WO2018092516A1 - Hollow-fiber membrane, filtration module, and wastewater treatment device - Google Patents

Hollow-fiber membrane, filtration module, and wastewater treatment device Download PDF

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WO2018092516A1
WO2018092516A1 PCT/JP2017/038111 JP2017038111W WO2018092516A1 WO 2018092516 A1 WO2018092516 A1 WO 2018092516A1 JP 2017038111 W JP2017038111 W JP 2017038111W WO 2018092516 A1 WO2018092516 A1 WO 2018092516A1
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hollow fiber
fiber membrane
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limit
resin film
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French (fr)
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大輝 宮田
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住友電気工業株式会社
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D63/00Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02Hollow fibre modules
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08Hollow fibre membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12Composite membranes; Ultra-thin membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/26Polyalkenes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/30Polyalkenyl halides
    • B01D71/32Polyalkenyl halides containing fluorine atoms
    • B01D71/36Polytetrafluoroethene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/38Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • C02F3/12Activated sludge processes
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/08Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/12Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage

Abstract

The hollow-fiber membrane according to an embodiment of the present invention comprises: a cylindrical framework material which comprises polytetrafluoroethylene as the main component and has porosity; and a resinous coating film which has hydrophilicity and covers the outer surface and inner pore surfaces of the framework material. The hollow-fiber membrane has a peripheral surface which has a contact angle with pure water of 40-80° and which, in water, has a contact angle with heavy oil C of 110-150°.

Description

中空糸膜、濾過モジュール及び排水処理装置Hollow fiber membrane, filtration module and waste water treatment device
 本発明は、中空糸膜、濾過モジュール及び排水処理装置に関する。本出願は、2016年11月17日出願の日本出願第2016-224141号に基づく優先権を主張し、上記日本出願に記載された全ての記載内容を援用するものである。 The present invention relates to a hollow fiber membrane, a filtration module, and a wastewater treatment apparatus. This application claims priority based on Japanese Patent Application No. 2016-224141 filed on November 17, 2016, and incorporates all the description content described in the above Japanese application.
 例えば排水処理等の多様な目的で、被処理水を濾過して固形物を除去する濾過膜の一種として、多孔質体を比較的径が小さい筒状に形成した中空糸膜が用いられることがある。このような中空糸膜の材質としては、機械的強度及び化学的安定性に比較的優れるポリテトラフルオロエチレンを主成分とするものが知られている。 For example, for various purposes such as wastewater treatment, a hollow fiber membrane in which a porous body is formed in a cylindrical shape having a relatively small diameter is used as a kind of filtration membrane that removes solids by filtering water to be treated. is there. As a material for such a hollow fiber membrane, a material mainly composed of polytetrafluoroethylene which is relatively excellent in mechanical strength and chemical stability is known.
 ポリテトラフルオロエチレンは、比較的大きい疎水性を有するため、透水性が小さくなりやすく、特に中空糸膜の空孔径が小さい場合には濾過能力が不十分となりやすい。また、中空糸膜が比較的大きい疎水性を有する場合、被処理水中の油分等の疎水性ファウラントが中空糸膜の表面に付着して目詰まりを生じるファウリングと呼ばれる現象が発生しやすくなるという不都合もある。 Since polytetrafluoroethylene has a relatively large hydrophobicity, its water permeability tends to be small, and especially when the pore diameter of the hollow fiber membrane is small, the filtration capacity tends to be insufficient. In addition, when the hollow fiber membrane has a relatively large hydrophobicity, a phenomenon called fouling in which hydrophobic foulants such as oil in the water to be treated adhere to the surface of the hollow fiber membrane and become clogged easily occurs. There are also inconveniences.
 そこで、ポリテトラフルオロエチレンから形成される多孔質膜に親水性材料の水溶液を含浸し、親水性材料を架橋することにより不溶化して多孔質膜の空孔内面に固定することで多孔質膜を親水化処理することが提案されている(国際公開第2010/092938号公報参照)。このように多孔質膜を親水化することによって、透水性が向上して濾過能力が増大すると共に、疎水性ファウラントの付着が抑制されるのでファウリングが発生し難くなる。 Therefore, the porous membrane formed from polytetrafluoroethylene is impregnated with an aqueous solution of a hydrophilic material, and the hydrophilic material is cross-linked to be insolubilized and fixed to the pore inner surface of the porous membrane. Hydrophilic treatment has been proposed (see International Publication No. 2010/092938). By hydrophilizing the porous membrane in this way, the water permeability is improved and the filtration capacity is increased, and the adhesion of the hydrophobic foulant is suppressed, so that fouling is hardly generated.
国際公開第2010/092938号公報International Publication No. 2010/092938
 しかしながら、上記公報に記載される親水化処理は、親水性材料の水溶液と相溶性を有するイソプロピルアルコールに多孔質膜を浸漬する工程と、空孔内にイソプロピルアルコールを含んだ多孔質膜を疎水性材料の水溶液に浸漬して多孔質膜の空孔内に親水性材料を導入する工程と、空孔内の親水性材料を架橋して空孔内面に固定する工程とを行う必要がある。このように複雑な親水化処理は、濾過膜の価格を上昇させる。 However, the hydrophilization treatment described in the above publication includes a step of immersing the porous membrane in isopropyl alcohol compatible with an aqueous solution of a hydrophilic material, and a porous membrane containing isopropyl alcohol in the pores. It is necessary to perform a step of introducing a hydrophilic material into the pores of the porous membrane by dipping in an aqueous solution of the material, and a step of cross-linking the hydrophilic material in the pores and fixing it to the inner surface of the pores. Such a complicated hydrophilization treatment increases the price of the filtration membrane.
 本発明の一態様に係る中空糸膜は、ポリテトラフルオロエチレンを主成分とし、多孔性を有する筒状の骨材と、親水性を有し、上記骨材の外表面及び空孔内面を被覆する樹脂皮膜とを備え、外周面の純水接触角が40°以上80°以下であり、外周面の水中でのC重油接触角が110°以上150°以下である中空糸膜である。 A hollow fiber membrane according to an aspect of the present invention is mainly composed of polytetrafluoroethylene, has a porous cylindrical aggregate, and has a hydrophilic property, and covers the outer surface and the inner surface of a pore of the aggregate. A hollow fiber membrane having a pure water contact angle of 40 ° to 80 ° on the outer peripheral surface and a C heavy oil contact angle in water of the outer peripheral surface of 110 ° to 150 °.
図1は、本発明の一実施形態の排水処理装置の構成を示す模式図である。FIG. 1 is a schematic diagram showing a configuration of a wastewater treatment apparatus according to an embodiment of the present invention. 図2は、図1の排水処理装置の濾過モジュールの模式的断面図である。FIG. 2 is a schematic cross-sectional view of the filtration module of the waste water treatment apparatus of FIG. 図3は、図2の濾過モジュールの中空糸膜の模式的部分断面図である。FIG. 3 is a schematic partial cross-sectional view of the hollow fiber membrane of the filtration module of FIG.
[本開示が解決しようとする課題]
 本発明は、上述のような事情に基づいてなされたものであり、比較的安価で、処理能力が大きく、かつファウリングが生じ難い中空糸膜、濾過モジュール及び排水処理装置を提供することを課題とする。
[Problems to be solved by this disclosure]
The present invention has been made based on the above-described circumstances, and it is an object to provide a hollow fiber membrane, a filtration module, and a wastewater treatment device that are relatively inexpensive, have a large treatment capacity, and are less likely to cause fouling. And
[発明の効果]
  本発明の一態様に係る中空糸膜は、比較的安価で、処理能力が大きく、かつファウリングが生じ難い。
[The invention's effect]
The hollow fiber membrane according to one embodiment of the present invention is relatively inexpensive, has a large processing capacity, and is less likely to cause fouling.
[本発明の実施形態の説明]
 本発明の一態様に係る中空糸膜は、ポリテトラフルオロエチレンを主成分とし、多孔性を有する筒状の骨材と、親水性を有し、上記骨材の外表面及び空孔内面を被覆する樹脂皮膜とを備え、外周面の純水接触角が40°以上80°以下であり、外周面の水中でのC重油接触角が110°以上150°以下である。
[Description of Embodiment of the Present Invention]
A hollow fiber membrane according to an aspect of the present invention is mainly composed of polytetrafluoroethylene, has a porous cylindrical aggregate, and has a hydrophilic property, and covers the outer surface and the inner surface of a pore of the aggregate. A pure water contact angle on the outer peripheral surface is 40 ° to 80 °, and a C heavy oil contact angle in water on the outer peripheral surface is 110 ° to 150 °.
