WO2024122107A1 - 複合半透膜、及びスパイラル型膜エレメント - Google Patents

複合半透膜、及びスパイラル型膜エレメント Download PDF

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Publication number
WO2024122107A1
WO2024122107A1 PCT/JP2023/028734 JP2023028734W WO2024122107A1 WO 2024122107 A1 WO2024122107 A1 WO 2024122107A1 JP 2023028734 W JP2023028734 W JP 2023028734W WO 2024122107 A1 WO2024122107 A1 WO 2024122107A1
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Prior art keywords
composite semipermeable
membrane
semipermeable membrane
surface roughness
functional layer
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PCT/JP2023/028734
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English (en)
French (fr)
Japanese (ja)
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倫次 宮部
阿槻 平原
泰輔 山口
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to JP2024562572A priority Critical patent/JP7762318B2/ja
Priority to EP23900235.5A priority patent/EP4631607A4/en
Priority to CN202380076327.4A priority patent/CN120076861A/zh
Publication of WO2024122107A1 publication Critical patent/WO2024122107A1/ja
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    • 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
    • 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
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
    • 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
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/218—Additive materials
    • B01D2323/2182—Organic additives
    • B01D2323/21825—Ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/218—Additive materials
    • B01D2323/2182—Organic additives
    • B01D2323/21833—Esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/218—Additive materials
    • B01D2323/2182—Organic additives
    • B01D2323/21834—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/06—Surface irregularities
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/20—Specific permeability or cut-off range
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/306—Pesticides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Definitions

  • the present invention relates to a composite semipermeable membrane having a porous support and a separation functional layer, and a spiral-type membrane element (hereinafter sometimes abbreviated as "membrane element”) using the same.
  • Composite semipermeable membranes are called RO (reverse osmosis), NF (nanofiltration), FO (forward osmosis) membranes, etc. depending on their filtration performance and processing method, and can be used for ultrapure water production, seawater desalination, brackish water desalination, wastewater recycling, etc.
  • RO reverse osmosis
  • NF nanofiltration
  • FO forward osmosis
  • partial desalination loose-type membranes which allow inorganic salts to pass through more easily than the RO membranes used in desalination processes, and their application to the production of drinking water as described above is being considered.
  • partial desalination loose-type NF membranes in that they either have good blocking performance against organic compounds such as herbicides and odorous components but insufficient water permeability, or they have good water permeability but insufficient blocking performance against the organic compounds.
  • a composite semipermeable membrane that is often used industrially is, for example, a composite semipermeable membrane in which a skin layer containing a polyamide resin obtained by reacting a polyfunctional amine component with a polyfunctional acid halide component is formed on the surface of a porous support as a separation functional layer.
  • a method is known for improving the permeability of such composite semipermeable membranes while maintaining blocking performance by increasing the surface area by providing fine irregularities in the separation functional layer.
  • Patent Document 1 discloses a method for producing a composite reverse osmosis membrane having an average surface roughness of the skin layer of 55 nm or more, in which a solution A containing a polyfunctional amine component is brought into contact with a solution B containing a polyfunctional acid halide component to form a skin layer on a microporous support, and a compound having a solubility parameter of 8 to 14 (cal/cm 3 ) 1/2 is present in solution A or solution B.
  • the average surface roughness of the skin layer can be said to be calculated using values measured in air using an atomic force microscope (AFM).
  • AFM atomic force microscope
  • the surface roughness measured in air using an atomic force microscope is difficult to correlate with water permeability, especially when the size of the fine irregularities in the separation functional layer is above a certain level.
  • the size of the fine irregularities in the separation functional layer when actually used for membrane separation tends to differ from the surface roughness of the separation functional layer measured in air, and it was found that there are limitations to using this as an indicator to control the size of the fine irregularities in the separation functional layer (i.e., the microscopic surface area) to improve water permeability.
  • the object of the present invention is to provide a composite semipermeable membrane that can improve both the blocking performance for organic compounds and water permeability by controlling the microscopic surface area of the separation functional layer using an index different from conventional indicators, and a spiral membrane element using the same.
