CN105854641A - Method for preparing narrow-hole-diameter-distribution polyacrylonitrile nano-filtration membrane - Google Patents
Method for preparing narrow-hole-diameter-distribution polyacrylonitrile nano-filtration membrane Download PDFInfo
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- CN105854641A CN105854641A CN201610414879.3A CN201610414879A CN105854641A CN 105854641 A CN105854641 A CN 105854641A CN 201610414879 A CN201610414879 A CN 201610414879A CN 105854641 A CN105854641 A CN 105854641A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- 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
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Abstract
The invention discloses a method for preparing a narrow-hole-diameter-distribution polyacrylonitrile nano-filtration membrane. The problems that a large quantity of difficultly-recycled organic solvents and a large quantity of difficultly-recycled hole forming agents are used in the traditional membrane preparing process, environment pollution is caused, and membrane hole diameter distribution is wide are solved. The method includes the steps that a metal chloride saline solution serves as a solvent, polyacrylonitrile membrane casting liquid is obtained through solution polymerization, then is put into a water coagulation bath, metal ions and chloride ions are gradually diffused into water, and polyacrylonitrile is subjected to phase transformation to be the membrane. As the ions have the hole forming effect, a water channel for ion hole forming is formed in the polyacrylonitrile membrane, the obtained membrane hole diameter distribution is narrow, hydrophilia is good, and the contradictory problems of the low filter accuracy and the low filter efficiency of the membrane can be solved. The filter membrane is simple in preparing technology, low in cost and free of organic waste liquid. Under the pressure of 0.1 MPa, the rejection rate of the polyacrylonitrile filter membrane for direct yellow 27 with the molecular weight of 662 is 95% or above, and the flux is 70 L/m<2>h to 100 L/m<2>h. The filter membrane can be applied to fine separation, dye desalination and wastewater treatment.
Description
Technical field
The present invention relates to a kind of narrower bore footpath distribution polypropylene nitrile NF membrane and preparation method thereof, belong to macromolecular material and film field.
Background technology
Membrane technology, due to advantages such as it are efficient, energy consumption is low and cost of investment is little, is widely applied in water processes.Conventional film
Material is high due to its cost of manufacture, and energy consumption is big, and raw materials recovery utilizes difficulty and limited source, greatly limit its development.At present
Main is that main raw material(s) prepares one by methods such as blending and modifying, surface-coated and surface graft modifications with PVDF, PAN
Series multiwell film.1970～1980, Desalination Engineering company was between hyperfiltration technique and reverse osmosis technology
Membrane separating process referred to as " hydridization filters (Hybrid filtration) ".This separation film the rejection of sodium chloride is generally 50%～
70%, the rejection of fluorescence probe can be reached 90% especially.In the time of coming years, U.S. Film-Tech
Company is manufactured that a kind of utilized thin film composite membranes, also they is called ultra-low-pressure reverse osmosis film.It is about because this film can remove size
The molecule of 1 nanometer, Film-Tech company determines that this class membrane technology is called nanofiltration.The most several companies, such as the UOP of the U.S.,
Hydranautics, Desalination etc. are also proposed similar film.The aperture of the film made due to this process is in nanoscale model
In enclosing, and molecular cut off is between 200～1000, is suitable for separating the dissolved constituent that size is about 1nm, can allow part or
Most of inorganic salt passes through, and therefore characterizes this filter process with " nanofiltration " this word, uses till today always.
China starts desk study Nanofiltration-membrane technique [chemical equipment technology, 2002,23 (8): 14-17] in early days in the nineties in last century,
The research side participating in this technology includes that National Bureau of Oceanography's Hangzhou water treatment centers, Beijing ecology are cyclized center, Chinese Academy of Sciences's Dalian compound
Institute, Shanghai atomic nucleus institute, Tianjin University of Technology etc., but nowadays the research great majority of NF membrane still rest on laboratory stage,
Owing to being limited by many-sided condition, it is impossible to carry out deeper into research.Only two acetic acid of batch production can be accomplished at present
Cellulose rolling NF membrane and Triafol T hollow fiber nanofiltration membrane two kinds [Treatment of Industrial Water, 2004,24 (3): 5-8].
