JP2008178868A - Fiber-reinforced type hollow fiber membrane - Google Patents
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Abstract
Description
本発明は、ピンホールの発生が抑制され、濾過時のリークが少ない繊維強化型中空糸膜に関する。 The present invention relates to a fiber-reinforced hollow fiber membrane in which the generation of pinholes is suppressed and leakage during filtration is small.
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.
特許文献１には、平均粒子径５〜５０００ｎｍで、嵩密度が０．０５〜０．５ｍｌ／ｇの無機粒子を含有する分離膜が開示されているが、実際に適用されているのは平膜であり、より製膜が困難な中空糸膜への利用は開示されていない。 Patent Document 1 discloses a separation membrane containing inorganic particles having an average particle diameter of 5 to 5000 nm and a bulk density of 0.05 to 0.5 ml / g. Application to a hollow fiber membrane which is a membrane and is more difficult to form is not disclosed.
特許文献２には、光照射により有機物の分解を促進する粒径３０〜４０ｎｍ程度の微細なアナターゼ型酸化チタン粒子の表面を、多孔質の燐酸カルシウムによって被覆した安定化アナターゼ型酸化チタン粒子の光触媒物質を保持してなる中空糸分離膜が開示されている。しかし、この分離膜は、使用中にアナターゼ型酸化チタン粒子が欠落てしまうおそれがある。
中空糸膜の製造においては、特に高分子多孔質からなる薄膜を基膜上に形成させる場合には、形成される半透膜層にピンホールが多発して、濾過時にリーク（充分に濾過されないままで、被処理液が通過する現象）が発生するおそれがある。 In the production of hollow fiber membranes, particularly when a thin film made of a polymer porous material is formed on a base membrane, pinholes frequently occur in the formed semipermeable membrane layer, and leakage occurs during filtration (not sufficiently filtered). The phenomenon that the liquid to be treated passes) may occur.
本発明は、半透膜層にピンホールが発生することが抑制され、濾過運転時のリークの発生を抑制することができ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 that can suppress the occurrence of pinholes in the semipermeable membrane layer and can suppress the occurrence of leakage during filtration operation.
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）〜（ｄ）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。 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 (d). A fiber-reinforced hollow fiber membrane is provided.
（ａ）ポリマー成分１５〜２５質量％
（ｂ）良溶媒４０〜８０質量％
（ｃ）貧溶媒１〜４０質量％
（ｄ）シリカ、チタニア、アルミナから選ばれる無機微粒子１〜２０質量％
請求項２の発明は、（ｄ）成分の無機微粒子が、平均一次粒子径が１〜５０nm、見掛け比重が１０〜２００ｇ／Ｌのものである、請求項１記載の繊維強化型中空糸膜を提供する。
(A) Polymer component 15-25 mass%
(B) Good solvent 40-80 mass%
(C) 1-40 mass% of poor solvents
(D) 1 to 20% by mass of inorganic fine particles selected from silica, titania and alumina
The invention according to claim 2 is the fiber-reinforced hollow fiber membrane according to claim 1, wherein the inorganic fine particles of component (d) have an average primary particle diameter of 1 to 50 nm and an apparent specific gravity of 10 to 200 g / L. provide.
請求項３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又は２記載の繊維強化型中空糸膜を提供する。 The invention of claim 3 provides the fiber-reinforced hollow fiber membrane according to claim 1 or 2, wherein the good solvent of component (b) is selected from N-methylpyrrolidone, dimethylsulfoxide, dimethylformamide, and dimethylacetamide. To do.
請求項４の発明は、（ｃ）成分の貧溶媒が、グリコール類、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る請求項１〜３のいずれかに記載の繊維強化型中空糸膜を提供する。 The invention according to claim 4 is the fiber-reinforced hollow fiber membrane according to any one of claims 1 to 3, wherein the poor solvent of component (c) is selected from glycols, diols, glycerin and polyvinylpyrrolidone. provide.
