JP2015205258A - Fiber reinforced porous hollow fiber membrane and production method of the same - Google Patents
Fiber reinforced porous hollow fiber membrane and production method of the same Download PDFInfo
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Abstract
Description
本発明は、繊維補強多孔質中空糸膜およびその製造方法に関する。さらに詳しくは、燃料電池車の加湿装置等の加湿膜あるいは浄水処理や下廃水処理等の処理膜として有効に用いられる繊維補強多孔質中空糸膜およびその製造方法に関する。 The present invention relates to a fiber-reinforced porous hollow fiber membrane and a method for producing the same. More specifically, the present invention relates to a fiber-reinforced porous hollow fiber membrane that is effectively used as a humidifying membrane for a humidifier of a fuel cell vehicle or a treatment membrane for water purification treatment or sewage wastewater treatment, and a method for producing the same.
多孔質中空糸膜は、燃料電池スタックの隔膜加湿に用いられているが、燃料電池の場合、車載用では4000NL/分程度の多量の空気加湿が必要であり、かかる高流量の空気により発生する荷重影響で多孔質中空糸膜が破断するおそれがあり、耐久性の付与が特に必要とされている。また、一般的に数年〜20年といった長期間にわたって使用されることから、疲労による多孔質中空糸膜の破断を回避する必要もある。 Porous hollow fiber membranes are used for membrane humidification of fuel cell stacks, but in the case of fuel cells, a large amount of air humidification of about 4000 NL / min is required for in-vehicle use, and is generated by such high flow rate air. There is a possibility that the porous hollow fiber membrane may break due to the load, and it is particularly necessary to impart durability. Moreover, since it is generally used over a long period of several years to 20 years, it is also necessary to avoid breakage of the porous hollow fiber membrane due to fatigue.
また、膜ろ過による浄水処理や下廃水処理は、これまでの凝集沈殿のろ過方式と比較し、運転の維持や管理が容易であり、処理水質も良好であることから、膜ろ過は近年水処理分野で幅広く用いられている。近年の水資源確保の観点より、高強度で単位容積当りの膜面積が大きい多孔質中空糸膜モジュールが多く用いられている。例えば廃水処理の場合、一般的には単位容積当りの膜面積が50〜100m2の多孔質中空糸膜モジュールが用いられ、かかる膜モジュールに毎分数十リットルから数百リットルといった量の水が供給されることとなり、その際発生する荷重影響により、多孔質中空糸膜が破断するおそれがある。また、多孔質中空糸膜モジュールが工業用途に用いられる場合には、通常数年〜10年といった長期間にわたって使用されることから、加湿膜として用いられる多孔質中空糸膜モジュールと同様に疲労による多孔質中空糸膜の破断を回避する必要もある。 In addition, membrane filtration has recently been used for water treatment because it is easier to maintain and manage the operation, and the quality of the treated water is better than conventional filtration methods for coagulation sedimentation. Widely used in the field. From the viewpoint of securing water resources in recent years, porous hollow fiber membrane modules having a high strength and a large membrane area per unit volume are often used. For example, in the case of wastewater treatment, a porous hollow fiber membrane module having a membrane area of 50 to 100 m 2 per unit volume is generally used, and water of several tens to hundreds of liters per minute is used in the membrane module. The porous hollow fiber membrane may be broken due to the influence of the load generated at that time. In addition, when the porous hollow fiber membrane module is used for industrial applications, it is usually used over a long period of time, such as several years to 10 years, and therefore, due to fatigue similar to the porous hollow fiber membrane module used as a humidifying membrane. It is also necessary to avoid breakage of the porous hollow fiber membrane.