  • the present invention includes the following aspects.
  • a composite semipermeable membrane comprising a porous support and a separation functional layer formed of a polyamide resin on the porous support,
  • the separating functional layer is a composite semipermeable membrane having a surface roughness Ra1 of 90 to 150 nm when measured in an area of 5 ⁇ m ⁇ 5 ⁇ m in water with an atomic force microscope (AFM).
  • AFM atomic force microscope
  • the surface roughness Ra1 measured in water can be used as an index to measure the size of the fine irregularities of the separation functional layer in a state close to the state in which it is actually used for membrane separation, and by controlling this within a predetermined range, the water permeability can be improved by increasing the microscopic surface area without reducing the blocking performance against organic compounds.
  • FIG. 1 the surface roughness measured in water
  • the separation functional layer 1a formed on the porous support 1b of the composite semipermeable membrane 1 in the atmosphere tends to be observed in a state in which the fine irregularities of the separation functional layer 1a are collapsed or crushed compared to the state in which it is actually used for membrane separation, and by using the surface roughness Ra1 measured in water as an index, the size of the fine irregularities of the separation functional layer in a state close to the state in which it is actually used for membrane separation can be measured more accurately.
  • the benzene rings tend to be densely arranged, making it easier to adjust the rejection rate for organic compounds to a certain level or higher.
  • permeability to the simulated water is within this range, it becomes easier to achieve both blocking performance against organic compounds and permeability, which are in a trade-off relationship.
  • the spiral membrane element of the present invention has the composite semipermeable membrane of the present invention as described above, and by controlling the microscopic surface area of the separation functional layer with an index different from conventional indicators, it is possible to provide a spiral membrane element that can improve both the blocking performance against organic compounds and the water permeability.
  • the present invention provides a composite semipermeable membrane and a spiral membrane element that can improve both the blocking performance for organic compounds and water permeability by controlling the microscopic surface area of the separation functional layer using a different index than conventional methods.
  • FIG. 2 is a conceptual diagram illustrating the difference between a separation functional layer of a composite semipermeable membrane in air and a separation functional layer of a composite semipermeable membrane in water.
  • FIG. 2 is a partially cutaway perspective view showing an example of a spiral membrane element.
  • the composite semipermeable membrane of the present invention is a composite semipermeable membrane comprising a porous support and a separation functional layer formed of a polyamide resin on the porous support, wherein the separation functional layer has a surface roughness Ra1 of 90 to 150 nm when an area of 5 ⁇ m ⁇ 5 ⁇ m is measured in water with an atomic force microscope (AFM).
  • AFM atomic force microscope
  • the separation functional layer may be capable of separating, for example, monovalent inorganic ions, monovalent organic ions, divalent inorganic ions, divalent organic ions, organic compounds with a molecular weight of 100 to 150, organic compounds with a molecular weight of 150 to 250, and organic compounds with a molecular weight of more than 250, depending on the size of the solute to be separated.
  • the surface roughness Ra1 measured in water can be used as an index to measure the size of the fine irregularities on the separation functional layer in a state close to the state actually used for membrane separation, and by controlling this within a specified range, the microscopic surface area can be increased and water permeability can be improved without reducing blocking performance.
  • composite semipermeable membranes used in the production of drinking water that have the ability to block organic compounds (e.g., molecular weight 150 to 250) such as herbicides and odorous components, and that have good water permeability when removing these compounds.
  • organic compounds e.g., molecular weight 150 to 250
  • the composite semipermeable membrane of the present invention is particularly effective as a separation membrane for removing such organic compounds.
  • a polyamide-based resin As a material for forming the separation functional layer, a polyamide-based resin is used, which can form the separation functional layer by interfacial polymerization and can control the size of the fine irregularities in the separation functional layer.