In recent years, polyacrylonitrile has certain development in terms of NF membrane.Xu Chenyan et al. with polyacrylonitrile as raw material, diformazan
Base sulfoxide is solvent, and polyethylene glycol 200 is that porogen prepares basement membrane.Chitosan is coated on polyacrylonitrile basement membrane, through glycerol
After aqueous solution processes, take out and after drying, obtain chitosan/polyacrylonitrile composite nanometer filtering film, and have studied it to amino acid whose separation property
Can, obtain remarkable result.
Using a large amount of difficult organic solvent reclaimed and porogen for tradition film-forming process, cause environmental pollution, membrane aperture is distributed relatively
The problems such as width, the present invention designs a kind of narrower bore footpath of preparation distribution polypropylene nitrile NF membrane.With metal chloride brine solution as solvent,
First passing through polymerisation in solution and obtain polyacrylonitrile casting solution, then put it in water coagulating bath, metal ion and chloride ion are gradually
It is diffused in water, polyacrylonitrile generation phase in version film forming.Ion plays the effect of pore, forms ion and cause in polyacrylonitrile film
The aquaporin in hole, the membrane aperture narrowly distributing therefore obtained, good hydrophilic property, it is possible to resolve the filtering accuracy of film is relatively low with filter efficiency
Contradictory problems.This filter membrane preparation technology is simple, and low cost does not has organic liquid waste to produce.Under 0.1MPa pressure, polypropylene
Nitrile filter membrane reaches more than 95% to the rejection of the Direct Yellow 27 that molecular weight is 662, and flux is 70-100L/m2h.This filtration
Film is expected to be applied to fine separation, dye desalination, sewage disposal.
Summary of the invention
For the deficiencies in the prior art, what the present invention intended to solve technical problem is that film-forming process uses a large amount of difficult organic solvent reclaimed
And porogen, cause the problems such as environmental pollution, membrane aperture wider distribution.
The present invention solves described film-forming process and uses a large amount of difficult organic solvent reclaimed and cause environmental pollution, membrane aperture wider distribution etc.
The technical scheme of problem is to design a kind of narrower bore footpath distribution polypropylene nitrile NF membrane with metal chloride brine solution as solvent, its
Feature is to comprise the following steps:
A) metal chloride salt is dissolved in deionized water, obtains the metal chloride salt of mass percent concentration 10%-100%
Aqueous solution, then pours in there-necked flask by the metal chloride brine solution configured, logical nitrogen deoxygenation 1-30min,
Under agitation be added dropwise over accounting in there-necked flask the acrylonitrile of ionized water mass percent 2%-50%；
B) in controlling flask, solution temperature is 5-90 DEG C and keeps constant temperature, is under agitation added dropwise over accounting for acrylonitrile monemer quality hundred
The initiator of proportion by subtraction 0.1%-10%, causes acrylonitrile monemer polymerization, and the response time is 20-240min；
C) solution after polymerization is cooled to room temperature, vacuum defoamation, obtain casting solution；
D) preparing pH with dilute hydrochloric acid is the aqueous solution of 2-5, as coagulating bath；
E) pouring on the sheet glass of dry cleansing by the casting solution that step c) obtains, scraping thickness with knifing rod is 20-2000 μm
Uniform film, is then dipped into film in the coagulating bath that step d) obtains together with sheet glass, controls the temperature of coagulating bath
Degree, for 0-90 DEG C, reacts 0.5-24h, obtains the polyacrylonitrile film containing part metals chloride salt；Solidified by control
The temperature of bath controls the phase transition rate of polyacrylonitrile, thus controls pore size and the distribution of film；
The dilute hydrochloric acid of the polyacrylonitrile film pH=1-3 containing part metals chloride salt f) obtained by step c) rinses 3-5 time,
Remove the metal ion in membrane removal, finally repeatedly rinse 3-5 time with deionized water, obtain a kind of narrower bore footpath distribution polypropylene
Nitrile NF membrane；
G) narrower bore footpath distribution polypropylene nitrile NF membrane above-mentioned steps obtained is used for retaining dyestuff and the difference point of different molecular weight
The Polyethylene Glycol of son amount, by dyestuff and the concentration of Polyethylene Glycol in solution before and after ultraviolet, liquid chromatograph test filtration,
Thus calculate the rejection of film, it is 90%-100% to the dyestuff of more than 660 molecular weight and the rejection of Polyethylene Glycol,
Being 1%-30% to the dyestuff of less than 600 molecular weight and the rejection of Polyethylene Glycol, its flux is 30-120L/m2h。
Metal chloride salt of the present invention be any one or two kinds in zinc chloride, barium chloride, iron chloride, calcium chloride with
Upper mixture.Described initiator is benzoyl peroxide, tert-butyl hydroperoxide, potassium peroxydisulfate, sodium peroxydisulfate, persulfuric acid
In ammonium, azodiisobutyronitrile, sodium pyrosulfite, DMA, sodium sulfite, ferrous sulfate, ferrous chloride
Any one or two or more mixture.The dyestuff of described different molecular weight be light blue, Congo red, Direct Yellow 27, amaranth,
Any one or two or more mixture in methylene blue, methyl orange, Xylene Red A.The poly-second two of described different molecular weight
The molecular weight of alcohol is 200,400,500,600,650,700,800,1000,2000.