 当該中空糸膜は、ポリテトラフルオロエチレンを主成分とし、多孔性を有する筒状の骨材の外表面及び空孔内面を樹脂皮膜により被覆したことによって親水化されているので、透水性が向上して処理能力が比較的大きく、かつファウリングが比較的生じ難い。また、当該中空糸膜は、外周面の純水接触角及び水中でのC重油接触角を上記範囲内としたことによって、樹脂皮膜の形成材料として適度な親水性を有する材料を使用することになる。これにより樹脂皮膜形成材料の水溶液を骨材に含浸して乾燥させるだけで骨材の外表面及び空孔内面を被覆する樹脂皮膜を容易に形成することができる。このため、当該中空糸膜は、比較的安価でありながら、処理能力が大きく、かつファウリングが生じ難い。 The hollow fiber membrane is made of polytetrafluoroethylene as a main component and is made hydrophilic by covering the outer surface and the inner surface of pores with a porous cylindrical aggregate with a resin film, thereby improving water permeability. Thus, the processing capacity is relatively large and fouling is relatively difficult to occur. In addition, the hollow fiber membrane uses an appropriately hydrophilic material as a resin film forming material by setting the contact angle of pure water on the outer peripheral surface and the contact angle of C heavy oil in water within the above range. Become. Thereby, the resin film which coat | covers the outer surface of an aggregate and a void | hole inner surface can be easily formed only by impregnating the aggregate with the aqueous solution of the resin film forming material and drying it. For this reason, the hollow fiber membrane is relatively inexpensive, has a large processing capacity, and does not easily cause fouling.
 上記樹脂皮膜の主成分がエチレン-ビニルアルコール共重合体であるとよく、上記エチレン-ビニルアルコール共重合体におけるエチレンの共重合比としては20mol%以上60mol%以下が好ましい。このように、上記樹脂皮膜の主成分がエチレン-ビニルアルコール共重合体であり、上記エチレン-ビニルアルコール共重合体におけるエチレンの共重合比が上記範囲内であることによって、比較的大きい透水性を付与すると共にファウリングを防止できる樹脂皮膜を比較的容易かつ確実に形成することができる。 The main component of the resin film is preferably an ethylene-vinyl alcohol copolymer, and the copolymerization ratio of ethylene in the ethylene-vinyl alcohol copolymer is preferably 20 mol% or more and 60 mol% or less. As described above, the main component of the resin film is an ethylene-vinyl alcohol copolymer, and the ethylene copolymer ratio in the ethylene-vinyl alcohol copolymer is within the above range. A resin film that can be applied and can prevent fouling can be formed relatively easily and reliably.
 上記骨材が、筒状の支持層と、この支持層の外周面に積層される濾過層とを有するとよい。上記支持層の平均厚さとしては0.3mm以上1.0m以下が好ましく、上記支持層の平均孔径としては1μm以上3μm以下が好ましく、上記支持層の気孔率としては40%以上90%以下が好ましい。上記濾過層の平均厚さとしては10μm以上100μm以下が好ましく、上記濾過層の平均孔径としては0.01μm以上0.45μm以下が好ましく、上記樹脂皮膜の平均厚さとしては50nm以下が好ましい。このように、上記骨材が、筒状の支持層と、この支持層の外周面に積層される濾過層とを有することによって、当該中空糸膜を、比較的製造が容易でありながら、比較的強度が大きく、かつ被処理水から比較的小さい不純物を除去できるものとすることができる。また、上記支持層の平均厚さ、平均孔径及び気孔率、上記濾過層の平均厚さ及び平均孔径並びに上記樹脂皮膜の平均厚さをそれぞれ上記範囲内とすることによって、製造がより容易となり、かつ処理能力の低下を防止することができる。 It is preferable that the aggregate has a cylindrical support layer and a filtration layer laminated on the outer peripheral surface of the support layer. The average thickness of the support layer is preferably 0.3 mm to 1.0 m, the average pore diameter of the support layer is preferably 1 μm to 3 μm, and the porosity of the support layer is 40% to 90%. preferable. The average thickness of the filtration layer is preferably 10 μm or more and 100 μm or less, the average pore diameter of the filtration layer is preferably 0.01 μm or more and 0.45 μm or less, and the average thickness of the resin film is preferably 50 nm or less. In this way, the aggregate has a cylindrical support layer and a filtration layer laminated on the outer peripheral surface of the support layer, so that the hollow fiber membrane can be comparatively easily manufactured. It is possible to remove the relatively small impurities from the water to be treated. Further, by making the average thickness, average pore diameter and porosity of the support layer, the average thickness and average pore diameter of the filtration layer and the average thickness of the resin film within the above ranges, respectively, the production becomes easier. And the fall of processing capability can be prevented.
 バブルポイントとしては、60kPa以上200kPa以下が好ましい。このように、バブルポイントが上記範囲内であることによって、透水性が比較的大きく、かつ比較的小さい不純物を除去できるものとなる。 The bubble point is preferably 60 kPa or more and 200 kPa or less. Thus, when the bubble point is within the above range, the water permeability is relatively large and relatively small impurities can be removed.
 本発明の別の態様に係る濾過モジュールは、一方向に引き揃えられた状態で保持される複数本の当該中空糸膜と、この複数本の中空糸膜の両端部を固定する一対の保持部材とを備える。 A filtration module according to another aspect of the present invention includes a plurality of hollow fiber membranes that are held in a state aligned in one direction, and a pair of holding members that fix both ends of the plurality of hollow fiber membranes. With.
 当該濾過モジュールは、当該中空糸膜を用いるため、比較的安価で、処理能力が大きく、ファウリングが生じ難い。また、当該濾過モジュールは、複数本の中空糸膜の両端部を固定する一対の保持部材を備えることによって、被処理水中に浸漬することで複数本の中空糸膜を容易かつ確実に同時に使用することができるため、被処理水を比較的容易かつ迅速に濾過することができる。 Since the filtration module uses the hollow fiber membrane, it is relatively inexpensive, has a large processing capacity, and is less likely to cause fouling. Moreover, the said filtration module is equipped with a pair of holding member which fixes the both ends of a plurality of hollow fiber membranes, and uses a plurality of hollow fiber membranes simultaneously easily and reliably by being immersed in to-be-processed water. Therefore, the water to be treated can be filtered relatively easily and quickly.
 本発明の別の態様に係る排水処理装置は、活性汚泥を含む被処理水を貯留する処理水槽と、この処理水槽内に配設される当該濾過モジュールとを備える。 The waste water treatment apparatus according to another aspect of the present invention includes a treated water tank for storing treated water including activated sludge, and the filtration module disposed in the treated water tank.
 当該排水処理装置は、処理水槽に貯留され、活性汚泥を含む被処理水を当該濾過モジュールによって濾過する。これにより当該排水処理装置は比較的安価で処理能力が大きく、ファウリングが生じ難いため、比較的低コストで、排水を比較的確実に処理することができる。 The waste water treatment device is stored in a treated water tank, and the treated water containing activated sludge is filtered by the filtration module. As a result, the wastewater treatment apparatus is relatively inexpensive, has a large treatment capacity, and is unlikely to generate fouling, so that the wastewater can be treated relatively reliably at a relatively low cost.
 ここで、「主成分」とは質量含有率が最も大きい成分を意味し、好ましくは90質量%以上含有する成分とされる。「純水接触角」とは、JIS-R3257(1999)に規定される「静滴法」により測定される値である。また、「水中でのC重油接触角」とは、純水中に測定面を下向き水平に配置し、測定対象物の下面にC重油の油滴を静置した場合にJIS-R3257(1999)に規定される「接触角」と同様に測定される測定面と油滴との間の角度である。また、「平均孔径」とは、米国PMI社の細孔直径分布測定装置(パームポロメーター)を用いて測定される値である。また、「気孔率」とは、ASTM D792に準拠してされる値である。また、「バブルポイント」とは、イソプロピルアルコールを用い、ASTM-F316-86に準拠して測定される値である。 Here, “main component” means a component having the largest mass content, and preferably 90% by mass or more. “Pure water contact angle” is a value measured by the “static drop method” defined in JIS-R3257 (1999). The “contact angle of C heavy oil in water” means JIS-R3257 (1999) when the measurement surface is placed horizontally downward in pure water and oil droplets of C heavy oil are allowed to stand on the lower surface of the measurement object. Is the angle between the measurement surface and the oil droplet measured in the same manner as the “contact angle” defined in the above. The “average pore diameter” is a value measured using a pore diameter distribution measuring device (palm porometer) manufactured by PMI, USA. Further, the “porosity” is a value made in accordance with ASTM D792. The “bubble point” is a value measured using isopropyl alcohol according to ASTM-F316-86.
