CN108704493A - A kind of preparation method of flushing-free PVDF tube-type micropore films - Google Patents
A kind of preparation method of flushing-free PVDF tube-type micropore films Download PDFInfo
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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
- 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
- B01D69/04—Tubular membranes
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Abstract
A kind of preparation method of flushing-free PVDF tube-type micropore films, it is related to a kind of preparation method of 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, organic additive, inorganic 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 a kind of preparation methods of 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 weeks 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 preparation method of flushing-free PVDF tube-type micropore films.
A kind of preparation method of flushing-free PVDF tube-type micropore films of the present invention is to carry out according to the following steps：
One, weigh in parts by weight 10~30 parts of PVDF, 50~100 parts of decentralized media, 0.1~20 portion of organic additive and
0.1~10 part of inorganic additive；
Two, successively by weigh 10~30 parts of PVDF, 0.1~20 portion of organic additive and 0.1~10 part of inorganic additive
It is added in 50~100 parts of decentralized media, 3~48h is stirred under conditions of temperature is at 30~95 DEG C, obtains casting solution；
Three, it is sent into spinning box after filtering casting solution, after standing and defoaming 5~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 ripe with spinning technique using non-solvent phase inversion, it is easy to accomplish；And
The DF flushing-free films of import are prepared using sintering process, and low production efficiency, film quality is not easily controlled.2) product diameter be 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；Original can be improved simultaneously
The effective filtration area of material preparation membrane；Improve the utilization rate of raw material；Further, it is also possible to improve the rapids of film surface boundary-layer
Flow degree, avoids pollutant accumulation and blocking.3) it can run under low pressure, film can be significantly reduced in water process and separation process
Energy consumption, while the pollution level of film is reduced, extend scavenging period.4) film that can prepare more small-bore improves the retention energy of film
Power further mitigates fouling membrane.And existing tube-type micropore film and hollow fiber microporous membrane do not have still and exempt to rush currently on the market
The function of washing.Therefore, which may replace the DF films of import and current existing microporous film products, realizes in wastewater treatment and returns
There is important application with, feed separation and concentration, instead of fields such as traditional sedimentation basins or filtering ponds.Film prepared by the present invention can
The packing density for improving component, improves the utilization rate of raw material, improves the porosity of film, reduces operating pressure and operating cost,
Flushing-free operation may be implemented.
Specific implementation mode
Specific implementation mode one：A kind of preparation method of flushing-free PVDF tube-type micropore films of present embodiment is by following step
It is rapid to carry out：
One, weigh in parts by weight 10~30 parts of PVDF, 50~100 parts of decentralized media, 0.1~20 portion of organic additive and
0.1~10 part of inorganic additive；
Two, successively by weigh 10~30 parts of PVDF, 0.1~20 portion of organic additive and 0.1~10 part of inorganic additive
It is added in 50~100 parts of decentralized media, 3~48h is stirred under conditions of temperature is at 30~95 DEG C, obtains casting solution；
Three, it is sent into spinning box after filtering casting solution, after standing and defoaming 5~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.
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：Institute in step 1
It is one kind in lithium chloride, ammonium chloride, zinc chloride, lithium nitrate, lithium perchlorate and water or in which several mixed to state inorganic additive
Close object.It is other identical as one of specific implementation mode one to three.
Specific implementation mode five：Unlike one of present embodiment and specific implementation mode one to four：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；Outer coagulating bath medium be water, ethyl alcohol, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide,
It is 0~20cm that one kind or in which several mixture spinning in n-methyl-2-pyrrolidone and acetone, which do journey,；Winding speed is
3~30m/min.It is other identical as one of specific implementation mode one to four.
Present embodiment OD indicates that outer aperture, ID indicate internal orifice dimension.
Specific implementation mode six：Unlike one of present embodiment and specific implementation mode one to five：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 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 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 six.
Specific implementation mode eight：Unlike one of present embodiment and specific implementation mode one to seven：Step 4 obtains
Flushing-free PVDF tube-type micropores film realized at 0.1~0.2MPa flushing-free run, film surface average pore size control 0.001
~0.5 μm；Operating flux is 300~2000L/ (m2·h)；Continuous operation is cleaned 1 time after 20~30 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 seven.
