JP5811738B2 - Method for repairing hollow fiber membrane module and hollow fiber membrane module - Google Patents

Method for repairing hollow fiber membrane module and hollow fiber membrane module Download PDF

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JP5811738B2
JP5811738B2 JP2011208961A JP2011208961A JP5811738B2 JP 5811738 B2 JP5811738 B2 JP 5811738B2 JP 2011208961 A JP2011208961 A JP 2011208961A JP 2011208961 A JP2011208961 A JP 2011208961A JP 5811738 B2 JP5811738 B2 JP 5811738B2
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hollow fiber
fiber membrane
repair
membrane module
leak
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JP2013066870A (en
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規孝 柴田
規孝 柴田
充 日根野谷
充 日根野谷
敬裕 森
敬裕 森
田中 利典
利典 田中
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Mitsubishi Chemical Corp
Mitsubishi Rayon Co Ltd
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Mitsubishi Rayon Co Ltd
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本発明は、中空糸膜モジュールの補修方法及び中空糸膜モジュールに関する。   The present invention relates to a method for repairing a hollow fiber membrane module and a hollow fiber membrane module.

下水処理、浄水処理、再生水の精製等においては、濾過手段として中空糸膜モジュールが広く使用されている。特に膜濾過設備の大型化が必要な用途においては、浸漬型中空糸膜モジュールと呼ばれる、中空糸膜の両端が集水管にポッティング材で接着固定され、該中空糸膜の接着固定部分以外の部分が露出した状態で被処理水に浸漬するタイプのモジュールが使用されている。   Hollow fiber membrane modules are widely used as filtration means in sewage treatment, water purification, reclaimed water purification, and the like. Particularly in applications that require an increase in the size of membrane filtration equipment, both ends of the hollow fiber membrane, called a submerged hollow fiber membrane module, are bonded and fixed to a water collection tube with a potting material, and the portions other than the adhesive fixed portion of the hollow fiber membrane A module of a type that is immersed in the water to be treated in a state where is exposed.

このような中空糸膜モジュールにおいては、濾過中に被処理水に含まれる異物等によって中空糸膜の表面が傷付き、その部分にリーク部(被処理水が濾過水側に漏れ込んでしまう部分。)が生じることがある。このような中空糸膜のリーク部を補修する方法としては、例えば、下記の方法(i)及び(ii)が知られている。
(i)リーク部が生じた中空糸膜の開口端に紫外線硬化型樹脂を充填して硬化させ、該中空糸膜の開口端を塞ぐ方法(特許文献1)。
(ii)リーク部が生じた中空糸膜の開口端にホットメルト樹脂を充填して硬化させ、該中空糸膜の開口端を塞ぐ方法(特許文献2)。
つまり、前記方法(i)及び(ii)は、いずれもリーク部が生じた中空糸膜の開口端を塞いで、該中空糸膜を濾過に使用しないようにする補修方法である。
In such a hollow fiber membrane module, the surface of the hollow fiber membrane is damaged by foreign matters contained in the water to be treated during filtration, and a leak portion (a portion in which the water to be treated leaks into the filtered water side) .) May occur. For example, the following methods (i) and (ii) are known as methods for repairing such leaked portions of the hollow fiber membrane.
(I) A method of filling the opening end of the hollow fiber membrane where the leaked portion is filled with an ultraviolet curable resin and curing it, thereby closing the opening end of the hollow fiber membrane (Patent Document 1).
(Ii) A method of filling the open end of the hollow fiber membrane in which a leak portion has occurred with hot melt resin and curing it, thereby closing the open end of the hollow fiber membrane (Patent Document 2).
That is, both the methods (i) and (ii) are repair methods in which the open end of the hollow fiber membrane in which the leak portion is generated is blocked and the hollow fiber membrane is not used for filtration.

また、濾過中は、ポッティング材による接着固定部分の被処理水側の端面近傍で中空糸膜に大きな破断応力が加わり、その部分で中空糸膜にリーク部が生じることがある。このようなリーク部を補修する方法としては、下記の方法(iii)が知られている。
(iii)ポッティング材による接着固定部分の被処理水側の中空糸膜の外周部に、リーク部を覆うように液状の水性フッ素系ゴムを供給して固形化させる方法(特許文献3)。
Further, during filtration, a large breaking stress may be applied to the hollow fiber membrane in the vicinity of the end surface on the treated water side of the portion to be bonded and fixed by the potting material, and a leak portion may occur in the hollow fiber membrane at that portion. As a method for repairing such a leak portion, the following method (iii) is known.
(Iii) A method in which a liquid aqueous fluororubber is supplied and solidified on the outer peripheral portion of the hollow fiber membrane on the treated water side of the bonded fixing portion by the potting material so as to cover the leak portion (Patent Document 3).

特開平7−136253号公報JP 7-136253 A 特開平5−168875号公報JP-A-5-168875 特開2003−93850号公報JP 2003-93850 A

しかし、前記方法(i)〜(iii)では、補修後に、モジュールにおける中空糸膜の濾過面積が大きく減少するため、処理効率が低下する問題がある。   However, in the methods (i) to (iii), the filtration area of the hollow fiber membrane in the module is greatly reduced after the repair, so that there is a problem that the processing efficiency is lowered.

本発明は、中空糸膜に生じたリーク部を安定して補修でき、かつ補修後の処理効率の低下を抑制できる中空糸膜モジュールの補修方法、及び該補修方法で補修した中空糸膜モジュールの提供を目的とする。   The present invention provides a method for repairing a hollow fiber membrane module capable of stably repairing a leak portion generated in the hollow fiber membrane and suppressing a reduction in processing efficiency after the repair, and a hollow fiber membrane module repaired by the repair method. For the purpose of provision.

