CN108273386A - A kind of preparation method of hollow-fibre membrane - Google Patents
A kind of preparation method of hollow-fibre membrane Download PDFInfo
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- CN108273386A CN108273386A CN201710683405.3A CN201710683405A CN108273386A CN 108273386 A CN108273386 A CN 108273386A CN 201710683405 A CN201710683405 A CN 201710683405A CN 108273386 A CN108273386 A CN 108273386A
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- hollow
- fiber
- fibre membrane
- casting solution
- fibre
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- 239000000835 fiber Substances 0.000 title claims abstract description 117
- 239000012528 membrane Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 49
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000005266 casting Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 claims abstract description 22
- 239000004332 silver Substances 0.000 claims abstract description 22
- 230000000845 anti-microbial effect Effects 0.000 claims abstract description 12
- 229920005594 polymer fiber Polymers 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 229910001868 water Inorganic materials 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 15
- 238000000108 ultra-filtration Methods 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012510 hollow fiber Substances 0.000 claims description 12
- 230000001112 coagulating effect Effects 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000004513 sizing Methods 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 238000012805 post-processing Methods 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229960003511 macrogol Drugs 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 2
- 229920006306 polyurethane fiber Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 28
- 238000001125 extrusion Methods 0.000 description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- 230000000844 anti-bacterial effect Effects 0.000 description 9
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229940113088 dimethylacetamide Drugs 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 230000004907 flux Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 229920004934 Dacron® Polymers 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 235000012489 doughnuts Nutrition 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- -1 polyethylene pyrrole Pyrrolidone Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0095—Drying
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- 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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2853—Anaerobic digestion processes using anaerobic membrane bioreactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/50—Control of the membrane preparation process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Abstract
The present invention provides a kind of preparation methods of hollow-fibre membrane, include the following steps：1) contg. silver fiber beam and polymer fiber Shu Jinhang are woven, to obtain contg. silver fiber woven tube；And 2) the contg. silver fiber woven tube obtained step 1) is coextruded with casting solution and core liquid, is then separated, to obtain the hollow-fibre membrane.Method provided by the invention, which is not only able to the hollow-fibre membrane for having both high mechanical properties and anti-microbial property is prepared, to be had both, and easy to operate, be can be realized using existing industrial equipment, is advantageously implemented industrialized production.
Description
This application claims enjoy the entitled " method of modifying and doughnut of hollow woven tube submitted on January 5th, 2017
The Chinese patent application CN201710006850.6 of the preparation method of film ", that submits on January 5th, 2017 is entitled " a kind of hollow
The priority of the Chinese patent application CN201710006968.9 of the preparation method of tunica fibrosa ", entire contents are by quoting simultaneously
Enter herein.
Technical field
The present invention relates to a kind of preparation methods of hollow-fibre membrane.
Background technology
Membrane separation technique is widely used in water treatment field.Wherein, Kynoar is a kind of high comprehensive performance
Membrane material, it has higher tensile strength and excellent chemical stability, corrosion resistance and heat resistance, therefore is commonly used for micro-
The material of the seperation films such as filter, ultrafiltration and nanofiltration.With the development of membrane technology, Kynoar wastewater treatment, biologic medical and
The fields such as food manufacturing receive more and more attention.But due to the hydrophobicity of Kynoar, make it in use,
The microorganisms such as bacterium are easy in film surface absorption, are proliferated and cause biological pollution, membrane flux can be caused to be greatly lowered, caused
The deterioration of membrane separating property, the reduction of producing water water quality and membrane lifetime shortening.Therefore in UF membrane field, biological pollution is prevented
Controlling particularly important, current main method includes：Chlorine is continuously passed through in staying water to be sterilized, but can be to water inlet
Water quality pollutes；Or filter staying water, microorganism in water removal is gone, so again so that flow process is more cumbersome；Or
In the process of running, the oxidants such as sodium hypochlorite are periodically frequently added, sterilization treatment is carried out to membrane module, kill microorganism, but
It is frequent chemical cleaning to damage membrane structure, reduces the service life of film.Therefore, preparing itself has anti-microbial property
Seperation film it is particularly significant.
