CN108786468A - A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films - Google Patents
A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films Download PDFInfo
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- CN108786468A CN108786468A CN201810671265.2A CN201810671265A CN108786468A CN 108786468 A CN108786468 A CN 108786468A CN 201810671265 A CN201810671265 A CN 201810671265A CN 108786468 A CN108786468 A CN 108786468A
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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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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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
- B01D69/04—Tubular membranes
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Abstract
A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films, it is related to a kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films.The present invention is to solve existing import flushing-free DF film diameters are big, wall thickness, membrane filtration area prepared by the raw material of unit mass is small, film wire packing density is low, membrane porosity is low, operating pressure is high, to make the increased problem of energy consumption.Stirring and dissolving in decentralized medium is added in Kynoar and organic additive in certain sequence, enters spinning box standing and defoaming after filtering；Flushing-free tubular membrane is made using hollow-fibre membrane spinning-drawing machine, film wire prepares corresponding membrane module after processing.The present invention may replace existing flushing-free microporous film products.
Description
Technical field
The present invention relates to the methods that a kind of thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films.
Background technology
Optimization technique of the membrane technology as 21 century drinking water treatment has energy with conventional water treatment Technical comparing
Consume low, separative efficiency is high, it is simple for process, without adding additive, not influencing the advantages that health, but due to concentration polarization and
The presence of the problems such as fouling membrane, causes permeation flux to decline with the extension of run time；A large amount of energy consumption quilt in operating process
For the recycling of material liquid to control concentration polarization and fouling membrane, microporous barrier (including micro-filtration and ultrafiltration) technology is seriously hindered
More massive commercial Application.In membrane separating process, due to solute (especially macromolecular, colloidal suspended substance and biology point
Son etc.) pollution, so that film permeation flux is remarkably decreased, separating property changes, as in food industry fouling membrane can cause it is micro-
Biological self reproducing damages product quality.Crucial equipment is membrane module in membrane separating process, and the core of membrane module is performance
Good film, i.e., big flux, highly selective lock out operation may be implemented in film used, and answers the stabilization of extend as far as possible film
Operating time.However during actual separation, the performance of film can change a lot with the extension of operating time, very
Typically through the flux of film can be at any time passage and reduce.Such as in ultra-filtration process, the elimination of pollution will make ultra filtration
Journey efficiency improves 30%, reduces investment 15%, and have preferable separating effect.Many due to generating fouling membrane, film is dirty
Dye phenomenon is more complicated, therefore without the general method suitable for various fouling membrane situations.It is generated in the application process of film
The pollution of film is very difficult to avoid completely, but reduces the dirt of film by taking appropriate measures to different fouling membrane situations
Dye degree is feasible.The characteristics of particular situation will be according to its membrane material and membrane separating process is encountered, from design, technological process
Consideration is made a concrete analysis of to links such as equipment selection, operation, the storage and transportation of film and maintenance downtimes, which kind of method determination takes
Reduce the pollution of film, formulates the concrete measure safeguarded membrane module with prevent fouling membrane, the influence of concentration polarization and fouling membrane is made to subtract
It is small to arrive minimum level.
Control method as fouling membrane has summed up chemical method and physical method.There is liquid to be treated in chemical method
Pre-treatment, exploitation low absorbability can membrane material, film surface improvement and drug cleaning etc..Physical method has back washing etc. online
Cleaning, the optimization of operating condition utilize electrophoresis or the device of Taylor vortexs, fluidised form control etc..Research both domestic and external is being developed
A large amount of research is carried out in terms of high performance membrane material, has developed a large amount of hydrophilic film material, has been the development of membrane technology and big
Sizable application plays the role of actively promoting.But exists rinse repeatedly in use, cleans and medicine such as washes at the processes, need one
In the fixed operation cycle and reagent consumption, film flushing process is time-consuming, laborious, can also weaken the intensity and separating property of film wire, to
Influence separating effect.
