chlorination lithium 5kg, gather
Ethylene glycol (PEG200) 5kg, Polyethylene Glycol (PEG20000) 4kg, PES polymer 18kg, successively plus
Enter in the casting solution reactor of 150L, and after being sufficiently stirred for 20min in reactor when adding materials, then
A kind of material under interpolation, casting solution temperature of reaction kettle is heated to 115 DEG C, by above-mentioned casting film liquid system 140
Dissolve 34h under conditions of rev/min, obtain homogeneous casting film liquid system after vacuum, standing and defoaming 46h.
The preparation of gel in coagulation bath：2,2'-ethylenedioxybis(ethanol). and diethylene glycol are fully dissolved in deionized water, obtain three
Glycol concentration 28wt% and the gel of diethylene glycol concentration 12wt%, and the gel that this is formed coagulates as first
Glue is bathed, and the temperature of the first coagulation bath is risen to 95 DEG C；The aqueous solution that 2,2'-ethylenedioxybis(ethanol). mass content is 13% as
The gel of the second coagulation bath, and adjust 65 DEG C of the temperature of the second coagulation bath；Deionized water is as the 3rd gel
Bath, and the temperature of regulation the 3rd coagulation bath is 55 DEG C.
The preparation of core liquid：Dimethyl acetylamide, PEG200 and aluminum chloride solids are dissolved in deionized water,
Wherein, the mass content of dimethyl acetylamide, PEG200 and aluminum chloride solids is respectively 40wt%, 18wt%
And 10wt%, and add core liquid reactor, start the stirring of core liquid reactor and heat core liquid kettle temperature control
At 70 DEG C, treat above-mentioned solution stirring dissolving and form uniform solution completely, stand-by after processing through standing, deaeration.
The preparation of hollow fiber ultrafiltration membrane：The casting solution of above-mentioned preparation is entered under the nitrogen pressure of 0.7MPa
Preheating temperature is to enter the entrance of spinning pump after 95 DEG C of filter, through metering spinning pump by pipeline and initial
Bubble in casting solution is discharged, when not containing bubble in the casting solution flowing out by preprepared spinning head even
Connect.
Open casting solution reactor pipe valve and start spinning pump, above-mentioned casting solution is delivered to spray through dosing pump
The core being exhausted liquid pipe is connected to spinning head with casting solution after the outflow of spinning head annular space by the annular space of silk head
Core liquid entrance.
The doughnut of nascent state is sequentially entered after the air dry-spinning path of 8cm the first coagulation bath, the second gel
Bath, the 3rd coagulation bath, the doughnut of the nascent state gel time in the first coagulation bath is 60sec；?
Gel time in two coagulation baths is 240sec；Gel time in the 3rd coagulation bath is 420sec, finally exists
By the hollow fiber ultrafiltration membrane with topological structure prepared by the present invention under conditions of the windup rate of 27m/min,
Can be made into curtain, pressure type membrane module after washing again and dry film preparation again.
This hollow fiber ultrafiltration membrane product has following structure and performance technologies feature：
(1) double cortex constructions, section is spongiosiss, and wherein outer surface pore size is 12nm, interior table
Face pore size is 8nm；
(2) thickness of first internal layer adjacent with outer surface is 4.5um；Second internal layer adjacent with inner surface
Thickness is 4.2um；
(3) porosity of hollow fiber ultrafiltration membrane product is 85%；
(4) the contact angle size of hollow fiber ultrafiltration membrane product is 55 °, elongation at break 200%, and fracture is strong
Degree 3.2MPa, 25 DEG C, the stable pure water flux size under 0.1MPa be 500LMH.
Embodiment 5
The preparation of casting solution：Weigh solvent N-methyl ketopyrrolidine (NMP) 72kg, aluminum trichloride (anhydrous) 3kg,
Glycerol 3kg, polyvinyl pyrrolidone (K30) 2kg, PVDF polymer 20kg, are added sequentially to 150L
Casting solution reactor in, and after being sufficiently stirred for 20min in reactor when adding materials, then add lower one kind
Material, casting solution temperature of reaction kettle is heated to 120 DEG C, by above-mentioned casting film liquid system in 150 revs/min of condition
Lower dissolving 36h, obtains homogeneous casting film liquid system after vacuum, standing and defoaming 48h.
