JP2008178869A - Fiber-reinforced type hollow fiber membrane - Google Patents
Fiber-reinforced type hollow fiber membrane Download PDFInfo
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Abstract
Description
本発明は、透水性能が優れた繊維強化型中空糸膜に関する。 The present invention relates to a fiber-reinforced hollow fiber membrane having excellent water permeability.
中空糸多孔質膜は、一般に紡糸原液（液状製膜組成物）となるポリマー溶液を二重紡糸口金から押し出した後、凝固・乾燥させることにより製造されるもので、食品分野、医薬品分野、電子工業分野、水処理分野等の各種分野において汎用されている。 A hollow fiber porous membrane is generally produced by extruding a polymer solution, which is a spinning dope (liquid film-forming composition), from a double spinneret and then coagulating and drying. It is widely used in various fields such as industrial field and water treatment field.
中空糸多孔質膜を比較的濁度の低い水処理分野に適用する場合は、例えば、所要数を束ねた中空糸多孔質膜をケースハウジング内に収容し、膜モジュールとして利用されている。しかしながら、比較的濁度の高い水処理分野に適用する場合は、ケーシングフリーの膜モジュール（ケーシングを使用せず、中空糸膜が露出した状態の膜モジュール）として利用されている。 When the hollow fiber porous membrane is applied to the water treatment field having a relatively low turbidity, for example, a required number of hollow fiber porous membranes are accommodated in a case housing and used as a membrane module. However, when applied to the water treatment field with relatively high turbidity, it is used as a casing-free membrane module (a membrane module in which a hollow fiber membrane is exposed without using a casing).
このようなケーシングフリーの膜モジュールの場合、１本の中空糸多孔質膜は非常に細く、機械的強度の低いものであるため、使用を継続する間に中空糸多孔質膜が破断し、水処理能力が低下するという問題がある。更に、機械的強度が低いため、激しいエアーバブリング洗浄や逆圧洗浄が行えず、処理能力を充分に回復することが困難であるという問題もある。 In the case of such a casing-free membrane module, one hollow fiber porous membrane is very thin and has a low mechanical strength. There is a problem that the processing capacity is reduced. Furthermore, since the mechanical strength is low, there is a problem that it is difficult to recover the processing capacity sufficiently because it is impossible to perform intense air bubbling cleaning or back pressure cleaning.
中空糸多孔質膜の強度を高める方法として、組紐の外表面に半透膜層を形成したものが知られているが、透水性能の点で改善の余地がある。
本発明は、透水性能が優れている繊維強化型中空糸膜を提供することを課題とする。 An object of the present invention is to provide a fiber-reinforced hollow fiber membrane having excellent water permeability.
請求項１の発明は、組紐外表面に半透膜層を有しており、前記半透膜層が下記（ａ）〜（ｃ）成分を含む液状製膜組成物から形成されたものである繊維強化型中空糸膜を提供する。。
（ａ）ポリサルホン系樹脂及び／又はポリエーテルスルホン系樹脂１５〜３０質量％
（ｂ）良溶媒４０〜８０質量％
（ｃ）貧溶媒１〜４５質量％（ポリアルキレングリコールは含まない）
請求項２の発明は、（ｂ）成分の良溶媒が、N−メチルピロリドン、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミドから選ばれるものである請求項１記載の繊維強化型中空糸膜を提供する。
請求項３の発明は、（ｃ）成分の貧溶媒がエチレングリコールである請求項１又は２記載の繊維強化型中空糸膜を提供する。
請求項４の発明は、（ｃ）成分の貧溶媒がグリコール類とポリビニルピロリドンの組み合わせである請求項１又は２記載の繊維強化型中空糸膜を提供する。
請求項５の発明は、（ｃ）成分の貧溶媒がエチレングリコールとポリビニルピロリドンの組み合わせである請求項１又は２記載の繊維強化型中空糸膜を提供する。
請求項６の発明は、組紐が、内径０．２〜３．０ｍｍで、外径０．５〜５．０ｍｍのものである、請求項１〜５のいずれか１項に記載の繊維強化型中空糸膜を提供する。
The invention of claim 1 has a semipermeable membrane layer on the braid outer surface, and the semipermeable membrane layer is formed from a liquid film-forming composition containing the following components (a) to (c). A fiber-reinforced hollow fiber membrane is provided. .
