CN106731866A - A kind of preparation method for weaving tube enhancement type hollow fiber ultrafiltration membrane - Google Patents
A kind of preparation method for weaving tube enhancement type hollow fiber ultrafiltration membrane Download PDFInfo
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- CN106731866A CN106731866A CN201611097232.9A CN201611097232A CN106731866A CN 106731866 A CN106731866 A CN 106731866A CN 201611097232 A CN201611097232 A CN 201611097232A CN 106731866 A CN106731866 A CN 106731866A
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- casting solution
- hollow fiber
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- 239000012528 membrane Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 17
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 17
- 238000009941 weaving Methods 0.000 title claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 150000001448 anilines Chemical class 0.000 claims abstract description 10
- 238000005266 casting Methods 0.000 claims description 63
- 239000002904 solvent Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- 238000009987 spinning Methods 0.000 claims description 18
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 16
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 230000001112 coagulating effect Effects 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- UZOFELREXGAFOI-UHFFFAOYSA-N 4-methylpiperidine Chemical class CC1CCNCC1 UZOFELREXGAFOI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 8
- 229920000767 polyaniline Polymers 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000012805 post-processing Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- -1 ether ketone Chemical class 0.000 claims description 4
- 239000001087 glyceryl triacetate Substances 0.000 claims description 4
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- 229960002622 triacetin Drugs 0.000 claims description 4
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 229920002972 Acrylic fiber Polymers 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920004933 Terylene® Polymers 0.000 claims description 3
- 150000003053 piperidines Chemical class 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001174 sulfone group Chemical group 0.000 claims description 2
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 claims 1
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 8
- 230000003373 anti-fouling effect Effects 0.000 abstract description 4
- 238000005191 phase separation Methods 0.000 abstract description 3
- 230000004907 flux Effects 0.000 description 26
- 230000004044 response Effects 0.000 description 13
- 238000004140 cleaning Methods 0.000 description 10
- 102000004169 proteins and genes Human genes 0.000 description 10
- 108090000623 proteins and genes Proteins 0.000 description 10
- 238000011109 contamination Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 9
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 8
- 229940098773 bovine serum albumin Drugs 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 239000002352 surface water Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 4
- 230000010148 water-pollination Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000009954 braiding Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to a kind of preparation method for weaving tube enhancement type hollow fiber ultrafiltration membrane, the method prepares polymer/phenyl amines polymer binary blend film using wet method phase inversion, this feature in surface that film is more readily migrated into phase separation using hydrophilic phenyl amines polymer, improve the interface performance of membrane superficial tissue and film, so as to strengthen the hydrophilicity and antifouling property of film, in addition, by adding dispersant, improve the compatibility of two kinds of polymer, present invention process is simple, to appointed condition without particular/special requirement, cost is relatively low, it is easy to industrial applications.
Description
Technical field
Preparation and technical field of modification the present invention relates to polymer separation film material, more particularly to a kind of enhancing of woven tube
The preparation method of type hollow fiber ultrafiltration membrane.
Background technology
Compared with conventional separation techniques, membrane technology have efficiently, accurate, energy-conservation, it is simple the features such as, therefore, extensively should
For fields such as food, medicine, biology, environmental protection, petrochemical industries, huge economic benefit and social benefit is generated, it has also become
One of most important means in current separation science.Seperation film is the core of technical field of membrane, is the emphasis studied all the time.
Wherein, milipore filter by over half a century development, either in terms of material of preparing, filming technology, preparation of membrane module etc.,
It is all highly developed.However, during film use, what the pollution problem of film govern application of membrane field always enters one
Step extension.Research shows：The hydrophily for improving film surface is a kind of effective ways for suppressing fouling membrane.It is conventional at present to commodity
The method that milipore filter carries out hydrophilic modifying mainly has：
（1）Surface application methods：It is to apply one layer of hydrophilic polymer by the surface of film, then is consolidated overlay by post-processing
It is scheduled on the surface of film.The tape casting, R.H.Li of such as K.Lang (185-196 of Deseation 104 (1996)) use etc.