2003, Duraflow companies of U.S. Joseph Lander and William Matheson produced a new generation
Flushing-free DF films, and carry out and be used for field of waste water treatment.The film has intensity height, long lifespan, need not backwash, only logical
Positive cleaning is carried out when amount decays to 50%, cleaning agent selects low-concentration sulfuric acid or sodium hypochlorite, can be replied after cleaning flux,
The features such as cleaning frequency can be 1~2 week to two months；Compared with traditional seperation film, can save medicament, it is easy to operate
Applied to the fields such as wastewater treatment and reuse, substitution settling tank.But it is shown according to the U.S. Duraflow related datas provided, it should
DF films use sintering process to prepare at present, and a diameter of 2.5cm of tubular membrane of preparation or so, wall is thicker, prepared by the raw material of unit mass
Membrane filtration area is small, membrane module filling film wire density is low；The porosity of this outer membrane is low, operating pressure is high (0.35~
0.42MPa), to make energy consumption increase.Therefore, it is necessary to open up new approach, develop new high packing density, high porosity,
The flushing-free microporous barrier of ow operating pressure.
Invention content
The present invention is to solve existing import flushing-free DF film diameters are big, wall thickness, film mistake prepared by the raw material of unit mass
Filtering surface product is small, film wire packing density is low, membrane porosity is low, operating pressure is high, to make the increased problem of energy consumption.And it provides a kind of
The method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films.
A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films of the present invention is according to the following steps
It carries out：
One, 10~30 parts of PVDF, 50~100 parts of decentralized media and 0.1~20 portion of organic additive are weighed in parts by weight；
Two, weigh 10~30 portions of PVDF and 0.1~20 portion of organic additives 50~100 parts of dispersions are added sequentially to be situated between
In matter, temperature be at 60~150 DEG C under conditions of stirring 6~for 24 hours, obtain casting solution；
Three, it is sent into spinning box after filtering casting solution, after standing and defoaming 8~for 24 hours, using hollow-fibre membrane spinning mechanism
Film；
Four, by the film of preparation first in water impregnate 12~for 24 hours, then in protect liquid immersion 6~48h, finally opposite
Humidity is drying at room temperature under conditions of 30~75%, obtains flushing-free PVDF tube-type micropore films.
Beneficial effects of the present invention：
The present invention has the advantage that compared with external current import DF flushing-free films：1) preparation process is simple, is easy to
Realize the production of film.The present invention realizes that solution is prepared and spinning technique is ripe using the thermotropic phase phase inversion of low temperature, is easy to real
It is existing；And the DF flushing-free films of import are prepared using sintering process, low production efficiency, film quality is not easily controlled.2) product diameter is
2.0~8.0mm is much smaller than the diameter (about 2.5cm) of import DF films, therefore packing density is high, improves water-yielding capacity；It can carry simultaneously
The effective filtration area of plateau material preparation membrane；Improve the utilization rate of raw material；Further, it is also possible to improve film surface boundary-layer
Turbulent extent, avoid pollutant accumulation and blocking.3) it can run, film can be significantly reduced in water process and detach under low pressure
The energy consumption of journey, while the pollution level of film is reduced, extend scavenging period.4) film that can prepare more small-bore improves cutting for film
Ability is stayed, fouling membrane is further mitigated.And existing tube-type micropore film and hollow fiber microporous membrane do not have still currently on the market
The function of flushing-free.Therefore, the present invention may replace the DF films of import and current existing microporous film products, realize in wastewater treatment
With reuse, feed separation and concentration, instead of the application in the fields such as traditional sedimentation basin or filtering ponds.