(A) Polysulfone resin and / or polyethersulfone resin 15 to 30% by mass
(B) Good solvent 40-80 mass%
(C) 1 to 45 mass% of poor solvent (not including polyalkylene glycol)
The invention of claim 2 provides the fiber-reinforced hollow fiber membrane according to claim 1, wherein the good solvent of component (b) is selected from N-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide.
The invention of claim 3 provides the fiber-reinforced hollow fiber membrane according to claim 1 or 2, wherein the poor solvent of component (c) is ethylene glycol.
The invention of claim 4 provides the fiber-reinforced hollow fiber membrane according to claim 1 or 2, wherein the poor solvent of component (c) is a combination of glycols and polyvinylpyrrolidone.
The invention of claim 5 provides the fiber-reinforced hollow fiber membrane according to claim 1 or 2, wherein the poor solvent of component (c) is a combination of ethylene glycol and polyvinylpyrrolidone.
The invention of claim 6 is a fiber-reinforced type according to any one of claims 1 to 5, wherein the braid has an inner diameter of 0.2 to 3.0 mm and an outer diameter of 0.5 to 5.0 mm. A hollow fiber membrane is provided.
本発明の繊維強化型中空糸膜は、透水性能が優れており、組紐を含んでいるため機械的強度も高い。 The fiber-reinforced hollow fiber membrane of the present invention is excellent in water permeability and has high mechanical strength because it includes braids.
＜繊維強化型中空糸膜＞
本発明の繊維強化型中空糸膜は、基材となる組紐の外表面に特定の液状製膜組成物により形成された半透膜層を有している。半透膜層は、一部が組紐内部に侵入した構造であってもよいが、組紐の内表面には形成されていない。
<Fiber-reinforced hollow fiber membrane>
The fiber-reinforced hollow fiber membrane of the present invention has a semipermeable membrane layer formed of a specific liquid film-forming composition on the outer surface of a braid serving as a base material. The semipermeable membrane layer may have a structure in which a part thereof penetrates into the braid, but is not formed on the inner surface of the braid.
半透膜層の厚みは、５０〜５００μmが好ましく、１００〜４００μmがより好ましく、１５０〜３００μmが更に好ましい。 The thickness of the semipermeable membrane layer is preferably 50 to 500 μm, more preferably 100 to 400 μm, and still more preferably 150 to 300 μm.
本発明の繊維強化型中空糸膜は、外径が好ましくは１．５〜３．０ｍｍ、より好ましくは１．８〜２．５ｍｍで、内径が好ましくは０．５〜１．５ｍｍ、より好ましくは０．７〜１．３ｍｍである。 The fiber-reinforced hollow fiber membrane of the present invention preferably has an outer diameter of 1.5 to 3.0 mm, more preferably 1.8 to 2.5 mm, and an inner diameter of preferably 0.5 to 1.5 mm. Is 0.7 to 1.3 mm.
〔組紐〕
組紐は、フッ素樹脂、ポリエステル、ポリアミド、ポリウレタン、アクリル樹脂、メタクリル樹脂、ポリエチレン、ポリプロピレン、ポリスチレン、塩化ビニル、セルロース、セルロースアセテート等の天然又は合成樹脂繊維、ステンレス、黄銅、銅等の金属繊維、ガラス繊維、炭素繊維等からなるものを用いることができる。
〔braid〕
Braid is made of fluororesin, polyester, polyamide, polyurethane, acrylic resin, methacrylic resin, polyethylene, polypropylene, polystyrene, vinyl chloride, cellulose, cellulose acetate and other natural or synthetic resin fibers, stainless steel, brass, copper and other metal fibers, glass What consists of a fiber, carbon fiber, etc. can be used.