本発明の中空糸膜モジュールの補修方法は、中空糸膜モジュールが有する中空糸膜に生じたリーク部を補修する方法であって、
前記中空糸膜のリーク部の膜外から膜内に硬化性の補修剤を充填し、前記リーク部を塞いだ状態で前記補修剤を硬化させる補修工程を有する方法である。
前記中空糸膜モジュールは、複数本の中空糸膜が集束され、その一方又は両方の端部が開口した状態で、両端がポッティング材により集水管に接着固定されている浸漬型モジュールであることが好ましい。
前記補修剤は、注射針を用いて前記中空糸膜のリーク部の膜外から膜内に注入して充填することが好ましい。
また、前記中空糸膜のリーク部の膜内に前記補修剤を充填した後、該中空糸膜にバブルポイント以下の圧力で気体を圧入し、前記補修剤をリーク部に凝集させた状態で硬化させることが好ましい。
前記注射針の外径は、1mm以下であることが好ましい。
前記補修剤は、エポキシ樹脂であることが好ましい。
前記補修剤の硬化前の粘度は、500〜20000mPa・sであることが好ましい。
本発明の中空糸膜モジュールは、本発明の補修方法により補修された中空糸膜モジュールである。
The repair method of the hollow fiber membrane module of the present invention is a method of repairing a leak portion generated in the hollow fiber membrane of the hollow fiber membrane module,
It is a method including a repairing step in which a curable repair agent is filled from the outside of the leak portion of the hollow fiber membrane into the membrane, and the repair agent is cured in a state where the leak portion is closed.
The hollow fiber membrane module is a submerged module in which a plurality of hollow fiber membranes are converged and one or both ends thereof are open, and both ends are bonded and fixed to a water collecting pipe with a potting material. preferable.
The repair agent is preferably filled by injecting into the membrane from the outside of the leak portion of the hollow fiber membrane using an injection needle.
In addition, after the repair agent is filled in the membrane of the leak portion of the hollow fiber membrane, a gas is injected into the hollow fiber membrane at a pressure below the bubble point, and the repair agent is aggregated in the leak portion and cured. It is preferable to make it.
The outer diameter of the injection needle is preferably 1 mm or less.
The repair agent is preferably an epoxy resin.
The viscosity of the repair agent before curing is preferably 500 to 20000 mPa · s.
The hollow fiber membrane module of the present invention is a hollow fiber membrane module repaired by the repair method of the present invention.

本発明の中空糸膜モジュールの補修方法によれば、中空糸膜に生じたリーク部を安定して補修でき、かつ補修後の処理効率の低下を抑制できる。
本発明の中空糸膜モジュールは、本発明の補修方法によって中空糸膜に生じたリーク部が安定して補修されており、かつ補修後の処理効率の低下も抑制されている。
According to the method for repairing a hollow fiber membrane module of the present invention, it is possible to stably repair a leak portion generated in the hollow fiber membrane and to suppress a reduction in processing efficiency after the repair.
In the hollow fiber membrane module of the present invention, the leaked portion generated in the hollow fiber membrane by the repair method of the present invention is stably repaired, and the reduction in the processing efficiency after repair is also suppressed.

本発明の中空糸膜モジュールの一例を示した正面図である。It is the front view which showed an example of the hollow fiber membrane module of this invention. 中空糸膜のリーク部を模式的に示した斜視図である。It is the perspective view which showed typically the leak part of the hollow fiber membrane. 図2の中空糸膜を膜の長さ方向に沿って切断したときの断面図である。It is sectional drawing when the hollow fiber membrane of FIG. 2 is cut | disconnected along the length direction of a membrane. 中空糸膜のリーク部の膜内に補修剤を充填した様子を示した断面図である。It is sectional drawing which showed a mode that the repair agent was filled in the film | membrane of the leak part of a hollow fiber membrane. 中空糸膜のリーク部の膜内に補修剤を注入する様子を示した斜視図である。It is the perspective view which showed a mode that a repair agent was inject | poured in the film | membrane of the leak part of a hollow fiber membrane.

(中空糸膜モジュール)
図1は、本発明の補修方法で補修される中空糸膜モジュールの一例を示す正面図である。
中空糸膜モジュール10は、シート状に配列された複数本の中空糸膜11と、中空糸膜11の長さ方向の両端部に設けられた2本の集水管20a,20bからなる集水部とを備え、全体として平たい矩形の形状を有している。各々の中空糸膜11の両端部は、開口した状態でポッティング材により集水管20a,20b内に着脱不能に接着固定され、中空糸膜11の中空部と集水管20a,20b内の流路が連通している。
なお、中空糸膜11の端部は、両端が開口端であることが好ましいが、一方のみが開口端で、他方の端部が封止されていてもよい。
(Hollow fiber membrane module)
FIG. 1 is a front view showing an example of a hollow fiber membrane module repaired by the repair method of the present invention.
The hollow fiber membrane module 10 includes a plurality of hollow fiber membranes 11 arranged in a sheet shape, and two water collection pipes 20a and 20b provided at both ends in the length direction of the hollow fiber membrane 11. And has a flat rectangular shape as a whole. Both ends of each hollow fiber membrane 11 are opened and fixed in a non-removable manner in the water collecting pipes 20a and 20b with a potting material, and the hollow part of the hollow fiber membrane 11 and the flow paths in the water collecting pipes 20a and 20b are connected. Communicate.
In addition, as for the edge part of the hollow fiber membrane 11, although it is preferable that both ends are open ends, only one side may be an open end and the other edge part may be sealed.

図1に示される中空糸膜モジュール10は、浸漬型膜モジュールと呼ばれ、これを被処理水に浸漬し、吸引濾過することにより、水を膜の外側から内側に透過させ、集水管20a,20bの備える端面のうちの少なくとも1箇所に形成された取水口(図示略)から、濾過水を得るものである。   The hollow fiber membrane module 10 shown in FIG. 1 is referred to as a submerged membrane module, which is immersed in water to be treated and filtered by suction, thereby allowing water to permeate from the outside of the membrane to the inside of the water collecting pipe 20a, The filtered water is obtained from a water intake (not shown) formed in at least one of the end faces of 20b.

中空糸膜11の分画レベルは、精密ろ過膜(MF)、限外濾過膜(UF)、ナノろ過膜(NF)等のいずれのレベルであってもよく、濾過の対象等に応じて、孔径、空孔率、膜厚、外径等が適宜決定される。例えば、有機物やウイルスの除去を目的とする中空糸膜の場合は、限外濾過膜、なかでも膜分画分子量が数万から数十万の中空糸膜を用いることが好ましい。また、中空糸膜11の外径としては、例えば0.1〜10mmであり、好ましくは0.5〜5mmである。   The fraction level of the hollow fiber membrane 11 may be any level of a microfiltration membrane (MF), an ultrafiltration membrane (UF), a nanofiltration membrane (NF), etc. The pore diameter, porosity, film thickness, outer diameter, etc. are appropriately determined. For example, in the case of a hollow fiber membrane for the purpose of removing organic substances and viruses, it is preferable to use an ultrafiltration membrane, particularly a hollow fiber membrane having a membrane molecular weight cut off from tens of thousands to hundreds of thousands. Moreover, as an outer diameter of the hollow fiber membrane 11, it is 0.1-10 mm, for example, Preferably it is 0.5-5 mm.

