CN103717295B - The manufacture method of multiple aperture plasma membrane and manufacture device - Google Patents
The manufacture method of multiple aperture plasma membrane and manufacture device Download PDFInfo
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- CN103717295B CN103717295B CN201280037926.7A CN201280037926A CN103717295B CN 103717295 B CN103717295 B CN 103717295B CN 201280037926 A CN201280037926 A CN 201280037926A CN 103717295 B CN103717295 B CN 103717295B
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- 239000002243 precursor Substances 0.000 claims abstract description 234
- 239000012528 membrane Substances 0.000 claims abstract description 233
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 153
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 75
- 230000008569 process Effects 0.000 claims abstract description 47
- 239000007800 oxidant agent Substances 0.000 claims abstract description 45
- 230000001590 oxidative effect Effects 0.000 claims abstract description 39
- 230000000873 masking effect Effects 0.000 claims abstract description 33
- 239000011550 stock solution Substances 0.000 claims abstract description 31
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 16
- 238000007711 solidification Methods 0.000 claims abstract description 14
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000003814 drug Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 17
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 17
- 238000011144 upstream manufacturing Methods 0.000 claims description 17
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 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
- ATTRMYMZQWIZOR-RRKCRQDMSA-N 4-amino-1-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-6-methyl-1,3,5-triazin-2-one Chemical compound CC1=NC(N)=NC(=O)N1[C@@H]1O[C@H](CO)[C@@H](O)C1 ATTRMYMZQWIZOR-RRKCRQDMSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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Abstract
A kind of manufacture method of multiple aperture plasma membrane, and there is the manufacture device of the multiple aperture plasma membrane of the decomposer possessing decomposition container, described multiple aperture plasma membrane manufacture method has following decomposition process: import in decomposition container by the multiple aperture plasma membrane precursor formed by the solidification of the masking stock solution containing hydrophilic polymer and hydrophobic polymer, in this decomposition container, previous porous membrane precursor is made to contact with the heated medicinal liquid containing oxidant, the previous porous membrane precursor contacting aforementioned medicinal liquid is incubated, the aforementioned hydrophilic polymer of residual in previous porous membrane precursor is made to decompose by aforementioned oxidizer.
Description
Technical field
The present invention relates to the manufacture method of the multiple aperture plasma membranes such as hollow-fibre membrane and manufacture device.
The application based on 08 03rd, the 2011 Japanese Patent Application 2011-170064 CLAIM OF PRIORITY in Japanese publication,
Its content is incorporated herein.
Background technology
For the concentration of useful component in the fields such as field of food industry, medical field, electronics industry, recovery,
Not composition removing, make water etc. for, be made up of cellulose acetate, polyacrylonitrile, polysulfones, fluorine resin etc., pass through example
Hollow-fibre membrane such as wet type or the Porous of dry-and wet-type spinning manufacture is used for secondary filter film, ultrafilter membrane, osmosis filtration
Film etc..
When manufacturing hollow-fibre membrane by wet type or dry-and wet-type spinning, first, preparation is containing hydrophobic polymer and parent
The masking stock solution of waterborne polymeric.Then, by by this ring-type ejection of masking stock solution and make its masking solidified in solidification liquid
Operation, forms coagulum i.e. hollow-fibre membrane precursor.It addition, masking stock solution both can import via the sky portion of walking with air contact
(dry-and wet-type spin processes) in solidification liquid, (wet-spinning) in solidification liquid can also be introduced directly into.
Here, in the film of the hollow-fibre membrane precursor after film making process, generally, hydrophilic polymer is with the state of solution
Residual.If during hydrophilic polymer residues in film like this, then hollow-fibre membrane is difficult to play high water-permeability (film water permeable ability).
It is therefoie, for example, patent documentation 1 is recorded, impregnate in the medicinal liquid of the low temperature containing oxidants such as hypochlorites
Hollow-fibre membrane precursor after film making process, after making medicinal liquid low temperature be held in hollow-fibre membrane precursor, heats guarantor in the gas phase
Hold the hollow-fibre membrane precursor of medicinal liquid, made the hydrophilic polymer of residual in hollow-fibre membrane precursor decompose.Add under gas phase
After heat, carry out washing hydrophilic polymer and the washing procedure of analyte thereof.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-220202 publication
Summary of the invention
The problem that invention is to be solved
But, according to the technology of patent documentation 1, in order to the hollow-fibre membrane precursor after fully decomposing film making process remains
Hydrophilic polymer, need to circulate the dipping process of medicinal liquid under repeatedly low temperature, the heat resolve operation in gas phase and
Thereafter washing procedure, needs long-time.
Like this, the most it is not found to make at short notice in the multiple aperture plasma membrane precursors such as hollow-fibre membrane precursor
The technology that the hydrophilic polymer of residual decomposes.
The present invention is carried out, after its problem is that offer can make film making process at short notice in view of above-mentioned problem
Multiple aperture plasma membrane precursor in residual hydrophilic polymer decompose multiple aperture plasma membrane manufacture method and manufacture device.
For solving the scheme of problem
The present inventor furthers investigate, and result contemplates, and as the medicinal liquid containing oxide, uses the high temperature after heating
Medicinal liquid, by the medicinal liquid after making this heating with remain the film making process of hydrophilic polymer after multiple aperture plasma membrane precursor connect
Touch such that it is able to make medicinal liquid before the multiple aperture plasma membrane being impregnated with and being caused by oxidant contained in medicinal liquid of multiple aperture plasma membrane precursor
In body, the decomposition of hydrophilic polymer of residual is carried out the most simultaneously, and it is as a result, it is possible at short notice after film making process
Multiple aperture plasma membrane precursor decomposes hydrophilic polymer.
[1] manufacture method of a kind of multiple aperture plasma membrane, it has a following decomposition process: will by containing hydrophilic polymer and
The multiple aperture plasma membrane precursor that the masking stock solution of hydrophobic polymer solidifies and formed imports in decomposition container, in this decomposition container,
Make previous porous membrane precursor contact with the heated medicinal liquid containing oxidant, the previous porous matter of aforementioned medicinal liquid will be contacted
Film precursor is incubated, and makes the aforementioned hydrophilic polymer of residual in previous porous membrane precursor decompose by aforementioned oxidizer.
[2] according to the manufacture method of the multiple aperture plasma membrane described in [1], wherein, aforementioned many by contact with aforementioned medicinal liquid in advance
Hole membrane precursor heating.
[3] according to the manufacture method of the multiple aperture plasma membrane described in [1] or [2], in aforementioned decomposition process, hold in aforementioned decomposition
In device, carry out respectively the most aforementioned medicinal liquid and previous porous membrane precursor contact and contact after aforementioned medicinal liquid aforementioned many
The insulation of hole membrane precursor.
[4] according to the manufacture method of the multiple aperture plasma membrane described in [3], aforementioned medicinal liquid is as aforementioned oxidation containing sodium hypochlorite
The aqueous solution of agent, when making aforementioned medicinal liquid and previous porous membrane precursor multiple-contact, in the aforementioned medicinal liquid that the 1st time uses before
The concentration stating sodium hypochlorite is 2000～120000mg/L.
[5] according to the manufacture method of the multiple aperture plasma membrane according to any one of [1]～[4], wherein, at aforementioned decomposition container
In, temperature is more than 60 DEG C, and relative humidity is more than 90%.
[6] according to the manufacture method of the multiple aperture plasma membrane according to any one of [1]～[5], wherein, aforementioned decomposition container supplies
There is steam.
[7] according to the manufacture method of the multiple aperture plasma membrane according to any one of [1]～[6], wherein, by by previous porous matter
Film precursor imports in aforementioned medicinal liquid, makes aforementioned medicinal liquid contact with previous porous membrane precursor.
[8] according to the manufacture method of the multiple aperture plasma membrane according to any one of [1]～[7], wherein, by previous porous matter
Spray aforementioned medicinal liquid on film precursor, make aforementioned medicinal liquid contact with previous porous membrane precursor.
[9] the manufacture device of a kind of multiple aperture plasma membrane, it is the manufacture device of the multiple aperture plasma membrane with decomposer, described point
Solve device and decompose the multiple aperture plasma membrane precursor solidified by the masking stock solution containing hydrophilic polymer and hydrophobic polymer and formed
The aforementioned hydrophilic polymer of middle residual,
Aforementioned decomposer has decomposition container, and described decomposition container makes previous porous membrane precursor and containing oxidant
Heated medicinal liquid contact, is incubated the previous porous membrane precursor contacting aforementioned medicinal liquid, is made by aforementioned oxidizer aforementioned
In multiple aperture plasma membrane precursor, the aforementioned hydrophilic polymer of residual decomposes.