組紐の内径及び外径は特に制限されるものではないが、取り扱い易さや製造技術上の問題から、内径が好ましくは０．２〜３．０ｍｍ、より好ましくは０．５〜２．０ｍｍで、外径が好ましくは０．５〜５．０ｍｍ、より好ましくは１．０〜３．０ｍｍのものを用いることができる。 The inner diameter and outer diameter of the braid are not particularly limited, but from the viewpoint of ease of handling and manufacturing technology, the inner diameter is preferably 0.2 to 3.0 mm, more preferably 0.5 to 2.0 mm. The outer diameter is preferably 0.5 to 5.0 mm, more preferably 1.0 to 3.0 mm.
〔液状製膜組成物〕
（ａ）成分のポリマー成分は、ポリサルホン系樹脂及びポリエーテルスルホン系樹脂のいずれか一方又は両方を組み合わせて用いることができる。
[Liquid film-forming composition]
As the polymer component of component (a), either one or both of a polysulfone resin and a polyethersulfone resin can be used.
組成物中の（ａ）成分の含有量は、１５〜３０質量％であり、１５〜２５質量％が好ましく、１６〜２４質量％がより好ましく、１７〜２３質量％が更に好ましい。 Content of (a) component in a composition is 15-30 mass%, 15-25 mass% is preferable, 16-24 mass% is more preferable, 17-23 mass% is still more preferable.
（ｂ）成分の良溶媒としては、N−メチルピロリドン、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミドから選ばれるもの等を挙げることができる。 Examples of the good solvent for component (b) include those selected from N-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide.
組成物中の（ｂ）成分の含有量は、４０〜８０質量％であり、４５〜７５質量％が好ましく、５０〜７０質量％がより好ましく、５０〜６０質量％が更に好ましい。 Content of (b) component in a composition is 40-80 mass%, 45-75 mass% is preferable, 50-70 mass% is more preferable, 50-60 mass% is still more preferable.
（ｃ）成分の貧溶剤は、グリコール類（ポリアルキレングリコールは含まない）、ジオール類、グリセリン及びポリビニルピロリドンから選ばれるものであり、テトラエチレングリコール、プロピレングリコール、エチレングリコール等のグリコール類、ペンタンジオール、ヘキサンジオール、ヘプタンジオール等のジオール類、グリセリン、ポリビニルピロリドン等を挙げることができるが、エチレングリコール単独、エチレングリコール等のグリコール類とポリビニルピロリドンの組み合わせ（特にエチレングリコールとポリビニルピロリドンの組み合わせ）が好ましい。 The poor solvent of component (c) is selected from glycols (not including polyalkylene glycol), diols, glycerin and polyvinylpyrrolidone, and glycols such as tetraethylene glycol, propylene glycol and ethylene glycol, pentanediol Diols such as hexanediol and heptanediol, glycerin, polyvinylpyrrolidone and the like, but ethylene glycol alone, a combination of glycols such as ethylene glycol and polyvinylpyrrolidone (particularly a combination of ethylene glycol and polyvinylpyrrolidone) is preferred. .
組成物中の（ｃ）成分の含有量は、１〜４５質量％であり、１〜４０質量％が好ましく、２〜３５質量％がより好ましく、３〜３０質量％が更に好ましい。 Content of (c) component in a composition is 1-45 mass%, 1-40 mass% is preferable, 2-35 mass% is more preferable, and 3-30 mass% is still more preferable.
本発明で用いる液状製膜組成物は、本発明の課題を解決できる範囲内で、（ａ）〜（ｃ）成分以外の公知の製膜用成分を含有することができる。 The liquid film-forming composition used in the present invention can contain known film-forming components other than the components (a) to (c) within a range in which the problems of the present invention can be solved.
＜繊維強化型中空糸膜の製造方法＞
本発明の繊維強化型中空糸膜の製造方法の一実施形態を説明する。まず、第１工程として、液状製膜組成物を中空糸状の組紐の表面に付着させる工程の処理をする。
<Method for producing fiber-reinforced hollow fiber membrane>
An embodiment of a method for producing a fiber-reinforced hollow fiber membrane of the present invention will be described. First, as a first step, a process of attaching a liquid film-forming composition to the surface of a hollow fiber braid is performed.