Narrower bore footpath distribution polypropylene nitrile NF membrane flux prepared by the present invention is big, and the pore-size distribution of 90% is between 0.32-0.46nm.
Preparation technology of the present invention is simple, and the used time is few, low cost, energy-conserving and environment-protective.Preparation process makees solvent with metal chloride brine solution,
Saline solution is recyclable, discharges without organic pollution.
Detailed description of the invention
The specific embodiment of the present invention is described below, but the present invention should not be limited by the examples.
Embodiment 1.
A) calcium chloride is dissolved in deionized water, obtains the calcium chloride water of mass percent concentration 100%, then will join
The calcium chloride water put is poured in there-necked flask, logical nitrogen deoxygenation 1min, under agitation in there-necked flask by
Be added dropwise to account for the acrylonitrile of ionized water mass percent 50%；
B) in controlling flask, solution temperature is 5 DEG C and keeps constant temperature, is under agitation added dropwise over accounting for acrylonitrile monemer mass percent
The Ammonium persulfate. of 0.1% and ferrous sulfate, cause acrylonitrile monemer polymerization, and the response time is 20min；
C) solution after polymerization is cooled to room temperature, vacuum defoamation, obtain casting solution；
D) preparing pH with dilute hydrochloric acid is the aqueous solution of 2, as coagulating bath；
E) being poured on the sheet glass of dry cleansing by the casting solution that step c) obtains, scraping thickness with knifing rod is the uniform of 20 μm
Film, then film is dipped in the coagulating bath that step d) obtains together with sheet glass, control coagulating bath temperature be
0 DEG C, react 0.5h, obtain the polyacrylonitrile film containing partial oxidation calcium；Poly-third is controlled by the temperature controlling coagulating bath
The phase transition rate of alkene nitrile, thus control pore size and the distribution of film；
The dilute hydrochloric acid of the polyacrylonitrile film pH=1 containing partial oxidation calcium f) obtained by step c) rinses 3 times, goes in membrane removal
Metal ion, finally rinses with deionized water 3 times repeatedly, obtains a kind of narrower bore footpath distribution polypropylene nitrile NF membrane；
Narrower bore footpath distribution polypropylene nitrile NF membrane above-mentioned steps obtained is used for retaining dyestuff and the difference point of different molecular weight
The Polyethylene Glycol of son amount, it is 100% to the dyestuff of more than 660 molecular weight and the rejection of Polyethylene Glycol, to 600
The dyestuff of following molecular weight and the rejection of Polyethylene Glycol are 30%, and its flux is 30L/m2h。
Embodiment 2.