請求項５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１〜４のいずれかに記載の繊維強化型中空糸膜を提供する。 The invention of claim 5 is a fiber-reinforced hollow fiber according to any one of claims 1 to 4, 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. Providing a membrane.
本発明の繊維強化型中空糸膜は、半透膜層においてピンホールの発生が抑制されており、本発明の繊維強化型中空糸膜を用いた濾過膜モジュールにより濾過運転した場合でも、リークの発生が抑制される。 In the fiber reinforced hollow fiber membrane of the present invention, the occurrence of pinholes in the semipermeable membrane layer is suppressed, and even when the filtration operation is carried out by the filtration membrane module using the fiber reinforced hollow fiber membrane of the present invention Occurrence is suppressed.
＜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、疎水性ポリマーでもよいし、親水性ポリマーでもよい。親水性ポリマーとしては、酢酸セルロース、セルロースプロピオネート、セルロースブチレート、再生セルロース、これらの混合物等のセルロース系材料を挙げることができる。また、ポリビニルアルコール等も使用できる。疎水性ポリマーとしては、ポリサルホン系樹脂、ポリエーテルスルホン系樹脂、ポリフッ化ビニリデン系樹脂、ポリアクリロニトリル樹脂、ポリイミド樹脂、ポリアラミド樹脂、ポリプロピレン樹脂、ポリエチレン樹脂等を挙げることができる。
[Liquid film-forming composition]
The polymer component of component (a) may be a hydrophobic polymer or a hydrophilic polymer. Examples of the hydrophilic polymer include cellulose materials such as cellulose acetate, cellulose propionate, cellulose butyrate, regenerated cellulose, and a mixture thereof. Moreover, polyvinyl alcohol etc. can also be used. Examples of the hydrophobic polymer include polysulfone resins, polyethersulfone resins, polyvinylidene fluoride resins, polyacrylonitrile resins, polyimide resins, polyaramid resins, polypropylene resins, and polyethylene resins.
組成物中の（ａ）成分の含有量は、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。 The content of the component (a) in the composition is preferably 15 to 25% by mass, more preferably 16 to 24% by mass, and still more preferably 17 to 23% by mass.
（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％が好ましく、４５〜７５質量％がより好ましく、５０〜７０質量％が更に好ましい。 40-80 mass% is preferable, as for content of (b) component in a composition, 45-75 mass% is more preferable, and 50-70 mass% is still more preferable.
（ｃ）成分の貧溶剤は、グリコール類、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、ポリエチレングリコール、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。これらの中でグリコール類が好ましく、更にはポリエチレングリコールやエチレングリコールが好ましい。また、ポリエチレングリコール又は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, diols, glycerin and polyvinylpyrrolidone, and glycols such as polyethylene glycol, tetraethylene glycol, propylene glycol and ethylene glycol, pentanediol, hexanediol and heptane. Examples include diols such as diol, glycerin, polyvinylpyrrolidone, and the like. Among these, glycols are preferable, and polyethylene glycol and ethylene glycol are more preferable. Further, polyethylene glycol or a combination of ethylene glycol and polyvinyl pyrrolidone is preferable.
組成物中の（ｃ）成分の含有量は、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。 The content of the component (c) in the composition is preferably 1 to 40% by mass, more preferably 2 to 35% by mass, and still more preferably 3 to 30% by mass.
（ｄ）成分の無機微粒子は、シリカ、チタニア、アルミナから選ばれるものである。 The inorganic fine particles of component (d) are selected from silica, titania and alumina.
（ｄ）成分の無機微粒子の平均一次粒子径は１〜５０ｎｍが好ましく、５〜４０ｎｍがより好ましく、１０〜３０ｎｍが更に好ましい。平均一次粒子径が前記範囲であると、液状製膜組成物中での分散性がよく、沈降や不均一化を起こさない。 The average primary particle size of the inorganic fine particles of component (d) is preferably 1 to 50 nm, more preferably 5 to 40 nm, and still more preferably 10 to 30 nm. When the average primary particle size is in the above range, the dispersibility in the liquid film-forming composition is good, and precipitation and non-uniformity do not occur.