The preparation of gel in coagulation bath：2,2'-ethylenedioxybis(ethanol). and diethylene glycol are fully dissolved in deionized water, obtain three
Glycol concentration 28wt% and the gel of diethylene glycol concentration 12wt%, and the gel that this is formed coagulates as first
Glue is bathed, and the temperature of the first coagulation bath is risen to 95 DEG C；The aqueous solution that 2,2'-ethylenedioxybis(ethanol). mass content is 13% as
The gel of the second coagulation bath, and adjust 65 DEG C of the temperature of the second coagulation bath；Deionized water is as the 3rd gel
Bath, and the temperature of regulation the 3rd coagulation bath is 55 DEG C.
The preparation of core liquid：Dimethyl acetylamide, glycerol and sodium chloride are dissolved in deionized water, wherein, two
The mass content of methylacetamide, glycerol and sodium chloride is respectively 30wt%, 20wt% and 7wt%, and adds
Core liquid reactor, starts the stirring of core liquid reactor and heats core liquid kettle temperature control at 60 DEG C, treat above-mentioned molten
Liquid stirring and dissolving simultaneously forms uniform solution completely, stand-by after processing through standing, deaeration.
The preparation of hollow fiber ultrafiltration membrane：The casting solution of above-mentioned preparation is entered under the nitrogen pressure of 0.8MPa
Preheating temperature is to enter the entrance of spinning pump after 100 DEG C of filter, through metering spinning pump by pipeline and just
Bubble in beginning casting solution is discharged, by preprepared spinning head when not containing bubble in the casting solution flowing out
Connect.
Open casting solution reactor pipe valve and start spinning pump, above-mentioned casting solution is delivered to spray through dosing pump
The core being exhausted liquid pipe is connected to spinning head with casting solution after the outflow of spinning head annular space by the annular space of silk head
Core liquid entrance.
The doughnut of nascent state sequentially entered after the air dry-spinning path of 10cm the first coagulation bath, second coagulate
Glue bath, the 3rd coagulation bath, the doughnut of the nascent state gel time in the first coagulation bath is 45sec；?
Gel time in second coagulation bath is 240sec；Gel time in the 3rd coagulation bath is 360sec, finally
By the Hollow Fiber Ultrafiltration with topological structure prepared by the present invention under conditions of the windup rate of 30m/min
Film, then can be made into curtain, pressure type membrane module after washing again and dry film preparation.
This hollow fiber ultrafiltration membrane product has following structure and performance technologies feature：
(1) double cortex constructions, section is spongiosiss, and wherein outer surface pore size is 10nm, interior table
Face pore size is 6nm；
(2) thickness of first internal layer adjacent with outer surface is 6.5um；Second internal layer adjacent with inner surface
Thickness is 5.6um；
(3) porosity of hollow fiber ultrafiltration membrane product is 70%；
(4) the contact angle size of doughnut product is 60 °, elongation at break 220%, fracture strength 3.5MPa,
25 DEG C, the stable pure water flux size under 0.1MPa be 480LMH.
Comparative example 1
The preparation of casting solution：Weigh N-methyl ketopyrrolidine (NMP) 66.5kg, anhydrous tri-chlorination lithium 3kg,
Polyethylene Glycol (PEG200) 3kg, polyvinyl pyrrolidone (K30) 2.5kg, PVDF polymer 20kg,
It is added sequentially in the casting solution reactor of 150L, and in reactor, when adding materials, be sufficiently stirred for 20min
Afterwards, a kind of material then under adding, casting solution temperature of reaction kettle is heated to 100 DEG C, by above-mentioned casting film liquid system
Dissolve 24h under conditions of 130 revs/min, obtain homogeneous casting film liquid system after vacuum, standing and defoaming 36h.
Coagulation bath is prepared：It is deionized water respectively as first, second, and third gel using conventional gel
The gel of bath, and control the temperature of coagulation bath to be respectively 90 DEG C, 60 DEG C and 50 DEG C successively.
The preparation of core liquid：Core liquid reactor will be added in deionized water, start stirring and the heating of core liquid reactor
By core liquid kettle temperature control at 70 DEG C, stand-by after processing through standing, deaeration；
The preparation of hollow fiber ultrafiltration membrane：The casting solution of above-mentioned preparation is entered under the nitrogen pressure of 0.6MPa
Preheating temperature is to enter the entrance of spinning pump after 80 DEG C of filter, through metering spinning pump by pipeline and initial
Bubble in casting solution is discharged, when not containing bubble in the casting solution flowing out by preprepared spinning head even
Connect.
Open casting solution reactor pipe valve and start spinning pump, above-mentioned casting solution is delivered to spray through dosing pump
The core being exhausted liquid pipe is connected to spinning head with casting solution after the outflow of spinning head annular space by the annular space of silk head
Core liquid entrance.