A) calcium chloride is dissolved in deionized water, obtains the calcium chloride water of mass percent concentration 10%, then will configuration
Good calcium chloride water is poured in there-necked flask, logical nitrogen deoxygenation 30min, in there-necked flask dropwise under agitation
Add the acrylonitrile of the ionized water mass percent 2% that accounts for；
B) in controlling flask, solution temperature is 90 DEG C and keeps constant temperature, is under agitation added dropwise over accounting for acrylonitrile monemer percent mass
Benzoyl peroxide than 10%, causes acrylonitrile monemer polymerization, and the response time is 240min；
C) solution after polymerization is cooled to room temperature, vacuum defoamation, obtain casting solution；
D) preparing pH with dilute hydrochloric acid is the aqueous solution of 5, as coagulating bath；
E) pouring on the sheet glass of dry cleansing by the casting solution that step c) obtains, scraping thickness with knifing rod is the equal of 2000 μm
Even film, is then dipped into film in the coagulating bath that step d) obtains together with sheet glass, controls the temperature of coagulating bath
It is 90 DEG C, reacts 24h, obtain the polyacrylonitrile film containing partial oxidation calcium；Control poly-by the temperature controlling coagulating bath
The phase transition rate of acrylonitrile, thus control pore size and the distribution of film；
The dilute hydrochloric acid of the polyacrylonitrile film pH=3 containing partial oxidation calcium f) obtained by step c) rinses 3 times, goes in membrane removal
Metal ion, finally rinses with deionized water 3 times repeatedly, obtains a kind of narrower bore footpath distribution polypropylene nitrile NF membrane；
Narrower bore footpath distribution polypropylene nitrile NF membrane above-mentioned steps obtained is used for retaining dyestuff and the difference point of different molecular weight
The Polyethylene Glycol of son amount, it is 90% to the dyestuff of molecular weight more than 660 and the rejection of Polyethylene Glycol, to molecular weight
The dyestuff of less than 600 and the rejection of Polyethylene Glycol are 1%, and its flux is 120L/m2h。
Embodiment 3.
A) zinc chloride is dissolved in deionized water, obtains the solder(ing)acid of mass percent concentration 50%, then will configuration
Good solder(ing)acid is poured in there-necked flask, logical nitrogen deoxygenation 10min, in there-necked flask dropwise under agitation
Add the acrylonitrile of the ionized water mass percent 20% that accounts for；
B) in controlling flask, solution temperature is 20 DEG C and keeps constant temperature, is under agitation added dropwise over accounting for acrylonitrile monemer percent mass
Potassium peroxydisulfate-ferrous sulfate than 0.2%, causes acrylonitrile monemer polymerization, and the response time is 90min；
C) solution after polymerization is cooled to room temperature, vacuum defoamation, obtain casting solution；
D) preparing pH with dilute hydrochloric acid is the aqueous solution of 3, as coagulating bath；
E) being poured on the sheet glass of dry cleansing by the casting solution that step c) obtains, scraping thickness with knifing rod is the equal of 200 μm
Even film, is then dipped into film in the coagulating bath that step d) obtains together with sheet glass, controls the temperature of coagulating bath
It is 40 DEG C, reacts 4h, obtain the polyacrylonitrile film containing partial oxidation zinc；Control poly-by the temperature controlling coagulating bath
The phase transition rate of acrylonitrile, thus control pore size and the distribution of film；
The dilute hydrochloric acid of the polyacrylonitrile film pH=2 containing partial oxidation zinc f) obtained by step c) rinses 5 times, goes in membrane removal
Metal ion, finally rinses with deionized water 5 times repeatedly, obtains a kind of narrower bore footpath distribution polypropylene nitrile NF membrane；
G) narrower bore footpath distribution polypropylene nitrile NF membrane above-mentioned steps obtained is used for retaining dyestuff and the difference point of different molecular weight
The Polyethylene Glycol of son amount, it is 98% to the dyestuff of molecular weight more than 660 and the rejection of Polyethylene Glycol, to molecular weight
The dyestuff of less than 600 and the rejection of Polyethylene Glycol are 28%, and its flux is 80L/m2h。
Embodiment 4.