[10] according to the manufacture device of the multiple aperture plasma membrane described in [9], aforementioned decomposer has further:
By the heater of heating in aforementioned decomposition container,
Make the moving device that previous porous membrane precursor is advanced in aforementioned decomposition container,
Make the medicine gas-liquid contacting device that the previous porous membrane precursor advanced in aforementioned decomposition container contacts with aforementioned medicinal liquid.
[11] according to the manufacture device of the multiple aperture plasma membrane described in [10], wherein, aforementioned medicine gas-liquid contacting device is arranged at aforementioned
Multiple positions in decomposition container.
[12] according to the manufacture device of the multiple aperture plasma membrane described in [10] or [11], wherein, aforementioned heater is to aforementioned
The steam feedway of supply steam in decomposition container.
[13] according to the manufacture device of the multiple aperture plasma membrane according to any one of [10]～[12], wherein, aforementioned medicinal liquid contacts
Device possesses the dipper that input has aforementioned medicinal liquid and previous porous membrane precursor to advance in this medicinal liquid.
[14] according to the manufacture device of the multiple aperture plasma membrane described in [13], wherein, aforementioned dipper is cascade (cascade)
Formula, described tandem type refers to, is divided into multiple region in groove, by upstream side region overflow medicinal liquid supplied successively under
The region of trip side.
[15] according to the manufacture device of the multiple aperture plasma membrane according to any one of [10]～[14], wherein, aforementioned medicinal liquid contacts
Device possesses the injection apparatus spraying aforementioned medicinal liquid to aforementioned multiple aperture plasma membrane precursor.
[16] according to the manufacture device of the multiple aperture plasma membrane according to any one of [10]～[15], wherein, aforementioned decomposition container
Inside having heat exchange department, described heat exchange department makes aforementioned by aforementioned medicinal liquid with the heat exchange of the gas in aforementioned decomposition container
Medicine liquid heating.
[17] according to the manufacture device of the multiple aperture plasma membrane according to any one of [10]～[16], wherein, aforementioned moving device
Having multiple traveling roller, the part in this traveling roller is for driving roller.
[18] according to the manufacture device of the multiple aperture plasma membrane according to any one of [10]～[17], wherein, wherein, aforementioned traveling
Device possesses multiple traveling roller, at least 1 in this traveling roller is provided with before preventing the deviation of previous porous membrane precursor
State the guide rod of traveling roller.
[19] according to the manufacture device of the multiple aperture plasma membrane according to any one of [10]～[18], wherein, aforementioned moving device
Possess multiple traveling roller, at least 1 in this traveling roller, it is formed with the row for limiting previous porous membrane precursor from the teeth outwards
The control flume entered.
[20] according to the manufacture device of the multiple aperture plasma membrane according to any one of [9]～[19], wherein, aforementioned decomposition container shape
Become to have to be imported by previous porous membrane precursor the entrance in aforementioned decomposition container and the outlet derived by aforementioned decomposition container,
Said inlet and said outlet are respectively arranged with water-stop portion, described water-stop portion by aforementioned decomposition container with outward
Portion's air block, and it is capable of importing and the derivation of previous porous membrane precursor.
[21] according to the manufacture device of the multiple aperture plasma membrane described in [20], wherein, aforementioned water-stop portion has for replacing this
The liquid displacement device of the liquid in water-stop portion.
[22] according to the manufacture device of the multiple aperture plasma membrane according to any one of [9]～[21], wherein, aforementioned decomposition container shape
Become and there is side of sidewall portion and for closing the top of the upper end of this side of sidewall portion,
Aforementioned top has top and the rake tilted by this top down side.
The effect of invention
In accordance with the invention it is possible at short notice by the hydrophilic polymer of residual in the multiple aperture plasma membrane precursor after film making process
Thing decomposes.
Accompanying drawing explanation
Fig. 1 is the structural representation of an example of the decomposer of the display present invention.
Fig. 2 is that the position of steam feedway, moving device and the dipper in the decomposer of explanatory diagram 1 is closed
The oblique view of system.
Fig. 3 is the oblique view of the travel path of the hollow-fibre membrane precursor in the decomposer of explanatory diagram 1.
Fig. 4 is the oblique view of an example of the traveling roller showing and being provided with guide rod.
Symbol description
10 decomposers
11 decomposition containers
12 steam feedwaies
15 medicine gas-liquid contacting devices
30 hollow-fibre membrane precursors
Detailed description of the invention
The manufacture method of the multiple aperture plasma membrane of the present invention has film making process and decomposition process, and described film making process makes containing parent
The masking stock solution of waterborne polymeric and hydrophobic polymer solidifies and forms multiple aperture plasma membrane precursor, and described decomposition process is by masking work
During the multiple aperture plasma membrane precursor of gained imports decomposition container in sequence, in this decomposition container, make multiple aperture plasma membrane precursor and containing oxidant
Medicinal liquid contact, the multiple aperture plasma membrane precursor insulation of medicinal liquid will be contacted, utilize oxidant to make in multiple aperture plasma membrane precursor the parent of residual
Waterborne polymeric decomposes.In the present invention, as the medicinal liquid with multiple aperture plasma membrane precursor thereof, use the medicinal liquid after actively heating.
Hereinafter, as an example of multiple aperture plasma membrane, list hollow-fibre membrane, describe the present invention in detail.It addition, this specification
In, the material after being terminated by the washing procedure after decomposition process is referred to as hollow-fibre membrane (multiple aperture plasma membrane), is completed by washing procedure
The material in front stage is referred to as hollow-fibre membrane precursor (multiple aperture plasma membrane precursor).
[film making process]
In film making process, first, modulation is containing hydrophobic polymer and the masking stock solution of hydrophilic polymer.Then,
This masking stock solution is shootd out to solidification liquid from being formed with the ring-type nozzle shooing out mouth, by making it solidify in solidification liquid
Film making process, forms hollow-fibre membrane precursor.
Masking stock solution can be walked portion via the sky with air contact, by the dry-and wet-type imported in solidification liquid by film making process
Spin processes is carried out, it is also possible to carried out by wet-spinning masking stock solution being introduced directly in solidification liquid.It addition, manufacture here
The structure of hollow-fibre membrane precursor be not particularly limited, such as can possess Porous base material, it is also possible to be multilamellar knot
Structure and for process time friction etc. there is durability.
It addition, as the example of Porous base material, be not particularly limited, the hollow form with various fibrages can be listed
Sennit or braid etc., various material can be used alone or in combination.As the fiber for hollow sennit or braid, can enumerate
Go out synthetic fibers, semisynthetic fibre, regenerated fiber, natural fiber etc., it addition, the form of fiber can be monofilament, multifibres, spinning
Any one.
As long as hydrophobic polymer can solidify and form the material that obtains hollow-fibre membrane precursor, as long as this
The material of sample then can use without particular limitation, can list the polysulfones such as polysulfones or polyether sulfone system resin, Kynoar
Deng fluorine resin, polyacrylonitrile, cellulose derivative, polyamide, polyester, polymethacrylates, polyacrylate etc..Separately
Outward, it is possible to use the copolymer of these resins, it is possible to use in a part for these resins or copolymer, imported replacement
The material of base.Additionally, both the different similar polymers such as molecular weight can be used in mixed way, it is also possible to be mixed with two or more
Different types of resin.In the middle of these, fluorine resin, wherein Kynoar or interpolymerized vinylidene fluoride monomer are constituted with other monomers
The copolymer excellent in te pins of durability to oxidants such as hypochlorous acid.Therefore, in decomposition process the most described later etc., by oxidation
When agent carries out such process manufacture hollow-fibre membrane precursor, as hydrophobic polymer, it is suitable for selecting fluorine resin.
Hydrophilic polymer is in order to the viscosity of masking stock solution is adjusted the optimum range of the formation to hollow-fibre membrane, scheme
The material seeking the stabilisation of masking state and add, is preferably used Polyethylene Glycol, polyvinylpyrrolidone etc..Among these, from
From the viewpoint of the control in the aperture of hollow-fibre membrane, doughnut film strength, preferably polyethylene ketopyrrolidine or in poly-second
The copolymerization copolymer of other monomers in alkene pyrrolidone.
Use furthermore it is also possible to mix resin of more than two kinds in hydrophilic polymer.Such as hydrophilic polymer
Thing, if using the material of higher molecular weight, then has the tendency being easily formed the good hollow-fibre membrane of membrane structure.On the other hand, from
In hydrophilic polymer removal step described later, easily remove from hollow-fibre membrane precursor from the viewpoint of, preferably less than molecule
The hydrophilic polymer of amount.Accordingly it is also possible to according to purpose, hydrophilic polymeies of the same race different for molecular weight is suitably mixed into
Exercise and use.
By above-mentioned hydrophobic polymer and hydrophilic polymer being mixed in they solvable solvents (good solvent), from
And masking stock solution can be prepared.Other adding ingredient can also be added as required in masking stock solution.