第１工程の処理としては、ノズルを用い、ノズル内を走行する中空糸状の組紐外表面に液状製膜組成物を塗布する方法、液状製膜組成物を入れた容器中に中空糸状の組紐を浸漬し、所要時間放置する方法、液状製膜組成物を入れた容器中に中空糸状の組紐を連続的に潜らせる方法、中空糸状の組紐の編組工程（組紐を編む工程）において、編まれている状態の組紐表面に液状製膜組成物を連続的に噴霧、噴射又は塗布する方法等を適用できる。 As a process of the first step, using a nozzle, a method of applying a liquid film-forming composition to the outer surface of a hollow fiber-shaped braid that runs in the nozzle, a hollow fiber-shaped braid is placed in a container containing the liquid film-forming composition. In a method of immersing and allowing to stand for a required time, a method of continuously hollowing a hollow fiber-like braid in a container containing a liquid film-forming composition, For example, a method of continuously spraying, spraying, or applying the liquid film-forming composition to the braid surface in a state of being applied can be applied.
第１工程の処理時間は、液状製膜組成物の種類及び濃度、組紐の密度、中空糸状多孔質膜の透水性能等に応じて、所望の厚みの半透膜層が形成されるように調整する。 The processing time of the first step is adjusted so that a semipermeable membrane layer having a desired thickness is formed according to the type and concentration of the liquid membrane-forming composition, the braid density, the water permeability of the hollow fiber porous membrane, and the like. To do.
具体的には、各実施例に記載のものと同一の組紐及び同一の液状製膜組成物を用いる場合は、各実施例における半透膜層の厚みを基準として、液状製膜組成物の濃度を増減したり、液状製膜組成物への浸漬時間を増減することで、半透膜層の厚みを増減させることができる。 Specifically, when the same braid and the same liquid film-forming composition as those described in each example are used, the concentration of the liquid film-forming composition is based on the thickness of the semipermeable membrane layer in each example. The thickness of the semipermeable membrane layer can be increased / decreased by increasing / decreasing or increasing / decreasing the immersion time in the liquid film-forming composition.
第２工程は、組紐の表面に付着した液状製膜組成物を凝固させる工程である。この工程の処理には、湿式法や乾式法等を適用できるが、瞬時に成形できる湿式法や半乾式湿式法が好ましい。 The second step is a step of solidifying the liquid film-forming composition attached to the braid surface. For the treatment in this step, a wet method, a dry method, or the like can be applied, but a wet method or a semi-dry wet method that can be molded instantaneously is preferable.
湿式法を適用する場合は、水等の凝固浴中に組紐を浸漬した後、乾燥する方法を適用できる。乾式法を適用する場合は、液状製膜組成物の濃度、溶媒の種類に応じて、１段処理するか、又は温度及び湿度条件を変化させて２段以上の処理をすることができる。処理温度及び湿度は、温度３０〜２００℃、好ましくは６０〜１５０℃、相対湿度３０〜９５％、好ましくは６０〜９０％であり、処理時間は０．５〜６０分間、好ましくは２〜３０分間である。 When the wet method is applied, a method of drying after braiding the braid in a coagulation bath such as water can be applied. In the case of applying the dry method, depending on the concentration of the liquid film-forming composition and the type of the solvent, it can be processed in one step, or two or more steps can be performed by changing the temperature and humidity conditions. The treatment temperature and humidity are 30 to 200 ° C., preferably 60 to 150 ° C., 30 to 95% relative humidity, preferably 60 to 90%, and the treatment time is 0.5 to 60 minutes, preferably 2 to 30. For minutes.
本発明の繊維強化型中空糸膜は、内圧式や外圧式の中空糸膜（中空糸膜モジュール）として、各種水処理に適用することができる。 The fiber reinforced hollow fiber membrane of the present invention can be applied to various water treatments as an internal pressure type or external pressure type hollow fiber membrane (hollow fiber membrane module).