A) iron chloride is dissolved in deionized water, obtains the ferric chloride in aqueous solution of mass percent concentration 50%, then will configuration
Good ferric chloride in aqueous solution is poured in there-necked flask, logical nitrogen deoxygenation 20min, in there-necked flask dropwise under agitation
Add the acrylonitrile of the ionized water mass percent 10% that accounts for；
B) in controlling flask, solution temperature is 60 DEG C and keeps constant temperature, is under agitation added dropwise over accounting for acrylonitrile monemer percent mass
Potassium peroxydisulfate-sodium sulfite than 1%, causes acrylonitrile monemer polymerization, and the response time is 60min；
C) solution after polymerization is cooled to room temperature, vacuum defoamation, obtain casting solution；
D) preparing pH with dilute hydrochloric acid is the aqueous solution of 2, as coagulating bath；
E) being poured on the sheet glass of dry cleansing by the casting solution that step c) obtains, scraping thickness with knifing rod is the equal of 400 μm
Even film, is then dipped into film in the coagulating bath that step d) obtains together with sheet glass, controls the temperature of coagulating bath
It is 60 DEG C, reacts 12h, obtain the polyacrylonitrile film containing partial oxidation ferrum；Control poly-by the temperature controlling coagulating bath
The phase transition rate of acrylonitrile, thus control pore size and the distribution of film；
The dilute hydrochloric acid of the polyacrylonitrile film pH=2 containing partial oxidation ferrum f) obtained by step c) rinses 4 times, goes in membrane removal
Metal ion, finally rinses with deionized water 4 times repeatedly, obtains a kind of narrower bore footpath distribution polypropylene nitrile NF membrane；
Narrower bore footpath distribution polypropylene nitrile NF membrane above-mentioned steps obtained is used for retaining dyestuff and the difference point of different molecular weight
The Polyethylene Glycol of son amount, it is 95% to the dyestuff of molecular weight more than 660 and the rejection of Polyethylene Glycol, to molecular weight
The dyestuff of less than 600 and the rejection of Polyethylene Glycol are 20%, and its flux is 90L/m2h。
Claims (6)
1. a preparation method for narrower bore footpath distribution polypropylene nitrile NF membrane, is characterized in that comprising the following steps:
A) metal chloride salt is dissolved in deionized water, obtains the metal chloride salt of mass percent concentration 10%-100%
Aqueous solution, then pours in there-necked flask by the metal chloride brine solution configured, logical nitrogen deoxygenation 1-30min,
Under agitation be added dropwise over accounting in there-necked flask the acrylonitrile of ionized water mass percent 2%-50%；
B) in controlling flask, solution temperature is 5-90 DEG C and keeps constant temperature, is under agitation added dropwise over accounting for acrylonitrile monemer quality hundred
The initiator of proportion by subtraction 0.1%-10%, causes acrylonitrile monemer polymerization, and the response time is 20-240min；
C) solution after polymerization is cooled to room temperature, vacuum defoamation, obtain casting solution；
D) preparing pH with dilute hydrochloric acid is the aqueous solution of 2-5, as coagulating bath；
E) being poured on the sheet glass of dry cleansing by the casting solution that step c) obtains, scraping thickness with knifing rod is 20-2000 μm
Uniform film, is then dipped into film in the coagulating bath that step d) obtains together with sheet glass, controls the temperature of coagulating bath
Degree, for 0-90 DEG C, reacts 0.5-24h, obtains the polyacrylonitrile film containing part metals chloride salt；Solidified by control
The temperature of bath controls the phase transition rate of polyacrylonitrile, thus controls pore size and the distribution of film；
The dilute hydrochloric acid of the polyacrylonitrile film pH=1-3 containing part metals chloride salt f) obtained by step c) rinses 3-5 time,
Remove the metal ion in membrane removal, finally repeatedly rinse 3-5 time with deionized water, obtain a kind of narrower bore footpath distribution polypropylene
Nitrile NF membrane；
G) narrower bore footpath distribution polypropylene nitrile NF membrane above-mentioned steps obtained is used for retaining dyestuff and the difference point of different molecular weight
The Polyethylene Glycol of son amount, by dyestuff and the concentration of Polyethylene Glycol in solution before and after ultraviolet, liquid chromatograph test filtration,
Thus calculate the rejection of film, it is 90%-100% to the dyestuff of molecular weight more than 660 and the rejection of Polyethylene Glycol,
Being 1%-30% to the dyestuff of molecular weight less than 600 and the rejection of Polyethylene Glycol, its flux is 30-120L/m2h。
The preparation method of a kind of narrower bore footpath the most as claimed in claim 1 distribution polypropylene nitrile NF membrane, is characterized in that described metal
Chloride salt is any one or two or more mixture in zinc chloride, barium chloride, iron chloride, calcium chloride.