The kind of solvent is not particularly limited, when carrying out solidifying operation with dry-and wet-type spinning, in order to by walking portion at sky
Make masking stock solution moisture absorption thus adjust the aperture of hollow-fibre membrane, preferably select easily and the mixed uniformly solvent of water.As this
Solvent, can enumerate DMF, N,N-dimethylacetamide, dimethyl sulfoxide, METHYLPYRROLIDONE, N-first
Base methylmorpholine-N-oxide etc., these can use more than a kind.It addition, do not damaging hydrophobic polymer or hydrophilic polymer
In deliquescent scope in a solvent, it is also possible to be used in mixed way the poor solvent of hydrophobic polymer or hydrophilic polymer.
The temperature of masking stock solution is not particularly limited, usually 20～40 DEG C.
Crossing thin or overrich due to the concentration of the hydrophobic polymer in masking stock solution all can make stability during masking reduce,
Exist and be difficult to be formed the tendency of suitable hollow fiber film structure, therefore lower limit is preferably 10 mass %, more preferably 15 mass %.Separately
Outward, the upper limit is preferably 30 mass %, more preferably 25 mass %.
On the other hand, in order to be able to be more easily formed hollow-fibre membrane precursor, the lower limit of the concentration of hydrophilic polymer is excellent
Elect 1 mass %, more preferably 5 mass % as.From the viewpoint of the treatability of masking stock solution, the concentration of hydrophilic polymer upper
Limit is preferably 20 mass %, more preferably 12 mass %.
As solidification liquid, water, alcohols, glycerol, ethylene glycol etc. can be used alone or as a mixture, it is also possible to for water and hydrophobicity
The mixed liquor of the good solvent of polymer.The temperature of solidification liquid is not particularly limited, usually 60～90 DEG C.
[decomposition process]
In decomposition process, make the hollow-fibre membrane precursor formed in film making process contact with the medicinal liquid containing oxidant, make
In hollow-fibre membrane precursor, the hydrophilic polymer of residual decomposes under the effect of oxidant.Decomposition process possesses airtight at 1
Carry out in the decomposition container of property.
Here, the medicinal liquid after heating and hollow-fibre membrane precursor thereof are made.Preferably by making to be heated to more than 30 DEG C and 120
Medicinal liquid below DEG C and hollow-fibre membrane precursor thereof, make medicinal liquid be impregnated with rapidly to hollow-fibre membrane precursor, it addition, after being impregnated with
Oxidant in medicinal liquid directly acts on the hydrophilic polymer in hollow-fibre membrane precursor.I.e., it is possible to make medicinal liquid fine to hollow
The decomposition of the hydrophilic polymer being impregnated with and being caused by the oxidant contained by medicinal liquid of dimension film precursor is carried out the most simultaneously,
It is as a result, it is possible to decompose hydrophilic polymer at short notice.It is further preferred that supply such as normal pressure (1 in decomposition container
Atmospheric pressure) under the steam of the high temperature such as saturated steam, thus, by more than the medicine liquid heating in decomposition container to 60 DEG C and
The scope of less than 100 DEG C.
For the hollow-fibre membrane precursor contacted with medicinal liquid, heat the most in advance, be more preferably previously heated to more than 30 DEG C
Less than 120 DEG C.Further preferably by the steam of the high temperature such as the saturated steam under normal pressure (1 atmospheric pressure) is supplied to dividing
Solve container, make the hollow-fibre membrane precursor advanced in decomposition container be previously heated to more than 60 DEG C less than 120 DEG C, the most in advance
First it is heated to about 100 DEG C.Then itself and medicinal liquid is made by being heated in advance in decomposition container by hollow-fibre membrane precursor like this
Contact, the further seepage velocity of the medicinal liquid in raising hollow-fibre membrane precursor.
It addition, in such a situation it is preferred at the table of hollow-fibre membrane precursor when will heat hollow-fibre membrane precursor in advance
The condensed water that face generates first removes from this surface before contacting with medicinal liquid.Thus, it is possible to the medicine that suppression is caused by this condensed water
The dilution of liquid or medicinal liquid are impregnated with obstruction in film.
Preferably after contacting with medicinal liquid, the hollow-fibre membrane precursor insulation after medicinal liquid being contacted and soaked with oxidant,
Preferably it is maintained at this temperature.Now, preferably the temperature of hollow-fibre membrane precursor is maintained at the temperature identical with the temperature of medicinal liquid,
Specifically maintain more than 30 DEG C less than 120 DEG C, be preferably kept at the scope of more than 60 DEG C less than 100 DEG C.As long as at this model
In enclosing, can be supplied to decomposition container by steam such as the saturated steams by the high temperature under normal pressure (1 atmospheric pressure),
Decomposition container inside holding contacts the hollow-fibre membrane precursor after medicinal liquid.If wanting, exceeding this temperature is incubated, such as, produce and make
With the needs of air drier, then there is the probability producing the moisture state being unable to maintain that hollow-fibre membrane precursor, or produce
Use the needs of steam under pressure, then there is the probability that device becomes large-scale.By the hollow-fibre membrane after medicinal liquid will be contacted
Precursor is incubated, and in hollow-fibre membrane precursor, the decomposition rate of the hydrophilic polymer of residual improves further.
It addition, particularly when insulation, preferably the temperature in decomposition container is set to more than 60 DEG C, preferably passes through water simultaneously
Relative humidity is maintained more than 90% by the supply of steam.Thus, the moisture being impregnated with in the medicinal liquid in hollow-fibre membrane precursor
Evaporation is inhibited.If moisture evaporates, then the temperature of hollow-fibre membrane precursor reduces, and in hollow-fibre membrane precursor, residual is hydrophilic
The decomposition rate of property polymer is slack-off.Therefore, if maintaining relative humidity as mentioned above, then can suppress in hollow-fibre membrane precursor
The reduction of the decomposition rate of the hydrophilic polymer of residual.
As the oxidant used in medicinal liquid, it is possible to use ozone, hydrogen peroxide, permanganate, bichromate, over cure
Hydrochlorate etc., but excellent from the strong decomposability of oxidizing force, treatability excellent, cheap etc. from the viewpoint of, particularly preferred hypochlorite.
As hypochlorite, sodium hypochlorite, calcium hypochlorite etc., particularly preferred sodium hypochlorite can be listed.Medicinal liquid, can be by by these
Oxidant is dissolved in water to be prepared.
During it addition, use the aqueous solution being dissolved with sodium hypochlorite as medicinal liquid, from the decomposition institute guaranteeing hydrophilic polymer
The sodium hypochlorite amount that needs and do one's utmost to suppress from the viewpoint of sodium hypochlorite usage amount, the sodium hypochlorite concentration of this aqueous solution is excellent
Elect 2000～120000mg/L as.
It addition, in the case of making medicinal liquid and hollow-fibre membrane precursor multiple-contact as described later, at least the 1st time connect
The concentration touching the preferred sodium hypochlorite of chemical reagent used is 2000～120000mg/L.
Decomposition process can preferably be carried out by the decomposer 10 of such as Fig. 1.
The decomposer 10 of Fig. 1 has: a decomposition container 11；With as the heater in heat resolve container 11,
The steam feedway 12 of the saturated steam of the normal pressure of high temperature is supplied in decomposition container 11；With as making hollow-fibre membrane
The moving device that precursor 30 is advanced in decomposition container 11,1 guide-in roller 13 and 8 traveling roller 14a～14h；With make decompose
The hollow-fibre membrane precursor 30 advanced in container 11 contacts the medicine gas-liquid contacting device 15 of medicinal liquid.
Decomposition container 11 is for having side of sidewall portion, for closing the top (roof) of the upper end of this side of sidewall portion and bottom and shape
Become possesses bubble-tight container, and bottom is provided with mozzle 18a, 18b at 2.
In decomposition container 11, it is imported into entrance and the hollow-fibre membrane precursor of decomposition container 11 at hollow-fibre membrane precursor 30
30 exits being exported decomposition container 11 are respectively provided with from extraneous air blocks in decomposition container 11 and is capable of
The importing of hollow fiber film precursor 30 and the water-stop portion 16,17 of derivation, have air-tightness in decomposition container 11.
