CN108043248B - PVA-PVDF hollow fiber ultrafiltration membrane, preparation method, preparation device and application - Google Patents
PVA-PVDF hollow fiber ultrafiltration membrane, preparation method, preparation device and application Download PDFInfo
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- CN108043248B CN108043248B CN201711360585.8A CN201711360585A CN108043248B CN 108043248 B CN108043248 B CN 108043248B CN 201711360585 A CN201711360585 A CN 201711360585A CN 108043248 B CN108043248 B CN 108043248B
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- 239000012528 membrane Substances 0.000 title claims abstract description 109
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 67
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 65
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 30
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 101
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 101
- 210000004379 membrane Anatomy 0.000 claims description 67
- 239000000243 solution Substances 0.000 claims description 59
- 210000002469 basement membrane Anatomy 0.000 claims description 34
- 239000003431 cross linking reagent Substances 0.000 claims description 34
- 239000000835 fiber Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000004132 cross linking Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- 235000012489 doughnuts Nutrition 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 238000005273 aeration Methods 0.000 claims description 6
- 238000006136 alcoholysis reaction Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000007701 flash-distillation Methods 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 29
- 239000011248 coating agent Substances 0.000 abstract description 27
- 239000002131 composite material Substances 0.000 abstract description 27
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract 1
- 229940068984 polyvinyl alcohol Drugs 0.000 description 90
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 90
- 239000010408 film Substances 0.000 description 78
- 239000011148 porous material Substances 0.000 description 18
- 230000004907 flux Effects 0.000 description 17
- 239000007788 liquid Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 8
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- -1 runner It is narrow Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 229920002492 poly(sulfone) Polymers 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000007373 indentation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 229920002307 Dextran Polymers 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000010148 water-pollination Effects 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 241000500881 Lepisma Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000005446 dissolved organic matter Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a small-aperture organic hollow fiber ultrafiltration composite membrane, which is mainly characterized in that narrow-slit blade coating is adopted, a layer of PVA solution is coated on a PVDF hollow fiber base membrane in a controllable manner, and the PVA is further promoted to spread and adhere on the surface more uniformly. The invention has the following advantages: (1) the average aperture of the composite membrane is controlled, so that the composite membrane can be applied to a certain specific system; (2) the thickness of the film is controlled, so that the composite film has good integrity and ideal permeability; (3) the narrow slit coating process of the unitized operation is convenient for industrial amplification.
Description
Technical field
The present invention relates to hollow fiber porous film field, especially a kind of high antipollution, in the small and uniform PVDF in aperture
The preparation method of hollow fiber composite hyperfiltration membrane.
Background technique
Kynoar (PVDF) is a kind of semicrystalline polymeric, and crystalline melt point is 170 DEG C, and thermal decomposition temperature exists
300 DEG C or more, have the characteristics that good thermal stability, chemical stability and mechanical stability, on the other hand, PVDF resin is simultaneous
Have the characteristic of fluororesin and resins for universal use, there is good high temperature resistant and resistance to chemical corrosion；The pH range that can be born reaches
It is even broader to 1~12；It is oxidation resistance membrane material most outstanding, is amenable to harsh oxidant cleaning condition, resistance to biology
Degradation and ray radiation.It pollutes more serious raw water and is generally rich in organic matter, need periodically clear using the oxidant of higher concentration
It washes, therefore the membrane module of PVDF material becomes the preferred core element of these engineering of water treatment.Therefore, Kynoar (PVDF)
Film is widely used in the fields such as chemical industry, medicine, weaving, metallurgy, is most widely used membrane material currently on the market.And PVDF is super
Filter membrane has two as hydrophobic film in water treatment applications: 1) mass transfer driving force is high, and energy consumption is larger；This is because
Pvdf membrane has lower surface energy, and wetting ability is poor, causes water flux extremely low.2) PVDF film is easy to pollute.This is because
It not will form hydrogen bond between film surface and hydrone, so that being easy adsorbed proteins, organic matter etc. causes fouling membrane, cause film logical
