CN105579627B - The manufacture device and manufacture method of hollow form multiple aperture plasma membrane - Google Patents
The manufacture device and manufacture method of hollow form multiple aperture plasma membrane Download PDFInfo
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- CN105579627B CN105579627B CN201480053725.5A CN201480053725A CN105579627B CN 105579627 B CN105579627 B CN 105579627B CN 201480053725 A CN201480053725 A CN 201480053725A CN 105579627 B CN105579627 B CN 105579627B
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- scavenging
- resin solution
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- plasma membrane
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- 210000000170 cell membrane Anatomy 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000002000 scavenging effect Effects 0.000 claims abstract description 173
- 229920005989 resin Polymers 0.000 claims abstract description 162
- 239000011347 resin Substances 0.000 claims abstract description 162
- 239000007788 liquid Substances 0.000 claims abstract description 148
- 238000007711 solidification Methods 0.000 claims abstract description 114
- 230000008023 solidification Effects 0.000 claims abstract description 113
- 239000002904 solvent Substances 0.000 claims abstract description 78
- 230000001112 coagulating effect Effects 0.000 claims abstract description 38
- 239000004615 ingredient Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 238000009987 spinning Methods 0.000 claims description 10
- 239000012528 membrane Substances 0.000 abstract description 15
- 239000007789 gas Substances 0.000 description 133
- 238000005191 phase separation Methods 0.000 description 21
- 229920001477 hydrophilic polymer Polymers 0.000 description 15
- 229920001600 hydrophobic polymer Polymers 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 9
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229940113088 dimethylacetamide Drugs 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
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- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- -1 Kynoar Polymers 0.000 description 3
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- 238000009835 boiling Methods 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 239000007800 oxidant agent Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical class CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
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- 238000005422 blasting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
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- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
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Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
-
- 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
- B01D69/085—Details relating to the spinneret
-
- 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
- B01D69/087—Details relating to the spinning process
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The manufacture device and manufacture method of the hollow form multiple aperture plasma membrane with homogeneous membrane structure can be manufactured while preventing spinning-nozzle from condensing it is an object of the invention to provide a kind of.The hollow form multiple aperture plasma membrane manufacture device (1) for solidifying to manufacture hollow form multiple aperture plasma membrane by film formative resin solution is provided with spinning-nozzle (3), coagulating basin (7) and scavenging arrangement (9)；Wherein, spinning-nozzle (3) has discharge opening, and the discharge opening spues in thread film formative resin solution downward；Coagulating basin (7) stores the solidification liquid (5) for solidifying film formative resin solution, and the coagulating basin (7) is configured to, make the liquid level of the solidification liquid (5) the lower section of the discharge opening of the spinning-nozzle (3) and with the discharge opening of the spinning-nozzle (3) at a distance of defined distance；The surface for the film formative resin solution that scavenging arrangement (9) covering is navigated between solidification liquid (5) liquid level in discharge opening and coagulating basin (7), and scavenging gas is flowed around film formative resin solution；Scavenging is less than 50% gas with the relative humidity for the non-solvent ingredients that gas is film formative resin solution.
Description
Technical field
The present invention relates to the manufacture device of hollow form multiple aperture plasma membrane and manufacture method, more particularly to using dry-and wet-type spin processes
Hollow form multiple aperture plasma membrane manufacture device and manufacture method.
Background technology
In recent years, because the care of environmental pollution is improved and defined reinforcement, as method for treating water, using in separation
Completeness and it is compactness in terms of the method for excellent hollow form multiple aperture plasma membrane be just concerned by people.It is used as hollow form multiple aperture plasma membrane
Manufacture method, it is known that have to utilize and Polymer Solution is occurred the non-solvent phase point for being separated and carrying out porous by non-solvent
From method, and it is used as non-solvent phase separation method, it is known to dry-and wet-type spin processes (for example, patent document 1 and 2).
In the dry-and wet-type spin processes that patent document 1 is recorded, in order to improve the mechanical strength of hollow form multiple aperture plasma membrane, make hollow
Ropy is run from the through hole at spinning-nozzle center towards solidification liquid direction, is coated with hollow ropy surface from spinning-nozzle
After the film formative resin solution annular in shape spued below, make it in the sky of the non-solvent ingredients evaporated comprising solidification liquid
Run in gas.Then, by importing film formative resin solution in solidification liquid and it is solidified in solidification liquid, so as to manufacture
Inside has the hollow form Porous of intensity support.
In addition, in the dry-and wet-type spin processes that patent document 2 is recorded, in order to improve the quality of hollow form multiple aperture plasma membrane, spinning
Between silk nozzle and coagulating basin, the film formative resin solution that spinning-nozzle is spued is surrounded with container.Thus, from spinning-nozzle
Side towards on the direction of coagulating basin side, atmosphere formation low humidity lower-temperature atmosphere region, low humidity high-temperature atmosphere region inside container and
High humidity high-temperature atmosphere region, and film formative resin solution is absorbed after non-solvent ingredients in high humidity high-temperature atmosphere region, will
Film formative resin solution is imported in solidification liquid, film formative resin solution is solidified and is manufactured hollow form Porous.
Prior art literature
Patent document
Patent document 1：Japanese Patent Laid-Open 2008-126199 publications
Patent document 2：Japanese Patent Laid 4084103
The content of the invention
Problems to be solved by the invention
However, as described in Patent Document 1, the sky for including non-solvent ingredients between spinning-nozzle and solidification liquid level
When being run in gas, there is the problem of non-solvent ingredients in atmosphere can condense below the spinning-nozzle of low temperature.In order to prevent this
Problem, the temperature of spinning-nozzle must be set to be higher than close dew temperature.In addition, make to be spued below spinning-nozzle in annular shape
Film formative resin solution diameter refinement, until can engage with the hollow rope form support surface of operation, but refined at it
In interval, when film formative resin solution absorbs substantial amounts of non-solvent ingredients, the phase separation of film formative resin solution can be caused,
And make Refinement operation unstable, as a result, leaving situations below：Produced on the circumferencial direction of gained hollow form multiple aperture plasma membrane
Thickness is uneven, and produces irregular variation in diameter.
In order to solve these problems, as described in patent document 2, it is considered to set and hold between spinning-nozzle and coagulating basin
Device, and from spinning-nozzle side towards the direction of coagulating basin side on, make atmosphere formation low humidity lower-temperature atmosphere region in container, low humidity
High-temperature atmosphere region and high humidity high-temperature atmosphere region.However, in this case, need to be provided for film between each region to be formed
The intercommunicating pore that property resin solution passes through, makes each region be connected by intercommunicating pore.Accordingly, there exist problems with：Pass through connection
Hole Shi Ge regions are connected, the air flow between meeting generating region, and the flowing can influence the film for running on intercommunicating pore to be formed
The flowing of property resin solution atmosphere.That is, the temperature and humidity state in the unstable each region of air flow is in container
It is very difficult to keep constant in the horizontal direction and time-axis direction in interior space, and makes the temperature and humidity in space in container in water
Square changed to time-axis direction, so as to form inequality.Flowed in the unstable atmosphere of such humidity and non-uniform temperature
Radial direction that can be in film formative resin solution if forming phase separation structure while logical film formative resin solution and time
The inequality of phase separation structure formation is produced on direction of principal axis, so that the thickness on the circumferencial direction of hollow form multiple aperture plasma membrane can not be prevented
Uneven generation and irregular variation in diameter.