It addition, each water-stop portion 16,17 of this example is respectively provided with the liquid of the liquid (water) in displacement water-stop portion 16,17
Displacement apparatus, figure slightly, thereby, it is possible to by the liquid in water-stop portion 16,17 with fresh liquid displacement.Displacement is preferably being decomposed
Operation is the most often carried out, can also intermittence carry out as required.Import the hollow in the water-stop portion 16 of entrance fine
The dimension film precursor 30 hydrophilic polymer containing a large amount of film making process source, the therefore liquid in the water-stop portion 16 of entrance
In, along with the importing of hollow-fibre membrane precursor 30, hydrophilic polymer gradually concentrates.Its result, imports in decomposition container 11
Hollow-fibre membrane precursor 30 through by water-stop portion 16, the hydrophilic polymer in the liquid of attached water sealing 16 the most on the contrary
Thing.It is therefore preferable that arrange liquid displacement device in the water-stop portion 16 of entrance, the liquid in water-stop portion 16 is suitably handed over
Change, suppress the concentration of hydrophilic polymer in this liquid.On the other hand, the hollow-fibre membrane precursor 30 of decomposition process is completed
In be attached with the analyte of hydrophilic polymer.Therefore, in the liquid in the water-stop portion 17 of outlet, owing to completing decomposition
The hollow-fibre membrane precursor 30 of operation passes through, and the analyte of hydrophilic polymer gradually concentrates.Its result, in decomposition container 11
The hollow-fibre membrane precursor 30 derived is through by water-stop portion 17, the hydrophilic polymer in the liquid of possible attached water sealing 17
The analyte of thing, the hollow-fibre membrane precursor 30 of the washing procedure after being sent to likely is contaminated.It is therefore preferable that at watertight
It is also provided with liquid displacement device in envelope portion 17, the liquid in water-stop portion 17 is suitably exchanged, suppress hydrophilic polymer
Analyte concentration in this liquid.
It addition, imported the new liquid in water-stop portion 16,17 by liquid displacement device, preferably without used newly
Fresh water but it also may be the liquid liquid etc. after fresh water dilution such as will extracted out from water-stop portion 16,17.Separately
Outward, it is also possible in water-stop portion 16,17, limit supplies with fresh water diluent body limit circulation.
Steam feedway (heater) 12 possesses the steam supply source (figure is slightly) being arranged on outside decomposition container 11,
With the top being arranged in decomposition container 11, the saturated steam of the normal pressure of the high temperature from steam supply source is imported and decomposes
Pipe arrangement 12a in container 11.Each branch 12b as in figure 2 it is shown, pipe arrangement 12a is branched off into 3 systems in downstream, in branch
Side (pipe arrangement side face), spray downwards multiple ejiction opening 12c of saturated steam and formed along the long side direction of branch 12b
1 row.As long as it addition, steam feedway can supply steam in decomposition container 11, be not limited to this example.
The travel path of moving device hollow-fibre membrane precursor 30 in decomposition container 11 is arranged in side, most upstream, by
Hollow-fibre membrane precursor 30 is imported the guide-in roller 13 in decomposition container 11 and makes the hollow-fibre membrane precursor 30 of importing downstream
Multiple traveling roller 14a～14h that skidding enters are constituted.Traveling roller 14a～14h of this example is had altogether 4 groups by what upper roller and lower roll were formed
Roller is constituted.It addition, the axial length that traveling roller 14a～14h is formed is more than guide-in roller 13.Thus, guide-in roller 13 lead
The hollow-fibre membrane precursor 30 entered, can in the figure along traveling roller 14a～14h front side to rear side, (that is, upstream side is to downstream
Side.) repeatedly winding while advance, be described in detail later.
Among these travelings roller 14a～14h, from upstream side, the 1st group of lower roll 14a to roller and the 3rd group are under roller
Roller 14e is the driving roller possessing drive mechanism, and the traveling roller beyond this driving roller is the free roll not possessing drive mechanism.Separately
Outward, below, n-th group from upstream side is referred to as n-th pair of roller to roller.
Like this, if the part among traveling roller 14a～14h is for driving roller, then hollow-fibre membrane precursor can be suppressed
The breakage of the film of 30.
That is, if assuming that all traveling rollers are free roll, then during the number of the rotary resistance of free roll, only free roll is endowed
Hollow fiber film precursor, causes the increase of the layer tension of hollow-fibre membrane precursor.On the other hand, if a part is for driving roller, then should
Drive roller can eliminate the layer tension being given hollow-fibre membrane precursor by the rotary resistance of the free roll of its upstream side, thus, energy
Enough the film of the hollow-fibre membrane precursor that suppression layer tension causes is broken.
As in figure 2 it is shown, traveling roller 14a～14h configures in parallel to each other.And, each branch of steam feedway 12
Between portion 12b is according to each roller between the 1st pair of roller and the 2nd pair of roller, between the 2nd pair of roller and the 3rd pair of roller, between the 3rd pair of roller and the 4th pair of roller
Top configures abreast with each traveling roller 14a～14h.
In this embodiment, medicine gas-liquid contacting device 15 possesses the 1st dipper 15a and the 2nd dipper 15b having put into medicinal liquid, point
Be not arranged on the lower section of the lower roll 14a of the 1st pair of roller and the lower roll 14e of the 3rd pair of roller lower section this at 2 position (multiple position).And
And, the bottom of lower roll 14a and the bottom of lower roll 14e impregnated in respectively in the 1st dipper 15a and the 2nd dipper 15b and configure.By
This, hollow-fibre membrane precursor 30 is advanced in each dipper 15a, 15b, and its result makes hollow-fibre membrane precursor 30 contact and glue
(pick-up) medicinal liquid.
It addition, in Fig. 2, in order to be easier to understand pipe arrangement 12a or its branch 12b and guide-in roller 13 and traveling roller 14a～
14h and the position relationship of dipper 15a, 15b, eliminate the diagram beyond these.
Each the most so-called tandem type of dipper 15a, 15b, by more than 1 in the direction of principal axis of lower roll 14a, 14e, groove
Riser is divided into figure multiple regions slightly, enables the medicinal liquid overflowed by the region of front side in figure to supply to figure rear side successively
Region.Being described in detail later, in this embodiment, in figure, the region of front side is equivalent to the upstream side of the hollow-fibre membrane precursor 30 advanced, figure
The region of middle rear side is equivalent to the downstream of the hollow-fibre membrane precursor 30 advanced.It addition, the region set in the 1st dipper 15a
Number be k1, the number in region in the 2nd dipper 15b be k2(k1、k2It is the integer of more than 2.).
It addition, among each dipper 15a, 15b, the region of side, most upstream is by the medicinal liquid supply being arranged on outside decomposition container 11
Source 15c, 15d continuously feed medicinal liquid respectively, among each dipper 15a, 15b, arrange the most continuously in the region of most downstream side
Go out medicinal liquid.
Liquid stream is discharged to the bottom of decomposition container 11, with the condensed water one of saturated steam from dipper 15a, 15b
Rise and discharge from mozzle 18a, 18b.
It addition, symbol 20 is for setting up the dividing plate bottom decomposition container 11 in figure, by arranging this dividing plate 20, make from
The medicinal liquid of 1 dipper 15a can be discharged by mozzle 18a, and the medicinal liquid from the 2nd dipper 15b can be arranged by mozzle 18b
Go out.
In the decomposition process of decomposer 10 based on Fig. 1, first, by steam feedway 12 to decomposition container
Supply the saturated steam of the normal pressure of high temperature in 11 continuously, heat in being full of decomposition container 11 with saturated steam.Here,
Temperature in decomposition container 11 is preferably the saturated steam temperature the most about 100 DEG C of normal pressure, it is also possible to be the temperature lower than 100 DEG C
Degree.On the other hand, each dipper 15a, the 15b being configured in decomposition container 11 is by supplying pump 19a, 19b by medicinal liquid supply source
15c, 15d supply medicinal liquid.Here, it is also possible between supply pump 19a and the 1st dipper 15a outside decomposition container 11 and supply
To arranging heater (figure is slightly) between pump 19b and the 2nd dipper 15b, by medicinal liquid after decomposition container 11 external heat, resupply
To each dipper 15a, 15b.
Then, after the medicinal liquid in each dipper 15a, 15b becomes steady temperature, will be via water-stop portion by guide-in roller 13
The hollow-fibre membrane precursor 30 of 16 imports in decomposition container 11.The hollow-fibre membrane precursor 30 gait of march in decomposition container 11
It is preferably such as 4～50m/min.
Import the saturated steam heating that the hollow-fibre membrane precursor 30 in decomposition container 11 is filled in decomposition container 11.
And, as it is shown on figure 3, in the 1st pair of roller, thereon on roller 14b and lower roll 14a, while the front side from Fig. 3 is to after in Fig. 3
Side repeatedly (k1Secondary) winding, while advance to the upper roller 14d of the 2nd pair of roller.
Here, at the lower roll 14a of the 1st pair of roller, the 1st dipper not shown in Fig. 3 it is configured with, therefore at doughnut
The lower roll 14a of the 1st pair of roller of film precursor 30 Multiple through then out each time in, be saturated steam warmed-up medicinal liquid attachment, be impregnated with
In hollow-fibre membrane precursor 30.It addition, in this embodiment, number of times that hollow-fibre membrane precursor 30 contacts with medicinal liquid and with the 1st medicine
The number in the region that the riser (figure is slightly) in liquid bath is separated is set to k the most equally1.Therefore, hollow-fibre membrane precursor 30 passes through for the 1st time
During the lower roll 14a of the 1st pair of roller, contact with the medicinal liquid of most upstream side region in the region of the 1st dipper, the 2nd time by time, with the
The medicinal liquid contact in the 2nd upstream side region in the region of 1 dipper.So, hollow-fibre membrane precursor 30 is every time by lower roll 14a
Time, contact with the medicinal liquid in further downstream region.In Fig. 3, the travel path of solid arrow explanation hollow-fibre membrane precursor 30, dotted line
Arrow shows the direction of rotation of each roller.