Silver ion and Nano silver grain are the most commonly used one of high-efficient antibacterial agents, are all had preferably to fungi and bacterium
Inhibiting effect.Silver nano-grain is introduced in membrane body or surface, can effectively build the seperation film with anti-microbial property.How
The leakage of silver nano-grain in use is prevented, keeps the antibacterial ability of film more lasting, is needed in real process
The major issue of solution.
CN 201410153107.X are disperseed nano silver particles in preparation liquid using ultrasonic method, will when inversion of phases forms a film
Silver particles are embedded in hollow-fibre membrane.CN201210042292.6, which is disclosed, loads to silver particles in molecular sieve, then mixes
It is miscellaneous to the hollow-fibre membrane in preparation liquid, preparing film surface enrichment silver molecular sieve.But the common trait of the above technology be
In prolonged operational process, silver ion fixation can not stablize, and cause it in the process of running, and antibacterial material can not stop
It loses, causes the anti-microbial property of film to decline and even disappear.And the cross-linking reaction used at present generally only occurs in the end of polymer,
The one side degree of cross linking is inadequate, and on the other hand this antibiotic layer liquid is unstable.Therefore, it is necessary to develop efficient stable, general economy
Antibacterial film preparation method.
In addition, hollow-fibre membrane in commercial Application, is often accompanied by the environment such as high pressure, aeration, backwash, in high-velocity flow and
Under the washing away of air-flow, self-strength deficiency then will appear the phenomenon that film wire is broken.
Therefore, this field needs a kind of for the method with high mechanical properties and the hollow-fibre membrane of anti-microbial property.
Invention content
In order to solve the above technical problem, the present invention provides a kind of preparation methods of new hollow-fibre membrane.The system
Preparation Method includes：
1) contg. silver fiber beam and polymer fiber Shu Jinhang are woven, to obtain contg. silver fiber woven tube；
2) the contg. silver fiber woven tube for obtaining step 1) is coextruded with casting solution and core liquid, is then separated, with
Obtain the hollow-fibre membrane.
According to the preferred embodiment of the present invention, the preparation method further includes before step 1) to the contg. silver fiber
And/or polymer fiber is cleaned.According to one embodiment, to the contg. silver fiber and/or gathered with lye and deionized water
Fibres are closed to be cleaned.Preferably, the lye is the sodium hydroxide solution of 5%-15%.Preferably, with caustic dip
Temperature is -60 minutes 20 minutes, and the time is -30 minutes 5 minutes.
According to the preferred embodiment of the present invention, the preparation method further includes after step 2) by the doughnut
Film carries out hydrophiling post-processing.According to a preferred embodiment, the hydrophiling, which post-processes, is：The hollow fibre that step 2) is obtained
Dimension film impregnates -24 hours 2 hours in 40 DEG C -90 DEG C of water, carries out hydrophiling and fenestra sizing post-processing；By hydrophilicity-imparting treatment
Hollow-fibre membrane afterwards has just obtained having both high mechanical properties and antibacterial in 20 DEG C of -60 DEG C of dryings -48 hours 2 hours after dry
The hollow fiber ultrafiltration membrane of performance.
According to the preferred embodiment of the present invention, described to be woven to：By contg. silver fiber beam and polymer fiber beam along core
Liquid pipe carries out " people " font and is cross-woven.
Preferably, the polymer fiber beam is that 100-1000 root filaments form by number.Preferably, contg. silver fiber
Beam is made of the filament that number is 1-10 root argentiferous.
According to the present invention, the contg. silver fiber beam commercially available can also be made by oneself.
According to the preferred embodiment of the present invention, it is fine to be selected from polyester fiber, Fypro, polyolefin for the filament
At least one of dimension, polyester fiber, polyurethane fiber, polysulfone fibre or glass fibre, preferably polyester fiber and/or polyamide
Fiber.