Therefore, the present invention makes to solve the above problems a little, porous its object is to provide a kind of hollow form
The manufacture device and manufacture method of plasma membrane, it can prevent the condensation of spinning-nozzle, meanwhile, it can manufacture with homogeneous membrane structure
Empty shape multiple aperture plasma membrane.
The means solved the problems, such as
In order to solve the above problems, the present invention has following characteristics：
A kind of hollow form multiple aperture plasma membrane for solidifying to manufacture hollow form multiple aperture plasma membrane by film formative resin solution is manufactured
Device, it is characterised in that
Provided with spinning-nozzle, coagulating basin and scavenging arrangement；
The spinning-nozzle has discharge opening, and the discharge opening spues in thread film formative resin solution downward；
The coagulating basin stores the solidification liquid for solidifying film formative resin solution, and the coagulating basin is configured to,
Make the liquid level of the solidification liquid the lower section of the discharge opening of the spinning-nozzle and with the discharge opening of the spinning-nozzle at a distance of advising
Fixed distance；
The film formative resin that the scavenging arrangement covering is navigated between the solidification liquid liquid level in discharge opening and coagulating basin
The surface of solution, and scavenging gas is flowed around film formative resin solution；
The scavenging is less than 50% gas with the relative humidity for the non-solvent ingredients that gas is film formative resin solution.
According to the present invention as constructed as above, the non-solvent ingredients of film formative resin solution can be blasted by scavenging arrangement
Relative humidity is less than 50% gas, so that the atmosphere between discharge opening and solidification liquid level keeps relative humidity to be less than 50%,
And can prevent from producing condensation near discharge opening below spinning-nozzle.In addition, passing through scavenging gas cover layer formative resin
The mode of solution surface is to carrying out scavenging around it, moreover it is possible to prevent film formative resin solution in spinning-nozzle and the liquid of solidification liquid
Non-solvent ingredients are absorbed when being run between face and cause phase separation, and can originate in the phase separation of film formative resin solution
In solidification liquid, therefore, in the beginning and progress of phase separation in, the humidity and temperature of the radial direction of film formative resin solution are equal
One.Thus, the hollow form multiple aperture plasma membrane with homogeneous membrane structure can be manufactured.
In addition, in the present invention, being preferably characterized as, the non-solvent that scavenging arrangement will rise comprising spontaneous coagulation liquid level
The gas of composition is removed from the surface of film formative resin solution.
According to the present invention as constructed as above, can prevent film formative resin solution from comprising spontaneous coagulation liquid level rise it is non-
Absorb above-mentioned non-solvent in the hot and humid atmosphere of solvent and cause film formative resin solution before being contacted with solidification liquid
Start to be separated.Thus, the phase separation of film formative resin solution originates in solidification liquid, therefore, phase separation beginning with
During progress, the humidity and temperature of the radial direction of film formative resin solution are homogeneous.
In addition, in the present invention, being preferably characterized as, between the discharge opening and the solidification liquid, film shape is not made
The resin solution that becomes second nature absorbs the structure of non-solvent ingredients, and the film formative resin solution that the spinning-nozzle is spued
The space run between the discharge opening and the solidification liquid.
According to the present invention as constructed as above, scavenging can be carried out with gas in the way of around cover layer formative resin solution
Flowing.
In addition, in the present invention, it is preferable that the structure of scavenging arrangement is as follows：
With barrel member, internal flow of the scavenging gas in the barrel member；Wherein, the barrel member is surrounded and run on
Around film formative resin solution between discharge opening and the liquid level of solidification liquid.
According to the present invention as constructed as above, it can make to flow inside barrel member from the scavenging gas that scavenging arrangement flows out
It is dynamic, thus, it can prevent scavenging from leaving film formative resin solution with gas, and the beginning around film formative resin solution can be formed
There is the environment that scavenging gas flows eventually.
In addition, in the present invention, it is preferable that scavenging arrangement is provided with scavenging nozzle, it is used to make scavenging gas spray from spinning
The radial outside for the film formative resin solution that the discharge opening of mouth is spued flows towards film formative solution resin.In this feelings
Under condition, preferably scavenging nozzle makes scavenging gas in the whole circumference direction Uniform Flow of film formative resin solution.
According to the present invention as constructed as above, scavenging arrangement can make the footpath of scavenging gas from film formative resin solution outside
Side, flows preferably along whole circumference evenly towards film formative resin solution.Thus, can be to film formative resin solution
Surrounding carries out uniform scavenging.
In addition, in the present invention, it is preferable that scavenging arrangement is preferably provided with the gas-filtering device of filtering scavenging gas.
According to the present invention as constructed as above, it can suppress to be attached to film formative resin with foreign matter contained in gas by scavenging
Solution and the generation for causing film defect.
In addition, in the present invention, it is preferable that scavenging arrangement has the humidity adjustment dress for being used to adjust scavenging gas humidity
Put.In addition, in the present invention, it is preferable that scavenging arrangement has the temperature adjustment device for being used for adjusting scavenging gas temperature.
According to the present invention constituted with these, by humidity adjusting apparatus can adjust scavenging gas humidity and/or
The temperature of scavenging gas can be adjusted by temperature adjustment device, thus, can suitably suppress film formative resin solution in fortune
Start to be separated when row is between discharge opening and the liquid level of solidification liquid.
In addition, in order to solve the above problems, the present invention has following characteristics：
The present invention is a kind of porous to manufacture the hollow form of hollow form multiple aperture plasma membrane by the solidification of film formative resin solution
Membrane manufacturing method；Methods described has following process：
Spinning process：Spue downward is in thread film formative resin solution；
Solidify process：It is being arranged in the lower section of discharge opening and coagulating basin from the position of discharge opening predetermined distance, is making institute
State the solidification of film formative resin solution；And be further equipped with：
Scavenging process：During spinning process is carried out, scavenging gas direction is made to run in discharge opening and coagulating basin
The surface flow of film formative resin solution between solidification liquid liquid level, to carrying out scavenging around film formative resin solution；
Wherein, the scavenging is less than 50% gas with the relative humidity that gas is non-solvent ingredients.
It is small by blasting the relative humidity of non-solvent ingredients of film formative resin solution according to the present invention as constructed as above
In 50% gas, the atmosphere between discharge opening and solidification liquid level can be made to keep relative humidity to be less than 50%, and spinning can be prevented
Condensation is produced near discharge opening below nozzle.In addition, passing through side of the scavenging with gas cover layer formative resin solution surface
Formula can prevent film formative resin solution from being inhaled when running between spinning-nozzle and solidification liquid liquid level to carrying out scavenging around it
Receive non-solvent ingredients and start situation about being separated, and the phase separation that film formative resin can be made molten originates in solidification liquid, because
This, when the beginning and progress of phase separation, the humidity and temperature of the radial direction of film formative resin solution are homogeneous.
In addition, in the present invention, it is characterised in that as the scavenging gas, use the non-of film formative resin solution
The relative humidity of solvent composition is less than 10% gas.
According to the present invention as constructed as above, it can further suppress film formative resin solution and run on spinning-nozzle with coagulating
When between solid-liquid liquid level absorb non-solvent ingredients and start be separated situation.
In addition, in the present invention, it is characterised in that as the solidification liquid, temperature in use is more than 50 DEG C, less than 90 DEG C
Solidification liquid.
According to the present invention as constructed as above, due to the film formative resin solution heating contacted with solidification liquid, therefore until
Non-solvent before be separated stopping, the structure immobilization of film formative resin solution caused by the absorption of non-solvent ingredients is inhaled
The increase of receipts amount, causes set retardation, becomes excessively fine and close therefore, it is possible to suppress the surface texture of cortina in gained, water permeable ability
Decline.