And, as it has been described above, the 1st dipper of this example is tandem type, the medicinal liquid overflowed from the region of upstream side is by successively
Supply the region to downstream.
In the region of more upstream side, the hollow-fibre membrane precursor 30 remaining more hydrophilic polymer contacts with medicinal liquid,
Now, a part for hydrophilic polymer travels to the medicinal liquid in this region from hollow-fibre membrane precursor 30, and that divides a word with a hyphen at the end of a line is hydrophilic
The decomposition of property polymer is carried out in the medicinal liquid in this region.Its result, the oxidant of the medicinal liquid in this region is gradually divided a word with a hyphen at the end of a line
The decomposition of hydrophilic polymer is consumed, and its concentration reduces.And, in the 1st dipper of tandem type, oxidant is dense like this
The medicinal liquid that degree reduces is supplied to the region of further downstream.
Like this, in the 1st dipper, hollow-fibre membrane precursor 30 is made to contact k with medicinal liquid1Time secondary, when the 1st contact
Until kth1During secondary contact, the concentration of the oxidant in the medicinal liquid of use slowly reduces.
The hollow-fibre membrane precursor 30 contacted with the medicinal liquid of downstream side region, owing to a part for hydrophilic polymer is upper
Trip side has been decomposed, and therefore the residual quantity of hydrophilic polymer is low, it is not necessary to use the medicinal liquid containing oxidant with high concentration.
Therefore, by using the 1st dipper of tandem type like this, making in time contacting for the 1st time until kth1During secondary contact
The concentration of the oxidant in the medicinal liquid used reduces such that it is able to uses oxidant the most lavishly, can cut down its usage amount.
It addition, " make when the 1st contact until kth1The concentration of the oxidant in the medicinal liquid used during secondary contact reduces "
Form not only include form that oxidant concentration reduces continuously along with tending to the region in downstream, also include interim reduction
Form.The interim form reduced refers to, such as, in multiple regions of the part in Zone Full, and oxidant dense
Degree does not reduces and is constant form.
It addition, in this embodiment, in the number in the region in the 1st dipper, and hollow-fibre membrane precursor the 30 and the 1st dipper
The number of times of medicinal liquid contact is identical, is all set to k1, then for carrying out the form of 1 contact in 1 region but it also may by the 1st medicine
The number in the region in liquid bath is set to less than k1, the form of medicinal liquid Yu hollow-fibre membrane precursor 30 multiple-contact for making 1 region.
It addition, as the form making the concentration of oxidant reduce like this, the dipper exemplifying tandem type here is carried out
Illustrate, but as long as the concentration of oxidant can be reduced, be not limited to use the form of the dipper of tandem type.
It addition, in the case of making medicinal liquid and hollow-fibre membrane precursor multiple-contact like this, the medicinal liquid used is for containing
Sodium hypochlorite as the aqueous solution of oxidant, the concentration of the preferred sodium hypochlorite of chemical reagent that at least the 1st time contact is used is
2000～120000mg/L.
It addition, the hollow-fibre membrane precursor 30 imported in decomposition container 11 by guide-in roller 13 is filled in decomposition container 11
Saturated steam heating time, as it has been described above, at its Surface Creation condensed water.It is therefore preferable that arrange in decomposition container 11 right
Hollow-fibre membrane precursor 30 before contact medicinal liquid is jetted the blowing device (figure slightly) of the fluids such as steam (gas), passes through fluid
(gas) removes condensed water.As the additive method of removing condensed water, for example, it is also possible between guide-in roller 13 and upper roller 14b
Removing roller (figure is slightly) is set separately, is removed by centrifugal force time on the surface of this removing roller by hollow-fibre membrane precursor
Condensed water.Or, by hollow-fibre membrane precursor 30 by the centrifugal force etc. time on guide-in roller 13 or upper roller 14b, at medicinal liquid
Before contact, condensed water is naturally in the case of hollow-fibre membrane precursor 30 removes, it is also possible to need not specially arrange winding-up dress
Put or removing roller.
Decomposition container 11, roller 14a～14h, the 1st and the 2nd dipper 15a, 15b, mozzle 18a, 18b, steam supplies
As long as the material of device 12 has the material of antioxidant and thermostability, be not particularly limited, such as can exemplify titanium,
Politef, PEEK, pottery etc..It addition, as special material shape, it is also possible to exemplify, at the oxytolerant such as rustless steel, aluminum
Change in the material that material lacks, with foregoing illustrative raw material to decomposition container 11 lining cutting inner surface, to roller 14a～14h coating
Outer surface person etc..
It addition, the surface of traveling roller 14a～14h can be smooth, but in the case of smoothing, hollow-fibre membrane precursor 30
Traveling drawing lines offsets lax on the surface of roller, it is possible to cause hollow-fibre membrane precursor 30 to be wound around mutually.It is therefore preferable that at this
The surface of a little traveling roller 14a～14h forms the control flume of the traveling for controlling hollow-fibre membrane precursor.It addition, such as Fig. 4 institute
Show, traveling roller 14a near surface, such as clamp traveling roller 14a to position install 2 and axial lead along it
Bar 40,40 is preferable, thereby, it is possible to avoid hollow-fibre membrane precursor 30 lax and be wound around from traveling roller 14a skew.In figure, symbol
41 is the axle of traveling roller 14a, and symbol 42 be the fixed part fixing axle 41, in this embodiment, this fixed part 42 is fixed with guide rod 40,
40。
It addition, exemplified with the form at traveling roller 14a installation guide rod 40,40 in Fig. 4, as required, can be to traveling roller
At least 1 in 14a～14h arranges guide rod.Alternatively, it is also possible to as required at least 1 in traveling roller 14a～14h is set
Put control flume.Guide rod and control flume and can also be used for 1 traveling roller.
It addition, in the case of being separated into multiple region by riser in dipper 15a, 15b, preferably corresponding to dipper
15a, 15b and the surface of traveling roller 14a, 14e that arranges, for making this surface not contact with riser, and in the position corresponding to riser
Put formation groove.It addition, further preferred traveling roller 14a, 14e only by each region corresponding to dipper 15a, 15b respectively
Vertical roller is constituted.
Then, hollow-fibre membrane precursor 30 is in the 2nd pair of roller, while repeatedly wind on upper roller 14d and lower roll 14c, limit with
The front side traveling in rear lateral view from figure on the contrary of the situation of the 1st pair of roller, then advances to the upper roller 14f of the 3rd pair of roller.
In the 3rd pair of roller, identical with the situation of the 1st pair of roller, hollow-fibre membrane precursor 30 is on upper roller 14f and lower roll 14e
Rear side repeatedly (k in lateral view before from figure2Secondary) wind and advance.
Here, the lower roll 14e of the 3rd pair of roller is configured with the 2nd dipper not shown in Fig. 3, therefore each hollow-fibre membrane
When precursor 30 passes through the lower roll 14e of the 3rd pair of roller, hollow-fibre membrane precursor 30 contacts with the medicinal liquid being saturated steam heating, leaching
Thoroughly in hollow-fibre membrane precursor 30.And, the 2nd dipper is also tandem type, and hollow-fibre membrane precursor 30 is wound on lower roll 14e
On, at the k identical with the number of times of the medicinal liquid contacted in the 2nd dipper2Region by while riser (figure slightly) segmentation, oxidant
The region supply of the medicinal liquid upstream side in groove successively that reduces of concentration to the region in downstream.And, hollow-fibre membrane
Precursor 30, when the 1st time by the lower roll 14e of the 3rd pair of roller, connects with the medicinal liquid in the region of side, most upstream in the region of the 2nd dipper
Touch, when passing through for the 2nd time, contact with the medicinal liquid in the region of the 2nd upstream side in the region of the 2nd dipper.Like this, at the 2nd medicine
In liquid bath, hollow-fibre membrane precursor 30 also every time by lower roll 14e time gradually medicinal liquid with the region of further downstream contact.
Therefore, in the 2nd dipper, make hollow-fibre membrane precursor 30 and medicinal liquid k2During secondary contact, when the 1st contact
Until kth2During secondary contact, the concentration of the oxidant in the medicinal liquid used the most slowly reduces.
It addition, the 2nd adoptable form of dipper is identical with the 1st dipper.
