CN105722585A - Porous hollow fiber membrane and method for manufacturing same - Google Patents
Porous hollow fiber membrane and method for manufacturing same Download PDFInfo
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- CN105722585A CN105722585A CN201480061790.2A CN201480061790A CN105722585A CN 105722585 A CN105722585 A CN 105722585A CN 201480061790 A CN201480061790 A CN 201480061790A CN 105722585 A CN105722585 A CN 105722585A
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- fibre membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 256
- 238000000034 method Methods 0.000 title claims abstract description 160
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 68
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 76
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 16
- 239000000835 fiber Substances 0.000 claims description 238
- 229920005989 resin Polymers 0.000 claims description 159
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- DSCFFEYYQKSRSV-FEPQRWDDSA-N (1s,2s,4s,5r)-6-methoxycyclohexane-1,2,3,4,5-pentol Chemical compound COC1[C@@H](O)[C@@H](O)C(O)[C@H](O)[C@H]1O DSCFFEYYQKSRSV-FEPQRWDDSA-N 0.000 claims description 29
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
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- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
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- 229920003055 poly(ester-imide) Polymers 0.000 description 2
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
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- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000001330 spinodal decomposition reaction Methods 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZHLKXBJTJHRTTE-UHFFFAOYSA-N Chlorobenside Chemical compound C1=CC(Cl)=CC=C1CSC1=CC=C(Cl)C=C1 ZHLKXBJTJHRTTE-UHFFFAOYSA-N 0.000 description 1
- 241000223935 Cryptosporidium Species 0.000 description 1
- 229920006370 Kynar Polymers 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
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
- B01D69/1071—Woven, non-woven or net mesh
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/021—Pore shapes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/021—Pore shapes
- B01D2325/0212—Symmetric or isoporous membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
- B01D2325/0231—Dense layers being placed on the outer side of the cross-section
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/40—Fibre reinforced membranes
Abstract
Provided is a porous hollow fiber membrane and a method for manufacturing same, the porous hollow fiber membrane being able to be used suitably in devices for processing various water-based fluids for use in applications such as water purification, drinking-water processing, and seawater clarification; having excellent fractionation characteristics and permeability with minimal decrease in performance over time; having excellent recovery in membrane separation characteristics by washing: and having excellent separation characteristics, filtration stability, and mechanical strength. The present invention is a porous hollow fiber membrane having a porous layer made of a thermoplastic resin in at least an outer surface and the vicinity thereof, the average pore diameter (Ad) at a depth of 1 [mu]m from the surface as seen in cross-section being no more than 0.6 of the average pore diameter (Bd) from a depth of 2 to 3 [mu]m, and a method for manufacturing said membrane.
Description
Technical field
The stain resistance used in the present invention relates to main antibacterial in removing water, virus, SS composition etc. can be excellent Porous hollow-fibre membrane.It is specifically related to the film properties of long-term stability, based on the Porous hollow-fibre membrane of restorative excellence of film properties of washing.The present invention separately relates to the Porous hollow-fibre membrane being applicable to the water process such as clean water treatment and the manufacture method thereof that can be used as secondary filter film or ultrafilter membrane.
The application advocates JIUYUE in 2013 Japanese Patent Applications 2013-193213 in Japanese publication on the 18th and JIUYUE in 2013 priority in the Japanese Patent Application 2013-193214 of Japanese publication on the 18th, by its content quotation in herein.
Background technology
Manufacture in the filtration treatment in clean water field of tap water at the water source of fresh water such as effluent Chuan Shui and/or lakes and marhshes water, subsoil water, be widely used sand filtration and coagulation sedimentation and sand filtration and use in the past.But, in these process, have following worry: innoxious Cryptosporidium (Network リ プ ト ス Port リ ジ ジ ウ system) probably cannot be fully achieved in chlorine resistance height and chlorbenside bacterium after filtration and can cause pollution of waterhead, etc..In this context, more adopting and can be easier to and precision removes the membrane filter method of turbidity well, it is individually being adopted or is combined with other the water technology such as coagulation sedimentation and/or sand filtration and adopts.On the other hand, when carrying out desalinization based on reverse osmosis membrane (reverseosmosismembrane, inverse soak into film), the sea water being supplied in reverse osmosis membrane is also advance with the pre-treatment such as coagulation sedimentation, sand filtration to implement turbidity removal process, is then supplied in reverse osmosis membrane and carries out desalting processing.In these process, adopt the turbidity removal based on membrane filtration to substitute coagulation sedimentation or sand and filter or situation about being combined with other water technology also increases.
As the requirement characteristic that the Porous hollow-fibre membrane used in membrance separation requires, for instance list following each point.
(1) removal being removed material is high.
(2) high through the permeability of material.
(3) permeability processing fluid is high.
(following, (1), (2), (3) are called membrance separation characteristic in the lump.)
(4) fully high relative to the fracture strength of stretching etc., not easy fracture and/or leakage.
(5) reduce with retaining characteristic not easily time dependent.
(6) the permeability not easily time dependent ground processing fluid reduces.
(following, (5), (6) are called together the retentivity of membrance separation characteristic.)
(7) based on the restorative excellence retaining characteristic of washing.
(8) based on the restorative excellence of the permeability of washing.
(following, (7), (8) are called the restorative of membrance separation characteristic together.)
It is said that in general, in membrane filtration process, along with the process of membrane filtration operation time, fouling material is adhered to, is accumulated in the film surface of the side supplying former water, the phenomenon that resistance of membrane filtration increases and occurs membrane filtration efficiency to reduce.Till that time, in order to remove the fouling material being attached to film surface, thereby through carrying out washing, air washing (airscrub, エ ア ス Network ラ Block), recover resistance of membrane filtration for washing operations such as the de-liquid of feedwater or chemical washings, start membrane filtration again.It is repeatedly performed membrane filtration operation and washing operation that a left side is stated, membrane filtration process can be used.Washing operation needs the facility (utility) of electricity and water etc., additionally cannot obtain the water of production in the period carrying out washing operation, thus be preferably that washing operation frequency is low and the washing operation time is short.Therefore, if the increase effect that can obtain the resistance of membrane filtration generated along with the process of membrane filtration operation time is little, recover the separation film that resistance of membrane filtration effect is big based on washing operation, then be highly useful.
In the prior art, film surface being carried out hydrophiling and improving on the direction of the increase of stain resistance, the filtration resistance suppressed in membrane filtration operation, a lot of technological development has been carried out.Such as, by being mixed into the hydrophilic macromolecule such as polyvinyl pyrrolidone (PVP) and/or polyvinyl alcohol (PVA) in the masking stock solution used when obtaining the multiple aperture plasma membrane formed by hydrophobic polymer, after masking also remaining these hydrophilic macromolecules, improve film surface hydrophilic thus improving stain resistance.Although the method is the method that masking is easy, film production efficiency is high, excellent, but stain resistance is still insufficient.
It addition, have following technology in the prior art: be initially formed the film formed by hydrophobic polymer, carry out various surface treatment behind and cover the surface of hydrophobic polymer film with hydrophilic macromolecule, thus wanting to improve stain resistance.In these methods, and in masking stock solution, it is mixed into hydrophilic macromolecule and compared with the method for masking, manufacturing process is complicated, is additionally difficult to control to operation, etc., problem is many in practical.
About above-mentioned technology, both it is conceived to the chemical property on film surface, chemical composition, utilizes the hydrophiling on film surface to improve the such technological thought of stain resistance and become basis.On the other hand, as the example of the relation of the shape Yu membrance separation characteristic that have mentioned film surface, patent documentation 1 and 2 can be listed.Patent document 1 discloses that a kind of invention relating to there is the complex reverse osmosis membrane on polyamide-based top layer, it is shown that by the specific surface area on the film surface of former water supply side is set to specific scope, thus improving the water permeability of complex reverse osmosis membrane.Additionally, patent document 2 discloses that a kind of invention relating to still there is the complex reverse osmosis membrane on polyamide-based top layer, disclose and can obtain a kind of complex reverse osmosis membrane, it shows high prevention performance when meansigma methods Z on the meansigma methods X of horizontal range and, mutually adjacent summit with the concavo-convex difference on base meets specific relation when between the adjacent vertex making the concave-convex surface on film surface of former water supply side.But, any one in patent documentation 1 and 2 all relates to the investigation of complex reverse osmosis membrane, it does not have any mentioning improves stain resistance further.
On the other hand, in recent years, uprising and the enhancing of control according to the care for environmental pollution, uses the embrane method of the filter membrane that the completeness separated and/or compactedness etc. are excellent and the water that carries out processes and attracts attention.In the purposes that such water processes, for filter membrane, it is desirable to excellent stalling characteristic and/or water permeability, and require high mechanical strength.
In the past, as the filter membrane that water permeability is excellent, it is known to: manufactured by wet type or dry-and wet-type spin processes, the filter membrane of polysulfones, polyacrylonitrile, cellulose ethanoate or polyvinylidene fluoride etc..These filter membranes, by macromolecular solution is carried out micron-scale phase separation, then make this macromolecular solution solidify in non-solvent and manufacture, have high void content and asymmetric structure.
Among above-mentioned filter membrane raw material, the chemical-resistant of polyvinylidene fluoride resin and excellent heat resistance, thus it is suitable for use as the raw material separating film.But the filter membrane formed by polyvinylidene fluoride hollow fiber membrane proposed so far has following problem: the situation that stalling characteristic, any one the above character filtered in stability and mechanical strength are insufficient is more, and the manufacture method of the filter membrane additionally all met is complicated.
In order to improve the mechanical strength separating film, it is proposed that hollow form group rope () as supporter, is arranged the separation film (patent documentation 3) of porous layer by one in its surface.But, this porous layer has following problem: cause having big macrovoid inside membrane structure because of its method for making, it is easy to the film outer surface damage that reason external cause causes etc. and cause stalling characteristic reduce.
To this, it is thus proposed that a kind of separation film, wherein, by the control being separated, making compacted zone thickening to a certain extent, simultaneously inhibit macrovoid and improve stalling characteristic (patent documentation 4).But, when thickening compacted zone like this, then have following problem: make it possible to atomic little material and/or dissolubility organic polymer is blocked in compacted zone, it is possible to make to filter stability and reduce.
On the other hand, following separation film is proposed, wherein, by polyvinylidene fluoride resin and plasticizer melting mixing are extruded, carry out cooling down and solidifying, then extract plasticizer, obtain Porous hollow-fibre membrane, then make outer surface compacted zone extend when having moistened, improve the void content of surface compact layer, thus not easily being polluted (patent documentation 5) by muddy water.But, about the separation film of this technology, void content is both high, and the aperture of compacted zone is also substantially uniform, thus problem following under still remaining, that is, the atomic little material and/or the dissolubility organic polymer that have passed through surface are easily blocked in inside compacted zone, additionally have following problem in method for making, namely, must substantially extend, thus not easily be combined with supporter, not easily take into account mechanical strength.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 09-19630 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2005-169332 publication
Patent documentation 3: No. 5472607 description of U.S. Patent No.
Patent documentation 4: No. 09/142279 pamphlet of International Publication
Patent documentation 5: No. 2011/007714 pamphlet of International Publication
Summary of the invention
The problem solved is wanted in invention
The problem of the present invention is in that to provide a kind of Porous hollow-fibre membrane, it can be applicable in the process of the various aqueous fluids such as clean water treatment, beverage process or seawater clearing, while have excellence retain characteristic and permeability, while suppressing performance by the time to reduce, based on the restorative excellence of the membrance separation characteristic of washing.
It addition, another object of the present invention is to solve relevant problem, it is provided that a kind of stalling characteristic filters the Porous hollow-fibre membrane of stability and mechanical strength.
For solving the scheme of problem
In order to solve above-mentioned problem, the present invention has following such embodiment.
(1) a kind of Porous hollow-fibre membrane, it is the Porous hollow-fibre membrane at least at outer surface with porous layer, and the average pore size (Ad) of 1 μm from outer surface to the degree of depth in the cross section structure of previous porous matter hollow-fibre membrane is less than 0.6 relative to the ratio (Ad/Bd) from the average pore size (Bd) of the degree of depth 2 μm to 3 μm.
(2) according to the Porous hollow-fibre membrane described in (1), wherein, the average pore size P1 of outer surface is 0.05～1.0 μm, and percent opening A1 is 15～65%.
(3) according to the Porous hollow-fibre membrane described in (1) or (2), wherein, the average pore size P2 of the layer of 10 μm from outer surface to the degree of depth in cross section structure is 0.1～5.0 μm, and percent opening A2 is 10～50%.
(4) according to Porous hollow-fibre membrane according to any one of (1)～(3), wherein, from outer surface to the degree of depth, the structure of 5 μm is that aperture is directed away from the direction of outer surface and cumulative three-dimensional mesh structure.
(5) according to the Porous hollow-fibre membrane according to any one of (1)～(4), wherein, from outer surface to the degree of depth average pore size of the porous layer of 5 μm less than being present in than 5 μm of average pore sizes further from the porous layer at the position of aforementioned external surfaces of the degree of depth.
(6) according to the Porous hollow-fibre membrane according to any one of (1)～(5), wherein, being present in than 5 μm of average pore sizes further from the porous layer at the position of aforementioned external surfaces of the degree of depth is less than 10 μm.
(7) according to the Porous hollow-fibre membrane according to any one of (1)～(6), wherein, constitute the thermoplastic resin of 5 μm of these parts from outer surface to the degree of depth to be formed by identical thermoplastic resin.
(8) according to Porous hollow-fibre membrane according to any one of (1)～(7), wherein, in the porous layer at the position 10 μm farther unlike the degree of depth from outer surface, without the aperture macrovoid more than 10 μm and one part.