[本発明の実施形態の詳細]
 以下、本発明の各実施形態について図面を参照しつつ詳説する。
[Details of the embodiment of the present invention]
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
[排水処理装置]
 図1に示す本発明の一実施形態の排水処理装置は、活性汚泥を含む被処理水を貯留する処理水槽Tと、この処理水槽T内に配設される1又は複数の濾過モジュール1とを備える。また、当該排水処理装置は、濾過モジュール1を通して処理水槽T内の被処理水を吸い出す濾過ポンプ2をさらに備える。
[Wastewater treatment equipment]
The waste water treatment apparatus of one embodiment of the present invention shown in FIG. 1 includes a treated water tank T for storing treated water containing activated sludge, and one or a plurality of filtration modules 1 disposed in the treated water tank T. Prepare. In addition, the wastewater treatment apparatus further includes a filtration pump 2 that sucks out the water to be treated in the treated water tank T through the filtration module 1.
 また、当該排水処理装置は、図示しないが、活性汚泥に空気(酸素)を供給するための曝気装置、活性汚泥が高濃度に付着する担体、濾過モジュール1を洗浄するための気泡を供給するバブリング装置、過剰な活性汚泥を排出する汚泥引き抜き装置、処理水槽T中に他の構成要素を支持するためのフレーム、制御装置等を有してもよい。 In addition, although not shown, the wastewater treatment apparatus is an aeration apparatus for supplying air (oxygen) to activated sludge, a carrier on which activated sludge adheres at a high concentration, and a bubbling for supplying bubbles for cleaning the filtration module 1. You may have a device, the sludge extraction apparatus which discharges | emits excess activated sludge, the frame for supporting another component in the treated water tank T, a control apparatus, etc.
 当該排水処理装置は、例えば生活排水、汚水、工場排水等の被処理水中の有機物を好気性の微生物である活性汚泥を用いて分解し、濾過モジュール1を用いて不純物を分離して排出する。つまり、当該排水処理装置は、膜分離活性汚泥法により排水を処理する装置である。 The wastewater treatment apparatus decomposes organic matter in water to be treated, such as domestic wastewater, sewage, and factory effluent, using activated sludge that is an aerobic microorganism, and separates and discharges impurities using the filtration module 1. In other words, the wastewater treatment device is a device that treats wastewater by the membrane separation activated sludge method.
〔処理水槽〕
 処理水槽Tは、濾過モジュール1を浸漬できるよう、被処理水を貯留する。処理水槽Tの材質としては、例えば樹脂、金属、コンクリート等を用いることができる。
[Treatment tank]
The treated water tank T stores the treated water so that the filtration module 1 can be immersed therein. As a material of the treated water tank T, for example, resin, metal, concrete, or the like can be used.
〔濾過モジュール〕
 濾過モジュール1は、それ自体が本発明の一実施形態である。
[Filtration module]
The filtration module 1 is itself an embodiment of the present invention.
 濾過モジュール1は、図2に示すように、一方向(上下方向)に引き揃えられた状態で保持される複数本の中空糸膜3と、この複数本の中空糸膜3の両端部をそれぞれ固定する一対の保持部材(第1保持部材4及び第2保持部材5)とを備える。 As shown in FIG. 2, the filtration module 1 includes a plurality of hollow fiber membranes 3 held in a state of being aligned in one direction (vertical direction), and both ends of the plurality of hollow fiber membranes 3. A pair of holding members (first holding member 4 and second holding member 5) to be fixed is provided.
<中空糸膜>
 中空糸膜3は、それ自体が本発明の一実施形態である。
<Hollow fiber membrane>
The hollow fiber membrane 3 itself is an embodiment of the present invention.
 当該中空糸膜3は、図3に示すように、ポリテトラフルオロエチレンを主成分とし、多孔性を有する筒状の骨材6と、親水性を有し、上記骨材の外表面及び空孔内面を被覆する樹脂皮膜7とを備える。 As shown in FIG. 3, the hollow fiber membrane 3 has a cylindrical aggregate 6 having polytetrafluoroethylene as a main component and having porosity, a hydrophilic property, and an outer surface and pores of the aggregate. And a resin film 7 covering the inner surface.
 当該中空糸膜3の外周面の純水接触角の下限としては、40°であり、45°が好ましく、50°がさらに好ましい。一方、当該中空糸膜3の外周面の純水接触角の上限としては、80°であり、75°が好ましく、70°がさらに好ましい。当該中空糸膜3の外周面の純水接触角が上記下限に満たない場合、当該中空糸膜3の透水量が不十分となるおそれや、ファウリングの発生を防止できないおそれがある。逆に、当該中空糸膜3の外周面の純水接触角が上記上限を超える場合、樹脂皮膜7の形成が容易でなくなることで当該中空糸膜3の製造コストが増大するおそれがある。 The lower limit of the pure water contact angle on the outer peripheral surface of the hollow fiber membrane 3 is 40 °, preferably 45 °, more preferably 50 °. On the other hand, the upper limit of the pure water contact angle on the outer peripheral surface of the hollow fiber membrane 3 is 80 °, preferably 75 °, and more preferably 70 °. When the pure water contact angle of the outer peripheral surface of the hollow fiber membrane 3 is less than the lower limit, there is a possibility that the water permeability of the hollow fiber membrane 3 may be insufficient or the occurrence of fouling may not be prevented. On the contrary, when the pure water contact angle of the outer peripheral surface of the hollow fiber membrane 3 exceeds the upper limit, the formation of the resin film 7 is not easy, and the manufacturing cost of the hollow fiber membrane 3 may increase.
 当該中空糸膜3の外周面の水中でのC重油接触角の下限としては、110°であり、115°が好ましく、120°がさらに好ましい。一方、当該中空糸膜3の外周面の水中でのC重油接触角の上限としては、150°であり、145°が好ましく、140°がさらに好ましい。当該中空糸膜3の外周面の水中でのC重油接触角が上記下限に満たない場合、樹脂皮膜7の形成が容易でなくなることで製造コストが増大するおそれがある。逆に、当該中空糸膜3の外周面の水中でのC重油接触角が上記上限を超える場合、当該中空糸膜3の透水量が不十分となるおそれや、ファウリングの発生を防止できないおそれがある。  The lower limit of the C heavy oil contact angle in water on the outer peripheral surface of the hollow fiber membrane 3 is 110 °, preferably 115 °, and more preferably 120 °. On the other hand, the upper limit of the C heavy oil contact angle in water on the outer peripheral surface of the hollow fiber membrane 3 is 150 °, preferably 145 °, and more preferably 140 °. When the C heavy oil contact angle in water of the outer peripheral surface of the hollow fiber membrane 3 is less than the lower limit, the formation of the resin film 7 is not easy and the manufacturing cost may increase. Conversely, when the C heavy oil contact angle in water on the outer peripheral surface of the hollow fiber membrane 3 exceeds the above upper limit, the water permeability of the hollow fiber membrane 3 may be insufficient or the occurrence of fouling may not be prevented. There is. *
 当該中空糸膜3のバブルポイントの下限としては、60kPaが好ましく、80kPaがより好ましい。一方、当該中空糸膜3のバブルポイントの上限としては、200kPaが好ましく、180kPaがより好ましい。バブルポイントが上記下限に満たない場合、当該中空糸膜3が不純物を十分に分離できないおそれがある。逆に、バブルポイントが上記上限を超える場合、当該中空糸膜3の透水量が不十分となるおそれがある。 The lower limit of the bubble point of the hollow fiber membrane 3 is preferably 60 kPa, and more preferably 80 kPa. On the other hand, the upper limit of the bubble point of the hollow fiber membrane 3 is preferably 200 kPa, and more preferably 180 kPa. If the bubble point is less than the lower limit, the hollow fiber membrane 3 may not be able to sufficiently separate impurities. On the other hand, when the bubble point exceeds the above upper limit, the water permeability of the hollow fiber membrane 3 may be insufficient.