Amount sharply declines, and membrane lifetime greatly shortens.For the above reasons, the application of PVDF ultrafiltration membrane has biggish limitation.But base
In other excellent performances of PVDF, it is still the main material of organic film preparation at present.In order to answer PVDF broadly
For water treatment field, carrying out hydrophilic modification to PVDF film has the modification of very important meaning PVDF ultrafiltration membrane main
It is membrane body modification, membrane surface modification.Membrane body is modified to be referred to and is modified to the matrix before film forming, it is main by being blended and altogether
It is poly- to realize.Membrane surface modification is to reach modified purpose by introducing hydrophilic radical in film surface.Membrane surface modification mainly includes
Surface coating modified, surface chemical modification, low-temperature plasma modified, the light-initiated graft modification in surface.Typical ultrafiltration fenestra
Diameter range: 5 ~ 50nm;The ultrafiltration membrane of different pore size is suitable for different applications, such as 25nm ultrafiltration membrane is suitable for routine
Water process project, bacterium, attenuation and other suspended solid impurities in main trap water.And to the material of some high COD
System needs the ultrafiltration membrane using more small-bore, to improve the rejection to dissolved organic matter.In addition, pore homogeneity is got over
The antifouling property of height, membranous system is stronger.It is super that Chinese patent (publication number :) proposes high pollution-resistant Kynoar (PVDF)
The technology of preparing of filter membrane, wherein prepared 25 ± 2nm ultrafiltration membrane most probable pore size accounting is more than 80%, thus stabilized flux ratio
High 10~the 50L/m of common PVDF ultrafiltration membrane2·h。
In addition, pvdf membrane uses external pressure type hollow fiber membrane component, external-compression type film can provide wider runner, can use
The mode that air-flow is cleaned swings film wire, reduces the influences of the factors to membrane flux such as cake layer, concentration polarization.PVDF flexibility
It is good, it is suitable for preparing external-compression type membrane component, thus, there is stronger pollutant carrying capacity, only because PVDF is unfavorable for preparing aperture
Diameter (being less than 20nm) seperation film, the main application fields of PVDF series membrane material are limited in purification of water quality.On the contrary, can prepare
The polysulfone material glass transition temperature of small-bore is high, and flexibility is poor, is suitable only for preparing inner pressed hollow-fibre membrane, runner
It is narrow, film wire cannot be made to swing by the way of air-flow scouring, the factors such as cake layer and concentration polarization can all influence membrane flux.
Composite membrane is the important method for preparing small-bore or even dense film, and the forming method of composite membrane mainly has polymer painting
It covers, interfacial polymerization, monomer catalytic polymerization, plasma polymerization, dynamic formation etc..Numerous seperation film researcher's uses is such as total
The method that mixed, copolymerization, grafting or crosslinking etc. are modified film surface or person's character enhances the hydrophily of PVDF resin.Surface changes
Property technique mainly realized by the methods of chemical surface treatment, surface grafting, surface coating.Wherein, it is surface coating modified because
Its easy to operate, significant effect, development is very fast, application field is very popular extensively.And polyvinyl alcohol (PVA) substance has height
Hydrophily, good stain resistance and film forming and become one of widely applied hydrophilic film material in the world, especially make
It is more widely studied for utilized thin film composite membranes.
Chinese patent (CN1459326 A) discloses a kind of preparation method of osmosis vaporizing compound membrane, by polyvinyl alcohol, water
Dissolution is mixed with additive and is made into casting solution, casting solution is equably scratched on ultrafiltration membrane with glass slicker, or will casting
Film liquid is laid on smooth ptfe substrate, dry film is peeled to be attached on polyacrylonitrile (PAN) counterdie forms PVA/
PAN composite membrane carries out the crosslinking of PVA separating layer using heat cross-linking or chemical crosslink technique.The invention is to porous support layer without spy
It is different to require.Chinese patent (CN104525000A) is by coating polysulfones counterdie with polyvinyl alcohol water solution, then with poly- second
Enol phosphate ammonium and the coating of glycerol mixed aqueous solution, then the aqueous solution of polyvinyl alcohol and glutaraldehyde is coated, be made compound and receive
Filter membrane.Wherein the molecular cut off of the polysulfones counterdie is 2-3 ten thousand.Chinese patent (CN104474924A) is by by polysulfones bottom
Film polyvinyl alcohol and ammonium alcohol polyvinyl phosphate mixing aqueous phase solution are handled, and are then carried out with pyromellitic trimethylsilyl chloride oil solution
Coating, drying, can be obtained polyvinyl alcohol ultrafiltration membrane.The molecular cut off of polysulfones counterdie is 5-6 ten thousand.