中空糸膜11の材質としては、中空糸膜状に成形可能な材質であれば制限はなく、例えばセルロース系、ポリオレフィン系、ポリビニールアルコール系、ポリスルホン系、ポリアクリロニトリル系、フッ素系等の樹脂が挙げられる。具体的には、ポリエチレン、ポリプロピレン、ポリフッ化ビニリデン、ポリ四フッ化エチレン、ポリスルホン等が挙げられる。   The material of the hollow fiber membrane 11 is not limited as long as it is a material that can be molded into a hollow fiber membrane, and examples thereof include cellulose-based, polyolefin-based, polyvinyl alcohol-based, polysulfone-based, polyacrylonitrile-based, and fluorine-based resins. Can be mentioned. Specific examples include polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, and polysulfone.

これらのなかでは、耐薬品性に優れる樹脂を選択することが好ましく、特にフッ素系樹脂が好適である。フッ素系樹脂のなかでも、中空糸膜とする際の賦形性と耐薬品性等から、ポリフッ化ビニリデン(PVDF)がより好ましい。ポリフッ化ビニリデンとしては、フッ化ビニリデンのホモポリマーの他、フッ化ビニリデンと共重合可能な単量体をフッ化ビニリデンに共重合させた共重合体が挙げられる。フッ化ビニリデンと共重合可能な単量体としては、例えばフッ化ビニル、四フッ化エチレン、三フッ化エチレン、ヘキサフルオロプロピレン等が挙げられ、1種以上を使用できる。   Among these, it is preferable to select a resin excellent in chemical resistance, and a fluorine resin is particularly preferable. Among the fluorine-based resins, polyvinylidene fluoride (PVDF) is more preferable from the viewpoint of formability and chemical resistance when forming a hollow fiber membrane. Examples of the polyvinylidene fluoride include a homopolymer of vinylidene fluoride and a copolymer obtained by copolymerizing a monomer copolymerizable with vinylidene fluoride with vinylidene fluoride. Examples of the monomer copolymerizable with vinylidene fluoride include vinyl fluoride, tetrafluoroethylene, ethylene trifluoride, hexafluoropropylene, and the like, and one or more kinds can be used.

中空糸膜11は、長期使用における膜破断防止等のため、その内部に、中空状の支持体を備えるものであってもよい。支持体としては、中空状のモノフィラメント糸、編紐、又は組紐等が挙げられる。   The hollow fiber membrane 11 may be provided with a hollow support in the inside thereof in order to prevent membrane breakage during long-term use. Examples of the support include hollow monofilament yarn, knitted string, braided string, and the like.

中空糸膜11を集水管20a,20b内に固定するためのポッティング材としては、ポリウレタン樹脂、エポキシ樹脂等の熱硬化性樹脂が好適に用いられる。ポッティング材により、中空糸膜11の内側と外側とが集水管20a,20b内において隔離される。   As a potting material for fixing the hollow fiber membrane 11 in the water collection tubes 20a and 20b, a thermosetting resin such as polyurethane resin or epoxy resin is preferably used. The potting material isolates the inside and the outside of the hollow fiber membrane 11 in the water collection pipes 20a and 20b.

集水管20a,20bの材質としては、機械的強度及び耐久性を有するものであればよく、例えばポリカーボネート、ポリスルホン、ポリプロピレン、アクリル樹脂、ABS樹脂、変性PPE樹脂、PPS樹脂、耐腐蝕性金属等が例示され、ポッティング材との接着性が良いものを選択することが好ましい。   The material of the water collecting pipes 20a and 20b may be any material having mechanical strength and durability, such as polycarbonate, polysulfone, polypropylene, acrylic resin, ABS resin, modified PPE resin, PPS resin, and corrosion-resistant metal. It is preferable to select one having good adhesion to the potting material.

図1の例のように、全体として平たい矩形の形状を有する浸漬型の中空糸膜モジュールとしては、例えば、ゼノン・エンバイロメント(株)のZeeweed500d、三菱レイヨン(株)のSADF2580等が挙げられる。このような中空糸膜モジュール10は、平たい矩形の形状を有するため、被処理水中に浸漬した際の集積度や洗浄性に優れる。
また、その集水部は、集水管20a,20bが中空糸膜11の両端部に着脱不能に固定された形態であるため、耐圧性が優れるとともに、構成がシンプルであって集積度の点で好ましい。
As an example of the immersion type hollow fiber membrane module having a flat rectangular shape as a whole as shown in FIG. 1, for example, Zeweed 500d of Zenon Environment Co., Ltd., SADF 2580 of Mitsubishi Rayon Co., Ltd. and the like can be mentioned. Since such a hollow fiber membrane module 10 has a flat rectangular shape, it has excellent integration and cleanability when immersed in the water to be treated.
Moreover, since the water collection part 20a, 20b is the form fixed to the both ends of the hollow fiber membrane 11 so that attachment or detachment is impossible, the pressure collection property is excellent, the structure is simple, and the degree of integration is high. preferable.

なお、中空糸膜モジュールの構成、形状としては、図示例のものに限定されず、被処理水槽の大きさ、被処理水に含まれる処理成分の性状、洗浄性等に鑑みて、適宜選択される。例えば集水管としては、軸方向に垂直な断面が矩形である管に限定されず、断面が円形(円環状)の管等も挙げられる。また、図1では、いわゆる浸漬型の膜モジュールを例として示している。   The configuration and shape of the hollow fiber membrane module are not limited to those shown in the drawings, and are appropriately selected in view of the size of the water tank to be treated, the properties of the treatment components contained in the water to be treated, the washability, and the like. The For example, the water collecting pipe is not limited to a pipe having a rectangular cross section perpendicular to the axial direction, and includes a pipe having a circular (annular) cross section. In FIG. 1, a so-called immersion type membrane module is shown as an example.

