WO2024070355A1 - 浸透気化膜 - Google Patents

浸透気化膜 Download PDF

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Publication number
WO2024070355A1
WO2024070355A1 PCT/JP2023/030397 JP2023030397W WO2024070355A1 WO 2024070355 A1 WO2024070355 A1 WO 2024070355A1 JP 2023030397 W JP2023030397 W JP 2023030397W WO 2024070355 A1 WO2024070355 A1 WO 2024070355A1
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WIPO (PCT)
Prior art keywords
group
functional layer
pervaporation membrane
porous support
separation functional
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/030397
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English (en)
French (fr)
Japanese (ja)
Inventor
威 矢野
武史 仲野
暁恵 池永
達也 鈴木
亜樹子 田中
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Nitto Denko Corp
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Nitto Denko Corp
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Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to US19/115,323 priority Critical patent/US20260022036A1/en
Priority to CN202380068351.3A priority patent/CN119947819A/zh
Priority to JP2024549882A priority patent/JPWO2024070355A1/ja
Priority to EP23871596.5A priority patent/EP4596090A1/en
Publication of WO2024070355A1 publication Critical patent/WO2024070355A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • 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
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/148—Organic/inorganic mixed matrix membranes
    • 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
    • B01D71/02—Inorganic material
    • B01D71/028—Molecular sieves
    • B01D71/0281—Zeolites
    • 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
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
    • 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
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
    • B01D71/4011—Polymethylmethacrylate
    • 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
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • 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
    • C02F1/448—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by pervaporation
    • 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
    • B01D2323/21—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/362—Pervaporation
    • 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
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C02F2101/322—Volatile compounds, e.g. benzene

Definitions

  • the present invention relates to a pervaporation membrane.
  • a method that utilizes microbial fermentation is known as a method for obtaining valuable non-petroleum-derived materials.
  • a method has been developed in which volatile organic compounds (fermented products) such as alcohol are produced by using microorganisms to ferment a carbon source such as glucose.
  • the fermentation of the carbon source is carried out, for example, in an aqueous solution.
  • the microbial fermentation may stop.
  • it is necessary to separate the fermented product from the aqueous solution.
  • Patent Document 1 discloses an example of a pervaporation membrane used in the pervaporation method.
  • the present invention relates to A separation functional layer; A porous support that supports the separation functional layer; Equipped with The porous support has a surface A1 facing the separation functional layer and including a plurality of openings H1; The average diameter L1 of the plurality of openings H1 is 0.5 ⁇ m or more, A pervaporation membrane is provided having a peel strength of 0.15 N/20 mm or greater as measured by the following test. Test: The pervaporation membrane is cut into a test piece having a width of 20 mm and a length of 150 mm. The test piece is used to peel the separating functional layer from the porous support at a peel angle of 180° and a pulling speed of 300 mm/min.
  • the present invention provides A separation functional layer; A porous support that is in direct contact with the separation functional layer and supports the separation functional layer; Equipped with A pervaporation membrane is provided, wherein the porous support is a fibrous structure.
  • the present invention provides a new pervaporation membrane suitable for separating volatile organic compounds from an aqueous solution containing the organic compounds.
  • FIG. 1 is a cross-sectional view showing a schematic diagram of a pervaporation membrane according to one embodiment of the present invention.
  • 1A to 1C are diagrams for explaining a method for manufacturing a pervaporation membrane.
  • 1A to 1C are diagrams for explaining a method for manufacturing a pervaporation membrane.
  • FIG. 1 is a schematic cross-sectional view of a membrane separation device equipped with a pervaporation membrane.
  • FIG. 11 is a perspective view showing a schematic diagram of a modified example of a membrane separation device.
  • FIG. 1 is a schematic diagram showing an example of a membrane separation system.
  • the pervaporation membrane according to the first aspect of the present invention comprises: A separation functional layer; A porous support that supports the separation functional layer; Equipped with The porous support has a surface A1 facing the separation functional layer and including a plurality of openings H1; The average diameter L1 of the plurality of openings H1 is 0.5 ⁇ m or more, The peel strength measured by the following test is 0.15 N/20 mm or more. Test: The pervaporation membrane is cut into a test piece having a width of 20 mm and a length of 150 mm. The test piece is used to peel the separating functional layer from the porous support at a peel angle of 180° and a pulling speed of 300 mm/min.