It addition, respectively in the 1st dipper and the 2nd dipper, the concentration of the oxidant in medicinal liquid from upstream side to
Downstream reduce in the case of, can according to kth in the 1st dipper1Medicinal liquid during secondary contact compares, in the 2nd dipper the 1st
The mode that the concentration of the oxidant of medicinal liquid during secondary contact is lower is set, it is also possible to do not carry out such setting.That is, with
The common k(=k of medicinal liquid1+ k2) in secondary contact, when the 1st contact until during kth time contact, the oxidation in the medicinal liquid of use
The concentration of agent might not slowly reduce can also.
Then hollow-fibre membrane precursor 30 is advanced from the upper roller 14f of the 3rd pair of roller to the lower roll 14g of the 4th pair of roller, right the 4th
In roller, limit roller 14h thereon and lower roll 14g repeatedly winding, in Bian Congtu, in rear lateral view, advance, then via the 4th in front side
The lower roll 14g of roller is derived outside decomposition container 11.
Like this, in decomposition container 11, first hollow-fibre membrane precursor 30 is saturated steam heating.Then, heating
Hollow-fibre membrane precursor 30 contact with heated medicinal liquid in the 1st dipper 15a.Contact with hollow-fibre membrane precursor 30
Medicinal liquid be directly impregnated with in hollow-fibre membrane precursor 30.It addition, the hollow-fibre membrane precursor 30 contacting, soaked with medicinal liquid passes through
Advance in decomposition container 11 thus be saturated steam insulation, the therefore hydrophilic polymer of the medicinal liquid by contacting, soaked with
The decomposition of thing also almost starts simultaneously at being impregnated with of medicinal liquid, carries out.
In the 1st pair of roller, like this medicinal liquid contact, be impregnated with the decomposition with hydrophilic polymer and be repeatedly alternately repeated.?
In 2nd pair of roller, hollow-fibre membrane precursor 30 insulation, carry out the decomposition of hydrophilic polymer.Then, in the 3rd pair of roller, with
The situation of 1 pair of roller is identical, the contact of medicinal liquid, is impregnated with the decomposition with hydrophilic polymer and is repeatedly alternately repeated, in the 4th pair of roller,
Hollow-fibre membrane precursor 30 insulation, carries out the decomposition of hydrophilic polymer.
The hollow-fibre membrane precursor 30 holdup time in the 1st dipper 15a and the 2nd dipper 15b is not particularly limited,
It is fully contacted according to medicinal liquid and hollow-fibre membrane precursor 30, is positioned at the hollow-fibre membrane precursor 30 on the 1st pair of roller and on the 3rd pair of roller
Always to maintain the state setting holdup time of medicinal liquid.
It addition, as the Concentraton gradient of oxidant in the 1st dipper 15a and the 2nd dipper 15b of tandem type, flow
It is not particularly limited, the Restzustand of the hydrophilic polymer from hollow-fibre membrane precursor 30, the service efficiency of oxidant
Viewpoint considers suitably to set.
As described above, according to have employed the decomposition process of such decomposer 10, make warmed-up medicinal liquid and hollow
Fiber membrane precursor 30 contacts, adheres to, therefore, it is possible to make medicinal liquid being impregnated with and by contained in medicinal liquid hollow-fibre membrane precursor 30
The decomposition of hydrophilic polymer that causes of oxidant carry out simultaneously, it is as a result, it is possible to decompose hydrophilic polymer at short notice
Thing.
It addition, the decomposer 10 of this example has decomposition container 11, heater in heat resolve container 11, makes
Moving device that hollow-fibre membrane precursor 30 is advanced in decomposition container 11 and make the doughnut advanced in decomposition container 11
The medicine gas-liquid contacting device 15 that film precursor 30 contacts with medicinal liquid, therefore in decomposition container 11, can carry out the heating of medicinal liquid, heating
Medicinal liquid and hollow-fibre membrane precursor 30 contact and the insulation of hydrophilic polymer contained by hollow-fibre membrane precursor 30,
Decompose, it is possible to make to carry out the device miniaturization of decomposition process, it is achieved the space saving that equipment is arranged.If be medicinal liquid contact,
The composition that the insulation of hollow-fibre membrane precursor is not carried out in 1 decomposition container in different containers respectively, then equipment is big
Type.
It addition, in this decomposer 10, in 1 decomposition container 11, not only heat medicinal liquid, the most in advance also contacts medicine
Hollow-fibre membrane precursor 30 before liquid, and, additionally it is possible to the hollow-fibre membrane precursor 30 after contact medicinal liquid is held in high temperature, because of
This can more improve the medicinal liquid wetting-out rate to hollow-fibre membrane precursor 30, and, more improve in hollow-fibre membrane precursor 30 and remain
The decomposition rate of hydrophilic polymer.If the contact of medicinal liquid, hollow-fibre membrane precursor insulation respectively at different containers
Inside carry out, then between each container, hollow-fibre membrane precursor is cooled, and the decomposition rate of hydrophilic polymer may step-down.
Further, in this embodiment, as heater, employing supplies the saturated of the normal pressure of high temperature in decomposition container 11
The steam feedway 12 of steam, therefore, it is possible to easily by medicinal liquid, medicinal liquid contact before and after hollow-fibre membrane precursor 30,
Each temperature of the gas phase in decomposition container 11 maintains based on saturated steam temperature mutually synthermal, and the efficiency of heating surface is excellent.Make
For heater, as long as steam feedway 12 can be then not limited in heat resolve container 11, but from by decomposing
The saturated steam of normal pressure it is full of, it is possible to prevent being dried of hollow-fibre membrane precursor 30, can effectively decompose hydrophilic in container 11
From the viewpoint of property polymer, preferably steam feedway 12.
It addition, as medicine gas-liquid contacting device 15, arrange the 1st dipper 15a and the 2nd dipper 15b, before making hollow-fibre membrane
Body 30 is repeatedly advanced in each dipper 15a, 15b, make medicinal liquid to the contact of hollow-fibre membrane precursor 30 with contact medicinal liquid after
The insulation of hollow-fibre membrane precursor 30 the most repeatedly alternate repetition is carried out, and is therefore contacting with hollow-fibre membrane precursor 30 and is adhering to
Medicinal liquid in oxidant before the decomposition of hydrophilic polymer is all consumed, it is possible to make medicinal liquid add once again and be attached to
On hollow-fibre membrane precursor 30, decomposition is made effectively to carry out.
It addition, as medicine gas-liquid contacting device, can use the hollow-fibre membrane precursor 30 advanced in decomposition container 11
Injection medicinal liquid injection apparatus, it is also possible to decomposition container 11 in traveling hollow-fibre membrane precursor 30 spray liquor and make it
Attachment.As injection apparatus, medicinal liquid supply source 15c, 15d can be used to be connected by pipe arrangement, possess spraying and supply from medicinal liquid
The equipment in the spraying portion of the medicinal liquid of source 15c, 15d.
Alternatively, it is also possible at the medicine gas-liquid contacting devices such as the injection apparatus by possessing spraying portion like this and medicinal liquid supply source
In the pipe arrangement that 15c, 15d connect, at least some of at the position imported in decomposition container 11, arrange and held with decomposing by medicinal liquid
The heat exchange of the gas in device 11 and heat the heat exchange department (figure is slightly) of medicinal liquid.Specifically, with such as by politef etc.
It is suitable that the big spiral pipe arrangements of surface area (heat transfer area) formed etc. constitute heat exchange department.Thus, from medicinal liquid supply source
Before the medicinal liquid of 15c, 15d is sprayed to hollow-fibre membrane precursor 30, join Bottomhole pressure and quilt by the spiral big at surface area
Effectively heat.It addition, heat exchange department is in addition to the helix tube type being made up of serpentine pipe, it is also possible to be board-like, multitube etc..
It addition, as medicine gas-liquid contacting device, it is also possible to and with the device of different shape, a part in decomposition container is adopted
With injection apparatus, other positions use dipper form etc..
It addition, arrange injection apparatus by the multiple positions at the travel path of hollow-fibre membrane precursor, additionally it is possible to make medicine
The insulation the most repeatedly alternate repetition contacting and contacting hollow-fibre membrane precursor after medicinal liquid of liquid and hollow-fibre membrane precursor
Carry out.
The position that arranges of injection apparatus is not particularly limited, and being preferably provided at can be to fine by the hollow on upper roller 14b
The position of dimension film precursor 30 spray liquor.Thus, the major part of the medicinal liquid of spraying contacts with hollow-fibre membrane precursor 30, it is possible to no
Waste medicinal liquid and effectively contact.
It addition, in order to more effectively make medicinal liquid contact with hollow-fibre membrane precursor 30, it is also possible to use and medicinal liquid is dropped to
Method on hollow-fibre membrane precursor 30.