このような中空糸膜モジュール10においては、その使用中に、被処理水に含まれる異物により中空糸膜11の表面が傷付く等して、ピンホールや破れが生じ、その部分が図2及び図3に示すようなリーク部30となることがある。リーク部とは、このように中空糸膜の内側と外側との隔離が不完全になり、被処理水が濾過水側に漏れ込んでしまう部分のことを言う。   In such a hollow fiber membrane module 10, during use, the surface of the hollow fiber membrane 11 is damaged by foreign matters contained in the water to be treated, thereby causing pinholes and tears, and the portions are shown in FIG. A leak portion 30 as shown in FIG. The leak portion refers to a portion in which the separation between the inner side and the outer side of the hollow fiber membrane is imperfect and the water to be treated leaks into the filtered water side.

(補修方法)
以下、本発明の中空糸膜モジュールの補修方法の一例として、中空糸膜モジュール10の中空糸膜11に生じたリーク部30の補修方法について説明する。中空糸膜モジュール10の補修方法としては、例えば、下記のリーク検査工程、補修工程及び補修確認工程を有する方法が挙げられる。
リーク検出工程:リーク検査を行って中空糸膜11に生じたリーク部30を検出する。
補修工程:図4に示すように、中空糸膜11のリーク部30の膜内に硬化性の補修剤40(以下、単に「補修剤40」という。)を充填し、リーク部30を塞いだ状態で補修剤40を硬化させる。
補修確認工程:前記補修工程後に、再度リーク検査を行ってリーク部30が補修されていることを確認する。
(Repair method)
Hereinafter, as an example of a method for repairing the hollow fiber membrane module of the present invention, a method for repairing the leak portion 30 generated in the hollow fiber membrane 11 of the hollow fiber membrane module 10 will be described. Examples of the repair method of the hollow fiber membrane module 10 include a method having the following leak inspection process, repair process, and repair confirmation process.
Leak detection step: A leak inspection is performed to detect the leak portion 30 generated in the hollow fiber membrane 11.
Repair process: As shown in FIG. 4, a curable repair agent 40 (hereinafter, simply referred to as “repair agent 40”) is filled in the membrane of the leak portion 30 of the hollow fiber membrane 11 to block the leak portion 30. The repair agent 40 is cured in the state.
Repair confirmation process: After the repair process, the leak inspection is performed again to confirm that the leak portion 30 is repaired.

リーク検査工程:
リーク部30を検出するリーク検査方法としては、微粒子を用いた検査方法や、いわゆる吸引法等が挙げられる。なかでも、中空糸膜モジュール10を水又は水溶液の中に浸漬した状態で、この中空糸膜モジュール10に対して、中空糸膜モジュール10の濾過方向の逆方向に気体を圧入して、気泡の発生箇所からリーク部30の位置を特定する方法が好ましい。具体的には、中空糸膜モジュール10をエタノール水溶液等の有機溶剤水溶液に浸漬し、その状態で気体を圧入する方法や、中空糸膜モジュール10をエタノール水溶液に浸漬して膜表面を親水化し、親水化された中空糸膜モジュール10を一旦取り出し、水の入った水槽に浸漬しなおし、その状態で気体を圧入する方法がある(例えば特開2001−205056号公報参照。)。また、有機溶剤水溶液に代えて、界面活性剤水溶液を用いる場合もある。
このような加圧気体を用いたリーク検査方法は、検出感度が高く、広く採用されている。
Leak inspection process:
Examples of the leak inspection method for detecting the leak portion 30 include an inspection method using fine particles, a so-called suction method, and the like. Among these, in a state where the hollow fiber membrane module 10 is immersed in water or an aqueous solution, a gas is pressed into the hollow fiber membrane module 10 in the direction opposite to the filtration direction of the hollow fiber membrane module 10 to thereby reduce the amount of bubbles. A method of identifying the position of the leak portion 30 from the occurrence location is preferable. Specifically, the hollow fiber membrane module 10 is immersed in an organic solvent aqueous solution such as an ethanol aqueous solution, and a gas is pressed in that state, or the hollow fiber membrane module 10 is immersed in an ethanol aqueous solution to hydrophilize the membrane surface, There is a method in which the hollow fiber membrane module 10 that has been made hydrophilic is once taken out, re-immersed in a water tank containing water, and gas is injected in that state (see, for example, Japanese Patent Application Laid-Open No. 2001-205056). Further, a surfactant aqueous solution may be used in place of the organic solvent aqueous solution.
Such a leak inspection method using a pressurized gas has high detection sensitivity and is widely adopted.

なお、図示例の中空糸膜モジュール10は、集水管20a,20bが中空糸膜11の両端部に着脱不能に固定され、中空糸膜11の端面を露出させることができない形態である。この形態の中空糸膜モジュール10について、加圧気体を用いてリーク検査を行う場合には、集水管20a,20b側から中空糸膜11に気体を圧入して、中空糸膜11からの気泡の発生箇所を特定する方法、すなわち、濾過方向の逆方向に気体を圧入する方法が好適に採用される。   In the illustrated hollow fiber membrane module 10, the water collecting pipes 20 a and 20 b are fixed to both ends of the hollow fiber membrane 11 so as not to be detachable, and the end face of the hollow fiber membrane 11 cannot be exposed. When a leak test is performed on the hollow fiber membrane module 10 of this form using a pressurized gas, gas is press-fitted into the hollow fiber membrane 11 from the water collecting pipes 20a and 20b side, and bubbles from the hollow fiber membrane 11 are removed. A method of specifying the generation point, that is, a method of press-fitting gas in the direction opposite to the filtration direction is preferably employed.