 当該中空糸膜3の平均外径の下限としては、1mmが好ましく、1.5mmがより好ましく、2mmがさらに好ましい。一方、当該中空糸膜3の平均外径の上限としては、6mmが好ましく、5mmがより好ましく、4mmがさらに好ましい。当該中空糸膜3の平均外径が上記下限に満たない場合、当該中空糸膜3の機械的強度が不十分となるおそれがある。逆に、当該中空糸膜3の平均外径が上記上限を超える場合、当該中空糸膜3の断面積に対する表面積の比が小さくなって当該中空糸膜3の濾過効率が低下するおそれがある。  The lower limit of the average outer diameter of the hollow fiber membrane 3 is preferably 1 mm, more preferably 1.5 mm, and further preferably 2 mm. On the other hand, the upper limit of the average outer diameter of the hollow fiber membrane 3 is preferably 6 mm, more preferably 5 mm, and even more preferably 4 mm. When the average outer diameter of the hollow fiber membrane 3 is less than the lower limit, the mechanical strength of the hollow fiber membrane 3 may be insufficient. On the contrary, when the average outer diameter of the hollow fiber membrane 3 exceeds the upper limit, the ratio of the surface area to the cross-sectional area of the hollow fiber membrane 3 may be reduced, and the filtration efficiency of the hollow fiber membrane 3 may be reduced. *
 当該中空糸膜3の平均内径の下限としては、0.3mmが好ましく、0.5mmがより好ましく、0.9mmがさらに好ましい。一方、当該中空糸膜3の平均内径の上限としては、4mmが好ましく、3mmがより好ましい。当該中空糸膜3の平均内径が上記下限に満たない場合、当該中空糸膜3内の処理済水を排出するときの圧損が大きくなるおそれがある。逆に、当該中空糸膜3の平均内径が上記上限を超える場合、当該中空糸膜3の厚さが小さくなって、当該中空糸膜3の機械的強度及び不純物の透過阻止効果が不十分となるおそれがある。 The lower limit of the average inner diameter of the hollow fiber membrane 3 is preferably 0.3 mm, more preferably 0.5 mm, and further preferably 0.9 mm. On the other hand, the upper limit of the average inner diameter of the hollow fiber membrane 3 is preferably 4 mm, and more preferably 3 mm. When the average inner diameter of the hollow fiber membrane 3 is less than the lower limit, the pressure loss when the treated water in the hollow fiber membrane 3 is discharged may increase. On the contrary, when the average inner diameter of the hollow fiber membrane 3 exceeds the upper limit, the thickness of the hollow fiber membrane 3 becomes small, and the mechanical strength of the hollow fiber membrane 3 and the impurity permeation preventing effect are insufficient. There is a risk.
 当該中空糸膜3の平均外径に対する平均内径の比の下限としては、3/10が好ましく、2/5がより好ましい。一方、当該中空糸膜3の平均外径に対する平均内径の比の上限としては、4/5が好ましく、3/5がより好ましい。当該中空糸膜3の平均外径に対する平均内径の比が上記下限に満たない場合、当該中空糸膜3の厚さが必要以上に大きくなって当該中空糸膜3の透水性が低下するおそれがある。逆に、当該中空糸膜3の平均外径に対する平均内径の比が上記上限を超える場合、当該中空糸膜3の厚さが小さくなって、当該中空糸膜3の機械的強度及び不純物の透過阻止効果が不十分となるおそれがある。 The lower limit of the ratio of the average inner diameter to the average outer diameter of the hollow fiber membrane 3 is preferably 3/10, and more preferably 2/5. On the other hand, the upper limit of the ratio of the average inner diameter to the average outer diameter of the hollow fiber membrane 3 is preferably 4/5, and more preferably 3/5. When the ratio of the average inner diameter to the average outer diameter of the hollow fiber membrane 3 is less than the above lower limit, the thickness of the hollow fiber membrane 3 may become unnecessarily large and the water permeability of the hollow fiber membrane 3 may be reduced. is there. On the contrary, when the ratio of the average inner diameter to the average outer diameter of the hollow fiber membrane 3 exceeds the upper limit, the thickness of the hollow fiber membrane 3 is reduced, and the mechanical strength and the permeation of impurities of the hollow fiber membrane 3 are reduced. There is a risk that the prevention effect will be insufficient.
 当該濾過モジュール1において、当該中空糸膜3の中心軸に沿う平均有効長さの下限としては、1mが好ましく、2mがより好ましい。一方、当該中空糸膜3の平均有効長さの上限としては、8mが好ましく、7mがより好ましい。当該中空糸膜3の平均有効長さが上記下限に満たない場合、当該濾過モジュール1の体積効率が小さくなるおそれがある。逆に、当該中空糸膜3の平均有効長さが上記上限を超える場合、当該中空糸膜3の自重によって当該中空糸膜3の撓みが大きくなり過ぎるおそれや、濾過モジュール1の設置時等における取り扱い性が低下するおそれがある。 In the filtration module 1, the lower limit of the average effective length along the central axis of the hollow fiber membrane 3 is preferably 1 m, and more preferably 2 m. On the other hand, the upper limit of the average effective length of the hollow fiber membrane 3 is preferably 8 m, and more preferably 7 m. When the average effective length of the hollow fiber membrane 3 is less than the lower limit, the volume efficiency of the filtration module 1 may be reduced. On the contrary, when the average effective length of the hollow fiber membrane 3 exceeds the upper limit, the hollow fiber membrane 3 may be excessively bent due to its own weight, or when the filtration module 1 is installed. There is a risk that the handleability will deteriorate.
(骨材)
 骨材6は、当該中空糸膜3の形状及び機械的特性を担保し、樹脂皮膜7によって表面(外表面及び空孔内面)の特性が改質される。
(aggregate)
The aggregate 6 ensures the shape and mechanical properties of the hollow fiber membrane 3 and the properties of the surface (outer surface and pore inner surface) are modified by the resin film 7.
 この骨材6は、比較的強度、耐薬品性及び空孔形成容易性に優れるポリテトラフルオロエチレンを主成分とする。 This aggregate 6 is mainly composed of polytetrafluoroethylene which is relatively excellent in strength, chemical resistance and ease of pore formation.
 また、骨材6は、筒状の支持層8と、この支持層8の外周面に積層される濾過層9とを有する構成とすることができる。このように骨材6の強度を担保する支持層8と不純物の透過を阻止する濾過層9とを有する多層構造とすることによって、強度を向上しつつ、実効的な空孔径が小さい骨材6を比較的容易に製造可能とすることができる。 Moreover, the aggregate 6 can be configured to have a cylindrical support layer 8 and a filtration layer 9 laminated on the outer peripheral surface of the support layer 8. Thus, by making it the multilayer structure which has the support layer 8 which ensures the intensity | strength of the aggregate 6, and the filtration layer 9 which prevents permeation | transmission of an impurity, the aggregate 6 with a small effective hole diameter is improved, improving an intensity | strength. Can be manufactured relatively easily.
 支持層8の平均厚さの下限としては、0.3mmが好ましく、0.5mmがより好ましい。一方、支持層8の平均厚さの上限としては、1.0mmが好ましく、0.8mmがより好ましい。支持層8の平均厚さが上記下限に満たない場合、骨材6ひいては当該中空糸膜3の強度が不十分となるおそれがある。逆に、支持層8の平均厚さが上記上限を超える場合、当該中空糸膜3の内腔径が小さくなって処理済水を排出するときの圧損が大きくなるおそれがある。 The lower limit of the average thickness of the support layer 8 is preferably 0.3 mm, and more preferably 0.5 mm. On the other hand, the upper limit of the average thickness of the support layer 8 is preferably 1.0 mm, and more preferably 0.8 mm. If the average thickness of the support layer 8 is less than the lower limit, the aggregate 6 and thus the strength of the hollow fiber membrane 3 may be insufficient. On the other hand, when the average thickness of the support layer 8 exceeds the above upper limit, the lumen diameter of the hollow fiber membrane 3 becomes small, and the pressure loss when the treated water is discharged may increase.
 支持層8の平均孔径の下限としては、1μmが好ましく、1.5μmがより好ましい。一方、支持層8の平均孔径の上限としては、3μmが好ましく、2.5μmがより好ましい。支持層8の平均孔径が上記下限に満たない場合、当該中空糸膜3の透水性が不十分となるおそれがある。逆に、支持層8の平均孔径が上記上限を超える場合、当該中空糸膜3が不純物の透過を十分に阻止できないおそれがある。 The lower limit of the average pore diameter of the support layer 8 is preferably 1 μm, more preferably 1.5 μm. On the other hand, the upper limit of the average pore diameter of the support layer 8 is preferably 3 μm, more preferably 2.5 μm. When the average pore diameter of the support layer 8 is less than the lower limit, the water permeability of the hollow fiber membrane 3 may be insufficient. Conversely, when the average pore diameter of the support layer 8 exceeds the upper limit, the hollow fiber membrane 3 may not be able to sufficiently prevent the permeation of impurities.
