WO2012035692A1 - Module à membrane de séparation d'eau - Google Patents

Module à membrane de séparation d'eau Download PDF

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Publication number
WO2012035692A1
WO2012035692A1 PCT/JP2011/003994 JP2011003994W WO2012035692A1 WO 2012035692 A1 WO2012035692 A1 WO 2012035692A1 JP 2011003994 W JP2011003994 W JP 2011003994W WO 2012035692 A1 WO2012035692 A1 WO 2012035692A1
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WO
WIPO (PCT)
Prior art keywords
water
membrane
water separation
spacer
separation membrane
Prior art date
Application number
PCT/JP2011/003994
Other languages
English (en)
Japanese (ja)
Inventor
敬子 中野
牛房　信之
泰子 小島
Original Assignee
株式会社日立製作所
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Filing date
Publication date
Application filed by 株式会社日立製作所 filed Critical 株式会社日立製作所
Publication of WO2012035692A1 publication Critical patent/WO2012035692A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/10—Spiral-wound membrane modules
    • B01D63/107—Specific properties of the central tube or the permeate channel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/10—Spiral-wound membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0086—Mechanical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/40—Details relating to membrane preparation in-situ membrane formation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/08—Patterned membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/20—Prevention of biofouling

Definitions

  • the present invention relates to a water separation membrane module structure.
  • a reverse osmosis membrane is used in advanced treatment of water purification.
  • a semi-permeable membrane is used on the surface of the reverse osmosis membrane, and the material of the semi-permeable membrane is roughly classified into cellulose acetate type and aromatic polyamide type.
  • aromatic polyamide-based reverse osmosis membranes are widely used for industrial use because of their high water permeability and electrolyte removal performance.
  • As the structure a composite semipermeable membrane structure in which an aromatic polyamide membrane is formed on a microporous support is often used, and the thickness of the aromatic polyamide portion is generally 200 to 300 nm.
  • a porous polysulfone membrane and a nonwoven fabric are combined to form a planar reverse osmosis membrane.
  • Reverse osmosis membranes are used to remove organic substances and electrolytes that dissolve in water during seawater desalination, pure water production used in the manufacture of precision electronic equipment such as semiconductors, advanced water treatment, and sewage / wastewater regeneration.
  • water is generally supplied to the reverse osmosis membrane through the following treatment process.
  • coarse impurities, waste, etc. contained in sewage are removed through a sieve called a screen.
  • a fine suspension such as sand is added to the flocculant if necessary, and then submerged in a sedimentation basin for separation.
  • the supernatant water still contains suspended solids, dissolved organic matter, etc., and is decomposed using microorganisms.
  • Microbial colonies and metabolites are sludge. Sludge and water are separated by settling in a sedimentation basin or passing through a microfiltration membrane.
  • the sewage primary treated water treated in this way contains almost no suspended solids, and has been purified to such a quality that it can be discharged into the river at this stage or reused depending on the application, such as greening spray water.
  • Japan at this stage, it is discharged into rivers and water is recycled using natural purification.
  • the reverse osmosis membrane is used in this final treatment to remove electrolytes and dissolved organic substances in the sewage primary treated water.
  • a bag-like reverse osmosis membrane is fixed to the center core, and it is rolled up like an umbrella and stored in a cylinder.
  • the main module is a cylindrical shape with a diameter of 4 inches, 8 inches, etc. and a length of 1 m.
  • a mesh called a spacer which is a plastic fiber with a thickness of 1 mm or less, woven with a mesh with a spacing of 2 to 3 mm is inserted to secure a water flow path.
  • the spacer lattice portion is pressed against the membrane, the spacer and the membrane are in contact with each other, and the fiber portion has a small gap between the membrane and the water flow path.
  • ultrafiltration membranes and nanofilter membranes may be formed with the same spiral structure.
  • Reverse osmosis membranes are a type of separation membrane, but there are two methods for water filtration using separation membranes.
  • One is a total filtration system, which is a system that allows the entire amount of supplied water to pass through the membrane. Components that cannot pass through the membrane are deposited on the membrane surface.
  • the other is a cross-flow filtration method, in which water flows parallel to the membrane surface, part of the permeate passes through the membrane to the permeate, and the rest is taken out from the module as concentrated water with the concentration of the lysate increased. .
  • the latter cross-flow filtration method is used for filtration through reverse osmosis membranes. This method reduces the increase in operating load due to the deposition of dissolved material on the membrane surface and the increase in concentration.
  • the cross-flow filtration method also has a problem that the dissolved matter is adsorbed on the membrane surface and the amount of permeated water deteriorates with time.
  • the adsorbed material on the membrane surface includes organic fouling that adsorbs organic matter in addition to the scale in which the electrolyte is deposited at a high concentration near the membrane surface, biofouling in which microorganisms in the water grow.