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 preparation method of flushing-free PVDF tube-type micropore films is to carry out according to the following steps：
One, 18 parts of Kynoar PVDF, 82 parts of N,N-dimethylformamides, 7 parts of polyethylene pyrroles are weighed in parts by weight
Pyrrolidone and 3 parts of lithium chlorides；
Two, weigh 18 parts of Kynoar PVDF, 7 parts of polyvinylpyrrolidones and 3 parts of lithium chlorides are added sequentially to
In 82 parts of n,N-Dimethylformamide, is stirred for 24 hours under conditions of temperature is at 55 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 3.6mm/2.4mm, inner core liquid is 20%
N,N-dimethylformamide aqueous solution, outer coagulating bath medium be water, dry journey is 5cm, winding speed 15m/min；
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 75%；Film list
Silk intensity is more than 7.5N；It can realize that flushing-free is run at 0.1~0.2MPa, film surface average pore size can be 0.01 μm；Operation
Flux reaches 550L/ (m2·h)(0.1MPa)；Antifouling property is good, and continuously-running cleans 1 time after 24 days, once purged
Membrane flux recovery rate is 96% or more.Flushing-free operation can be achieved.
Embodiment two：A kind of preparation method of flushing-free PVDF tube-type micropore films is to carry out according to the following steps：
One, 16 parts of Kynoar PVDF, 84 parts of DMAC N,N' dimethyl acetamides, 6 parts of polyethylene glycol are weighed in parts by weight
(molecular weight 3000) and 4 parts of lithium chlorides；
Two, successively by weigh 16 parts of Kynoar PVDF, 6 parts of polyethylene glycol (molecular weight 3000) and 4 parts of lithium chlorides
It is added in 84 parts of n,N-dimethylacetamide, is stirred for 24 hours under conditions of temperature is at 55 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%
DMAC N,N' dimethyl acetamide aqueous solution, outer coagulating bath medium be water, dry journey is 6cm, winding speed 18m/min；
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 85%；Film list
Silk intensity is more than 7.2N；It can realize that flushing-free is run at 0.1~0.2MPa, film surface average pore size can be 0.05 μm；Operation
Flux reaches 1210L/ (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.
Embodiment three：A kind of preparation method of flushing-free PVDF tube-type micropore films is to carry out according to the following steps：
One, 16 parts of Kynoar PVDF, 84 parts of DMAC N,N' dimethyl acetamides, 8 parts of polyethylene glycol are weighed in parts by weight
(molecular weight 3000) and 2 parts of lithium nitrates；
Two, successively by weigh 16 parts of Kynoar PVDF, 8 parts of polyethylene glycol (molecular weight 3000) and 2 parts of lithium nitrates
It is added in 84 parts of n,N-dimethylacetamide, is stirred for 24 hours under conditions of temperature is at 55 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%
DMAC N,N' dimethyl acetamide aqueous solution, outer coagulating bath medium be water, dry journey is 8cm, winding speed 18m/min；
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 7.2N；It can realize that flushing-free is run at 0.1~0.2MPa, film surface average pore size can be 0.04 μm；Operation
Flux reaches 930L/ (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.
Example IV：A kind of preparation method of flushing-free PVDF tube-type micropore films is to carry out according to the following steps：
One, 18 parts of Kynoar PVDF, 82 parts of n-methyl-2-pyrrolidone, 6 parts of polyethylene glycol are weighed in parts by weight
(molecular weight 1500) and 4 parts of lithium nitrates；
Two, successively by weigh 18 parts of Kynoar PVDF, 6 parts of polyethylene glycol (molecular weight 1500) and 4 parts of lithium nitrates
It is added in 82 parts of n-methyl-2-pyrrolidone, is stirred for 24 hours under conditions of temperature is at 55 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 18m/min；
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 0.1~0.2MPa, film surface average pore size can be 0.005 μm；Operation is logical
Amount reaches 510L/ (m2·h)(0.1MPa)；Antifouling property is good, and continuously-running cleans 1 time after 24 days, once purged film
Flux recovery rate is 95% or more.Flushing-free operation can be achieved.