Specific implementation mode
Specific implementation mode one：A kind of thermotropic phase inversion of low temperature of present embodiment prepares flushing-free PVDF tube-type micropore films
Method be to carry out according to the following steps：
One, 10~30 parts of PVDF, 50~100 parts of decentralized media and 0.1~20 portion of organic additive are weighed in parts by weight；
Two, weigh 10~30 portions of PVDF and 0.1~20 portion of organic additives 50~100 parts of dispersions are added sequentially to be situated between
In matter, temperature be at 60~150 DEG C under conditions of stirring 6~for 24 hours, obtain casting solution；
Three, it is sent into spinning box after filtering casting solution, after standing and defoaming 8~for 24 hours, using hollow-fibre membrane spinning mechanism
Film；
Four, by the film of preparation first in water impregnate 12~for 24 hours, then in protect liquid immersion 6~48h, finally opposite
Humidity is drying at room temperature under conditions of 30~75%, obtains flushing-free PVDF tube-type micropore films.
The film of preparation first impregnates 12 by present embodiment step 4 in water~and purpose for 24 hours is dissolution solvent and addition
Agent.
Specific implementation mode two：The present embodiment is different from the first embodiment in that：Disperse to be situated between described in step 1
Matter is one kind or in which several in N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone and acetone
The mixture of kind.It is other same as the specific embodiment one.
Specific implementation mode three：The present embodiment is different from the first and the second embodiment in that：Have described in step 1
Machine additive is polyethylene glycol, polyacrylonitrile (PAN), cationic surfactant, anion surfactant, non-ionic surface
Activating agent, acetone, ethyl alcohol, glycerine and different molecular quality polyvinylpyrrolidone in one kind or in which several mixing
Object.It is other the same as one or two specific embodiments.
Specific implementation mode four：Unlike one of present embodiment and specific implementation mode one to three：It is adopted in step 3
The process conditions being film-made with hollow-fibre membrane spinning-drawing machine：Spinning spinneret aperture OD/ID is 2.0~8.0mm/1.4~6mm；It is interior
Core liquid is one in water, ethyl alcohol, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone and acetone
Kind or in which several mixtures；The temperature of inner core liquid is 20~90 DEG C；Outer coagulating bath medium is water, ethyl alcohol, N, N- dimethyl
One kind in formamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone and acetone or in which several mixtures；Outside
The temperature of coagulating bath medium is 20~90 DEG C；It is 0~20cm that journey is done in spinning；Winding speed is 3~30m/min.It is other with it is specific
One of embodiment one to three is identical.
Present embodiment OD indicates that outer aperture, ID indicate internal orifice dimension.
Specific implementation mode five：Unlike one of present embodiment and specific implementation mode one to four：Institute in step 4
State protection liquid be 5~60% glycerine water solution, 1~15% Tween-20 aqueous solution, 1~15% Tween-40 aqueous solution, 1
~15% Tween-60 aqueous solution and one kind in 1~15% Tween-80 aqueous solution or in which several mixtures, are mixed
It is mixed by any ratio when closing object.It is other identical as one of specific implementation mode one to four.
Specific implementation mode six：Unlike one of present embodiment and specific implementation mode one to five：Step 4 obtains
Flushing-free PVDF tube-type micropore films OD/ID be 2.0~8.0mm/1.4~6mm；Porosity is 70~95%；Film monofilament is strong
Degree is more than 7N.It is other identical as one of specific implementation mode one to five.
Specific implementation mode seven：Unlike one of present embodiment and specific implementation mode one to six：Step 4 obtains
Flushing-free PVDF tube-type micropores film realized at 0.1~0.3MPa flushing-free run, film surface average pore size control 0.01
~0.5 μm；Operating flux is 300~2000L/ (m2·h)；Continuous operation is cleaned 1 time after 15~25 days, and once purged film is logical
Recovery rate is measured 95% or more.It is other identical as one of specific implementation mode one to six.
Present embodiment can be applied to wastewater treatment and reuse, feed separation and concentration, instead of traditional sedimentation basin or mistake
Flushing-free is realized in the fields such as filter tank.