(9) according to the Porous hollow-fibre membrane according to any one of (1)～(8), it is formed by phase separation method.
(10) according to the Porous hollow-fibre membrane according to any one of (1)～(9), wherein, previous porous matter layer is formed at the outer surface side of the supporter of hollow fiber.
(11) according to the Porous hollow-fibre membrane described in (10), wherein, the fibrous supporter of said hollow is to have passed through heat treated supporter.
(12) according to the Porous hollow-fibre membrane described in (10) or (11), wherein, the fibrous supporter of said hollow is hollow sennit (hollow).
(13) according to the Porous hollow-fibre membrane described in (11) or (12), wherein, supporter is the hollow sennit being undertaken justifying volume (ball) by 1 one thread that will be formed by multi-filament (multi-filament) and obtaining.
(14) manufacture method of a kind of Porous hollow-fibre membrane, it is for by spraying the film formative resin solution comprising thermoplastic resin and hydrophilic compounds from spinning-nozzle, then make the aforementioned film formative resin solution sprayed is that the saturated vapor of non-solvent contacts for the composition relative to film formative resin solution, being immersed in solidification liquid afterwards makes it solidify thus making the manufacture method of the Porous hollow-fibre membrane of Porous hollow-fibre membrane, wherein, aforementioned spinning-nozzle is 1 weight or dual above tubular nozzle, in previous porous matter hollow-fibre membrane, at least from outer surface to the degree of depth, the position of 5 μm is formed with identical film formative resin solution.
(15) manufacture method according to the Porous hollow-fibre membrane described in (14), wherein, the saturated vapor of aforementioned non-solvent is saturated steam.
(16) manufacture method according to the Porous hollow-fibre membrane described in (14) or (15), wherein, use spinning-nozzle, at the outer peripheral face coated film formative resin solution of supporter of hollow form and make film formative resin bed, aforementioned films formative resin bed is then made to contact with the saturated vapor of non-solvent.
(17) manufacture method according to the Porous hollow-fibre membrane described in (16), it is characterised in that aforementioned supporter uses and have passed through heat treated supporter.
(18) manufacture method according to the Porous hollow-fibre membrane described in (16) or (17), it is characterised in that supporter is sennit.
(19) manufacture method according to the Porous hollow-fibre membrane described in (17) or (18), wherein, supporter is the hollow form sennit obtained by being undertaken formed by multi-filament 1 one thread justifying volume.
It addition, embodiments of the present invention have following such side.1st main idea of the present embodiment solving foregoing relevant problem is, the percent opening of outer surface is the Porous hollow-fibre membrane of 15～65%.
It addition, the 2nd of present embodiment the to be intended to, there is the evaluation methodology of the Porous hollow-fibre membrane of following operation.
Operation (1): utilize scanning electron microscope that the section of Porous hollow-fibre membrane is observed, metering is apparent in the operation of the area in each hole of section surfaces
Operation (2): integrating will be carried out from the side that area is little at the fall into a trap area value in each hole measured of operation (1), using with relative to entire area 50% quite when the operation that calculates as average pore size index of hole
Additionally, present embodiment is a kind of Porous hollow-fibre membrane, it is the Porous hollow-fibre membrane at least near outer surface and its with the porous layer formed by thermoplastic resin, wherein, the average pore size Ad of 1 μm from surface to the degree of depth in cross section structure is less than 1/2 of the average pore size Bd from the degree of depth 2 μm to 3 μm.
Further, present embodiment is the manufacture method of a kind of Porous hollow-fibre membrane, wherein, the film formative resin solution comprising thermoplastic resin and hydrophilic compounds is sprayed from spinning-nozzle, contact with the saturated vapor of the non-solvent of film formative resin after immediately, be immersed in solidification liquid after afterwards and make it solidify.
It addition, embodiments of the present invention have following such side.
(1A) a kind of Porous hollow-fibre membrane, it is the Porous hollow-fibre membrane that at least outer surface side is formed by porous layer, and wherein, the percent opening of outer surface is 15～65%.
(2A) according to the Porous hollow-fibre membrane described in (1A), wherein, the average pore size indices P 1 of outer surface is 0.05～1.0 (μm).
(3A) according to the Porous hollow-fibre membrane described in (1A) or (2A), wherein, to near outer surface 10 μm, there is compacted zone, the scope that average pore size indices P 2 (μm) is 0.1～5.0 (μm) of this compacted zone.
(4A) according to the Porous hollow-fibre membrane described in (3A), wherein, the percent opening A2 (%) of compacted zone is 10～50%.
(5A) according to the Porous hollow-fibre membrane described in (1A)～(4A), wherein, the gross thickness of previous porous matter layer is less than 200 μm.
(6A) according to the multiple aperture plasma membrane described in (1A)～(5A), wherein, from outer surface, the pore size index obliquity ground of continuous print porous layer is cumulative.
(7A) evaluation methodology of the Porous hollow-fibre membrane that a kind of outer surface side is made up of porous layer shape, it comprises following each operation
Operation 1: utilize scanning electron microscope that the section of Porous hollow-fibre membrane is observed, the operation of the area in each hole that metering section surface manifests
Operation 2: integrating will be carried out from the side that area is little at the fall into a trap area value in each hole measured of operation 1, use with relative to entire area 50% quite when hole, thus calculating the operation of average pore size index
It addition, embodiments of the present invention have following such side further.
(1B) a kind of Porous hollow-fibre membrane, it is the Porous hollow-fibre membrane at least near outer surface and its with the porous layer formed by thermoplastic resin, wherein, the average pore size Ad of 1 μm from surface to the degree of depth in cross section structure is less than 1/2 of the average pore size Bd from the degree of depth 2 μm to 3 μm.
(2B) according to the Porous hollow-fibre membrane described in (1B), wherein, from outer surface to the degree of depth, the structure of 5 μm is the three-dimensional mesh structure that aperture is cumulative towards center.
(3B) according to the Porous hollow-fibre membrane described in (1B) or (2B), wherein, from outer surface to the degree of depth, the average pore size of the porous layer of 5 μm is less than the average pore size of the porous layer of the inner side being present in the degree of depth 5 μm.
(4B) according to the Porous hollow-fibre membrane according to any one of (1B)～(3B), wherein, the average pore size being present in the porous layer of the inner side of the degree of depth 5 μm is less than 10 μm.
(5B) according to the Porous hollow-fibre membrane according to any one of (1B)～(4B), wherein, constitute the thermoplastic resin of 5 μm of these parts from outer surface to the degree of depth to be formed by identical thermoplastic resin.
(6B) according to Porous hollow-fibre membrane according to any one of (1B)～(5B), wherein, in the porous layer of from outer surface to the degree of depth 10 μm, without the aperture macrovoid more than 10 μm.
(7B) according to the Porous hollow-fibre membrane according to any one of (1B)～(6B), wherein, previous porous matter layer is formed at the outer surface side of the supporter of hollow fiber.
(8B) according to the Porous hollow-fibre membrane described in (7B), wherein, the fibrous supporter of said hollow is hollow sennit.
(9B) according to the Porous hollow-fibre membrane described in (8B), wherein, the fibrous supporter of said hollow is to have passed through heat treated hollow sennit.
(10B) according to the Porous hollow-fibre membrane described in (8B) or (9B), wherein, supporter is the hollow sennit obtained by being undertaken formed by multi-filament 1 one thread justifying volume.
(11B) manufacture method of a kind of Porous hollow-fibre membrane, wherein, the film formative resin solution comprising thermoplastic resin and hydrophilic compounds is sprayed from spinning-nozzle, then contacts with the saturated vapor of the non-solvent of film formative resin, be immersed in solidification liquid afterwards and make it solidify.
(12B) manufacture method according to Porous hollow-fibre membrane described in (11B), wherein, spinning-nozzle is 1 weight or dual above tubular nozzle, at least from outer surface to the degree of depth 4 μm use identical film formative resin solutions to be formed.
(13B) manufacture method of the Porous hollow-fibre membrane of (12B), wherein, the saturated vapor of aforementioned non-solvent is the saturated steam of 100 DEG C.
(14B) manufacture method according to the Porous hollow-fibre membrane described in (12B) or (13B), wherein, before the saturated vapor making film formative resin solution and the non-solvent of film formative resin sprayed from spinning-nozzle contacts so that it is contact with dry air.
(15B) manufacture method according to the Porous hollow-fibre membrane described in (14B), wherein, after being supplied from nozzle discharging surface towards vertical lower section by aforementioned dry air, contacts to ground with the saturated vapor of aforementioned non-solvent relatively.
(16B) manufacture method according to Porous hollow-fibre membrane described in (14B) or (15B), wherein, utilizes aforementioned dry air, makes the relative humidity of non-solvent in the atmosphere near spinning-nozzle less than 10%.
The effect of invention
Porous hollow-fibre membrane about the present invention, it is at least at the Porous hollow-fibre membrane nearby with the porous layer comprising thermoplastic resin of outer surface and aforementioned external surfaces, by making the size of the average pore size (Ad) of 1 μm from surface to the degree of depth in the cross section structure of the thickness direction of previous porous matter hollow-fibre membrane be less than 0.6 relative to the ratio of the size from the average pore size (Bd) of the degree of depth 2 μm to 3 μm, thus so-called compacted zone is thin, its result, makes stalling characteristic, filters the Porous hollow-fibre membrane of stability, mechanical strength.
Additionally, according to the present invention it is believed that, owing to being the Porous hollow-fibre membrane that at least outer surface side is formed by porous layer, by making the Porous hollow-fibre membrane that percent opening is 15～65% of outer surface, thus becoming internal structure there is the structure of the thicker incline structure of specific surface, hence without internal stifled eye and wash restorative also high.It addition, the retentivity of membrance separation characteristic and the Porous hollow-fibre membrane of restorative excellence can be obtained.
The Porous hollow-fibre membrane of the present invention can provide following Porous hollow-fibre membrane, and it can be applicable to the process of the various aqueous fluids such as water purification film, drinking water treatment film, seawater clearing film, is particularly suitable for clean water treatment.Additionally, the Porous hollow-fibre membrane of the application is while what have an excellence retains characteristic, permeability, while having the sufficient film-strength that will not cause fracture and/or leakage when module shapes and/or time actually used, realize the suppression that the time dependent of these characteristics is reduced, based on the restorative excellence of the membrance separation characteristic of washing.
Additionally, Porous hollow-fibre membrane about the present invention, by making the average pore size Ad of 1 μm from surface to the degree of depth is the average pore size Bd from the degree of depth 2 μm to 3 μm less than 1/2 in cross section structure, thus so-called compacted zone is thin, its result, makes stalling characteristic, filters the Porous hollow-fibre membrane of stability, mechanical strength.
Accompanying drawing explanation
Fig. 1 show the cross sectional photograph of the porous layer of the Porous hollow-fibre membrane obtained by reference example 1.
Fig. 2 show the cross sectional photograph of the porous layer of the Porous hollow-fibre membrane obtained by reference example 2.
Fig. 3 show the cross sectional photograph of the porous layer of the Porous hollow-fibre membrane obtained by reference example 3.
Fig. 4 show the cross sectional photograph of the porous layer of the Porous hollow-fibre membrane obtained by reference example 4.
Fig. 5 show the cross sectional photograph of the porous layer of the Porous hollow-fibre membrane obtained by reference comparative example 1.
Fig. 6 show the cross sectional photograph of the porous layer near the outer surface portion of the Porous hollow-fibre membrane obtained by reference example 1.
Fig. 7 show the cross sectional photograph of the porous layer near the outer surface portion of the Porous hollow-fibre membrane obtained by reference example 2.
Fig. 8 show the cross sectional photograph of the porous layer near the outer surface portion of the Porous hollow-fibre membrane obtained by reference example 3.
Fig. 9 show the cross sectional photograph of the porous layer near the outer surface portion of the Porous hollow-fibre membrane obtained by reference example 4.
Figure 10 show the cross sectional photograph of the porous layer near the outer surface portion of the Porous hollow-fibre membrane obtained by reference comparative example 1.
The curve chart of the rheological parameters' change with time of the pressure reduction when filtration that Figure 11 show in reference example, reference comparative example operates.
Figure 12 show the ideograph manufacturing device of the Porous hollow-fibre membrane for manufacturing an embodiment of the invention.
Figure 13 show the bottom view of the aeration nozzle manufacturing device of the hollow form multiple aperture plasma membrane constituting Figure 12.
Description of reference numerals
1 manufactures device
10 spinning-nozzles
11 supporter through holes
12 resin solution streams
20A process container
21 tops
21a the 1st peristome
22a the 2nd peristome
22c through hole
23 sidepieces
24 gas supply pipes
25 pipe portions
30 coagulating basins
31 the 1st deflector rolls
32 the 2nd deflector rolls
33 top boards
33a, 33b peristome
40A, 40B, 40C ventilating unit
41, aeration nozzle
41a circular open portion
41b gas imports room
41c gas vent
41d resistance gives body
42 gas feed unit
43 filtering unit
44 gas conditioning unit
50 protection cylinders
50a through hole
51 upper ends
52 bottoms
52a peristome
A Porous hollow form film
A1 hollow rope form supporter
The film of A2 film formative resin solution
B solidification liquid
Detailed description of the invention
Hereinafter the preferred embodiment of the present invention is illustrated.