According to the preferred embodiment of the present invention, the casting solution used in step 2) include Kynoar, it is solvent, non-
Solvent and additive.
According to the preferred embodiment of the present invention, the casting solution is prepared by following steps：By Kynoar,
Solvent, non-solvent, additive mixing, are stirred -24 hours 12 hours, vacuum defoamation 12 is small in a kettle at 60 DEG C -120 DEG C
When -24 hours, to obtain the casting solution.
Preferably, the number-average molecular weight of the Kynoar is 100,000-50 ten thousand.It is described poly- inclined in the casting solution
The mass content of vinyl fluoride is preferably 10%-30%, more preferably 15%-25%.
Preferably, the additive is selected from polyvinylpyrrolidone, the molecular weight 1000- of molecular weight 3000-50000
In the polyvinyl alcohol of 10000 polyethylene glycol, the polyethylene oxide of molecular weight 10000-60000 and molecular weight 8000-50000
It is at least one.In the casting solution, the mass content of the additive is preferably 2%-20%, more preferably 5%-15%.
Preferably, the solvent is selected from n,N-Dimethylformamide, n,N-dimethylacetamide and N-Methyl pyrrolidone
At least one of.In the casting solution, the mass content of the solvent is preferably 50%-80%, more preferably 60%-
75%.
Preferably, the non-solvent is at least one of propylene glycol, glycerine, triethylene glycol and polyethylene glycol.It is described poly-
Ethylene glycol is preferably selected from polyethylene glycol 200, polyethylene glycol 400 and Macrogol 600.In the casting solution, the non-solvent
Mass content be preferably 5%-20%, more preferably 8%-12%.
According to the preferred embodiment of the present invention, the core liquid be the solvent mixed solution or water with it is described non-molten
The mixed solvent of agent.Preferably, in the core liquid, the weight percent concentration of water is 50%-100%, preferably 70%-
100%.
According to the preferred embodiment of the present invention, the temperature of the core liquid is controlled at 20 DEG C -80 DEG C, preferably 20 DEG C -60
℃
According to the preferred embodiment of the present invention, by immersing the product of coextrusion institute is carried out in coagulating bath and water-bath
State phase separation.The coagulating bath be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone at least
A kind of aqueous solution, mass concentration are preferably 0%-40%, more preferably 0%-20%.
According to the preferred embodiment of the present invention, the temperature of the coagulating bath is controlled at 30 DEG C -80 DEG C, preferably 50 DEG C -
70℃。
Compared with prior art, the beneficial effects of the invention are as follows：
1. using fibrage-coextrusion integral process, contg. silver fiber beam and polymer fiber, which are woven into fiber, to be compiled
Enhancement layer is knitted, and has been embedded into the ontology of hollow-fibre membrane.Compared to common hollow-fibre membrane, which has higher drawing
It stretches intensity and reaches 12.5MPa-50MPa, explosion resistant strength reaches 0.25MPa-1.5MPa, pure water flux 120L/m2h-500L/m2h。
2. the present invention obtains hollow-fibre membrane due to there is the introducing of argentiferous woven tube, imitated with fabulous antibacterial and sterilization
Fruit.Experiment shows that the hollow-fibre membrane is 82.5%-93.5%, the suppression to Staphylococcus aureus to the inhibiting rate of Escherichia coli
Rate processed is 75.1%-89.7%, has excellent antibacterial action.Meanwhile the hollow-fibre membrane cuts bovine serum albumin(BSA)
It is 95.3%-97.3% to stay rate, has excellent separating property.
3. since the argentiferous woven tube of the invention used is wrapped in the inside of Kynoar hollow membrane so that silver particles exist
The feature eluted, antibacterial time is grown is not easy during use.
