CN105396470B - Hollow fiber compound nanofiltration membrane and preparation method thereof - Google Patents
Hollow fiber compound nanofiltration membrane and preparation method thereof Download PDFInfo
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- CN105396470B CN105396470B CN201510918982.7A CN201510918982A CN105396470B CN 105396470 B CN105396470 B CN 105396470B CN 201510918982 A CN201510918982 A CN 201510918982A CN 105396470 B CN105396470 B CN 105396470B
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- hollow fiber
- membrane
- water
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- fiber compound
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- 239000012528 membrane Substances 0.000 title claims abstract description 124
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 92
- 150000001875 compounds Chemical class 0.000 title claims abstract description 41
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 89
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 57
- 239000007788 liquid Substances 0.000 claims abstract description 53
- 238000005266 casting Methods 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 230000001112 coagulating effect Effects 0.000 claims abstract description 27
- 239000012298 atmosphere Substances 0.000 claims abstract description 23
- 238000009987 spinning Methods 0.000 claims abstract description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940113088 dimethylacetamide Drugs 0.000 claims abstract description 14
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000012071 phase Substances 0.000 claims description 27
- 239000000835 fiber Substances 0.000 claims description 18
- 239000008346 aqueous phase Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229920002492 poly(sulfone) Polymers 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 235000012489 doughnuts Nutrition 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229920006393 polyether sulfone Polymers 0.000 claims description 9
- -1 m-aminophenyl Chemical group 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical compound NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 11
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 70
- 238000000034 method Methods 0.000 description 15
- 230000004907 flux Effects 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 8
- 238000005265 energy consumption Methods 0.000 description 7
- 238000007664 blowing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 235000004279 alanine Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical class OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000004885 piperazines Chemical class 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical class NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000013040 bath agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a kind of preparation method of hollow fiber compound nanofiltration membrane, comprise the following steps：Using casting solution as shell liquid, shell liquid and core liquid are extruded into outside coagulating bath by spinning head and obtain hollow fiber ultrafiltration membrane；Casting solution is calculated in mass percent including 15~30% filmogen, 2~10% hydrophilic polymer, 5~20% poor solvent and 40~78% solvent；The distance for entering water space of spinning head is 5~30cm, the atmosphere for entering water space is the mixed gas or air of at least one of alcohol vapour, N-methyl pyrrolidones steam, dimethyl acetamide steam and dimethyl sulfoxide (DMSO) steam with air, and the atmosphere relative humidity for entering water space is 30~80%；Hollow fiber compound nanofiltration membrane is obtained by interfacial polymerization preparative separation layer in the outer surface of hollow fiber ultrafiltration membrane.Obtained hollow fiber compound nanofiltration membrane mechanical strength is good, and permeance property is good under relatively low driving pressure, and driving pressure is small, and separative efficiency is high.Present invention also offers a kind of hollow fiber compound nanofiltration membrane.
Description
Technical field
The present invention relates to separation technical field of membrane, more particularly to a kind of hollow fiber compound nanofiltration membrane and its preparation side
Method.
Background technology
Membrane separation technique is selected mixing liquid using pressure as driving force by membrane aperture size and surface compatibility
Property separation.Compared with traditional separation method, membrane separation technique has selectivity height, energy consumption is low, separative efficiency is high and is easy to implement
The advantages that automation.
It is two kinds of common preparative separation membrane materials that thermally induced phase separation (hot method) and poor solvent, which cause phase separation method (wet method),
The method of material.Wherein, wet spinning preparative separation membrane process is simple, and process flexible is controllable, and energy consumption is low, industrially using wider
It is general.But seperation film prepared by wet method is generally uneven macroporous structure, and this structure can cause film mechanical strength, permeance property
It is low with cutoff performance.
The molecular cut off of NF membrane is 200~2000, and it is to monovalent ion and high valence ion (more than divalence and divalence
Ion) there is obvious retention difference, separating property is between reverse osmosis membrane and milipore filter.NF membrane by aperture screening and
The double action of road south charge effect realizes the separation of medium, thus compared with reverse osmosis membrane, NF membrane has lower driving
The separative efficiency of pressure and Geng Gao, and compared with milipore filter, NF membrane has smaller more accurately molecular cut off.On the market
NF membrane product is mostly the flat board rolling NF membrane using polysulfones/non-woven fabrics as supporting layer, and rolling NF membrane encapsulation process is complicated,
Easily knot dirt, anti-pollution ability is high to inflow requirement, and driving pressure is more than 0.7MPa, high energy consumption.
The content of the invention
Based on this, it is necessary to provide that a kind of mechanical strength is good, driving pressure is small, separative efficiency is high doughnut is compound to be received
Filter membrane and preparation method thereof.