  • Clean water or cleaning liquid is periodically flowed over the membrane surface and the adsorbed material is removed by shearing force.
  • organic matter is adsorbed, it cannot be completely removed by shearing force, and it gradually accumulates to remove water.
  • the amount of transmission decreases.
  • the power (pressure) is increased to obtain a constant permeation amount, but this leads to an increase in the power cost of the pump.
  • the reverse osmosis membrane gradually deteriorates due to the cleaning liquid, the ion rejection rate decreases.
  • Organic fouling has several stages. First, organic substances having affinity with the reverse osmosis membrane surface material are adsorbed on the membrane surface. As the amount of adsorption increases, it fills the gaps in the polymer network structure of the reverse osmosis membrane, making it difficult for water molecules to permeate. In addition, the adsorbed organic substances are entangled and grow into a gel-like lump. These gel-like lumps accumulate on the part where the film and the spacer are in contact with each other, such as the lattice part of the spacer or the fiber part of the spacer, or the gap is narrowed, and the channel is blocked.
  • This phenomenon of organic fouling is likely to occur upstream of the reverse osmosis membrane module.
  • water is not supplied to the downstream side of the module even though the membrane is in good condition. Since the original performance of the membrane cannot be exhibited, cleaning and membrane replacement are required.
  • the surface area of the reverse osmosis membrane is increased by forming pleats with a spacing of about 1 to 10 ⁇ m in the semipermeable membrane on the surface of the reverse osmosis membrane, A method is described in which it is easily adsorbed to a concave portion having a low flow velocity, and the convex portion is difficult to adsorb, thereby preventing a decrease in water permeability.
  • the area of the contact portion between the spacer and the membrane where the blockage is most likely to occur and the area where the gap is narrow is reduced.
  • unevenness is formed on the surface of the reverse osmosis membrane so that the contact with the spacer is a contact with a small area.
  • the channel blockage due to organic matter fouling is suppressed, and the membrane can be used effectively over a long period of time. Module replacement frequency can be reduced.
  • FIG. 4A is a diagram of the reverse osmosis membrane module 4 according to one embodiment of the present invention
  • FIG. 4B is a schematic diagram thereof.
  • a hollow central pipe 15 is provided at the center of the module 4, and a plurality of water separation membranes (reverse osmosis membranes) 11 are attached to the central pipe 15.
  • a set of two water separation membranes 11 are wound around the central pipe 15 in a spiral shape and overlap each other.
  • the end of the water separation membrane 11 on the outer side of the spiral is formed into a bag shape by sealing the two water separation membranes 11, and the end of the inner side of the spiral is attached to the central pipe 15 by bonding.
  • the inside of the 11 bags communicates with a hollow water channel in the central pipe 15 so that the water in the bag is collected in the central pipe 15.
  • a spacer 12 is installed between adjacent bags.
  • a water-conditioning mesh 13 is placed inside the bag.
  • the bag of the water separation membrane 11 is wound around the central pipe 15 while being overlapped with the spacer 12 and the mesh 13, and the outer cylindrical portion of the cylinder is hardened with a pressure resistant resin.
  • the water to be treated that has entered the water separation membrane module 4 is separated into two by the water separation membrane 11. Since the water separation membrane 11 is difficult to pass the dissolved component, it is separated into the permeated water having a small dissolved amount permeated through the membrane 11 and the concentrated water in which the dissolved component is concentrated, and is discharged out of the module 4.
  • the water to be treated for reverse osmosis membrane enters the module from the side of the cylindrical reverse osmosis membrane module, is outside the bag of the water separation membrane 11, and the spacer 12 is It is led to the arranged area. Only water molecules and components that do not need to be removed by the water separation membrane 11 from the water to be treated pass through the membrane 11 to be purified to become permeated water and enter the inside of the bag of the membrane 11. The permeated water inside the bag passes through the region where the water conditioning mesh 13 is disposed, is collected in a water channel in the central pipe 15, and is guided to the outside of the reverse osmotic pressure module.
  • the spiral-structured membrane module is also of a type in which treated water is introduced into the bag of the water separation membrane 11, the treated water is passed through the central pipe, and the permeated water flows out from the peripheral part. is there.
  • the spacer 12 is disposed inside the bag of the membrane 11 and the water conditioning mesh 13 is disposed outside the bag.
  • FIG. 3 shows a diagram of the water separation membrane 11, the spacer 12, and the mesh 13.
  • the spacer 12 is overlapped so as to contact the treated water side 8 of the water separation membrane 11, and the water conditioning mesh 13 is overlapped on the permeate side 9 of the water separation membrane 11 so that water can permeate uniformly.
  • a membrane module having a similar spiral structure is formed.
  • the water separation membrane 11 has unevenness on the surface, and the surface having the unevenness is arranged facing the spacer side.
  • FIG. 1 is a plan view of the combination of the water separation membrane 11 and the spacer 12, and FIG. 2 is a sectional view thereof.