（１）純水透過速度
長さ１ｍの中空糸膜の片端を封じ、中空糸膜の片端の内側にＰ１（＝０．１ＭＰａ）の圧力をかけて純水をデッドエンド濾過し、濾過時間、透過する純水量及び他方の片端の圧力Ｐ２を測定した。膜間圧力は、（Ｐ１＋Ｐ２）／２で算出し、単位圧力（＝０．１ＭＰａ）、単位時間、単位膜面積（外表面積換算）あたりに透過する純水量を算出した。
(1) Pure water permeation rate One end of a hollow fiber membrane having a length of 1 m is sealed, pure water is dead-end filtered by applying a pressure of P1 (= 0.1 MPa) to the inside of one end of the hollow fiber membrane, filtration time, The amount of pure water permeating and the pressure P2 at the other end were measured. The transmembrane pressure was calculated by (P1 + P2) / 2, and the amount of pure water permeating per unit pressure (= 0.1 MPa), unit time, and unit membrane area (external surface area conversion) was calculated.
（２）エアー発生圧力
水中に浸漬した中空糸膜（長さ１ｍ）の両端の内側にエアーを徐々にかけ、中空糸膜の外表面から最初にエアーが発生する圧力を測定した。この圧力は、一般的にバブルポイントとして定義され、膜細孔径の算出に使用されているが、ピンホールを内在した膜等においては、バブルポイントよりも小さくなる。バブルポイントは、膜細孔径、膜と水との接触角、水の表面張力を用いて容易に算出できる。
(2) Air generation pressure Air was gradually applied to the inside of both ends of the hollow fiber membrane (length 1 m) immersed in water, and the pressure at which air was first generated from the outer surface of the hollow fiber membrane was measured. This pressure is generally defined as a bubble point and is used to calculate the membrane pore diameter, but is smaller than the bubble point in a membrane having a pinhole. The bubble point can be easily calculated using the membrane pore diameter, the contact angle between the membrane and water, and the surface tension of water.
実施例１
ポリエーテルスルホン（住友化学製）２２質量％、Ｎ-メチルピロリドン５３質量％、エチレングリコール１０質量％、ポリビニルピロリドン１５質量％からなる製膜溶液（液状製膜組成物）を用いた。この製膜溶液を６０℃に加温し、コーティング容器にギアポンプで圧送するとともに、コーティング容器の中央に、内径１．０ｍｍ、外径１．９ｍｍ、厚み０．４５ｍｍのテトロンスリーブ（組紐、繊維密度３８目／インチ）を、９ｍ／分の速度にて走行させて、テトロンスリーブ外表面側から製膜溶液を塗布した。
Example 1
A film-forming solution (liquid film-forming composition) comprising 22% by mass of polyethersulfone (manufactured by Sumitomo Chemical), 53% by mass of N-methylpyrrolidone, 10% by mass of ethylene glycol, and 15% by mass of polyvinylpyrrolidone was used. This film-forming solution is heated to 60 ° C. and pumped to the coating container with a gear pump. At the center of the coating container, a Tetron sleeve (braid, fiber density with an inner diameter of 1.0 mm, an outer diameter of 1.9 mm, and a thickness of 0.45 mm). No. 38 / inch) was run at a speed of 9 m / min, and the film forming solution was applied from the outer surface side of the Tetron sleeve.
塗布されたテトロンスリーブは、走行中スリットを通過し、過剰塗布溶液の除去／真円度、編肉度調整を行った後、６０℃の水中で凝固／洗浄し、繊維強化型中空糸膜を得た。 The applied Tetron sleeve passes through the slit during running, and after removing excess coating solution / roundness and adjusting the knitting thickness, it is solidified / washed in water at 60 ° C. to form a fiber-reinforced hollow fiber membrane. Obtained.