  • a separation functional layer formed from a polyamide-based resin it is particularly preferable that the separation functional layer contains a polyamide-based resin obtained by polymerizing a polyfunctional amine component and a polyfunctional acid halogen component.
  • the polyfunctional amine component is a polyfunctional amine having two or more reactive amino groups, and examples of such polyfunctional amines include aromatic, aliphatic and alicyclic amines.
  • aromatic polyfunctional amines include m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2,6-diaminotoluene, N,N'-dimethyl-m-phenylenediamine, 2,4-diaminoanisole, amidole, and xylylenediamine.
  • aliphatic polyfunctional amines examples include ethylenediamine, propylenediamine, tris(2-aminoethyl)amine, and n-phenyl-ethylenediamine.
  • alicyclic polyfunctional amines examples include 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, and 4-aminomethylpiperazine.
  • polyfunctional amines may be used alone or in combination of two or more. In order to obtain a separation functional layer with high salt-rejection performance, it is preferable to use an aromatic polyfunctional amine.
  • m-phenylenediamine as the polyfunctional amine component, and it is preferable to use 20 to 100 mol %, more preferably 50 to 100 mol %, and most preferably 100 mol % in the polyfunctional amine component. This allows the separation functional layer to be formed from a polyamide resin containing a component derived from m-phenylenediamine.
  • the polyfunctional acid halide component is a polyfunctional acid halide having two or more reactive carbonyl groups.
  • polyfunctional acid halides include aromatic, aliphatic and alicyclic polyfunctional acid halides.
  • aromatic polyfunctional acid halides include trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyldicarboxylic acid dichloride, naphthalenedicarboxylic acid dichloride, benzenetrisulfonic acid trichloride, benzenedisulfonic acid dichloride, and chlorosulfonylbenzenedicarboxylic acid dichloride.
  • aliphatic polyfunctional acid halides examples include propanedicarboxylic acid dichloride, butanedicarboxylic acid dichloride, pentanedicarboxylic acid dichloride, propanetricarboxylic acid trichloride, butanetricarboxylic acid trichloride, pentanetricarboxylic acid trichloride, glutaryl halide, adipoyl halide, etc.
  • Examples of alicyclic polyfunctional acid halides include cyclopropanetricarboxylic acid trichloride, cyclobutanetetracarboxylic acid tetrachloride, cyclopentanetricarboxylic acid trichloride, cyclopentanetetracarboxylic acid tetrachloride, cyclohexanetricarboxylic acid trichloride, tetrahydrofurantetracarboxylic acid tetrachloride, cyclopentanedicarboxylic acid dichloride, cyclobutanedicarboxylic acid dichloride, cyclohexanedicarboxylic acid dichloride, and tetrahydrofurandicarboxylic acid dichloride.
  • polyfunctional acid halides may be used alone or in combination of two or more. In order to obtain a separation functional layer with high salt blocking performance, it is preferable to use an aromatic polyfunctional acid halide. It is also preferable to form a crosslinked structure by using a polyfunctional acid halide with a valence of three or more as at least a part of the polyfunctional acid halide component.
  • trimesic acid trichloride as the polyfunctional acid halide component, and it is preferable to use 20 to 100 mol %, more preferably 50 to 100 mol %, and most preferably 100 mol % in the polyfunctional acid halide component. This allows the separation functional layer to be formed from a polyamide-based resin containing a component derived from trimesic acid trichloride.
  • the separation functional layer containing a polyamide resin may be copolymerized with polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, and polyhydric alcohols such as sorbitol and glycerin.
  • polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, and polyhydric alcohols such as sorbitol and glycerin.
  • the porous support that supports the separation functional layer is not particularly limited as long as it can support the separation functional layer, and typically, an ultrafiltration membrane with micropores having an average pore size of about 10 to 500 ⁇ is preferably used.
  • materials that can be used to form the porous support include polysulfone, polyarylethersulfone such as polyethersulfone, polyimide, polyetherimide, polyvinylidene fluoride, and the like, but polysulfone and polyarylethersulfone are particularly preferred because of their chemical, mechanical, and thermal stability.