Pass through the effect of the following embodiment verification present invention：
Embodiment one：A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films is by following step
It is rapid to carry out：
One, 20 parts of Kynoar PVDF, 80 parts of N,N-dimethylformamides, 8 parts of polyethylene pyrroles are weighed in parts by weight
Pyrrolidone；
Two, weigh 20 parts of Kynoar PVDF and 8 parts of polyvinylpyrrolidones are added sequentially to 80 parts of N, N- bis-
In methylformamide, is stirred for 24 hours under conditions of temperature is at 115 DEG C, obtain casting solution；
Three, after casting solution being filtered be sent into spinning box in, standing and defoaming for 24 hours after, using hollow-fibre membrane spinning-drawing machine be film-made；
The process conditions being film-made using hollow-fibre membrane spinning-drawing machine：The hole diameter of spinneret OD/ID is 2.4mm/3.6mm, inner core liquid is 20%
Glycerine water solution, outer coagulating bath medium be water, dry journey is 3cm, winding speed 25m/min, inner core liquid temperature is 85 DEG C, outer
Coagulating bath medium temperature is 60 DEG C；
Four, the film of preparation is first impregnated for 24 hours in water, is then impregnated for 24 hours in 20% glycerine protection liquid, finally in phase
Drying at room temperature under conditions of being 50% to humidity, obtains flushing-free PVDF tube-type micropore films.
The diameter of obtained flushing-free PVDF tube-type micropore films：OD/ID is 3.0mm/2.4mm；Porosity 80%；Film list
Silk intensity is more than 7.8N；It can realize that flushing-free is run at 0.1~0.3MPa, film surface average pore size can be 0.01 μm；Operation
Flux reaches 650L/ (m2·h)(0.1MPa)；Antifouling property is good, and continuously-running cleans 1 time after 20 days, once purged
Membrane flux recovery rate is 96% or more.Flushing-free operation can be achieved.
Embodiment two：A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films is by following step
It is rapid to carry out：
One, 22 parts of Kynoar PVDF, 78 parts of DMAC N,N' dimethyl acetamides, 7 parts of polyethylene glycol are weighed in parts by weight
(molecular weight 3000)；
Two, weigh 22 parts of Kynoar PVDF and 7 parts of polyethylene glycol (molecular weight 3000) are added sequentially to 78 parts
In n,N-dimethylacetamide, is stirred for 24 hours under conditions of temperature is at 115 DEG C, obtain casting solution；
Three, after casting solution being filtered be sent into spinning box in, standing and defoaming for 24 hours after, using hollow-fibre membrane spinning-drawing machine be film-made；
The process conditions being film-made using hollow-fibre membrane spinning-drawing machine：The hole diameter of spinneret OD/ID is 3.2mm/2.0mm, inner core liquid is 30%
N,N-dimethylacetamide aqueous solution, outer coagulating bath medium be water, dry journey is 6cm, winding speed 20m/min, inner core liquid
Temperature is 90 DEG C, outer coagulating bath medium temperature is 50 DEG C；
Four, the film of preparation is first impregnated for 24 hours in water, is then impregnated for 24 hours in 20% glycerine protection liquid, finally in phase
Drying at room temperature under conditions of being 50% to humidity, obtains flushing-free PVDF tube-type micropore films.
The diameter of obtained flushing-free PVDF tube-type micropore films：OD/ID is 2.8mm/2.2mm；Porosity 82%；Film list
Silk intensity is more than 7.8N；It can realize that flushing-free is run at 0.1~0.3MPa, film surface average pore size can be 0.03 μm；Operation
Flux reaches 710L/ (m2·h)(0.1MPa)；Antifouling property is good, and continuously-running cleans 1 time after 18 days, once purged
Membrane flux recovery rate is 95% or more.Flushing-free operation can be achieved.