(first embodiment)
The Porous hollow-fibre membrane of present embodiment is following Porous hollow-fibre membrane, the Porous hollow-fibre membrane that its at least outer surface side being present embodiment is formed by porous layer, wherein, the percent opening of outer surface is 15～60% relative to the entire area of outer surface.Outer surface refers to herein, among two surfaces of film, when film being formed as hollow fiber (cylindrical shape) and makes Porous hollow-fibre membrane, towards the surface of side of the periphery of cylinder.The surface of the side of the inner circumferential towards cylinder is set to inner surface.Porous layer refers to herein, has the layer in the hole of aftermentioned character with the form being scattered in the substantially entirety of layer.Additionally, percent opening refers to herein, microscope etc. is utilized to observe the outer surface of Porous hollow-fibre membrane, utilize graphical analysis etc. and measure the area in hole, all well is added up to, the value obtained with the form of the area (membrane area in the visual field) of the area sum of percent opening (%)=all well/observable outer surface entirety.By being the Porous hollow-fibre membrane that at least outer surface side is formed by porous layer, and to make the percent opening of outer surface be 15～60% relative to the entire area of outer surface, thus making surface compact and the excellent Porous hollow-fibre membrane of water permeability.About the percent opening of outer surface, relative to the entire area of outer surface, it is preferred to less than more than 20% 60%, more preferably less than more than 25% 55%.
It addition, the average pore size index (or average pore size P1) in each hole that the porous layer of the Porous hollow-fibre membrane of present embodiment has can also be 0.05～1.0 (μm).Thus make the Porous hollow-fibre membrane of restorative excellence.The average pore size index of Porous hollow-fibre membrane is preferably 0.06～0.9 (μm), more preferably 0.75～0.8 (μm).
Being explained, average pore size index refers to, carries out arithmetic process to using image analysis software from the aperture that microphotograph reads thus the aperture calculated.Thus, have by deep or light small noise (noise) the excluded effect caused of pixel.In present embodiment, utilizing the outer surface of microscope photographing Porous hollow-fibre membrane, the meansigma methods in the aperture in the hole in metering photo is thus obtaining.
Additionally, Porous hollow-fibre membrane about present embodiment, when having observed the section of thickness direction, the average pore size P2 of the layer of 10 μm from surface to the degree of depth in its cross section structure is preferably 0.1～5.0 (μm), and the percent opening A2 in this layer is preferably 10～50%.If being in this scope, then there is the effect that can take into account resistance to non-clogging property and intensity.
Constituting the Porous rete aspect of the Porous hollow-fibre membrane of present embodiment, its thickness is preferably less than 200 μm.This is owing to having following tendency: by making the thickness of Porous rete be less than 200 μm, thus lower when membrance separation through resistance, obtain excellent water permeability, and can shorten and form the setting time when Porous rete by use as the masking stock solution of high-molecular resin solution, it is effective for suppressing macrovoid (defect), and the productivity ratio of excellence can be obtained.More preferably the thickness of Porous rete is less than 150 μm.
It addition, in constituting the Porous rete of Porous hollow-fibre membrane of present embodiment, its thickness is preferably more than 100 μm.This is owing to having following tendency: by making the thickness of Porous rete be more than 100 μm, thus mechanical strength no problem in practical can be obtained.But, when film external diameter is thin, even if having thickness also can maintain the situation of mechanical strength less than 100 μm, thus do not limited by this.
This Porous rete is the Porous rete near its at least outer surface with compacted zone., refer near outer surface, adjacent to (inner side of Porous rete) position of the outer surface of Porous rete in the position of the inside of Porous rete herein.Additionally, compacted zone refers to herein, in Porous rete, have accumulated the region of the more minute aperture of small-bore, but in the present embodiment, owing to water permeability and the separating property of Porous hollow-fibre membrane can be taken into account, thus in the compacted zone near surface, its average pore size index is preferably set to the scope of 0.01～1 μm.
About the thickness of the compacted zone in present embodiment, from the viewpoint of the stability of stalling characteristic improves improves this two side with water permeability, it is preferred to the scope of 10～125 μm.
In compacted zone near outer surface, from the viewpoint of improve the stability of stalling characteristic, more preferably its thickness is set to the scope of 25～100 μm.It is preferred that the scope that the thickness of compacted zone is 40～75 μm.
About the position of the compacted zone near outer surface, from the viewpoint of avoid the permeable resistance within film to raise, it is preferable that be present in the position within the outer surface of this Porous rete is 20 μm.Further, it is particularly preferred to this compacted zone constitutes the outer surface of Porous rete.
About this Porous rete, the inner side of the compacted zone near above-mentioned outer surface (further from the position of outer surface, from the deep position of outer surface viewing), it is preferable that there is the spongy layer that average pore size index is more than 2 μm.About this intermediate porous matter layer, particularly contributing to the water permeability in the Porous hollow-fibre membrane of present embodiment, thus its aperture is more big then more good, but then become macrovoid time excessive, its mechanical strength reduces.Therefore, its average pore size index is preferably less than 8 μm, is more preferably substantially absent from the pore of more than 10 μm.The more preferably scope of 3～5 μm.
Additionally, from the viewpoint of improve water permeability, at this intermediate porous matter layer, particularly at ratio 5 μm of positions further from outer surface of the degree of depth, it is preferable that have aperture from the compacted zone near outer surface be directed away from outer surface direction, namely, towards near inner surface and cumulative incline structure.In particular it is preferred that this intermediate porous matter layer adopts the three-dimensional mesh structure that pore reciprocally intersects three-dimensionally.
Additionally, it is preferable that the average pore size of the porous layer of 5 μm is less than the average pore size of the aforesaid porous layer existed than 5 μm of deeper of positions of the degree of depth apart from outer surface from outer surface to the degree of depth.Further, the average pore size of the porous layer existed than 5 μm of deeper of positions of the degree of depth apart from outer surface is particularly preferably less than 10 μm.Utilize this structure, there is following effect: the material coming off from the compacted zone near outer surface can be suppressed to be blocked in the situation of inside, and also can take into account quality.
It is explained, about the porous layer recorded so far, sometimes also multiple layer can be divided into (such as to noncontinuity according to the difference of raw material and/or average pore size, compacted zone and the layer except compacted zone), but this is with having there is also seriality (such as, along with the distance on distance surface, the meansigma methods of bore gradually changes etc.) situation about vary.In the case, layer also can be called position (such as, fine and close position and its outer position etc.) sometimes.
Then, the manufacture method of the Porous hollow-fibre membrane of present embodiment is illustrated.
Porous hollow-fibre membrane about present embodiment, can pass through to use annular nozzle, outer peripheral face at the supporter of hollow form, the material comprising Porous rete and solvent, the first masking stock solution and the second masking stock solution masking stock solution seriality is coated and stacking, these masking stock solutions are simultaneously solidified, thus manufacturing.
In the case, solidification can be the solidification being only derived from one side, and available the method obtains the multiple aperture plasma membrane structure of one from two kinds of masking stock solutions.
Such as, use the such double annular nozzle recorded in Fig. 1 of patent documentation 7, make hollow form supporter (sennit) by its supporter path, the the first masking stock solution (internal layer side masking stock solution) being derived from the first supply mouth is simultaneously sprayed with the second masking stock solution (outer layer side masking stock solution) being derived from the second supply mouth, after the first masking stock solution is coated the outer peripheral face of hollow form sennit, the second masking stock solution is coated on the coating layer of this aforementioned first masking stock solution.Hereafter so that the hollow form sennit sky being coated with masking stock solution walks the stipulated time, it is then immersed in solidification liquid and makes masking stock solution solidify, by washing and dry, thus the structure of specific Porous hollow-fibre membrane in present embodiment can be obtained.
It addition, when using double annular nozzle, it is possible in nozzle, the first masking stock solution and the second masking stock solution are collaborated in advance, from nozzle face, they are simultaneously sprayed, coat hollow form supporter.
Further, it is used as triple annular nozzles with central part, medial part and lateral part, while making hollow form supporter pass through central part, while the first masking stock solution being derived from medial part simultaneously being sprayed with the second masking stock solution being derived from lateral part, masking stock solution is coated the supporter of hollow form.
By using annular nozzle as described above, the first masking stock solution and the second masking stock solution can be coated with respectively equably, further, when the first masking stock solution is carried out stacking with the second masking stock solution, can make not generate bubble at interlayer.It is explained, it is possible to be sequentially coated with the first masking stock solution and the second masking stock solution.In the case, when being coated with the first film forming stock solution with the second film forming stock solution, can be coated with according to becoming successional mode, it is possible to be respectively provided with interval, but in order to not generate bubble when the first masking stock solution is carried out stacking with the second masking stock solution at interlayer, thus preferably carry out to seriality.
Although using two kinds of masking stock solutions in the above cases, but any one being all the masking stock solution containing macromolecule resin, additive and organic solvent.
As the macromolecule resin used in these masking stock solutions, for instance polysulfone resin, polyethersulfone resin, sulfonated polysulfone resin, polyvinylidene fluoride resin, polyacrylonitrile resin, polyimide resin, polyamide-imide resin or polyesterimide resin etc. can be listed.They can use as desired by suitably selecting, but wherein due to good chemical resistance, thus it is preferably polyvinylidene fluoride resin.
As additive, it is possible to use for the purpose of control of being separated etc., for instance, the hydrophilic polymer resin such as the single methanol system, glycol system, triol system or the polyvinyl pyrrolidone that are represented by Polyethylene Glycol can be used.They can use as desired by suitably selecting, but wherein owing to thickening effect is excellent, thus it is preferably polyvinyl pyrrolidone.
As organic solvent, if the organic solvent of the above-mentioned macromolecule resin of solubilized and additive is not particularly limited, for instance dimethyl sulfoxide, dimethyl acetylamide or dimethylformamide can be used.
The composition of two kinds of above-mentioned masking stock solutions is not particularly limited, and can use identical film forming stock solution, it is possible to use different film forming stock solution.But, from the viewpoint of prevent splitting and improve mechanical strength, in order to be formed integrative-structure by two kinds of masking stock solutions when solidification, thus the solvent used and macromolecule resin are preferably congener material.
When being manufactured the Porous hollow-fibre membrane of present embodiment by said method, it is preferable that as the viscosity of the first masking stock solution of internal layer side masking stock solution higher than the viscosity of the second masking stock solution as outer layer side masking stock solution.
This is because, the outer peripheral face of the supporter by the first higher for viscosity masking stock solution being coated said hollow shape, masking stock solution can be suppressed exceedingly to invade in the inside of hollow form supporter, the obturation of the hollow bulb of Porous hollow-fibre membrane can be prevented.
In order to realize this target, this first masking stock solution needs have sufficient viscosity, and the viscosity at 40 DEG C is preferably 50,000 more than mPa sec.It is more preferably 100,000 more than mPa sec, more preferably 150,000 more than mPa sec.Specifically, for instance, first film forming stock solution viscosity at 40 DEG C is the scope of 5～250,000 mPa sec, and second film forming stock solution viscosity at 40 DEG C is the scope of 10～300,000 mPa sec.
It addition, the viscosity method of adjustment of above-mentioned masking stock solution is not particularly limited, for instance, it is possible to by changing the molecular weight of macromolecule resin or changing the concentration of macromolecule resin and carry out.Method as the molecular weight changing macromolecule resin, it is possible to use two kinds of different for molecular weight macromolecule resins are carried out blended method.
About the viscosity adjustment of masking stock solution, can suitably select as described above, but in the first masking stock solution, utilizing the concentration of macromolecule resin to adjust, and make concentration become higher, this is in the internal layer that setting rate is slow, also tend to suppress macroporous generation, it is preferable that.It addition, by making the concentration of the first masking stock solution become higher, it is intended to the structural stability that porous layer is overall can be improved, it is preferable that.
On the other hand, in the second masking stock solution, the molecular weight of macromolecule resin is utilized to adjust, this percent opening tending to can maintain the outer surface of Porous rete higher, it is preferable that.
As described above, make masking stock solution carry out solidifying and when masking, under the effect being separated, form porous structure.About porous structure, various structure is obtained according to film forming condition, but representatively porous structure, can list: particle agglutination structure that the island structure become, by macromolecule resin, sponge structure that the island structure of side, sea derives, being become side, island by macromolecule resin is derived and by the three-dimensional mesh structure these three porous structure of the co-continuous structure derivation making macromolecule resin and the network-like ground of solvent mutually be wound around and obtain by Spinodal decomposition (decompositions of spinodaldecomposition, ス ピ ノ ダ Le).
As porous structure, suitably can select among these structures, but about particle agglutination structure, the structure easily becoming polymer resin layer generation coagulation and obtain, mechanical strength is tended to inferior, thus in the present embodiment, it is preferred to use sponge structure and/or three-dimensional mesh structure.
About sponge structure, it is intended to make the homogeneous texture that aperture does not change significantly relative to film thickness direction, it is adapted for improving the structure of the stability of stalling characteristic.
On the other hand, about three-dimensional mesh structure, compare with sponge structure, it is intended to make the structure that emptying aperture degree of communication each other is high, be adapted for improving diactinic structure.
About the composition of the first masking stock solution as internal layer side masking stock solution, suitably can select according to the membrane structure formed.
Also it is same in obtained the condition of sponge structure by the first masking stock solution, it is not particularly limited about composition, but the mass ratio (additive/macromolecule resin) preferably making the additive in masking stock solution and macromolecule resin is less than 0.45, more preferably less than 0.40.
By making this mass ratio be less than 0.45 so that homogeneous texture tends to densification, additionally also tends to be not likely to produce macrovoid.
On the other hand, when this mass ratio is too low, then tend to excessively diminish in aperture, and through performance tends to be easily reduced, thus preferably making this mass ratio is more than 0.3.
Example as the composition of masking stock solution, following composition can be listed: relative to the total quality of masking stock solution, polyvinylidene fluoride resin 20～30% mass, polyvinyl pyrrolidone 5～12% mass, dimethyl acetylamide 60～85% mass, and, the mass ratio (polyvinyl pyrrolidone/polyvinylidene fluoride resin) of polyvinyl pyrrolidone and polyvinylidene fluoride resin is in the scope of 0.3～0.45.