（ｄ）成分の無機微粒子の見掛け比重は１０〜２００ｇ／Ｌが好ましく、２０〜１７０ｇ／Ｌがより好ましく、３０〜１５０ｇ／Ｌが更に好ましい。見掛け比重が前記範囲であると、液状製膜組成物中での分散性がよく、取り扱い時に舞い上がったりしない。 The apparent specific gravity of the inorganic fine particles as component (d) is preferably 10 to 200 g / L, more preferably 20 to 170 g / L, still more preferably 30 to 150 g / L. When the apparent specific gravity is within the above range, the dispersibility in the liquid film-forming composition is good and does not rise during handling.
組成物中の（ｄ）成分の含有量は、１〜２０質量％が好ましく、１〜１５質量％がより好ましく、１〜１０質量％が更に好ましい。 1-20 mass% is preferable, as for content of (d) component in a composition, 1-15 mass% is more preferable, and 1-10 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）〜（ｄ）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 (d) within the 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）平均一次粒子径
動的光散乱法により測定した。
(1) Average primary particle diameter It measured by the dynamic light scattering method.
（２）見掛け比重
容積既知のメスシリンダー内に無機微粒子を重力のみにより充填し、その質量を測定して、質量を容積で割ることで求めた。
(2) Apparent specific gravity An inorganic fine particle was filled only in gravity into a graduated cylinder having a known volume, the mass was measured, and the mass was divided by the volume.
（３）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。
(3) 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.
（４）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。
(4) 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）１８質量％、ジメチルアセトアミド５３質量％、ポリエチレングリコール（＃２００）２１質量％、シリカ−１（日本アエロジル製９０G；平均一次粒子径２０ｎｍ、見掛け比重５０ｇ／Ｌ）８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。
Example 1
Polyethersulfone (manufactured by Sumitomo Chemical) 18% by mass, 53% by mass of dimethylacetamide, 21% by mass of polyethylene glycol (# 200), silica-1 (Nippon Aerosil 90G; average primary particle size 20 nm, apparent specific gravity 50 g / L) 8 A film-forming solution (liquid film-forming composition) consisting of mass% 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。この製膜溶液を用いて、実施例１と同様の方法にて、中空糸膜を得た。
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. Using this membrane-forming solution, a hollow fiber membrane was obtained in the same manner as in Example 1.
実施例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）２０質量％、ジメチルスルホキシド７１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％、シリカ−２（日本アエロジル製Ｒ９７２；平均一次粒子径１６ｎｍ、見掛け比重５０ｇ／Ｌ）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、実施例１と同様の方法にて、繊維強化型中空糸膜を得た。
Example 2
Cellulose acetate propionate (manufactured by Eastman Chemical) 20% by mass, 71% by mass of dimethyl sulfoxide, 5% by mass of polyethylene glycol (# 6000), 2% by mass of calcium chloride, silica-2 (R972 manufactured by Nippon Aerosil); average primary particle size 16 nm A film-forming solution (liquid film-forming composition) composed of 2% by mass with an apparent specific gravity of 50 g / L was used. Using this membrane-forming solution, a fiber-reinforced hollow fiber membrane was obtained in the same manner as in Example 1.
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、実施例２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 Example 2.
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５１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％、シリカ−１（日本アエロジル製９０G）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 3
A film-forming solution consisting of 22% by mass of polyethersulfone (manufactured by Sumitomo Chemical), 51% by mass of N-methylpyrrolidone, 10% by mass of ethylene glycol, 15% by mass of polyvinylpyrrolidone, and 2% by mass of silica-1 (Nippon Aerosil 90G) ( Liquid film-forming composition) 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４
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５１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％、チタニア（日本アエロジル製P-２５；平均一次粒子径２１ｎｍ、見掛け比重１３０ｇ／Ｌ）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、実施例３と同様の方法にて、繊維強化型中空糸膜を得た。
Example 4
Polyethersulfone (manufactured by Sumitomo Chemical) 22% by mass, N-methylpyrrolidone 51% by mass, ethylene glycol 10% by mass, polyvinylpyrrolidone 15% by mass, titania (Nippon Aerosil P-25; average primary particle size 21 nm, apparent specific gravity 130 g) / L) A film-forming solution (liquid film-forming composition) composed of 2% by mass was used. Using this membrane-forming solution, a fiber-reinforced hollow fiber membrane was obtained in the same manner as in Example 3.