4. the present invention provides a kind of preparation method of the above-mentioned hollow fiber ultrafiltration membrane for having both antibacterial and high mechanical properties,
This method is easy to operate, can be realized using existing industrial equipment, is advantageously implemented industrialized production.
Description of the drawings
Fig. 1 is the schematic diagram of the hollow-fibre membrane obtained according to the preparation method of the present invention.
Fig. 2 is after the hollow-fibre membrane obtained according to the preparation method of the present invention impregnates 12 hours in Escherichia coli solution
Stereoscan photograph.
Specific implementation mode
The present invention is described in detail with reference to embodiments, but the present invention is not limited by following embodiments.
The nano silver wire used in the present embodiment is purchased from Leqing Zhong Jin metals Co., Ltd.
Embodiment 1
1, the fibre bundle being made of 200 0.5 Denier dacron threads and the fibre bundle for replacing 4 nano silver wires are existed
In the sodium hydroxide solution of 5wt%, 30min is handled at a temperature of 60 DEG C, is then cleaned with deionized water, with 3000 revs/min
Speed centrifuge dripping 30min.
2, by Kynoar (molecular weight 210000), DMAC N,N' dimethyl acetamide, polyethylene glycol 400, polyethylene pyrrole
Pyrrolidone presses 15:70:10:5 weight ratio stirs 12 hours at a temperature of 80 DEG C, and filtering, vacuum defoamation 24 hours obtain casting film
Liquid.
3, casting solution extrudes into mold, 25 DEG C of H under 0.2MPa pressure by pressure2O exists as core liquid
Enter mold by core liquid pipe under 0.01MPa pressure；The fibre bundle on frame will be woven and carry out " people " font intersection volume along core liquid pipe
Knit so that core liquid pipe is fixed among the fiber braided tube woven, the fiber braided tube containing silver wire under the traction of friction pulley,
Nozzle is squeezed out to enter under the forward speed of 4m/min.Casting solution, core liquid, fiber braided tube are subjected to co-extrusion by extrusion die
Go out, immerses 60 DEG C of H2It is separated in O coagulating baths, obtains argentiferous hollow-fibre membrane.
4, obtained hollow-fibre membrane is impregnated 12 hours in 60 DEG C of hot water, after carrying out hydrophiling and fenestra sizing
Reason；By the hollow-fibre membrane after hydrophilicity-imparting treatment dry 24 hours at 30 DEG C, just obtained having both after dry high mechanical properties and
The hollow fiber ultrafiltration membrane of anti-microbial property.
Embodiment 2
1, the fibre bundle being made of 150 0.7 Denier glass fibers and the fibre bundle for replacing 6 nano silver wires are existed
In the sodium hydroxide solution of 10wt%, 25min is handled at a temperature of 50 DEG C, is then cleaned with deionized water, with 5000 revs/min
Speed centrifuge dripping 25min.
2, by Kynoar (molecular weight 210000), DMAC N,N' dimethyl acetamide, glycerine, polyvinyl alcohol 30000
By 15:70:10:5 weight ratio stirs 18 hours at a temperature of 80 DEG C, and filtering, vacuum defoamation 18 hours obtain casting solution.
3, casting solution extrudes into mold, 25 DEG C of H under 0.2MPa pressure by pressure2O exists as core liquid
Enter mold by core liquid pipe under 0.01MPa pressure；The fibre bundle on frame will be woven and carry out " people " font intersection volume along core liquid pipe
Knit so that core liquid pipe is fixed among the fiber braided tube woven, the fiber braided tube containing silver wire under the traction of friction pulley,
Nozzle is squeezed out to enter under the forward speed of 3m/min.Casting solution, core liquid, fiber braided tube are subjected to co-extrusion by extrusion die
Go out, immerses 60 DEG C of H2It is separated in O coagulating baths, obtains argentiferous hollow-fibre membrane.