補修工程:
中空糸膜モジュール10の中空糸膜11内の水を排出させ、図5に示すように、シリンジ51及びシリンジ51の先端に取り付けられた注射針52を有する注射器50を用い、注射針52を中空糸膜11のリーク部30内に挿入し、シリンジ51内に収容した補修剤40を注射針52から、中空糸膜11のリーク部30の膜内に注入して充填し、図4に示すように、リーク部30を塞いだ状態で補修剤40を硬化させる。
本発明の補修方法では、このように、中空糸膜11のリーク部30の膜内に補修剤40を充填して、リーク部30を補修剤40で塞ぐことで補修する。そのため、リーク部30が生じた中空糸膜11の開口端を塞がずに、リーク部30から被処理液が濾過水に漏れ込むことを防ぐことができるので、中空糸膜11におけるリーク部30の両側の膜部分は補修後も濾過に利用できる。よって、補修後の処理効率の低下が抑制される。
また、リーク部30に補修剤40を塗布して硬化させることでリーク部30を塞いで補修することも考えられるが、この方法を試みたところ、補修箇所の耐久性が充分に得られなかった。これに対し、本発明の補修方法は、リーク部30の膜内に補修剤40を充填して硬化させることでリーク部30を塞ぐので、補修剤40の硬化物がリーク部30から脱離し難く、補修した中空糸膜11を補修後に濾過に利用しても補修箇所の耐久性が充分に得られる。
Repair process:
The water in the hollow fiber membrane 11 of the hollow fiber membrane module 10 is discharged, and as shown in FIG. 5, the syringe 51 having the syringe 51 and the injection needle 52 attached to the tip of the syringe 51 is used, and the injection needle 52 is hollowed out. As shown in FIG. 4, the repair agent 40 inserted into the leak portion 30 of the thread membrane 11 and injected into the membrane of the leak portion 30 of the hollow fiber membrane 11 is injected from the injection needle 52 into the membrane of the hollow fiber membrane 11. In addition, the repair agent 40 is cured in a state where the leak portion 30 is blocked.
In the repairing method of the present invention, the repairing agent 40 is filled in the membrane of the leaking portion 30 of the hollow fiber membrane 11 and the leaking portion 30 is closed by the repairing agent 40 in this way. Therefore, it is possible to prevent the liquid to be treated from leaking into the filtrate from the leak portion 30 without blocking the open end of the hollow fiber membrane 11 in which the leak portion 30 is generated. The membrane parts on both sides can be used for filtration even after repair. Therefore, a reduction in processing efficiency after repair is suppressed.
In addition, it is conceivable to repair the leaked portion 30 by applying the repair agent 40 to the leaked portion 30 and curing the leaked portion 30, but when this method was tried, the durability of the repaired portion could not be sufficiently obtained. . In contrast, the repair method of the present invention fills the repair agent 40 in the film of the leak portion 30 and cures the leak portion 30 so that the cured product of the repair agent 40 is not easily detached from the leak portion 30. Even if the repaired hollow fiber membrane 11 is used for filtration after repair, the durability of the repaired portion can be sufficiently obtained.

注射針52の外径は、注射針52をリーク部30に挿入したときに、中空糸膜11が裂けてリーク部30がより大きくなることを抑制しやすいことから、1mm(19G)以下が好ましい。また、注射針52の外径は、注射針52の内径が充分に確保されて補修剤40の注入が容易になることから、0.5mm(25G)以上が好ましい。
なお、括弧内は、注射針の太さを表すG(ゲージ)という単位を用いて外径を示したものであり、数字が大きいほど外径が細くなる。
The outer diameter of the injection needle 52 is preferably 1 mm (19 G) or less because it is easy to prevent the hollow fiber membrane 11 from tearing and the leak portion 30 from becoming larger when the injection needle 52 is inserted into the leak portion 30. . The outer diameter of the injection needle 52 is preferably 0.5 mm (25 G) or more because the inner diameter of the injection needle 52 is sufficiently secured and the injection of the repairing agent 40 becomes easy.
In the parentheses, the outer diameter is shown using a unit called G (gauge) representing the thickness of the injection needle. The larger the number, the thinner the outer diameter.

補修剤40としては、中空糸膜のリーク部の補修が可能な硬化性の補修剤であればよく、熱硬化型接着剤(例えば、アクリル系接着剤、エポキシ系接着剤、オキセタン系接着剤等。)、湿気硬化型接着剤(例えば、ウレタン系接着剤、シリコーン系接着剤、変成シリコーン系接着剤、シアノアクリレート系瞬間接着剤等。)、紫外線硬化型接着剤(例えば、アクリル系、シアノアクリレート系等。)、ホットメルト樹脂、エポキシ樹脂等が挙げられる。   The repairing agent 40 may be a curable repairing agent capable of repairing the leaked portion of the hollow fiber membrane, such as a thermosetting adhesive (for example, an acrylic adhesive, an epoxy adhesive, an oxetane adhesive, etc. ), Moisture curable adhesives (eg, urethane adhesives, silicone adhesives, modified silicone adhesives, cyanoacrylate instantaneous adhesives, etc.), UV curable adhesives (eg, acrylic, cyanoacrylate, etc.) System, etc.), hot melt resins, epoxy resins and the like.

補修剤40として、紫外線によってのみ硬化する紫外線硬化型樹脂やホットメルト樹脂を使用する場合は、リーク部30が乾燥していないとこれらの補修剤がリーク部30に良好に付着しないため、補修時の前処理としてリーク部30の乾燥が不可欠となる。そのため、補修前に乾燥しなくてもよくなることから、熱硬化型接着剤、湿気硬化型接着剤、エポキシ樹脂が好ましい。
補修前の乾燥が不要であると、乾燥に要する時間を削減できるだけでなく、乾燥により中空糸膜が湿熱収縮を起こして有効膜面積が変動することを回避できる。また、中空糸膜を一旦乾燥させてしまうと、リーク部の補修後にリーク部が確実に閉塞されたかどうかを確認する補修確認工程や、中空糸膜モジュールを被処理水中に戻す時に、中空糸膜を再度親水化させる必要が生じ、時間や手間がかかる。これに対して、補修前に乾燥しない場合には、再度親水化させる作業が不要となり、時間も手間も削減できる。また、乾燥と親水化を繰り返すことによる中空糸膜の湿熱収縮による形状変化も回避できる。さらに、補修前に乾燥が不要であると、乾燥設備のある施設まで中空糸膜モジュール10を移動させる必要がなく、その使用現場、すなわち浄水場や下水処理場等で、速やかに補修することができる。これによりリーク部30の補修に伴う作業に要する時間、手間を大幅に削減でき、現場での作業効率が格段に向上する。
補修剤40としては、ポッティング材と同種の補修剤がより好ましい。また、耐水性に優れることから、エポキシ樹脂が特に好ましい。
When an ultraviolet curable resin or a hot melt resin that is cured only by ultraviolet rays is used as the repairing agent 40, these repairing agents do not adhere well to the leaking part 30 unless the leaking part 30 is dry. As a pretreatment, drying of the leak portion 30 is indispensable. Therefore, a thermosetting adhesive, a moisture curable adhesive, and an epoxy resin are preferable because they do not need to be dried before repair.
If drying before repair is unnecessary, not only the time required for drying can be reduced, but also the occurrence of fluctuations in the effective membrane area due to wet-heat shrinkage of the hollow fiber membrane due to drying can be avoided. In addition, once the hollow fiber membrane is dried, a repair confirmation process for confirming whether or not the leak portion is reliably blocked after repair of the leak portion, and when returning the hollow fiber membrane module to the water to be treated, Need to be hydrophilized again, which takes time and labor. On the other hand, when it is not dried before repairing, the work of making it hydrophilic again becomes unnecessary, and both time and labor can be reduced. Moreover, the shape change by the wet heat shrinkage | contraction of the hollow fiber membrane by repeating drying and hydrophilization can also be avoided. Furthermore, if drying is not required before repair, it is not necessary to move the hollow fiber membrane module 10 to a facility with a drying facility, and it is possible to quickly repair at the site of use thereof, that is, a water purification plant or a sewage treatment plant. it can. As a result, the time and labor required for the work associated with the repair of the leak portion 30 can be greatly reduced, and the work efficiency on site can be greatly improved.
As the repairing agent 40, a repairing agent of the same type as the potting material is more preferable. Moreover, since it is excellent in water resistance, an epoxy resin is especially preferable.