 支持層8の気孔率の下限としては、40%が好ましく、50%がより好ましい。一方、支持層8の気孔率の上限としては、90%が好ましく、85%がより好ましい。支持層8の気孔率が上記下限に満たない場合、当該中空糸膜3の透水性が不十分となるおそれがある。逆に、支持層8の気孔率が上記上限を超える場合、支持層8ひいては当該中空糸膜3の強度が不十分となるおそれがある。 The lower limit of the porosity of the support layer 8 is preferably 40%, more preferably 50%. On the other hand, the upper limit of the porosity of the support layer 8 is preferably 90%, more preferably 85%. When the porosity of the support layer 8 is less than the above lower limit, the water permeability of the hollow fiber membrane 3 may be insufficient. On the other hand, when the porosity of the support layer 8 exceeds the above upper limit, the strength of the support layer 8 and thus the hollow fiber membrane 3 may be insufficient.
 濾過層9の平均厚さの下限としては、10μmが好ましく、12μmがより好ましい。一方、濾過層9の平均厚さの上限としては、100μmが好ましく、80μmがより好ましい。濾過層9の平均厚さが上記下限に満たない場合、当該中空糸膜3が不純物の透過を十分に阻止できないおそれがある。逆に、濾過層9の平均厚さが上記上限を超える場合、当該中空糸膜3の透水性が不十分となるおそれがある。 The lower limit of the average thickness of the filtration layer 9 is preferably 10 μm, and more preferably 12 μm. On the other hand, as an upper limit of the average thickness of the filtration layer 9, 100 micrometers is preferable and 80 micrometers is more preferable. When the average thickness of the filtration layer 9 is less than the lower limit, the hollow fiber membrane 3 may not be able to sufficiently prevent the permeation of impurities. On the other hand, when the average thickness of the filtration layer 9 exceeds the upper limit, the water permeability of the hollow fiber membrane 3 may be insufficient.
 濾過層9の平均孔径の下限としては、0.01μmが好ましく、0.05μmがより好ましい。一方、濾過層9の平均孔径の上限としては、0.45μmが好ましく、0.3μmがより好ましい。濾過層9の平均孔径が上記下限に満たない場合、当該中空糸膜3の透水性が不十分となるおそれがある。逆に、濾過層9の平均孔径が上記上限を超える場合、当該中空糸膜3が不純物の透過を十分に阻止できないおそれがある。 The lower limit of the average pore diameter of the filtration layer 9 is preferably 0.01 μm, more preferably 0.05 μm. On the other hand, the upper limit of the average pore diameter of the filtration layer 9 is preferably 0.45 μm, and more preferably 0.3 μm. When the average pore diameter of the filtration layer 9 is less than the above lower limit, the water permeability of the hollow fiber membrane 3 may be insufficient. Conversely, when the average pore diameter of the filtration layer 9 exceeds the above upper limit, the hollow fiber membrane 3 may not be able to sufficiently prevent the permeation of impurities.
 濾過層9の気孔率の下限としては、40%が好ましく、50%がより好ましい。一方、濾過層9の気孔率の上限としては、80%が好ましく、70%がより好ましい。濾過層9の気孔率が上記下限に満たない場合、当該中空糸膜3の透水性が不十分となるおそれがある。逆に、濾過層9の気孔率が上記上限を超える場合、当該中空糸膜3の孔径が不均一になるおそれがある。 The lower limit of the porosity of the filtration layer 9 is preferably 40%, more preferably 50%. On the other hand, the upper limit of the porosity of the filtration layer 9 is preferably 80% and more preferably 70%. If the porosity of the filtration layer 9 is less than the lower limit, the water permeability of the hollow fiber membrane 3 may be insufficient. On the contrary, when the porosity of the filtration layer 9 exceeds the upper limit, the pore diameter of the hollow fiber membrane 3 may be nonuniform.
(樹脂皮膜)
 樹脂皮膜7は、骨材6の外表面及び空孔内面を被覆し、当該中空糸膜3に親水性を付与する。
(Resin film)
The resin film 7 covers the outer surface of the aggregate 6 and the inner surface of the pores, and imparts hydrophilicity to the hollow fiber membrane 3.
 樹脂皮膜7の主成分としては、親水性の部分と疎水性の部分とを有する高分子が用いられる。樹脂皮膜7が親水性の部分と疎水性の部分とを有する高分子を主成分とすることによって、高分子の疎水性の部分が骨材6に対する密着性を有し、高分子の親水性の部分が当該中空糸膜3の透水性を向上すると共にファウリングを抑制する。なお、樹脂皮膜7は、主成分とされる親水性の部分と疎水性の部分とを有する高分子以外に、例えば添加剤、反応残渣等の不純物を含んでもよい。 As the main component of the resin film 7, a polymer having a hydrophilic part and a hydrophobic part is used. Since the resin film 7 is mainly composed of a polymer having a hydrophilic portion and a hydrophobic portion, the hydrophobic portion of the polymer has adhesion to the aggregate 6, and the hydrophilic property of the polymer The portion improves the water permeability of the hollow fiber membrane 3 and suppresses fouling. The resin film 7 may contain impurities such as additives and reaction residues in addition to the polymer having a hydrophilic part and a hydrophobic part as main components.
 樹脂皮膜7の主成分とされる親水性の部分と疎水性の部分とを有する高分子としては、例えばエチレン-ビニルアルコール共重合体、ポリビニルフォルマール、フェノール系高分子等を用いることができ、中でもエチレン-ビニルアルコール共重合体を好適に用いることができる。エチレン-ビニルアルコール共重合体は、エチレン部分が疎水性を発現し、ビニルアルコール部分(特にそのヒドロキシ基)が親水性を発現する。 As the polymer having a hydrophilic part and a hydrophobic part as the main component of the resin film 7, for example, ethylene-vinyl alcohol copolymer, polyvinyl formal, phenolic polymer, etc. can be used. Among these, an ethylene-vinyl alcohol copolymer can be preferably used. In the ethylene-vinyl alcohol copolymer, the ethylene portion exhibits hydrophobicity, and the vinyl alcohol portion (particularly, the hydroxy group) exhibits hydrophilicity.
 樹脂皮膜7の主成分とされるエチレン-ビニルアルコール共重合体におけるエチレンの共重合比の下限としては、20mol%が好ましく、22mol%がより好ましく、24mol%がさらに好ましい。一方、樹脂皮膜7の主成分とされるエチレン-ビニルアルコール共重合体におけるエチレンの共重合比の上限としては、60mol%が好ましく、55mol%がより好ましく、50mol%がさらに好ましい。樹脂皮膜7の主成分とされるエチレン-ビニルアルコール共重合体におけるエチレンの共重合比が上記下限に満たない場合、骨材6に対する密着性が不十分となり、骨材6の表面を均一に被覆することが容易でなくなるおそれがある。逆に、樹脂皮膜7の主成分とされるエチレン-ビニルアルコール共重合体におけるエチレンの共重合比が上記上限を超える場合、親水性が小さくなることで当該中空糸膜3の透水性が不十分となるおそれがある。 The lower limit of the copolymerization ratio of ethylene in the ethylene-vinyl alcohol copolymer as the main component of the resin film 7 is preferably 20 mol%, more preferably 22 mol%, and even more preferably 24 mol%. On the other hand, the upper limit of the copolymerization ratio of ethylene in the ethylene-vinyl alcohol copolymer as the main component of the resin film 7 is preferably 60 mol%, more preferably 55 mol%, and even more preferably 50 mol%. When the ethylene copolymerization ratio in the ethylene-vinyl alcohol copolymer, which is the main component of the resin film 7, is less than the lower limit, the adhesion to the aggregate 6 is insufficient and the surface of the aggregate 6 is uniformly coated. It may not be easy to do. On the contrary, when the ethylene copolymerization ratio in the ethylene-vinyl alcohol copolymer as the main component of the resin film 7 exceeds the above upper limit, the water permeability of the hollow fiber membrane 3 is insufficient due to the decrease in hydrophilicity. There is a risk of becoming.