（J.Membrane Sci.,105(1995)71-78）Using spin-coating method, F.R.Chen etc.（J.Mem Sci.,109(1996)
247-256）Using infusion method.Hydrophilic polymer coating, the hydrophilicity and antipollution of film silk are introduced by film surface
Performance is obviously improved, however, due between this coating and film, only being connected by intermolecular force, in use and clearly
During washing, it is easy to cause coming off for hydrophilic coating, the maintenance that this hydrophilicity can not be permanent；
（2）Surface grafting method：It is the method being grafted by chemical bond, and hydrophilic functional group is grafted into surface and hole
It is interior, the surface for being grafted on film that this hydrophilic radical can be steady in a long-term, the performance of permanent improvement film.Such as Hideyuki
Yamagishi etc.（J.Membrane Sci., 109（1996）247-256）Connect on hydrophobic membrane surface using the method for ultraviolet radioactive
Branch methacrylic acid carries out sulfonation treatment introducing sulfonate group to poly (ether sulfone) film surface or is re-introduced into it on its basis
His hydrophilic functional group.However, this method is not widely used, its limitation is that grafted monomers are difficult
Selection, severe reaction conditions, grafting rate are low and relatively costly；
（3）Blend method：It is dissolved in same solvent after two or more polymer is blended, or its is molten
Liquid mixes, and finally prepares a kind of method of perforated membrane.This kind of method is simple to operate, is easy to application.However, the compatibility of polymer
It is the problem that must take into consideration, only compatibility is preferably blended casting solution and film silk of good performance can be just obtained.
The content of the invention
In view of the above-mentioned state of the art, the technical problems to be solved by the invention are to provide a kind of process is simple,
The preparation method of the braiding tube enhancement type hollow fiber ultrafiltration membrane of film hydrophily and antifouling property can be strengthened.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：One kind braiding tube enhancement type Hollow Fiber Ultrafiltration
The preparation method of film, prepares as follows：
Step（1）, by mass fraction for the polymer and mass fraction of 5-30% divide for the additive of 0.1-20% is dissolved in quality
Number is in the good solvent of 50-90%, temperature is 20-90 DEG C, and uniform casting solution A is obtained after filtering；
Step（2）, by mass fraction for 5-30% phenyl amines polymer be dissolved in mass fraction be 0.1-20% dispersant with
During mass fraction is for the mixed solvent of the good solvent of 50-90%, temperature is 20-70 DEG C, and uniform casting solution B is obtained after filtering；
Step（3）, by step（1）The casting solution A and step of gained（2）The casting solution B of gained is proportionally common at 20-70 DEG C
Mixed, stirring, standing and defoaming obtains that casting solution is blended；
Step（4）, by step（3）The blending casting solution of gained, is coated in hollow woven tube by spinning equipment；
Step（5）, will be by step（4）The woven tube of coating is incorporated into film-forming in coagulating bath by pulling equipment.
Further, the step（1）In polymer be Kynoar, polysulfones, polyether sulfone, polyether sulphone, polychlorostyrene
One or more in ethene, polyacrylonitrile, polyether-ether-ketone, polyamide, polyimides.
Further, the step（1）In additive be lithium chloride, ethanol, acetone, lithium perchlorate, polyvinyl pyrrole
One or more in alkanone, polyethylene glycol.
Further, the step（1）With step（2）In good solvent be dimethylformamide, dimethylacetylamide, N-
One or more in methyl pyrrolidone, dimethyl sulfoxide (DMSO), sulfolane, triethyl phosphate, glyceryl triacetate.
Further, the step（2）In phenyl amines polymer be polyaniline or poly dimethyl aniline, mean molecule
It is 5-30 ten thousand to measure, and fibre length is 100-2000 nanometers, and phenyl amines polymer is a kind of high temperature resistant, solvent resistant, chemicals-resistant
High intensity, high performance material, it is widely used in the fields such as gas separation, infiltration evaporation, while as a kind of hydrophily
Membrane material, in the preparation process of blend film, it is easier to migrate to the surface of film, improve membrane interface energy, enhancing film surface
Wettability, so as to suppress the absorption of film surface contaminant, extends the service life of film.
Further, the step（2）In dispersant be one or more in piperidines, 4- methyl piperidines, pyridine.
Further, the step（3）The ratio of casting solution A and casting solution B is 1 in blending casting solution:10-10:1.
Further, the woven tube is terylene, polyamide fibre, polyvinyl, polypropylene fibre or acrylic fibers woven tube, the internal diameter of the woven tube
It is 0.3-1.8mm, external diameter is 0.5-2.3mm.