  • the thickness of such a porous support is usually about 25 to 125 ⁇ m, preferably about 40 to 75 ⁇ m, but is not necessarily limited to these. It is preferable that the porous support is reinforced by backing with a base material such as woven fabric or nonwoven fabric.
  • the method for forming a separation functional layer containing a polyamide resin on the surface of a porous support is not particularly limited, and any known method can be used. Examples include an interfacial condensation method, a phase separation method, and a thin film coating method.
  • the interfacial condensation method is a method in which an amine aqueous solution containing a polyfunctional amine component is contacted with an organic solution containing a polyfunctional acid halide component and interfacially polymerized to form a separation functional layer, and the separation functional layer is placed on a porous support, or a method in which a separation functional layer of a polyamide resin is directly formed on a porous support by the interfacial polymerization on the porous support. Details of the conditions for such an interfacial condensation method are described in JP-A-58-24303 and JP-A-1-180208, and the like, and these known techniques can be appropriately adopted.
  • the separation functional layer formed on the porous support has fine irregularities, and the size of the irregularities can be measured using the surface roughness Ra1 as an index when an area of 5 ⁇ m x 5 ⁇ m is measured in water with an atomic force microscope (AFM).
  • AFM atomic force microscope
  • the surface roughness Ra1 is preferably 90 nm or more, more preferably 95 nm or more, even more preferably 100 nm or more, and particularly preferably 105 nm or more.
  • the surface roughness Ra1 is preferably 150 nm or less, more preferably 140 nm or less, even more preferably 130 nm or less, and particularly preferably 125 nm or less.
  • the magnitude of the fine irregularities in the separation functional layer can also be known to some extent from the surface roughness Ra2 measured in an area of 5 ⁇ m x 5 ⁇ m in air using an atomic force microscope (AFM).
  • AFM atomic force microscope
  • using the surface roughness Ra1 measured in water as an indicator allows for a more appropriate measurement of the magnitude of the fine irregularities in the separation functional layer under conditions closer to those actually used in membrane separation.
  • the surface roughness Ra1 measured in water and the surface roughness Ra2 measured in air refer to the planar surface roughness Ra defined by the following formula (Math 1).
  • Planar surface roughness can be calculated using values measured using an atomic force microscope (AFM).
  • the average surface roughness (Ra) is a three-dimensional extension of the centerline average roughness Ra defined in JIS B0601 so that it can be applied to the measurement surface, and is the average value of the absolute value of the deviation from the reference surface to the specified surface.
  • the measurement surface refers to the surface indicated by all the measurement data
  • the specified surface refers to a specific part of the measurement surface specified by a clip (the specified area is 5 ⁇ m x 5 ⁇ m) that is the surface to be measured for roughness
  • a method for producing a composite semipermeable membrane by forming a polyamide-based skin layer (separation functional layer) by a method including a step of coating a porous support with solution A containing a polyfunctional amine component and a step of contacting the solution A phase with solution B containing a polyfunctional acid halogen component it is preferable to add an interface modifier such as an alkanolamine compound, an alkyl ketone compound, or an alkyl ester compound to the solution A.
  • alkanolamine compound examples include ethanolamine, methanolamine, propanolamine, butanolamine, etc., and may be any of monoalkanolamine, dialkanolamine, and trialkanolamine.
  • the hydrogen atom bonded to the nitrogen atom of the alkanolamine compound may be substituted with an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, etc.
  • monoethanolamine, diethanolamine, and triethanolamine are preferred, and monoethanolamine and triethanolamine are more preferred.
  • alkyl ketone compounds include acetone, diisopropyl ketone, and cyclohexanone
  • alkyl ester compounds include ethyl acetate, propyl acetate, and butyl acetate.
  • the concentration of the interfacial modifier in solution A is preferably 0.1 to 10.0% by mass, and more preferably 1.0 to 5.0% by mass.