A kind of preparation method of hollow fiber compound nanofiltration membrane, comprises the following steps：
Using the casting solution as shell liquid, the shell liquid and core liquid are extruded by the spinning head of hollow-fibre membrane spinning-drawing machine, entered
In the outside coagulating bath for entering hollow-fibre membrane spinning-drawing machine, hollow fiber ultrafiltration membrane is obtained；Wherein, wherein the casting solution is with quality
Percentage meter include 15~30% filmogen, 2~10% hydrophilic polymer, 5~20% poor solvent and 40~
78% solvent；The core liquid is in N-methyl pyrrolidones, dimethylformamide, dimethyl acetamide and dimethyl sulfoxide (DMSO)
At least one and mixed liquor of water, or the core liquid is water；The distance for entering water space of the spinning head is 5~30cm, institute
The atmosphere stated into water space is that alcohol vapour, N-methyl pyrrolidones steam, dimethyl acetamide steam and dimethyl sulfoxide (DMSO) steam
The mixed gas of at least one of vapour and air, or it is described enter water space atmosphere be air, it is described enter water space atmosphere
Relative humidity is enclosed for 30~80%；And
The hollow fiber ultrafiltration membrane is placed in aqueous phase solution and soaked 5~20 minutes, it is molten that taking-up is placed in oil phase after drying
Interface polymerization reaction is carried out in liquid and forms separating layer in the outer surface of the hollow fiber ultrafiltration membrane, the reaction time is 2~60s,
Take out and be cleaned and dried, under 70~100 DEG C of constant temperature, carry out heat treatment 10~50 minutes, obtain the doughnut and answer
Close NF membrane.
The preparation method of above-mentioned hollow fiber compound nanofiltration membrane, hollow fiber ultrafiltration membrane is prepared for using wet method, then in
The outer surface of fibre ultrafiltration film is prepared for separating layer using interfacial polymerization method in situ, obtains hollow fiber compound nanofiltration membrane.
Obtained hollow fiber compound nanofiltration membrane mechanical strength is good, and permeance property is good under relatively low driving pressure.With flat board rolling
NF membrane is compared, and obtained hollow fiber compound nanofiltration membrane is big with filling area, and driving pressure is small, and separative efficiency is high and is not easy
The advantages that incrustation.
In one of the embodiments, the core liquid and the temperature difference of the outside coagulating bath are 25~50 DEG C.
In one of the embodiments, the percent by volume of air described in the mixed gas is 75%~95%.
In one of the embodiments, the mass percent of water described in the mixed liquor is 30%~70%.
In one of the embodiments, coagulator is N-methyl pyrrolidones, dimethylacetamide in the outside coagulating bath
Solidified in the mixed liquor of at least one of amine and dimethyl sulfoxide (DMSO), dimethylformamide and water, or the outside coagulating bath
Agent is water.
In one of the embodiments, the poor solvent is in water, ethanol, glycerine, isopropanol, normal propyl alcohol and glacial acetic acid
At least one；The solvent is dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE and phosphorus
At least one of sour trimethyl.
In one of the embodiments, the filmogen is polyether sulfone, polysulfones, polyvinyl chloride, Kynoar and gathered
At least one of acrylonitrile；The hydrophilic polymer is SPSF, sulfonated polyether sulfone, polyvinyl alcohol, chitosan, amino
Change at least one of polysulfones, carboxylated polysulfones, carboxymethyl cellulose, polyethylene glycol and polyvinylpyrrolidone.
In one of the embodiments, the aqueous phase solution is in terms of mass fraction including 0.5~5% polyamino list
Body, 0.1~0.5% surfactant and 94.5~99.4% water, the oil-phase solution are mass fraction 0.01~0.2%
Polynary solution of acid chloride, wherein the solvent of the polynary solution of acid chloride is at least one of n-hexane and toluene.
In one of the embodiments, the polyamino monomer be piperazine, polyethyleneimine, triaminobenzene, to diaminourea
At least one of benzene and m-aminophenyl；The surfactant is polysorbas20, Span 10, dodecyl sodium sulfate, stearic acid
At least one of glyceride, dodecyl alanine, neopelex and ferric tri-dodecanesulfonate；It is described polynary
Acyl chlorides is at least one of trimesoyl chloride, terephthalyl chloride and isophthaloyl chloride.
A kind of hollow fiber compound nanofiltration membrane, it is made using the preparation method of above-mentioned hollow fiber compound nanofiltration membrane.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method of the hollow fiber compound nanofiltration membrane of an embodiment；
Fig. 2 is that the pure water flux for the hollow fiber ultrafiltration membrane that embodiment 1 and comparative example obtain changes with time pass
System's figure.