It addition, medicine gas-liquid contacting device can use possesses passage and and the hollow-fibre membrane that hollow-fibre membrane precursor passes through
Precursor by direction intersecting angle (such as 90 degree.) medicinal liquid of the leading type (GUIDE type) of medicinal liquid feed path that arranges supplies
To device, it would however also be possible to employ make medicinal liquid be attached to the form of side face side of hollow-fibre membrane precursor by passage.As this
Chemicals feeder, for example, it is also possible to divert commercially available OILING GUIDE(オ イ リ Application グ ガ イ De) (Tang Qianxi road work
Industry Co., Ltd. system) etc..
It addition, as the shape of decomposition container 11, in illustrated example, exemplify the top of upper end for closed side wall portion
(roof) be smooth shape, preferably top be to there is top and from top along the shape of rake of inclined downward.Top is
During such shape, the condensed water of the steam of top attachment flows to side of sidewall portion via rake, is possible to prevent to drop to medicinal liquid
On medicinal liquid in groove 15a, 15b or hollow-fibre membrane precursor 30.Therefore, it can dilution or the medicine of the medicinal liquid that suppression condensed water causes
Liquid is impregnated with obstruction in film.
[washing procedure]
Preferably impregnated in, at the laggard hollow-fibre membrane precursor of being about to of decomposition process, the washing procedure carrying out washing in cleaning mixture.
As the cleaning mixture used in washing procedure, as long as clarification, liquid that the analyte of hydrophilic polymer dispersibles or dissolves
Body, is just not particularly limited, owing to clean result is high, therefore preferably water.As the water used, tap water, industrial can be listed
Water, river, well water etc., it is also possible to mixed alcohol, inorganic salts, oxidant, surfactant etc. use wherein.It addition, conduct
Cleaning mixture, it is also possible to use the good solvent of hydrophobic polymer and the mixed liquor of water.
In order to suppress relatively low by the viscosity of the solution of hydrophilic polymer, prevent from spreading the reduction of translational speed, washing
Temperature is the highest more suitable, preferably more than 50 DEG C, more preferably more than 80 DEG C.Further, carry out while making cleaning mixture boiling
During washing, moreover it is possible to the foaming caused by boiling wipe off on the outer surface of hollow-fibre membrane precursor attachment hydrophilic polymer or
Dirt, therefore, it is possible to effectively wash.By this washing procedure, available hollow-fibre membrane.
[drying process]
The drying process of dried, hollow fibrous membrane is carried out after washing procedure.As the method for drying process, the most especially
Limit, carried out by the method that hollow-fibre membrane is imported the drying devices such as air drier.
[other]
Between film making process and decomposition process, it is also possible to carry out the hollow-fibre membrane precursor leaching that will obtain in film making process
Stain is to carrying out the preparation washing procedure that washs in cleaning mixture.As cleaning mixture, the liquid that can illustrate from washing procedure selects
Select.
It addition, in the above description, exemplify hollow-fibre membrane as multiple aperture plasma membrane, illustrate its manufacture method and system
Manufacturing apparatus, but multiple aperture plasma membrane is not limited to hollow-fibre membrane, for example, it is also possible to exemplify flat film, tubular membrane etc..
Embodiment
Hereinafter, list embodiment and specifically describe the present invention.
＜ embodiment ＞
[film making process]
According to becoming the mode of the mass ratio shown in table 1, by Kynoar A(ア ト Off ィ Na Japan system, trade name
Kynar301F(カ イ Na 301F)), Kynoar B(ア ト Off ィ Na Japan system, trade name Kynar9000LD(カ イ Na
9000LD)), polyvinylpyrrolidone (ISP company system, trade name K-90), N,N-dimethylacetamide mix respectively, preparation
Masking stock solution (1) and masking stock solution (2).Hereinafter, sometimes Kynoar is referred to as PVDF, polyvinylpyrrolidone is referred to as
PVP。
Then, prepare be formed centrally within hollow bulb, outside it according to the mode shape successively that can be coated with 2 kinds of liquid successively
Become nozzle (Fig. 1 with reference to Japanese Unexamined Patent Publication 2005-42074 publication shooing out mouth of double-layer circular.), it is incubated in 30 DEG C
Under state, import the polyester multifibres single fiber braid (multifibres as Porous base material to hollow bulb；420T/180F), exist simultaneously
Its periphery from inner side successively coating masking stock solution (2), masking stock solution (1), be incubated the solidification liquid in 80 DEG C (5 mass parts N,
N-dimethyl acetylamide and the mixed liquor of 95 mass parts water) in make it solidify.So, obtain, at proximity, there is 1 layer point
The hollow-fibre membrane precursor that the porous layer of the biggest incline structure of level layer and aperture is applied in braid.It addition,
Among the masking stock solution (1) and (2) of coating, the main stock solution of the membrane structure forming hollow-fibre membrane is to coat the masking in outside
Stock solution (1).
Further, prepare be formed centrally within the internal diameter hollow bulb bigger than the external diameter of this hollow-fibre membrane precursor,
The nozzle shooing out mouth of double-layer circular is sequentially formed (with reference to Japan spy according to the mode that can be coated with 2 kinds of liquid successively outside it
Open Fig. 1 of 2005-42074 publication.), when being incubated in 30 DEG C, import in hollow bulb and obtain as mentioned above
Hollow-fibre membrane precursor, from inner side, be coated with glycerol (with Wako Pure Chemical Industries one-level), masking successively in its periphery former simultaneously
Liquid (1), identical with situation about using before, make it solidify being incubated in the solidification liquid of 80 DEG C.So, it is thus achieved that be coated with further
Have porous layer 2 Rotating fields, the hollow-fibre membrane precursor with braid supporter.
Further, this hollow-fibre membrane precursor is prepared in the water of 100 DEG C washing 5 minutes.
Spinning speed (gait of march of hollow-fibre membrane precursor) now is set as 20m/min.
[table 1]
| Composition | Masking stock solution (1) | Masking stock solution (2) |
| Kynoar A | 12 | 3 |
| Kynoar B | 8 | 2 |
| Polyvinyl pyrrolidone | 10 | 2 |
| DMAC N,N' dimethyl acetamide | 70 | 93 |
| Stock solution temperature | 60℃ | 50℃ |
| Kynoar concentration in stock solution | 20% | 5% |
[decomposition process]
In decomposer 10 as shown in Figure 1, it is continuously introduced into the hollow-fibre membrane precursor 30 obtained like this, is passing through
Decomposition process is carried out under the heating of the saturated steam of normal pressure.The condition of decomposition process is as follows.
The hollow-fibre membrane precursor 30 gait of march in decomposition container 1l is 20m/min, and hollow-fibre membrane precursor 30 exists
1st pair of roller, the 2nd pair of roller, the 3rd pair of roller, the 4th pair of roller each pair of roller on by being respectively necessary for 66 seconds.It addition, the condition that arranges is:
Hollow-fibre membrane precursor 30 adhesion sodium hypochlorite (oxidant) aqueous solution in the 1st dipper 15a and the 2nd dipper 15b respectively
10 times.
The concentration of the aqueous sodium hypochlorite solution being respectively fed to the 1st dipper 15a and the 2nd dipper 15b is:
120000mg/L, quantity delivered be: 50ml/min, and the aqueous sodium hypochlorite solution supplied to each groove 15a, 15b is directly heated to
100℃。
[washing procedure and drying process]
By described in the embodiment 4 of Japanese Unexamined Patent Publication 2008-161755 publication by decompression operation. cleaning mixture supply work
Sequence. the washing procedure that decompression operation is constituted, by the hydrophilic polymer that can the wash washing of residual in hollow-fibre membrane precursor 30
Remove, obtain hollow-fibre membrane.
Then, hollow-fibre membrane is imported in air drier and be dried.
In the present embodiment, the hollow-fibre membrane precursor holdup time in decomposition container is 270 seconds.
It addition, for the hollow-fibre membrane obtained by the present embodiment, measuring the hydrophilic polymer i.e. concentration of PVP is
1.2%, meet hollow-fibre membrane and can play sufficient film water permeable ability, PVP concentration condition below 2%.
It addition, obtained the extinction spectrum of hollow-fibre membrane by infrared spectrophotometer, by comparing in this absorption spectrum
The absorption intensity of hydrophobic polymer and the absorption intensity of hydrophilic polymer, it is possible to hold the parent of residual in hollow-fibre membrane
The amount of waterborne polymeric.Use PVDF as hydrophobic polymer, use as hydrophilic polymer PVP to manufacture hollow-fibre membrane
Time, obtain carbonylic stretching vibration (1700cm based on PVP-1) absorption intensity that causes and C-H stretching vibration based on PVDF
(1400cm-1) absorption intensity that causes.And, if the absorption intensity that C-H stretching vibration based on PVDF causes is 100%,
The absorption intensity of the carbonylic stretching vibration being obtained PVP by the ratio of they absorption intensities is equivalent to how many %, using this value (%) as residual
The amount of the hydrophilic polymer stayed.
＜ comparative example ＞
Hollow-fibre membrane precursor is formed by the film making process identical with embodiment.