The preparation method of a kind of narrower bore footpath the most as claimed in claim 1 distribution polypropylene nitrile NF membrane, is characterized in that described initiation
Agent be benzoyl peroxide, tert-butyl hydroperoxide, potassium peroxydisulfate, sodium peroxydisulfate, Ammonium persulfate., azodiisobutyronitrile,
Any one or two kinds in sodium pyrosulfite, DMA, sodium sulfite, ferrous sulfate, ferrous chloride with
Upper mixture.
The preparation method of a kind of narrower bore footpath the most as claimed in claim 1 distribution polypropylene nitrile NF membrane, is characterized in that described difference
The dyestuff of molecular weight is in light blue, Congo red, Direct Yellow 27, amaranth, methylene blue, methyl orange, Xylene Red A
Any one or two or more mixture.
The preparation method of a kind of narrower bore footpath the most as claimed in claim 1 distribution polypropylene nitrile NF membrane, is characterized in that described difference
The molecular weight of the Polyethylene Glycol of molecular weight is 200,400,500,600,650,700,800,1000,2000.
6. a preparation method for narrower bore footpath distribution polypropylene nitrile NF membrane, is characterized in that the narrower bore footpath distribution polypropylene nitrile NF membrane of preparation
Flux is big, and the pore-size distribution of 90% is between 0.32-0.46nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110052174A (en) * | 2019-04-04 | 2019-07-26 | 天津工业大学 | A kind of preparation method of the polyacrylonitrile-radical filter membrane of high throughput bubbles |
| CN110052177A (en) * | 2019-04-04 | 2019-07-26 | 天津工业大学 | A kind of preparation method of hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane |
| CN111133087A (en) * | 2017-08-01 | 2020-05-08 | 西姆莱斯股份公司 | Cold treatment |
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| EP2486974A1 (en) * | 2011-02-10 | 2012-08-15 | LANXESS Deutschland GmbH | Filtration membrane |
| CN102806022A (en) * | 2012-09-06 | 2012-12-05 | 天津工业大学 | Method for preparing polyacrylonitrile (PAN)-base microporous membrane |
| CN103212302A (en) * | 2013-04-03 | 2013-07-24 | 北京工业大学 | Method for preparing macromolecule hollow porous fiber membrane by using chemical reaction inductive phase conversion method |
| CN105133187A (en) * | 2015-07-22 | 2015-12-09 | 东华大学 | Method for manufacturing electrospun nanofiber gas filtering material in mass manner |
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2016
- 2016-06-12 CN CN201610414879.3A patent/CN105854641B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2486974A1 (en) * | 2011-02-10 | 2012-08-15 | LANXESS Deutschland GmbH | Filtration membrane |
| CN102806022A (en) * | 2012-09-06 | 2012-12-05 | 天津工业大学 | Method for preparing polyacrylonitrile (PAN)-base microporous membrane |
| CN103212302A (en) * | 2013-04-03 | 2013-07-24 | 北京工业大学 | Method for preparing macromolecule hollow porous fiber membrane by using chemical reaction inductive phase conversion method |
| CN105133187A (en) * | 2015-07-22 | 2015-12-09 | 东华大学 | Method for manufacturing electrospun nanofiber gas filtering material in mass manner |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111133087A (en) * | 2017-08-01 | 2020-05-08 | 西姆莱斯股份公司 | Cold treatment |
| CN110052174A (en) * | 2019-04-04 | 2019-07-26 | 天津工业大学 | A kind of preparation method of the polyacrylonitrile-radical filter membrane of high throughput bubbles |
| CN110052177A (en) * | 2019-04-04 | 2019-07-26 | 天津工业大学 | A kind of preparation method of hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane |
| CN110052177B (en) * | 2019-04-04 | 2021-04-30 | 天津工业大学 | Preparation method of hollow microsphere reinforced high-flux polyacrylonitrile filter membrane |
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