Embodiment three：A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films is by following step
It is rapid to carry out：
One, 18 parts of Kynoar PVDF, 82 parts of DMAC N,N' dimethyl acetamides, 8 parts of polyethylene glycol are weighed in parts by weight
(molecular weight 3000)；
Two, weigh 18 parts of Kynoar PVDF and 8 parts of polyethylene glycol (molecular weight 3000) are added sequentially to 82 parts
In n,N-dimethylacetamide, is stirred for 24 hours under conditions of temperature is at 105 DEG C, obtain casting solution；
Three, after casting solution being filtered be sent into spinning box in, standing and defoaming for 24 hours after, using hollow-fibre membrane spinning-drawing machine be film-made；
The process conditions being film-made using hollow-fibre membrane spinning-drawing machine：The hole diameter of spinneret OD/ID is 3.2mm/2.0mm, inner core liquid is 30%
Glycol water, outer coagulating bath medium be water, dry journey is 8cm, winding speed 18m/min, inner core liquid temperature is 80 DEG C,
Outer coagulating bath medium temperature is 30 DEG C；
Four, the film of preparation is first impregnated for 24 hours in water, is then impregnated for 24 hours in 20% glycerine protection liquid, finally in phase
Drying at room temperature under conditions of being 30% to humidity, obtains flushing-free PVDF tube-type micropore films.
The diameter of obtained flushing-free PVDF tube-type micropore films：OD/ID is 2.6mm/2.0mm；Porosity 85%；Film list
Silk intensity is more than 7.1N；It can realize that flushing-free is run at 0.1~0.3MPa, film surface average pore size can be 0.1 μm；Operation is logical
Amount reaches 970L/ (m2·h)(0.1MPa)；Antifouling property is good, and continuously-running cleans 1 time after 20 days, once purged film
Flux recovery rate is 95% or more.Flushing-free operation can be achieved.
Example IV：A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films is by following step
It is rapid to carry out：
One, 18 parts of Kynoar PVDF, 82 parts of n-methyl-2-pyrrolidone, 8 parts of polyethylene glycol are weighed in parts by weight
(molecular weight 1500)；
Two, weigh 18 parts of Kynoar PVDF and 8 parts of polyethylene glycol (molecular weight 1500) are added sequentially to 82 parts
In n-methyl-2-pyrrolidone, is stirred for 24 hours under conditions of temperature is at 105 DEG C, obtain casting solution；
Three, after casting solution being filtered be sent into spinning box in, standing and defoaming for 24 hours after, using hollow-fibre membrane spinning-drawing machine be film-made；
The process conditions being film-made using hollow-fibre membrane spinning-drawing machine：The hole diameter of spinneret OD/ID is 4.0mm/2.4mm, inner core liquid is 30%
Ethanol water, outer coagulating bath medium be water, dry journey is 6cm, winding speed 20m/min, inner core liquid temperature is 80 DEG C, outer
Coagulating bath medium temperature is 60 DEG C；
Four, the film of preparation is first impregnated for 24 hours in water, is then impregnated for 24 hours in 20% glycerine protection liquid, finally in phase
Drying at room temperature under conditions of being 50% to humidity, obtains flushing-free PVDF tube-type micropore films.
The diameter of obtained flushing-free PVDF tube-type micropore films：OD/ID is 3.2mm/2.6mm；Porosity 75%；Film list
Silk intensity is more than 8N；It can realize that flushing-free is run at 0.1~0.3MPa, film surface average pore size can be 0.2 μm；Operating flux
Up to 1220L/ (m2·h)(0.1MPa)；Antifouling property is good, and continuously-running cleans 1 time after 20 days, and once purged film is logical
Recovery rate is measured 95% or more.Flushing-free operation can be achieved.