4, obtained hollow-fibre membrane is impregnated 12 hours in 70 DEG C of hot water, after carrying out hydrophiling and fenestra sizing
Reason；By the hollow-fibre membrane after hydrophilicity-imparting treatment dry 24 hours at 30 DEG C, just obtained having both after dry high mechanical properties and
The hollow fiber ultrafiltration membrane of anti-microbial property.
Embodiment 3
1, the fibre bundle being made of 200 0.5 Denier nylon fiber silks and the fibre bundle for replacing 8 nano silver wires are existed
In the sodium hydroxide solution of 10wt%, 30min is handled at a temperature of 50 DEG C, is then cleaned with deionized water, with 5000 revs/min
Speed centrifuge dripping 25min.
2, by Kynoar (molecular weight 210000), DMAC N,N' dimethyl acetamide, Macrogol 600, polyvinyl alcohol
30000 press 18:68:9:5 weight ratio stirs 24 hours at a temperature of 80 DEG C, and filtering, vacuum defoamation 18 hours obtain casting film
Liquid.
3, casting solution extrudes into mold, 25 DEG C of H under 0.2MPa pressure by pressure2O exists as core liquid
Enter mold by core liquid pipe under 0.01MPa pressure；The fibre bundle on frame will be woven and carry out " people " font intersection volume along core liquid pipe
Knit so that core liquid pipe is fixed among the fiber braided tube woven, the fiber braided tube containing silver wire under the traction of friction pulley,
Nozzle is squeezed out to enter under the forward speed of 3m/min.Casting solution, core liquid, fiber braided tube are subjected to co-extrusion by extrusion die
Go out, immerses 60 DEG C of n,N-dimethylacetamide/H2O (weight ratios 1:4) it is separated in coagulating bath, obtains the hollow fibre of argentiferous
Tie up film.
4, obtained hollow-fibre membrane is impregnated 6 hours in 60 DEG C of hot water, after carrying out hydrophiling and fenestra sizing
Reason；By the hollow-fibre membrane after hydrophilicity-imparting treatment dry 24 hours at 25 DEG C, just obtained having both after dry high mechanical properties and
The hollow fiber ultrafiltration membrane of anti-microbial property.
Embodiment 4
1, by the fibre bundle of 10 nano silver wires of the fibre bundle being made of 300 0.5 Denier nylon fiber silks and replacement
In the sodium hydroxide solution of 15wt%, handle 30min at a temperature of 60 DEG C, then cleaned with deionized water, with 10000 turns/
The speed centrifuge dripping 15min of minute.
2, by Kynoar (molecular weight 430000), DMAC N,N' dimethyl acetamide, glycerine, PEG 20000
By 20:64:10:6 weight ratio stirs 18 hours at a temperature of 90 DEG C, and filtering, vacuum defoamation 18 hours obtain casting solution.
3, casting solution extrudes into mold, 25 DEG C of H under 0.2MPa pressure by pressure2O exists as core liquid
Enter mold by core liquid pipe under 0.01MPa pressure；The fibre bundle on frame will be woven and carry out " people " font intersection volume along core liquid pipe
Knit so that core liquid pipe is fixed among the fiber braided tube woven, the fiber braided tube containing silver wire under the traction of friction pulley,
Nozzle is squeezed out to enter under the forward speed of 1.5m/min.Casting solution, core liquid, fiber braided tube are total to by extrusion die
It squeezes out, immerses 60 DEG C of n,N-dimethylacetamide/H2O (weight ratios 1:6) it is separated in coagulating bath, it is hollow to obtain argentiferous
Tunica fibrosa.
4, obtained hollow-fibre membrane is impregnated 6 hours in 60 DEG C of hot water, after carrying out hydrophiling and fenestra sizing
Reason；Hollow-fibre membrane after hydrophilicity-imparting treatment is 24 hours dry at 2 DEG C, it has just obtained having both high mechanical properties after dry and resist
The hollow fiber ultrafiltration membrane of bacterium performance.