これらの要求を満足させる膜として、特許文献１〜２には、支持体となる中空糸状編紐の外表面上に、熱可塑性樹脂をそれの良溶媒に溶解させた紡糸原液を塗布または含浸させ、熱可塑性樹脂の貧溶媒からなる凝固液で凝固させることにより得られる繊維強化多孔質中空糸膜が提案されている。一般に、繊維強化多孔質中空糸膜は、二重環状紡糸ノズルの中央部のノズル(内側ノズル)から繊維材料製支持体を通過させ、外側のノズルから多孔質膜形成用紡糸原液を吐出することにより、繊維材料製支持体外表面上に紡糸原液を塗布または含浸させ、凝固させることにより得られている。 As membranes that satisfy these requirements, Patent Documents 1 and 2 apply or impregnate a spinning stock solution in which a thermoplastic resin is dissolved in a good solvent on the outer surface of a hollow fiber knitted string as a support. A fiber-reinforced porous hollow fiber membrane obtained by coagulating with a coagulating liquid composed of a poor solvent of a thermoplastic resin has been proposed. In general, a fiber-reinforced porous hollow fiber membrane is made by passing a fiber material support from a nozzle (inner nozzle) in the center of a double annular spinning nozzle and discharging a spinning stock solution for forming a porous membrane from an outer nozzle. Thus, the spinning solution is applied or impregnated on the outer surface of the fiber material support and solidified.
特許文献３〜９においても、管状編物の外表面上に膜を形成した構造体が提案されているが、かかる多孔質中空糸膜は欠陥のない膜を形成することが困難であり、また編組と膜が一体化した構造体に負荷を加えると膜部分での亀裂等が発生しやすい点において課題が残っている。 Patent Documents 3 to 9 also propose a structure in which a membrane is formed on the outer surface of a tubular knitted fabric. However, such a porous hollow fiber membrane is difficult to form a defect-free membrane, and braided. When a load is applied to a structure in which the film and the film are integrated, there remains a problem in that a crack or the like is likely to occur in the film portion.
本発明の目的は、多孔質中空糸膜モジュールの耐荷重性、耐疲労性を向上せしめることを可能とする、高流量の気体あるいは液体などの流体による多孔質中空糸膜の破断あるいは疲労による破断を抑制しうる多孔質中空糸膜およびその製造方法を提供することにある。 It is an object of the present invention to improve the load bearing capacity and fatigue resistance of a porous hollow fiber membrane module, and to break the porous hollow fiber membrane by a fluid such as a high flow rate gas or liquid, or a fracture due to fatigue. An object of the present invention is to provide a porous hollow fiber membrane capable of suppressing the above and a method for producing the same.
かかる本発明の目的は、１本または複数本の多孔質中空糸膜の外周表面を4本以上の繊維状物によって編組した編物で補強してなる繊維補強多孔質中空糸膜によって達成され、かかる多孔質中空糸膜は、１本または複数本の多孔質中空糸膜の外周表面に、4本以上の繊維状物を編み組みしながら編組することによって製造される。 The object of the present invention is achieved by a fiber-reinforced porous hollow fiber membrane formed by reinforcing the outer peripheral surface of one or a plurality of porous hollow fiber membranes with a knitted fabric braided with four or more fibrous materials. The porous hollow fiber membrane is produced by braiding four or more fibrous materials on the outer peripheral surface of one or a plurality of porous hollow fiber membranes.
本発明に係る繊維補強多孔質中空糸膜は、１本または複数本の多孔質中空糸膜の外周表面が4本以上の繊維状物によって編組した編物により補強されているため、多孔質中空糸膜が補強されるとともに多孔質中空糸膜の揺れを抑制することができることから、高流量の気体あるいは液体による多孔質中空糸膜の破断あるいは疲労による破断を有効に抑制するといったすぐれた効果を奏する。 The fiber-reinforced porous hollow fiber membrane according to the present invention is porous porous fiber because the outer peripheral surface of one or more porous hollow fiber membranes is reinforced by a knitted fabric braided with four or more fibrous materials. Since the membrane is reinforced and the vibration of the porous hollow fiber membrane can be suppressed, it has an excellent effect of effectively suppressing the fracture of the porous hollow fiber membrane due to a high flow rate gas or liquid or the fracture due to fatigue. .