Further, the step（5）In coagulating bath be water, methyl alcohol, ethanol, ethylene glycol, propyl alcohol, dimethyl formyl
In amine, dimethylacetylamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), sulfolane, triethyl phosphate, glyceryl triacetate
One or more, mass fraction of the water in coagulating bath is 30-100%.
Further, the step（5）The film for obtaining also by post processing, the post processing mode be acid treatment, alkali process,
The acid treatment, alkali process are one or more in hydrochloric acid, sulfuric acid, NaOH, potassium hydroxide, ammoniacal liquor, and mass fraction is
0.1-10%, process time is 1-72 hours.
Compared with prior art, the advantage of the invention is that：The present invention prepares polymer/benzene using wet method phase inversion
Amine polymer binary blend film, the table of film is more readily migrated into using hydrophilic phenyl amines polymer in phase separation
This feature in face, improves the interface performance of membrane superficial tissue and film, so that strengthen the hydrophilicity and antifouling property of film, separately
Outward, by adding dispersant, the compatibility of two kinds of polymer is improve, present invention process is simple, appointed condition is wanted without special
Ask, cost is relatively low, be easy to industrial applications, hollow fiber ultrafiltration membrane prepared by the present invention, the hydrophilicity and anti-soil on film surface
Metachromia can be remarkably reinforced, and the water contact angle on film surface is 20-60 degree；Under 0.1MPa, film pure water flux is 50-1200LMH；
Static protein adsorption quantity is less than 2ug/cm2, and dynamic protein contamination test, attenuation rate is less than 10%, its flux after cleaning
Response rate reaches more than 96%；10-2000ppm oily waste waters are separated, attenuation rate is less than 10%, after cleaning, flux response rate
Up to more than 90%.
Specific embodiment
The above of the invention is described in further detail below by way of specific embodiment.
Embodiment 1
Step（1）, by Kynoar, the polyvinylpyrrolidone that mass fraction is 8%, mass fraction that mass fraction is 16%
Lithium chloride for 0.1% is added in dimethylacetylamide good solvent and dissolves, and stirring, filtering at being 60 DEG C in temperature obtain uniform
Casting solution A；
Step（2）, by the polyaniline that mass fraction is 16%（Mean molecule quantity is 100,000 dalton）Being dissolved in mass fraction is
In 6.4% 4- methyl piperidines dispersant and the mixed solvent of dimethylacetylamide good solvent, stirring, mistake at being 60 DEG C in temperature
Filter, obtains uniform casting solution B；
Step（3）, by casting solution A and casting solution B according to 9:1 ratio is blended in being added to reactor, stirs 3 hours, stands de-
Bubble, obtains that casting solution is blended；
Step（4）, above-mentioned blending casting solution is coated in hollow internal diameter for 0.8mm by the spinning head on spinning equipment, outward
Footpath is in the woven tube of 1.2mm；
Step（5）, the woven tube after coating is incorporated into the coagulating bath of pure water by pulling equipment, film-forming.
By to film silk performance test：Film surface water contact angle is 50 degree；Under 0.1MPa, pure water flux is 400LMH；
Static bovine serum albumin(BSA) adsorbance is 1.5ug/cm2；In protein contamination test process, the attenuation rate of film is 5%,
Flux response rate is up to 96%；The oily waste water of 100ppm is separated, its attenuation rate is 5%, and after physical cleaning, flux response rate reaches
96%。
Embodiment 2
Step（1）, by Kynoar, the polyvinylpyrrolidone that mass fraction is 6%, mass fraction that mass fraction is 16%
For 2% polyethylene glycol, the lithium chloride that mass fraction is 0.1% be added in 1-METHYLPYRROLIDONE good solvent and dissolve, in temperature
To be stirred at 60 DEG C, being filtered, uniform casting solution A is obtained；
Step（2）, by the polyaniline that mass fraction is 16%（Mean molecule quantity is 100,000 dalton）Being dissolved in mass fraction is
In 6.4% piperidines dispersant and the mixed solvent of dimethylacetylamide good solvent, stirring, filtering, obtain at being 60 DEG C in temperature
Uniform casting solution B；
Step（3）, by casting solution A and casting solution B according to 7:3 ratios are blended in being added to reactor, stir 3 hours, stand de-
Bubble, obtains that casting solution is blended；
Step（4）, above-mentioned blending casting solution is coated in hollow internal diameter for 0.8mm by the spinning head on spinning equipment, outward
Footpath is in the woven tube of 1.2mm；
Step（5）, just apply after woven tube be incorporated into the coagulating bath of pure water by pulling equipment, film-forming.