Embodiment
For the ease of understanding the present invention, the present invention is described more fully below with reference to relevant drawings.In accompanying drawing
Give the preferred embodiment of the present invention.But the present invention can realize in many different forms, however it is not limited to herein
Described embodiment.On the contrary, the purpose for providing these embodiments is to make the understanding to the disclosure more saturating
It is thorough comprehensive.
Reference picture 1, the preparation method of the hollow fiber compound nanofiltration membrane of an embodiment, comprises the following steps.
Step S100：Prepare casting solution；Wherein, casting solution is calculated in mass percent including 15~30% filmogen, and 2
~10% hydrophilic polymer, 5~20% poor solvent and 40~78% solvent.
Wherein, poor solvent (nonsolvent) refers to dissolve for the filmogen in casting solution or solubility property
Bad solvent, on the contrary what can be dissolved each other with the filmogen in casting solution is then solvent.
In one of the embodiments, the step of preparing casting solution be specially：By filmogen, hydrophilic polymer, no
Good solvent and solvent mixing, dissolving deaeration, obtain casting solution.
Preferably, filmogen is at least one in polyether sulfone, polysulfones, polyvinyl chloride, Kynoar and polyacrylonitrile
Kind.
Hydrophilic polymer plays a part of pore former and conditioning agent in casting solution, to adjust the hollow of casting solution formation
The microcellular structure and pore-size distribution of fiber ultrafiltration membrane, it is hollow so as to be improved in the mechanical strength for ensureing hollow fiber ultrafiltration membrane simultaneously
The hydrophily and water flux of fiber ultrafiltration membrane.
Preferably, hydrophilic polymer be SPSF, sulfonated polyether sulfone, chitosan, polyvinyl alcohol, amination polysulfones,
At least one of carboxylated polysulfones, carboxymethyl cellulose, polyethylene glycol and polyvinylpyrrolidone.It is furthermore preferred that poly- second two
The molecular weight of alcohol is 5000~20000.It is furthermore preferred that polyvinylpyrrolidone is the polyvinylpyrrolidine that K values are 30,60 or 90
Ketone, wherein different K values represent the average molecular weight range of corresponding polyvinylpyrrolidone respectively.
The component of poor solvent and its ratio form the spongy micropore knot of gradient for hollow fiber ultrafiltration membrane in casting solution
Structure and pore-size distribution play an important role.Preferably, poor solvent is in water, ethanol, glycerine, isopropanol, normal propyl alcohol and glacial acetic acid
At least one.Preferably, solvent be dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE and
At least one of trimethyl phosphate.
Step S200：Using casting solution as shell liquid, shell liquid and core liquid are extruded by the spinning head of hollow-fibre membrane spinning-drawing machine, entered
In the outside coagulating bath for entering hollow-fibre membrane spinning-drawing machine, hollow fiber ultrafiltration membrane is obtained.
Using hollow-fibre membrane spinning-drawing machine, enter outside by an intersegmental gap after casting solution and core liquid are extruded by spinning head
Coagulating bath, the gap are into water space.In the present embodiment, the atmosphere for entering water space is alcohol vapour, N-methyl pyrrolidones
The mixed gas of at least one of steam, dimethyl acetamide steam and dimethyl sulfoxide (DMSO) steam with air, or enter between water
The atmosphere of gap is air.The atmosphere relative humidity for entering water space is 30~80%.If the phase of the atmosphere into water space is not controlled
To humidity, the atmosphere for entering water space contains more steam, and steam is poor solvent, and casting solution enters water space into high humility
Atmosphere and moisture, its surface can rapid split-phase formation big holes；And by controlling the relative humidity of the atmosphere into water space
Or the steam in air is substituted for solvent vapo(u)r, casting solution is entered into water space atmosphere, its surface will not rapid split-phase, casting
Solvent evaporates slow split-phase in atmosphere in film liquid makes the surface of hollow fiber ultrafiltration membrane form small and fine and close mesh.
By adjusting the distance into water space, atmosphere and atmosphere relative humidity, casting solution and core liquid can be made to enter outside coagulate
Gu double diffusion occurs in bath：Coagulator of the solvent into coagulating bath diffusion and coagulating bath in casting solution spreads to casting solution.
With the progress of double diffusion, the composition inside casting solution constantly changes, and solvent and hydrophilic polymer extract from casting solution,
Solidification precipitating obtains hollow fiber ultrafiltration membrane.
Preferably, when the atmosphere for entering water space is mixed gas, in mixed gas the percent by volume of air be 75%~
95%.