  • unevenness is provided on the surface of the water separation membrane 11.
  • 1 indicated by a black dot is an apex of unevenness of the film, and a portion indicated by a dotted line indicates the fiber 2 of the spacer 12. Since the unevenness 1 is narrower than the width of the spacer fiber 2, the film 11 contacts the fiber 2 at the apex of the unevenness regardless of the spacer hole. That is, as shown in the cross-sectional view of FIG. 2, the film 11 and the fiber 2 of the spacer are in contact with each other at a point, and the distance 3 between the film 11 and the fiber 2 is secured.
  • a membrane module having the same membrane area as the conventional one can be formed by reducing the spacer thickness by about 0.2 mm as required.
  • the distance between the fiber 2 of the spacer and the film 11 is constant.
  • the lattice point portion of the spacer is in contact with the film when the spiral structure is formed, so the distance is narrow. Organic matter accumulates here and it is easy to block.
  • the distance between the irregularities on the film surface should be 1/10 or less so as not to interfere with the mesh structure of 2 to 3 mm spacing of the spacers. And the interval so that the least common multiple of the film surface irregularities is as large as possible. Considering the ease of production, etc., it is preferably formed in the range of 100 to 500 ⁇ m.
  • the depth of the unevenness is desirably 100 ⁇ m or more from the viewpoint of securing the flow path.
  • a reverse osmosis membrane using an aromatic polyamide as a semipermeable membrane is generally formed by first forming a polysulfone membrane as a support membrane, and an organic solvent solution of a dicarboxylic acid or tricarboxylic acid as a raw material for the polyamide membrane on the surface thereof.
  • An aqueous solution of diamine or triamine is sequentially applied to form a film by interfacial polymerization.
  • the uneven shape on the reverse osmosis membrane surface can be formed by several methods.
  • One is a method in which irregularities are formed on the surface of the polysulfone membrane, and the semipermeable membrane is formed in an irregular shape. After forming the polysulfone membrane, it gives vibration during solvent drying when embossing and forming a porous membrane, sprays polysulfone fine particles on the surface during solvent drying, forms a smooth polysulfone membrane, and prints a polysulfone solution in a dot pattern Such a method is conceivable.
  • the second is a method of forming surface irregularities after forming a reverse osmosis membrane, such as embossing or folding the membrane to wrinkle the surface.
  • unevenness is not necessary on the permeate side (water conditioning mesh side) of the water separation membrane 11. This is because in the permeated water, the concentration of dissolved matter is small and clogging is unlikely to occur. Further, when there is no unevenness on the permeate side, it is easier to create a bag by bonding and sealing the film 11. In other words, the surface of the water separation membrane 11 has a rougher surface (the unevenness is larger) on the surface to be treated and the concentrated water side than the surface on the permeated water side.
  • Example 1 An acrylic mold in which the quadrangular pyramids (vertices are cut off) shown in FIG. 6 was prepared. One side of the quadrangular pyramid is 0.1 mm and the depth is 0.15 mm.
  • a flat membrane reverse osmosis membrane (LFC3 made by Nitto Denko) is cut to a size of 100 x 25 mm, wetted with pure water and placed on a mold with the semipermeable membrane facing the acrylic side, and silicon rubber from the nonwoven fabric side. Rubbing with a squeegee, the unevenness of the acrylic mold was transferred to the film. As a result, an uneven shape having a difference between the peak and the bottom of about 100 ⁇ m was formed on the surface of the film.
  • the NFC LFC3 manufactured by Nitto Denko is classified as a nanofilter membrane, but is treated here as a kind of reverse osmosis membrane, and hereinafter referred to as a reverse osmosis membrane.
  • a simple module for evaluation was produced using this membrane.
  • a spacer (fiber spacing 2.5 mm, fiber diameter 0.5 mm) taken out from a commercially available spiral-type reverse osmosis membrane module was cut into 100 mm ⁇ 25 mm, and a cell composed of three acrylic plates 16 as shown in FIG.
  • the eight reverse osmosis membranes 11 and the four spacers 12 are alternately stacked so that the semipermeable membrane surface is on the spacer side, and the upper and lower sides are sandwiched between Viton sheets 17, and a load of 5 kg is applied to the whole.
  • water to be treated filtered through a 0.1 ⁇ m pore microfiltration membrane was pressurized to 0.05 MPa with nitrogen and passed through the cell, and the time required for 500 ml to pass through was measured. At this pressure, water molecules do not pass through the semipermeable membrane by reverse osmosis, and water passes between the semipermeable membrane and the semipermeable membrane.
  • Example 2 Prepare a sample water in which 0.2 g of polystyrene (standard product with a molecular weight of 1,000 to 4,000,000 for size exclusion chromatography) is dispersed in 1 L of water, and flow it through the simple module prepared in Experiment 1 at a pressure of 0.05 MPa. The possibility of blockage of the flow path was examined. Since polystyrene is insoluble in water, it was considered to be an accelerated test simulating a lump that grew like a gel. In order to save sample water, 1 L is flowed through a simple module and collected, and the collected liquid is pressurized again and flowed repeatedly.
  • polystyrene standard product with a molecular weight of 1,000 to 4,000,000 for size exclusion chromatography
  • SYMBOLS 1 The peak part of the unevenness