Embodiment five：A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films is by following step
It is rapid to carry out：
One, 18 parts of Kynoar PVDF, 82 parts of n-methyl-2-pyrrolidone, 7 parts of polyethylene glycol are weighed in parts by weight
(molecular weight 1500)；
Two, weigh 18 parts of Kynoar PVDF and 7 parts of polyethylene glycol (molecular weight 1500) are added sequentially to 82 parts
In n-methyl-2-pyrrolidone, is stirred for 24 hours under conditions of temperature is at 105 DEG C, obtain casting solution；
Three, after casting solution being filtered be sent into spinning box in, standing and defoaming for 24 hours after, using hollow-fibre membrane spinning-drawing machine be film-made；
The process conditions being film-made using hollow-fibre membrane spinning-drawing machine：The hole diameter of spinneret OD/ID is 3.2mm/2.0mm, inner core liquid is 30%
N-methyl-2-pyrrolidone aqueous solution, outer coagulating bath medium be water, dry journey is 2cm, winding speed 30m/min, inner core liquid
Temperature is 80 DEG C, outer coagulating bath medium temperature is 60 DEG C；
Four, the film of preparation is first impregnated for 24 hours in water, is then impregnated for 24 hours in 20% glycerine protection liquid, finally in phase
Drying at room temperature under conditions of being 50% to humidity, obtains flushing-free PVDF tube-type micropore films.
The diameter of obtained flushing-free PVDF tube-type micropore films：OD/ID is 2.7mm/2.1mm；Porosity 82%；Film list
Silk intensity is more than 7.6N；It can realize that flushing-free is run at 0.1~0.3MPa, film surface average pore size can be 0.35 μm；Operation
Flux reaches 1350L/ (m2·h)(0.1MPa)；Antifouling property is good, and continuously-running cleans 1 time after 24 days, once purged
Membrane flux recovery rate is 95% or more.Flushing-free operation can be achieved.
Claims (7)
1. a kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films, it is characterised in that the thermotropic phase of low temperature
The method that conversion method prepares flushing-free PVDF tube-type micropore films is to carry out according to the following steps：
One, 10~30 parts of PVDF, 50~100 parts of decentralized media and 0.1~20 portion of organic additive are weighed in parts by weight；
Two, weigh 10~30 portions of PVDF and 0.1~20 portion of organic additives are added sequentially to 50~100 parts of decentralized media
In, temperature be at 60~150 DEG C under conditions of stirring 6~for 24 hours, obtain casting solution；
Three, it is sent into spinning box after filtering casting solution, after standing and defoaming 8~for 24 hours, is film-made using hollow-fibre membrane spinning-drawing machine；
Four, by the film of preparation first in water impregnate 12~for 24 hours, then in protect liquid immersion 6~48h, finally in relative humidity
Drying at room temperature under conditions of being 30~75% obtains flushing-free PVDF tube-type micropore films.
2. the method that the thermotropic phase inversion of a kind of low temperature according to claim 1 prepares flushing-free PVDF tube-type micropore films,
It is characterized in that decentralized medium described in step 1 is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl -2- pyrroles
One kind in pyrrolidone and acetone or in which several mixtures.
3. the method that the thermotropic phase inversion of a kind of low temperature according to claim 1 prepares flushing-free PVDF tube-type micropore films,
It is characterized in that organic additive described in step 1 be polyethylene glycol, polyacrylonitrile (PAN), cationic surfactant, it is cloudy from
The polyvinylpyrrolidone of sub- surfactant, nonionic surface active agent, acetone, ethyl alcohol, glycerine and different molecular quality
In one kind or in which several mixtures.
4. the method that the thermotropic phase inversion of a kind of low temperature according to claim 1 prepares flushing-free PVDF tube-type micropore films,
It is characterized in that using the process conditions of hollow-fibre membrane spinning-drawing machine film in step 3：Spinning spinneret aperture OD/ID is 2.0
~8.0mm/1.4~6mm；Inner core liquid is water, ethyl alcohol, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl -2-
One kind in pyrrolidones and acetone or in which several mixtures；The temperature of inner core liquid is 20~90 DEG C；Outer coagulating bath medium
For in water, ethyl alcohol, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone and acetone one kind or
Wherein several mixtures；The temperature of outer coagulating bath medium is 20~90 DEG C；It is 0~20cm that journey is done in spinning；Winding speed be 3~
30m/min。
5. the method that the thermotropic phase inversion of a kind of low temperature according to claim 1 prepares flushing-free PVDF tube-type micropore films,
It is characterized in that described in step 4 protect liquid be 5~60% glycerine water solution, 1~15% Tween-20 aqueous solution, 1~
15% Tween-40 aqueous solution, 1~15% Tween-60 aqueous solution and 1~15% Tween-80 aqueous solution in one kind or
Wherein several mixtures.