  • the surface roughness Ra1 can also be adjusted by the difference in solubility parameters between the solutions A and B, or the solubility parameters of compounds added to the solutions A and/or B.
  • a compound having a solubility parameter of 8 to 17 (cal/cm 3 ) 1/2 is present in at least one selected from the solution A, the solution B, and the microporous support.
  • Solubility parameter adjusters include alcohols such as ethanol, propanol, butanol, and pentanol, as well as nitrogen compounds such as ethylamine, triethylamine, and n-butylamine.
  • the solubility parameter can be adjusted by changing the type and concentration of the polyfunctional amine component or polyfunctional acid halogen component used.
  • spiral-type membrane element of the present invention is characterized by having the composite semipermeable membrane as described above, and for the parts other than the composite semipermeable membrane, any of the configurations of conventional membrane elements can be adopted.
  • the spiral membrane element of the present invention for example as shown in FIG. 2, comprises a perforated central tube 5 and a wound body R wound around the central tube 5 and including a separation membrane 1.
  • the permeate side flow passage in the membrane leaf L can be formed by the permeate side flow passage material 3 (also called the permeate side spacer).
  • FIG. 2 shows an example in which the sealing portion includes both end sealing portions and an outer peripheral sealing portion 12.
  • the both end sealing portions are formed by sealing two edge portions on both sides of the membrane leaf L in the axial direction A1 with an adhesive.
  • the outer peripheral sealing portion 12 is formed by sealing the edge portion at the outer peripheral tip of the membrane leaf L with an adhesive.
  • the area surrounded by the opposing separation membrane 1, both end sealing portions, and the outer peripheral sealing portion 12 becomes the permeate side flow path, which is structured to communicate with the opening 5a of the central tube 5.
  • a central sealing portion in which the perforated central tube 5 and the base end sides of both end sealing portions of the membrane leaf L are sealed with adhesive.
  • the membrane leaf L and the supply side flow path material 2 are wound around the central tube 5 in a wound body R via such a central sealing portion.
  • the adhesive is not particularly limited, and any conventionally known adhesive can be used, such as a urethane adhesive or an epoxy adhesive.
  • a first end member 10 having a function such as a seal carrier may be provided on the upstream side of the membrane element wound body R, and a second end member 20 having a function such as an anti-telescope material may be provided on the downstream side.
  • a typical 8-inch diameter spiral membrane element about 15 to 30 sets of membrane leaves L are wound.
  • the membrane element When the membrane element is used, it is housed in a pressure vessel, and the feed liquid 7 is supplied from one end of the membrane element.
  • the supplied feed liquid 7 flows along the feed-side flow path material 2 in a direction parallel to the axial direction A1 of the central tube 5, and is discharged as a concentrated liquid 9 from the other end of the membrane element.
  • the permeated liquid 8 that permeates the separation membrane 1 while the feed liquid 7 flows along the feed-side flow path material 2 flows along the permeation-side flow path material 3, then flows from the opening 5a into the interior of the central tube 5, and is discharged from the end of the central tube 5.
  • the feed-side flow channel material 2 generally has the role of ensuring gaps for evenly supplying the fluid to the membrane surface.
  • nets, knitted fabrics, textured sheets, etc. can be used as the feed-side flow channel material 2, and materials with a maximum thickness of about 0.1 to 3 mm can be used as needed.
  • the feed-side flow channel material 2 When flow channel materials are placed on both sides of the separation membrane 1, it is common to use different flow channel materials, the feed-side flow channel material 2 on the feed liquid side and the permeate-side flow channel material 3 on the permeate liquid side. It is preferable to use a thick, coarse-meshed net-like flow channel material for the feed-side flow channel material 2, while using a fine-meshed woven or knitted flow channel material for the permeate-side flow channel material 3.
  • the permeate side flow passage material 3 is provided so as to be interposed between opposing separation membranes 1 in the membrane leaf L. This permeate side flow passage material 3 is required to support the pressure applied to the membrane from the back side of the membrane and to ensure a flow passage for the permeate 8.