 樹脂皮膜7の主成分とされるエチレン-ビニルアルコール共重合体の平均分子量の下限としては、5,000が好ましく、10,000がより好ましい。一方、樹脂皮膜7の主成分とされるエチレン-ビニルアルコール共重合体の平均分子量の上限としては、100,000が好ましく、50,000がより好ましい。樹脂皮膜7の主成分とされるエチレン-ビニルアルコール共重合体の平均分子量が上記下限に満たない場合、樹脂皮膜7が剥離し易くなるおそれがある。逆に、樹脂皮膜7の主成分とされるエチレン-ビニルアルコール共重合体の平均分子量が上記上限を超える場合、樹脂皮膜7の形成が容易でなくなることで当該中空糸膜3の製造コストが上昇するおそれがある。なお、「平均分子量」とは、JIS-K7252-1(2008)「プラスチック-サイズ排除クロマトグラフィーによる高分子の平均分子量及び分子量分布の求め方-第1部:通則」に準拠して、ゲル浸透クロマトグラフィー(GPC)を用いて測定される質量平均分子量を指す。 The lower limit of the average molecular weight of the ethylene-vinyl alcohol copolymer that is the main component of the resin film 7 is preferably 5,000, and more preferably 10,000. On the other hand, the upper limit of the average molecular weight of the ethylene-vinyl alcohol copolymer as the main component of the resin film 7 is preferably 100,000 and more preferably 50,000. If the average molecular weight of the ethylene-vinyl alcohol copolymer as the main component of the resin film 7 is less than the lower limit, the resin film 7 may be easily peeled off. On the contrary, when the average molecular weight of the ethylene-vinyl alcohol copolymer, which is the main component of the resin film 7, exceeds the upper limit, the formation of the resin film 7 becomes difficult and the manufacturing cost of the hollow fiber membrane 3 increases. There is a risk. "Average molecular weight" refers to gel permeation in accordance with JIS-K7252-1 (2008) "Plastics-Determination of average molecular weight and molecular weight distribution of polymers by size exclusion chromatography-Part 1: General rules". It refers to the weight average molecular weight measured using chromatography (GPC).
 樹脂皮膜7の平均厚さの下限としては、2nmが好ましく、5nmがより好ましい。一方、樹脂皮膜7の平均厚さの上限としては、50nmが好ましく、30nmがより好ましい。樹脂皮膜7の平均厚さが上記下限に満たない場合、骨材6を連続的に被覆することができず、当該中空糸膜3の透水性及び耐ファウリング性を十分に向上できないおそれがある。逆に、樹脂皮膜7の平均厚さが上記上限を超える場合、当該中空糸膜3の気孔率が低下することにより透水性が不十分となるおそれがある。 The lower limit of the average thickness of the resin film 7 is preferably 2 nm, and more preferably 5 nm. On the other hand, as an upper limit of the average thickness of the resin film 7, 50 nm is preferable and 30 nm is more preferable. When the average thickness of the resin film 7 is less than the lower limit, the aggregate 6 cannot be continuously coated, and the water permeability and fouling resistance of the hollow fiber membrane 3 may not be sufficiently improved. . On the contrary, when the average thickness of the resin film 7 exceeds the upper limit, water permeability may be insufficient due to a decrease in the porosity of the hollow fiber membrane 3.
 当該中空糸膜3における樹脂皮膜7の量の下限としては、0.1質量%が好ましく、0.2質量%がより好ましい。一方、当該中空糸膜3における樹脂皮膜7の量の上限としては、2質量%が好ましく、1質量%がより好ましい。当該中空糸膜3における樹脂皮膜7の量が上記下限に満たない場合、骨材6を連続的に被覆することができず、当該中空糸膜3の透水性及び耐ファウリング性を十分に向上できないおそれがある。逆に、当該中空糸膜3における樹脂皮膜7の量が上記上限を超える場合、当該中空糸膜3の気孔率が低下することにより透水性が不十分となるおそれがある。 The lower limit of the amount of the resin film 7 in the hollow fiber membrane 3 is preferably 0.1% by mass, and more preferably 0.2% by mass. On the other hand, the upper limit of the amount of the resin film 7 in the hollow fiber membrane 3 is preferably 2% by mass, and more preferably 1% by mass. When the amount of the resin film 7 in the hollow fiber membrane 3 is less than the lower limit, the aggregate 6 cannot be continuously coated, and the water permeability and fouling resistance of the hollow fiber membrane 3 are sufficiently improved. It may not be possible. On the other hand, when the amount of the resin film 7 in the hollow fiber membrane 3 exceeds the upper limit, the porosity of the hollow fiber membrane 3 may be reduced, resulting in insufficient water permeability.
(中空糸膜の製造方法)
 当該中空糸膜3は、骨材6に溶媒を含浸させる工程と、溶媒を含浸した骨材6に樹脂皮膜7を形成する材料(樹脂皮膜形成材料)の水溶液を導入する工程と、樹脂皮膜形成材料の水溶液を含んだ骨材6を乾燥する工程とを備える工程により製造することができる。
(Method for producing hollow fiber membrane)
The hollow fiber membrane 3 includes a step of impregnating the aggregate 6 with a solvent, a step of introducing an aqueous solution of a material (resin film forming material) for forming the resin film 7 into the aggregate 6 impregnated with the solvent, and resin film formation. And a step of drying the aggregate 6 containing the aqueous solution of the material.
 上記含浸工程で用いる溶媒としては、ポリテトラフルオロエチレンの濡れ性が高く、水との親和性が高いものであればよく、例えばイソプロピルアルコール等を用いることができる。 The solvent used in the impregnation step is not particularly limited as long as polytetrafluoroethylene has high wettability and high affinity with water. For example, isopropyl alcohol or the like can be used.
 上記導入工程では、例えば樹脂皮膜形成材料の水溶液に骨材6を浸漬することで、骨材6の空孔内に樹脂皮膜形成材料の水溶液を導入する。ここで、骨材6の空孔内に樹脂皮膜形成材料の水溶液との相溶性が高い溶媒が充填されていることにより、樹脂皮膜形成材料の水溶液の表面張力が緩和され、比較的容易に樹脂皮膜形成材料の水溶液を骨材6の空孔内に導入することができる。 In the introducing step, the aqueous solution of the resin film forming material is introduced into the pores of the aggregate 6 by immersing the aggregate 6 in the aqueous solution of the resin film forming material, for example. Here, since the pores of the aggregate 6 are filled with a solvent having high compatibility with the aqueous solution of the resin film forming material, the surface tension of the aqueous solution of the resin film forming material is relaxed, and the resin is relatively easily An aqueous solution of the film forming material can be introduced into the pores of the aggregate 6.
 樹脂皮膜形成材料の水溶液に骨材6を浸漬する時間の下限としては、例えば樹脂皮膜形成材料野種類、水溶液の濃度、温度等の条件によもよるが、5分が好ましく、30分がより好ましい。一方、樹脂皮膜形成材料の水溶液に骨材6を浸漬する時間の上限としては、6時間が好ましく、9時間がより好ましい。樹脂皮膜形成材料の水溶液に骨材6を浸漬する時間が上記下限に満たない場合、骨材6の空孔内に樹脂皮膜形成材料を十分に導入できないおそれがある。逆に、樹脂皮膜形成材料の水溶液に骨材6を浸漬する時間が上記上限を超える場合、樹脂の付きすぎによる骨材6の気孔率の低下のおそれがある。 The lower limit of the time for immersing the aggregate 6 in the aqueous solution of the resin film forming material is preferably 5 minutes, more preferably 30 minutes, although it depends on conditions such as the type of the resin film forming material, the concentration of the aqueous solution, and the temperature. preferable. On the other hand, the upper limit of the time for immersing the aggregate 6 in the aqueous solution of the resin film forming material is preferably 6 hours, and more preferably 9 hours. If the time for immersing the aggregate 6 in the aqueous solution of the resin film forming material is less than the lower limit, the resin film forming material may not be sufficiently introduced into the pores of the aggregate 6. On the contrary, when the time for immersing the aggregate 6 in the aqueous solution of the resin film forming material exceeds the above upper limit, the porosity of the aggregate 6 may be lowered due to excessive resin attachment.