実施例２
ポリエーテルスルホン（住友化学製）２２質量％、Ｎ-メチルピロリドン５０質量％、エチレングリコール１３質量％、ポリビニルピロリドン１５質量％からなる製膜溶液（液状製膜組成物）を用い、実施例１と同様にして繊維強化型中空糸膜を得た。
Example 2
Using a film-forming solution (liquid film-forming composition) consisting of 22% by mass of polyethersulfone (manufactured by Sumitomo Chemical), 50% by mass of N-methylpyrrolidone, 13% by mass of ethylene glycol, and 15% by mass of polyvinylpyrrolidone, Example 1 A fiber reinforced hollow fiber membrane was obtained in the same manner.
実施例３
ポリエーテルスルホン（住友化学製）２２質量％、Ｎ-メチルピロリドン５８質量％、エチレングリコール５質量％、ポリビニルピロリドン１５質量％からなる製膜溶液（液状製膜組成物）を用い、１ｍ／分の速度で走行させた以外は実施例１と同様にして繊維強化型中空糸膜を得た。
Example 3
Using a film-forming solution (liquid film-forming composition) consisting of 22% by mass of polyethersulfone (manufactured by Sumitomo Chemical), 58% by mass of N-methylpyrrolidone, 5% by mass of ethylene glycol, and 15% by mass of polyvinylpyrrolidone, 1 m / min A fiber-reinforced hollow fiber membrane was obtained in the same manner as in Example 1 except that it was run at a speed.
比較例１
ポリエーテルスルホン（住友化学製）１８質量％、ジメチルスルホキシド３７質量％、ポリエチレングリコール（＃２００）４５質量％からなる製膜溶液（液状製膜組成物）を用いた。この製膜溶液を８０℃に加温し、コーティング容器にギアポンプで圧送するとともに、コーティング容器の中央に、内径１．０ｍｍ、外径１．９ｍｍ、厚み０．４５ｍｍのテトロンスリーブ（組紐、繊維密度３８目／インチ）を、１ｍ／分の速度にて走行させて、テトロンスリーブ外表面側から製膜溶液を塗布した。
Comparative Example 1
A film-forming solution (liquid film-forming composition) comprising 18% by mass of polyethersulfone (manufactured by Sumitomo Chemical), 37% by mass of dimethyl sulfoxide, and 45% by mass of polyethylene glycol (# 200) was used. This film-forming solution is heated to 80 ° C. and pumped to the coating container with a gear pump. At the center of the coating container, a Tetron sleeve (braid, fiber density with an inner diameter of 1.0 mm, an outer diameter of 1.9 mm, and a thickness of 0.45 mm). The film forming solution was applied from the outer surface side of the Tetron sleeve.
塗布されたテトロンスリーブは、走行中スリットを通過し、過剰塗布溶液の除去／真円度、編肉度調整を行った後、３０℃の水中で凝固／洗浄し、繊維強化型中空糸膜を得た。 The applied tetron sleeve passes through the slit during running, and after removing excess coating solution / roundness and adjusting the knitting thickness, it is solidified / washed in water at 30 ° C. to form a fiber-reinforced hollow fiber membrane. Obtained.
比較例２
酢酸プロピオン酸セルロース（イーストマンケミカル製）２１質量％、ジメチルスルホキシド７２質量％、ポリエチレングリコール（＃６０００）５質量％、塩化カルシウム２質量％からなる製膜溶液（液状製膜組成物）を用いた。この製膜溶液を用いて、比較例１と同様の方法にて、中空糸膜を得た。
Comparative Example 2
A film-forming solution (liquid film-forming composition) comprising 21% by mass of cellulose acetate propionate (manufactured by Eastman Chemical), 72% by mass of dimethyl sulfoxide, 5% by mass of polyethylene glycol (# 6000), and 2% by mass of calcium chloride was used. . Using this membrane forming solution, a hollow fiber membrane was obtained in the same manner as in Comparative Example 1.
上記実施例１〜３及び比較例１〜２で得られた中空糸膜について、純水透過速度（０．１ＭＰａ下の値）及びエアー発生圧力を測定した。結果を表１に示す。 About the hollow fiber membrane obtained by the said Examples 1-3 and Comparative Examples 1-2, the pure water permeation | transmission rate (value below 0.1 MPa) and the air generation pressure were measured. The results are shown in Table 1.