Preferably, core liquid and the temperature difference of outside coagulating bath are 25~50 DEG C.Temperature differences effect casting solution split-phase film forming mistake
Solvent and the exchange rate of coagulating bath in journey, and then the inside pore size and pore-size distribution of hollow fiber ultrafiltration membrane are influenceed, temperature
Spending low surface exchange, first split-phase forms aperture rapidly, otherwise forms macropore, can control surfaces externally and internally film split-phase fast by temperature difference
Degree, so as to promote bore diameter gradient to be distributed.It is furthermore preferred that the temperature of outside coagulating bath is 25 DEG C of room temperature.
Preferably, coagulator is N-methyl pyrrolidones, dimethyl acetamide and dimethyl sulfoxide (DMSO), two in outside coagulating bath
Coagulator is water in the mixed liquor of at least one of NMF and water, or outside coagulating bath.It is it is furthermore preferred that outside solidifying
Admittedly the coagulator bathed is water.
Preferably, core liquid is in N-methyl pyrrolidones, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO)
At least one and mixed liquor of water, or core liquid is water.It is furthermore preferred that when core liquid is mixed liquor, the mass fraction of mixed liquor reclaimed water
For 30%~70%.
Preferably, after hollow fiber ultrafiltration membrane is cleaned and dried in water, then step S300 is carried out.Specifically, hollow fibre
The drying condition of dimension milipore filter is to dry in the shade.
In one of the embodiments, the ratio between internal-and external diameter of hollow fiber ultrafiltration membrane is 1:1.1~1.5, doughnut surpasses
The thickness of filter membrane is 50~100 microns.
Obtained hollow fiber ultrafiltration membrane, molecular cut off are 10000~30000, and hollow fiber ultrafiltration membrane can be low
Driving pressure under there is higher pure water flux.Its when driving pressure is less than 0.05MPa pure water flux up to 100LMH with
On.Wherein, LMH is L/ (m2H), the liter number of every square metre of liquid passed through per hour is represented.
The diffusion of casting solution can be slowed down by entering water space and core liquid in step S200, avoided the formation of uneven macroporous structure and led
Cause the mechanical strength of hollow fiber ultrafiltration membrane low, obtain that aperture is suitable and the hollow fiber ultrafiltration membrane of uniform pore diameter change, it does not have
There is internal stress defect point, mechanical strength is good, has good resistance to pressure, aperture size and shape under the effect of pressure in a big way
Shape being capable of stable for extended periods of time.And the radial direction section structure of hollow fiber ultrafiltration membrane is unsymmetric structure, hollow fiber ultrafiltration membrane
Aperture increased successively by outer layer to internal layer, therefore can greatly reduce filtration resistance, be realized under low driving pressure high
Effect filtering.
Step S300：In the outer surface of hollow fiber ultrafiltration membrane by interfacial polymerization method preparative separation layer in situ, obtain
Hollow fiber compound nanofiltration membrane.Wherein, separating layer is located at the outer surface of hollow fiber ultrafiltration membrane.
In one of the embodiments, step S300 is specially：Hollow fiber ultrafiltration membrane is placed in aqueous phase solution and soaks 5
~20 minutes, taking-up was placed in progress interface polymerization reaction in oil-phase solution and formed in the outer surface of hollow fiber ultrafiltration membrane after drying
Separating layer, reaction time are 2~60s, take out and are cleaned and dried, under 70~100 DEG C of constant temperature, carry out heat treatment 10~50
Minute, obtain hollow fiber compound nanofiltration membrane.Because the mechanical strength of hollow fiber ultrafiltration membrane is good, the micropore in heat treatment process
Degree of caving in is small, and the water flux of obtained hollow fiber compound nanofiltration membrane is big.
Preferably, the temperature that hollow fiber ultrafiltration membrane is handled in aqueous phase solution and oil-phase solution is room temperature.It is excellent
Choosing, hollow fiber ultrafiltration membrane is taken out after being soaked in aqueous phase solution, and dry condition is to blow away hollow fibre using compressed air
Tie up the unnecessary liquid of ultrafiltration membrane surface.Preferably, hollow fiber ultrafiltration membrane takes after carrying out interface polymerization reaction in oil-phase solution
Go out, dry condition is to dry in the shade.
Preferably, separating layer is PA membrane or polyimide film.Preferably, the thickness of separating layer is received for 30~70
Rice.
Preferably, aqueous phase solution is in terms of mass fraction, including 0.5~5% polyamino monomer, 0.1~0.5% surface
Activating agent and 94.5~99.4% water.It is furthermore preferred that polyamino monomer be piperazine, polyethyleneimine, triaminobenzene, to diamino
At least one of base benzene and m-aminophenyl.It is furthermore preferred that surfactant be polysorbas20, Span 10, dodecyl sodium sulfate,
At least one of tristerin, dodecyl alanine, neopelex and ferric tri-dodecanesulfonate.