Embodiment 5
1, the fibre bundle being made of 300 0.5 Denier polyester fiber silks and the fibre bundle for replacing 8 nano silver wires are existed
In the sodium hydroxide solution of 15wt%, 15min is handled at a temperature of 60 DEG C, is then cleaned with deionized water, with 10000 revs/min
The speed centrifuge dripping 15min of clock.
2, by Kynoar (molecular weight 210000), DMAC N,N' dimethyl acetamide, glycerine, PEG 20000
By 20:64:10:6 weight ratio stirs 18 hours at a temperature of 90 DEG C, and filtering, vacuum defoamation 18 hours obtain casting solution.
3, casting solution extrudes into mold, 25 DEG C of H under 0.2MPa pressure by pressure2O exists as core liquid
Enter mold by core liquid pipe under 0.01MPa pressure；The fibre bundle on frame will be woven and carry out " people " font intersection volume along core liquid pipe
Knit so that core liquid pipe is fixed among the fiber braided tube woven, the fiber braided tube containing silver wire under the traction of friction pulley,
Nozzle is squeezed out to enter under the forward speed of 1.5m/min.Casting solution, core liquid, fiber braided tube are total to by extrusion die
It squeezes out, immerses in 60 DEG C of water coagulating bath and be separated, obtain argentiferous hollow-fibre membrane.
4, obtained hollow-fibre membrane is impregnated 6 hours in 60 DEG C of hot water, after carrying out hydrophiling and fenestra sizing
Reason；By the hollow-fibre membrane after hydrophilicity-imparting treatment dry 24 hours at 25 DEG C, just obtained having both after dry high mechanical properties and
The hollow fiber ultrafiltration membrane of anti-microbial property.
Embodiment 6
1, the fibre bundle being made of 150 0.5 Denier polyester fiber silks and the fibre bundle for replacing 6 nano silver wires are existed
In the sodium hydroxide solution of 15wt%, 15min is handled at a temperature of 60 DEG C, is then cleaned with deionized water, with 10000 revs/min
The speed centrifuge dripping 15min of clock.
2, by Kynoar (molecular weight 210000), DMAC N,N' dimethyl acetamide, glycerine, PEG 20000
By 15:71:8.5:5.5 weight ratio stirs 24 hours at a temperature of 80 DEG C, and filtering, vacuum defoamation 12 hours obtain casting solution.
3, casting solution extrudes into mold, 25 DEG C of H under 0.2MPa pressure by pressure2O exists as core liquid
Enter mold by core liquid pipe under 0.01MPa pressure；The fibre bundle on frame will be woven and carry out " people " font intersection volume along core liquid pipe
Knit so that core liquid pipe is fixed among the fiber braided tube woven, the fiber braided tube containing silver wire under the traction of friction pulley,
Nozzle is squeezed out to enter under the forward speed of 3m/min.Casting solution, core liquid, fiber braided tube are subjected to co-extrusion by extrusion die
Go out, immerses in 60 DEG C of water coagulating bath and be separated, obtain argentiferous hollow-fibre membrane.
4, obtained hollow-fibre membrane is impregnated 12 hours in 60 DEG C of hot water, after carrying out hydrophiling and fenestra sizing
Reason；By the hollow-fibre membrane after hydrophilicity-imparting treatment dry 24 hours at 25 DEG C, just obtained having both after dry high mechanical properties and
The hollow fiber ultrafiltration membrane of anti-microbial property.
Comparative example 1
1, the fibre bundle being made of 200 0.5 Denier dacron threads is immersed in the sodium hydroxide solution of 5wt%, 60
30min is handled at a temperature of DEG C, is then cleaned with deionized water, with 3000 revs/min of speed centrifuge dripping 30min.
2, by Kynoar (molecular weight 210000), DMAC N,N' dimethyl acetamide, polyethylene glycol 400, polyethylene pyrrole
Pyrrolidone presses 15:70:10:5 weight ratio stirs 12 hours at a temperature of 80 DEG C, and filtering, vacuum defoamation 24 hours obtain casting film
Liquid.