In addition, in the present invention, it is characterised in that from temperature be more than 30 DEG C, spue in less than 60 DEG C of spinning-nozzle institute
State film formative resin solution.
According to the present invention as constructed as above, the situation low compared to film formative resin solution temperature, due to until non-molten
Non-solvent uptake untill be separated stopping, the structure immobilization of film formative resin solution caused by the absorption of agent composition
Increase, causes set retardation, becomes excessively fine and close therefore, it is possible to suppress the surface texture of cortina in gained, water permeable ability declines.
In addition, in the present invention, it is characterised in that as the solidification liquid, use the good of the film formative resin solution
The mass ratio of solvent composition and non-solvent ingredients is 20:80~60:40 solidification liquid.
According to the present invention as constructed as above, because non-solvent ingredients are into the film formative resin solution contacted with solidification liquid
Diffusion velocity decline and cause set retardation, become excessively fine and close therefore, it is possible to the surface texture that suppresses gained hollow fiber membrane,
Water permeable ability declines.
Invention effect
As described above, according to the present invention, while preventing spinning-nozzle from condensing, can manufacture with homogeneous membrane structure
Empty shape multiple aperture plasma membrane.
Brief description of the drawings
Fig. 1 is the schematic diagram for the manufacture device for showing the hollow form multiple aperture plasma membrane in embodiment of the present invention.
Fig. 2 is the ground plan of the scavenging nozzle in embodiment of the present invention.
Fig. 3 is the schematic diagram for the manufacture device for showing the hollow form multiple aperture plasma membrane in the variation of embodiment of the present invention.
Fig. 4 is the schematic diagram for the manufacture device for showing the hollow form multiple aperture plasma membrane in the variation of embodiment of the present invention.
Fig. 5 is the schematic diagram for the manufacture device for showing the hollow form multiple aperture plasma membrane in the variation of embodiment of the present invention.
Symbol description
1st, 51,61 manufacture device
3 spinning-nozzles
5 solidification liquids
7 coagulating basins
9 scavenging arrangements
23rd, 63 scavenging nozzle
53 barrel members
63 scavengings
Embodiment
To the of the manufacture device (following, there is a situation where referred to as " manufacture device ") of the hollow form multiple aperture plasma membrane of the present invention
One embodiment is illustrated.
In Fig. 1, the manufacture device of present embodiment is shown.The manufacture device 1 of present embodiment is by hydrophobic polymer
Film formative resin solution formed by good solvent is dissolved in hydrophilic polymer to be coated on behind hollow rope form support surface,
The film formative resin solution in importing solidification liquid is set to be solidified in solidification liquid, so as to manufacture internal with intensity support
The device of empty shape multiple aperture plasma membrane, it is provided with：Spinning-nozzle 3, the coagulating basin 7 for storing solidification liquid 5 and spinning-nozzle 3 spued
Film formative resin solution conveys the scavenging arrangement 9 of scavenging gas.
Spinning-nozzle 3 is by making hollow rope form support A1The support passed through is molten with through hole 11 and film formative resin
The nozzle that the resin solution stream 13 of liquid is formed.Telling for resin solution stream 13 is formed with below spinning-nozzle 3
The discharge opening of outlet (following, to there is a situation where referred to as " resin solution discharge opening ") and support through hole 11 (below, is present
The referred to as situation of " support discharge opening ").Resin solution discharge opening is ring-type, is spued with support with the support of through hole 11
Mouth is in concentric circles and is formed at the more lateral of support discharge opening.
In the spinning-nozzle 3, make hollow rope form support A1By support through hole 11, from support discharge opening to
Lower section spue, meanwhile, film formative resin solution is flowed in resin solution stream 13, and from resin solution discharge opening to
Lower section spues.In this way, can be in hollow rope form support A1Outer peripheral face on formed film formative resin solution film A2, from
And make hollow filamentous A '.
It is used as hollow rope form support A1, knitted rope (Knitting New-York can be used) or braid (Group New-York).As constitute knitted rope or
The fiber of braid, can enumerate synthetic fibers, semisynthetic fibre, regenerated fiber and natural fiber etc..In addition, the form of fiber can be
Any one in monofilament, multifilament, spun yarn.
Film formative resin solution generally comprises hydrophobic polymer, hydrophilic polymer and dissolves the good molten of them
Agent.As needed, film formative resin solution can also include other adding ingredients.
As hydrophobic polymer, can enumerate the fluorine resins such as the polysulfones such as polysulfones and polyether sulfone system resin, Kynoar,
Polyacrylonitrile, cellulose derivative, polyamide, polyester, polymethacrylates and polyacrylate etc..In addition, or
The copolymer of these materials.Can be used alone a kind of hydrophobic polymer, and also two or more may be used.
In above-mentioned hydrophobic polymer, in terms of to the excellent durability of the oxidants such as hypochlorous acid, preferred fluorine system
Resin, and preferably Kynoar or the copolymer being made up of vinylidene fluoride and other monomers.
Hydrophilic polymer be in order to by the viscosity of film formative resin solution adjust to formed hollow form multiple aperture plasma membrane A
OK range is added with realizing the stabilisation of film state, preferably uses polyethylene glycol or PVP etc..
In these, in terms of gained hollow form multiple aperture plasma membrane A pore size control and hollow form multiple aperture plasma membrane A intensity, preferably
The copolymer of PVP or PVP and other monomer copolymerizations.
In addition, the resin that can be also mixed with two or more in hydrophilic polymer.For example, as hydrophilic polymer, if
Using the hydrophilic polymer of higher molecular weight, with the trend for being easily formed the good hollow form multiple aperture plasma membrane A of membrane structure.Separately
On the one hand, from the point of view of in terms of being easier to remove from hollow form multiple aperture plasma membrane A, the hydrophilic polymer of low molecule amount is suitable
's.Accordingly it is also possible to according to purpose, the different hydrophilic polymer of the same race of molecular weight suitably mix to use.
As good solvent, can enumerate DMF, DMA, dimethyl sulfoxide (DMSO), N- methyl-
2-Pyrrolidone and N-methylmorpholine-N- oxides etc., and a kind of the above material can be used.In addition, not damaging hydrophobicity
In the deliquescent scope of polymer or hydrophilic polymer in a solvent, hydrophobic polymer or hydrophily can be also used in mixed way
The non-solvent of polymer.
The temperature of film formative resin solution is not particularly limited, but usually 10~100 DEG C.Film formative resin is molten
In the case that liquid is same composition, when temperature is uprised, it is separated and the phase separation structure coarsening after structure immobilization, film is permeable
Ability also becomes strong.
But, with the species and the difference of composition of film formative resin solution, if keeping high temperature for a long time, produce sometimes
Filming formative resin solution gelation or rotten situation, in addition, when the component of polymer in film formative resin solution is adopted
During with the high material of molecular weight, and film formative resin solution polymer ratio of components it is high when, there is film formative resin molten
The solution viscosity of liquid is uprised, and the situation of stable film is difficult under low temperature.Therefore, from these points of view, film during spinning is formed
Property resin solution temperature preferred scope be 20~80 DEG C, more preferably 30~60 DEG C.
Even if however, using be easy to when being kept for a long time under high temperature produce gelation or rotten film formative resin it is molten
Liquid, as long as using following methods, i.e., film formative resin solution gelation will not be produced or rotten before outflow spinning-nozzle
At a temperature of supplied or be brought rapidly up to set point of temperature and to the greatest extent may be used before it will flow out spinning-nozzle or in spinning-nozzle
The method that energy ground shortens high temperature hold time, then be easy to produce even in the film formative resin solution that spinning-nozzle is spued
In gelation or rotten temperature province, it can also carry out stablizing film.
Stability when hydrophobic polymer concentration in film formative resin solution is excessively dilute or overrich can all reduce film,
With the trend for being difficult to obtain target hollow form multiple aperture plasma membrane A, therefore, lower limit is preferably 10 mass %, more preferably 15 mass %.
In addition, the upper limit is preferably 30 mass %, more preferably 25 mass %.On the other hand, in order to hollow form multiple aperture plasma membrane is more readily formed
A, the concentration limit of hydrophilic polymer is preferably 1 mass %, more preferably 5 mass %.From the processing of film formative resin solution
Property aspect from the point of view of, the upper limit of concentration of hydrophilic polymer is preferably 20 mass %, more preferably 12 mass %.
Coagulating basin 7 is the storage tank for storing the solidification liquid 5 of the non-solvent comprising hydrophobic polymer, and it can make solidification film
The film A of formative resin solution2Coagulating basin 5 contacted with film formative resin solution.By making film formative resin solution
Film A2Solidification, filamentous A ' becomes hollow form multiple aperture plasma membrane A.
Solidification liquid 5 is the good solvent of the non-solvent of hydrophobic polymer, hydrophilic polymer, can enumerate water, ethanol, methanol
Deng or these materials mixture, wherein, in terms of security and running management, preferably film formative resin solution institute
The solvent and the mixed liquor of water used.The good solvent of solidification liquid and the ratio of components of non-solvent, the temperature of solidification liquid do not have especially
Limit, but generally good solvent：The ratio of components of non-solvent is 5:95~80:20, temperature is 10~110 DEG C.
The containing ratio of good solvent is higher in synthermal solidification liquid, the film formative resin solution being impregnated in solidification liquid
It is separated and gets over coarsening with the phase separation structure after structure immobilization, film water permeable ability is also stronger, but there is situations below：Phase
The mutual diffusion velocity of the non-solvent in the good solvent and solidification liquid in hollow form multiple aperture plasma membrane after separation and structure immobilization
Decline, mechanical strength embodies delay.Hollow form multiple aperture plasma membrane in the state of it can not fully demonstrate the mechanical strength is with being oriented to
When roller etc. is contacted, situations such as there is the section deformation or surface damage for producing hollow form multiple aperture plasma membrane.
Therefore, the good solvent of solidification liquid and the ratio of components of non-solvent are preferably 10:90~70:30, more preferably 20:80~
60:40。
In addition, with the solidification liquid constituted, solidification liquid temperature is lower, is impregnated in the film formative resin solution in solidification liquid
Phase separation structure after phase separation and structure immobilization is more densified, but there is situations below：Phase separation structure immobilization
The mutual diffusion velocity of the non-solvent in the good solvent and solidification liquid in hollow form multiple aperture plasma membrane afterwards declines, and mechanical strength embodies
Delay.Conversely, when solidification liquid temperature is high, being impregnated in the film formative resin solution in solidification liquid in phase separation and structure immobilization
Phase separation structure coarsening afterwards, film water permeable ability also becomes strong, in the hollow form multiple aperture plasma membrane after phase separation and structure immobilization
The mutual diffusion velocity of residual good solvent and the non-solvent in solidification liquid accelerate, therefore, mechanical strength, which embodies, becomes early.
However, solidification liquid temperature is higher, for keeping the constant attemperator of solidification liquid temperature more to need reinforcing.Separately
Outside, in solidification liquid the transpiration of good solvent and the solidification liquid level of non-solvent also becomes violent, and low temperature portion becomes prone to produce
Condensation.In addition, when solidification liquid temperature is more than the boiling point of solidification liquid, cause to solidify slosh due to the boiling of solidification liquid,
Become to be difficult to stable film.
Therefore, as the temperature of solidification liquid, preferably 40 DEG C~be less than solidification liquid boiling temperature, more preferably 50~90 DEG C.
That is, by the film formative resin solution temperature for being immersed in solidification liquid is high, solidification liquid good solvent containing ratio
When high and solidification liquid temperature height is combined, even if making film formative resin in atmosphere not as conventional dry-and wet-type method
Solution absorbs non-solvent ingredients and is impregnated in solidification liquid, can also form the phase separation structure that surface texture is thick, water permeable ability is strong.
In coagulating basin 7, the 1st guide roller 15 that is configured near its bottom is provided with and attached in the edge part of coagulating basin 7
The 2nd guide roller 17 closely configured.1st guide roller 15 makes filamentous A ' be wound in solidification liquid 5 and makes traffic direction obliquely upward
Reversion.2nd guide roller 17 by by exterior guiding from the hollow form multiple aperture plasma membrane A formed in solidification liquid 5 to coagulating basin 7.
On the top of coagulating basin 7, the top plate 19 rising for suppressing solidification liquid 5 is provided with.It is formed with out on top plate 19
Oral area 19a and opening portion 19b, wherein, filamentous A ' and be arranged at spinning spray that opening portion 19a is spued for spinning-nozzle 3
The liquid level of the scavenging gas that the circular open portion 23a of scavenging nozzle 23 below mouth 3 is spued towards solidification liquid 5 is flowed into；Open
Oral area 19b is used to guide to the hollow form multiple aperture plasma membrane A outside coagulating basin 7 by the self-solidifying solid-liquid 5 of the 2nd guide roller 17 to pass through, and
And flowed out to for the scavengings that are spued of circular open portion 23a of scavenging nozzle 23 with gas outside coagulating basin 7.Opening portion 19b
Be preferably capable making filamentous A ' in the way of not contacted with top plate 19 by, while being supplied in sweeping for the underlying space of top plate 19
The minimal aperture area that gas can be discharged smoothly with gas.Scavenging for example room air, factory can be used to compress with gas
Air and factory's drying compressed air etc., in this case, scavenging with the non-solvent that gas is film formative resin solution into
The relative humidity divided is less than 50% gas.
Scavenging arrangement 9 is a kind of following device：By the gas of the non-solvent ingredients of the solidification liquid risen comprising spontaneous coagulation groove 7
The non-solvent ingredients and heat of atmosphere are removed around filamentous A ', and the progress scavenging around filamentous A '.Scavenging arrangement 9 is set
Have：The scavenging nozzle 23 and the gas supply device to the supply scavenging gas of scavenging nozzle 23 being arranged at below spinning-nozzle 3
25。
Scavenging nozzle 23 is annular component, and is provided with：Center on the upside of the opening portion 19a of top plate 19 vertical direction
Circular open portion 23a；Led by being connected to gas supply device 25 and being imported with the gas that scavenging constitutes with the annulus of gas
Enter the room 23b；And the scavenging of room 23b supplies is imported by gas towards the spinning-nozzle 3 and discharge for being exposed to circular open portion 23a
With the annular gas discharge opening 23c of gas.
Scavenging nozzle 23 is arranged to be close to the top plate 19 of coagulating basin 7, and the solidification in scavenging nozzle 23 and coagulating basin 7
Be formed with that film formative resin solution runs on that the circular open portion 23a of scavenging nozzle 23 spued between the liquid level of liquid 5 sweeps
Traffic coverage R in gas gas.The knot for making film formative resin solution absorb non-solvent ingredients is not provided with traffic coverage R
Structure.
Traffic coverage R is arranged to following structure：The scavenging that the circular open portion 23a of without prejudice to scavenging nozzle 23 is spued is used
Liquid level of the gas along solidification liquid 5 to around flowing out, the annular membrane formative resin solution that spinning-nozzle 23 is spued with it is hollow
The abutment of rope form support is located at the more top of the liquid level of solidification liquid 5.Herein, if the circular open portion 23a of scavenging nozzle 23
Depth deepen, then traffic coverage R is similarly, elongated with the distance between the liquid level of solidification liquid 5 below spinning-nozzle 3, spin
The point that the annular membrane formative resin solution that silk nozzle 3 is spued is engaged with hollow rope form support also can be away from solidification liquid 5
Liquid level.When traffic coverage R is too short, by the flowing of the circular open portion 23a scavenging gases spued, there is the liquid of solidification liquid 5
Face is rocked, filamentous A ' and the possibility of the contact condition variation of solidification liquid 5.Conversely, when traffic coverage R is long, for that will solidify
The supply for the required scavenging gas that the non-solvent ingredients that the liquid level of liquid 5 is evaporated fully are removed around filamentous A ' increases
Plus.Therefore, traffic coverage R preferred in present invention length is 5~30mm, more preferably 10~20mm.
Circular open portion 23a's is centrally disposed into consistent with the center of support discharge opening and resin solution discharge opening.Cause
This, circular open portion 23a can pass through filamentous A '.It is in concentric circles that gas, which imports room 23b with scavenging nozzle 23, and is formed at
Circular open portion 23a more outer circumferential side.
Fig. 2 is the ground plan of scavenging nozzle.
Gas discharge opening 23c imports room 23b with gas and connected, as shown in Fig. 2 being opened towards circular open portion 23a center
Mouthful, accordingly, it is capable to which the lateral center in scavenging gas from circular open portion 23a periphery is spued.Circular open portion 23a is spued
Scavenging met with gas with filamentous A ', and such as arrow Y1Shown, along filamentous A ' traffic direction, that is, changing direction is
Downwards, until flowing to the liquid level of solidification liquid 5.
In present embodiment, length and the gas of gas discharge opening 23c above-below direction import room 23b above-below direction
Length is identical, and assigns discharge resistance with gas provided with the scavenging spued to gas discharge opening 23c in gas discharge opening 23c
Ring-type resistance assigns body 23d.It is the structure that flow path resistance is formed while making scavenging gas permeation, example that resistance, which assigns body 23d,
Such as, mesh, continuous foamed body and porous plastid etc. can be used.Resistance imparting body 23d is arranged at gas discharge opening 23c, phase
The gas flow pressure loss of the annulus imported for gas in the 23b of room, gas discharge pressure is with more than ten times to decades of times
When degree becomes big, the pressure inequality for acting on gas discharge opening 23c diminishes.Therefore, the gas from gas discharge opening 23c spues
Amount can be uniformed more in a circumferential direction, and can more stably carry out scavenging.In addition, gas discharge opening 23c is preferably provided with to gas
The scavenging that body discharge opening 23c is spued carries out the rectification body of rectification with the flowing of gas.Rectification body is located at gas discharge opening 23c
When, the directive property increase for the scavenging gas that gas discharge opening 23c is spued, and scavenging efficiency raising.It is used as rectification body, example
Such as, usable grid, honeycomb structured body and mesh being made up of plate object etc..In addition, the scavenging arrangement 9 in present embodiment
In the downstream of gas supply device 25 scavenging is supplied to provided with the gas-filtering device 27 and adjustment for filtering scavenging gas
The gas adjustment mechanism 29 of the temperature and humidity of the scavenging gas of nozzle 23.In present embodiment, in gas-filtering device 27
Downstream be provided with gas adjustment mechanism 29.
As gas-filtering device 27, known filter can be used, for example, fiber is rolled into cavernous cylinder
Object, the object that Porous piece is processed, the porous sintered article of tubular, hollow form multiple aperture plasma membrane etc..If scavenging arrangement 9
Provided with gas-filtering device 27, then the foreign matters such as dust contained by scavenging gas are can remove, thus, it can prevent by circular open
Adhere to foreign matter on portion 23a filamentous A '.Thus, gained hollow form multiple aperture plasma membrane A quality can be improved.
The gas filtration precision of gas-filtering device 27, can be according to the purity of the gas for being supplied to scavenging nozzle 23, made
Hollow form multiple aperture plasma membrane A filtering accuracy made etc. is suitably selected, but due to being attached to the foreign matter on filamentous A ' solidifying
Gu it may cause to occur membrane structure exception in process, may cause film surface damage etc. in the process after solidification process, from
From the viewpoint of the generation for suppressing these film defects, preferably filtering accuracy is high.Specifically, as gas filtration precision, preferably
For less than 1 μm, more preferably less than 0.1 μm, further preferred less than 0.01 μm.
The gas humidity that gas adjustment mechanism 29 has the humidity for adjusting the scavenging gas for being supplied to scavenging nozzle 23 is adjusted
Engagement positions and adjustment are supplied at least one in the gas temperature adjusting apparatus of the temperature of the scavenging gas of scavenging nozzle 23,
At least one in humidity and temperature so as to control scavenging gas.
In order to reduce the non-relative humidity in scavenging gas, scavenging is dehumidified with gas, cooling condensation can be used
The dehydrating units such as device use gas-heating apparatus as gas temperature adjusting apparatus as gas adjustment mechanism 29.In the gas
In body adjusting apparatus 29, dehydrating unit is passed the gas through, so that the non-solvent ingredients dehumidified into gas will not be in spinning-nozzle 3
Below condensation and film formative resin solution will not absorb non-solvent ingredients and cause the relative humidity of phase separation, and according to need
Will, set point of temperature is heated to by gas-heating apparatus.In addition, in factory etc., when the relative humidity of supply at room temperature is 1%
During the dry air of left and right, gas humidity adjusting apparatus can also be omitted, and by gas temperature adjusting apparatus by dry air
Set point of temperature is adjusted to as heat drying air, scavenging nozzle 23 is supplied to.
Therefore, it is possible to meeting in the conventional dry-and wet-type film method of the film formative resin solution importing that spinning-nozzle is spued
Produce in the solidification liquid for making the such hot and humid atmosphere of nozzle face condensation, without absorbing non-solvent ingredients.
Next, the manufacture method to the hollow form multiple aperture plasma membrane A using above-mentioned manufacture device 1 is described in detail.
In the manufacture method of present embodiment, first, spued downwards hollow rope from the support discharge opening of spinning-nozzle 3
Shape support A1, meanwhile, film formative resin solution is spued downwards from resin solution discharge opening, so that in hollow rope form branch
Hold body A1Outer peripheral face formation film formative resin solution film A2And make hollow filamentous A '.Then, making is thread
Body A ' is run on after traffic coverage R, by the opening portion 19a of top plate 19, is sent into coagulating basin 7.
In addition, during filamentous A ' is made, in manufacture device 1, by starting scavenging arrangement 9, to running on Operational Zone
Between R filamentous A ' around carry out scavenging.
In this case, first, the scavenging gas provided by gas-filtering device 27 gas supply device 25
Body is filtered, and is carried out by gas adjustment mechanism 29 after temperature and humidity adjustment, and supply gas imports room 23b.Now, from
Can further prevent spit face 10a condense from the aspect of, preferably by gas adjustment mechanism 29 by scavenging adjusted with gas to
Dew point is less than the surface temperature of the spit face of spinning-nozzle 3.In addition, wanting spinning-nozzle 3 or filamentous A ' temperature without departing from setting
Determine state, preferably scavenging is supplied with the temperature of gas with the design temperature identical temperature with spinning-nozzle 3.
Then, gas is imported in the 23b of room, and body 23d is assigned to scavenging gas by being arranged at gas discharge opening 23c resistance
The pressure distribution of body is uniformed.Then, the resistance that the scavenging gas that gas is imported in the 23b of room passes through gas discharge opening 23c
Power assigns body 23d and spued to circular open portion 23a center, and scavenging is delivered to below spinning-nozzle 3 with gas.Spue
To circular open portion 23a scavenging gas from circular open portion the 23a lateral center flowing in periphery, then, change direction
To downward, flowed to the liquid level direction of solidification liquid 5.Thus, scavenging gas is while be rejected to solidifying near up to below spinning-nozzle 3
The steam or air of solid-liquid, while surrounding around filamentous A '.
Then, the filamentous A ' for covering traffic coverage R is impregnated in solidification liquid 5 and solidifies it, obtain hollow form porous
Plasma membrane A.
Specifically, in solidification process, the film A of spinning process formation film formative resin solution is passed through2Filamentous
The solidification liquid 5 that A ' is imported in coagulating basin 7 by the opening portion 19a of the top plate 19 of coagulating basin 7, and contacted with solidification liquid 5.Make silk
When shape body A ' is impregnated in solidification liquid 5, the film A contacted with solidification liquid 52In, the non-solvent ingredients diffusion leaching contained by solidification liquid 5
Enter, film A2The hydrophobic polymer of film formative resin solution when having exceeded the boundary existed in the solution as liquid phase,
Hydrophobic polymer and good solvent are dissolved in the hydrophilic polymer of good solvent and are initially separated, and are transferred to solid phase from liquid phase.
Thus, the eyed structure as membrane bone frame is formed.The hydrophobic polymer of film formative resin solution occurs to be separated simultaneously completely
When stopping the formation of eyed structure, the eyed structure as membrane bone frame is fixed.However, now, hydrophobic polymer is due to good
Solvent and in the state that is swelled, therefore the state that mechanical strength is weak, be easily deformed under external force is presented.With film A2
Internal good solvent diffuses to solidification liquid 5, film A2In liquid phase part composition in, good solvent composition reduce, non-solvent into
Divide increase, hydrophobic polymer is changed to solid state, film A from solvent swelling state2Mechanical strength be significantly increased.Form with
Under hollow form multiple aperture plasma membrane A：It has been internally formed hydrophobic polymer and gelatinous hydrophilic polymer in outer peripheral face and film
Thing is interlaced, the increased state of dimensional strength to external force three-dimensional mesh structure.Hollow form as obtained by solidification is more
Hole plasma membrane A is transferred to the subsequent handling in the outside of coagulating basin 7 by the 2nd guide roller 17.
As described above, according to manufacture device 1, the steam of solidification liquid 5 can be gone around filamentous A ' by scavenging arrangement 9
Remove, and to carrying out scavenging around filamentous A ', accordingly, it is capable to the humidity for suppressing the periphery atmosphere below spinning-nozzle 3 rises, and energy
Suppress the condensation below spinning-nozzle 3.Thus, the gained hollow form multiple aperture plasma membrane A control of membrane superficial tissue precision, film can be improved
The homogenization of table structure and hollow form multiple aperture plasma membrane A quality.
In addition, according to manufacture device 1, filamentous A ' can be made to be surrounded when running on traffic coverage R by scavenging with gas, no
Start to be separated, but just start to be separated when the solidification liquid 5 with coagulating basin 7 is contacted.When thus, can make to start to be separated
The humidity and temperature of the radial direction of film formative resin solution are homogeneous.
In addition, the invention is not limited in above-mentioned embodiment, without departing from the spirit and scope of the present invention, each constitute can
Suitably changed.
Fig. 3 is the schematic diagram for the manufacture device for showing the hollow form multiple aperture plasma membrane in variation.As shown in figure 3, variation
In manufacture device 51, in addition to the composition with manufacture device 1, also with barrel member 53.
Barrel member 53 is constituted in the way of being the filamentous A ' that traffic coverage R is run on to surround.Barrel member 53 is close
Feud is installed on below scavenging nozzle 23, and the liquid level of the solidification liquid 5 extended to below scavenging nozzle 23 in coagulating basin 7
Near.Barrel member 53 has circular cross-section, and central shaft is arranged to the central shaft one with the circular open portion 23a of scavenging nozzle 23
Cause.In addition, the upper end of barrel member 53 has flange part 55, the flange part 55 is installed on scavenging nozzle 23 by using magnet etc.
Below.And by the way that barrel member 53 is installed on below scavenging nozzle 23, from the circular open portion 23a of scavenging nozzle 23 to solidifying
The liquid level of solid-liquid 5 is formed about circular stream, and the scavenging gas that the circular open portion 23a of scavenging nozzle 23 is spued passes through this
Traffic direction in stream in filamentous A ' flows.In addition, between being formed between the lower end of barrel member 53 and the liquid level of solidification liquid 5
Gap 57, it is used to make the scavenging gas of arrival liquid level to be flowed out out of barrel member 53.
Surrounded in this way, running on around traffic coverage R filamentous A ' by barrel member 53, and pass through scavenging gas stream
To barrel member 53, scavenging gas can be suppressed and peeled off at the space flowed along filamentous A ' from filamentous A '.Thus,
Filamentous A ' can be surrounded with scavenging gas in the interval Zone R domain of whole service, and can be to filamentous in the interval Zone R domain of whole service
Scavenging is carried out around A '.
The circular flow diameter of barrel member 53 is smaller, can more obtain high scavenging effect with gas supply with few scavenging
Rate, but due to filamentous A ' vibration in the charge and discharge operations or film of barrel member etc., be preferably set to filamentous A ' not with it is interior
It is appropriately sized that wall is contacted, and is normally set to run on 4~16 times or so of the filamentous A ' of inside diameter.
In addition, the circular flow path length of barrel member 53 is preferably following length：The annular membrane formative spued with nozzle
The abutment of the hollow rope form support of resin solution is located at the more top of the lower end of barrel member 53, and the scavenging use in barrel member 53
The flow regime of gas is stable.
Scavenging gas from scavenging nozzle 23 flow into barrel member 53 when, because its flow direction and speed change, cylinder
When the circular flow path length of component 53 is too short, there may be situations below：The scavenging gas flowing of barrel member 53 is easy to mixed
Disorderly, filamentous A ' vibration is induced, so as to reduce scavenging efficiency.Conversely, the length be set as needed for the above length when, exist with
Lower situation：The scavenging of internal flow is set to be changed with the temperature of gas by surface heat release.In such a situation it is preferred to adopt
The heat preserving method of temperature adjustment device etc. is covered around barrel member 53 and set to heat-insulating material.
In present embodiment, the value of circular flow path length/circle flow diameter of barrel member 53 is preferably 2~40, more excellent
Select 4~20.
Fig. 4 is the schematic diagram of the manufacture device for the hollow form multiple aperture plasma membrane for showing further variation.As shown in figure 4,
Manufacture device 61 further in variation is provided with scavenging nozzle 63, to replace the scavenging nozzle 23 of manufacture device 1.
Scavenging nozzle 63 is provided with：Receive the inflow entrance 65 for the scavenging gas that the grade of gas supply device 25 is flowed out and will sweep
The spitting unit 67 that gas gas spues to filamentous A '.The discharge scavenging gas in the horizontal direction of spitting unit 67, with operation
Interval R substantially the same heights.Therefore, scavenging nozzle 63 can be in whole service interval R with horizontal direction discharge scavenging gas.
, also can be in whole service interval R to carrying out scavenging around filamentous A ' by setting such scavenging nozzle 63.
In addition, as shown in figure 5, can also be provided with：The sidepiece wind deflector 68 that surrounds around traffic coverage R and with being arranged at fortune
Row interval R lower end, i.e., the bottom wind deflector of the opening portion 69 for passing through filamentous A ' set along the liquid level of solidification liquid 5
71.By setting sidepiece wind deflector 68 and bottom wind deflector 71, the scavenging gas that scavenging nozzle 63 is spued can be promoted in water
Square to flowing.
Then, embodiments of the invention are illustrated.
Following manufacture device is used in embodiment：Scavenging nozzle is provided below in spinning-nozzle as shown in Figure 3, pacifies
Lower ending opening face loaded on the barrel member below the scavenging nozzle is set as from a distance from the solidification liquid liquid level 5mm in coagulating basin.
As the spinning-nozzle of manufacture device, following nozzle is used：With the branch to the following hollow rope form support that spues
Body discharge hole is held, and with the film formative resin solution that concentric circles can be formed with ring-type discharge and the support discharge hole
Resin solution discharge opening.
As scavenging arrangement, magnetic stainless steel SUS430 scavenging nozzle and barrel member are used；Wherein, scavenging nozzle
Diameter 60mm, opening diameter 30mm, height 10mm, opening internal face is by internal diameter 30mm, thickness 2mm, height 8mm, nominal mistake
The internal face of filter precision 1 μ SUS metallic particles sintered bodies is constituted；Barrel member is diameter 30mm, internal diameter 12mm, length
150mm, and upper end is diameter 60mm, the polypropylene barrel member of thickness 8mm round flange being embedded in by neodium magnet.
Barrel member makes flange surface be adsorbed in below the scavenging nozzle of the stainless steel of magnetic and is fixed by magnetic force.
As film formative resin solution, it can prepare in accordance with the following methods：By Kynoar P1 (ア Le ケ マ company systems
Make, trade name：カ イ Na ー 761A), Kynoar P2 (ア Le ケ マ companies manufacture, trade name：カ イ ナ ー 301A), it is poly-
Vinyl pyrrolidone (Japanese catalyst Co. manufacture, trade name：K-79), DMAC N,N' dimethyl acetamide (DMAc) (サ system ソ
Application Off ァ イ Application ケ ミ カ Le company manufactures) mixed according to mass ratio as shown below, the stirring and dissolving at 60 DEG C is prepared into bag
Film formative resin solution A, B of pbz polymer weight poly (vinylidene fluoride) and the film formative comprising low molecular weight polyvinylidene fluoride
This 3 kinds of solution of resin solution C.
(film formative resin solution A)
By Kynoar P1 (matter average molecular weight (hreinafter referred to as Mw) Mw：7.2×105) 18.8 mass %, polyethylene
Base pyrrolidones M1 (Mw：9.0×104) 12.2 mass % and as solvent the mass % of DMAC N,N' dimethyl acetamide 69 mix.
(film formative resin solution B)
Using 15.2 mass % Kynoar P1,8.6 mass % PVP M1 and it is used as solvent
The mass % of DMAC N,N' dimethyl acetamide 76.2 is mixed.
(film formative resin solution C)
By 19.2 mass % Kynoar P2 (Mw：5.2×105), 10.1 mass % PVP
M1 and the mass % of DMAC N,N' dimethyl acetamide 70.7 mixing as solvent.
As hollow rope form support, using internal diameter 1.5mm, external diameter 2.5mm, internal diameter 1mm, external diameter 1.4mm major diameter
Hollow rope form support A and thin diameter hollow rope form support B, it is in order to flatness contractingization and high outside dimension are stabilized
Heating stretching heat treatment has been carried out using heating metal mouth.
(embodiment 1)
The temperature of spinning-nozzle is set to 32 DEG C, and the temperature for supplying the film formative resin solution of spinning-nozzle is set to 32 DEG C,
Solidification liquid temperature is set to 70 DEG C, uses DMA：The mass ratio of water is 30:70 liquid is used as solidification liquid, system
Film speed is set to 30m/min, is adjusted the temperature of factory's dry air to 32 DEG C and relative humidity by heat exchanger and is changed into about
Less than 1% dry air is fed to scavenging nozzle with 6L/min, and uses hollow rope form support A, hollow rope form support B
With film formative resin solution A, external diameter 2.8mm hollow form multiple aperture plasma membrane and external diameter 1.6mm hollow form multiple aperture plasma membrane are made.
The discharge-amount of film formative resin solution is 64.8cc/min when making external diameter 2.8mm hollow form multiple aperture plasma membrane,
The discharge-amount of film formative resin solution is 24.2cc/min when making external diameter 1.6mm hollow form multiple aperture plasma membrane.
(embodiment 2)
It is other as be the same as Example 1 is carried out in addition to using film formative resin solution B as film formative resin solution
Film.
(embodiment 3)
It is other as be the same as Example 1 is carried out in addition to using film formative resin solution C as film formative resin solution
Film.
(embodiment 4)
Except the temperature of film formative resin solution that the temperature of spinning-nozzle is set into 50 DEG C, spinning-nozzle is supplied is set to
50 DEG C, with heat exchanger the temperature of factory's dry air adjusted to 50 DEG C and supplied beyond scavenging nozzle, it is other as implemented
Example 3 is filmed.
(embodiment 5)
It is other as be the same as Example 2 is filmed in addition to the temperature of solidification liquid is set into 80 DEG C.
(embodiment 6)
Except by DMAC N,N' dimethyl acetamide：The mass ratio of water is 40:Beyond 60 as the composition of solidification liquid, it is other as
Embodiment 5 is filmed.
In any example in embodiment 1~6, condensed all without being produced at spinning-nozzle.
In addition, being gone as the DMA of the solvent composition for the hollow form multiple aperture plasma membrane being made with hot wash
Remove, and removed with hot wash after with oxidant, the PVP as hydrophilic polymer composition is decomposed
Afterwards, hollow form multiple aperture plasma membrane sample obtained by being dried in 100 DEG C of hot blast, should with 30,000 times of multiplying power observation with electron microscope
Sample surfaces, as a result, having no that notable structure is uneven in a circumferential direction, even and if membrane superficial tissue passes through the film time
Afterwards, change is not produced yet.
In addition, the mean surface pore size for comparing gained hollow form multiple aperture plasma membrane is found, its size is the ＜ embodiments of embodiment 1
2 ＜ embodiments 3, the ＜ embodiments 4 of embodiment 3, the ＜ embodiments 6 of 2 ＜ embodiments of embodiment 5.
As comparative example, constituted and film forming condition and carried out in the way of not starting scavenging nozzle by the device of embodiment 1
Film.
In comparative example, as time goes by, condensation is produced below spinning-nozzle.In addition, with same as Example 1
Method is handled the hollow form multiple aperture plasma membrane of making, observes the hollow form multiple aperture plasma membrane sample surfaces made, its result hair
It is existing, inequality is produced in the surface texture of circumferencial direction, and the surface texture of film changes after the film time.
Claims (13)
1. a kind of hollow form multiple aperture plasma membrane manufacture device, described device is a kind of by making the solidification of film formative resin solution make
Make the hollow form multiple aperture plasma membrane manufacture device of hollow form multiple aperture plasma membrane, it is characterised in that：It is provided with：Spinning-nozzle, coagulating basin and
Scavenging arrangement；
The spinning-nozzle has discharge opening, and the discharge opening spues in thread film formative resin solution downward；
The coagulating basin stores the solidification liquid for solidifying the film formative resin solution, and the coagulating basin is configured to,
Make the liquid level of the solidification liquid the lower section of the discharge opening of the spinning-nozzle and with the discharge opening of the spinning-nozzle at a distance of advising
Fixed distance；
The film shape that the scavenging arrangement covering is run between the solidification liquid liquid level in the discharge opening and the coagulating basin
Become second nature the surface of resin solution, and scavenging gas is flowed around the film formative resin solution；
The scavenging gas is less than 10% gas for the relative humidity of the non-solvent ingredients of the film formative resin solution.
2. the hollow form multiple aperture plasma membrane manufacture device recorded such as claim 1, it is characterised in that：The scavenging arrangement will be included certainly
The gas for solidifying the non-solvent ingredients that liquid level rises is removed from the surface of the film formative resin solution.
3. the hollow form multiple aperture plasma membrane manufacture device recorded such as claim 1 or 2, it is characterised in that：In the discharge opening and institute
State between solidification liquid, film formative resin solution is absorbed the structure of non-solvent ingredients, and told from the spinning-nozzle
The film formative resin solution gone out is run in the space of the discharge opening and the solidification liquid.
4. the hollow form multiple aperture plasma membrane manufacture device recorded such as claim 1 or 2, it is characterised in that：It, which has, is centered around operation
The barrel member around the film formative resin solution between the liquid level of the discharge opening and the solidification liquid, the scavenging
Device is configured to, and makes scavenging gas in the internal flow of the barrel member.
5. the hollow form multiple aperture plasma membrane manufacture device recorded such as claim 1 or 2, it is characterised in that：The scavenging arrangement is provided with
Scavenging nozzle, the scavenging nozzle is used to make the institute that the scavenging gas is spued from the discharge opening of the spinning-nozzle
The radial outside of film formative resin solution is stated, towards film formative solution resin flowing.
6. the hollow form multiple aperture plasma membrane manufacture device recorded such as claim 5, it is characterised in that：The scavenging nozzle makes described sweep
Whole circumference direction Uniform Flow of the gas gas in the film formative resin solution.
7. the hollow form multiple aperture plasma membrane manufacture device recorded such as claim 1 or 2, it is characterised in that：The scavenging arrangement is provided with
Gas-filtering device for filtering scavenging gas.
8. the hollow form multiple aperture plasma membrane manufacture device recorded such as claim 1 or 2, it is characterised in that：The scavenging arrangement has
Humidity adjusting apparatus for adjusting scavenging gas humidity.
9. the hollow form multiple aperture plasma membrane manufacture device recorded such as claim 1 or 2, it is characterised in that：The scavenging arrangement has
Temperature adjustment device for adjusting scavenging gas temperature.
10. a kind of manufacture method of hollow form multiple aperture plasma membrane, methods described is a kind of by making film formative resin solution solidify
To manufacture the hollow form multiple aperture plasma membrane manufacture method of hollow form multiple aperture plasma membrane；It is characterized in that：
Methods described has following process：
Spinning process：Spue downward is in thread film formative resin solution；
Solidify process：It is being arranged in the lower section of discharge opening and coagulating basin from the position of discharge opening predetermined distance, is making the film
Formative resin solution solidifies；And be further equipped with：
Scavenging process：During the spinning process is carried out, scavenging gas is made to be coagulated towards the discharge opening is run on described
Gu the surface flow of the film formative resin solution between the solidification liquid liquid level in groove, to the film formative resin solution
Around carry out scavenging；
Wherein, the scavenging is less than 10% gas with the relative humidity that gas is non-solvent ingredients.
11. such as the manufacture method for the hollow form multiple aperture plasma membrane that claim 10 is recorded, it is characterised in that：As the solidification liquid,
Temperature in use is more than 50 DEG C, less than 90 DEG C of solidification liquid.
12. such as the manufacture method for the hollow form multiple aperture plasma membrane that claim 10 or 11 is recorded, it is characterised in that：More than 30 DEG C,
At less than 60 DEG C of temperature, spue the film formative resin solution from spinning-nozzle.
13. such as the manufacture method for the hollow form multiple aperture plasma membrane that claim 10 or 11 is recorded, it is characterised in that：As solidification liquid,
The use of the good solvent composition of the film formative resin solution and the mass ratio of non-solvent ingredients is 20:80~60:40 solidification
Liquid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-156928 | 2013-07-29 | ||
| JP2013156928 | 2013-07-29 | ||
| PCT/JP2014/069966 WO2015016228A1 (en) | 2013-07-29 | 2014-07-29 | Device and method for producing hollow porous membrane |
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| CN105579627A CN105579627A (en) | 2016-05-11 |
| CN105579627B true CN105579627B (en) | 2017-09-29 |
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| CN201480053725.5A Expired - Fee Related CN105579627B (en) | 2013-07-29 | 2014-07-29 | The manufacture device and manufacture method of hollow form multiple aperture plasma membrane |
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| JP (1) | JP5776918B2 (en) |
| CN (1) | CN105579627B (en) |
| WO (1) | WO2015016228A1 (en) |
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| CN107904679B (en) * | 2017-12-18 | 2019-11-15 | 杭州新天元织造有限公司 | A kind of colored fiber regenerative system and its regeneration method using discarded duds object |
| CN114892290B (en) * | 2022-05-09 | 2023-05-05 | 苏州中色德源环保科技有限公司 | Coreless liquid dry-wet hollow fiber membrane spinning process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004025067A (en) * | 2002-06-26 | 2004-01-29 | Mitsubishi Rayon Co Ltd | Method and device for manufacturing porous hollow fiber membrane |
| JP2012110856A (en) * | 2010-11-26 | 2012-06-14 | Mitsubishi Rayon Co Ltd | Apparatus for manufacturing hollow porous membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0544104A (en) * | 1991-08-01 | 1993-02-23 | Unitika Ltd | Method for dry-jet wet spinning |
| CN1099310C (en) * | 1998-04-16 | 2003-01-22 | 中国科学院大连化学物理研究所 | Preparation of asymmetrical hollow polyimide fibre membrane |
| JP2007119973A (en) * | 2005-10-31 | 2007-05-17 | Teijin Techno Products Ltd | Dry-wet spinning apparatus and dry-wet spinning method |
| JP2008126199A (en) * | 2006-11-24 | 2008-06-05 | Mitsubishi Rayon Co Ltd | Hollow porous film and its manufacturing method |
| JP2010236139A (en) * | 2009-03-31 | 2010-10-21 | Toray Ind Inc | Method for producing acrylic fiber |
| JP5790180B2 (en) * | 2011-06-13 | 2015-10-07 | 三菱レイヨン株式会社 | Method for producing porous hollow fiber membrane |
| US20150042004A1 (en) * | 2012-03-14 | 2015-02-12 | Mitsubishi Rayon Co., Ltd. | Device for producing hollow porous film and method for producing hollow porous film |
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2014
- 2014-07-29 JP JP2014542027A patent/JP5776918B2/en active Active
- 2014-07-29 CN CN201480053725.5A patent/CN105579627B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004025067A (en) * | 2002-06-26 | 2004-01-29 | Mitsubishi Rayon Co Ltd | Method and device for manufacturing porous hollow fiber membrane |
| JP2012110856A (en) * | 2010-11-26 | 2012-06-14 | Mitsubishi Rayon Co Ltd | Apparatus for manufacturing hollow porous membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5776918B2 (en) | 2015-09-09 |
| CN105579627A (en) | 2016-05-11 |
| JPWO2015016228A1 (en) | 2017-03-02 |
| WO2015016228A1 (en) | 2015-02-05 |
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