Embodiment five：A kind of preparation method of flushing-free PVDF tube-type micropore films is to carry out according to the following steps：
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) and 3 parts of lithium perchlorates；
Two, by weigh 18 parts of Kynoar PVDF, 7 parts of polyethylene glycol (molecular weight 1500) and 3 parts of lithium perchlorates according to
It is secondary to be added in 82 parts of n-methyl-2-pyrrolidone, it is stirred for 24 hours under conditions of temperature is at 55 DEG C, obtains 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 6cm, winding speed 18m/min；
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 0.1~0.2MPa, film surface average pore size can be 0.01 μm；Operation
Flux reaches 820L/ (m2·h)(0.1MPa)；Antifouling property is good, and continuously-running cleans 1 time after 24 days, once purged
Membrane flux recovery rate is 96% or more.Flushing-free operation can be achieved.
Claims (8)
1. a kind of preparation method of flushing-free PVDF tube-type micropore films, it is characterised in that the preparation of flushing-free PVDF tube-type micropore films
Method is to carry out according to the following steps：
One, 10~30 parts of PVDF, 50~100 parts of decentralized media, 0.1~20 portion of organic additive and 0.1 are weighed in parts by weight
~10 parts of inorganic additives；
Two, weigh 10~30 parts of PVDF, 0.1~20 portion of organic additive and 0.1~10 part of inorganic additive are sequentially added
Into 50~100 parts of decentralized media, 3~48h is stirred under conditions of temperature is at 30~95 DEG C, obtains casting solution；
Three, it is sent into spinning box after filtering casting solution, after standing and defoaming 5~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. a kind of preparation method of flushing-free PVDF tube-type micropore films according to claim 1, it is characterised in that step 1
Described in decentralized medium be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone and acetone in
A kind of or in which several mixture.
3. a kind of preparation method of flushing-free PVDF tube-type micropore films according to claim 1, it is characterised in that step 1
Described in organic additive be polyethylene glycol, polyacrylonitrile (PAN), cationic surfactant, anion surfactant, it is non-from
Subtype surfactant, acetone, ethyl alcohol, glycerine and different molecular quality polyvinylpyrrolidone in one kind or in which several
Mixture.
4. a kind of preparation method of flushing-free PVDF tube-type micropore films according to claim 1, it is characterised in that step 1
Described in inorganic additive be one kind or in which several in lithium chloride, ammonium chloride, zinc chloride, lithium nitrate, lithium perchlorate and water
Mixture.
5. a kind of preparation method of flushing-free PVDF tube-type micropore films according to claim 1, it is characterised in that step 3
The middle process conditions being film-made using hollow-fibre membrane spinning-drawing machine：Spinning spinneret aperture OD/ID be 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-pyrrolidone and acetone
In one kind or in which several mixtures；Outer coagulating bath medium is water, ethyl alcohol, N,N-dimethylformamide, N, N- dimethyl
One kind in acetamide, n-methyl-2-pyrrolidone and acetone or in which several mixtures；It is 0~20cm that journey is done in spinning；Volume
It is 3~30m/min around speed.
6. a kind of preparation method of flushing-free PVDF tube-type micropore films according to claim 1, it is characterised in that step 4
Described in protection liquid be 5~60% glycerine water solution, 1~15% Tween-20 aqueous solution, 1~15% Tween-40 it is water-soluble
Liquid, 1~15% Tween-60 aqueous solution and one kind in 1~15% Tween-80 aqueous solution or in which several mixtures.
7. a kind of preparation method of flushing-free PVDF tube-type micropore films according to claim 1, it is characterised in that step 4
The OD/ID of obtained flushing-free PVDF tube-type micropore films is 2.0~8.0mm/1.4~6mm；Porosity is 70~95%；Film list
Silk intensity is more than 7N.
8. a kind of preparation method of flushing-free PVDF tube-type micropore films according to claim 1, it is characterised in that step 4
Obtained flushing-free PVDF tube-type micropores film realizes that flushing-free is run at 0.1~0.2MPa, and the control of film surface average pore size exists
0.001~0.5 μm；Operating flux is 300~2000L/ (m2·h)；Continuous operation is cleaned 1 time after 20~30 days, once purged
Membrane flux recovery rate 95% or more.
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| CN110193295A (en) * | 2019-06-19 | 2019-09-03 | 黑龙江大学 | A kind of preparation method of high no pollution flux PVDF tube-type micropore film |
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