Then, hollow-fibre membrane precursor is put into 30 DEG C (non-heated) having the sodium hypochlorite concentration identical with embodiment
Medicinal liquid maceration tank in impregnate 80 seconds, make hollow-fibre membrane precursor contact with medicinal liquid and keep.Then, medicinal liquid will be maintained
Hollow-fibre membrane precursor import in decomposition container, keep 80 seconds under the vapor atmosphere of normal pressure.Afterwards, carry out and implement
The washing procedure that example 1 is identical.
Further, in the same manner as aforementioned, hollow-fibre membrane precursor is impregnated 80 seconds in maceration tank, at decomposition container
Interior holding 80 seconds.Further, carry out washing procedure same as in Example 1 and obtain hollow-fibre membrane.Leaching in medicinal liquid
Stain time and the retention time in decomposition container are altogether 320 seconds.
Then, it is dried in hollow-fibre membrane is imported air drier.
About the hollow-fibre membrane obtained like this, measure the concentration of PVP identically with embodiment, be 2.5%, be unsatisfactory for
Hollow-fibre membrane can play sufficient film water permeable ability condition i.e. below 2%.From this result, in the side of comparative example
In method, while it is desirable to the time more longer than embodiment, but cannot fully decompose in the hollow-fibre membrane precursor after film making process residual
The hydrophilic polymer stayed.It addition, make hollow-fibre membrane precursor keep the maceration tank of medicinal liquid to keep with making hollow-fibre membrane precursor
The decomposition container of high temperature is the most independent groove, and therefore these are arranged needs bigger space.
Claims (21)
1. a manufacture method for multiple aperture plasma membrane, it has a following decomposition process: will be by containing hydrophilic polymer and hydrophobic
Property polymer the solidification of masking stock solution and the multiple aperture plasma membrane precursor that formed is continuously introduced in decomposition container, in this decomposition container,
Make previous porous membrane precursor contact with the heated medicinal liquid containing oxidant, make to contact the previous porous matter of aforementioned medicinal liquid
Film precursor is incubated while advancing in steam, before making to remain in previous porous membrane precursor by aforementioned oxidizer
State hydrophilic polymer to decompose, derive from aforementioned decomposition container,
Described medicinal liquid continuously feeds from the outside of described decomposition container.
2. the manufacture method of multiple aperture plasma membrane as claimed in claim 1, wherein, the previous porous that will contact with aforementioned medicinal liquid in advance
Membrane precursor heats.
3. the manufacture method of multiple aperture plasma membrane as claimed in claim 1, wherein, in aforementioned decomposition process, holds in aforementioned decomposition
In device, carry out respectively the most aforementioned medicinal liquid and previous porous membrane precursor contact and contact after aforementioned medicinal liquid aforementioned many
The insulation of hole membrane precursor.
4. the manufacture method of multiple aperture plasma membrane as claimed in claim 3, wherein, aforementioned medicinal liquid is as aforementioned containing sodium hypochlorite
The aqueous solution of oxidant, when making aforementioned medicinal liquid and previous porous membrane precursor multiple-contact, in the aforementioned medicinal liquid that the 1st time uses
The concentration of aforementioned sodium hypochlorite be 2000～120000mg/L.
5. the manufacture method of multiple aperture plasma membrane as claimed in claim 1, wherein, in aforementioned decomposition container, temperature be 60 DEG C with
On, relative humidity is more than 90%.
6. the manufacture method of multiple aperture plasma membrane as claimed in claim 1, wherein, by importing aforementioned by previous porous membrane precursor
In medicinal liquid, aforementioned medicinal liquid is made to contact with previous porous membrane precursor.
7. the manufacture method of the multiple aperture plasma membrane as according to any one of claim 1～6, wherein, by previous porous plasma membrane
Spray aforementioned medicinal liquid on precursor, make aforementioned medicinal liquid contact with previous porous membrane precursor.
8. a manufacture device for multiple aperture plasma membrane, it is the manufacture device of the multiple aperture plasma membrane with decomposer, and described decomposition fills
Put in the multiple aperture plasma membrane precursor that decomposition is formed by the masking stock solution solidification containing hydrophilic polymer and hydrophobic polymer residual
The aforementioned hydrophilic polymer stayed,
Aforementioned decomposer has decomposition container, and described decomposition container makes the previous porous membrane precursor being continuously introduced into and containing aerobic
The heated medicinal liquid contact of agent, while making the previous porous membrane precursor contacting aforementioned medicinal liquid advance in steam
It is incubated, makes the aforementioned hydrophilic polymer of residual in previous porous membrane precursor decompose, before derivation by aforementioned oxidizer
State multiple aperture plasma membrane precursor,
Configuration dipper in described decomposition container, by the medicinal liquid containing oxidant continuously from described decomposition container be externally supplied in
This dipper.
9. the manufacture device of multiple aperture plasma membrane as claimed in claim 8, wherein, aforementioned decomposer has further:
By the heater of heating in aforementioned decomposition container,
Make the moving device that previous porous membrane precursor is advanced in aforementioned decomposition container,
Make the medicine gas-liquid contacting device that the previous porous membrane precursor advanced in aforementioned decomposition container contacts with aforementioned medicinal liquid.
10. the manufacture device of multiple aperture plasma membrane as claimed in claim 9, wherein, aforementioned medicine gas-liquid contacting device is arranged at aforementioned point
Solve the multiple positions in container.
The manufacture device of 11. multiple aperture plasma membranes as claimed in claim 9, wherein, aforementioned heater is to aforementioned decomposition container
The steam feedway of interior supply steam.
The manufacture device of 12. multiple aperture plasma membranes according to claim 9, wherein, aforementioned medicine gas-liquid contacting device possesses input to be had
The dipper that aforementioned medicinal liquid and previous porous membrane precursor are advanced in this medicinal liquid.
The manufacture device of 13. multiple aperture plasma membranes as claimed in claim 12, wherein, aforementioned dipper is tandem type, described cascade
Formula refers to, is divided into multiple region in groove, and the medicinal liquid overflowed from the region of upstream side is supplied the region to downstream successively.
The manufacture device of 14. multiple aperture plasma membranes as claimed in claim 9, wherein, aforementioned medicine gas-liquid contacting device possesses to aforementioned many
Hole membrane precursor sprays the injection apparatus of aforementioned medicinal liquid.
The manufacture device of 15. multiple aperture plasma membranes as claimed in claim 9, wherein, has heat exchange department, institute in aforementioned decomposition container
State heat exchange department and make aforementioned medicine liquid heating by the heat exchange of the gas in aforementioned medicinal liquid and aforementioned decomposition container.
The manufacture device of 16. multiple aperture plasma membranes as claimed in claim 9, wherein, aforementioned moving device has multiple traveling roller, should
A part in traveling roller is for driving roller.
The manufacture device of 17. multiple aperture plasma membranes as claimed in claim 9, wherein, aforementioned moving device possesses multiple traveling roller, should
It is provided with in traveling roller at least 1 for preventing previous porous membrane precursor from deviateing the guide rod of aforementioned traveling roller.
The manufacture device of 18. multiple aperture plasma membranes as claimed in claim 9, wherein, aforementioned moving device possesses multiple traveling roller, should
In traveling roller at least 1, is formed with the control flume of traveling for controlling previous porous membrane precursor from the teeth outwards.
The manufacture device of 19. multiple aperture plasma membranes as claimed in claim 8, wherein, aforementioned decomposition container is formed previous porous
Membrane precursor imports the entrance in aforementioned decomposition container and the outlet derived by aforementioned decomposition container,
Said inlet and said outlet are respectively arranged with water-stop portion, and described water-stop portion is by empty with outside in aforementioned decomposition container
Vapour lock is broken, and is capable of importing and the derivation of previous porous membrane precursor.
The manufacture device of 20. multiple aperture plasma membranes as claimed in claim 19, wherein, aforementioned water-stop portion has for replacing this water
The liquid displacement device of the liquid in sealing.
The manufacture device of 21. multiple aperture plasma membranes as according to any one of claim 8～20, wherein, aforementioned decomposition container is formed
For there is side of sidewall portion and for closing the top of the upper end of this side of sidewall portion,
Aforementioned top has top and the rake tilted by this top down side.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011170064 | 2011-08-03 | ||
| JP2011-170064 | 2011-08-03 | ||
| PCT/JP2012/069878 WO2013018900A1 (en) | 2011-08-03 | 2012-08-03 | Porous film manufacturing method and apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103717295A CN103717295A (en) | 2014-04-09 |
| CN103717295B true CN103717295B (en) | 2016-11-30 |
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ID=
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101410244A (en) * | 2006-03-25 | 2009-04-15 | 赫克塞尔合成有限公司 | A thermoplastic toughening material and related method |
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101410244A (en) * | 2006-03-25 | 2009-04-15 | 赫克塞尔合成有限公司 | A thermoplastic toughening material and related method |
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