また、繊維状物が多孔質中空糸膜束の外表面に存在することによって、多孔質中空糸膜束内を流れる流体の乱流を生じさせることも可能となり、加湿用途の多孔質中空糸膜にあってはその加湿効率を高めることが可能となり、ろ過用途の多孔質中空糸膜の場合にも、ろ過効率を向上せしめることができるといった効果も奏する。 In addition, since the fibrous material is present on the outer surface of the porous hollow fiber membrane bundle, it is possible to generate a turbulent flow of the fluid flowing in the porous hollow fiber membrane bundle. In this case, it is possible to increase the humidification efficiency, and the filtration efficiency can be improved even in the case of a porous hollow fiber membrane for filtration.
さらに、多孔質中空糸膜(束)表面上の繊維状物の存在は、隣接する多孔質中空糸膜同志の接触を回避することをも可能とするので、有効に使用される膜表面の減少を抑制し、また各膜間の間隔を均一化させ、かかる間隙に流体が均一に流入し、多孔質中空糸膜全体が効率よく機能することとなる。 Furthermore, the presence of the fibrous material on the surface of the porous hollow fiber membrane (bundle) also makes it possible to avoid contact between adjacent porous hollow fiber membranes, so that the membrane surface used effectively can be reduced. In addition, the spacing between the membranes is made uniform, the fluid flows uniformly into the gaps, and the entire porous hollow fiber membrane functions efficiently.
多孔質中空糸膜としては、公知の多孔質中空糸膜形成材料(ポリマー)、例えばセルロースアセテート、セルロースプロピオネート、セルロースブチレート、再生セルロースまたはこれらの混合物等のセルロース系材料、ポリビニルアルコール等の親水性ポリマー、ポリスルホン系樹脂、ポリフェニルスルホン樹脂、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の疎水性ポリマーから製造された、内径350〜1400μm、外径500〜2000μmのものなどが用いられる。 Examples of porous hollow fiber membranes include known porous hollow fiber membrane-forming materials (polymers) such as cellulose-based materials such as cellulose acetate, cellulose propionate, cellulose butyrate, regenerated cellulose, and mixtures thereof, and polyvinyl alcohol. Manufactured from hydrophobic polymers such as hydrophilic polymer, polysulfone resin, polyphenylsulfone resin, polyethersulfone resin, polyvinylidene fluoride resin, polyacrylonitrile resin, polyimide resin, polyaramid resin, polypropylene resin, polyethylene resin, Those having an inner diameter of 350 to 1400 μm and an outer diameter of 500 to 2000 μm are used.
多孔質中空糸膜は、加湿膜用として用いられる場合は、一般的に水蒸気透過係数が0.1〜0.5g/cm2・分・MPag、空気透過性が0.001〜0.05cm3/cm2・分・100kPagのポリフェニルスルホン樹脂などを材料とする多孔質中空糸膜が、また浄水器等のろ過膜として用いられる場合は、一般に純水透過係数が4〜200g/cm2・時間・100kPag、分画分子量(90％阻止性能)6,000〜200,000のポリスルホン樹脂などを材料とする多孔質中空糸膜が用いられる。 When used as a humidifying membrane, the porous hollow fiber membrane generally has a water vapor transmission coefficient of 0.1 to 0.5 g / cm 2 · min · MPag and an air permeability of 0.001 to 0.05 cm 3 / cm 2 · min. When a porous hollow fiber membrane made of 100 kPag polyphenylsulfone resin or the like is used as a filtration membrane for a water purifier or the like, the pure water permeability coefficient is generally 4 to 200 g / cm 2 · hours · 100 kPag, A porous hollow fiber membrane made of a polysulfone resin having a molecular weight (90% blocking performance) of 6,000 to 200,000 is used.