  • the permeate side flow passage material 3 is formed from a tricot knit, and it is even more preferable that the tricot knit is resin-impregnated and reinforced or fused after the knit is formed.
  • the spiral membrane element of the present invention is a composite semipermeable membrane comprising a porous support and a separation functional layer formed of a polyamide resin on the porous support, and the separation functional layer is characterized by having a composite semipermeable membrane with a surface roughness Ra1 of 90 to 150 nm when measured in an area of 5 ⁇ m x 5 ⁇ m in water with an atomic force microscope (AFM).
  • AFM atomic force microscope
  • the outer periphery of the wound body R is provided with an exterior material 15.
  • the exterior material 15 includes various sheets, films, tapes, etc., and fiber-reinforced resin (FRP) is used for reinforcement as necessary.
  • FRP fiber-reinforced resin
  • a preferred method for forming the fiber-reinforced resin is to use roving, in which fibers are impregnated with a curable resin, and wrap this around the outer periphery of the wound body R.
  • Composite semipermeable membranes may be called RO (reverse osmosis) membranes, NF (nanofiltration) membranes, partial desalting loose-type NF membranes, and selective separation-type NF membranes depending on the size of the solute to be separated, and the composite semipermeable membrane of the present invention can be applied to any type of separation membrane.
  • RO reverse osmosis
  • NF nanofiltration
  • partial desalting loose-type NF membranes partial desalting loose-type NF membranes
  • selective separation-type NF membranes depending on the size of the solute to be separated
  • composite semipermeable membranes that have blocking performance against organic compounds (e.g., molecular weight 150 to 250) such as herbicides and odorous components, and have good water permeability when removing these compounds, as composite semipermeable membranes used in the production of drinking water, and the composite semipermeable membrane of the present invention is particularly effective as a separation membrane for removing such organic compounds.
  • organic compounds e.g., molecular weight 150 to 250
  • the composite semipermeable membrane of the present invention is particularly effective as a separation membrane for removing such organic compounds.
  • It can be used for other purposes as well as for use as a spiral separation membrane element.
  • it is suitable for producing ultrapure water and desalinizing brine or seawater, and can also contribute to the closure of wastewater by removing and recovering pollution sources or active substances contained in contaminants that cause pollution, such as dye wastewater and electrochemical paint wastewater.
  • pollution sources or active substances contained in contaminants that cause pollution such as dye wastewater and electrochemical paint wastewater.
  • It can also be used for advanced treatments such as concentrating active ingredients in food applications and removing harmful ingredients in water purification and sewage applications.
  • It can also be used for wastewater treatment in oil fields and shale gas fields.
  • the surface roughness Ra defined by the above formula (Equation 1) was calculated using values measured using an atomic force microscope (AFM) (Hitachi High-Tech Science Corporation, AFM5300E).
  • the average surface roughness (Ra) is a three-dimensional extension of the center line average roughness Ra defined in JIS B0601 so that it can be applied to the measurement surface, and is the average value of the absolute value of the deviation from the reference surface to the specified surface.
  • the measurement surface refers to the surface shown by all the measurement data
  • the specified surface refers to a specific part of the measurement surface that is the target of roughness measurement and is specified by a clip (the specified area is 5 ⁇ m ⁇ 5 ⁇ m)
  • the AFM measurement in air was performed on three samples each, and the average value of the surface roughness Ra2 was obtained.
  • the surface shape was measured using an atomic force microscope (AFM) (Hitachi High-Tech Science Corporation, AFM5300E) in the same manner, except that instead of performing the AFM measurement in air as described above in (1), the AFM measurement was performed in water as follows.
  • AFM atomic force microscope
  • the sample was immersed in ultrapure water and placed in a holder for submerged measurements while still wet.
  • the holder was filled with ultrapure water and AFM measurements were performed.
  • AFM measurements in water were performed on three samples each, and the average surface roughness Ra1 was calculated.