Claims (6)
（ａ）ポリサルホン系樹脂及び／又はポリエーテルスルホン系樹脂１５〜３０質量％
（ｂ）良溶媒４０〜８０質量％
（ｃ）貧溶媒１〜４５質量％（ポリアルキレングリコールは含まない） A fiber-reinforced hollow fiber membrane having a semipermeable membrane layer on the braid outer surface, wherein the semipermeable membrane layer is formed from a liquid membrane-forming composition containing the following components (a) to (c).
(A) Polysulfone resin and / or polyethersulfone resin 15 to 30% by mass
(B) Good solvent 40-80 mass%
(C) 1 to 45 mass% of poor solvent (not including polyalkylene glycol)
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| CN102188911A (en) * | 2011-05-10 | 2011-09-21 | 浙江开创环保科技有限公司 | Polyvinylidene hollow fiber membrane with filament support material and preparation method thereof |
| CN103272492A (en) * | 2013-06-19 | 2013-09-04 | 天津工业大学 | Enhanced-cellulose hollow fiber membrane and preparation method thereof |
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| JP5371867B2 (en) * | 2009-03-31 | 2013-12-18 | 旭化成メディカル株式会社 | Hollow fiber membrane and method for producing the same |
| JP5626865B2 (en) * | 2010-08-13 | 2014-11-19 | 旭化成ケミカルズ株式会社 | Composite porous hollow fiber membrane, membrane module, membrane filtration device, water treatment method |
| CN102343221A (en) * | 2011-09-29 | 2012-02-08 | 浙江开创环保科技有限公司 | Polyethersulfone membrane with supporting materials and preparation method thereof |
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| JPH06233921A (en) * | 1993-02-10 | 1994-08-23 | Nok Corp | Production of polysulfone porous hollow yarn membrane |
| JP2002119833A (en) * | 2000-10-16 | 2002-04-23 | Nok Corp | Method for washing porous hollow fiber membrane manufactured by dry wet spinning method |
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| JP2006150270A (en) * | 2004-11-30 | 2006-06-15 | Daicel Chem Ind Ltd | Hollow fiber semipermeable membrane |
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| JPS52120288A (en) * | 1976-04-02 | 1977-10-08 | Asahi Chem Ind Co Ltd | Hollow gas-permeable membrane |
| DE3141672A1 (en) * | 1981-10-21 | 1983-05-05 | Bayer Ag, 5090 Leverkusen | SEMIPERMEABLE MEMBRANES |
| JP2003311133A (en) * | 2002-04-19 | 2003-11-05 | Daicel Chem Ind Ltd | Hollow fiber semipermeable membrane |
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| JPH06233921A (en) * | 1993-02-10 | 1994-08-23 | Nok Corp | Production of polysulfone porous hollow yarn membrane |
| JP2002119833A (en) * | 2000-10-16 | 2002-04-23 | Nok Corp | Method for washing porous hollow fiber membrane manufactured by dry wet spinning method |
| JP2003225542A (en) * | 2001-12-07 | 2003-08-12 | Kolon Ind Inc | Composite hollow fiber membrane reinforced with woven fabric |
| JP2006150270A (en) * | 2004-11-30 | 2006-06-15 | Daicel Chem Ind Ltd | Hollow fiber semipermeable membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102188911A (en) * | 2011-05-10 | 2011-09-21 | 浙江开创环保科技有限公司 | Polyvinylidene hollow fiber membrane with filament support material and preparation method thereof |
| CN102188911B (en) * | 2011-05-10 | 2013-04-03 | 浙江开创环保科技有限公司 | Polyvinylidene hollow fiber membrane with filament support material and preparation method thereof |
| CN103272492A (en) * | 2013-06-19 | 2013-09-04 | 天津工业大学 | Enhanced-cellulose hollow fiber membrane and preparation method thereof |
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