中空糸膜11の内部での流動性が高くなりすぎず、リーク部30を補修剤40で塞ぐことが容易になることから、補修剤40の硬化前の粘度は、500mPa・s以上が好ましく、1000mPa・s以上がより好ましい。また、中空糸膜11のリーク部30の膜内への注入が容易になることから、補修剤40の硬化前の粘度は、20000mPa・s以下が好ましく、10000mPa・s以下がより好ましい。   Since the fluidity inside the hollow fiber membrane 11 does not become too high and it becomes easy to close the leak portion 30 with the repair agent 40, the viscosity of the repair agent 40 before curing is preferably 500 mPa · s or more, 1000 mPa · s or more is more preferable. Moreover, since the injection | pouring into the film | membrane of the leak part 30 of the hollow fiber membrane 11 becomes easy, 20000 mPa * s or less is preferable and the viscosity before hardening of the repair agent 40 is more preferable.

中空糸膜11のリーク部30の膜内に補修剤40を充填した後は、該中空糸膜11にバブルポイント以下の圧力で気体を圧入して、補修剤40をリーク部30に凝集させた状態で硬化させることが好ましい。これにより、リーク部30の膜内に注入した補修剤40が中空糸膜11の開口端側に流動することを抑制できるので、補修後の濾過面積の減少がより小さくなり、補修後の処理効率の低下をより抑制できる。また、補修剤40がリーク部30の膜内に凝集することで、リーク部30がより安定して塞がれるので、より確実にリーク部30を補修することができる。
気体を圧入する方向は、中空糸膜11の開口端側から膜の長さ方向の中央に向かう方向、すなわち、被処理水を加圧して中空糸膜11の外側から内側に水を透過させて濾過水を得る場合の濾過方向と反対方向が好ましい。中空糸膜11の両端が開口端となっている場合は、中空糸膜11の両方の開口端側から気体を圧入する。
なお、前記バブルポイントとは、中空糸膜11に開口端側から気体を圧入したときに、リーク部30から気泡が発生する最低圧力である。
After filling the repair agent 40 into the membrane of the leak portion 30 of the hollow fiber membrane 11, gas was injected into the hollow fiber membrane 11 at a pressure equal to or lower than the bubble point to aggregate the repair agent 40 into the leak portion 30. It is preferable to cure in the state. Thereby, since it can suppress that the repair agent 40 inject | poured in the film | membrane of the leak part 30 flows into the opening end side of the hollow fiber membrane 11, the reduction of the filtration area after repair becomes smaller, and the processing efficiency after repair Can be further suppressed. Further, since the repair agent 40 aggregates in the film of the leak portion 30, the leak portion 30 is more stably blocked, so that the leak portion 30 can be repaired more reliably.
The direction in which the gas is injected is the direction from the open end side of the hollow fiber membrane 11 toward the center of the length direction of the membrane, that is, the water to be treated is pressurized to allow water to permeate from the outside to the inside of the hollow fiber membrane 11. The direction opposite to the filtration direction when obtaining filtered water is preferred. When both ends of the hollow fiber membrane 11 are open ends, gas is injected from both open end sides of the hollow fiber membrane 11.
The bubble point is the lowest pressure at which bubbles are generated from the leak portion 30 when a gas is pressed into the hollow fiber membrane 11 from the opening end side.

中空糸膜11内に気体を圧入する際の圧力は、10〜100kPaが好ましい。前記圧力が下限値以上であれば、補修剤40がリーク部30の膜内で凝集しやすい。また、前記圧力が上限値以下であれば、リーク部30の膜内に注入した補修剤40がリーク部30から放出されることを抑制しやすい。   The pressure when the gas is pressed into the hollow fiber membrane 11 is preferably 10 to 100 kPa. If the pressure is equal to or higher than the lower limit value, the repair agent 40 tends to aggregate in the film of the leak portion 30. Moreover, if the said pressure is below an upper limit, it will be easy to suppress that the repair agent 40 inject | poured in the film | membrane of the leak part 30 is discharge | released from the leak part 30. FIG.

補修剤40の硬化は、補修剤40の種類に応じて適宜行えばよい。例えば、補修剤40が湿気硬化型接着剤であれば、中空糸膜11のリーク部30の膜内に充填したときに、中空糸膜11中の水分により硬化反応が進行する。また、補修剤40が熱硬化型接着剤であれば、リーク部30の膜内に充填した後に熱硬化型接着剤の種類に応じた温度で加熱することで硬化反応が進行する。   The curing of the repair agent 40 may be appropriately performed according to the type of the repair agent 40. For example, if the repair agent 40 is a moisture curable adhesive, the curing reaction proceeds due to moisture in the hollow fiber membrane 11 when filled in the leaked portion 30 of the hollow fiber membrane 11. If the repair agent 40 is a thermosetting adhesive, the curing reaction proceeds by heating at a temperature corresponding to the type of the thermosetting adhesive after filling the film of the leak portion 30.