3, casting solution extrudes into mold, 25 DEG C of H under 0.2MPa pressure by pressure2O exists as core liquid
Enter mold by core liquid pipe under 0.01MPa pressure；The fibre bundle on frame will be woven and carry out " people " font intersection volume along core liquid pipe
Knit so that core liquid pipe is fixed among the fiber braided tube woven, the fiber braided tube containing silver wire under the traction of friction pulley,
Nozzle is squeezed out to enter under the forward speed of 4m/min.Casting solution, core liquid, fiber braided tube are subjected to co-extrusion by extrusion die
Go out, immerses in 60 DEG C of H2O coagulating baths and be separated, obtain hollow-fibre membrane.
4, obtained hollow-fibre membrane is impregnated 12 hours in 60 DEG C of hot water, after carrying out hydrophiling and fenestra sizing
Reason；Hollow-fibre membrane after hydrophilicity-imparting treatment is 24 hours dry at 30 DEG C, just obtain hollow fiber ultrafiltration membrane after dry.
Embodiment 1-6 and comparative example 1 hollow fiber ultrafiltration membrane being prepared are tested for the property.
Test condition is as follows：Water flux is measured using the outer press filtering device of the homemade dead end in laboratory, that is, after cleaning
The present 0.15MPa precompressed 30min of wet film, then measure its external pressure water flux in 0.1MPa；It is subsequently passed BSA (molecular weight
6700) solution measures rejection, and flux recovery rate is measured after water cleans；The interface bond strength of woven tube and separating layer is adopted
It is measured with water kickback pressure；The water contact angle of dry film is measured by the contact angle measurement of OCA20 (Dataphysics, Germany)；
Dry film surface and fracture morphology are observed by field emission scanning electron microscope SIRION-100 (FEI, Finland).Institute in antibacterial tests
The model bacterium of selection is Escherichia coli and staphylococcus aureus.
The water flux of prepared fibrage enhancing hollow fiber ultrafiltration membrane, rejection, backwash membrane fracture pressure, contact
Angle, fracture strength, Escherichia coli sterilizing rate, staphylococcus aureus sterilizing rate are shown in Table 1.
Table 1
Method provided by the invention is not only able to that the hollow-fibre membrane for having both high mechanical properties and anti-microbial property is prepared
It has both, and easy to operate, can be realized using existing industrial equipment, be advantageously implemented industrialized production.
Although hereinbefore having been made with reference to some embodiments, invention has been described, Ben Fafan is not being departed from
In the case of enclosing, various improvement can be carried out to it, and component therein can be replaced with equivalent.Especially, as long as not
There are structural conflict, the various features in presently disclosed each embodiment can be combined with each other by any way
The description that the case where using, not combined in the present specification to these carries out exhaustive is provided merely for the sake of length and saving is omitted
The considerations of source.Therefore, the invention is not limited in specific embodiments disclosed herein, but fall into the institute of the scope of the claims
There is technical solution.
Claims (10)
1. a kind of preparation method of hollow-fibre membrane, including：
1) contg. silver fiber beam and polymer fiber Shu Jinhang are woven, to obtain contg. silver fiber woven tube；
2) the contg. silver fiber woven tube for obtaining step 1) is coextruded with casting solution and core liquid, is then separated, to obtain
The hollow-fibre membrane.
2. according to the method described in claim 1, it is characterized in that, the polymer fiber beam is fine for 100-1000 roots by number
Tie up silk composition；Contg. silver fiber beam is made of the filament that number is 1-10 root argentiferous.
3. according to the method described in claim 2, it is characterized in that, the filament is selected from polyester fiber, Fypro, gathers
At least one of olefin(e) fibre, polyester fiber, polyurethane fiber, polysulfone fibre or glass fibre, preferably polyester fiber and/or
Fypro.
4. method according to any one of claim 1-3, which is characterized in that the casting solution used in step 2) includes
Kynoar, solvent, non-solvent and additive.