  • the porous support has a surface A2 that faces the surface A1 and includes a plurality of openings H2, and the average diameter L2 of the plurality of openings H2 is 0.5 ⁇ m or more.
  • the porous support is a fiber structure.
  • the pervaporation membrane according to the fourth aspect of the present invention comprises: A separation functional layer; A porous support that is in direct contact with the separation functional layer and supports the separation functional layer; Equipped with The porous support is a fibrous structure.
  • the fiber structure is a nonwoven fabric or a stretched porous membrane containing fibrils.
  • the air permeability in the thickness direction of the porous support is 50 seconds/100 mL or less, expressed as air permeability determined in accordance with the air permeability measurement method B (Gurley method) specified in JIS L1096:2010.
  • the separation functional layer contains a silicone resin.
  • the porous support has a surface A1 that faces the separation functional layer and is treated with a molecular bonding agent, and the molecular bonding agent includes a compound having a reactive group F1 that can react with the surface A1 and a reactive group F2 that can react with the silicone resin contained in the separation functional layer.
  • the separation functional layer contains a (meth)acrylic resin.
  • the separation functional layer includes a filler.
  • the filler includes at least one selected from the group consisting of zeolite and silica.
  • a pervaporation membrane according to any one of the first to eleventh aspects is used to separate volatile organic compounds from an aqueous solution containing the organic compounds.
  • the organic compound is a fermentation product produced by a microorganism.
  • the pervaporation membrane 10 of this embodiment includes a separation functional layer 1 and a porous support 5 that supports the separation functional layer 1.
  • the separation functional layer 1 has, for example, a surface 1a that is in direct contact with the porous support 5 and a surface that is exposed to the outside of the pervaporation membrane 10.
  • the pervaporation membrane 10 is, for example, composed only of the separation functional layer 1 and the porous support 5.
  • the pervaporation membrane 10 is typically a membrane (separation membrane) that preferentially allows the organic compound C to permeate from an aqueous solution S containing a volatile organic compound C.
  • the porous support 5 has surfaces A1 and A2 facing each other.
  • Surface A1 faces the separation functional layer 1, and more specifically faces the separation functional layer 1 side.
  • Surface A1 for example, is in direct contact with the separation functional layer 1.
  • Surface A1 includes a plurality of openings H1.
  • the openings H1 are, for example, connected to holes included in the porous support 5.
  • the openings H1 are typically gaps between fibers on surface A1.
  • the average diameter L1 of the multiple openings H1 is 0.5 ⁇ m or more, and may be preferably 1 ⁇ m or more, 2 ⁇ m or more, 5 ⁇ m or more, 8 ⁇ m or more, 10 ⁇ m or more, 13 ⁇ m or more, or even 15 ⁇ m or more.
  • the upper limit of the average diameter L1 is not particularly limited, and may be, for example, 10 mm or less, 1 mm or less, 100 ⁇ m or less, or even 50 ⁇ m or less.
  • the average diameter L1 can be determined by the following method. First, the surface A1 of the porous support 5 is observed using a scanning electron microscope (SEM). The observation of the surface A1 is performed, for example, on the porous support 5 removed from the pervaporation membrane 10. Note that the observation of the surface A1 may also be performed on the porous support 5 before it is used to fabricate the pervaporation membrane 10.
  • SEM scanning electron microscope
  • the magnification and observation range of the SEM when observing the surface A1 can be appropriately adjusted depending on the size of the opening H1.
  • Examples of the magnification of the SEM are 50 times, 5000 times, 20000 times, etc.
  • the magnification of the SEM is adjusted to about 50 times, and the opening H1 is specified within a range larger than 2.0 mm vertical x 2.5 mm horizontal in the obtained SEM image.
  • the magnification of the SEM is adjusted to about 20000 times, and the opening H1 is specified within a range larger than 4.8 ⁇ m vertical x 6.0 ⁇ m horizontal in the obtained SEM image.