In obtained the condition of three-dimensional mesh structure of porous layer by the first masking stock solution, also without being particularly limited to, but the mass ratio (additive/macromolecule resin) preferably making the additive in masking stock solution and macromolecule resin is more than 0.45, more preferably more than 0.51.
Additionally, it is preferred that the ratio of organic solvent is set to relative to below 68% mass of the total quality of masking stock solution.This is because, by so setting, it is intended to suppress macroporous generation, and tend to improve the structural stability that porous layer is overall.It is more preferably below the 60 weight % of the total quality relative to masking stock solution.
Example as the composition of masking stock solution, following composition can be listed: relative to the total quality of masking stock solution, polyvinylidene fluoride resin 20～30% mass, polyvinyl pyrrolidone 10～20% mass, dimethyl acetylamide 55～68% mass, and, the mass ratio (polyvinyl pyrrolidone/polyvinylidene fluoride resin) of polyvinyl pyrrolidone and polyvinylidene fluoride resin is more than 0.45.
In the composition as the second masking stock solution of outer layer side masking stock solution, if being such that near the outer surface of Porous rete there is compacted zone, the aperture inner surface towards Porous rete can be formed and cumulative incline structure, then also without special restriction by being separated.
About the composition of the second masking stock solution, suitably can select according to the membrane structure of target, but from the viewpoint of the surface percent opening of Porous rete can be improved, it is preferable that the ratio of organic solvent is set to more than 70% mass.
Can form, further, since exist, the tendency not having big macroporous incline structure, thus the mass ratio of additive/macromolecule resin is preferably more than 0.45.Example as the composition of masking stock solution, following composition can be listed: polyvinylidene fluoride resin 15～25% mass, polyvinyl pyrrolidone 5～15% mass, dimethyl acetylamide 70～80% mass, and, (polyvinyl pyrrolidone/polyvinylidene fluoride resin) is more than 0.45.
Thickness during coating respective about outer layer and internal layer, can suitably set, but makes the ratio of organic solvent tend to higher outer layer when thickening, then tend to easily produce macrovoid when masking, thus preferably making the thickness of outer layer is less than 150 μm.It is more preferably less than 100 μm, more preferably less than 80 μm.On the other hand, the lower limit of outer layer thickness is 5 μm.
When using hollow form sennit as supporter, in order to prevent masking stock solution to the excessive immersion within supporter, it is possible to make in advance to be infiltrated on supporter relative to the non-solvent of masking stock solution.As the non-solvent in the masking stock solution situation of the above-mentioned composition of use, glycerol can be exemplified.But, the non-solvent too high with respect to the coagulation ability of the masking stock solution used and/or, the too high non-solvent of viscosity, owing to hindering Porous rete to reduce significantly to the intrusion within supporter and peel resistance, thus not preferred.
It addition, when employing polyvinyl pyrrolidone as additive, formed in the washing after membrane structure after solidification, it is preferred to use sodium hypochlorite etc., implement the chemical solution washing of Porous hollow-fibre membrane.
(multiple aperture plasma membrane)
Material as Porous rete, list polyvinylidene fluoride, polysulfones, polyacrylonitrile, polyvinyl pyrrolidone or Polyethylene Glycol etc., consider from the viewpoint such as chemical-resistant, thermostability, it is preferred to the combination of polyvinylidene fluoride or polyvinylidene fluoride and polyvinyl pyrrolidone.
Porous rete can be the monolayer being made up of the wantonly a kind of layer formed in raw material these, it is also possible to be by the composite porous film layer by these monolayer stackings more than 2 layers.
(the second embodiment)
Hereinafter, another preferred implementation of present embodiment is illustrated.
The hollow form Porous hollow-fibre membrane of present embodiment is following Porous hollow-fibre membrane, and wherein, in the cross section structure when its thickness direction cuts off and observes, from surface to the degree of depth, the layer of 1 μm is (hereinafter referred to as porous layer A.) the size of average pore size Ad relative to the layer from the degree of depth 2 μm to 3 μm (hereinafter referred to as porous layer B.) ratio of size of Bd is less than 0.6, it is preferred to less than 1/2 (less than 0.5).
This is, the Porous hollow-fibre membrane of present embodiment is characterised by, having the film of the minimum layer in aperture in the porous layer A forming outer surface substantially less than 1 μm, atomic little material and/or dissolubility organic polymer coming off from outer surface are not easily blocked inside film.
It addition, about present embodiment Porous hollow-fibre membrane porous layer A with, from the layer of the degree of depth 4 μm to 5 μm (hereinafter referred to as porous layer C.) till, more preferably aperture demonstrates cumulative structure.Aperture is in uniform situation, and atomic little material and/or dissolubility organic polymer coming off from outer surface are easily blocked in the layer near outer surface, becomes and reduces the main cause filtering stability.The film obtained based on thermally induced phase separation, plasticizer extraction and/or extension method easily forms such structure.On the other hand, when aperture noncontinuity become big, cause the lower thickness of the layer comprising outer surface, mechanical strength reduces, and produces the problem such as outer surface peeling.
The cumulative ratio in aperture is more big, the atomic little material and/or the dissolubility organic polymer that have then passed through porous layer A are more not easily blocked in the layer of the inner surface side of porous layer A, thus filter stability and improve, but the layer then contributing to filtering time excessive becomes the layer being only to comprise outer surface, because of outside reason etc., stalling characteristic is easily reduced.Therefore, in cross section structure, can also be more than 5/3 (that is, Ad/Bd is less than 0.6) relative to the aperture Bd of the aperture Ad, porous layer B of the porous layer A forming outer surface.Further, more than 2 times (Ad/Bd is less than 0.5) are preferably become relative to Ad, Bd, more preferably more than 3 times (Ad/Bd is less than 0.33), more preferably more than 4 times (Ad/Bd is less than 0.25).When can maintain stalling characteristic, it is preferred that become more than 5 times (Ad/Bd is less than 0.2).
Being explained, what porous layer B preferably represented is with the porous layer A constituting outer surface clamps a layer and adjacent layer between the two layers.In the aperture easily forming porous layer towards internal (direction away from outer surface), the phase separation method of cumulative structure is also, in this region that outer surface is immediately below, owing to the diffusion immersion speed of solidification liquid is fast, solidify when not being separated fully, thus be not easily formed the porous layer B with structure sufficiently large for porous layer A.
Aperture Ad substantially decides filtering feature, suitably select according to filtered thing, but in the present embodiment, owing to water permeability and the stalling characteristic of Porous hollow-fibre membrane can be taken into account, thus it is preferably set to the scope of 0.01～1 μm, it is more preferably the scope of 0.02～0.5 μm, more preferably the scope of 0.04～0.2 μm.
About the Porous hollow-fibre membrane in present embodiment, it is preferred that with from porous layer A to the aperture of porous layer C Comparatively speaking, the aperture from porous layer C to the layer forming inner surface becomes big.If the aperture from porous layer C to the layer forming inner surface diminishes, atomic little material and/or dissolubility organic polymer coming off from porous layer C are easily blocked in inside film.
Aperture from porous layer C to the layer forming inner surface suitably selects according to purpose.If the preferential system of water permeability is then preferably big, if the system that stalling characteristic is preferential, then be preferably maintained close to the aperture of Cd.The system that stalling characteristic is preferential in separating film is many, and in this case, the aperture from porous layer C to the layer forming inner surface is preferably less than 8 μm, is more preferably created substantially absent the pore of more than 10 μm.More preferably less than 5 μm.It is explained, from porous layer C to formed inner surface layer structure formation in, following method can be taked: different stock solution (De プ) is carried out stacking and forms the method for multiple structure of more than 2 layers, the method controlled according to the composition of solidification liquid and temperature.
On the other hand, formed from porous layer A to the layer of porous layer C preferably by a stock solution.That is, comprise: identical constitute raw material, the thermoplastic resin more specifically substantially constituting the identical compound of layer and other film constitute additive etc..This be due to, when making multiple structure, then having and produce interfacial structure at interlayer, the atomic little material come off from outer surface and/or dissolubility organic polymer are susceptible to the probability of blocking, and the intensity having layer one by one reduces, and the probability of spallation problems occurs.
In Porous hollow-fibre membrane in present embodiment, it is preferable that do not have and be called the defect that macroporous aperture is more than 10 μm.As the structure made near outer surface towards internal and cumulative method, it is contemplated that be greatly reduced stock solution viscosity, but easily simultaneously produce macrovoid near outer surface in this art, cause that stalling characteristic is substantially reduced because of the reason of outside etc..Therefore in present embodiment, it is preferable that not there is macrovoid or a macroporous part from porous layer A to porous layer C.Particularly, in the porous layer of the layer of from outer surface to the degree of depth 10 μm, more preferably without the aperture macrovoid more than 10 μm and one part, when observing cross section structure, it is preferred that without aforementioned macrovoid in the universe of section.
It is explained, " from outer surface to the degree of depth till the layer of 10 μm, comprising macrovoid and one part " in present embodiment also includes: a macroporous part hangs the situation of the more lateral (close to outer surface) of the degree of depth 10 μm at distance outer surface from above.
The hollow form Porous hollow-fibre membrane of present embodiment can be only made up of above-mentioned porous layer, but in order to obtain the mechanical strength of excellence, thus it is particularly preferably the hollow form Porous hollow-fibre membrane on the supporter of hollow form with this porous layer.It is explained, herein, for the position relationship of clear and definite porous layer Yu supporter, thus is expressed as on supporter, but there is also porous layer and be infiltrated on the situation within supporter by the space of supporter.In present embodiment, porous layer is formed at the outer surface side of the supporter of hollow fiber.
About supporter, if having high mechanical strength, and can be integrated with porous layer, so can suitably select and use, it is not particularly limited, but low cost of manufacture, the shape stability (positive round) of flexibility and section can be taken into account, also excellent with the cementability of porous layer, thus it is preferably sennit.Wherein, it is preferred to the hollow form sennit obtained by being undertaken formed by multi-filament 1 one thread justifying volume.Composition raw material as supporter, from the viewpoint of good chemical resistance, it is preferably polyester fiber, acrylic fibers, vinylal fibre, polyamide-based fiber, or polyolefin series fiber, polyvinyl chloride fiber, it is particularly preferred to for polyester fiber, acrylic fibers or polyvinyl chloride fiber.It addition, about supporter, it is preferred that control external diameter, while the supporter carrying out heat treatment at the temperature of the heat distortion temperature higher than fiber and the melt temperature lower than fiber and obtaining.According to this structure, there is the such effect of densification of the space part of the stabilisation of supporter external diameter, the suppressionization of retractility, supporter.
In the case, porous layer and supporter (hollow form sennit) refer to, are not necessarily required to and are close to, but when their cementability is low, then having when hollow-fibre membrane has been carried out stretching that they separate, there is the probability of de-nest () in porous layer.Therefore, in the hollow form Porous hollow-fibre membrane of present embodiment, it is preferable that this porous layer in part through in the braiding eye (order) of hollow form sennit, thus being immersed in sennit, porous layer is integrated with hollow form sennit.
In order to give porous layer and supporter with sufficient cementability, thus more preferably make porous layer immerse hollow form sennit thickness more than 50%.Further, the porous layer by invading more than 50% in different braiding eyes is connected to each other, is turned into the state of the part having wrapped into supporter, this from the viewpoint of peel resistance it is preferred that.Additionally, when the part having wrapped into a part for supporter is to exist with connecting in fiber axis direction, then peel resistance increases further, it is thus preferred to.Further, if being helical form towards the axial connected mode of fiber, then peel resistance significantly improves, thus it is preferred that.Being explained, in this case, the above-mentioned thickness in present embodiment also is indicated as exposing the thickness of the part on supporter.
Porous layer utilizes film formative resin to be formed.As film formative resin, thermoplastic resin can be used as described above, for instance list polysulfone resin, polyethersulfone resin, sulfonated polysulfone resin, polyvinylidene fluoride resin, polyacrylonitrile resin, polyimide resin, polyamide-imide resin or polyesterimide resin etc..Among them, due to good chemical resistance, thus it is preferably polyvinylidene fluoride resin.
Then, the manufacture method of the hollow form Porous hollow-fibre membrane of present embodiment is illustrated.
The Porous hollow-fibre membrane of present embodiment is formed preferably by non-solvent phase separation method.Non-solvent phase separation method refers to, the method utilizing the absorption of non-solvent (water etc.) and bringing out the porous being separated.
Utilize heat to bring out in the thermally induced phase separation being separated, owing to the transmission speed of heat is fast, thus be not easily formed the aperture of porous layer towards internal and cumulative structure.By electron beam irradiation, microparticle fill and/or extend and in the method for porous, in its method for making formed homogeneous texture.Relative to these technology, non-solvent phase separation method has the effect that non-solvent diffusion velocity internally is slow, thus easily forms the structure cumulative towards inside.
Specifically, the Porous hollow-fibre membrane of present embodiment can by manufacturing as follows: uses annular nozzle by the outer surface of resin-coated for the film formative of the material comprising porous layer and the solvent supporter at hollow form, make film formative resin bed, then make saturated steam (condition such as temperature sees below) contact with the surface of film formative resin bed, then utilize solidification liquid to solidify.
The manufacture device of present embodiment is illustrated.Figure 12 represents the manufacture device of present embodiment.The manufacture device 1g of present embodiment possesses spinning-nozzle 10, is arranged in the process container 20A in the downstream of spinning-nozzle 10, receives the coagulating basin 30 of solidification liquid B, the discharging surface 10a of spinning-nozzle is carried out the scavenging unit 40A of scavenging by scavenging gas.