By to film silk performance test:Film surface water contact angle is 46 degree；Under 0.1MPa, pure water flux is 460LMH；
Static bovine serum albumin(BSA) adsorbance is 1.2ug/cm2；In protein contamination test process, the attenuation rate of film is 2%,
Flux response rate is up to more than 98%；The oily waste water of 500ppm is filtered, its attenuation rate is 6%, after physical cleaning, flux is replied
Rate is up to 94%.
Embodiment 3
Step（1）, it is 0.1% by polysulfones that mass fraction is 20%, the polyvinylpyrrolidone that mass fraction is 8%, mass fraction
Lithium chloride be added in dimethylacetylamide good solvent and dissolve, stirring, filtering, obtain uniform casting film at being 60 DEG C in temperature
Liquid A；
Step（2）, by the polyaniline that mass fraction is 16%（Mean molecule quantity is 100,000 dalton）Being dissolved in mass fraction is
In 6.4% 4- methyl piperidines dispersant and the mixed solvent of dimethylacetylamide good solvent, stirring, mistake at being 60 DEG C in temperature
Filter, obtains uniform casting solution B；
Step（3）, by casting solution A and casting solution B according to 9:1 ratio is blended in being added to reactor, stirs 3 hours, stands de-
Bubble, obtains that casting solution is blended；
Step（4）, above-mentioned blending casting solution is coated in hollow internal diameter for 1.4mm, outer by the spinning head on spinning equipment
Footpath is in the woven tube of 1.8mm；
Step（5）, the woven tube after coating is incorporated into the coagulating bath of pure water by pulling equipment, film-forming；
Step（6）, in the hydrochloric acid solution by the film of above-mentioned gained as 1%, after immersion 24h, taking-up is dried.
By to film silk performance test：Film surface water contact angle is 32 degree；Pure water flux is 530LMH under 0.1MPa；It is quiet
State bovine serum albumin(BSA) adsorbance is 0.6ug/cm2, in protein contamination test process, the attenuation rate of film is 3%, is led to
Amount response rate filters the oily waste water of 1000ppm up to more than 98%, and its attenuation rate is 8%, and after physical cleaning, flux is replied
Rate is up to 93%.
Embodiment 4
Step（1）, by Kynoar, the polyvinylpyrrolidone that mass fraction is 8%, mass fraction that mass fraction is 16%
Lithium chloride for 0.1% is added in dimethylacetylamide good solvent and dissolves, and stirring, filtering at being 60 DEG C in temperature obtain uniform
Casting solution A；
Step（2）, by the poly dimethyl aniline that mass fraction is 16%（Mean molecule quantity is 100,000 dalton）It is dissolved in quality point
During number is for 6.4% 4- methyl piperidines dispersant and the mixed solvent of dimethylacetylamide good solvent, stirred at being 60 DEG C in temperature
Mix, filter, obtain uniform casting solution B；
Step（3）, by casting solution A and casting solution B according to 9:1 ratio is blended in being added to reactor, stirs 3 hours, stands de-
Bubble, obtains that casting solution is blended；
Step（4）, above-mentioned blending casting solution is coated in hollow internal diameter for 0.8mm by the spinning head on spinning equipment, outward
Footpath is in the woven tube of 1.2mm；
Step（5）, the woven tube after coating is incorporated into the coagulating bath of pure water by pulling equipment, film-forming.