かかる多孔質中空糸膜は、1本の多孔質中空糸膜または複数本の多孔質中空糸膜を束ねたものについて、その外周表面が4本以上、好ましくは4〜8本の繊維状物によって編み組みされて編物状とされる。編み組みは基本的には丸打ち紐作製の要領にて行われる。繊維の本数がこれより少ないと、編み組みを行うことができず、また編み組が密に行われ、あるいは本数を多くすることで、空隙の割合がこれより少なくなってしまうと多孔質中空糸膜本来の性能、すなわち流体の透過性能が著しく低下してしまうため好ましくない。なお、編み組みする際の多孔質中空糸膜の本数は、多孔質中空糸膜の径や材質、あるいは用途によって適宜設定することができ、特に限定されるものではないが、より一層強度を向上させるといった観点からは、好ましくは複数本、例えば3本以上の多孔質中空糸膜束が用いられる。 Such a porous hollow fiber membrane is a bundle of one porous hollow fiber membrane or a plurality of porous hollow fiber membranes, and the outer peripheral surface thereof is 4 or more, preferably 4 to 8 fibrous materials. Braided into a knitted shape. The braiding is basically performed in the manner of making a round string. If the number of fibers is less than this, braiding cannot be performed, and if the braiding is performed densely or the number of voids is reduced by increasing the number of fibers, the porous hollow fiber This is not preferable because the original performance of the membrane, that is, the fluid permeation performance is significantly deteriorated. The number of porous hollow fiber membranes when braiding can be appropriately set depending on the diameter, material, or application of the porous hollow fiber membrane, and is not particularly limited, but further improves the strength. From the viewpoint of making them, a plurality of, for example, three or more porous hollow fiber membrane bundles are preferably used.
多孔質中空糸膜の補強に用いられる繊維材料としては、糸繊度33〜300デシテックス程度のポリエステル、ポリプロピレン、ポリエチレン、レーヨン、ビニロン、ポリアミド、ポリイミド、アラミドなどの有機繊維基材が挙げられ、好ましくはポリエステルが用いられる。 Examples of the fiber material used for reinforcing the porous hollow fiber membrane include organic fiber base materials such as polyester, polypropylene, polyethylene, rayon, vinylon, polyamide, polyimide, and aramid having a yarn fineness of about 33 to 300 dtex, preferably Polyester is used.
本発明においては、多孔質中空糸膜(束)が繊維状物によって補強されているため、強度の上昇を図ることが可能となり、多孔質中空糸膜の揺れも抑制されることから、高流量の気体あるいは液体による多孔質中空糸膜の破断あるいは疲労による破断を有効に抑制することができる。 In the present invention, since the porous hollow fiber membrane (bundle) is reinforced with a fibrous material, it becomes possible to increase the strength, and the vibration of the porous hollow fiber membrane is also suppressed. Breakage due to fatigue or fatigue of the porous hollow fiber membrane due to the gas or liquid can be effectively suppressed.
また、多孔質中空糸膜(束)外表面の繊維状物の存在は、多孔質中空糸膜束内を流れる流体の乱流を生じさせることも可能となり、これによって多孔質中空糸膜表面に絶えず新しい流体が接触するため、加湿用途の多孔質中空糸膜にあってはその加湿効率を高めることが可能となり、ろ過用途の多孔質中空糸膜の場合にも、ろ過効率を向上せしめることができるといった効果も奏する。 In addition, the presence of the fibrous material on the outer surface of the porous hollow fiber membrane (bundle) can also cause turbulence of the fluid flowing in the porous hollow fiber membrane bundle, and thereby the surface of the porous hollow fiber membrane is Because new fluids are constantly in contact with each other, it is possible to increase the humidification efficiency of a porous hollow fiber membrane for humidification, and it is possible to improve the filtration efficiency even for a porous hollow fiber membrane for filtration. There is also an effect that can be done.
さらに、隣接する多孔質中空糸膜同志の接触を回避することをも可能とするので、有効に使用される膜表面の減少を抑制し、また各膜間の間隔を均一化させ、かかる間隙に流体が均一に流入し、多孔質中空糸膜全体が効率よく機能することとなる。 In addition, since it is possible to avoid contact between adjacent porous hollow fiber membranes, it is possible to suppress a decrease in the membrane surface that is effectively used, and to make the gaps between the membranes uniform and to prevent such gaps. The fluid flows in uniformly, and the entire porous hollow fiber membrane functions efficiently.