(process container)
Process container 20A is: according to the gas of the non-solvent by including aforementioned films formative resin (hereinafter referred to as " process gas ".) carry out holding, make the mode contacted with process gas of the fibrillar A ' from spinning-nozzle 10 ejection carry out constituting thus the container that formed.
Non-solvent refers to herein, does not have (such as, at normal-temperature dissolution degree less than 1% mass) solvent of the ability of dissolving film formation resin under the reaction condition of this operation.As non-solvent, the mixture etc. of the good solvent used in the alcohols such as water, ethanol, acetone, toluene, ethylene glycol or water and film formative resin solution can be used.Wherein it particularly preferably is water.
The process container 20A used in the present embodiment is the cylinder of the sidepiece 23 with flat top 21, flat bottom 22 and cylindrical shape, form the 1st peristome 21a of importing fibrillar A ' at top 21, form the 2nd peristome 22a of importing fibrillar A ' in bottom 22.The peristome of the 1st peristome 21a and the 2nd peristome 22a is equal, or utilize heat buoyancy to suppress the process gas in process container 20A thus compared to the 2nd peristome 22a from the 1st peristome 21a situation about more flowing out, thus sometimes also can the opening diameter of the 2nd peristome 22a be increased the opening diameter compared to the 1st peristome 21a.It addition, the top of the liquid level of the 2nd peristome 22a solidification liquid B that is configured in coagulating basin 30.That is, in present embodiment, process container 20A separates with the solidification liquid B in coagulating basin, and the 2nd peristome 22a is not solidified liquid B blocking.
In this process with, in container 20A, importing fibrillar A ' from the 1st peristome 21a, the fibrillar A ' contacting the process gas in process container 20A exports to outside from the 2nd peristome 22a.
It addition, passed through the inside of process container 20A from the process gas of gas supply pipe 24 supply, then discharged by the 1st aperture portion 21a and the 2nd peristome 22a.
(scavenging unit)
Scavenging unit 40A is that it possesses the scavenging nozzle 41 of the discharging surface 10a being arranged on spinning-nozzle 10, supplies the gas feed unit 42 of scavenging gas to scavenging nozzle 41 according to flowing out that process gas near spinning-nozzle 10 carries out replacing with scavenging gas and the mode removed carries out constituting thus the gas removal unit that formed.
Scavenging nozzle 41 comprises the component of ring-type, possess: the circular open portion 41a of central authorities, it is connected to gas feed unit 42 and imports the gas formed by annulus of scavenging gas and import room 41b, import the annular gas ejiction opening 41c of scavenging gas of room 41b supply towards the discharging surface 10a of the spinning-nozzle 10 exposed in circular open portion 41a, ejection from gas.
About circular open portion 41a, the mode consistent with the center of the supporter ejiction opening of spinning-nozzle 10 and resin solution ejiction opening according to its center configures.Thus, fibrillar A ' is by circular open portion 41a.It is the outer circumferential side at circular open portion 41a that gas imports room 41b, forms concentric circles with scavenging nozzle 41.Gas vent 41c imports room 41b with gas and connects, and as shown in Figure 123, towards the center of circular open portion 41a, opening, thus is sprayed from the outer circumferential side of circular open portion 41a towards center by scavenging gas.
In present embodiment, the lower surface of the scavenging nozzle 41 in scavenging unit 40A, it is provided with the protection cylinder 50 protected for being covered by fibrillar A '.
Protection cylinder 50 is cylindrical structural member, forms through hole 50a.It addition, the upper end 51 of protection cylinder 50 is to be close to, according to through hole 50a and the circular open portion 41a of scavenging nozzle 41 mode connected, the lower surface being fixed on scavenging nozzle 41.The bottom 52 of protection cylinder 50 is to keep apart with process container 20A and arrange, and forms gap Q between protection cylinder 50 and disposal container 20A.
About the aperture area of the perforated area of through hole 50a and the peristome 52a of side, bottom 52, preferably little in can making the fibrillar A ' scope passed through non-contiguously.The sectional area of through hole 50a is more little, even if then the quantity delivered of scavenging gas is few, it is possible to accelerate flow velocity, it is possible to improve scavenging ability.It addition, the aperture area of the peristome 52a of side, bottom 52 is more little, then more can prevent from flowing in through hole 50a from the 1st peristome 21a process gas flowed out.
But, it is fast with Shangdi that scavenging gas is preferably, towards the flow velocity of the 1st peristome 21a, the amount of being not required from side, bottom 52, and it is little with Shangdi that the aperture area of the peristome 52a of side, bottom 52 is preferably the amount of being not required.Exceedingly fast towards the flow velocity of the scavenging gas of the 1st peristome 21a, or, when the aperture area of the peristome 52a of bottom 52 is exceedingly little, then have following possibility: scavenging gas is by invading in process container 20A in the 1st peristome 21a so that process with the temperature and humidity variation of the gas in container 20A.
The material of protection cylinder 50 is preferably not by the material from process container 20A effluent air corrosion and/or infringement.As the material meeting these requirements, list polyethylene, polypropylene, fluorine resin, rustless steel, aluminum, pottery or glass etc..It addition, about the material of protection cylinder 50, in order to suppress the scavenging gas because being flowing in through hole 50a heat radiation and/or, be derived from being heated of outside atmosphere and cause that the temperature of scavenging gas changes, thus preferably thermal conductivity is low.As the raw material that thermal conductivity is low, list polyethylene, polypropylene, fluorine resin, pottery or glass etc..Further; material as protection cylinder 50; in order to run in the guide the state of the fibrillar A ' of through hole 50a from external observation; thus it is preferably the high material of the transparency, it is particularly preferred to for the high polyethylene of the transparency, polypropylene that the transparency is high, the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resins (PFA) of fluorine resin that the transparency is high or glass.
Protection cylinder 50 is preferably and can load and unload relative to scavenging nozzle.When protection cylinder 50 is to load and unload, then owing to can take away from scavenging nozzle 41, thus hands is accessible near discharging surface 10a, can improve operability when masking starts.As handling unit, the mechanicalness handling unit such as threaded fastener and/or fixture or make use of Magnet and the handling unit of the magnet adsorption of the metal being adsorbed in Magnet is easy and is suitable for.
In present embodiment, pass through from the fibrillar A ' of spinning-nozzle 10 ejection in the through hole 50a of protection cylinder 50 after by gas vent 41c.
It addition, about from the gas vent 41c of the scavenging nozzle 41 scavenging gas sprayed, with fibrillar A ' concurrently, be flowing in by the fibrillar A ' in through hole 50a around from upper end 51 towards bottom 52.And, spray from through hole 50a towards from the 1st peristome 21a process gas flowed out.Thereafter, about scavenging gas, in the Q of gap, and from the 1st aperture portion 21a process flowed out with gas together, according to the 1st peristome 21a mode kept apart towards flows outside.
Utilize scavenging unit 40A, with scavenging gas by from the 1st peristome 21a process gas displacement flowed out, thus can remove near discharging surface 10a, thus the condensation of the discharging surface 10a caused by non-solvent can be prevented.Thus, the quality of the accurate control of the membrane superficial tissue of the Porous hollow-fibre membrane A obtained, the homogenization of membrane superficial tissue, Porous hollow-fibre membrane A can be improved.
Scavenging gas is preferably dry air.In present embodiment, dry air refers to the gas that relative humidity (vapour pressure relative to saturated vapour pressure) is 0～9%.Factory etc. is fed with the dry air that relative humidity at room temperature is about 1%, it is preferable that utilize gas temperature adjustment unit dry air to be adjusted to set point of temperature and becomes heat drying air, be supplied in scavenging nozzle 41.
(manufacture method of Porous hollow-fibre membrane)
The manufacture method of the Porous hollow-fibre membrane A employing above-mentioned manufacture device 1a is illustrated.This manufacture method has spinning process, scavenging operation, solidification operation.
[spinning process]
In spinning process in the present embodiment, while hollow rope form supporter A1 being sprayed downwards from the supporter ejiction opening of spinning-nozzle 10, while film formative resin solution being sprayed downwards from resin solution ejiction opening, thus the film A2 of the outer peripheral face formation film formative resin solution at hollow rope form supporter A1, thus making the fibrillar A ' of hollow.
Film formative resin solution generally comprises film formative resin and hydrophilic resin and the solvent dissolving them.Film formative resin solution comprises other adding ingredient also dependent on needs.Hydrophilic resin is in order to the viscosity of film formative resin solution is adjusted to the scope suitably forming hollow form Porous hollow-fibre membrane A, seeks the stabilisation of masking state and the material that adds, it is preferred to use Polyethylene Glycol or polyvinyl pyrrolidone etc..Among them, from the viewpoint of the pore size control of the hollow form Porous hollow-fibre membrane obtained and/or hollow form Porous doughnut film strength, it is preferred to by the copolymer making other monomer copolymerization obtain in polyvinyl pyrrolidone or polyvinyl pyrrolidone.
It addition, about hydrophilic resin, it is possible to undertaken mixing by resin of more than two kinds and use.Such as, as hydrophilic resin, when using the hydrophilic resin of more high molecular, then have the tendency easily forming the good hollow form Porous hollow-fibre membrane of membrane structure.On the other hand, about low-molecular-weight hydrophilic resin, from the viewpoint of it is preferred for be easier to from hollow form Porous hollow-fibre membrane A removing.Therefore, it is possible to according to purpose, by suitably blended for different for molecular weight hydrophilic resin of the same race and use.
As solvent, list DMF, N,N-dimethylacetamide, dimethyl sulfoxide, METHYLPYRROLIDONE or N-methylmorpholine-N-oxide etc., more than a kind in them can be used.Additionally, it is possible to not damaging film formative resin and/or hydrophilic resin to the deliquescent scope in solvent, undertaken mixing by the poor solvent of film formative resin and/or hydrophilic resin and/or non-solvent and use.
The temperature of film formative resin solution is not particularly limited, but is typically set to 20～40 DEG C.Film formative resin solution viscosity at 40 DEG C was preferably for 20,000～500,000 mPa seconds, more preferably 50,000～300,000 mPa seconds, more preferably 70,000～250,000 mPa second.When viscosity is too low, then phase separation speed increases, Ad and Bd becomes excessive and stalling characteristic reduction.On the other hand, the speed being then separated when viscosity is too high reduces, and not easily makes Bd be sufficiently above Ad.
Concentration about the film formative resin in film formative resin solution, cross thin or overrich, stability during masking tends to reduce, tend to not easily obtain the hollow form Porous hollow-fibre membrane of purpose, thus relative to the total quality of film formative resin solution, lower limit is preferably 10 mass %, more preferably 15 mass %.It addition, about the upper limit, be preferably 30 mass % relative to the total quality of film formative resin solution, more preferably 25 mass %.Specifically, resin is formed about film, relative to the total quality of film formative resin solution, it is also possible to be 10～30 such scopes of mass %, it is also possible to be preferably 15～25 such scopes of mass %.
On the other hand, about the lower limit of the concentration of hydrophilic resin, in order to be more readily formed hollow form Porous hollow-fibre membrane, thus it is preferably 1 mass % relative to the total quality of film formative resin solution, more preferably 5 mass %.About the upper limit of the concentration of hydrophilic resin, from the viewpoint of the handlability of film formative resin solution is preferably 20 mass % relative to the total quality of film formative resin solution, more preferably 12 mass %.Specifically, relative to the total quality of film formative resin solution, it is also possible to be 1～20 such scope of mass %, it is also possible to be preferably 5～20 such scopes of mass %.
Composition about film formative resin solution, if can be formed from porous layer A to structure cumulative for porous layer C by being separated, it is not particularly limited, but from the viewpoint of the surface percent opening of porous layer can be improved, preferably the ratio of solvent is set to for the total quality of film formative resin solution more than 68 mass %, is more preferably set to more than 70%.
Can form, further, since exist, the tendency not having big macroporous cumulative structure, thus the mass ratio of hydrophilic resin/film formative resin is preferably more than 0.45.During lower than this value, then have and easily form macroporous tendency, and tend to easily be formed without co-continuous structure and form island structure, result in the reduction of surface percent opening and/or the formation of homogeneous texture, not preferably.
[scavenging operation]
Scavenging operation in present embodiment is that scavenging gas is delivered to the operation of the discharging surface 10a of spinning-nozzle 10.
Specifically, in scavenging operation, first, utilize filtering unit 43 to be filtered by the scavenging gas supplied from gas feed unit 432, utilize gas conditioning unit 44 to adjust temperature and humidity, be then supplied in gas and import room 41b.Now, owing to being more possible to prevent the condensation of discharging surface 10a, thus preferably by gas conditioning unit 44, it is adjusted lower than the mode of the surface temperature of the discharging surface of spinning-nozzle 10 according to the dew point (dewpoint) making scavenging gas.It addition, want the temperature so that spinning-nozzle 10 and/or fibrillar A ' not from setting state change, it is preferable that the temperature of scavenging gas is set to the temperature identical with the design temperature of spinning-nozzle 10 and supplies.
Then, import room 41b at gas, by being arranged at the resistance imparting body 41d of gas vent 41c, the pressure distribution of scavenging gas is carried out homogenization.Then, by making the scavenging gas that gas imports in the 41b of room give body 41d by the resistance in gas vent 41c, spray towards the center of circular open portion 41a, thus scavenging gas is delivered to discharging surface 10a.About the scavenging gas sprayed from gas vent 41c, with fibrillar A ' concurrently, it is flowing in by the fibrillar A ' in through hole 50a around from upper end 51 towards bottom 52.And, from through hole 50a, spray towards from the 1st peristome 21a process gas flowed out.Thereafter, scavenging gas with the process from the 1st aperture portion 21a outflow with gas together, is discharged towards outside according to the 1st peristome 21a mode kept apart in the Q of gap.