  • the opening H1 is specified by converting the SEM image into a binary image of the opening H1 and the other parts (non-openings) other than the opening H1 using software (e.g., Image J).
  • software e.g., Image J
  • the area (opening area h) is calculated by image processing.
  • the diameter of a circle having the same area as the calculated area is regarded as the diameter d of the opening H1.
  • the aperture ratio R1 of the surface A1 is not particularly limited, and may be, for example, 70% or less, 50% or less, or even 30% or less.
  • the aperture ratio R1 may be 1 to 30%.
  • the aperture ratio R1 can be measured by the following method. First, the surface 5a of the porous support 5 is observed with an SEM by the method described above for the average diameter L1, and the openings H1 are identified. The ratio of the total area of the openings H1 in the SEM image can be regarded as the aperture ratio R1.
  • surface A2 of the porous support 5 includes, for example, a plurality of openings H2.
  • the openings H2 are, for example, connected to holes contained in the porous support 5.
  • the openings H2 are typically gaps between the fibers in surface A2.
  • the average diameter L2 of the multiple openings H2 is 0.5 ⁇ m or more, and may be preferably 1 ⁇ m or more, 2 ⁇ m or more, 5 ⁇ m or more, 8 ⁇ m or more, 10 ⁇ m or more, 13 ⁇ m or more, or even 15 ⁇ m or more.
  • the upper limit of the average diameter L2 is not particularly limited, and may be, for example, 10 mm or less, 1 mm or less, 100 ⁇ m or less, or even 50 ⁇ m or less.
  • the average diameter L2 can be determined by the method described above for the average diameter L1.
  • the average diameter L2 may be approximately the same as the average diameter L1 described above, or may be greater than the average diameter L1.
  • the ratio L2/L1 of the average diameter L2 ( ⁇ m) to the average diameter L1 ( ⁇ m) is, for example, 0.3 to 30.
  • the ratio L2/L1 may be, for example, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, 5 or less, or even 3 or less.
  • the ratio L2/L1 may be, for example, 0.3 or more, 0.5 or more, or even 0.8 or more.
  • the aperture ratio R2 of the surface A2 is not particularly limited, and may be, for example, 70% or less, 50% or less, or even 30% or less.
  • the aperture ratio R2 may be 1 to 30%.
  • the aperture ratio R2 can be measured by the method described above for the aperture ratio R1.
  • the aperture ratio R2 of the surface A2 may be approximately the same as the aperture ratio R1, or may be higher than the aperture ratio R1.
  • of the difference between the aperture ratio R2 (%) and the aperture ratio R1 (%) may be, for example, 30% or less, 20% or less, 10% or less, or even 5% or less.
  • the pervaporative membrane 10 of this embodiment has a peel strength of 0.15 N/20 mm or more as measured by the following test.
  • Test A test piece of 20 mm width x 150 mm length is cut from the pervaporation membrane 10. Using the test piece, the separating functional layer 1 is peeled off from the porous support 5 at a peel angle of 180° and a pulling speed of 300 mm/min.
  • the pervaporation membrane 10 to be evaluated is cut into a width of 20 mm x length of 150 mm to prepare a test piece.
  • the entire surface of the porous support 5 of the test piece is superimposed on an acrylic test plate via a double-sided tape (e.g., No. 5000NS, manufactured by Nitto Denko Corporation), and a 2 kg roller is moved back and forth once to press them together.
  • the acrylic test plate has a size of, for example, a width of 150 mm x length of 150 mm.
  • the separation function layer 1 is peeled off by hand from the porous support 5 by 90 mm in the direction from one end of the test piece to the other end.
  • the peeled separation function layer 1 and the vicinity of one end of the test piece are gripped with a chuck, and the remaining separation function layer 1 is peeled off from the porous support 5 at a peel angle of 180° and a tensile speed of 300 mm/min.
  • the average peel force at this time is specified as the peel strength.
  • the initial chuck distance in the tensile testing machine is 150 mm. The test is performed in an atmosphere of 25°C.