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Dans les modules de séparation à structure hélicoïdale pour le traitement de l'eau, une substance organique est adsorbée à la surface d'une membrane, obstruant une structure à maille polymère et réduisant la quantité d'infiltration d'eau. Le problème, c'est que la substance organique adsorbée se développe en un amas gélifié et colmate les parties étroites de l'espace entre la membrane et une cale, ce qui dégrade fortement la quantité d'eau qui s'infiltre à travers le module. Pour régler ce problème, dans ce module de séparation d'eau, doté d'un tuyau central, une pluralité de membranes de séparation d'eau (11) qui sont fixées au tuyau central et qui sont prévues de façon hélicoïdale à la périphérie du tuyau central de façon à se chevaucher, et une cale (12) qui se trouve entre la pluralité de membranes de séparation d'eau du côté où l'eau non traitée entre, des concavités et des convexités ayant une taille qui n'interfère pas avec la forme de la maille de la cale (12) et ayant une taille qui peut établir des voies de passage de l'eau sont appliquées à la surface des membranes de séparation d'eau (9, 11), ce qui permet de supprimer le colmatage des parties étroites de l'espace entre les membranes (11) et la cale (12).
PCT/JP2011/003994 2010-09-16 2011-07-13 Module à membrane de séparation d'eau WO2012035692A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-207458 2010-09-16
JP2010207458A JP2012061419A (ja) 2010-09-16 2010-09-16 水分離膜モジュール