By to film silk performance test：Film surface water contact angle is 35 degree；Under 0.1MPa, pure water flux is 450LMH；
Static bovine serum albumin(BSA) adsorbance is 0.8ug/cm2；In protein contamination test process, the attenuation rate of film is 3%,
Flux response rate is up to 98%；The oily waste water of 100ppm is separated, its attenuation rate is 3%, and after physical cleaning, flux response rate reaches
98%。
Embodiment 5
Step（1）, by Kynoar, the polyvinylpyrrolidone that mass fraction is 8%, mass fraction that mass fraction is 16%
Lithium chloride for 0.1% is added in dimethylacetylamide good solvent and dissolves, and stirring, filtering at being 60 DEG C in temperature obtain uniform
Casting solution A；
Step（2）, by the poly dimethyl aniline that mass fraction is 16%（Mean molecule quantity is 300,000 dalton）It is dissolved in quality point
During number is for 6.4% 4- methyl piperidines dispersant and the mixed solvent of dimethylacetylamide good solvent, stirred at being 60 DEG C in temperature
Mix, filter, obtain uniform casting solution B；
Step（3）, casting solution A and casting solution B is according to 9:1 ratio is blended in being added to reactor, stirs 3 hours, standing and defoaming,
Obtain that casting solution is blended；
Step（4）, above-mentioned blending casting solution is coated in hollow internal diameter for 0.8mm by the spinning head on spinning equipment, outward
Footpath is in the woven tube of 1.2mm；
Step（5）, the woven tube after coating is incorporated into the coagulating bath of pure water by pulling equipment, film-forming.
By to film silk performance test：Film surface water contact angle is 35 degree；Under 0.1MPa, pure water flux is 1000LMH；
Static bovine serum albumin(BSA) adsorbance is 1.0ug/cm2；In protein contamination test process, the attenuation rate of film is 3%,
Flux response rate is up to 98%；The oily waste water of 100ppm is separated, its attenuation rate is 4%, and after physical cleaning, flux response rate reaches
98%。
Embodiment 6
Step（1）, Kynoar that mass fraction is 16%, the polyethylene glycol that mass fraction is 8% are added to N- methyl pyrroles
Dissolved in pyrrolidone good solvent, stirring, filtering, obtain uniform casting solution A at being 90 DEG C in temperature；
Step（2）, by the polyaniline that mass fraction is 16%（Mean molecule quantity is 300,000 dalton）Being dissolved in mass fraction is
In 6.4% 4- methyl piperidines dispersant and the mixed solvent of 1-METHYLPYRROLIDONE good solvent, stirred at being 60 DEG C in temperature,
Filtering, obtains uniform casting solution B；
Step（3）, by casting solution A and casting solution B according to 1：10 ratios are blended in being added to reactor, stir 3 hours, stand de-
Bubble, obtains that casting solution is blended；
Step（4）, above-mentioned blending casting solution is coated in hollow internal diameter for 1.4mm by the spinning head on spinning equipment, outward
Footpath is in the woven tube of 1.8mm；
Step（5）, the woven tube after coating is incorporated into the coagulating bath of pure water by pulling equipment, film-forming.
By to film silk performance test：Film surface water contact angle is 24 degree；Under 0.1MPa, pure water flux is 1200LMH；
Static bovine serum albumin(BSA) adsorbance is 0.4ug/cm2；In protein contamination test process, the attenuation rate of film is 2%,
Flux response rate reaches about 100%；The oily waste water of 500ppm is separated, its attenuation rate is 4%, after physical cleaning, flux is replied
Rate is up to 98%.
Embodiment 7
Step（1）, Kynoar that mass fraction is 16%, the polyethylene glycol that mass fraction is 8% are added to N- methyl pyrroles
Dissolved in pyrrolidone good solvent, stirring, filtering, obtain uniform casting solution A at being 90 DEG C in temperature；
Step（2）, by the polyaniline that mass fraction is 16%（Mean molecule quantity is 300,000 dalton）Being dissolved in mass fraction is
In 6.4% 4- methyl piperidines dispersant and the mixed solvent of N- dimethyl pyrrolidone good solvents, stirred at being 60 DEG C in temperature
Mix, filter, obtain uniform casting solution B；
Step（3）, by casting solution A and casting solution B according to 1：10 ratios are blended in being added to reactor, stir 3 hours, stand de-
Bubble, obtains that casting solution is blended；
Step（4）, above-mentioned blending casting solution is coated in hollow internal diameter for 1.4mm by the spinning head on spinning equipment, outward
Footpath is in the woven tube of 1.8mm；
Step（5）, it is 25% that the woven tube after coating is incorporated into ethanol content by pulling equipment, and the alcohol of balance of water is water-soluble
In liquid coagulating bath, film-forming.