  • Example 1 An aqueous amine solution containing 2.5 mass % m-phenylenediamine (MPD), 0.1 mass % sodium dodecyl sulfate, 2.6 mass % triethylamine, 1.7 mass % monoethanolamine as an interface modifier, 0.03 mass % sodium hydroxide, 6 mass % camphorsulfonic acid, 1.5 mass % magnesium nitrate and 4 mass % isopropyl alcohol was applied onto a polysulfone porous support formed on a polyester nonwoven fabric, and then the excess amine aqueous solution was removed to form an aqueous solution coating layer.
  • MPD m-phenylenediamine
  • 0.1 mass % sodium dodecyl sulfate 2.6 mass % triethylamine
  • 1.7 mass % monoethanolamine as an interface modifier
  • 0.03 mass % sodium hydroxide 6 mass % camphorsulfonic acid
  • 1.5 mass % magnesium nitrate 1.5 mass % magnesium
  • Example 2 A composite semipermeable membrane was produced under the same conditions as in Example 1, except that diethanolamine was used as the interface conditioner instead of monoethanolamine. The evaluation results are shown in Table 1.
  • Example 3 A composite semipermeable membrane was produced under the same conditions as in Example 1, except that the interfacial regulator in Example 1 was changed from monoethanolamine to triethanolamine. The evaluation results are shown in Table 1.
  • Example 4 A composite semipermeable membrane was prepared under the same conditions as in Example 1, except that the content of monoethanolamine as an interface conditioner was changed to 2.0% by mass. The evaluation results are shown in Table 1.
  • Example 1 A composite semipermeable membrane was produced under the same conditions as in Example 1, except that the monoethanolamine was not used as an interface conditioner and the amine aqueous solution was prepared so that the other components had the same concentrations. The evaluation results are shown in Table 1.
  • Example 1 where the surface roughness Ra1 was above a certain level, high water permeability was obtained while maintaining an atrazine rejection rate of 95.0% or more.
  • Example 2 where the surface roughness Ra1 measured in water was greater, resulted in higher water permeability compared to Comparative Example 1, where the surface roughness Ra2 measured in air was greater.
  • Comparative Example 1 which did not use an interfacial modifier, the surface roughness Ra1 was less than a certain value, and although the atrazine rejection rate was high, the water permeability was insufficient. Furthermore, in Comparative Examples 2 and 3, which used a commercially available product, the surface roughness Ra1 was small, and the atrazine rejection rate or water permeability was insufficient.
  • the present invention provides a composite semipermeable membrane and a spiral membrane element that can improve both the blocking performance for organic compounds and water permeability by controlling the microscopic surface area of the separation functional layer using a different index than conventional methods.
  • composite semipermeable membranes used in the production of drinking water that have the ability to block organic compounds (e.g., molecular weight 150 to 250) such as herbicides and odorous components, and that have good water permeability when removing these compounds.
  • organic compounds e.g., molecular weight 150 to 250
  • the composite semipermeable membrane of the present invention is particularly effective as a separation membrane for removing such organic compounds.
  • Separation membrane 1a Separation functional layer 1b: Porous support 5: Central tube A1: Axial direction R: Rolled body

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
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  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
PCT/JP2023/028734 2022-12-08 2023-08-07 複合半透膜、及びスパイラル型膜エレメント Ceased WO2024122107A1 (ja)

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EP23900235.5A EP4631607A4 (en) 2022-12-08 2023-08-07 SEMI-PERMEABLE COMPOSITE MEMBRANE AND SPIRAL-TYPE MEMBRANE ELEMENT
CN202380076327.4A CN120076861A (zh) 2022-12-08 2023-08-07 复合半透膜和螺旋型膜元件

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WO2026048470A1 (ja) * 2024-08-29 2026-03-05 日東電工株式会社 複合半透膜、及びスパイラル型膜エレメント

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WO2026048470A1 (ja) * 2024-08-29 2026-03-05 日東電工株式会社 複合半透膜、及びスパイラル型膜エレメント

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