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WO2012035692A1 true WO2012035692A1 (fr) 2012-03-22

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015128375A (ja) * 2014-01-06 2015-07-16 東京インキ株式会社 農業用ハウス保温材
WO2016159333A1 (fr) * 2015-03-31 2016-10-06 東レ株式会社 Membrane de séparation
CN106422792A (zh) * 2016-08-09 2017-02-22 厦门建霖工业有限公司 一种高回收率卷式反渗透膜元件

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110975631B (zh) * 2019-12-19 2021-12-17 沃顿科技股份有限公司 一种卷式膜元件产水隔网

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JPS5424280A (en) * 1977-07-25 1979-02-23 Yuasa Battery Co Ltd Filter
JPH11114381A (ja) * 1997-10-16 1999-04-27 Nitto Denko Corp スパイラル型膜エレメント
JP2000051671A (ja) * 1998-08-06 2000-02-22 Nitto Denko Corp スパイラル型分離膜エレメント
JP2000051668A (ja) * 1999-08-24 2000-02-22 Toray Ind Inc 液体分離素子および造水方法
JP2000334272A (ja) * 1999-05-31 2000-12-05 Nitto Denko Corp スパイラル型分離膜エレメント
JP2000342941A (ja) * 1999-06-08 2000-12-12 Nitto Denko Corp 液体分離膜モジュール
JP2006247453A (ja) * 2005-03-08 2006-09-21 Toray Ind Inc 液体分離素子、およびそれを用いた逆浸透装置、逆浸透膜処理方法
JP2008507406A (ja) * 2004-07-26 2008-03-13 パイオネティクス コーポレイション テキスチャード膜およびカートリッジによる電気化学イオン交換
JP2010099591A (ja) * 2008-10-23 2010-05-06 Nitto Denko Corp 分離膜エレメント

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JPS5424280A (en) * 1977-07-25 1979-02-23 Yuasa Battery Co Ltd Filter
JPH11114381A (ja) * 1997-10-16 1999-04-27 Nitto Denko Corp スパイラル型膜エレメント
JP2000051671A (ja) * 1998-08-06 2000-02-22 Nitto Denko Corp スパイラル型分離膜エレメント
JP2000334272A (ja) * 1999-05-31 2000-12-05 Nitto Denko Corp スパイラル型分離膜エレメント
JP2000342941A (ja) * 1999-06-08 2000-12-12 Nitto Denko Corp 液体分離膜モジュール
JP2000051668A (ja) * 1999-08-24 2000-02-22 Toray Ind Inc 液体分離素子および造水方法
JP2008507406A (ja) * 2004-07-26 2008-03-13 パイオネティクス コーポレイション テキスチャード膜およびカートリッジによる電気化学イオン交換
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015128375A (ja) * 2014-01-06 2015-07-16 東京インキ株式会社 農業用ハウス保温材
WO2016159333A1 (fr) * 2015-03-31 2016-10-06 東レ株式会社 Membrane de séparation
JPWO2016159333A1 (ja) * 2015-03-31 2017-04-27 東レ株式会社 分離膜
KR20170131474A (ko) * 2015-03-31 2017-11-29 도레이 카부시키가이샤 분리막
US10639595B2 (en) 2015-03-31 2020-05-05 Toray Industries, Inc. Separation membrane
US11103836B2 (en) 2015-03-31 2021-08-31 Toray Industries, Inc. Separation membrane
KR102337389B1 (ko) 2015-03-31 2021-12-10 도레이 카부시키가이샤 분리막
CN106422792A (zh) * 2016-08-09 2017-02-22 厦门建霖工业有限公司 一种高回收率卷式反渗透膜元件

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