補修確認工程:
補修工程で補修した中空糸膜モジュール10に対してリーク検査を行い、リーク部30が補修できているかどうかを確認する。
補修確認工程におけるリーク検査は、前記リーク検査工程と同様にして行える。
Repair confirmation process:
A leak inspection is performed on the hollow fiber membrane module 10 repaired in the repair process, and it is confirmed whether or not the leak portion 30 has been repaired.
The leak inspection in the repair confirmation process can be performed in the same manner as the leak inspection process.

以上説明した本発明の補修方法によれば、中空糸膜に生じたリーク部の膜内に補修剤を充填して硬化させることでリーク部を補修することができ、かつ補修後の処理効率の低下も抑制できる。また、補修箇所の耐久性が充分に得られる。
なお、本発明の補修方法は、前記した方法には限定されない。例えば、補修方法において、補修剤を注入する際に注射針を使用しなくてもよい。また、注射針を使用する場合でも、例えば補修剤がカートリッジ型であるとき等は、カートリッジに注射針を装着して補修剤の注入を行ってもよい。
また、リーク検査工程、補修確認工程の一方又は両方を行わない方法であってもよい。
According to the repair method of the present invention described above, the leak part can be repaired by filling the film of the leak part generated in the hollow fiber membrane with a repair agent and curing, and the processing efficiency after repair is improved. The decrease can also be suppressed. Further, sufficient durability of the repaired portion can be obtained.
The repair method of the present invention is not limited to the above-described method. For example, in the repair method, the injection needle may not be used when the repair agent is injected. Even when an injection needle is used, for example, when the repair agent is a cartridge type, the injection of the repair agent may be performed by attaching the injection needle to the cartridge.
Moreover, the method which does not perform one or both of a leak inspection process and a repair confirmation process may be sufficient.

本発明の中空糸膜モジュールは、前述した本発明の補修方法によってリーク部を補修した中空糸膜モジュールであり、補修前に比べて処理効率の低下が抑制されており、補修箇所の耐久性にも優れている。   The hollow fiber membrane module of the present invention is a hollow fiber membrane module in which a leak portion is repaired by the above-described repair method of the present invention, and a reduction in processing efficiency is suppressed compared to before repair, and the durability of the repaired portion is improved. Is also excellent.

以下、実施例によって本発明を詳細に説明するが、本発明は以下の記載によっては限定されない。
[実施例1]
PET(ポリエチレンテレフタレート)繊維を編むことにより中空状に加工し、その表面にPVDF(ポリフッ化ビニリデン)多孔質部を形成した多孔質中空糸膜(三菱レイヨン(株)製、内径1000μm、外径2800μm)を多数本備え、これらの中空糸膜が露出している状態の浸漬型の中空糸膜モジュールについて、以下のようにして、リーク検査工程、補修工程及び補修確認工程を行った。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description.
[Example 1]
Porous hollow fiber membrane (Mitsubishi Rayon Co., Ltd., inner diameter 1000 μm, outer diameter 2800 μm) processed into a hollow shape by knitting PET (polyethylene terephthalate) fiber and having a PVDF (polyvinylidene fluoride) porous portion formed on the surface thereof The immersion type hollow fiber membrane module in which these hollow fiber membranes are exposed were subjected to a leak inspection process, a repair process, and a repair confirmation process as follows.

リーク検査工程:
上述の中空糸膜モジュールを親水化溶液(日信化学工業(株)製、オルフィンEXP4036、0.3wt%水溶液:表面張力25.8mN/m)に10分間浸漬後、一旦取り出し、水の入った水槽に浸漬しなおし、その状態で、中空糸膜モジュールの中空糸膜に対して内側から加圧空気を100kPaで注入し、リーク検査を実施した。
中空糸膜から気泡が発生した箇所をリーク部としてマーキングした後、中空糸膜モジュール内部の水を排出させ、リーク部とその周囲の液滴を水が滴下しない程度にウェスペーパーでぬぐった。
補修工程:
補修剤として、カートリッジ型の二液硬化エポキシ接着剤(Henkel製 E−30CL)を使用し、そのカートリッジの先端に外径0.8mm(21G)の注射針(テルモ製)を取り付け、該注射針をリーク部に挿入し、中空糸膜のリーク部の膜内に補修剤を3mL注入して充填し、硬化させた。
補修確認工程:
硬化後、前記リーク検査工程と同様にしてリーク検査を行い、リーク部が補修されていることを確認したところ、気泡の発生はなく、リーク部が補修されていることが確認された。
Leak inspection process:
The hollow fiber membrane module described above was immersed in a hydrophilization solution (manufactured by Nissin Chemical Industry Co., Ltd., Olfin EXP4036, 0.3 wt% aqueous solution: surface tension 25.8 mN / m) for 10 minutes, and then taken out and filled with water. It was immersed again in the water tank, and in that state, pressurized air was injected at 100 kPa from the inside into the hollow fiber membrane of the hollow fiber membrane module, and a leak test was performed.
After marking a portion where bubbles were generated from the hollow fiber membrane as a leak portion, water inside the hollow fiber membrane module was discharged, and the leak portion and surrounding droplets were wiped with waste paper to such an extent that water did not drop.
Repair process:
As a repairing agent, a cartridge-type two-component curing epoxy adhesive (E-30CL manufactured by Henkel) was used, and an injection needle (made by Terumo) having an outer diameter of 0.8 mm (21 G) was attached to the tip of the cartridge. Was inserted into the leak portion, and 3 mL of a repair agent was injected into the membrane of the leak portion of the hollow fiber membrane to be cured.
Repair confirmation process:
After curing, a leak inspection was performed in the same manner as in the leak inspection step, and it was confirmed that the leak portion was repaired. As a result, there was no generation of bubbles and it was confirmed that the leak portion was repaired.

前記補修方法により補修した後の中空糸膜モジュールを用いて、水中で1000時間の濾過運転を行い、その後、再度リーク検査を実施したが、補修したリーク部からの気泡の発生はなく、補修箇所は優れた耐久性を有していた。   Using the hollow fiber membrane module after repair by the repair method, filtration operation was performed in water for 1000 hours, and then a leak inspection was performed again. However, there was no generation of bubbles from the repaired leak portion, and the repair location Had excellent durability.

[実施例2]
実施例1と同様にしてリーク検査を実施し、気泡として検出されたリーク部にマーキングを行い、モジュール内部の水を排出した後、濾過方向と逆方向にバブルポイント以下の20kPaで乾燥空気を圧入して中空糸膜を乾燥させた。
次いで、実施例1と同様にして中空糸膜のリーク部の膜内に補修剤を注入して充填し、濾過方向と逆方向にバブルポイント以下の20kPaで乾燥空気を5分間圧入しながら補修剤を硬化させた。
次いで、実施例1と同様にしてリーク検査を行い、リーク部が補修されていることを確認したところ、気泡の発生はなく、リーク部が補修されていることが確認された。
[Example 2]
A leak test was performed in the same manner as in Example 1. After marking the leaked part detected as bubbles and discharging the water inside the module, dry air was injected under 20 kPa below the bubble point in the direction opposite to the filtration direction. Then, the hollow fiber membrane was dried.
Next, in the same manner as in Example 1, the repair agent was injected and filled into the membrane of the leak portion of the hollow fiber membrane, and the repair agent was injected while pressing dry air at 20 kPa below the bubble point in the direction opposite to the filtration direction for 5 minutes. Was cured.
Next, a leak inspection was performed in the same manner as in Example 1, and it was confirmed that the leak portion was repaired. As a result, no bubbles were generated, and it was confirmed that the leak portion was repaired.

前記補修方法により補修した後の中空糸膜モジュールを用いて、水中で1000時間の濾過運転を行い、その後、再度リーク検査を実施したが、補修したリーク部からの気泡の発生はなく、補修箇所は優れた耐久性を有していた。   Using the hollow fiber membrane module after repair by the repair method, filtration operation was performed in water for 1000 hours, and then a leak inspection was performed again. However, there was no generation of bubbles from the repaired leak portion, and the repair location Had excellent durability.

[比較例1]
実施例1と同様にしてリーク検査工程を実施した後、補修工程において、補修剤である二液硬化エポキシ接着剤(Henkel製 E−30CL)をリーク部周辺の表面に塗布し、硬化させることでリーク部を塞いで補修を行った。次いで、実施例1と同様にして補修確認工程を実施したところ気泡の発生はなく、リーク部が補修されていることが確認された。
前記補修方法により補修した後の中空糸膜モジュールを用いて、水中で1000時間の濾過運転を行い、その後、再度リーク検査を実施したところ、気泡が発生し、濾過運転中に補修箇所の一部が剥離したことが確認された。
[Comparative Example 1]
After performing the leak inspection process in the same manner as in Example 1, in the repair process, a two-part curing epoxy adhesive (E-30CL manufactured by Henkel), which is a repair agent, is applied to the surface around the leak portion and cured. The leak was closed and repaired. Subsequently, when the repair confirmation process was implemented similarly to Example 1, it was confirmed that there was no bubble generation and the leak part was repaired.
Using the hollow fiber membrane module after being repaired by the repair method, a filtration operation was performed in water for 1000 hours, and then a leak inspection was performed again. As a result, bubbles were generated and a part of the repaired part was found during the filtration operation. It was confirmed that was peeled off.

10 中空糸膜モジュール
11 中空糸膜
20a,20b 集水管
30 リーク部
40 補修剤
50 注射器
51 シリンジ
52 注射針
DESCRIPTION OF SYMBOLS 10 Hollow fiber membrane module 11 Hollow fiber membrane 20a, 20b Water collecting pipe 30 Leak part 40 Repair agent 50 Syringe 51 Syringe 52 Injection needle

Claims (8)

中空糸膜モジュールが有する中空糸膜に生じたリーク部を補修する方法であって、
前記中空糸膜のリーク部の膜外から膜内に硬化性の補修剤を充填し、前記リーク部を塞いだ状態で前記補修剤を硬化させる補修工程を有する、中空糸膜モジュールの補修方法。
A method of repairing a leak portion generated in a hollow fiber membrane of a hollow fiber membrane module,
A repair method for a hollow fiber membrane module, comprising a repairing step of filling a curable repair agent into the membrane from outside the leak portion of the hollow fiber membrane and curing the repair agent in a state where the leak portion is closed.
前記中空糸膜モジュールが、複数本の中空糸膜が集束され、その一方又は両方の端部が開口した状態で、両端がポッティング材により集水管に接着固定されている浸漬型モジュールである、請求項1に記載の中空糸膜モジュールの補修方法。   The hollow fiber membrane module is a submerged module in which a plurality of hollow fiber membranes are converged and one or both ends thereof are open, and both ends are bonded and fixed to a water collecting pipe with a potting material. Item 2. A method for repairing a hollow fiber membrane module according to Item 1. 前記補修剤を、注射針を用いて前記中空糸膜のリーク部の膜外から膜内に注入して充填する、請求項1又は2に記載の中空糸膜モジュールの補修方法。 The method for repairing a hollow fiber membrane module according to claim 1 or 2, wherein the repair agent is injected and filled into the membrane from outside the leak portion of the hollow fiber membrane using an injection needle. 前記中空糸膜のリーク部の膜内に前記補修剤を充填した後、該中空糸膜にバブルポイント以下の圧力で気体を圧入し、前記補修剤をリーク部に凝集させた状態で硬化させる、請求項1〜3のいずれか一項に記載の中空糸膜モジュールの補修方法。   After filling the repair agent into the membrane of the leak portion of the hollow fiber membrane, a gas is injected into the hollow fiber membrane at a pressure equal to or lower than the bubble point, and the repair agent is hardened in a state of being aggregated in the leak portion. The repair method of the hollow fiber membrane module as described in any one of Claims 1-3. 前記注射針の外径が1mm以下である、請求項3に記載の中空糸膜モジュールの補修方法。   The repair method of the hollow fiber membrane module of Claim 3 whose outer diameter of the said injection needle is 1 mm or less. 前記補修剤がエポキシ樹脂である、請求項1〜5のいずれか一項に記載の中空糸膜モジュールの補修方法。   The repair method of the hollow fiber membrane module as described in any one of Claims 1-5 whose said repair agent is an epoxy resin. 前記補修剤の硬化前の粘度が500〜20000mPa・sである、請求項1〜6のいずれか一項に記載の中空糸膜モジュールの補修方法。   The repair method of the hollow fiber membrane module as described in any one of Claims 1-6 whose viscosity before hardening of the said repair agent is 500-20000 mPa * s. 請求項1〜7のいずれか一項に記載の方法により補修された中空糸膜モジュール。   The hollow fiber membrane module repaired by the method as described in any one of Claims 1-7.
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