  • the separation functional layer 1 is soft and difficult to hold directly with a zipper
  • the following method using an evaluation sheet may be performed.
  • the pervaporation membrane 10 to be evaluated is cut to a width of 20 mm x length of 150 mm to prepare a test piece.
  • the entire surface of the separation functional layer 1 provided in the test piece is superimposed on the evaluation sheet, and a 2 kg roller is moved back and forth once to press them together.
  • the entire surface of the porous support 5 provided in the test piece is superimposed on an acrylic test plate via a double-sided tape (for example, No. 5000NS, manufactured by Nitto Denko Corporation), and a 2 kg roller is moved back and forth once to press them together.
  • a double-sided tape for example, No. 5000NS, manufactured by Nitto Denko Corporation
  • the separation functional layer 1 is peeled off from the porous support 5 by the same method as described above, except that the evaluation sheet is held with a zipper instead of the separation functional layer 1.
  • the average value of the peeling force at this time can be specified as the peel strength.
  • the evaluation sheet is not particularly limited as long as it does not peel off from the separation functional layer 1 during the test.
  • a film made of polyethylene terephthalate (PET) can be used as the evaluation sheet.
  • the above peel strength is preferably 0.2 N/20 mm or more, and may be 0.3 N/20 mm or more, 0.4 N/20 mm or more, 0.5 N/20 mm or more, 0.6 N/20 mm or more, 0.7 N/20 mm or more, 0.8 N/20 mm or more, 0.9 N/20 mm or more, or even 1.0 N/20 mm or more.
  • the upper limit of the peel strength is not particularly limited, and may be, for example, 20 N/20 mm or 10 N/20 mm.
  • the separation functional layer 1 is sufficiently fixed to the porous support 5 that it cannot be peeled off by hand from the porous support 5, and if an attempt is made to peel it off forcefully, the separation functional layer 1 may break.
  • This phenomenon is presumed to be caused by the above peel strength (N/20 mm) being greater than the breaking strength (N/20 mm) of the separation functional layer 1. Therefore, in this case, the breaking strength of the separation functional layer 1 is separately specified, and the above peel strength can be considered to be equal to or greater than the breaking strength (i.e., peel strength (N/20 mm) ⁇ breaking strength (N/20 mm)).
  • the breaking strength of the separation functional layer 1 can be determined by the following method. First, a layer having the same composition and thickness as the separation functional layer 1 of the pervaporation membrane 10 is prepared on a release liner, and the release liner is removed to prepare a free-standing membrane of the separation functional layer 1. Next, the free-standing membrane of the separation functional layer 1 is cut into a width of 20 mm and a length of 60 mm to prepare a test piece. The test piece is set in a commercially available tensile tester, and a tensile test is performed under the following measurement conditions. Measurement conditions Temperature: 25°C Tensile direction: longitudinal direction of test piece Initial chuck distance: 20 mm Tensile speed: 300 mm/min
  • Breaking strength (N/20 mm) Strength B (N/mm 2 ) ⁇ thickness (mm) ⁇ 20 ⁇ (1/20)
  • the separation functional layer 1 is, for example, a layer that allows the organic compound C to preferentially permeate from the above-mentioned aqueous solution S, and is typically a dense layer (non-porous layer) in which no pores can be identified when observed at a magnification of 5000 times using a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the separation functional layer 1 contains a silicone resin.
  • the silicone resin is formed, for example, from a silicone resin composition.
  • the silicone resin may be formed from a condensation type silicone resin composition, but is preferably formed from an addition type silicone resin composition.
  • the silicone resin may be formed from a UV-curable silicone resin composition.
  • An addition type silicone resin composition can be cured using almost no metal species (especially tin) that can promote hydrolysis of the silicone resin. Therefore, the separation functional layer 1 containing the silicone resin formed from the addition type silicone resin composition contains almost no metal species that can promote hydrolysis of the silicone resin, and tends to have high durability against the above-mentioned aqueous solution S.
  • the addition type silicone resin composition is a type of silicone resin composition that cures by addition reaction.