By to film silk performance test：Film surface water contact angle is 32 degree；Under 0.1MPa, pure water flux is 980LMH；
Static bovine serum albumin(BSA) adsorbance is 0.9ug/cm2；In protein contamination test process, the attenuation rate of film is 3%,
Flux response rate reaches about 99.5%；The oily waste water of 500ppm is separated, its attenuation rate is 4%, after physical cleaning, flux is replied
Rate is up to 98%.
Comparative examples
Step（1）, by Kynoar, the polyvinylpyrrolidone that mass fraction is 8%, mass fraction that mass fraction is 16%
Lithium chloride for 0.1% is added in dimethylacetylamide good solvent and dissolves, and stirring, filtering at being 60 DEG C in temperature stand de-
Bubble, obtains uniform casting solution；
Step（2）, above-mentioned casting solution is coated in hollow internal diameter for 0.8mm by the spinning head on spinning equipment, external diameter is
In the woven tube of 1.2mm；
Step（3）, the woven tube after coating is incorporated into the coagulating bath of pure water by pulling equipment, film-forming.
By to film silk performance test：Film surface water contact angle is 65 degree；Under 0.1MPa, pure water flux is 200LMH；
Static bovine serum albumin(BSA) adsorbance is 20.2ug/cm2；In protein contamination test process, the attenuation rate of film is
10%, flux response rate is up to 78%；The oily waste water of 100ppm is separated, its attenuation rate is 50%, after physical cleaning, flux is returned
Multiple rate is up to 30%.
In above example, the woven tube be terylene, polyamide fibre, polyvinyl, polypropylene fibre or acrylic fibers woven tube, the woven tube
Internal diameter is 0.3-1.8mm, and external diameter is 0.5-2.3mm.
The present invention prepares polymer/phenyl amines polymer binary blend film using wet method phase inversion, using hydrophily
Phenyl amines polymer this feature in surface of film is more readily migrated into phase separation, improve membrane superficial tissue and film
Interface performance, so that strengthen the hydrophilicity and antifouling property of film, in addition, by adding dispersant, improve two kinds of polymerizations
The compatibility of thing, present invention process is simple, and to appointed condition without particular/special requirement, cost is relatively low, is easy to industrial applications.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those of skill in the art that it still can be right
Technical scheme described in foregoing embodiments is modified, or which part technical characteristic is replaced on an equal basis；And this
A little modifications are replaced, and do not make the spirit and model of the essence disengaging various embodiments of the present invention technical scheme of appropriate technical solution
Enclose.
Claims (10)
1. it is a kind of weave tube enhancement type hollow fiber ultrafiltration membrane preparation method, it is characterised in that prepare as follows：
Step（1）, by mass fraction for the polymer and mass fraction of 5-30% divide for the additive of 0.1-20% is dissolved in quality
Number is in the good solvent of 50-90%, temperature is 20-90 DEG C, and uniform casting solution A is obtained after filtering；
Step（2）, by mass fraction for 5-30% phenyl amines polymer be dissolved in mass fraction be 0.1-20% dispersant with
During mass fraction is for the mixed solvent of the good solvent of 50-90%, temperature is 20-70 DEG C, and uniform casting solution B is obtained after filtering；
Step（3）, by step（1）The casting solution A and step of gained（2）The casting solution B of gained is proportionally common at 20-70 DEG C
Mixed, stirring, standing and defoaming obtains that casting solution is blended；
Step（4）, by step（3）The blending casting solution of gained, is coated in hollow woven tube by spinning equipment；
Step（5）, will be by step（4）The woven tube of coating is incorporated into film-forming in coagulating bath by pulling equipment.
2. it is according to claim 1 it is a kind of weave tube enhancement type hollow fiber ultrafiltration membrane preparation method, it is characterised in that
The step（1）In polymer be Kynoar, polysulfones, polyether sulfone, polyether sulphone, polyvinyl chloride, polyacrylonitrile, polyethers
One or more in ether ketone, polyamide, polyimides.
3. it is according to claim 1 it is a kind of weave tube enhancement type hollow fiber ultrafiltration membrane preparation method, it is characterised in that
The step（1）In additive in lithium chloride, ethanol, acetone, lithium perchlorate, polyvinylpyrrolidone, polyethylene glycol
One or more.