Preferably, oil-phase solution is the polynary solution of acid chloride of mass fraction 0.01~0.2%, wherein polynary solution of acid chloride
Solute is polynary acyl chlorides, and the solvent of polynary solution of acid chloride is at least one of n-hexane and toluene.It is furthermore preferred that polynary acyl chlorides
For at least one of trimesoyl chloride, terephthalyl chloride and isophthaloyl chloride.
Separating layer even compact made from step S300, there is certain positive charge more than needed, can retain high valence ion and
Pass through monovalent ion.
The preparation method of above-mentioned hollow fiber compound nanofiltration membrane, hollow fiber ultrafiltration membrane is prepared for using wet method, then in
The outer surface of fibre ultrafiltration film is prepared for separating layer using interfacial polymerization method in situ, obtains hollow fiber compound nanofiltration membrane.
Obtained hollow fiber compound nanofiltration membrane, using separating layer as retention layer, is cut using hollow fiber ultrafiltration membrane as supporting layer
Layer is stayed to be combined closely with supporting layer.Changed from retention layer aperture size into the radial direction section structure of supporting layer, retain layer
Even compact aperture is smaller, is trapped material and forms cake layer in separation layer surface, permeating medium is by retention layer entrance aperture
The hollow fiber ultrafiltration membrane gradually increased, flow resistance are gradually reduced, and so as to accelerate separating rate, reduce filtering energy consumption,
Improve the service life of hollow fiber compound nanofiltration membrane.
Obtained hollow fiber compound nanofiltration membrane tool intensity is good, and permeance property is good under relatively low driving pressure,
The lower pure water fluxs of 0.25MPa or so reach 30LMH.Further, since the driving pressure that hollow fiber compound nanofiltration membrane needs is low, dividing
The cake layer short texture that absciss layer surface is formed, also can effectively avoid the increase of filtration resistance, and cake layer is easily rinsed
Totally, effectively avoiding aperture from blocking causes water flux to decline, and improves anti-clogging and the use of hollow fiber compound nanofiltration membrane
Life-span.Compared with flat board rolling NF membrane, obtained hollow fiber compound nanofiltration membrane is big with filling area, and mechanical strength is good,
The advantages that driving pressure is small, and separative efficiency is high and is not easy incrustation.
Present invention also offers doughnut made from a kind of preparation method using above-mentioned hollow fiber compound nanofiltration membrane
Composite nanometer filtering film.
Above-mentioned hollow fiber compound nanofiltration membrane, small organic molecule and high valence ion that can be in effectively catching water, low
Energy consumption under by simple water cleaning systems clean water is produced using industry water or municipal tap water.It can be applied to family expenses end
Small organic molecule, heavy metal ion and the unnecessary calcium ions and magnesium ions removed on water purification product in drinking water are held, are that people are real-time
The drinking water of cleaning health is provided.Reverse osmosis membrane that the above-mentioned alternative part existing product of hollow fiber compound nanofiltration membrane uses or
Person's milipore filter, there is wide market application foreground.
Specific examples below.
Embodiment 1
By 18g polyether sulfones, 5g sulfonated polyether sulfones, 5g water and the mixing of 72g dimethyl acetamides, stirring 24h dissolvings, Ran Houjing
Put deaeration and obtain the casting solution of homogeneous transparent.
The distance that setting spinning head enters water space is 10cm, and the atmosphere for being set into water space is dimethyl sulfoxide (DMSO) steam and sky
The percent by volume of the mixed gas of gas, wherein air is 75%, and the relative humidity of mixed gas is 40%.Core liquid is 50 DEG C
Mass fraction is 30% N-methyl pyrrolidone solution, the coagulator using 25 DEG C of water as outside coagulating bath.Using hollow fibre
Film spinning-drawing machine is tieed up, using casting solution as shell liquid, shell liquid and core liquid are extruded by spinning head, into outside coagulating bath, obtained hollow
Fiber ultrafiltration membrane.Dried in the shade after hollow fiber ultrafiltration membrane is rinsed into 24h in water.
By 5g piperazines, 0.2g dodecyl sodium sulfates, 94.8g water is hybridly prepared into aqueous phase solution.By the equal benzene trigalloyls of 0.05g
Chlorine, 0.02g isophthaloyl chlorides are dissolved in 99.95g n-hexanes and are configured to oil-phase solution.It is molten that hollow fiber ultrafiltration membrane is placed in aqueous phase
Soaked 10 minutes in liquid, be placed in progress interface polymerization reaction 30s in oil-phase solution after then taking out the liquid for blowing surface off, take out
It is cleaned and dried, is placed in baking oven under 100 DEG C of constant temperature and carries out heat treatment 45 minutes, obtain doughnut composite nanometer filter
Film.