 上記水溶液中の樹脂皮膜形成材料含有量(固形分含有量)の下限としては、0.1質量%が好ましく、0.2質量%がより好ましい。一方、上記水溶液中の樹脂皮膜形成材料含有量の上限としては、2質量%が好ましく、1質量%がより好ましい。上記水溶液中の樹脂皮膜形成材料含有量が上記下限に満たない場合、骨材6の表面を連続して被覆する樹脂皮膜7を形成できないおそれがある。逆に、上記水溶液中の樹脂皮膜形成材料含有量が上記上限を超える場合、水溶液を骨材6の空孔内に含浸できないおそれや、骨材6の空孔を閉塞させるおそれがある。 The lower limit of the resin film forming material content (solid content) in the aqueous solution is preferably 0.1% by mass, and more preferably 0.2% by mass. On the other hand, the upper limit of the content of the resin film forming material in the aqueous solution is preferably 2% by mass and more preferably 1% by mass. When the content of the resin film forming material in the aqueous solution is less than the lower limit, the resin film 7 that continuously covers the surface of the aggregate 6 may not be formed. On the contrary, when the content of the resin film forming material in the aqueous solution exceeds the upper limit, there is a possibility that the aqueous solution cannot be impregnated in the pores of the aggregate 6 or the pores of the aggregate 6 are blocked.
 上記乾燥工程では、骨材6の空孔内の上記水溶液中の溶剤を蒸発させることにより、樹脂皮膜形成材料を骨材6の外表面及び空孔内面に膜状に付着させる。 In the drying step, the resin film forming material is attached to the outer surface of the aggregate 6 and the inner surface of the pores in a film form by evaporating the solvent in the aqueous solution in the pores of the aggregate 6.
 この乾燥工程における乾燥温度(雰囲気温度)としては、例えば0℃以上60℃以下、典型的には常温とすることができる。また、この乾燥工程における乾燥時間としては、例えば5分以上24時間以下とすることができる。 The drying temperature (atmosphere temperature) in this drying step can be, for example, 0 ° C. or higher and 60 ° C. or lower, typically room temperature. Moreover, as drying time in this drying process, it is 5 minutes or more and 24 hours or less, for example.
<上側保持部材>
 第1保持部材4は、複数の当該中空糸膜3の上端を保持する。この第1保持部材4は、保持する当該中空糸膜3の内腔と連通する内部空間を形成し、この内部空間から当該中空糸膜3によって濾過された処理済水を排出する排水ノズル10を有する。つまり、第1保持部材4の排水ノズル10に濾過ポンプ2が接続される。
<Upper holding member>
The first holding member 4 holds the upper ends of the plurality of hollow fiber membranes 3. The first holding member 4 forms an internal space that communicates with the lumen of the hollow fiber membrane 3 to be held, and a drain nozzle 10 that discharges the treated water filtered by the hollow fiber membrane 3 from the internal space. Have. That is, the filtration pump 2 is connected to the drain nozzle 10 of the first holding member 4.
<下側保持部材>
 第2保持部材5は、複数の当該中空糸膜3の下端を保持する。第2保持部材5は、上記第1保持部材4と同様に内部空間を形成してもよく、当該中空糸膜3の開口を閉塞するような方法で当該中空糸膜3の下端を保持してもよい。第2保持部材5は、当該中空糸膜3を折り返す部材であってもよい。つまり、当該濾過モジュール1において、隣接する当該中空糸膜3は下端が接続されていてもよい。
<Lower holding member>
The second holding member 5 holds the lower ends of the plurality of hollow fiber membranes 3. The second holding member 5 may form an internal space in the same manner as the first holding member 4 and holds the lower end of the hollow fiber membrane 3 in such a way as to close the opening of the hollow fiber membrane 3. Also good. The second holding member 5 may be a member that turns back the hollow fiber membrane 3. That is, in the filtration module 1, the lower ends of the adjacent hollow fiber membranes 3 may be connected.
〔利点〕
 当該中空糸膜3は、外周面の純水接触角及び水中でのC重油接触角を一定の範囲内としたことによって、上述のように、一定の疎水性を有する樹脂皮膜形成材料を用いて樹脂皮膜7を形成することになるので、疎水性の骨材6の外表面及び空孔内面に樹脂皮膜形成材料を比較的容易に密着させられる。このため、当該中空糸膜3は、樹脂皮膜形成材料を骨材6の空孔内で化学反応させることなく、上記浸漬工程及び乾燥工程によって処理能力(透水性)及び耐ファウリング性を向上する樹脂皮膜7を比較的一定の品質で、比較的安価に形成することができる。また、当該濾過ユニット及び排水処理装置は、当該中空糸膜3を用いるため、比較的安価で、処理能力が大きく、かつファウリングが生じ難い。
〔advantage〕
The hollow fiber membrane 3 uses a resin film-forming material having a certain hydrophobicity as described above by setting the pure water contact angle on the outer peripheral surface and the C heavy oil contact angle in water within a certain range. Since the resin film 7 is formed, the resin film forming material can be brought into close contact with the outer surface of the hydrophobic aggregate 6 and the inner surface of the pores relatively easily. For this reason, the said hollow fiber membrane 3 improves processing capability (water permeability) and fouling resistance by the said immersion process and a drying process, without making the resin film formation material chemically react in the void | hole of the aggregate 6. FIG. The resin film 7 can be formed with a relatively constant quality and at a relatively low cost. Moreover, since the said filtration unit and waste water treatment apparatus use the said hollow fiber membrane 3, it is comparatively cheap, a processing capacity is large, and it is hard to produce fouling.
[その他の実施形態]
 今回開示された実施の形態は全ての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は、上記実施形態の構成に限定されるものではなく、特許請求の範囲によって示され、特許請求の範囲と均等の意味及び範囲内での全ての変更が含まれることが意図される。
[Other Embodiments]
The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is not limited to the configuration of the embodiment described above, but is defined by the scope of the claims, and is intended to include all modifications within the meaning and scope equivalent to the scope of the claims. The
 当該濾過モジュールは、内周面側の負圧により被処理水を内周面側に透過する浸漬式のものに限られず、例えば中空糸膜の外周面側を高圧にして被処理水を中空糸膜の内周面側に透過する外圧式、中空糸膜の内周面側を高圧にして被処理水を中空糸膜の外周面側に透過する内圧式等、任意の形式のものとすることができる。 The said filtration module is not restricted to the immersion type which permeate | transmits to-be-processed water to the inner peripheral surface side with the negative pressure of the inner peripheral surface side, For example, the outer peripheral surface side of a hollow fiber membrane is made into high pressure, and treated water is hollow fiber It shall be of any type such as an external pressure type that permeates to the inner peripheral surface side of the membrane, an internal pressure type that allows high pressure on the inner peripheral surface side of the hollow fiber membrane and the treated water to permeate the outer peripheral surface side of the hollow fiber membrane. Can do.
 当該濾過モジュールは、活性汚泥を含む水以外の被処理水を濾過するために使用されてもよい。 The filtration module may be used for filtering treated water other than water containing activated sludge.
 当該排水処理装置は、当該濾過モジュールが配設される処理水槽以外に、被処理水中の浮遊物質を沈殿させる水槽、専ら活性汚泥により有機物の分解を行う水槽等をさらに備えてもよい。 The waste water treatment apparatus may further include a water tank for precipitating suspended solids in the water to be treated, a water tank for exclusively decomposing organic substances using activated sludge, and the like in addition to the treated water tank in which the filtration module is disposed.
 以下、実施例に基づき本発明を詳述するが、この実施例の記載に基づいて本発明が限定的に解釈されるものではない。 Hereinafter, the present invention will be described in detail based on examples, but the present invention is not construed as being limited based on the description of the examples.
<中空糸膜>
 ポリテトラフルオロエチレンから形成され、平均厚さ600μm、平均孔径2μm、気孔率80%の支持層と、平均厚さ15μm、平均孔径0.3μm、気孔率60%の濾過層とを有する平均外径2.3mmの筒状の骨材の外表面及び空孔内面に、エチレン-ビニルアルコール共重合体により平均厚さ20nmの樹脂皮膜を形成した中空糸膜の試作例1~3を作成した。
<Hollow fiber membrane>
An average outer diameter formed of polytetrafluoroethylene and having a support layer having an average thickness of 600 μm, an average pore diameter of 2 μm, and a porosity of 80%, and a filtration layer having an average thickness of 15 μm, an average pore diameter of 0.3 μm, and a porosity of 60% Experimental examples 1 to 3 of hollow fiber membranes were prepared in which a resin film having an average thickness of 20 nm was formed from an ethylene-vinyl alcohol copolymer on the outer surface and the inner surface of a pore of a 2.3 mm cylindrical aggregate.