なお、特許文献１０〜１２には、多孔質中空糸膜(束)外表面に繊維状物を螺旋状に巻き付けたものが開示されているが、後記各比較例に示される通り、多孔質中空糸膜(束)外表面に繊維状物を螺旋状に巻き付けただけでは、本発明の編み組みした編物を用いたものと比べると、長期間にわたって苛酷な条件下で使用される多孔質中空糸膜に要求される十分な強度まで補強することは難しい。 In addition, Patent Documents 10 to 12 disclose a porous hollow fiber membrane (bundle) whose outer surface is spirally wound with a fibrous material. As shown in each comparative example described later, A porous hollow fiber that is used under severe conditions for a long period of time compared to the one using the braided knitted fabric of the present invention only by spirally winding a fibrous material on the outer surface of the yarn membrane (bundle) It is difficult to reinforce to a sufficient strength required for the membrane.
得られた繊維補強多孔質中空糸膜は、１本または複数本がその中空内部のみが外部に開放されるように多孔質中空糸膜端部を束着管端部にポッティング剤を介して各々固定させることによって、中空糸膜モジュールを形成し、燃料電池車の加湿装置等の加湿膜あるいは浄水処理、下廃水処理等の処理膜として用いられる。 The obtained fiber-reinforced porous hollow fiber membranes each have one or a plurality of porous hollow fiber membranes, with the hollow hollow membrane end portion opened to the outside via a potting agent so that only the hollow interior is opened to the outside. By fixing, a hollow fiber membrane module is formed and used as a humidifying membrane for a humidifying device of a fuel cell vehicle or a treatment membrane for water purification treatment, wastewater treatment, or the like.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例１
水蒸気透過係数が0.290g/cm2・分・MPag、空気透過性が2cm3/cm2・分・100kPagのポリフェニルスルホン樹脂製多孔質中空糸膜(直径750μm、内径525μm)4本の外側を8本のポリエステル製糸(東レ製品テトロン；糸繊度280デシテックス)を用いて、毎分1mの速さで編み組みした。得られた編物補強多孔質中空糸膜束は図１に示される。
Example 1
Four porous hollow fiber membranes (diameter 750 μm, inner diameter 525 μm) made of polyphenylsulfone resin with a water vapor permeability coefficient of 0.290 g / cm 2・ min ・ MPag and air permeability of 2 cm 3 / cm 2・ min ・ 100 kPag 8 polyester yarns (Toray product Tetoron; yarn fineness 280 dtex) were knitted at a speed of 1 m / min. The resulting knitted fabric reinforced porous hollow fiber membrane bundle is shown in FIG.
編物補強多孔質中空糸膜束について、下記引張試験および疲労試験が行われた。
引張試験：編物補強多孔質中空糸膜束の両端部10mmの各外表面にエポキシ樹脂をコーテ
ィングして硬化させ、この硬化部分を引っ張り試験器(島津製作所製小型卓
上試験器EZTest)にセットし、標線間距離25mm、引張速度毎分20mmで引張試
験を行い、下記式により伸び率(％)を算出
伸び率＝(試験終了後の標線間距離−試験開始時の標線間距離)
／試験開始時の標線間距離×100
疲労試験：編組中空糸膜束の両端部10mmの各外表面にエポキシ樹脂をコーティングして
硬化させ、この硬化部分を伸縮試験器(島津製作所製サーボパルサーEHF-
LM005k1-010)にセットし、標線間距離25mm、周波数10Hzでの繰り返し伸縮試
験を実施して振幅率を算出し、破断した場合にはそれまでの繰り返し回数を
測定
The following tensile test and fatigue test were performed on the knitted fabric-reinforced porous hollow fiber membrane bundle.