Embodiment 2
By 15g Kynoar, 10g polyvinylpyrrolidones (K30), 20g glycerine and 55g N-methyl pyrrolidones mix
Close, be heated to 80 DEG C of stirring and dissolvings, deaeration obtains casting solution.
It is 30cm to set spinning head to enter the distance of water space, be set into the atmosphere of water space for dimethyl acetamide steam and
The percent by volume of the mixed gas of air, wherein air is 85%, and the relative humidity of mixed gas is 80%.Core liquid is 50 DEG C
Mass fraction be 50% dimethylformamide in water, the coagulator using 25 DEG C of water as outside coagulating bath.Using hollow fibre
Film spinning-drawing machine is tieed up, using casting solution as shell liquid, shell liquid and core liquid are extruded by spinning head, into outside coagulating bath, obtained hollow
Fiber ultrafiltration membrane.Dried in the shade after hollow fiber ultrafiltration membrane is rinsed into 24h in water.
By 5g polyethyleneimines, 0.5g Spans 10 and 94.5g water are hybridly prepared into aqueous phase solution.By the equal benzene trigalloyls of 0.03g
Chlorine, 0.07g isophthaloyl chlorides and 99.9g toluene are configured to oil-phase solution.Hollow fiber ultrafiltration membrane is placed in aqueous phase solution and soaked
Bubble 5 minutes, progress interface polymerization reaction 60s in oil-phase solution is placed in after then taking out the liquid for blowing surface off, it is dry to take out cleaning
It is dry, it is placed in baking oven under 70 DEG C of constant temperature and carries out heat treatment 50 minutes, obtains hollow fiber compound nanofiltration membrane.
Embodiment 3
By 15g polyacrylonitrile, 2g polyvinyl alcohol, 10g glycerine and the mixing of 73g dimethyl sulfoxide (DMSO)s, it is molten to be heated to 60 DEG C of stirrings
Solution, deaeration obtain casting solution.
It is 5cm to set spinning head to enter the distance of water space, is set into the atmosphere of water space mixing for alcohol vapour and air
Gas is closed, the wherein percent by volume of air is 95%, and the relative humidity of mixed gas is 40%.The quality point that core liquid is 75 DEG C
Number is 70% dimethylacetamide amine aqueous solution, the coagulator using 25 DEG C of water as outside coagulating bath.Using hollow-fibre membrane spinning
Machine, using casting solution as shell liquid, shell liquid and core liquid are extruded by spinning head, into outside coagulating bath, obtain Hollow Fiber Ultrafiltration
Film.Dried in the shade after hollow fiber ultrafiltration membrane is rinsed into 24h in water.
3.5g triaminobenzenes, 1.5g para diaminobenzenes, 0.5g ferric tri-dodecanesulfonates and 94.5g water are hybridly prepared into water
Phase solution.0.1g trimesoyl chlorides, 0.02g terephthalyl chlorides and 99.88 n-hexanes are configured to oil-phase solution.By doughnut
Milipore filter, which is placed in aqueous phase solution, to be soaked 8 minutes, is then taken out to be placed in oil-phase solution after the liquid for blowing surface off and is carried out interface
Polymerisation 2s, take out and be cleaned and dried, be placed in baking oven under 100 DEG C of constant temperature and carry out heat treatment 10 minutes, in obtaining
Hollow fiber composite nanometer filtering film.
Embodiment 4
30g polysulfones, 10g SPSFs, 20g ethanol and 40g dimethyl acetamides are mixed, dissolving is stirred at room temperature, then
Deaeration obtains casting solution.
The distance that setting spinning head enters water space is 20cm, and the atmosphere for being set into water space is N-methyl pyrrolidones steam
With the mixed gas of air, the wherein percent by volume of air is 75%, and the relative humidity of mixed gas is 30%.Core liquid is 60
DEG C mass fraction be 30% dimethyl sulphoxide aqueous solution, the coagulator using 25 DEG C of water as outside coagulating bath.Using hollow fibre
Film spinning-drawing machine is tieed up, using casting solution as shell liquid, shell liquid and core liquid are extruded by spinning head, into outside coagulating bath, obtained hollow
Fiber ultrafiltration membrane.Dried in the shade after hollow fiber ultrafiltration membrane is rinsed into 24h in water.
0.5g m-aminophenyls, 0.1g dodecyl alanines and 99.4g water are hybridly prepared into aqueous phase solution.By 0.1g
Trimesoyl chloride, 0.02g terephthalyl chlorides and 99.88g n-hexanes are configured to oil-phase solution.Hollow fiber ultrafiltration membrane is placed in water
Soaked 8 minutes in phase solution, be placed in progress interface polymerization reaction 2s in oil-phase solution after then taking out the liquid for blowing surface off, take
Go out to be cleaned and dried, be placed in baking oven under 100 DEG C of constant temperature and carry out heat treatment 10 minutes, obtain doughnut composite nanometer filter
Film.