 中空糸膜の試作例1は、エチレン-ビニルアルコール共重合体におけるエチレンの共重合比を27mol%とした。中空糸膜の試作例2は、エチレン-ビニルアルコール共重合体におけるエチレンの共重合比を32mol%とした。中空糸膜の試作例3は、エチレン-ビニルアルコール共重合体におけるエチレンの共重合比を44mol%とした。 In Experimental Example 1 of the hollow fiber membrane, the copolymerization ratio of ethylene in the ethylene-vinyl alcohol copolymer was 27 mol%. In Experimental Example 2 of the hollow fiber membrane, the copolymerization ratio of ethylene in the ethylene-vinyl alcohol copolymer was 32 mol%. In Experimental Example 3 of the hollow fiber membrane, the ethylene copolymerization ratio in the ethylene-vinyl alcohol copolymer was 44 mol%.
 樹脂皮膜の形成は、先ず、骨材をイソプロピルアルコールに1時間浸漬し、次に、上記エチレン-ビニルアルコール共重合体の0.4質量%濃度の水溶液に6時間浸漬したものを室温で3時間乾燥させることによって行った。 The resin film is formed by first immersing the aggregate in isopropyl alcohol for 1 hour, and then immersing the aggregate in an aqueous solution of 0.4% by mass of the ethylene-vinyl alcohol copolymer for 6 hours at room temperature. This was done by drying.
 これらの中空糸膜の試作例1~3について、中空糸膜を切り開いて平面状とし、外周面の純水接触角及び水中でのC重油接触角を測定した。なお、「純水接触角」は、JIS-R3257(1999)規定される「静滴法」により測定した。また、「水中でのC重油接触角」は、純水中に切り開いた中空糸膜の外周面を下向き水平に配置し、中空糸膜の外周面にC重油の油滴を静置して、JIS-R3257(1999)に規定される「接触角」と同様に中空糸膜の外周面と油滴との間の角度として測定した。 For these hollow fiber membrane prototypes 1 to 3, the hollow fiber membranes were cut open to form a flat surface, and the pure water contact angle on the outer peripheral surface and the C heavy oil contact angle in water were measured. The “pure water contact angle” was measured by the “static drop method” defined in JIS-R3257 (1999). In addition, the “contact angle of C heavy oil in water” means that the outer peripheral surface of the hollow fiber membrane cut open in pure water is placed horizontally downward, and oil droplets of C heavy oil are allowed to stand on the outer peripheral surface of the hollow fiber membrane, Similar to the “contact angle” defined in JIS-R3257 (1999), it was measured as the angle between the outer peripheral surface of the hollow fiber membrane and the oil droplets.
 また、中空糸膜の試作例1~3を用いて、有効長40cmの中空糸膜を48本備える濾過モジュールを作成し、透水量を測定した。透水量は、純水中に濾過モジュールを浸漬し、中空糸膜の内腔を吸引して中空糸膜の内外の差圧を20kPaとして吸引される水量を測定した。 Further, a filtration module including 48 hollow fiber membranes having an effective length of 40 cm was prepared using the hollow fiber membrane prototype examples 1 to 3, and the water permeability was measured. The amount of water permeated was measured by immersing the filtration module in pure water, sucking the lumen of the hollow fiber membrane, and measuring the amount of water sucked by setting the differential pressure inside and outside the hollow fiber membrane to 20 kPa.
 次の表1に、中空糸膜の試作例1~3の外周面の純水接触角及び水中でのC重油接触角並びに濾過モジュールの透水量の測定結果を示す。 Table 1 below shows the measurement results of the pure water contact angle, the C heavy oil contact angle in water, and the water permeability of the filtration module in the outer peripheral surfaces of the prototypes 1 to 3 of the hollow fiber membrane.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 さらに、中空糸膜の試作例1~3を用いた濾過モジュールによって活性汚泥水を5日間濾過した後にその外観を確認したところ、いずれも、ファウリングは見られなかった。 Furthermore, when the activated sludge water was filtered for 5 days with a filtration module using hollow fiber membrane prototypes 1 to 3, no fouling was observed.
 以上のように、中空糸膜の外周面の純水接触角及び水中でのC重油接触角を一定の範囲内とすることによって、比較的安価に製造可能でありながら、透水量が比較的大きく、ファウリングを効果的に防止できることが確認された。 As described above, by making the pure water contact angle on the outer peripheral surface of the hollow fiber membrane and the C heavy oil contact angle in water within a certain range, the water permeability is relatively large while being able to be manufactured relatively inexpensively. It was confirmed that fouling can be effectively prevented.
1 濾過モジュール
2 濾過ポンプ
3 中空糸膜
4 第1保持部材
5 第2保持部材
6 骨材
7 樹脂皮膜
8 支持層
9 濾過層
10 排水ノズル
T 処理水槽
DESCRIPTION OF SYMBOLS 1 Filtration module 2 Filtration pump 3 Hollow fiber membrane 4 1st holding member 5 2nd holding member 6 Aggregate 7 Resin film 8 Support layer 9 Filtration layer 10 Drain nozzle T Treatment water tank

Claims (6)

  1.  ポリテトラフルオロエチレンを主成分とし、多孔性を有する筒状の骨材と、
     親水性を有し、上記骨材の外表面及び空孔内面を被覆する樹脂皮膜と
     を備え、
     外周面の純水接触角が40°以上80°以下であり、
     外周面の水中でのC重油接触角が110°以上150°以下である中空糸膜。
    A cylindrical aggregate mainly composed of polytetrafluoroethylene and having porosity;
    A resin film having hydrophilicity and covering the outer surface of the aggregate and the inner surface of the pores;
    The pure water contact angle of the outer peripheral surface is 40 ° or more and 80 ° or less,
    A hollow fiber membrane having a C heavy oil contact angle in water of an outer peripheral surface of 110 ° or more and 150 ° or less.
  2.  上記樹脂皮膜の主成分がエチレン-ビニルアルコール共重合体であり、
     上記エチレン-ビニルアルコール共重合体におけるエチレンの共重合比が20mol%以上60mol%以下である請求項1に記載の中空糸膜。
    The main component of the resin film is an ethylene-vinyl alcohol copolymer,
    The hollow fiber membrane according to claim 1, wherein a copolymerization ratio of ethylene in the ethylene-vinyl alcohol copolymer is 20 mol% or more and 60 mol% or less.
  3.  上記骨材が、筒状の支持層と、この支持層の外周面に積層される濾過層とを有し、
     上記支持層の平均厚さが0.3mm以上1.0m以下であり、
     上記支持層の平均孔径が1μm以上3μm以下であり、
     上記支持層の気孔率が40%以上90%以下であり、
     上記濾過層の平均厚さが10μm以上100μm以下であり、
     上記濾過層の平均孔径が0.01μm以上0.45μm以下であり、
     上記樹脂皮膜の平均厚さが50nm以下である請求項1又は請求項2に記載の中空糸膜。
    The aggregate has a cylindrical support layer and a filtration layer laminated on the outer peripheral surface of the support layer,
    The average thickness of the support layer is 0.3 mm or more and 1.0 m or less,
    The average pore diameter of the support layer is 1 μm or more and 3 μm or less,
    The porosity of the support layer is 40% or more and 90% or less,
    The filtration layer has an average thickness of 10 μm or more and 100 μm or less,
    The average pore size of the filtration layer is 0.01 μm or more and 0.45 μm or less,
    The hollow fiber membrane according to claim 1 or 2, wherein the average thickness of the resin coating is 50 nm or less.
  4.  バブルポイントが60kPa以上200kPa以下である請求項1、請求項2又は請求項3に記載の中空糸膜。 The hollow fiber membrane according to claim 1, 2 or 3, wherein the bubble point is 60 kPa or more and 200 kPa or less.
  5.  一方向に引き揃えられた状態で保持される複数本の請求項1に記載の中空糸膜と、この複数本の中空糸膜の両端部を固定する一対の保持部材とを備える濾過モジュール。 A filtration module comprising a plurality of the hollow fiber membranes according to claim 1, which are held in a state of being aligned in one direction, and a pair of holding members for fixing both ends of the plurality of hollow fiber membranes.
  6.  活性汚泥を含む被処理水を貯留する処理水槽と、この処理水槽内に配設される請求項5に記載の濾過モジュールとを備える排水処理装置。 A wastewater treatment apparatus comprising a treated water tank for storing treated water containing activated sludge and the filtration module according to claim 5 disposed in the treated water tank.
PCT/JP2017/038111 2016-11-17 2017-10-23 Hollow-fiber membrane, filtration module, and wastewater treatment device WO2018092516A1 (en)

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