The doughnut of nascent state is sequentially entered after the air dry-spinning path of 6cm the first coagulation bath, the second gel
Hollow fiber ultrafiltration membrane is finally wound under conditions of the windup rate of 22m/min by bath, the 3rd coagulation bath,
Prepare dry film after washing again again, carry out structure and performance characterization.Its structural characterization result such as Fig. 3.
Under above-mentioned condition, the hollow fiber ultrafiltration membrane of preparation is different from the hollow fiber ultrafiltration membrane structure of the present invention, with
When this comparative example under the conditions of hollow fiber ultrafiltration membrane porosity be 60%, elongation at break be 95%, fracture
Intensity 1.2MPa, 25 DEG C, the stable pure water flux size under 0.1MPa be 200LMH.
The content not being described in detail in this specification belongs to prior art known to professional and technical personnel in the field.
Claims (10)
1. a kind of hollow fiber ultrafiltration membrane, including exodermiss, endodermiss first internal layer adjacent with exodermiss
And second internal layer adjacent with endodermiss.
2. hollow fiber ultrafiltration membrane according to claim 1 is it is characterised in that radial direction along its section
Direction, the aperture of described first internal layer is gradually reduced.
3. hollow fiber ultrafiltration membrane according to claim 1 and 2 is it is characterised in that along its section
Radial direction, the aperture of described second internal layer is gradually increased.
4. the hollow fiber ultrafiltration membrane according to any one of claim 1-3 is it is characterised in that outer surface
Pore size be 10-18nm, preferably 12-16nm.
5. the hollow fiber ultrafiltration membrane according to any one of claim 1-4 is it is characterised in that inner surface
Pore size be 6-14nm, preferably 8-12nm.
6. the hollow fiber ultrafiltration membrane according to any one of claim 1-5 is it is characterised in that described
The thickness of one internal layer is 1.0-6.5 μm, preferably 2.2-4.5 μm.
7. the hollow fiber ultrafiltration membrane according to any one of claim 1-6 is it is characterised in that described
The thickness of two internal layers is 0.7-5.6 μm, preferably 1.4-4.2 μm.
8. the hollow fiber ultrafiltration membrane according to any one of claim 1-7, its preparation process includes：
Step S1, prepares casting solution, wherein, described casting solution includes polymer, porogen and solvent；
Step S2, prepares the first coagulation bath, the second coagulation bath and the 3rd coagulation bath, wherein, described first gel
Bathe aqueous solution for 2,2'-ethylenedioxybis(ethanol). and diethylene glycol it is preferable that the concentration of 2,2'-ethylenedioxybis(ethanol). is 20-30wt%, diethylene glycol dense
Spend for 10-20wt%；Described second coagulation bath is the aqueous solution of 2,2'-ethylenedioxybis(ethanol). or glycerol it is preferable that described three is sweet
The concentration of alcohol or glycerol is 10-15wt%；3rd coagulation bath is water, preferably deionized water.
Step S3, prepares core liquid；
Casting solution and core liquid are extruded by device for spinning, are obtained the doughnut of nascent state by step S4；
Step S5, the doughnut of described nascent state is immersed described first coagulation bath, described second gel successively
Bath and described 3rd coagulation bath, obtain hollow fiber ultrafiltration membrane of the present invention.
9. hollow fiber ultrafiltration membrane according to claim 8 is it is characterised in that described polymer includes
Main polymer and hydrophilic polymer, described main polymer is selected from polyacrylonitrile, polysulfones, cellulose, gathers
At least one in ether sulfone, SPSF, polyimides, Polyetherimide, polyvinylidene fluoride and polyether-ketone,
At least one preferably in polyvinylidene fluoride, polyether sulfone and polyacrylonitrile, more preferably polyvinylidene fluoride；Institute
State hydrophilic polymer be selected from Polyethylene Glycol and Polyvinylpyrrolidone at least one, preferably PEG2000,
At least one in PVPk30 and PVPk90.