  • the addition type silicone resin composition contains, for example, polyorganosiloxane P1 having an alkenyl group and polyorganosiloxane P2 having a hydrosilyl (SiH) group.
  • the addition type silicone resin composition preferably further contains a curing catalyst (hydrosilylation catalyst).
  • the addition type silicone resin composition may be a commercially available silicone resin composition to which a curing catalyst has been added. However, the addition type silicone resin composition may not contain a curing catalyst.
  • a reaction between the alkenyl group of polyorganosiloxane P1 and the hydrosilyl group of polyorganosiloxane P2 can proceed by heat treatment to form a silicone resin.
  • polyorganosiloxane P2 functions as a crosslinking agent.
  • alkenyl group in polyorganosiloxane P1 examples include vinyl groups and hexenyl groups.
  • the number of alkenyl groups in polyorganosiloxane P1 is, for example, 2 or more.
  • the alkenyl groups are located, for example, at the terminals of polyorganosiloxane P1.
  • Polyorganosiloxane P1 is, for example, a polyalkylalkylsiloxane such as polydimethylsiloxane, polydiethylsiloxane, or polymethylethylsiloxane; a polyalkylarylsiloxane; or a polyorganosiloxane such as poly(dimethylsiloxane-diethylsiloxane) to which an alkenyl group has been introduced.
  • a polyalkylalkylsiloxane such as polydimethylsiloxane, polydiethylsiloxane, or polymethylethylsiloxane
  • a polyalkylarylsiloxane such as poly(dimethylsiloxane-diethylsiloxane) to which an alkenyl group has been introduced.
  • the weight average molecular weight of polyorganosiloxane P1 is, for example, 1,000 or more, and may be 10,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or even 400,000 or more.
  • the upper limit of the weight average molecular weight of polyorganosiloxane P1 is not particularly limited, and is, for example, 1,000,000.
  • the number of hydrosilyl groups in polyorganosiloxane P2 is, for example, 2 or more.
  • the hydrosilyl groups may be located at the terminals of polyorganosiloxane P2 or may be included in the main chain of polyorganosiloxane P2.
  • polyorganosiloxane P2 examples include polymethylhydrogensiloxane, poly(dimethylsiloxane-methylhydrogensiloxane), and hydrosilyl-terminated polydimethylsiloxane.
  • the weight average molecular weight of polyorganosiloxane P2 is, for example, 100 or more, and may be 10,000 or more. The larger the weight average molecular weight of polyorganosiloxane P2, the higher the separation characteristics of pervaporation membrane 10 tend to be.
  • the upper limit of the weight average molecular weight of polyorganosiloxane P2 is not particularly limited, and is, for example, 1 million.
  • the weight ratio P2/P1 of polyorganosiloxane P2 to polyorganosiloxane P1 is, for example, 500 wt% or less, and may be 100 wt% or less, 50 wt% or less, 20 wt% or less, 10 wt% or less, or even 5 wt% or less.
  • the lower limit of the weight ratio P2/P1 is, for example, 0.01 wt% or more.
  • the curing catalyst examples include platinum-based catalysts.
  • the addition type silicone resin composition may contain a curing catalyst having platinum.
  • platinum-based catalysts include chloroplatinic acid, platinum olefin complexes, and chloroplatinic acid olefin complexes.
  • the addition type silicone resin composition may not contain a curing catalyst.
  • the addition type silicone resin composition may contain a compound that generates catalytically active species that catalyze the addition reaction when irradiated with active energy rays such as ultraviolet (UV) rays.
  • active energy rays such as ultraviolet (UV) rays.
  • UV ultraviolet
  • the addition type silicone resin composition may further contain an organic solvent in addition to the above-mentioned components.
  • organic solvents include hydrocarbon solvents such as cyclohexane, n-hexane, and n-heptane; aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and methyl acetate; ketone solvents such as acetone and methyl ethyl ketone; and alcohol solvents such as methanol, ethanol, and butanol.
  • the organic solvent may be used alone or in combination of two or more.
  • the addition type silicone resin composition may be a solvent-free type that does not substantially contain any solvent such as an organic solvent.