Comparative example
By 35g polyether sulfones, 25g polyethylene glycol and 40g N-methyl pyrrolidones mix at room temperature, and stirring promotes dissolving,
Then deaeration obtains the casting solution of transparent and homogeneous.
Using hollow-fibre membrane spinning-drawing machine, casting solution shell liquid is extruded by spinning head, into outside coagulating bath, outside is solidifying
Admittedly that bathes obtains hollow fiber ultrafiltration membrane.Coagulator using 25 DEG C of water as outside coagulating bath.
By 9g piperazines, 1g dodecyl sodium sulfates, 90g water is hybridly prepared into aqueous phase solution；0.5g trimesoyl chlorides is molten
Solution is configured to oil-phase solution liquid in 99.5g n-hexanes.Hollow fiber ultrafiltration membrane is placed in aqueous phase solution and soaks 8 minutes, then
Progress interface polymerization reaction 2s in oil-phase solution is placed in after taking out the liquid for blowing surface off, takes out and is cleaned and dried, be placed in baking oven
Heat treatment 10 minutes is carried out under 60 DEG C of constant temperature, obtains hollow fiber compound nanofiltration membrane.
Reference picture 2, by the hollow fiber ultrafiltration membrane that embodiment 1 and comparative example obtain under conditions of pressure is 2Bar
Measure its pure water flux respectively to change with time relation, respectively a curves and b curves in corresponding diagram 2.
A curves can be seen that from Fig. 2, and the pure water flux for the hollow fiber ultrafiltration membrane that embodiment 1 obtains changes over time not
Greatly, its pure water flux stably reaches 120LMH.And b curves can be seen that from Fig. 2, hollow fiber ultrafiltration membrane that comparative example obtains
Nearly 10% was have dropped in 2 hours.It is indicated above that the hollow fiber ultrafiltration membrane that embodiment 1 obtains has good structure steady
It is qualitative, good supporting role can be played, while high water flux and low filtration resistance are kept, so as to reduce NF membrane
Filtration resistance and filtering energy consumption, realize the efficient nanofiltration filtering under low pressure.
Embodiment 1~4 and comparative example are tested to its pure water flux at 0.2 mpa respectively, concentration is 1000ppm's
Na2SO4Rejection and concentration be 1000ppm MgCl2Rejection, obtained result is as shown in the table.As can be seen here, it is real
The hollow fiber compound nanofiltration membrane that example 1~4 obtains is applied, pure water flux reaches 30LMH, and the energy under relatively low energy consumption at 0.2 mpa
Divalent ion in enough effectively catching water.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that come for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (6)
1. a kind of preparation method of hollow fiber compound nanofiltration membrane, it is characterised in that comprise the following steps：
Using casting solution as shell liquid, the shell liquid and core liquid are extruded by the spinning head of hollow-fibre membrane spinning-drawing machine, into hollow fibre
In the outside coagulating bath for tieing up film spinning-drawing machine, hollow fiber ultrafiltration membrane is obtained；Wherein, the casting solution be calculated in mass percent including
15~30% filmogen, 2~10% hydrophilic polymer, 5~20% poor solvent and 40~78% solvent；Institute
Core liquid is stated as at least one of N-methyl pyrrolidones, dimethylformamide, dimethyl acetamide and dimethyl sulfoxide (DMSO) and water
Mixed liquor, the mass percent of water described in the mixed liquor be 30%~70%；The spinning head enter water space away from
From for 5~30cm, it is described enter water space atmosphere be alcohol vapour, N-methyl pyrrolidones steam, dimethyl acetamide steam
And the mixed gas of at least one of dimethyl sulfoxide (DMSO) steam and air, the volume basis of air described in the mixed gas
Than for 75%~95%, it is described enter water space atmosphere relative humidity be 30~80%；The core liquid and the outside coagulating bath
Temperature difference be 25~50 DEG C；And
The hollow fiber ultrafiltration membrane is placed in aqueous phase solution and soaked 5~20 minutes, takes out and is placed in after drying in oil-phase solution
Carry out interface polymerization reaction and form separating layer in the outer surface of the hollow fiber ultrafiltration membrane, the reaction time is 2~60s, is taken out
It is cleaned and dried, under 70~100 DEG C of constant temperature, carries out heat treatment 10~50 minutes, obtains that the doughnut is compound to be received
Filter membrane；Wherein described aqueous phase solution is lived in terms of mass fraction including 0.5~5% polyamino monomer, 0.1~0.5% surface
Property agent and 94.5~99.4% water, the oil-phase solution is the polynary solution of acid chloride of mass fraction 0.01~0.2%, wherein institute
The solvent for stating polynary solution of acid chloride is at least one of n-hexane and toluene.