6. the method that the thermotropic phase inversion of a kind of low temperature according to claim 1 prepares flushing-free PVDF tube-type micropore films,
It is characterized in that the OD/ID for the flushing-free PVDF tube-type micropore films that step 4 obtains is 2.0~8.0mm/1.4~6mm；Porosity
It is 70~95%；Film filament strength is more than 7N.
7. the method that the thermotropic phase inversion of a kind of low temperature according to claim 1 prepares flushing-free PVDF tube-type micropore films,
It is characterized in that the flushing-free PVDF tube-type micropores film that step 4 obtains realizes that flushing-free is run at 0.1~0.3MPa, film table
Face average pore size control is at 0.01~0.5 μm；Operating flux is 300~2000L/ (m2·h)；Continuous operation is clear after 15~25 days
It washes 1 time, once purged membrane flux recovery rate is 95% or more.
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| CN201810671265.2A Pending CN108786468A (en) | 2018-06-26 | 2018-06-26 | A kind of method that the thermotropic phase inversion of low temperature prepares flushing-free PVDF tube-type micropore films |
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| CN1608718A (en) * | 2003-10-17 | 2005-04-27 | 天津膜天膜工程技术有限公司 | Hollow fiber film and its prepn process |
| WO2007080862A1 (en) * | 2006-01-11 | 2007-07-19 | Toyo Boseki Kabushiki Kaisha | Polyvinylidene fluoride hollow yarn type microporous film and process for production of the same |
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| CN103585892A (en) * | 2013-11-25 | 2014-02-19 | 北京碧水源膜科技有限公司 | Method for preparing enhanced hollow fiber membrane employing low-temperature thermal induced phase method, product, and application and equipment thereof |
| CN105381724A (en) * | 2014-09-05 | 2016-03-09 | 浙江省化工研究院有限公司 | High tensile strength PVDF hollow fiber membrane preparation method |
| CN107096396A (en) * | 2017-05-19 | 2017-08-29 | 开源环保（集团）有限公司 | A kind of polyvinylidene fluoride hollow fiber miillpore filter and preparation method thereof |
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| CN1608718A (en) * | 2003-10-17 | 2005-04-27 | 天津膜天膜工程技术有限公司 | Hollow fiber film and its prepn process |
| WO2007080862A1 (en) * | 2006-01-11 | 2007-07-19 | Toyo Boseki Kabushiki Kaisha | Polyvinylidene fluoride hollow yarn type microporous film and process for production of the same |
| CN101733023A (en) * | 2010-02-02 | 2010-06-16 | 顾涌 | Method for manufacturing polyvinylidene fluoride hollow fiber membrane |
| CN103585892A (en) * | 2013-11-25 | 2014-02-19 | 北京碧水源膜科技有限公司 | Method for preparing enhanced hollow fiber membrane employing low-temperature thermal induced phase method, product, and application and equipment thereof |
| CN105381724A (en) * | 2014-09-05 | 2016-03-09 | 浙江省化工研究院有限公司 | High tensile strength PVDF hollow fiber membrane preparation method |
| CN107096396A (en) * | 2017-05-19 | 2017-08-29 | 开源环保（集团）有限公司 | A kind of polyvinylidene fluoride hollow fiber miillpore filter and preparation method thereof |
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Application publication date: 20181113 |