Summary of the invention
It is fast for flux decline of the existing polymer ultrafiltration membrane when handling the material system of high concentration impurities, be not easy it is extensive
Multiple problem, the present invention propose the composite hyperfiltration membrane that a kind of separating layer aperture is small and homogeneity is good, and the present invention is with narrow slit blade coating
Polyvinyl alcohol water solution is uniformly applied to the outer surface of basement membrane with doctor blade process, by being cross-linked to form aperture by main feature
The UF membrane layer of diameter, while PVA further being promoted more uniformly to sprawl and adhere on surface.Emphasis solves: (1) composite membrane is flat
Equal pore size control makes it can be applied to certain a kind of specific system；(2) thickness for controlling film keeps composite membrane existing good complete
Property can possess ideal flux again；(3) the narrow slit coating processes of blocking operation are convenient to industrialization amplification.
The first aspect of the invention provides:
A kind of PVA-PVDF hollow fiber ultrafiltration membrane, comprising: the hollow fiber basement membrane of PVDF material, in the appearance of basement membrane
Face is covered with separating layer made of polyvinyl alcohol is cross-linked with each other.
In one embodiment, basement membrane outer diameter is 0.3~3.0mm, 0.1~1mm of thickness；It is preferred that outer diameter is 1.0 ~ 1.3mm,
0.28 ~ 0.32mm of thickness.
In one embodiment, the average pore size of basement membrane is 20~500nm, preferably 20~35nm.
In one embodiment, 5~10nm of PVDF hollow fiber ultrafiltration membrane average pore size, molecular cut off range 50000
~200000, most probable pore size accounting is greater than 80%.
In one embodiment, 40 ~ 75 DEG C of separating layer water droplet contact angle.
In one embodiment, separating layer is to carry out cross-linking reaction by polyvinyl alcohol and crosslinking agent to obtain.
In one embodiment, include repetitive structure as shown in the formula (I) in separating layer:
(I)；
In formula, R refers to the substituted or unsubstituted alkyl containing 1~10 carbon atom.
In one embodiment, the alkyl is selected from straight chain, band branch or with cricoid alkyl.
The second aspect of the invention provides:
A kind of preparation method of PVA-PVDF hollow fiber ultrafiltration membrane, includes the following steps:
I) doughnut PVDF basement membrane is provided；
Ii) in aqueous solution of the outer surface of the doughnut PVDF basement membrane coating containing polyvinyl alcohol (PVA)；
Iii) hollow-fibre membrane for obtaining step ii) is sent into narrow slit, is scraped to the aqueous solution containing polyvinyl alcohol (PVA)
It removes, then is dried；Narrow slit diameter is greater than PVDF basement membrane diameter；
Iv) step iii) obtained in hollow-fibre membrane immerse in the solution containing crosslinking agent PVA and crosslinking agent occur
Cross-linking reaction, drying obtain PVA-PVDF hollow fiber ultrafiltration membrane.
In one embodiment, the step iii) in, the big 0.05~1mm of narrow slit diameter ratio PVDF basement membrane diameter；Again
Preferably 0.2~0.5mm.
In one embodiment, the step ii) in, the degree of polymerization of PVA is 50 in the aqueous solution of polyvinyl alcohol (PVA)
~2100, PVA alcoholysis degree are that 50~99%, PVA concentration is 0.1~5wt%.
In one embodiment, the step ii) in, the degree of polymerization of PVA is in the aqueous solution of polyvinyl alcohol (PVA)
500~1700, alcoholysis degree is that 88~99%, PVA concentration is 0.5~3 wt %.
In one embodiment, the aqueous solution of polyvinyl alcohol (PVA) needs to pre-process by deaeration, and de-aeration is flash distillation
Deaeration, de-aeration are 4~10 hours, 10~50 DEG C of deaeration.
In one embodiment, step iii) it carries out 1~3 time.
In one embodiment, 2~5vol.% of crosslinking agent is contained in the solution containing crosslinking agent, pH < 7, solvent is water.
In one embodiment, crosslinking agent is cross-link agent.
In one embodiment, in the solution containing crosslinking agent containing 2~5vol.% of crosslinking agent, 10~20vol.% of methanol,
1~2vol.% of glacial acetic acid, 1~3vol.% of sulfuric acid.
In one embodiment, the step iv) in, the temperature of cross-linking reaction is 10~50 DEG C, the film wire residence time 1
~2.5 min.
In one embodiment, the step iv) in, drying box temperature be 40~80 DEG C, the film wire residence time be 1~
5min。
The third aspect of the invention provides:
A kind of preparation facilities of PVA-PVDF hollow fiber ultrafiltration membrane, comprising:
The inside of film wire input module, film wire input module is equipped with film wire channel, is equipped in film wire input module front end convex
Wire outlet head out, Wire outlet head are connected to film wire channel；
It further include coat module, coat module is located at film wire input module front end, and the inside of coat module is equipped with cavity, out
Silk is within the cavity, and the front end of coat module offers narrow slit, and the axial direction of narrow slit and the axial direction of Wire outlet head are located at
On same straight line；PVA solution inlet is additionally provided in coat module, PVA solution inlet is connected to cavity.
Further include: wrap-up, for pulling hollow-fibre membrane to move from film wire channel to narrow slit.
Further include: there is the solution containing crosslinking agent cross-linking reaction slot, inside, is placed in the film wire export direction of narrow slit, use
In making the PVA on film wire surface crosslink reaction.
The fourth aspect of the invention provides:
Application of the PVA-PVDF hollow fiber ultrafiltration membrane in liquid filtering.
Beneficial effect
The small-bore PVA/PVDF doughnut composite hyperfiltration membrane of the knife coating preparation proposed through the invention, has
Good complete asymmetry, outer surface coat aperture very little (5~10nm) and aperture are announced narrow.Due to supporting layer structure
Continuity, film wire can bear biggish axial tension, and tensile strength can be more than 5.0MPa, since PVA and PVDF material all has
There is good flexibility, the extensibility of film wire can reach 150% or more.When the BSA solution or dextran solution characterization using 1g/L
When its contamination resistance, under 2.0 bar pressure, stabilized flux can be more than 145 L/ (m after 2 hours2Hr), with former membrane flux
It is close；And after running 5 hours, the stabilized flux of composite membrane is also maintained at 135 L/ (m2Hr), and the flux of PVDF original film exists
Under higher operating pressure, 75 L/ (m have been decayed to2·hr).Therefore, this small-bore ultrafiltration membrane is considered to have stronger anti-
Pollutant performance is suitable for the feed separation of high concentrations of solutes.
Detailed description of the invention
Fig. 1 is the knife coating preparation compound membrane process of PVA/PVDF；
Fig. 2 is narrow annular channel squeegee apparatus；
Fig. 3 is former PVDF hollow-fibre membrane section electromicroscopic photograph；
Fig. 4 is former PVDF hollow fiber membrane surface electromicroscopic photograph；
Fig. 5 is PVA/PVDF composite membrane cross-section electromicroscopic photograph；
Fig. 6 is PVA/PVDF composite film surface electromicroscopic photograph；
Fig. 7 is the graph of pore diameter distribution of former film and composite membrane；
Fig. 8 is the molecular cut off measurement curve graph of former film and composite membrane；
Fig. 9 is the flux decline curve of former film and composite membrane；
Figure 10 is the graph of pore diameter distribution for the hollow-fibre membrane being prepared in embodiment 1 and reference examples 2.
Wherein, 1, film wire input module；2, coat module；3, film wire channel；4, hollow-fibre membrane；5, Wire outlet head；6, chamber
Body；7, PVA solution inlet；8, narrow slit；9, heating sheet.
Specific embodiment
Below by specific embodiment, invention is further described in detail.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Specific skill is not specified in embodiment
Art or condition person described technology or conditions or carry out according to the literature in the art according to product description.Examination used
Production firm person is not specified in agent or instrument, and being can be with conventional products that are commercially available.
The value expressed using range format should be interpreted as not only including clearly enumerating as range in a flexible way
The numerical value of limit value, but also including covering all single numbers or subinterval in the range, like each numerical value and sub-district
Between be expressly recited out.For example, the concentration range of " about 0.1% to about 5% " should be understood as not only including clearly enumerating
4%) and subinterval (example the concentration of about 0.1% to about 5% further includes the single concentration in how (e.g., 1%, 2%, 3% and
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).Heretofore described percentage in the absence of special instructions,
Refer to weight percent.
" one embodiment " for addressing in the present specification, " another embodiment ", " embodiment " etc., refer to
In conjunction with the specific features of embodiment description, structure or it is included at least one embodiment generally described herein.
It is not centainly to refer to the same embodiment that statement of the same race, which occur, in multiple places in the description.Furthermore, it is understood that in conjunction with any
When embodiment describes a specific features, structure or feature, what is advocated is that this spy is realized in conjunction with other embodiments
Sign, structure or feature are also fallen in the application scope of the claimed.
The present invention provides a kind of PVA-PVDF hollow-fibre membrane, the hollow fiber basement membranes including PVDF material, in base
The outer surface of film is covered with separating layer made of polyvinyl alcohol is cross-linked with each other.
As the PVDF hollow-fibre membrane of basement membrane, outer diameter is 0.3~3.0mm, 0.1~1mm of thickness；It is preferred that outer diameter is
1.0 ~ 1.3mm, 0.28 ~ 0.32mm of thickness, the average pore size of basement membrane are 20~500nm, preferably 20~35nm.Because outer diameter is big
Or wall thickness it is big when, the good mechanical property of doughnut, but, when outer diameter is big or wall thickness is relatively thin, proof to external pressure ability is weaker.
After the separating layer made of covering polyvinyl alcohol and being cross-linked with each other, PVDF hollow fiber ultrafiltration membrane average pore size 5~
10nm, molecular cut off range 50000~200000, most probable pore size accounting are greater than 80%, since pore-size distribution is concentrated, right
Preferable antifouling property is shown during liquid filtering, is slowed down under flux.
Simultaneously as separating layer is that PVA is crosslinked to obtain, there is preferable hydrophily, the water droplet contact angle 40 of separating layer~
75℃。
Separating layer is to carry out cross-linking reaction by PVA and crosslinking agent to obtain, when the crosslinking agent (such as penta 2 using some aldehyde radicals
Aldehyde) when, the structure of separating layer may is that
(I)；
In formula, R refers to the substituted or unsubstituted alkyl containing 1~10 carbon atom.
In one embodiment, the alkyl is selected from straight chain, band branch or with cricoid alkyl.
The preparation method of above-mentioned PVA-PVDF film will be gathered mainly using narrow slit blade coating as main feature with doctor blade process
Vinyl alcohol aqueous solution is uniformly applied to the outer surface of basement membrane, by being cross-linked to form the UF membrane layer of small-bore, while further
PVA is promoted more uniformly to sprawl and adhere on surface.
The device of use is as shown in Figure 2, comprising: the inside of film wire input module 1, film wire input module 1 is logical equipped with film wire
Road 3 is equipped with the Wire outlet head 5 of protrusion in 1 front end of film wire input module, and Wire outlet head 5 is connected to film wire channel 3；It further include coating die
Block 2, coat module 2 are located at 1 front end of film wire input module, and the inside of coat module 2 is equipped with cavity 6, and Wire outlet head 5 is located at cavity 6
Interior, the front end of coat module 2 offers narrow slit 8, and it is straight that the axial direction of narrow slit 8 with the axial direction of Wire outlet head 5 is located at same
On line；PVA solution inlet 7 is additionally provided in coat module 2, PVA solution inlet 7 is connected to cavity 6.Further include: winding
Device, for pulling hollow-fibre membrane to move from film wire channel 3 to narrow slit 8.Further include: cross-linking reaction slot, inside have containing
The solution of crosslinking agent is placed in the film wire export direction of narrow slit 8, for making the PVA on film wire surface crosslink reaction.
In the structure, 8 diameter ratio PVDF basement membrane diameter of narrow slit is bigger, can make to be formed between narrow slit 8 and film wire tiny
On the one hand space can remove extra PVA solution, on the other hand, can also be improved the uniform program of PVA solution, at one
In embodiment, the 8 big 0.05~1mm of diameter ratio PVDF basement membrane diameter of narrow slit；It is further preferably 0.2~0.5mm.
In preparation process, PVA solution well prepared in advance and the solution containing crosslinking agent are needed.
It is that 50~99%, PVA is dense that the degree of polymerization of PVA, which is 50~2100, PVA alcoholysis degree, in the aqueous solution of polyvinyl alcohol (PVA)
Degree is 0.1~5wt%.In a preferred embodiment, in the aqueous solution of polyvinyl alcohol (PVA) PVA the degree of polymerization be 500~
1700, alcoholysis degree is that 88~99%, PVA concentration is 0.5~3 wt %, and the aqueous solution of polyvinyl alcohol (PVA) needs pre- by deaeration
Processing, de-aeration are flash distillation deaeration, and de-aeration is 4~10 hours, 10~50 DEG C of deaeration.Suitably PVA aqueous solution is dense
It spends related to the degree of polymerization, alcoholysis degree.
Contain 2~5vol.% of crosslinking agent in solution containing crosslinking agent, pH < 7, solvent is water, and crosslinking agent can be aldehyde radical
Crosslinking agent.In one embodiment, in the solution containing crosslinking agent containing 2~5vol.% of crosslinking agent, 10~20vol.% of methanol,
1~2vol.% of glacial acetic acid, 1~3vol.% of sulfuric acid.
Preparation process is:
First hollow-fibre membrane 4 is successively passed through from film wire channel 3, Wire outlet head 5, cavity 6, narrow slit 8, then one will be pierced by
End is fixed on wrap-up, and after being pulled, PVDF hollow fiber film thread can sequentially pass through above-mentioned channel.At this point, from PVA
PVA solution is added in solution inlet 7, after solution enters cavity 6, the outer surface of the hollow-fibre membrane 4 of movement can be covered in, then
After travelling forward, the predation of narrow slit 8 will receive, most of PVA solution of outer surface is struck off, it is hollow after being removed in narrow slit 8
The surface of tunica fibrosa 4 only remaining one layer of thin and uniform PVA solution layer, after being air-dried using one section, makes film wire surface
Moisture, after solvent removal, then film wire is placed in the solution containing crosslinking agent and carries out cross-linking reaction, make between PVA molecule into
Row crosslinking, forms separating layer.After PVA reaction, hollow-fibre membrane obtains PVA/PVDF composite hollow fiber membrane by baking oven.?
In one preferred embodiment, in the surrounding of narrow slit 8, it is additionally provided with heating sheet 9, effect is after striking off PVA solution hollow
Tunica fibrosa surface formed thin layer when, just progress pre-add heated drying, remove the solvent in PVA layers faster, make PVA surface more
Reach stable, uniform state fastly, fenestra can be made to be more evenly distributed.
Characterization test:
1, using the microstructure of electron microscope (SEM) characterization of membrane；
2, characterize its contamination resistance using 1g/L dextran solution, condition is: 2.0 bar operating pressures, filtering 2 are small
When after measure flux.
3, gel chromatography molecular cut off is passed through as standard using PEG solution.
Embodiment 1
Selecting 20 ± 2nm ultrafiltration membrane most probable pore size accounting is more than that 80% PVDF hollow-fibre membrane is as basement membrane outer diameter
1.0mm, thickness 0.28mm.The aqueous solution of the polyvinyl alcohol of configuration quality concentration 0.5%, warming while stirring, until 90 DEG C of left sides
It is right.2h is maintained at this temperature, stops heating, is cooled to room temperature, and is transferred to deaeration in 50 DEG C of Debubbling tank after dissolution completely, is obtained
Poly-vinyl alcohol solution, by metering pump by coating liquid indentation, PVA solution inlet 7, meanwhile, basement membrane penetrates wire vent from horizontal direction
First 5.In cavity 6, after membrane surface contacts PVA coating liquid, basement membrane is pulled out from narrow annular channel 8, and 8 diameter of narrow slit compares doughnut
The big 0.5mm of film diameter improves the uniformity of coat, promotes moisture evaporation.Coating is repeated 3 times with drying process.After coating
Basement membrane immerses crosslinker solution, in the solution containing crosslinking agent containing crosslinking agent 2vol.%, methanol 10vol.%, glacial acetic acid 1vol.%,
Sulfuric acid 1vol.%, remaining is water, and temperature 50 C, film wire is in reaction chamber residence time 2min.After cross-linking reaction, film wire penetrates dry
Dry case, drying box temperature are 50 DEG C, and the film wire residence time is 1min.Finally by dry PVA/PVDF composite hollow fiber membrane
It is wound by up- coiler.
Embodiment 2
Select 20 ± 2nm ultrafiltration membrane most probable pore size accounting be more than 80% PVDF hollow-fibre membrane as basement membrane, outer diameter is
1.3mm, thickness 0.32mm.The aqueous solution of the polyvinyl alcohol of configuration quality concentration 2%, warming while stirring, until 90 DEG C or so.
2h is maintained at this temperature, stops heating, is cooled to room temperature, and is transferred to deaeration in 50 DEG C of Debubbling tank after dissolution completely, is gathered
Glycohol solution, by metering pump by coating liquid indentation, PVA solution inlet 7, meanwhile, basement membrane penetrates Wire outlet head from horizontal direction
5.In cavity 6, after membrane surface contacts PVA coating liquid, basement membrane is pulled out from narrow annular channel 8, and 8 diameter of narrow slit compares hollow-fibre membrane
The big 0.3mm of diameter improves the uniformity of coat, promotes moisture evaporation.Coating is repeated 3 times with drying process.Base after coating
Film immerses crosslinker solution, contains crosslinking agent 5vol.%, methanol 20vol.%, glacial acetic acid 2vol.%, sulphur in the solution containing crosslinking agent
Sour 3vol.%, remaining is water, and temperature 50 C, film wire is in reaction chamber residence time 2min.After cross-linking reaction, film wire penetrates drying
Case, drying box temperature are 50 DEG C, and the film wire residence time is 1min.Finally by dry PVA/PVAF composite hollow fiber membrane by
Up- coiler winding.
Embodiment 3
Select 20 ± 2nm ultrafiltration membrane most probable pore size accounting be more than 80% PVDF hollow-fibre membrane as basement membrane, outer diameter is
1.3mm, thickness 0.32mm.The aqueous solution of the polyvinyl alcohol of configuration quality concentration 2%, warming while stirring, until 90 DEG C or so.
2h is maintained at this temperature, stops heating, is cooled to room temperature, and is transferred to deaeration in 50 DEG C of Debubbling tank after dissolution completely, is gathered
Glycohol solution, by metering pump by coating liquid indentation, PVA solution inlet 7, meanwhile, basement membrane penetrates Wire outlet head from horizontal direction
5.In cavity 6, after membrane surface contacts PVA coating liquid, basement membrane is pulled out from narrow annular channel 8, and 8 diameter of narrow slit compares hollow-fibre membrane
The big 0.4mm of diameter improves the uniformity of coat, promotes moisture evaporation.Coating is repeated 3 times with drying process.Base after coating
Film immerses crosslinker solution, in the solution containing crosslinking agent containing crosslinking agent 4vol.%, methanol 15vol.%, glacial acetic acid 1.5vol.%,
Sulfuric acid 2vol.%, remaining is water, and 40 DEG C of temperature, film wire is in reaction chamber residence time 1.5min.After cross-linking reaction, film wire penetrates dry
Dry case, drying box temperature are 50 DEG C, and the film wire residence time is 1min.Finally by dry PVA/PVAF composite hollow fiber membrane
It is wound by up- coiler.
Embodiment 4
Select 20 ± 2nm ultrafiltration membrane most probable pore size accounting be more than 80% PVDF hollow-fibre membrane as basement membrane, outer diameter is
1.3mm, thickness 0.32mm.The aqueous solution of the polyvinyl alcohol of configuration quality concentration 2%, warming while stirring, until 90 DEG C or so.
2h is maintained at this temperature, stops heating, is cooled to room temperature, and is transferred to deaeration in 50 DEG C of Debubbling tank after dissolution completely, is gathered
Glycohol solution, by metering pump by coating liquid indentation, PVA solution inlet 7, meanwhile, basement membrane penetrates Wire outlet head from horizontal direction
5.In cavity 6, after membrane surface contacts PVA coating liquid, basement membrane is pulled out from narrow annular channel 8, and 8 diameter of narrow slit compares hollow-fibre membrane
The big 0.4mm of diameter, the outer periphery of narrow slit 8 are additionally provided with heating sheet 9, and heating sheet 9 controls its temperature at 55 DEG C, improves coat
The uniformity, promote moisture evaporation.Coating is repeated 3 times with drying process.Basement membrane after coating immerses crosslinker solution, containing crosslinking
Contain crosslinking agent 4vol.%, methanol 15vol.%, glacial acetic acid 1.5vol.%, sulfuric acid 2vol.% in the solution of agent, remaining is water, temperature
40 DEG C of degree, film wire is in reaction chamber residence time 1.5min.After cross-linking reaction, film wire penetrates drying box, and drying box temperature is 50 DEG C,
The film wire residence time is 1min.Finally wound by dry PVA/PVAF composite hollow fiber membrane by up- coiler.
Reference examples 1
Using the PVDF basement membrane in embodiment 1 as control.
Reference examples 2
Difference with embodiment 1 is that PVA solution is not coated by narrow slit 8, and it is molten that hollow-fibre membrane is immersed in PVA
In liquid, then carries out cross-linking reaction and obtain.
It such as Figure 10, is not coated by narrow slit 8, pore size distribution is uneven, is coated by narrow slit 8, even aperture distribution, and collect
Stablize in 10nm or so in middle aperture.