上記実施例１〜４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。 For the hollow fiber membranes obtained in Examples 1 to 4 and Comparative Examples 1 and 2, the pure water permeation rate (value under 0.1 MPa) and the air generation pressure were measured. The results are shown in Table 1.
Claims (5)
（ａ）ポリマー成分１５〜２５質量％
（ｂ）良溶媒４０〜８０質量％
（ｃ）貧溶媒１〜４０質量％
（ｄ）シリカ、チタニア、アルミナから選ばれる無機微粒子１〜２０質量％ 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 (d).
(A) Polymer component 15-25 mass%
(B) Good solvent 40-80 mass%
(C) 1-40 mass% of poor solvents
(D) 1 to 20% by mass of inorganic fine particles selected from silica, titania and alumina
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| JP2010253470A (en) * | 2009-03-31 | 2010-11-11 | Asahi Kasei Kuraray Medical Co Ltd | Hollow fiber membrane and manufacturing method of the same |
| 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 |
| JP2012040464A (en) * | 2010-08-13 | 2012-03-01 | Asahi Kasei Chemicals Corp | Composite porous hollow fiber membrane, membrane module, membrane filtering device, and water-treating method |
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| 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 |
| CN103272492B (en) * | 2013-06-19 | 2014-12-10 | 天津工业大学 | Enhanced-cellulose hollow fiber membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52120288A (en) * | 1976-04-02 | 1977-10-08 | Asahi Chem Ind Co Ltd | Hollow gas-permeable membrane |
| JPS5879505A (en) * | 1981-10-21 | 1983-05-13 | バイエル・アクチエンゲゼルシヤフト | Semi-permeable membrane |
| JPH06233921A (en) * | 1993-02-10 | 1994-08-23 | Nok Corp | Production of polysulfone porous hollow yarn membrane |
| JP2003311133A (en) * | 2002-04-19 | 2003-11-05 | Daicel Chem Ind Ltd | Hollow fiber semipermeable membrane |
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| JP4724914B2 (en) * | 2000-10-16 | 2011-07-13 | Ｎｏｋ株式会社 | Dry / wet spinning method of porous hollow fiber membrane |
| KR100493113B1 (en) * | 2001-12-07 | 2005-05-31 | 주식회사 코오롱 | A braid-reinforced hollow fiber membrane |
| 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 |
|---|---|---|---|---|
| JPS52120288A (en) * | 1976-04-02 | 1977-10-08 | Asahi Chem Ind Co Ltd | Hollow gas-permeable membrane |
| JPS5879505A (en) * | 1981-10-21 | 1983-05-13 | バイエル・アクチエンゲゼルシヤフト | Semi-permeable membrane |
| JPH06233921A (en) * | 1993-02-10 | 1994-08-23 | Nok Corp | Production of polysulfone porous hollow yarn membrane |
| JP2003311133A (en) * | 2002-04-19 | 2003-11-05 | Daicel Chem Ind Ltd | Hollow fiber semipermeable membrane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010253470A (en) * | 2009-03-31 | 2010-11-11 | Asahi Kasei Kuraray Medical Co Ltd | Hollow fiber membrane and manufacturing method of the same |
| JP2012040464A (en) * | 2010-08-13 | 2012-03-01 | Asahi Kasei Chemicals Corp | Composite porous hollow fiber membrane, membrane module, membrane filtering device, and water-treating 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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