5. according to the method described in claim 4, it is characterized in that, the Kynoar number-average molecular weight is 100,000-50 ten thousand；
Preferably, in the casting solution, the mass content of the Kynoar is 10%-30%, more preferably 15%-25%.
6. method according to claim 4 or 5, which is characterized in that the additive is selected from molecular weight 3000-50000's
Polyvinylpyrrolidone, the polyethylene glycol of molecular weight 1000-10000, the polyethylene oxide of molecular weight 10000-60000 and molecule
Measure at least one of the polyvinyl alcohol of 8000-50000；Preferably, in the casting solution, the mass content of the additive
For 2%-20%, more preferably 5%-15%.
7. according to the method described in claim 1, it is characterized in that, the solvent is selected from n,N-Dimethylformamide, N, N- bis-
At least one of methylacetamide and N-Methyl pyrrolidone；Preferably, in the casting solution, the quality of the solvent contains
Amount is 50%-80%, more preferably 60%-75%.
8. according to the method described in claim 1, it is characterized in that, the non-solvent is propylene glycol, glycerine, triethylene glycol and gathers
At least one of ethylene glycol, the polyethylene glycol are preferably selected from polyethylene glycol 200, polyethylene glycol 400 and Macrogol 600
At least one；Preferably, in the casting solution, the mass content of the non-solvent is 5%-20%, more preferably 8%-
12%.
9. according to the method described in claim 1, it is characterized in that, the temperature of the coagulating bath is controlled at 30 DEG C -80 DEG C, preferably
It is 50 DEG C -70 DEG C；The temperature of the core liquid is controlled at 20 DEG C -80 DEG C, preferably 20 DEG C -60 DEG C.
10. according to the method described in claim 1, it is characterized in that, the hollow-fibre membrane is carried out parent after step 2)
Aquation post-processes, and the hydrophiling post-processing is：The hollow-fibre membrane that step 2) obtains is impregnated 2 in 40 DEG C -90 DEG C of water
- 24 hours hours carried out hydrophiling and fenestra sizing post-processing；By the hollow-fibre membrane after hydrophilicity-imparting treatment at 20 DEG C -60 DEG C
It is -48 hours 2 hours dry, just obtain having both the hollow fiber ultrafiltration membrane of high mechanical properties and anti-microbial property after dry.
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| CN201710683405.3A Pending CN108273386A (en) | 2017-01-05 | 2017-08-11 | A kind of preparation method of hollow-fibre membrane |
| CN202311534013.2A Pending CN117619161A (en) | 2017-01-05 | 2017-08-11 | Antibacterial hollow fiber membrane and preparation method and application thereof |
| CN201710683044.2A Active CN108273399B (en) | 2017-01-05 | 2017-08-11 | Enhanced hollow fiber membrane and preparation method and application thereof |
| CN201710683431.6A Active CN108273392B (en) | 2017-01-05 | 2017-08-11 | Method for modifying hollow braided tube and method for producing hollow fiber membrane |
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| CN104264358A (en) * | 2014-09-26 | 2015-01-07 | 天诺光电材料股份有限公司 | Warp knitted fabric |
| CN205590868U (en) * | 2015-11-04 | 2016-09-21 | 宜兴中大纺织有限公司 | Silver fibre anti -bacterial fabric |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111804156A (en) * | 2019-04-11 | 2020-10-23 | 德威华泰科技股份有限公司 | Porous device and method for preparing enhanced hollow fiber membrane at high speed |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108273399B (en) | 2020-12-18 |
| CN108273399A (en) | 2018-07-13 |
| CN117379992A (en) | 2024-01-12 |
| CN108273392A (en) | 2018-07-13 |
| CN117619161A (en) | 2024-03-01 |
| CN108273398A (en) | 2018-07-13 |
| CN108273392B (en) | 2021-07-30 |
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Application publication date: 20180713 |