Characterization test
Embodiment 1 is compared with reference examples 1, by Fig. 3,4 and Fig. 5,6 as can be seen that composite film surface has composite layer.Pass through
Fig. 7 can be seen that most probable pore size 9nm, and accounting 80% or so has the advantages that pore-size distribution is narrow.As seen in Figure 8, it makes
The molecular cut off of standby PVA-PVDF film is 60000 or so.As shown in figure 9, anti-when characterizing it using 1g/L dextran solution
When pollution capacity, under 2.0 bar pressure, stabilized flux can be more than 145 L/ (m after 2 hours2Hr), close with former membrane flux；
And after running 5 hours, the stabilized flux of composite membrane is also maintained at 135 L/ (m2Hr), and the flux of PVDF original film is higher
Under operating pressure, 75 L/ (m have been decayed to2·hr)。
The characterization result for the hollow-fibre membrane that the above various embodiments and reference examples are prepared is summarized as follows:
As can be seen from the table, PVA-PVDF film prepared by the present invention has preferable strainability.
Claims (4)
1. the preparation facilities of PVA-PVDF hollow fiber ultrafiltration membrane is for reducing the application in ultrafiltration membrane pore-size distribution, special
Sign is, includes the following steps:
I) doughnut PVDF basement membrane is provided；
Ii) aqueous solution containing polyvinyl alcohol is coated in the outer surface of doughnut PVDF basement membrane；
Iii) hollow-fibre membrane for obtaining step ii) is sent into narrow slit, is struck off to the aqueous solution containing polyvinyl alcohol, then carry out
It is dry；Narrow slit diameter is greater than PVDF basement membrane diameter；Big 0.05~the 1mm of narrow slit diameter ratio PVDF basement membrane diameter；
Iv) step iii) obtained in hollow-fibre membrane immerse in the solution containing crosslinking agent and send out polyvinyl alcohol and crosslinking agent
Raw cross-linking reaction, drying obtain PVA-PVDF hollow fiber ultrafiltration membrane；
The preparation facilities of the PVA-PVDF hollow fiber ultrafiltration membrane includes:
The inside of film wire input module, film wire input module is equipped with film wire channel, is equipped with protrusion in film wire input module front end
Wire outlet head, Wire outlet head are connected to film wire channel；
It further include coat module, coat module is located at film wire input module front end, and the inside of coat module is equipped with cavity, Wire outlet head
Within the cavity, the front end of coat module offers narrow slit, and the axial direction of narrow slit and the axial direction of Wire outlet head are located at same
On straight line；PVA solution inlet is additionally provided in coat module, PVA solution inlet is connected to cavity；
Further include: wrap-up, for pulling hollow-fibre membrane to move from film wire channel to narrow slit；
Further include: there is the solution containing crosslinking agent cross-linking reaction slot, inside, the film wire export direction of narrow slit is placed in, for making
The PVA on film wire surface crosslinks reaction.
2. application according to claim 1, which is characterized in that the step ii) in, in the aqueous solution of polyvinyl alcohol
The degree of polymerization of PVA is 50~2100, and polyvinyl alcohol alcoholysis degree is that 50~99%, PVA concentration is 0.1~5wt%；The water of polyvinyl alcohol
Solution needs to pre-process by deaeration, and de-aeration is flash distillation deaeration, and de-aeration is 4~10 hours, 10~50 DEG C of deaeration.
3. application according to claim 1, which is characterized in that step iii) it carries out 1~3 time.
4. application according to claim 1, which is characterized in that solvent is water in the solution containing crosslinking agent；Crosslinking agent is
Cross-link agent；In solution containing crosslinking agent containing 2~5vol.% of crosslinking agent, 10~20vol.% of methanol, glacial acetic acid 1~
2vol.%, 1~3vol.% of sulfuric acid；The step iv) in, drying box temperature be 40~80 DEG C, the film wire residence time be 1~
5min。
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| EP4168164A4 (en) * | 2020-06-23 | 2024-08-07 | Commw Scient Ind Res Org | Dual-layer membrane |
| CN111729519A (en) * | 2020-07-06 | 2020-10-02 | 广东石油化工学院 | Titanium dioxide/polyvinylidene fluoride electrostatic spinning hydrophilic film material and preparation method and application thereof |
| CN115105960B (en) * | 2021-03-22 | 2023-10-31 | 国家能源投资集团有限责任公司 | Repairing method of waste reverse osmosis membrane element |
| CN113230904B (en) * | 2021-04-28 | 2022-04-05 | 利得膜(北京)新材料技术有限公司 | Continuous modification equipment and hydrophilic modification method for e-PTFE hollow fiber membrane yarn |
| CN114272773B (en) * | 2021-12-24 | 2023-04-28 | 中化(宁波)润沃膜科技有限公司 | High-strength high-flux porous nanofiltration membrane and preparation method thereof |
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