Tensile test: A coat of epoxy resin is applied to the outer surfaces of both ends of the knitted reinforced porous hollow fiber membrane bundle.
This cured part is pulled by a tensile tester (a small table manufactured by Shimadzu Corporation).
Set the tester to EZTest) and perform a tensile test at a distance between the marked lines of 25 mm and a tensile speed of 20 mm per minute.
Test, and calculate the percent elongation by the following formula
Elongation rate = (Distance between marked lines after completion of test-Distance between marked lines at start of test)
/ Distance between marked lines at start of test x 100
Fatigue test: Epoxy resin coating on each outer surface of 10mm on both ends of braided hollow fiber membrane bundle
Cured, and this cured part is stretch tester (Shimadzu servo pulsar EHF-
LM005k1-010), repeated expansion and contraction test with distance between marked lines 25mm, frequency 10Hz
Perform an experiment to calculate the amplitude ratio.
Measurement
その結果、引張試験においては、伸び率57％、荷重20Nにおいても多孔質中空糸膜の破断、破損はみられず、また、疲労試験においては、伸縮繰り返し回数20,000回においても、図２に示されるように多孔質中空糸膜の破断、破損はなく、その際の振幅率は5.4％であった。いずれの試験後においても、編物補強多孔質中空糸膜束の空気透過量は、加湿器に要求される性能を十分に満たす2cm3/cm2・分・100kPagであり、これは試験前の多孔質中空糸膜と同等であった。 As a result, in the tensile test, the porous hollow fiber membrane was not broken or broken even at an elongation rate of 57% and a load of 20 N. In the fatigue test, it was shown in FIG. As shown, the porous hollow fiber membrane was not broken or damaged, and the amplitude rate at that time was 5.4%. After any of the tests, the air permeation amount of the knitted fabric reinforced porous hollow fiber membrane bundle is 2 cm 3 / cm 2 · min · 100 kPag that sufficiently satisfies the performance required for the humidifier. It was equivalent to a hollow fiber membrane.
比較例１
実施例１で用いられた編物補強多孔質中空糸膜束の代わりにポリフェニルスルホン樹脂製多孔質中空糸膜1本について、引張試験が行われたところ、伸び率57％、荷重2.0Nで多孔質中空糸膜の破断が確認された。
Comparative Example 1
When a tensile test was conducted on one porous hollow fiber membrane made of polyphenylsulfone resin instead of the knitted fabric-reinforced porous hollow fiber membrane bundle used in Example 1, it was porous at an elongation of 57% and a load of 2.0 N. The hollow fiber membrane was confirmed to be broken.
比較例２
実施例１で用いられた編物補強多孔質中空糸膜束の代わりにポリフェニルスルホン樹脂製多孔質中空糸膜4本を、糸繊度500デシテックスのポリエステル繊維2本を用いて多孔質中空糸膜束外周面に相互対称となるよう螺旋状に結束させた多孔質中空糸膜束について、疲労試験が行われたところ、伸縮繰り返し回数990回において、図３に示されるように多孔質中空糸膜の破断が確認された。
Comparative Example 2
Instead of the knitted fabric-reinforced porous hollow fiber membrane bundle used in Example 1, four porous hollow fiber membranes made of polyphenylsulfone resin and two polyester fibers having a yarn fineness of 500 dtex were used. A fatigue test was conducted on the porous hollow fiber membrane bundle that was spirally bound so as to be symmetrical with each other on the outer circumferential surface. As shown in FIG. Breaking was confirmed.