4. it is according to claim 1 it is a kind of weave tube enhancement type hollow fiber ultrafiltration membrane preparation method, it is characterised in that
The step（1）With step（2）In good solvent be dimethylformamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, diformazan
One or more in base sulfoxide, sulfolane, triethyl phosphate, glyceryl triacetate.
5. it is according to claim 1 it is a kind of weave tube enhancement type hollow fiber ultrafiltration membrane preparation method, it is characterised in that
The step（2）In phenyl amines polymer be polyaniline or poly dimethyl aniline, mean molecule quantity be 5-30 ten thousand, fiber is long
Spend is 100-2000 nanometers.
6. it is according to claim 1 it is a kind of weave tube enhancement type hollow fiber ultrafiltration membrane preparation method, it is characterised in that
The step（2）In dispersant be one or more in piperidines, 4- methyl piperidines, pyridine.
7. it is according to claim 1 it is a kind of weave tube enhancement type hollow fiber ultrafiltration membrane preparation method, it is characterised in that
The step（3）The ratio of casting solution A and casting solution B is 1 in blending casting solution:10-10:1.
8. it is according to claim 1 it is a kind of weave tube enhancement type hollow fiber ultrafiltration membrane preparation method, it is characterised in that
The woven tube is terylene, polyamide fibre, polyvinyl, polypropylene fibre or acrylic fibers woven tube, and the internal diameter of the woven tube is 0.3-1.8mm, external diameter
It is 0.5-2.3mm.
9. it is according to claim 1 it is a kind of weave tube enhancement type hollow fiber ultrafiltration membrane preparation method, it is characterised in that
The step（5）In coagulating bath be water, methyl alcohol, ethanol, ethylene glycol, propyl alcohol, dimethylformamide, dimethylacetylamide, N-
One or more in methyl pyrrolidone, dimethyl sulfoxide (DMSO), sulfolane, triethyl phosphate, glyceryl triacetate, the water is solidifying
Gu the mass fraction in bath is 30-100%.
10. a kind of preparation method for weaving tube enhancement type hollow fiber ultrafiltration membrane according to claim 1, its feature exists
In the step（5）Also by post processing, the post processing mode is acid treatment, alkali process to the film for obtaining, at the acid treatment, alkali
It is one or more in hydrochloric acid, sulfuric acid, NaOH, potassium hydroxide, ammoniacal liquor to manage, and mass fraction is 0.1-10%, process time
It is 1-72 hours.
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| CN108854549A (en) * | 2018-06-28 | 2018-11-23 | 江苏泓膜业科技有限公司 | A kind of preparation method weaving tube enhancement type hollow fiber ultrafiltration membrane |
| CN108854602A (en) * | 2018-06-28 | 2018-11-23 | 江苏泓膜业科技有限公司 | A kind of enhanced hollow fiber ultrafiltration membrane and preparation method thereof |
| CN109012184A (en) * | 2018-07-19 | 2018-12-18 | 华中科技大学 | A kind of alkali process polyimide foraminous seperation film and the preparation method and application thereof |
| CN109851081A (en) * | 2018-12-11 | 2019-06-07 | 无锡康宇水处理设备有限公司 | A kind of water work with clean water treatment function |
| CN110180403A (en) * | 2019-04-30 | 2019-08-30 | 浙江汉青环境科技有限公司 | A kind of fiber tube enhancement type doughnut composite biological film and preparation method and application |
| CN110180410A (en) * | 2019-05-16 | 2019-08-30 | 深圳市新纳捷科技有限公司 | A kind of adjustable blended ultrafiltration membrane in aperture |
| CN110180409A (en) * | 2019-05-16 | 2019-08-30 | 深圳市新纳捷科技有限公司 | A kind of preparation method of the adjustable blended ultrafiltration membrane in aperture |
| CN113368711A (en) * | 2021-07-20 | 2021-09-10 | 浙江工业大学 | Preparation method of high-performance MABR hollow fiber composite membrane |
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| CN110180409A (en) * | 2019-05-16 | 2019-08-30 | 深圳市新纳捷科技有限公司 | A kind of preparation method of the adjustable blended ultrafiltration membrane in aperture |
| CN113368711A (en) * | 2021-07-20 | 2021-09-10 | 浙江工业大学 | Preparation method of high-performance MABR hollow fiber composite membrane |
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