In above-mentioned scavenging operation, make the surface temperature of the dew point deficiency spinning-nozzle 10 of non-solvent in the atmosphere near spinning-nozzle 10.When the dew point of the non-solvent in atmosphere near spinning-nozzle 10 becomes spinning-nozzle more than 10, then what condense prevents change difficulty.Herein, " dew point of the non-solvent in atmosphere " refers to: the amount of the non-solvent that atmosphere can comprise is consistent with the amount of the non-solvent comprised in this atmosphere, and when atmosphere temperature declines, the non-solvent becoming to completely include starts the temperature condensed.
Additionally, according to above-mentioned scavenging operation, owing to can more prevent condensation, thus preferably the relative humidity of the non-solvent in the atmosphere near spinning-nozzle is set to less than 10%, herein, " relative humidity of the non-solvent in atmosphere " refers to, utilizes in the atmosphere of a certain temperature saturated non-solvent amount × 100 of amount/this temperature of contained non-solvent and the value (unit: %) obtained.
[solidification operation]
Solidification operation is following operation: makes the film formative resin solution from spinning-nozzle 10 ejection contact with the process gas in process container 20A, is then immersed in the solidification liquid B in coagulating basin 30.
In solidification operation in the present embodiment, by making fibrillar A ' contact with the process gas in process container 20A and the solidification liquid B in coagulating basin 30, so that the film A2 of the film formative resin solution of fibrillar A ' solidifies, thus obtain Porous hollow-fibre membrane A.
Specifically, in spinning process, the fibrillar A ' of the film A2 of film formative resin solution will be defined, be directed in the inside of process container 20A from the 1st peristome 21a of process container 20A, thus contacting with process gas.In the film A2 contacted with process gas, non-solvent ingredients diffusion contained in process gas is immersed, and initiation is separated.
Herein, as process gas, list that non-solvent is in the air of saturation, non-solvent is in the saturated vapor of the air of unsaturated state, non-solvent, but in order to obtain the Porous hollow-fibre membrane of present embodiment, it is preferred to the saturated vapor of non-solvent.
It addition, when film formative resin is hydrophobic polymer, as non-solvent, the alcohols such as water, ethanol, acetone, toluene or ethylene glycol etc. can be used, but is particularly preferably water.
When process gas is the saturated vapor of non-solvent, all filled by non-solvent by the surrounding of the fibrillar A ' in process container 20A.Hereinafter, feature when being saturated steam under atmospheric pressure to process gas illustrates.
The temperature of the saturated steam under atmospheric pressure is about 100 DEG C, and the space become loaded with in the process container 20A of saturated steam is filled by 100% hydrone.Thus, when employing saturated steam as process gas, it is easy to make the atmosphere temperature of the surrounding of fibrillar A ' and humidity carry out homogenization.
It addition, saturated steam with other the gas containing moisture comparatively speaking, can increase the unit interval is supplied in the moisture by the fibrillar A ' in process container 20A and heat.It addition, the condensation heat when steam coagulation is extremely many, the efficiency of heating surface of condensation heat transfer is high, thus can the temperature near the top layer of fibrillar A ' be increased near 100 DEG C in moment.
Therefore, the moisture supply in condensing according to the saturated steam caused by the temperature difference with fibrillar A ', heat supply, can produce and make fibrillar A ' by the diverse action that is separated of the situation in the gas containing water with unsaturated state.
That is, utilize substantial amounts of moisture to supply so that film outer surface is advanced into solidification immediately via being separated, if thus that the viscosity of film formative resin solution is adjusted to comparison in advance is high, then can form, at film outer surface, the fine and close structure that be suitable to filter.And, substantial amounts of moisture spreads immediately and is immersed into inside film, is in the period in process container 20A at fibrillar A ', can cause until being separated of skin section of fibrillar A '.
Herein, owing to the temperature near the top layer of fibrillar A ' is increased near 100 DEG C, thus its phase separation speed is very fast, and the structure that the structure relative to porous layer A thus can be made sufficiently large is formed at the top layer more internal compared to for porous layer A.
Like this, by fixing at the process inside and outside surface texture of container 20A, until the fibrillar A ' that has been separated of ground, its internal top layer, it is then directed in coagulating basin 30 so that it is contact with solidification liquid B.Thus, the non-solvent ingredients diffusion of solidification liquid B is immersed in the inside of the film A2 of film formative resin solution.Owing to solidification liquid B is liquid, thus substantial amounts of non-solvent immerses hastily compared with saturated steam, thus solidifying via being separated to inside, thus making Porous hollow-fibre membrane A.
Solidification liquid B is the non-solvent of film formative resin, it is the good solvent of hydrophilic resin, enumerates water outlet, ethanol or methanol etc. and/or their mixture, but wherein, considering the aspect of safety, operation management, the solvent used in film formative resin solution and the mixed liquor of water are preferred.
When the solvent used in using film formative resin solution is with the mixed liquor of water, concentration about solvent, for the total quality of solvent and the mixed liquor of water, solvent is preferably the scope of 5～50% mass, more preferably the scope of 10～40% mass.During lower than this scope, then gathering way of non-solvent is accelerated sometimes, and internal structure becomes excessively fine and close sometimes.It addition, when exceeding this scope, then have and cannot immerse an adequate amount of non-solvent, in coagulating basin, solidify situation about being not fully complete.
The temperature of solidification liquid B is set to the scope of 30～95 DEG C, it is preferable that be set to 40～85 DEG C.The temperature making solidification liquid B is more than aforementioned minimum value, thus the water permeability of the hollow form Porous hollow-fibre membrane obtained uprises, by being set to below aforementioned higher limit, thus improving the film quality of the hollow form Porous hollow-fibre membrane obtained.
When employing the macromolecules such as polyvinyl pyrrolidone as hydrophilic resin, it is preferred that with hot wash Porous hollow-fibre membrane A, then carry out processing with the liquid containing oxidant and hydrophilic resin is decomposed, remove.
About the manufacture method of Porous hollow-fibre membrane of present embodiment and utilize its hollow-fibre membrane produced, it is possible to apply centered by the field that water processes.Such as, can be applicable to the manufacture method of the Porous hollow-fibre membrane of present embodiment and employ the method for clean water treatment of the hollow-fibre membrane utilizing it to produce and method that other water processes.It addition, about the manufacture method of Porous hollow-fibre membrane of present embodiment and utilize its hollow-fibre membrane produced, can be applicable to the purifier etc. possessing it in the structure, additionally can be used in the manufacture method of this purifier etc..
It is explained, in these purposes, the structure of above-mentioned embodiment appropriately respectively can be combined and use.
Embodiment
Further, present embodiment utilizes below example etc. to illustrate.
(graphical analysis)
About all physical property of multiple aperture plasma membrane, operate as described below and measure according to graphical analysis.
(1) the average pore size index of multiple aperture plasma membrane
About multiple aperture plasma membrane, use scanning electron microscope (SEM), section and surface are taken pictures, according to computer, the graphical analysis of its photo has been obtained the average pore size index on internal structure and surface.About the average pore size index obtained by graphical analysis, there are the image quality adjustment caused due to graphical analysis, image analysis software to there is also a little variation, but its difference is in the scope of common experimental error.
The outer surface of the multiple aperture plasma membrane for obtaining, is scanned type ultramicroscope (SEM) and observes.When multiple aperture plasma membrane is Porous hollow-fibre membrane, it is stipulated that the datum mark of Porous doughnut film outer surface, it is set to 0 ° of position, from 90 °, 180 ° and 270 ° of this 4 direction shooting SEM photograph.About observing multiplying power, depend on desired retaining aperture thus cannot treat different things as the same, but be 10,000～100 when secondary filter film, 000 times.Having following possibility when deviate from such scope: cannot observe the aperture of outer surface below 5000 times fully, when becoming more than 100,0000 times, then the quantity in the hole in the visual field tails off, it is difficult to say it is average aperture.The diameter in hole image analysis software identified is set to aperture, the aperture of all well in calculating SEM photograph, calculates pore size index according to its meansigma methods, evaluates the surface of multiple aperture plasma membrane or the structure of section with it quantitatively.Herein, for all well calculated, the mode becoming descending by area arranges data, integrating area from the hole outranked, use with relative to entire area be arbitrary ratio 50% quite when till hole, calculate pore size index.Such as, it does not have limit, but be set to this arbitrary ratio A.
(2) percent opening of multiple aperture plasma membrane
For the SEM photograph of multiple aperture plasma membrane, use above-mentioned graphical analysis to measure the area in hole, obtained the percent opening of multiple aperture plasma membrane.
Percent opening (%)=utilize graphical analysis and membrane area in the visual field in the area sum/SEM photograph of all well that identifies
(external diameter of supporter)
The external diameter of supporter, is determined by following method.
The sample of mensuration is cut to about 10cm, carries out harness by several, with polyurethane resin, entirety is covered.Polyurethane resin is also into the hollow bulb of supporter.
After curable urethane resin, razor blade is used to sample the thin slice of thickness (length direction of film) about 0.5mm.
Then, the section of the supporter for having sampled, use scialyscope (NikonCorporation (ニ コン society) system, PROFILEPROJECTORV-12), utilize object lens 100 to observe again.
Mark (line) is aligned in the position of the outer surface of the observed X-direction of supporter section, Y-direction, have read external diameter value.Measured 3 times and obtained the meansigma methods of external diameter.
(internal diameter of supporter)
The internal diameter of supporter, is determined by following method.
For the sample measured, the method same with the sample measuring external diameter is utilized to sample.
Then, the section to the supporter sampled, use scialyscope (NikonCorporation system, PROFILEPROJECTORV-12), utilize object lens 100 to observe again.
Mark (line) is aligned in the position of the inner surface of the observed X-direction of supporter section, Y-direction, have read inner diameter values.Measured 3 times and obtained the meansigma methods of internal diameter.
(external diameter of Porous hollow-fibre membrane)
The external diameter of Porous hollow-fibre membrane is determined by following method.
The sample of mensuration is cut to about 10cm, carries out harness by several, with polyurethane resin, entirety is covered.Polyurethane resin is also into the hollow bulb of supporter.
After curable urethane resin, razor blade is used to sample the thin slice of thickness (length direction of film) about 0.5mm.
Then, the section of the Porous hollow-fibre membrane for having sampled, use scialyscope (NikonCorporation system, PROFILEPROJECTORV-12), utilize object lens 100 to observe again.
Mark (line) is aligned in the position of the outer surface of the observed X-direction of Porous hollow-fibre membrane section, Y-direction, have read external diameter value.Measured 3 times and obtained the meansigma methods of external diameter.
(internal diameter of Porous hollow-fibre membrane)
The internal diameter of Porous hollow-fibre membrane is determined by following method.
For the sample measured, the method same with the sample determining external diameter is utilized to sample.
Then, the section of the Porous hollow-fibre membrane for having sampled, use scialyscope (NikonCorporation system, PROFILEPROJECTORV-12), utilize object lens 100 to observe again.
Mark (line) is aligned in the position of the supporter inner surface of the observed X-direction of Porous hollow-fibre membrane section, Y-direction, have read inner diameter values.Measured 3 times and obtained the meansigma methods of internal diameter.
(thickness of Porous rete)
The thickness of the Porous rete in embodiment etc. is the thickness from the surface of supporter to the surface of Porous hollow-fibre membrane, is determined by following method.
For the sample measured, the method same with the sample determining external diameter is utilized to sample.
Then, for the section of the Porous hollow-fibre membrane of sampling, use scialyscope (NikonCorporation system, PROFILEPROJECTORV-12), utilize object lens 100 to observe again.
Mark (line) is aligned in the outer surface of the thickness of position, direction and the position of inner surface during the 3 of observed Porous hollow-fibre membrane section, reads thickness.Similarly, according to 9 direction time, 12 time direction, 6 time the order in direction and read thickness.Measured 3 times and obtained the meansigma methods of internal diameter.
(aperture of Porous rete)
The aperture of porous layer, is determined by following method.
Use scanning electron microscope with multiplying power 10,000 times to wanting that the cross section structure measured shoots, obtain the average pore size index of this structure by the photo obtained is carried out image analysis processing.As image analysis processing software, employ the IMAGE-PROPLUSversion5.0 of MediaCybernetics company.
(water permeability of Porous hollow-fibre membrane)
The water permeability of Porous hollow-fibre membrane, is determined by following method.
The sample of mensuration is cut to 4cm, utilizes polyurethane resin to be sealed by the hollow bulb of one end face.
Then, sample is reduced pressure in ethanol more than 5 minutes, be then dipped in pure water and replace.
Add pure water (25 DEG C) to container, utilize the other end of tubule and sample to link, container is applied the air pressure of 200kPa, the amount from sample pure water out is determined 1 minute.Measured 3 times and obtained meansigma methods.By this numerical value surface area divided by sample, it is set to water permeability.
(stalling characteristic of Porous hollow-fibre membrane)
About the stalling characteristic of Porous hollow-fibre membrane, emit Vesicular protein (バ Block Le Port イ Application ト method) according to utilization and evaluated according to the JISK3832 maximum diameter of hole obtained.It is set to ethanol measure medium and be measured.
(average pore size index, aperture opening ratio)
About average pore size index, use SEM photograph (30,000 times) and Planetron, Inc. ((strain) プ ラ ネ ト ロ Application) Image-ProPlus processed carry out graphical analysis, obtained the average pore size index of outer surface photo observed from all directions.About average pore size index and aperture opening ratio, calculate according to following a series of each operation.
Operation (1)
Observe the section surfaces of Porous hollow-fibre membrane with SEM, measure the area in the aperture of all well caught by electron micrograph.
Operation (2)
The mode that the aperture calculated in operation (1) becomes descending by area is arranged data, from the hole outranked, area is carried out integrating, hole till when using and being suitable relative to the special ratios B (50%) of entire area, for its area, hole is considered as positive round, its diameter (aperture) is set to average pore size index thus calculating.
(embodiment 1)
Strengthen supporter yarn as hollow, employ polyester fiber (polyethylene terephthalate (PET), fiber number: 84dtex, long filament number (filamentnumber): 36, false twisting (falsetwisting) yarn).The bobbin used during about on the make empty enhancing supporter, prepare the bobbin of 5 spooling polyester fiber 5kg, as circle volume machine (ball), employ desk-top braiding machine (tall and erect mo(u)ld top half) (Yuan Jing fibre machinery company system, knitwear (meias) pin number: 12, pin size: 16 pin numbers (gauge, ゲ ジ), spindle circle diameter: 8mm).As rope feedway and collection apparatus, employ Nelson roller (Nelsonroll, ネ Le ソ Application ロ Le).As heating mouth die, employ the mouth die (outer diameter D: 5mm, internal diameter d:2.5mm, length L:300mm) of the stainless steel with heating unit.
5, the polyester fiber pulled out from bobbin is carried out closes yarn and becomes 1 (total fiber number；420dtex), circle volume machine is then utilized to carry out justifying volume and having weaved into hollow form sennit.Make this hollow form sennit by the heating mouth die of 210 DEG C, heat treated hollow form sennit will have been carried out and has been set to hollow enhancing supporter, and use devices for taking-up to batch with coiling speed 200m/ hour.
It is about 2.5mm that the hollow obtained strengthens the external diameter of supporter, and internal diameter is about 1.7mm.The quantity of ring (loop) constituting hollow form marshalling (hollow form) that hollow strengthens supporter is, every 1 week 12, the maximum open width weaving eye is about 0.1mm.It is 12000m that hollow strengthens the length of supporter.
By polyvinylidene fluoride (Arkema company (ア Le ケ マ society) system, trade name；Kynar (カ イ Na) 301F) 11.5 mass %, polyvinylidene fluoride (Arkema company system, trade name；Kynar9000LD) 11.5 mass % and polyvinyl pyrrolidone (catalyst company of Japan system, trade name；K-80) 12 mass % stir while being dissolved in N,N-dimethylacetamide 65 mass %, have modulated the 1st film formative resin solution.1st film formative resin solution viscosity at 40 DEG C was 210,000 mP seconds.
By polyvinylidene fluoride (Arkema company system, trade name；Kynar301F) 19 mass % and polyvinyl pyrrolidone (catalyst company of Japan system, trade name；K-80) 10 mass % stir while being dissolved in N,N-dimethylacetamide 71 mass %, have modulated the 2nd film formative resin solution.2nd film formative resin solution viscosity at 40 DEG C was 130,000 mP seconds.
Then, the manufacture device shown in Figure 12 is used to manufacture Porous hollow-fibre membrane.It is explained, in this example, as spinning-nozzle, employ the multiple annular nozzle of the resin solution stream (the 1st resin solution stream, the 2nd resin solution stream) being formed with supporter through hole and 2 kinds of film formative resin solutions that hollow enhancing supporter can be made to pass through.Lower surface at this spinning-nozzle forms supporter ejiction opening, the 1st resin solution ejiction opening and the 2nd resin solution ejiction opening.
(manufacture of Porous hollow-fibre membrane)
Above coagulating basin, it is configured with process container according to the mode with the gap of solidification liquid level formation 10mm.About process container and protection cylinder, configure according to the mode in the gap forming 5mm between lower ending opening portion and the 1st peristome of process container of protection cylinder.About scavenging nozzle, configure according to by the mode of its upper surface Yu the lower surface bonds of spinning-nozzle.
In scavenging nozzle, with 6L/ minute supplying temperature 32 DEG C and the relative humidity dry air less than 1%.In process container, for giving the saturated steam of 100 DEG C as process gas.Quantity delivered about steam, when dry air was supplied in scavenging nozzle with 6L/ minute, while monitoring the temperature of the thermocouple of the diameter 0.5mm inserting internal 5mm from the 1st peristome, bit by bit open flow rate regulating valve on one side, be set as the lower limit flow making electric thermo-couple temperature stablize more than 10 minutes at 100 DEG C.When this have adjusted, the steam sprayed from flow rate regulating valve carrying out cooling liquid, measure the quality of the draining obtained in the unit interval, be scaled the steam volume of 100 DEG C, result corresponds approximately to 5NL/ minute.
Coagulating basin becomes loaded with the solidification liquid of following composition: as the DMAC N,N' dimethyl acetamide of solvent composition be 10 mass %, pure water as non-solvent ingredients be 90 mass %.Coagulating basin is 75 DEG C of insulations.
In spinning-nozzle, with 23.2cm3/ minute quantity delivered supply the film formative resin solution 1 of 32 DEG C, with 25.0cm3/ minute quantity delivered supply the film formative resin solution 2 of 32 DEG C.Then, spray from resin solution ejiction opening by film formative resin solution 1 and film formative resin solution 2 concentric circles, be coated with film formative resin solution 1,2 from supporter ejiction opening with the hollow form sennit supporter outer peripheral face of pull-out in 20m/ minute.Thus, it is thus achieved that be coated with the fibrillar A ' of film formative resin solution at hollow form sennit supporter.This fibrillar A ' is made to pass sequentially through scavenging nozzle, process container, solidification liquid, it is thus achieved that Porous hollow-fibre membrane.
The Porous hollow-fibre membrane obtained is made to have carried out desolventizing by the hot water 1 minute in 98 DEG C.Then, it is immersed in the aqueous sodium hypochlorite solution of 30,000mg/L, then heat treated 2 minutes in the steam groove of 98 DEG C.Then, wash 15 minutes in the hot water of 98 DEG C, dried 10 minutes at 110 DEG C, then batched, thus obtaining Porous hollow-fibre membrane.
For the Porous hollow-fibre membrane obtained, with SEM amplifying observation by using liquid nitrogen to carry out section that is freezing sliding disconnected and that obtain, have taken photo.For the photo obtained, use Image-ProPlus (Planetron, Inc. system) to carry out graphical analysis, calculated the average pore size of each layer.Result is shown in table 1.
(embodiment 2)
As the 1st and the 2nd film formative resin solution, use by by polyvinylidene fluoride (Arkema company system, trade name Kynar761A) 19 mass % and polyvinyl pyrrolidone (catalyst company of Japan system, trade name K-80) quality 12% stirs while being dissolved in N, N-dimethyl acetylamide 69 mass % and the film formative resin solution that obtains, as solidification liquid, use N, N-dimethyl acetylamide is 20% mass, solidification liquid as the composition that pure water is 80% mass of non-solvent ingredients, in addition, operate similarly to Example 1 and obtain Porous hollow-fibre membrane.
This film formative resin solution viscosity at 40 DEG C was 250,000 mP seconds.
It addition, for the Porous hollow-fibre membrane obtained, calculated the average pore size of each layer similarly to Example 1.Result is shown in table 1.
(embodiment 3)
As the 1st and the 2nd film formative resin solution, use by by polyvinylidene fluoride (Arkema company system, trade name Kynar761A) 15 mass % and polyvinyl pyrrolidone (catalyst company of Japan system, trade name K-80) 11 mass % stir while being dissolved in N, N-dimethyl acetylamide 74 mass % and the film formative resin solution that obtains, in addition, operate similarly to Example 1 and obtain Porous hollow-fibre membrane.
This film formative resin solution viscosity at 40 DEG C was 80,000 mP seconds.
It addition, for the Porous hollow-fibre membrane obtained, calculated the average pore size of each layer similarly to Example 1.Result is shown in table 1.
(comparative example 1)
Employ identical with embodiment 1 the 1st, the 2nd film formative resin solution.
Coagulating basin becomes loaded with the solidification liquid of following composition: as the DMAC N,N' dimethyl acetamide of solvent composition be 8 mass %, pure water as non-solvent ingredients be 92 mass %.Coagulating basin is incubated at 70 DEG C.
In spinning-nozzle, with 17.4cm3/ minute quantity delivered supply the film formative resin solution 1 of 32 DEG C, with 18.7cm3/ minute quantity delivered supply the film formative resin solution 2 of 32 DEG C.Then, spray from resin solution ejiction opening by film formative resin solution 1 and film formative resin solution 2 concentric circles, be coated with film formative resin solution 1,2 from supporter ejiction opening with the hollow form sennit supporter outer peripheral face of pull-out in 15m/ minute.Thus, it is thus achieved that be coated with the fibrillar A ' of film formative resin solution at hollow form sennit supporter.
The hot and humid atmosphere formation cover that the fibrillar A ' obtained is directed in the steam that inside becomes loaded with solidification liquid (temperature 70 C) is interior thus having carried out hot and humid process.Now, the distance walked in the fibrillar A ' hot and humid atmosphere in hot and humid atmosphere formation is covered is 67mm.
Then so that carried out the fibrillar A ' of hot and humid process by the solidification liquid (temperature 70 C) in coagulating basin.Thus, the outer peripheral face at fibrillar A ' adheres to solidification liquid, so that the film of film formative resin solution solidifies, it is thus achieved that Porous hollow-fibre membrane.
For the Porous hollow-fibre membrane obtained, washing is dry similarly to Example 1.
It addition, for the Porous hollow-fibre membrane obtained, calculated the average pore size of each layer similarly to Example 1.
Result is shown in table 1.
(comparative example 2)
For GE company Porous hollow-fibre membrane (ZeeWeed500), calculate the average pore size of each layer similarly to Example 1.Result is shown in table 1.
(comparative example 3)
KubotaCorporation (Co., Ltd. Network ボ タ) is made to the Porous hollow-fibre membrane of (510 type), calculated the average pore size of each layer similarly to Example 1.Result is shown in table 1.
Table 1
< filters and evaluates >
Use the Porous hollow-fibre membrane obtained by embodiment 1～3 and comparative example 1 to make module respectively, use the activated sludge water of MLSS (suspended solid concentration)=9000mg/L, within 10 DEG C, filtration flow-rate 1.0m/ days, filtered with water temperature.
Its result, in the module employing the Porous hollow-fibre membrane of comparative example 1 and make, after operating 2 days, filtration pressure difference significantly increases, relative to this, in the module employing the Porous hollow-fibre membrane of embodiment 1～3 and make, filtration pressure difference does not find big change, can stably operate.
< reference example 1 >
(manufacture of Porous hollow-fibre membrane)
Porous doughnut film manufacturing device is used to manufacture Porous hollow-fibre membrane 1.
By polyvinylidene fluoride A (Arkema company system, trade name: Kynar761A), polyvinylidene fluoride B (Arkema company system, trade name: Kynar301F), polyvinylidene fluoride C (Arkema company system, trade name: Kynar9000LD), polyvinyl pyrrolidone (Japan's catalyst company system, trade name: K-80) and N, N-dimethyl acetylamide mixes according to the mode becoming the mass ratio shown in table 2, has modulated masking stock solution (1) and (5).
Film speed be 20m/min, 100% steam key area length be 5mm, coagulating bath (coagulationbath) temperature be 75 DEG C when, masking stock solution (1) plyability is coated outer layer, masking stock solution (5) plyability is coated internal layer, carries out masking.
The external diameter of the Porous hollow-fibre membrane 1 obtained is about 2.80mm, and internal diameter is about 1.2mm, the thickness average out to of Porous rete 11 about 150 μm, emits bubble point (bubblepoint) (Pi) 210kPa, water permeability is 49m3/m2/ h/MPa.Surface percent opening A1 is 40%, and pore size index P1 is 0.21 μm.The percent opening A2 of internal most compacted zone is 27%, and pore size index P2 is 0.46 μm.
Filter operating condition about MBR, implement filtration test under the conditions shown in Table 4.
< reference example 2 >
(manufacture of Porous hollow-fibre membrane)
Use Porous doughnut film manufacturing device, manufacture Porous hollow-fibre membrane 2 in the same manner as reference example 1.
By polyvinylidene fluoride A (Arkema company system, trade name: Kynar761A), polyvinylidene fluoride B (Arkema company system, trade name: Kynar301F), polyvinylidene fluoride C (Arkema company system, trade name: Kynar9000LD), polyvinyl pyrrolidone (Japan's catalyst company system, trade name: K-80) and N, N-dimethyl acetylamide mixes according to the mode becoming the mass ratio shown in table 2, has modulated masking stock solution (2) and (5).
Film speed be 20m/Min, 100% steam key area length be 5mm, coagulation bath temperature be 75 DEG C when, masking stock solution (2) plyability is coated outer layer, masking stock solution (5) plyability is coated internal layer, carries out masking.
The external diameter of the Porous hollow-fibre membrane 2 obtained is about 2.80mm, and internal diameter is about 1.2mm, the thickness average out to of Porous rete 11 about 150 μm, and emitting bubble point (Pi) is 197kPa, and water permeability is 49m3/m2/ h/MPa.Surface percent opening A1 is 41%, and pore size index P1 is 0.23 μm.The percent opening A2 of internal most compacted zone is 23%, and pore size index P2 is 0.45 μm.
< reference example 3 >
(manufacture of Porous hollow-fibre membrane)
Use Porous doughnut film manufacturing device, manufacture Porous hollow-fibre membrane 3 in the same manner as reference example 1.
By polyvinylidene fluoride A (Arkema company system, trade name: Kynar761A), polyvinylidene fluoride B (Arkema company system, trade name: Kynar301F), polyvinylidene fluoride C (Arkema company system, trade name: Kynar9000LD), polyvinyl pyrrolidone (Japan's catalyst company system, trade name: K-80) and N, N-dimethyl acetylamide mixes according to the mode becoming the mass ratio shown in table 2, has modulated masking stock solution (3) and (5).Film speed be 20m/Min, 100% steam key area length be 5mm, coagulation bath temperature be 75 DEG C when, masking stock solution (3) plyability is coated outer layer, masking stock solution (5) plyability is coated internal layer, carries out masking.
The external diameter of the Porous hollow-fibre membrane 3 obtained is about 2.80mm, and internal diameter is about 1.2mm, the thickness average out to of Porous rete 11 about 150 μm, emits bubble point (Pi) 164kPa, and water permeability is 98m3/m2/ h/MPa.Surface percent opening A1 is 45%, and pore size index P1 is 0.31 μm.The percent opening A2 of internal most compacted zone is 25%, and pore size index P2 is 0.67 μm.
< reference example 4 >
(manufacture of Porous hollow-fibre membrane)
Use Porous doughnut film manufacturing device, manufacture Porous hollow-fibre membrane 4 in the same manner as reference example 1.
By polyvinylidene fluoride B (Arkema company system, trade name: Kynar301F), polyvinylidene fluoride C (Arkema company system, trade name: Kynar9000LD), polyvinyl pyrrolidone (Japan's catalyst company system, trade name: K-80) and N, N-dimethyl acetylamide mixes according to the mode becoming the mass ratio shown in table 2, has modulated masking stock solution (4) and (5).
Film speed be 20m/min, 100% steam key area length be 5mm, coagulation bath temperature be 75 DEG C when, masking stock solution (4) plyability is coated outer layer, masking stock solution (5) plyability is coated internal layer, thus having carried out masking.
The external diameter of the Porous hollow-fibre membrane 4 obtained is about 2.80mm, and internal diameter is about 1.2mm, the thickness average out to of Porous rete 11 about 150 μm, emits bubble point (Pi) 91kPa, and water permeability is 168m3/m2/ h/MPa.Surface percent opening A1 is 50%, and pore size index P1 is 0.36 μm.The percent opening A2 of internal most compacted zone is 26%, and pore size index P2 is 1.1 μm.
Table 2
| Composition (quality %) | Molding stock solution (1) | Molding stock solution (2) | Molding stock solution (3) | Molding stock solution (4) | Molding stock solution (5) |
| Polyvinylidene fluoride A | 20 | 20 | 15 | 0 | 0 |
| Polyvinylidene fluoride B | 0 | 0 | 0 | 20 | 18 |
| Polyvinylidene fluoride C | 0 | 0 | 0 | 0 | 18 |
| Polyvinyl pyrrolidone | 13 | 10.5 | 10.5 | 10.5 | 18 |
| DMAC N,N' dimethyl acetamide | 73.5 | 73.5 | 73.5 | 73.5 | 99 |
Table 3
Table 4
| Flow | (m/d) | 1 |
| Full treating capacity | (m3/d) | (film for the treatment of capacity adjustment also operates) |
| HRT | (hr.) | 6 |
| Tank volume | (m3) | 0.15 |
| Water temperature sets | (℃) | 10 |
| Filtration cycle On/Off | (min.) | 7/1 |
| Aeration linear velocity | (m/hr) | 150 |
| Target MLSS concentration | (mg/L) | 8,000-10,000 |
< is with reference to comparative example 1 >
(manufacture of Porous hollow-fibre membrane)
Porous doughnut film manufacturing device is used to manufacture Porous hollow-fibre membrane 5.
By polyvinylidene fluoride B (Arkema company system, trade name: Kynar301F), polyvinylidene fluoride C (Arkema company system, trade name: Kynar9000LD), polyvinyl pyrrolidone (Japan's catalyst company system, trade name: K-80) and N, N-dimethyl acetylamide mixes according to the mode becoming the mass ratio shown in table 2, has modulated masking stock solution (4) and (5).When film speed to be 12.5m/min, high humidity high-temperature region length be 63.5mm, coagulation bath temperature are 75 DEG C, masking stock solution (4) plyability is coated outer layer, masking stock solution (5) plyability is coated internal layer, carries out masking.
The external diameter of the Porous hollow-fibre membrane 4 obtained is about 2.80mm, and internal diameter is about 1.2mm, the thickness average out to of Porous rete 11 about 150 μm, emits bubble point (Pi) 170kPa, and water permeability is 46m3/m2/ h/MPa.Surface percent opening A1 is 26%, and pore size index P1 is 0.17 μm.The percent opening A2 of internal most compacted zone is 5%, and pore size index P2 is 0.13 μm.
Industrial applicability
According to present embodiment, a kind of Porous hollow-fibre membrane and its evaluation methodology can be provided, this Porous hollow-fibre membrane can be applicable to the process of the various aqueous fluids such as clean water treatment, drinking water treatment, seawater clearing, while have excellence retain characteristic, permeability, while suppressing performance by the time to reduce, based on the restorative excellence of the membrance separation characteristic of washing.
The Porous hollow-fibre membrane of present embodiment makes following structure: relative to the aperture of the layer forming outer surface, the aperture of its internal layer is sufficiently large, not easily stifled eye.Therefore, the filtration stability of the hollow form Porous hollow-fibre membrane of present embodiment is high, it is preferable that be used as during the water such as the clean water treatment based on secondary filter, ultrafiltration etc. process the filter membrane used.
Claims (19)
1. a Porous hollow-fibre membrane, it is the Porous hollow-fibre membrane at least at outer surface with porous layer, wherein, in the cross section structure of the thickness direction of described Porous hollow-fibre membrane, from outer surface to the degree of depth, the average pore size Ad of the 1 μm ratio Ad/Bd relative to the average pore size Bd from the degree of depth 2 μm to 3 μm is less than 0.6.
2. Porous hollow-fibre membrane according to claim 1, wherein, the average pore size P1 of described outer surface is 0.05～1.0 μm, and percent opening A1 is 15～65%.
3. Porous hollow-fibre membrane according to claim 1 and 2, wherein, the average pore size P2 of the layer of 10 μm from outer surface to the degree of depth in described cross section structure is 0.1～5.0 μm, and percent opening A2 is 10～50%.
4. the Porous hollow-fibre membrane according to any one of claims 1 to 3, wherein, the structure from described outer surface to the degree of depth 5 μm is that aperture is directed away from the direction of outer surface and cumulative three-dimensional mesh structure.
5. the Porous hollow-fibre membrane according to any one of Claims 1 to 4, wherein, from described outer surface to the average pore size of the porous layer of the degree of depth 5 μm less than being present in than 5 μm of average pore sizes further from the porous layer at the position of described outer surface of the degree of depth.
6. the Porous hollow-fibre membrane according to any one of Claims 1 to 5, wherein, being present in than 5 μm of average pore sizes further from the porous layer at the position of described outer surface of the degree of depth is less than 10 μm.
7. the Porous hollow-fibre membrane according to any one of claim 1～6, wherein, substantially constitutes and is formed by the thermoplastic resin of same compound from described outer surface to the thermoplastic resin of 5 μm of these parts of the degree of depth.
8. the Porous hollow-fibre membrane according to any one of claim 1～7, wherein, in the porous layer at the position 10 μm farther unlike the degree of depth from described outer surface, without the aperture macrovoid more than 10 μm and a macroporous part.
9. the Porous hollow-fibre membrane according to any one of claim 1～8, it is formed by phase separation method.
10. the Porous hollow-fibre membrane according to any one of claim 1～9, wherein, described porous layer is formed at the outer surface side of the supporter of hollow fiber.
11. Porous hollow-fibre membrane according to claim 10, wherein, the supporter of described hollow fiber is to have passed through heat treated supporter.
12. the Porous hollow-fibre membrane according to claim 10 or 11, wherein, the supporter of described hollow fiber is hollow sennit.
13. the Porous hollow-fibre membrane according to claim 11 or 12, wherein, supporter is the hollow sennit obtained by being undertaken formed by multi-filament 1 one thread justifying volume.
14. the manufacture method of a Porous hollow-fibre membrane, it is by spraying the film formative resin solution comprising thermoplastic resin and hydrophilic compounds from spinning-nozzle, then make the film formative resin solution of described ejection is that the saturated vapor of non-solvent contacts for the composition relative to film formative resin solution, being immersed in solidification liquid afterwards makes it solidify thus making Porous hollow-fibre membrane, wherein
Described spinning-nozzle is 1 weight or dual above tubular nozzle, and in described Porous hollow-fibre membrane, at least from outer surface to the degree of depth, the position of 5 μm is formed with identical film formative resin solution.
15. the manufacture method of Porous hollow-fibre membrane according to claim 14, wherein, the saturated vapor of described non-solvent is saturated steam.
16. the manufacture method of the Porous hollow-fibre membrane according to claims 14 or 15, wherein, use spinning-nozzle, at the outer peripheral face coated film formative resin solution of hollow form supporter and make film formative resin bed, described film formative resin bed is then made to contact with the saturated vapor of non-solvent.
17. the manufacture method of Porous hollow-fibre membrane according to claim 16, it is characterised in that described supporter uses and have passed through heat treated supporter.
18. the manufacture method of the Porous hollow-fibre membrane according to claim 16 or 17, it is characterised in that described supporter is sennit.
19. the manufacture method of the Porous hollow-fibre membrane according to claim 17 or 18, wherein, described supporter is the hollow form sennit obtained by being undertaken formed by multi-filament 1 one thread justifying volume.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013193213 | 2013-09-18 | ||
| JP2013193214 | 2013-09-18 | ||
| JP2013-193213 | 2013-09-18 | ||
| JP2013-193214 | 2013-09-18 | ||
| PCT/JP2014/074680 WO2015041286A1 (en) | 2013-09-18 | 2014-09-18 | Porous hollow fiber membrane and method for manufacturing same |
Publications (1)
| Publication Number | Publication Date |
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| CN105722585A true CN105722585A (en) | 2016-06-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201480061790.2A Pending CN105722585A (en) | 2013-09-18 | 2014-09-18 | Porous hollow fiber membrane and method for manufacturing same |
Country Status (4)
| Country | Link |
|---|---|
| JP (2) | JP6020592B2 (en) |
| KR (1) | KR101826451B1 (en) |
| CN (1) | CN105722585A (en) |
| WO (1) | WO2015041286A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110382095A (en) * | 2017-02-28 | 2019-10-25 | 东丽株式会社 | Composite hollow fiber membrane and its manufacturing method |
| CN112672814A (en) * | 2018-09-20 | 2021-04-16 | 住友电气工业株式会社 | Hollow fiber membrane |
| CN114981001A (en) * | 2020-01-28 | 2022-08-30 | 东丽株式会社 | Method for filtering oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108579461A (en) * | 2013-10-11 | 2018-09-28 | 三菱化学株式会社 | Hollow porous membranes |
| JP6638276B2 (en) * | 2015-09-15 | 2020-01-29 | 三菱ケミカル株式会社 | Method for producing porous hollow fiber membrane |
| EP3409346A4 (en) | 2016-01-29 | 2019-09-25 | Toray Industries, Inc. | Separation membrane |
| JP6767141B2 (en) * | 2016-03-23 | 2020-10-14 | 旭化成株式会社 | Polyvinylidene fluoride porous membrane and its manufacturing method |
| EP3473331A4 (en) | 2016-06-17 | 2019-11-20 | Asahi Kasei Kabushiki Kaisha | Porous membrane, and method for manufacturing porous membrane |
| JP2018012058A (en) * | 2016-07-20 | 2018-01-25 | 三菱ケミカル株式会社 | Porous film |
| WO2018021545A1 (en) * | 2016-07-29 | 2018-02-01 | 東レ株式会社 | Separation membrane and production process therefor |
| JP7182960B2 (en) * | 2017-09-07 | 2022-12-05 | 旭化成株式会社 | SOY SAUCE MANUFACTURING METHOD USING POROUS MEMBRANE |
| JP7204382B2 (en) * | 2017-09-07 | 2023-01-16 | 旭化成株式会社 | SOY SAUCE MANUFACTURING METHOD USING POROUS MEMBRANE |
| KR102412426B1 (en) * | 2020-10-29 | 2022-06-23 | 서울대학교산학협력단 | Manufacturing method of growth body and the growth body manufactured thereby |
| KR102316399B1 (en) * | 2021-05-27 | 2021-10-22 | 김기영 | Sand core assembly automation system |
| WO2023276614A1 (en) * | 2021-06-28 | 2023-01-05 | 旭化成株式会社 | Forward osmosis membrane and forward osmosis membrane module including same |
| WO2023074670A1 (en) * | 2021-10-29 | 2023-05-04 | 株式会社クラレ | Porous membrane and method for manufacturing porous membrane |
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| CN110382095A (en) * | 2017-02-28 | 2019-10-25 | 东丽株式会社 | Composite hollow fiber membrane and its manufacturing method |
| US11369925B2 (en) | 2017-02-28 | 2022-06-28 | Toray Industries, Inc. | Composite hollow-fiber membrane and production method therefor |
| CN112672814A (en) * | 2018-09-20 | 2021-04-16 | 住友电气工业株式会社 | Hollow fiber membrane |
| CN112672814B (en) * | 2018-09-20 | 2022-08-02 | 住友电气工业株式会社 | Hollow fiber membrane |
| CN114981001A (en) * | 2020-01-28 | 2022-08-30 | 东丽株式会社 | Method for filtering oil |
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| CN114981001B (en) * | 2020-01-28 | 2024-02-27 | 东丽株式会社 | Method for filtering oil |
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| Publication number | Publication date |
|---|---|
| WO2015041286A1 (en) | 2015-03-26 |
| JPWO2015041286A1 (en) | 2017-03-02 |
| KR20160044582A (en) | 2016-04-25 |
| KR101826451B1 (en) | 2018-02-06 |
| JP6020592B2 (en) | 2016-11-02 |
| JP2016196004A (en) | 2016-11-24 |
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