実施例２
純水透過係数が16g/cm2・時間・100kPag、分画分子量(90％阻止性能)120,000のポリスルホン樹脂製多孔質中空糸膜(直径1500μm、内径900μm)3本の外側を8本のポリエステル製糸(東レ製品テトロン；糸繊度280デシテックス)を用いて、毎分1mの速さで編み組みを行い、編物補強多孔質中空糸膜束を得た。
Example 2
Pure water permeability coefficient of 16g / cm 2 · h · 100kPag, fractionation molecular weight (90% rejection) 120,000 polysulfone resin porous hollow fiber membrane (diameter 1500 .mu.m, the inner diameter 900 .mu.m) 3 present eight polyester reeling of the outer (Toray product Tetoron; yarn fineness 280 dtex) was knitted at a speed of 1 m / min to obtain a knitted fabric-reinforced porous hollow fiber membrane bundle.
得られた編物補強多孔質中空糸膜束について、実施例１と同様に引張試験および疲労試験が行われたところ、引張試験においては、伸び率42％、荷重14.2Nにおいても多孔質中空糸膜の破断、破損はみられず、また疲労試験においては、伸縮繰り返し回数20,000回においても、多孔質中空糸膜の破断、破損はみられず、その際の振幅率は2.7％であった。いずれの試験後においても、編物補強多孔質中空糸膜束の分画分子量は、ろ過性能が十分に担保される120,000であり、試験前の多孔質中空糸膜と同等であった。 The obtained knitted fabric reinforced porous hollow fiber membrane bundle was subjected to a tensile test and a fatigue test in the same manner as in Example 1. In the tensile test, the porous hollow fiber membrane was obtained even at an elongation of 42% and a load of 14.2N. In the fatigue test, no breakage or breakage of the porous hollow fiber membrane was observed even when the expansion and contraction was repeated 20,000 times, and the amplitude rate at that time was 2.7%. After any of the tests, the molecular weight cut off of the knitted fabric-reinforced porous hollow fiber membrane bundle was 120,000, which sufficiently secured the filtration performance, and was equivalent to the porous hollow fiber membrane before the test.
比較例３
実施例２で用いられた編物補強多孔質中空糸膜束の代わりにポリスルホン樹脂製多孔質中空糸膜1本について、引張試験が行われたところ、伸び率48％、荷重4.7Nで多孔質中空糸膜の破断が確認された。
Comparative Example 3
When a tensile test was conducted on one porous porous fiber membrane made of polysulfone resin instead of the knitted fabric-reinforced porous hollow fiber membrane bundle used in Example 2, the porous hollow fiber was stretched at 48% with a load of 4.7 N. The breakage of the yarn film was confirmed.
比較例４
実施例２で用いられた編物補強多孔質中空糸膜束の代わりにポリスルホン樹脂製多孔質中空糸膜3本を、糸繊度500デシテックスのポリエステル繊維2本を用いて中空糸膜束外周面に相互対称となるよう螺旋状に結束させた多孔質中空糸膜束について、疲労試験が行われたところ、伸縮繰り返し回数3,000回において多孔質中空糸膜の破断が確認された。
Comparative Example 4
Instead of the knitted fabric reinforced porous hollow fiber membrane bundle used in Example 2, three polysulfone resin porous hollow fiber membranes were mutually attached to the outer peripheral surface of the hollow fiber membrane bundle using two polyester fibers having a yarn fineness of 500 dtex. A fatigue test was performed on the porous hollow fiber membrane bundle that was spirally bound so as to be symmetrical. As a result, the porous hollow fiber membrane was confirmed to be broken after 3,000 expansion / contraction cycles.
本発明に係る繊維補強中空糸膜を用いて形成された多孔質中空糸膜モジュールは、耐荷重性、耐疲労性にすぐれることから、燃料電池車の加湿装置等の加湿膜あるいは浄水処理、下廃水処理等の処理膜として有効に用いられる。 Since the porous hollow fiber membrane module formed using the fiber reinforced hollow fiber membrane according to the present invention is excellent in load resistance and fatigue resistance, a humidifying membrane such as a humidifier of a fuel cell vehicle or a water purification treatment, Effectively used as a treatment membrane for sewage wastewater treatment.
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| JP7475186B2 (en) | 2020-04-14 | 2024-04-26 | Nok株式会社 | Polysulfone-based hollow fiber membrane and hollow fiber membrane module |
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