10. hollow fiber ultrafiltration membrane according to claim 8 or claim 9 is it is characterised in that with mass content
Meter, described casting solution includes main polymer 14-20wt%；Hydrophilic polymer 2-10wt%；Solvent 56-72
Wt%；Organic porogen 3-10wt%；With inorganic salt porogen 1-5wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510542674.9A CN106474943B (en) | 2015-08-28 | 2015-08-28 | Hollow fiber ultrafiltration membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510542674.9A CN106474943B (en) | 2015-08-28 | 2015-08-28 | Hollow fiber ultrafiltration membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106474943A true CN106474943A (en) | 2017-03-08 |
| CN106474943B CN106474943B (en) | 2019-07-19 |
Family
ID=58235974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510542674.9A Active CN106474943B (en) | 2015-08-28 | 2015-08-28 | Hollow fiber ultrafiltration membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106474943B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417024A (en) * | 2017-07-26 | 2017-12-01 | 冯婷婷 | A kind of medication chemistry sewage treatment process |
| CN113457465A (en) * | 2021-07-16 | 2021-10-01 | 桐乡市健民过滤材料有限公司 | Polyvinylidene fluoride hollow fiber ultrafiltration membrane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101406812A (en) * | 2008-11-04 | 2009-04-15 | 东华大学 | Method for producing thermoplastic polyurethane elastomer/polyvinylidene fluoride blended hollow fiber film |
| CN103111189A (en) * | 2013-02-05 | 2013-05-22 | 江苏苏净集团有限公司 | High-flux polyvinylidene fluoride hollow fiber membrane |
-
2015
- 2015-08-28 CN CN201510542674.9A patent/CN106474943B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101406812A (en) * | 2008-11-04 | 2009-04-15 | 东华大学 | Method for producing thermoplastic polyurethane elastomer/polyvinylidene fluoride blended hollow fiber film |
| CN103111189A (en) * | 2013-02-05 | 2013-05-22 | 江苏苏净集团有限公司 | High-flux polyvinylidene fluoride hollow fiber membrane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417024A (en) * | 2017-07-26 | 2017-12-01 | 冯婷婷 | A kind of medication chemistry sewage treatment process |
| CN113457465A (en) * | 2021-07-16 | 2021-10-01 | 桐乡市健民过滤材料有限公司 | Polyvinylidene fluoride hollow fiber ultrafiltration membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106474943B (en) | 2019-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106474942B (en) | The preparation method of hollow fiber ultrafiltration membrane | |
| CN105435656B (en) | A kind of composite nanometer filtering film and preparation method thereof | |
| US10335741B2 (en) | Method for preparing the network-pore polyvinylidene fluoride membrane based on polyvinyl alcohol gel | |
| CN102430348B (en) | Preparation method for polyethylene terephthalate (PET) braided tube/polymer composite hollow fiber microporous membrane | |
| CN105120992B (en) | Polyvinylidene fluoride hollow fiber membrane and its preparation | |
| CN101979132A (en) | Method for preparing asymmetric nanofiltration membrane by blending polyether sulfone and sulfonated polysulfone high polymers | |
| CN105413486A (en) | Cellulose acetate commixed nano-filtration membrane and preparation method thereof | |
| CN110523281A (en) | A kind of polyamide doughnut receives the preparation method of permeable membrane | |
| CN106731901A (en) | Polyester fiber weaves the preparation method of tube enhancement type composite hollow fibre forward osmosis membrane | |
| CN106731905A (en) | A kind of novel sulfonated polysulfones composite nanometer filtering film and preparation method thereof | |
| CN101733023A (en) | Method for manufacturing polyvinylidene fluoride hollow fiber membrane | |
| CN110141980A (en) | A kind of inner pressed hollow fiber nanofiltration membrane and preparation method thereof | |
| CN106474943A (en) | Hollow fiber ultrafiltration membrane | |
| CN107866155A (en) | A kind of method that polymer matrix MOFs hollow fiber ultrafiltration membranes are prepared using thermally induced phase separation | |
| CN109012227B (en) | Preparation method of enhanced polyvinylidene fluoride regenerated composite membrane | |
| CN108392991A (en) | A kind of compound forward osmosis membrane of waste water desalination polyamide | |
| Wang et al. | Explorations of complex thermally induced phase separation (C-TIPS) method for manufacturing novel diphenyl ether polysulfate flat microporous membranes | |
| CN105727766A (en) | High-charge compound ultrafiltration membrane and preparation method thereof | |
| CN111013400A (en) | Method for preparing polyvinylidene fluoride tubular membrane by low-temperature thermal induced phase method | |
| CN102784563B (en) | High-strength polyvinyl chloride hollow fiber ultrafilter membrane and its preparation method | |
| CN113996189A (en) | Preparation method of hollow fiber separation membrane with compact selective layer | |
| CN112808019B (en) | Method for preparing polyaryletherketone tubular membrane by using green solvent thermal-induced phase method | |
| KR20120094362A (en) | Acetylated alkyl cellulose membrane using thermal induced phase separation and preparing method thereof | |
| CN107670504B (en) | A method of the organic tubular nanofiltration membrane of solvent resistant is prepared using bidirectional circulating perfusion | |
| CN105561805B (en) | A kind of composite nanometer filtering film and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |