CN105579627A - Device and method for producing hollow porous membrane - Google Patents
Device and method for producing hollow porous membrane Download PDFInfo
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- CN105579627A CN105579627A CN201480053725.5A CN201480053725A CN105579627A CN 105579627 A CN105579627 A CN 105579627A CN 201480053725 A CN201480053725 A CN 201480053725A CN 105579627 A CN105579627 A CN 105579627A
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- resin solution
- scavenging
- film formative
- gas
- formative resin
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 64
- 239000012528 membrane Substances 0.000 title abstract description 18
- 230000002000 scavenging effect Effects 0.000 claims abstract description 177
- 229920005989 resin Polymers 0.000 claims abstract description 163
- 239000011347 resin Substances 0.000 claims abstract description 163
- 239000007788 liquid Substances 0.000 claims abstract description 144
- 238000007711 solidification Methods 0.000 claims abstract description 108
- 230000008023 solidification Effects 0.000 claims abstract description 108
- 239000002904 solvent Substances 0.000 claims abstract description 81
- 238000009987 spinning Methods 0.000 claims abstract description 9
- 210000000170 cell membrane Anatomy 0.000 claims description 76
- 239000004615 ingredient Substances 0.000 claims description 37
- 238000009434 installation Methods 0.000 claims description 36
- 230000001112 coagulating effect Effects 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 5
- 238000005345 coagulation Methods 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 4
- 230000002269 spontaneous effect Effects 0.000 claims description 4
- 238000009833 condensation Methods 0.000 abstract description 8
- 230000005494 condensation Effects 0.000 abstract description 8
- 229920001477 hydrophilic polymer Polymers 0.000 description 16
- 229920001600 hydrophobic polymer Polymers 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000005191 phase separation Methods 0.000 description 10
- 230000000873 masking effect Effects 0.000 description 9
- 230000008676 import Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 230000005068 transpiration Effects 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound 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
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying 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
- 239000004744 fabric Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 210000002706 plastid Anatomy 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 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
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The purpose of the present invention is to provide a production device and a production method with which condensation in a spinning nozzle can be inhibited, and a hollow porous membrane having a uniform membrane structure can be produced. Accordingly, a hollow-porous-membrane production device (1), which solidifies a membrane-forming resin solution to produce a hollow porous membrane, is provided with: a spinning nozzle (3) provided with a discharge port through which the membrane-forming resin solution is downwardly discharged in a filament shape; a solidification tank (7) which has, accommodated therein, a solidification liquid (5) for solidifying the membrane-forming resin solution, and which is disposed such that a liquid surface of the solidification liquid (5) is below the discharge port of the spinning nozzle (3) and separated therefrom by a prescribed distance; and a scavenging means (9) which covers a surface of the membrane-forming resin solution traveling between the discharge port and the liquid surface of the solidification liquid (5) in the solidification tank (7), and which distributes a scavenging gas around a periphery of the membrane-forming resin solution. The scavenging gas has a relative humidity which is less than 50% of that of a non-solvent component of the membrane-forming resin solution.
Description
Technical field
The present invention relates to manufacturing installation and the manufacture method of hollow form multiple aperture plasma membrane, particularly adopt manufacturing installation and the manufacture method of the hollow form multiple aperture plasma membrane of dry-and wet-type spin processes.
Background technology
In recent years, the care due to environmental pollution improves and the reinforcement of regulation, as method for treating water, is used in the method being separated the excellent hollow form multiple aperture plasma membrane of completeness and the aspect such as compactness and is just concerned by people.As the manufacture method of hollow form multiple aperture plasma membrane, the known utilization that has makes Polymer Solution be separated by non-solvent and carries out the non-solvent phase separation method of porous, and as non-solvent phase separation method, there will be a known dry-and wet-type spin processes (such as, 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, hollow ropy is run from the through hole at spinning-nozzle center towards solidification liquid direction, after hollow ropy surface is coated with the film formative resin solution in the form of a ring spued below spinning-nozzle, it is made to run in the air comprising the non-solvent ingredients that solidification liquid evaporates.Then, by importing film formative resin solution and make it solidify in solidification liquid in solidification liquid, thus manufacture the inner hollow form Porous with 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, between spinning-nozzle and coagulating basin, the film formative resin solution spued with container encirclement spinning-nozzle.Thus, from spinning-nozzle side towards the direction of coagulating basin side, the atmosphere of internal tank forms low humidity lower-temperature atmosphere region, low humidity high-temperature atmosphere region and high humidity high-temperature atmosphere region, and after making film formative resin solution absorb non-solvent ingredients in high humidity high-temperature atmosphere region, film formative resin solution is imported in solidification liquid, makes film formative resin solution solidify and manufacture hollow form Porous.
Prior art document
Patent document
Patent document 1: Japanese Patent Laid-Open 2008-126199 publication
Patent document 2: No. 4084103, Japanese Patent Laid
Summary of the invention
The problem that invention will solve
But, as described in Patent Document 1, when spinning-nozzle and solidifying runs in the air of non-solvent ingredients comprising between liquid level, there is the problem that the 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 higher than close dew temperature.In addition, make the diameter refinement in circular film formative resin solution spued below spinning-nozzle, until can engage with the hollow rope form support surface run, but in its refinement interval, when film formative resin solution absorbs a large amount of non-solvent ingredients, being separated of film formative resin solution can be caused, and make Refinement operation unstable, consequently, leave following situation: uneven at the circumferentially generation thickness of gained hollow form multiple aperture plasma membrane, and produce irregular variation in diameter.
In order to address these problems, described in patent document 2, consider to arrange container between spinning-nozzle and coagulating basin, and from spinning-nozzle side towards the direction of coagulating basin side, make atmosphere in container form low humidity lower-temperature atmosphere region, low humidity high-temperature atmosphere region and high humidity high-temperature atmosphere region.But, in this case, need between each region to arrange the intercommunicating pore passed through for film formative resin solution, each region is communicated with by intercommunicating pore.Therefore, there is following problem: by intercommunicating pore, each region is communicated with, interregional air flowing can be produced, and this flowing can affect the flowing of the film formative resin solution atmosphere running on intercommunicating pore.That is, the horizontal direction in the temperature and humidity state space in container in each region of air flowing instability and time-axis direction are very difficult to keep constant, and the temperature and humidity in space in container is changed with time-axis direction in the horizontal direction, thus formed uneven.Circulate while film formative resin solution in the unstable atmosphere that such humidity and temperature is uneven, form the words of phase separation structure, the inequality that phase separation structure is formed can be produced in the radial direction and time-axis direction of film formative resin solution, thus the generation of the thickness inequality circumferentially of hollow form multiple aperture plasma membrane and irregular variation in diameter cannot be prevented.
Therefore, the present invention makes to solve the problem a little, and its object is to the manufacturing installation and the manufacture method that provide a kind of hollow form multiple aperture plasma membrane, it can prevent the condensation of spinning-nozzle, meanwhile, can manufacture the hollow form multiple aperture plasma membrane with homogeneous membrane structure.
The means of dealing with problems
In order to solve the problem, the present invention has following characteristics:
Solidified the hollow form multiple aperture plasma membrane manufacturing installation manufacturing hollow form multiple aperture plasma membrane by film formative resin solution, it is characterized in that,
Be provided with spinning-nozzle, coagulating basin and scavenging arrangement;
Described spinning-nozzle has discharge opening, and this discharge opening spues in thread film formative resin solution downward;
The solidification liquid of described coagulating basin storage for solidifying film formative resin solution, and described coagulating basin is configured to, makes the liquid level of described solidification liquid in the below of the discharge opening of described spinning-nozzle and with the discharge opening of described spinning-nozzle at a distance of the distance specified;
Described scavenging arrangement covering navigates on the surface of the film formative resin solution between the solidification liquid liquid level in discharge opening and coagulating basin, and makes scavenging gas at the ambient dynamic of film formative resin solution;
Described scavenging gas is the gas that the relative humidity of the non-solvent ingredients of film formative resin solution is less than 50%.
According to the present invention as constructed as above, the gas that the relative humidity that can be blasted the non-solvent ingredients of film formative resin solution by scavenging arrangement is less than 50%, thus make discharge opening and the atmosphere of solidifying between liquid level keeps relative humidity to be less than 50%, and can prevent from producing condensation near the discharge opening below spinning-nozzle.In addition, scavenging is carried out to around it by the mode on scavenging gas cover layer formative resin solution surface, absorb non-solvent ingredients and causing when can also prevent film formative resin solution from running between spinning-nozzle and the liquid level of solidification liquid to be separated, and being separated of film formative resin solution can be made to originate in solidification liquid, therefore, the beginning be separated with carry out time in, the humidity and temperature of the radial direction of film formative resin solution is homogeneous.Thus, the hollow form multiple aperture plasma membrane with homogeneous membrane structure can be manufactured.
In addition, in the present invention, be preferably characterised in that, scavenging arrangement will comprise the surface removal of gas from film formative resin solution of the described non-solvent ingredients that spontaneous coagulation liquid level rises.
According to the present invention as constructed as above, can prevent film formative resin solution from from the hot and humid atmosphere comprising the non-solvent that spontaneous coagulation liquid level rises, absorbing above-mentioned non-solvent and be separated causing film formative resin solution before contacting with solidification liquid.Thus, being separated of film formative resin solution originates in solidification liquid, therefore, the beginning be separated with carry out time in, the humidity and temperature of the radial direction of film formative resin solution is homogeneous.
In addition, in the present invention, preferably be characterised in that, between described discharge opening and described solidification liquid, do not make film formative resin solution absorb the structure of non-solvent ingredients, and the described film formative resin solution that described spinning-nozzle spues run on the space between described discharge opening and described solidification liquid.
According to the present invention as constructed as above, scavenging gas can flow in the mode around cover layer formative resin solution.
In addition, in the present invention, preferably, the structure of scavenging arrangement is as follows:
Have barrel member, scavenging gas is in the internal flow of described barrel member; Wherein, described barrel member is around the film formative resin solution run between discharge opening and the liquid level of solidification liquid.
According to the present invention as constructed as above, the scavenging gas flowed out from scavenging arrangement can be made in barrel member internal flow, thus, can prevent scavenging gas from leaving film formative resin solution, and the environment that the surrounding that can form film formative resin solution has scavenging gas to flow all the time.
In addition, in the present invention, preferably, scavenging arrangement is provided with scavenging nozzle, its for the radial outside of film formative resin solution that makes scavenging gas and spue from the discharge opening of spinning-nozzle towards film formative solution resin flows.In this case, preferred scavenging nozzle makes scavenging gas at the whole circumferencial direction Uniform Flow of film formative resin solution.
According to the present invention as constructed as above, scavenging arrangement can make scavenging gas from the radial outside of film formative resin solution, preferably flows along whole even circumferential towards film formative resin solution.Thus, even scavenging can be carried out to the surrounding of film formative resin solution.
In addition, in the present invention, preferably, scavenging arrangement is preferably provided with the gas-filtering device filtering scavenging gas.
According to the present invention as constructed as above, can suppress be attached to film formative resin solution by foreign matter contained in scavenging gas and cause the generation of film defect.
In addition, in the present invention, preferably, scavenging arrangement has the humidity regulator for adjusting scavenging gas humidity.In addition, in the present invention, preferably, scavenging arrangement has the temperature adjustment device for adjusting scavenging gas temperature.
According to the present invention with these formations, the humidity of scavenging gas can be adjusted by humidity regulator and/or the temperature of scavenging gas can be adjusted by temperature adjustment device, thus, film formative resin solution can be suppressed aptly to start when running between discharge opening and the liquid level of solidification liquid to be separated.
In addition, in order to solve the problem, the present invention has following characteristics:
The present invention a kind ofly solidifies the hollow form multiple aperture plasma membrane manufacture method manufacturing hollow form multiple aperture plasma membrane by film formative resin solution; Described method has following operation:
Spinning process: spue in thread film formative resin solution downward;
Solidify operation: from the coagulating basin of the position of discharge opening predetermined distance, described film formative resin solution is solidified in the below being arranged at discharge opening; And possess further:
Scavenging operation: during carrying out spinning process, makes scavenging gas flow towards the surface of the film formative resin solution between the solidification liquid liquid level run in discharge opening and coagulating basin, carries out scavenging to the surrounding of film formative resin solution;
Wherein, described scavenging gas is the gas that the relative humidity of non-solvent ingredients is less than 50%.
According to the present invention as constructed as above, by the gas that the relative humidity of the non-solvent ingredients blasting film formative resin solution is less than 50%, discharge opening can be made and the atmosphere of solidifying between liquid level keeps relative humidity to be less than 50%, and can prevent from producing condensation near the discharge opening below spinning-nozzle.In addition, scavenging is carried out to around it by the mode on scavenging gas cover layer formative resin solution surface, can prevent film formative resin solution from absorbing non-solvent ingredients when running between spinning-nozzle and solidification liquid liquid level and start situation about being separated, and molten being separated of film formative resin can be made to originate in solidification liquid, therefore, the beginning be separated is with when carrying out, and the humidity and temperature of the radial direction of film formative resin solution is homogeneous.
In addition, in the present invention, it is characterized in that, as described scavenging gas, use the gas that the relative humidity of the non-solvent ingredients of film formative resin solution is less than 10%.
According to the present invention as constructed as above, film formative resin solution can be suppressed further to absorb non-solvent ingredients when running between spinning-nozzle and solidification liquid liquid level and start situation about being separated.
In addition, in the present invention, it is characterized in that, as described solidification liquid, serviceability temperature is the solidification liquid of more than 50 DEG C, less than 90 DEG C.
According to the present invention as constructed as above, because the film formative resin solution contacted with solidification liquid heats up, therefore until the stopping that being separated of film formative resin solution caused by the absorption of non-solvent ingredients, non-solvent uptake before structure immobilization increase, cause set retardation, therefore, the surface texture of cortina in gained can be suppressed to become too fine and close, and water permeable ability declines.
In addition, in the present invention, it is characterized in that, is the described film formative resin solution that spues the spinning-nozzle of more than 30 DEG C, less than 60 DEG C from temperature.
According to the present invention as constructed as above, the situation low compared to film formative resin solution temperature, non-solvent uptake till the stopping that being separated of the film formative resin solution caused by the absorption until non-solvent ingredients, structure immobilization increases, cause set retardation, therefore, the surface texture of cortina in gained can be suppressed to become too fine and close, and water permeable ability declines.
In addition, in the present invention, it is characterized in that, as described solidification liquid, use the solidification liquid that the described good solvent composition of film formative resin solution and the mass ratio of non-solvent ingredients are 20:80 ~ 60:40.
According to the present invention as constructed as above, set retardation is caused because non-solvent ingredients declines to the diffusion velocity in the film formative resin solution contacted with solidification liquid, therefore, it is possible to suppress the surface texture of gained hollow fiber membrane to become too fine and close, water permeable ability declines.
Invention effect
As mentioned above, according to the present invention, while preventing spinning-nozzle from condensing, the hollow form multiple aperture plasma membrane with homogeneous membrane structure can be manufactured.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the manufacturing installation of the hollow form multiple aperture plasma membrane shown 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 of the manufacturing installation of the hollow form multiple aperture plasma membrane shown in the variation of embodiment of the present invention.
Fig. 4 is the schematic diagram of the manufacturing installation of the hollow form multiple aperture plasma membrane shown in the variation of embodiment of the present invention.
Fig. 5 is the schematic diagram of the manufacturing installation of the hollow form multiple aperture plasma membrane shown in the variation of embodiment of the present invention.
Symbol description
1,51,61 manufacturing installations
3 spinning-nozzles
5 solidification liquids
7 coagulating basins
9 scavenging arrangements
23,63 scavenging nozzles
53 barrel members
63 scavengings
Detailed description of the invention
First embodiment of the manufacturing installation (following, to there is the situation being called " manufacturing installation ") of hollow form multiple aperture plasma membrane of the present invention is described.
In Fig. 1, the manufacturing installation of display present embodiment.The manufacturing installation 1 of present embodiment is after the film formative resin solution that hydrophobic polymer and hydrophilic polymer are dissolved in good solvent and are formed coats hollow rope form support surface, film formative resin solution in importing solidification liquid is solidified in solidification liquid, thus manufacturing the inner device with the hollow form multiple aperture plasma membrane of intensity support, it is provided with: the coagulating basin 7 of spinning-nozzle 3, storage solidification liquid 5 and the scavenging arrangement 9 to the film formative resin solution conveying scavenging gas that spinning-nozzle 3 spues.
Spinning-nozzle 3 is by making hollow rope form support A
1the nozzle that the support through hole 11 passed through is formed with the resin solution stream 13 of film formative resin solution.The discharge opening being formed with resin solution stream 13 below spinning-nozzle 3 is (following, there is the situation of " resin solution discharge opening " of being called) and the discharge opening (following, existence is called the situation of " support discharge opening ") of support through hole 11.Resin solution discharge opening is ring-type, is concentric circles and is formed at the more lateral of support discharge opening with the support discharge opening of support through hole 11.
In this spinning-nozzle 3, make hollow rope form support A
1by support through hole 11, spue downwards from support discharge opening, meanwhile, film formative resin solution is flowed in resin solution stream 13, and spues downwards from resin solution discharge opening.So, can at hollow rope form support A
1outer peripheral face on form the film A of film formative resin solution
2, thus make the filamentous A ' of hollow.
As hollow rope form support A
1, knitted rope (Knitting New-York can be used) or braid (Group New-York).As the fiber forming knitted rope or braid, synthetic fiber, semisynthetic fibre, regenerated fiber and natural fabric etc. can be enumerated.In addition, the form of fiber can be any one in monofilament, multifilament, staple fibre yarn.
Film formative resin solution usually comprises hydrophobic polymer, hydrophilic polymer and dissolves their good solvent.As required, film formative resin solution also can comprise other adding ingredient.
As hydrophobic polymer, fluorine resin, polyacrylonitrile, cellulose derivative, polyamide, polyester, polymethacrylates and the polyacrylate etc. such as the polysulfones such as polysulfones and polyether sulfone system resin, Kynoar can be enumerated.In addition, also can be 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, from the viewpoint of the excellent durability to oxidants such as hypochlorous acid, preferred fluorine resin, and preferably Kynoar or the copolymer that is made up of vinylidene fluoride and other monomer.
Hydrophilic polymer adds with the stabilisation realizing masking state to the viscosity of film formative resin solution is adjusted to the OK range forming hollow form multiple aperture plasma membrane A, preferably uses polyethylene glycol or PVP etc.In these, from the viewpoint of the pore size control of gained hollow form multiple aperture plasma membrane A and the intensity of hollow form multiple aperture plasma membrane A, the copolymer of preferably polyethylene base pyrrolidones or PVP and other monomer copolymerization.
In addition, the resin that also can be mixed with two or more in hydrophilic polymer.Such as, as hydrophilic polymer, if use the hydrophilic polymer of more high molecular, there is the trend being easy to form the good hollow form multiple aperture plasma membrane A of membrane structure.On the other hand, easier remove from hollow form multiple aperture plasma membrane A in, low-molecular-weight hydrophilic polymer is suitable.Therefore, also according to object, hydrophilic polymers of the same race different for molecular weight suitably can be mixed and uses.
As good solvent, DMF, DMA, dimethyl sulfoxide (DMSO), METHYLPYRROLIDONE and N-methylmorpholine-N-oxide etc. can be enumerated, and more than a kind these materials can be used.In addition, not damaging in hydrophobic polymer or hydrophilic polymer deliquescent scope in a solvent, also can the non-solvent of hydrophobic polymer used in combination or hydrophilic polymer.
The temperature of film formative resin solution is not particularly limited, but is generally 10 ~ 100 DEG C.When film formative resin solution is same composition, when temperature uprises, be separated and structure immobilization after phase separation structure coarsening, film water permeable ability also grow.
But, with the kind of film formative resin solution and the difference of composition, keep the words of high temperature for a long time, produce film formative resin solution gelation or rotten situation sometimes, in addition, when the component of polymer in film formative resin solution adopts the high material of molecular weight, and during the polymer ratio of components height of film formative resin solution, the solution viscosity that there is film formative resin solution uprises, and is difficult to the situation of stable masking under low temperature.Therefore, from these points of view, the preferable range of film formative resin solution temperature during spinning is 20 ~ 80 DEG C, more preferably 30 ~ 60 DEG C.
But, even if be easy to when keeping for a long time under employing high temperature produce gelation or rotten film formative resin solution, as long as employing following methods, namely the method for supplying or rapid temperature increases also shortens high temperature hold time as much as possible to set point of temperature before being about to flow out spinning-nozzle or in spinning-nozzle is carried out under can not producing the resin solution gelation of film formative or rotten temperature before flowing out spinning-nozzle, even if the film formative resin solution so spued at spinning-nozzle is easy to produce in gelation or rotten temperature province, also stable masking can be carried out.
Hydrophobic polymerizable substrate concentration in film formative resin solution crosses stability when rare or overrich all can reduce masking, and have the trend being difficult to obtain target hollow form multiple aperture plasma membrane A, therefore, lower limit is preferably 10 quality %, more preferably 15 quality %.In addition, the upper limit is preferably 30 quality %, more preferably 25 quality %.On the other hand, in order to more easily form hollow form multiple aperture plasma membrane A, the concentration limit of hydrophilic polymer is preferably 1 quality %, more preferably 5 quality %.From the viewpoint of the treatability of film formative resin solution, the upper limit of concentration of hydrophilic polymer is preferably 20 quality %, more preferably 12 quality %.
Coagulating basin 7 is that it can make the film A solidifying film formative resin solution for the storage tank of storage bag containing the solidification liquid 5 of the non-solvent of hydrophobic polymer
2coagulating basin 5 contact with film formative resin solution.By making the film A of film formative resin solution
2solidify, filamentous A ' becomes hollow form multiple aperture plasma membrane A.
Solidification liquid 5 is the non-solvent of hydrophobic polymer, the good solvent of hydrophilic polymer, the mixture of water, ethanol, methyl alcohol etc. or these materials can be enumerated, wherein, from the viewpoint of security and running management, be preferably the mixed liquor of the solvent that uses of film formative resin solution and water.The temperature of the good solvent of solidification liquid and the ratio of components of non-solvent, solidification liquid is not particularly limited, but good solvent usually: the ratio of components of non-solvent is 5:95 ~ 80:20, and temperature is 10 ~ 110 DEG C.
In synthermal solidification liquid, the containing ratio of good solvent is higher, impregnated in the film formative resin solution in solidification liquid be separated and structure immobilization after phase separation structure get over coarsening, film water permeable ability is also stronger, but there is following situation: to be separated and good solvent in hollow form multiple aperture plasma membrane after structure immobilization declines with the mutual diffusion velocity of non-solvent in solidification liquid, mechanical strength embodiment delay.When hollow form multiple aperture plasma membrane under the state that cannot fully demonstrate this mechanical strength contacts with guide roller etc., the situations such as the section deformation of existence generation hollow form multiple aperture plasma membrane or surface damage.
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, in solidification liquid with composition, solidification liquid temperature is lower, impregnated in film formative resin solution in solidification liquid to be separated and phase separation structure after structure immobilization gets over densification, but there is following situation: the mutual diffusion velocity of the good solvent in the hollow form multiple aperture plasma membrane after phase separation structure immobilization and the non-solvent in solidification liquid declines, mechanical strength embodies and postpones.Otherwise, during solidification liquid temperature height, impregnated in film formative resin solution in solidification liquid in the phase separation structure coarsening be separated and after structure immobilization, film water permeable ability also grow, to be separated and the mutual diffusion velocity of residual good solvent in hollow form multiple aperture plasma membrane after structure immobilization and non-solvent in solidification liquid accelerates, therefore, mechanical strength embodies and becomes early.
But solidification liquid temperature is higher, more need strengthening for keeping the attemperator of solidification liquid temperature constant.In addition, the transpiration of solidifying liquid level from the good solvent in solidification liquid and non-solvent also becomes violent, and low-temp. portion becomes and is easy to produce condensation.In addition, when solidification liquid temperature is more than the boiling point of solidification liquid, causes due to the boiling of solidification liquid solidifying slosh, become and be difficult to stable masking.
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 high for high, solidification liquid for the film formative resin solution temperature being immersed in solidification liquid good solvent containing ratio and solidification liquid temperature is high combine time, even if not as dry-and wet-type method in the past makes film formative resin solution absorb non-solvent ingredients and impregnated in solidification liquid like that in atmosphere, the phase separation structure that surface texture is thick, water permeable ability is strong also can be formed.
In coagulating basin 7, the 1st guide roller 15 being provided with configuration near bottom it and the 2nd guide roller 17 configured near the edge part of coagulating basin 7.1st guide roller 15 makes filamentous A ' reel in solidification liquid 5 and traffic direction is reversed obliquely upward.2nd guide roller 17 is by the exterior guiding of the hollow form multiple aperture plasma membrane A by being formed in solidification liquid 5 to coagulating basin 7.
On the top of coagulating basin 7, be provided with the top board 19 for suppressing solidification liquid 5 transpiration.Top board 19 is formed opening portion 19a and opening portion 19b, wherein, opening portion 19a is used for scavenging gas that the filamentous A ' that spues of the spinning-nozzle 3 and circular open portion 23a of scavenging nozzle 23 that is arranged at below spinning-nozzle 3 spues and flows into towards the liquid level of solidification liquid 5; The hollow form multiple aperture plasma membrane A that opening portion 19b is used for relying on the 2nd guide roller 17 self-solidifying solid-liquid 5 to guide to coagulating basin 7 outside passes through, and it is outside to flow out to coagulating basin 7 for the scavenging gas that the circular open portion 23a of scavenging nozzle 23 spues.The minimal aperture area that opening portion 19b preferably can make filamentous A ' can be discharged smoothly by, the scavenging gas that is supplied in the underlying space of top board 19 simultaneously in the mode do not contacted with top board 19.Scavenging gas such as can use room air, plant compressed air and factory's dried compressed air etc., and in this case, scavenging gas is the gas that the relative humidity of the non-solvent ingredients of film formative resin solution is less than 50%.
Scavenging arrangement 9 is following a kind of devices: the non-solvent ingredients and heat that comprise the atmosphere of the non-solvent ingredients of the solidification liquid that spontaneous coagulation groove 7 rises around are removed from filamentous A ', and carry out scavenging around filamentous A '.Scavenging arrangement 9 is provided with: be arranged at the scavenging nozzle 23 below spinning-nozzle 3 and supply the gas supply device 25 of scavenging gas to scavenging nozzle 23.
Scavenging nozzle 23 is annular component, and is provided with: the central circular openings portion 23a on the upside of the vertical direction being positioned at the opening portion 19a of top board 19; By being connected to gas supply device 25 and the gas that forms of the annulus being imported with scavenging gas imports room 23b; And spue and import by gas the annular gas discharge opening 23c of scavenging gas that room 23b supplies towards the spinning-nozzle 3 being exposed to circular open portion 23a.
Scavenging nozzle 23 is arranged to be close to the top board 19 of coagulating basin 7, and is formed with the traffic coverage R in the scavenging gas that circular open portion 23a that film formative resin solution runs on scavenging nozzle 23 spues between the liquid level of solidification liquid 5 in scavenging nozzle 23 and coagulating basin 7.The structure making film formative resin solution absorb non-solvent ingredients is not set in traffic coverage R.
Traffic coverage R is arranged to following structure: the scavenging gas not hindering the circular open portion 23a of scavenging nozzle 23 to spue flows out towards periphery along the liquid level of solidification liquid 5, and the abutment of the annular membrane formative resin solution that spinning-nozzle 23 spues and hollow rope form support is positioned at the more top of solidification liquid 5 liquid level.Herein, if the degree of depth of the circular open portion 23a of scavenging nozzle 23 deepens, then traffic coverage R too, distance below spinning-nozzle 3 and between the liquid level of solidification liquid 5 is elongated, and the point that the annular membrane formative resin solution that spinning-nozzle 3 spues engages with hollow rope form support also can away from the liquid level of solidification liquid 5.When traffic coverage R is too short, due to the flowing of the scavenging gas that circular open portion 23a spues, there is the slosh of solidification liquid 5, the possibility that filamentous A ' changes with the contact condition of solidification liquid 5.Otherwise when traffic coverage R is long, the supply of the required scavenging gas that the non-solvent ingredients for being evaporated by the liquid level of solidification liquid 5 is around fully removed from filamentous A ' increases.Therefore, in the present invention, the length of preferred traffic coverage R is 5 ~ 30mm, more preferably 10 ~ 20mm.
The center of circular open portion 23a is arranged to consistent with the center of support discharge opening and resin solution discharge opening.Therefore, circular open portion 23a can make filamentous A ' pass through.Gas imports room 23b and scavenging nozzle 23 is concentric circles, and be formed at the more outer circumferential side of circular open portion 23a.
Fig. 2 is the ground plan of scavenging nozzle.
Gas discharge opening 23c and gas import room 23b and are communicated with, and as shown in Figure 2, towards the central opening of circular open portion 23a, therefore, the outer circumferential side of scavenging gas from circular open portion 23a can be spued to center.The scavenging gas that circular open portion 23a spues and filamentous A ' meet, and as arrow Y
1shown in, along the traffic direction of filamentous A ', namely changing direction is downwards, until flow to the liquid level of solidification liquid 5.
In present embodiment, the length of the above-below direction of gas discharge opening 23c is identical with the length that gas imports the above-below direction of room 23b, and is provided with the ring-type resistance given body 23d that the scavenging gas spued to gas discharge opening 23c gives the resistance that spues in gas discharge opening 23c.Resistance given body 23d is the structure forming flow path resistance while of making scavenging gas permeation, such as, can use WEB, continuous foamed body and porous plastid etc.Resistance given body 23d is arranged at gas discharge opening 23c, imports the gas flow pressure loss of the annulus in the 23b of room relative to gas, gas spues pressure when becoming large with more than ten times to decades of times degree, and the pressure inequality acting on gas discharge opening 23c diminishes.Therefore, the gas discharge-amount from gas discharge opening 23c in a circumferential direction can more homogenization, and more stably can carry out scavenging.In addition, gas discharge opening 23c is preferably provided with the rectification body flowing of the scavenging gas that gas discharge opening 23c spues being carried out to rectification.When rectification body being located at gas discharge opening 23c, the directive property of the scavenging gas that gas discharge opening 23c spues increases, and scavenging efficiency improves.As rectification body, such as, grid, honeycomb structured body and the WEB etc. that are made up of plate object can be used.In addition, the scavenging arrangement 9 in present embodiment is provided with the gas-filtering device 27 of filtration scavenging gas and adjusts the gas adjustment mechanism 29 being supplied to the temperature and humidity of the scavenging gas of scavenging nozzle 23 in the downstream of gas supply device 25.In present embodiment, the downstream of gas-filtering device 27 is provided with gas adjustment mechanism 29.
As gas-filtering device 27, known filter can be used, such as, fiber is rolled into the porous sintered article, hollow form multiple aperture plasma membrane etc. of the object of cavernous cylinder, the object processed by Porous sheet, tubular.If scavenging arrangement 9 is provided with gas-filtering device 27, then can removes the foreign matters such as the dust contained by scavenging gas, thus, can prevent by the filamentous A ' of circular open portion 23a adheres to foreign matter.Thus, the quality of gained hollow form multiple aperture plasma membrane A can be improved.
The gas filtration precision of gas-filtering device 27, can according to being supplied to the purity of the gas of scavenging nozzle 23, the filtering accuracy etc. of manufactured hollow form multiple aperture plasma membrane A suitably selects, but due to be attached to foreign matter on filamentous A ' solidify in operation may cause occurring membrane structure abnormal, film surface damage etc. may be caused solidifying in the operation after operation, from the viewpoint of the generation of these film defects of suppression, preferred filtering accuracy is high.Specifically, as gas filtration precision, be preferably less than 1 μm, more preferably less than 0.1 μm, preferably less than 0.01 μm further.
Gas adjustment mechanism 29 has adjustment and is supplied to the gas humidity regulator of the humidity of the scavenging gas of scavenging nozzle 23 to be supplied at least one in the gas temperature regulator of the temperature of the scavenging gas of scavenging nozzle 23 with adjustment, thus can control at least one in the humidity and temperature of scavenging gas.
In order to reduce the non-relative humidity in scavenging gas, scavenging gas being dehumidified, the dehydrating units such as cooler condenser can be used as gas adjustment mechanism 29, and use gas-heating apparatus as gas temperature regulator.In this gas adjustment mechanism 29, gas is made to pass through dehydrating unit, thus dehumidifying can not to condense and film formative resin solution can not absorb non-solvent ingredients and cause the relative humidity be separated to the non-solvent ingredients in gas below spinning-nozzle 3, and as required, be heated to set point of temperature by gas-heating apparatus.In addition, in factory etc., when to supply the relative humidity under room temperature be the dry air of about 1%, also can omit gas humidity regulator, and by gas temperature regulator, dry air is adjusted to set point of temperature and become heat drying air, be supplied to scavenging nozzle 23.
Therefore, it is possible to can produce in the film formative resin solution importing spued by spinning-nozzle dry-and wet-type masking method in the past, nozzle face is condensed in the solidification liquid of such hot and humid atmosphere, and can not non-solvent ingredients be absorbed.
Next, the manufacture method of the hollow form multiple aperture plasma membrane A using above-mentioned manufacturing installation 1 is described in detail.
In the manufacture method of present embodiment, first, to spue downwards hollow rope form support A from the support discharge opening of spinning-nozzle 3
1, meanwhile, film formative resin solution is spued downwards from resin solution discharge opening, thus at hollow rope form support A
1outer peripheral face form the film A of film formative resin solution
2and make the filamentous A ' of hollow.Then, after the filamentous A ' of making runs on traffic coverage R, by the opening portion 19a of top board 19, send in coagulating basin 7.
In addition, in making filamentous A ' period, in manufacturing installation 1, by starting scavenging arrangement 9, scavenging is carried out around to the filamentous A ' running on traffic coverage R.
In this case, first, the scavenging gas provided by gas-filtering device 27 pairs of gas supply devices 25 is filtered, and after carrying out temperature and humidity adjustment by gas adjustment mechanism 29, supply gas imports room 23b.Now, from the viewpoint of preventing spit face 10a from condensing further, preferably by gas adjustment mechanism 29, scavenging gas is adjusted to the surface temperature of dew point lower than spinning-nozzle 3 spit face.In addition, the temperature wanting spinning-nozzle 3 or filamentous A ' does not depart from set condition, and the temperature of preferred scavenging gas is supplied with the temperature identical with the design temperature of spinning-nozzle 3.
Then, gas imports in the 23b of room, carries out homogenization by the resistance given body 23d being arranged at gas discharge opening 23c to the pressure distribution of scavenging gas.Then, gas is imported the scavenging gas in the 23b of room and is spued to the center of circular open portion 23a by the resistance given body 23d of gas discharge opening 23c, and is delivered to below spinning-nozzle 3 by scavenging gas.The scavenging gas spued to circular open portion 23a flows from the outer circumferential side of circular open portion 23a to center, then, redirects to downwards, flows to solidification liquid 5 liquid level direction.Thus, the steam or air that arrive the neighbouring solidification liquid of spinning-nozzle 3 are below got rid of in scavenging with gas, while surround filamentous A ' around.
Then, the filamentous A ' covering traffic coverage R be impregnated in solidification liquid 5 and make it solidify, obtaining hollow form multiple aperture plasma membrane A.
Specifically, solidify in operation, formed the film A of film formative resin solution by spinning process
2the solidification liquid 5 that imported in coagulating basin 7 by the opening portion 19a of the top board 19 of coagulating basin 7 of filamentous A ', and to contact with solidification liquid 5.When making filamentous A ' impregnated in solidification liquid 5, the film A contacted with solidification liquid 5
2in, the non-solvent ingredients diffusion contained by solidification liquid 5 is immersed, film A
2the hydrophobic polymer of film formative resin solution when having exceeded the boundary existed as liquid phase in the solution, hydrophobic polymer and good solvent or the hydrophilic polymer being dissolved in good solvent start to be separated, and are transferred to solid phase from liquid phase.Thus, the eyed structure as membrane bone frame is formed.When the hydrophobic polymer of film formative resin solution is separated completely and stops the formation of eyed structure, the eyed structure as membrane bone frame is fixed.But now, hydrophobic polymer is in swelling state due to good solvent, therefore present mechanical strength weak, hold yielding state under external force.Along with film A
2inner good solvent diffuses to solidification liquid 5, film A
2in liquid phase part composition in, good solvent composition reduce, non-solvent ingredients increase, hydrophobic polymer is changed to solid state from solvent swelling state, film A
2mechanical strength significantly increase.Define following hollow form multiple aperture plasma membrane A: its outer peripheral face and film inside define hydrophobic polymer and gelatinous hydrophilic polymer interlaced, three-dimensional mesh structure to the state that the dimensional strength of external force increases.The 2nd guide roller 17 is relied on to be transferred to subsequent handling outside coagulating basin 7 by the hollow form multiple aperture plasma membrane A solidifying gained.
As mentioned above, according to manufacturing installation 1, by scavenging arrangement 9, the steam of solidification liquid 5 is around removed from filamentous A ', and scavenging is carried out around to filamentous A ', therefore, the humidity of the periphery atmosphere below spinning-nozzle 3 can be suppressed to rise, and the condensation below spinning-nozzle 3 can be suppressed.Thus, the quality of the membrane superficial tissue precise hard_drawn tuhes of gained hollow form multiple aperture plasma membrane A, the homogenization of film list structure and hollow form multiple aperture plasma membrane A can be improved.
In addition, according to manufacturing installation 1, surrounded by scavenging gas when filamentous A ' can be made to run on traffic coverage R, do not start to be separated, but just start to be separated when contacting with the solidification liquid 5 of coagulating basin 7.Thus, the humidity and temperature of the radial direction of the film formative resin solution started when being separated can be made homogeneous.
In addition, the present invention is not limited to above-mentioned embodiment, and without departing from the spirit and scope of the present invention, each formation can suitably change.
Fig. 3 is the schematic diagram of the manufacturing installation of the hollow form multiple aperture plasma membrane shown in variation.As shown in Figure 3, the manufacturing installation 51 in variation, except having the formation of manufacturing installation 1, also has barrel member 53.
Barrel member 53 is that the mode of surrounding the filamentous A ' running on traffic coverage R is formed.Barrel member 53 is installed on below scavenging nozzle 23 hermetically, and near the liquid level extending to the solidification liquid 5 in coagulating basin 7 below scavenging nozzle 23.Barrel member 53 has circular cross-section, and its central shaft is arranged to consistent with the central shaft of the circular open portion 23a of scavenging nozzle 23.In addition, the upper end of barrel member 53 has flange part 55, and this flange part 55 is installed on below scavenging nozzle 23 by using magnet etc.And by barrel member 53 is installed on below scavenging nozzle 23, near the liquid level of solidification liquid 5, form circular stream from the circular open portion 23a of scavenging nozzle 23, the scavenging gas that the circular open portion 23a of scavenging nozzle 23 spues is flowed by the traffic direction of the inherent filamentous A ' of this stream.In addition, be formed with gap 57 between the lower end of barrel member 53 and the liquid level of solidification liquid 5, it flows out in barrel member 53 for making the scavenging gas of arrival liquid level.
So, the surrounding running on the filamentous A ' of traffic coverage R is surrounded by barrel member 53, and inner to barrel member 53 by scavenging gas flow, and scavenging gas can be suppressed to peel off from filamentous A ' at the space place of flowing along filamentous A '.Thus, filamentous A ' can be surrounded with scavenging gas in the interval Zone R territory of whole service, and scavenging can be carried out to around filamentous A ' in the interval Zone R territory of whole service.
The circular flow diameter of barrel member 53 is less, more can obtain high scavenging efficiency with few scavenging gas supply, but due to the vibration etc. of the filamentous A ' in the charge and discharge operations of barrel member or masking, preferably be set to filamentous A ' not with the suitable size of contact internal walls, be usually set to about 4 ~ 16 times of the diameter running on inner filamentous A '.
In addition, the circular flow path length of barrel member 53 is preferably following length: the abutment of the hollow rope form support of the annular membrane formative resin solution spued with nozzle is positioned at the more top of barrel member 53 lower end, and the flow regime of scavenging gas in barrel member 53 is stable.
When scavenging gas flows into barrel member 53 from scavenging nozzle 23, because its flow direction and speed change, when the circular flow path length of barrel member 53 is too short, following situation may be there is: the scavenging gas flowing of barrel member 53 is easy to chaotic, bring out the vibration of filamentous A ', thus reduce scavenging efficiency.Otherwise, when this length setting is required above length, there is following situation: by surperficial heat release, the temperature of the scavenging gas of internal flow is changed.In this case, preferably adopt and to cover around barrel member 53 and the heat preserving method of set temperature regulator etc. with heat-insulating material.
In present embodiment, the value of the circular flow path length/circular flow diameter of barrel member 53 is preferably 2 ~ 40, and more preferably 4 ~ 20.
Fig. 4 is the schematic diagram of the manufacturing installation of the hollow form multiple aperture plasma membrane showing further variation.As shown in Figure 4, the manufacturing installation 61 further in variation is provided with scavenging nozzle 63, to replace the scavenging nozzle 23 of manufacturing installation 1.
Scavenging nozzle 63 is provided with: the inflow entrance 65 accepting the scavenging gas that gas supply device 25 grade flows out and the spitting unit 67 spued to filamentous A ' by scavenging gas.Spitting unit 67 spues scavenging gas in the horizontal direction, has the height substantially identical with traffic coverage R.Therefore, scavenging nozzle 63 to spue scavenging gas with horizontal direction at the interval R of whole service.
By arranging such scavenging nozzle 63, also scavenging can be carried out at the interval R of whole service to around filamentous A '.
In addition, as shown in Figure 5, also can be provided with: surround the sidepiece wind deflector 68 around traffic coverage R and there is the lower end being arranged at traffic coverage R, namely along the bottom wind deflector 71 of the opening portion 69 making filamentous A ' pass through that the liquid level of solidification liquid 5 is arranged.By arranging sidepiece wind deflector 68 and bottom wind deflector 71, the scavenging gas that scavenging nozzle 63 can be promoted to spue flows in the horizontal direction.
Then, embodiments of the invention are described.
Adopt following manufacturing installation in embodiment: below spinning-nozzle as shown in Figure 3, be provided with scavenging nozzle, the lower ending opening face being installed on the barrel member below this scavenging nozzle is set as the distance from the solidification liquid liquid level 5mm in coagulating basin.
As the spinning-nozzle of manufacturing installation, use following nozzle: the support had to the hollow rope form support that spues spues hole below, and have and to spue the resin solution discharge opening of the hole shape concentrically film formative resin solution of round shape of spuing with this support with ring-type.
As scavenging arrangement, use scavenging nozzle and the barrel member of magnetic stainless steel SUS430; Wherein, the diameter 60mm of scavenging nozzle, opening diameter 30mm, height 10mm, opening internal face is made up of the internal face of the SUS metal particles sinter body of internal diameter 30mm, thickness 2mm, height 8mm, nominal filter fineness 1 μ; Barrel member is diameter 30mm, internal diameter 12mm, long 150mm, and upper end is the polypropylene barrel member of round flange of the diameter 60mm embedded by neodium magnet, thick 8mm.
Be fixed below the scavenging nozzle that barrel member makes flange surface be adsorbed in the stainless steel of magnetic by magnetic force.
As film formative resin solution, can prepare in accordance with the following methods: by Kynoar P1, (ア Le ケ マ company manufactures, trade name: カ イ ナ ー 761A), (ア Le ケ マ company manufactures Kynoar P2, trade name: カ イ ナ ー 301A), PVP (Japanese catalyst Co. manufacture, trade name: K-79), N, N-dimethylacetylamide (DMAc) (manufacture of サ system ソ Application Off ァ イ Application ケ ミ カ Le company) mixes according to mass ratio shown below, stirring and dissolving at 60 DEG C, be prepared into the film formative resin solution A comprising high molecular Kynoar, B and comprise these 3 kinds of solution of film formative resin solution C of low molecular weight polyvinylidene fluoride.
(film formative resin solution A)
By Kynoar P1 (matter average molecular weight (hreinafter referred to as Mw) Mw:7.2 × 10
5) 18.8 quality %, PVP M1 (Mw:9.0 × 10
4) 12.2 quality % and mixing as the DMA 69 quality % of solvent.
(film formative resin solution B)
Mix using the Kynoar P1 of 15.2 quality %, the PVP M1 of 8.6 quality % with as the DMA 76.2 quality % of solvent.
(film formative resin solution C)
By Kynoar P2 (Mw:5.2 × 10 of 19.2 quality %
5), the PVP M1 of 10.1 quality % and mixing as the DMA 70.7 quality % of solvent.
As hollow rope form support, use internal diameter 1.5mm, external diameter 2.5mm, internal diameter 1mm, the large diameter hollow rope form support A of external diameter 1.4mm and the hollow rope form support B of thin diameter, it uses heating of metal mouth to carry out adding hot-stretch heat treatment in order to low flexibleization and high outside dimension stabilisation.
(embodiment 1)
The temperature of spinning-nozzle is set to 32 DEG C, the temperature of the film formative resin solution of supply spinning-nozzle is set to 32 DEG C, solidification liquid temperature is set to 70 DEG C, use N, N-dimethylacetylamide: the mass ratio of water is that the liquid of 30:70 is as solidification liquid, film speed is set to 30m/min, by heat exchanger the temperature of factory's dry air is adjusted to 32 DEG C and the dry air that relative humidity becomes about less than 1% is fed to scavenging nozzle with 6L/min, and use hollow rope form support A, hollow rope form support B and film formative resin solution A, make the hollow form multiple aperture plasma membrane of external diameter 2.8mm and the hollow form multiple aperture plasma membrane of external diameter 1.6mm.
When making the hollow form multiple aperture plasma membrane of external diameter 2.8mm, the discharge-amount of film formative resin solution is 64.8cc/min, and when making the hollow form multiple aperture plasma membrane of external diameter 1.6mm, the discharge-amount of film formative resin solution is 24.2cc/min.
(embodiment 2)
Except using film formative resin solution B as except film formative resin solution, other is filmed as embodiment 1.
(embodiment 3)
Except using film formative resin solution C as except film formative resin solution, other is filmed as embodiment 1.
(embodiment 4)
Except the temperature of spinning-nozzle being set to 50 DEG C, the temperature of film formative resin solution of supply spinning-nozzle is set to 50 DEG C, with heat exchanger the temperature of factory's dry air is adjusted to 50 DEG C and supplies except scavenging nozzle, and other is filmed as embodiment 3.
(embodiment 5)
Except being set to except 80 DEG C by the temperature of solidification liquid, other is filmed as embodiment 2.
(embodiment 6)
Except using DMA: the mass ratio of water be 40:60 except the composition of solidification liquid, other is filmed as embodiment 5.
In arbitrary example in embodiment 1 ~ 6, all can not produce condensation at spinning-nozzle place.
In addition, as the N of the solvent composition of the hollow form multiple aperture plasma membrane made, the hot wash of N-dimethylacetylamide is removed, and with oxidant using as after removing with hot wash after the PVP of hydrophilic polymer composition is decomposed, dry gained hollow form multiple aperture plasma membrane sample in the hot blast of 100 DEG C, this sample surfaces is observed with the multiplying power of 30,000 times with electron microscope, consequently, have no remarkable structure in a circumferential direction uneven, even and if membrane superficial tissue is after the masking time, does not also change.
In addition, relatively the mean surface pore size of gained hollow form multiple aperture plasma membrane finds, its size is embodiment 1 < embodiment 2 < embodiment 3, embodiment 3 < embodiment 4, embodiment 2 < embodiment 5 < embodiment 6.
As comparative example, to be formed with the device of embodiment 1 and film forming condition and the mode not starting scavenging nozzle are filmed.
In comparative example, as time goes by, below spinning-nozzle, condensation is produced.In addition, process the hollow form multiple aperture plasma membrane made by the method identical with embodiment 1, observe the hollow form multiple aperture plasma membrane sample surfaces made, it found that, produce uneven at the surface texture of circumferencial direction, and the surface texture of film is changing after the masking time.
Claims (14)
1. a hollow form multiple aperture plasma membrane manufacturing installation, described device is a kind of hollow form multiple aperture plasma membrane manufacturing installation manufacturing hollow form multiple aperture plasma membrane by making film formative resin solution solidify, and it is characterized in that: it is provided with: spinning-nozzle, coagulating basin and scavenging arrangement;
Described spinning-nozzle has discharge opening, and this discharge opening spues in thread film formative resin solution downward;
The solidification liquid of described coagulating basin storage for solidifying described film formative resin solution, and described coagulating basin is configured to, makes the liquid level of described solidification liquid in the below of the discharge opening of described spinning-nozzle and with the discharge opening of described spinning-nozzle at a distance of the distance specified;
Described scavenging arrangement covering runs on the surface of the film formative resin solution between the described solidification liquid liquid level in described discharge opening and described coagulating basin, and makes scavenging gas at the ambient dynamic of described film formative resin solution;
Described scavenging gas is the gas that the relative humidity of the non-solvent ingredients of described film formative resin solution is less than 50%.
2. as the hollow form multiple aperture plasma membrane manufacturing installation that claim 1 is recorded, it is characterized in that: described scavenging arrangement will comprise the surface removal of gas from described film formative resin solution of the described non-solvent ingredients that spontaneous coagulation liquid level rises.
3. as the hollow form multiple aperture plasma membrane manufacturing installation of claim 1 or 2 record, it is characterized in that: between described discharge opening and described solidification liquid, do not make film formative resin solution absorb the structure of non-solvent ingredients, and the described film formative resin solution spued from described spinning-nozzle run the space of described discharge opening and described solidification liquid.
4. as the hollow form multiple aperture plasma membrane manufacturing installation of any one record in claims 1 to 3, it is characterized in that: it has the barrel member around the described film formative resin solution between the liquid level that is centered around and runs on described discharge opening and described solidification liquid, described scavenging arrangement is configured to, and makes scavenging gas in the internal flow of described barrel member.
5. as the hollow form multiple aperture plasma membrane manufacturing installation of any one record in Claims 1 to 4, it is characterized in that: described scavenging arrangement is provided with scavenging nozzle, the radial outside of described film formative resin solution of described scavenging nozzle for making described scavenging gas and spuing from the described discharge opening of described spinning-nozzle, towards described film formative solution resin flows.
6., as the hollow form multiple aperture plasma membrane manufacturing installation that claim 5 is recorded, it is characterized in that: described scavenging nozzle makes described scavenging gas at the whole circumferencial direction Uniform Flow of described film formative resin solution.
7., as the hollow form multiple aperture plasma membrane manufacturing installation that any one in claim 1 ~ 6 is recorded, it is characterized in that: described scavenging arrangement is provided with the gas-filtering device for filtering scavenging gas.
8., as the hollow form multiple aperture plasma membrane manufacturing installation that any one in claim 1 ~ 7 is recorded, it is characterized in that: described scavenging arrangement has the humidity regulator for adjusting scavenging gas humidity.
9., as the hollow form multiple aperture plasma membrane manufacturing installation that any one in claim 1 ~ 8 is recorded, it is characterized in that: described scavenging arrangement has the temperature adjustment device for adjusting scavenging gas temperature.
10. a manufacture method for hollow form multiple aperture plasma membrane, described method is a kind of hollow form multiple aperture plasma membrane manufacture method manufacturing hollow form multiple aperture plasma membrane by making film formative resin solution solidify; It is characterized in that:
Described method has following operation:
Spinning process: spue in thread film formative resin solution downward;
Solidify operation: from the coagulating basin of the position of discharge opening predetermined distance, described film formative resin solution is solidified in the below being arranged at discharge opening; And possess further:
Scavenging operation: during carrying out described spinning process, make scavenging gas flow towards the surface of the described film formative resin solution between the solidification liquid liquid level run in described discharge opening and described coagulating basin, scavenging is carried out to the surrounding of described film formative resin solution;
Wherein, described scavenging gas is the gas that the relative humidity of non-solvent ingredients is less than 50%.
The manufacture method of the 11. hollow form multiple aperture plasma membranes recorded as claim 10, is characterized in that: as described scavenging gas, uses the gas that the relative humidity of the non-solvent ingredients of film formative resin solution is less than 10%.
The manufacture method of the 12. hollow form multiple aperture plasma membranes recorded as claim 10 or 11, it is characterized in that: as described solidification liquid, serviceability temperature is the solidification liquid of more than 50 DEG C, less than 90 DEG C.
13. manufacture methods of hollow form multiple aperture plasma membranes recorded as any one in claim 10 ~ 12, is characterized in that: more than 30 DEG C, at the temperature of less than 60 DEG C, spue described film formative resin solution from spinning-nozzle.
The manufacture method of the 14. hollow form multiple aperture plasma membranes recorded as any one in claim 10 ~ 13, it is characterized in that: as solidification liquid, use the solidification liquid that the described good solvent composition of film formative resin solution and the mass ratio of non-solvent ingredients are 20:80 ~ 60:40.
Applications Claiming Priority (3)
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|---|---|---|---|
| JP2013156928 | 2013-07-29 | ||
| JP2013-156928 | 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 true CN105579627A (en) | 2016-05-11 |
| CN105579627B 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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| Country | Link |
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| JP (1) | JP5776918B2 (en) |
| CN (1) | CN105579627B (en) |
| WO (1) | WO2015016228A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114892290A (en) * | 2022-05-09 | 2022-08-12 | 苏州中色德源环保科技有限公司 | Coreless liquid dry-wet hollow fiber membrane spinning process |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| CN1231941A (en) * | 1998-04-16 | 1999-10-20 | 中国科学院大连化学物理研究所 | Preparation of asymmetrical hollow polyimide fibre membrane |
| JP2004025067A (en) * | 2002-06-26 | 2004-01-29 | Mitsubishi Rayon Co Ltd | Method and device for manufacturing porous hollow fiber membrane |
| JP2008126199A (en) * | 2006-11-24 | 2008-06-05 | Mitsubishi Rayon Co Ltd | Hollow porous film and its manufacturing method |
| JP2012110856A (en) * | 2010-11-26 | 2012-06-14 | Mitsubishi Rayon Co Ltd | Apparatus for manufacturing hollow porous membrane |
| JP2013000619A (en) * | 2011-06-13 | 2013-01-07 | Mitsubishi Rayon Co Ltd | Method for producing porous hollow fiber membrane |
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| JPH0544104A (en) * | 1991-08-01 | 1993-02-23 | Unitika Ltd | Method for dry-jet wet spinning |
| JP2007119973A (en) * | 2005-10-31 | 2007-05-17 | Teijin Techno Products Ltd | Dry-wet spinning apparatus and dry-wet spinning method |
| JP2010236139A (en) * | 2009-03-31 | 2010-10-21 | Toray Ind Inc | Method for producing acrylic fiber |
| 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 WO PCT/JP2014/069966 patent/WO2015016228A1/en active Application Filing
- 2014-07-29 CN CN201480053725.5A patent/CN105579627B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1231941A (en) * | 1998-04-16 | 1999-10-20 | 中国科学院大连化学物理研究所 | Preparation of asymmetrical hollow polyimide fibre membrane |
| JP2004025067A (en) * | 2002-06-26 | 2004-01-29 | Mitsubishi Rayon Co Ltd | Method and device for manufacturing porous hollow fiber membrane |
| JP2008126199A (en) * | 2006-11-24 | 2008-06-05 | Mitsubishi Rayon Co Ltd | Hollow porous film and its manufacturing method |
| JP2012110856A (en) * | 2010-11-26 | 2012-06-14 | Mitsubishi Rayon Co Ltd | Apparatus for manufacturing hollow porous membrane |
| JP2013000619A (en) * | 2011-06-13 | 2013-01-07 | Mitsubishi Rayon Co Ltd | Method for producing porous hollow fiber membrane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114892290A (en) * | 2022-05-09 | 2022-08-12 | 苏州中色德源环保科技有限公司 | Coreless liquid dry-wet hollow fiber membrane spinning process |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5776918B2 (en) | 2015-09-09 |
| JPWO2015016228A1 (en) | 2017-03-02 |
| CN105579627B (en) | 2017-09-29 |
| WO2015016228A1 (en) | 2015-02-05 |
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