2. the preparation method of hollow fiber compound nanofiltration membrane according to claim 1, it is characterised in that the outside solidification
Coagulator is at least one of N-methyl pyrrolidones, dimethyl acetamide and dimethyl sulfoxide (DMSO), dimethylformamide in bath
It is water with coagulator in the mixed liquor of water, or the outside coagulating bath.
3. the preparation method of hollow fiber compound nanofiltration membrane according to claim 1, it is characterised in that the poor solvent
For at least one of water, ethanol, glycerine, isopropanol, normal propyl alcohol and glacial acetic acid；The solvent is dimethylformamide, diformazan
At least one of yl acetamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE and trimethyl phosphate.
4. the preparation method of hollow fiber compound nanofiltration membrane according to claim 1, it is characterised in that the filmogen
For at least one of polyether sulfone, polysulfones, polyvinyl chloride, Kynoar and polyacrylonitrile；The hydrophilic polymer is sulphur
Change polysulfones, sulfonated polyether sulfone, polyvinyl alcohol, chitosan, amination polysulfones, carboxylated polysulfones, carboxymethyl cellulose, polyethylene glycol
And at least one of polyvinylpyrrolidone.
5. the preparation method of hollow fiber compound nanofiltration membrane according to claim 1, it is characterised in that the polyamino list
Body is at least one of piperazine, polyethyleneimine, triaminobenzene, para diaminobenzene and m-aminophenyl；
The surfactant is polysorbas20, Span 10, dodecyl sodium sulfate, tristerin, dodecylamino third
At least one of acid, neopelex and ferric tri-dodecanesulfonate；
The polynary acyl chlorides is at least one of trimesoyl chloride, terephthalyl chloride and isophthaloyl chloride.
6. a kind of hollow fiber compound nanofiltration membrane, it is characterised in that using the doughnut described in any one of Claims 1 to 5
The preparation method of composite nanometer filtering film is made.
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| CN109692580B (en) * | 2017-10-20 | 2021-06-04 | 宁波方太厨具有限公司 | Preparation method of hollow fiber membrane chromatographic ultrafiltration membrane |
| CN109692578A (en) * | 2017-10-20 | 2019-04-30 | 宁波方太厨具有限公司 | The preparation method of hollow-fibre membrane |
| CN109692577A (en) * | 2017-10-20 | 2019-04-30 | 宁波方太厨具有限公司 | The cross-linking modified preparation method of total coating of hollow fiber ultrafiltration membrane |
| CN109692576A (en) * | 2017-10-20 | 2019-04-30 | 宁波方太厨具有限公司 | The interface-cross-linked modification method for preparing of hollow fiber ultrafiltration membrane |
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| JP7064510B2 (en) * | 2017-12-27 | 2022-05-10 | 株式会社クラレ | Composite hollow fiber membrane and method for manufacturing composite hollow fiber membrane |
| CN108479433A (en) * | 2018-05-30 | 2018-09-04 | 佛山市航祥千安科技有限公司 | A kind of preparation method of hollow fiber compound nanofiltration membrane |
| CN109092061B (en) * | 2018-08-22 | 2020-01-14 | 西安理工大学 | Hydrophilic conductive nanofiltration membrane based on PVDF (polyvinylidene fluoride) membrane, preparation method and decontamination method |
| CN109316971A (en) * | 2018-10-19 | 2019-02-12 | 武汉大学深圳研究院 | A kind of hollow-fibre membrane crushing resistance and water flux Enhancement Method |
| CN110064312B (en) * | 2019-04-29 | 2022-03-08 | 袁书珊 | High-flux solvent-resistant interfacial polymerization composite membrane and preparation method thereof |
| CN112337317A (en) * | 2019-08-07 | 2021-02-09 | 北京新源国能科技集团股份有限公司 | Enhanced hollow fiber composite nanofiltration membrane and preparation method thereof |
| CN110652888B (en) * | 2019-11-13 | 2021-09-17 | 湖北瑞滤膜科技有限公司 | Low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with lining and preparation method thereof |
| CN110917912B (en) * | 2019-12-09 | 2021-09-24 | 南京惟新环保装备技术研究院有限公司 | Internal pressure type composite hollow fiber nanofiltration membrane yarn and preparation method thereof |
| CN112058093A (en) * | 2020-09-02 | 2020-12-11 | 蓝星（杭州）膜工业有限公司 | Preparation method of anti-pollution composite nanofiltration membrane with network structure |
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