  • the condensation type silicone resin composition is a type of silicone resin composition that cures by a condensation reaction.
  • the condensation type silicone resin composition includes, for example, a polyorganosiloxane P3 having a silanol (SiOH) group and a silane compound P4 having a functional group such as an alkoxy group, an alkenyloxy group, an acyloxy group, an amino group, a ketoxime group, or an amide group.
  • the condensation type silicone resin composition may or may not further contain a curing catalyst.
  • the condensation type silicone resin composition may be a commercially available silicone resin composition to which a curing catalyst has been added.
  • condensation type silicone resin composition for example, a reaction (condensation reaction) between the silanol groups of the polyorganosiloxane P3 and the above-mentioned functional groups of the silane compound P4 proceeds by heat treatment, and a silicone resin can be formed.
  • the silane compound P4 functions as a crosslinking agent.
  • the number of silanol groups in polyorganosiloxane P3 is, for example, 2 or more.
  • the silanol groups are located, for example, at the terminals of polyorganosiloxane P3.
  • Polyorganosiloxane P3 may have alkyl groups such as methyl groups and ethyl groups, or phenyl groups introduced as side chain substituents.
  • Polyorganosiloxane P3 is, for example, the polyorganosiloxane described above for polyorganosiloxane P1 to which silanol groups have been introduced.
  • the weight average molecular weight of polyorganosiloxane P3 is, for example, 1,000 or more, and may be 10,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or even 400,000 or more.
  • the upper limit of the weight average molecular weight of polyorganosiloxane P3 is not particularly limited, and is, for example, 1,000,000.
  • the silane compound P4 has functional groups such as an alkoxy group, an alkenyloxy group, an acyloxy group, an amino group, a ketoxime group, and an amide group.
  • the alkoxy group include a methoxy group and an ethoxy group.
  • the alkenyloxy group include an isopropenyloxy group.
  • the acyloxy group include an acetoxy group.
  • the amino group include a dimethylamino group, a diethylamino group, and an ethylmethylamino group.
  • the ketoxime group include an acetoxime group and a methylethylketoxime group.
  • amide group examples include an acetamide group, an N-methylacetamide group, and an N-ethylacetamide group.
  • the number of functional groups in the silane compound P4 is, for example, 2 or more. In particular, it is preferable that the silane compound P4 contains an alkoxysilyl group as the alkoxy group.
  • the silane compound P4 may be a low molecular weight compound having a molecular weight of about 1000 or less, or a high molecular weight compound having a polysiloxane skeleton.
  • the curing catalyst examples include tin-based catalysts.
  • the tin-based catalyst examples include organotin catalysts such as dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctate.
  • the condensation type silicone resin composition may further contain an organic solvent in addition to the above-mentioned components.
  • the organic solvent include those described above for the addition type silicone resin composition.
  • the condensation type silicone resin composition may be a solventless type that does not contain a solvent such as an organic solvent.
  • the UV-curable silicone resin composition is a type of silicone resin composition that cures by ultraviolet (UV) irradiation.
  • the curing reaction proceeds by, for example, radical polymerization, radical addition, ionic polymerization, etc.
  • the UV-curable silicone resin composition in which the curing reaction proceeds by radical polymerization includes, for example, polyorganosiloxane P5 having a double bond (specifically, a carbon-carbon double bond) derived from an alkenyl group or an acryloyl group.
  • the UV-curable silicone resin composition in which the curing reaction proceeds by radical addition includes, for example, polyorganosiloxane P5 having a double bond (specifically, a carbon-carbon double bond) derived from an alkenyl group or an acryloyl group, etc., and compound P6 having a functional group capable of radical addition such as a thiol group.
  • the UV-curable silicone resin composition in which the curing reaction proceeds by ionic polymerization includes, for example, polyorganosiloxane P7 having a functional group capable of ionic polymerization such as an epoxy group, and a compound that generates a catalytically active species that catalyzes ionic polymerization by UV irradiation.
  • UV irradiation causes a radical polymerization reaction between double bonds contained in the alkenyl groups and acryloyl groups of polyorganosiloxane P5, thereby forming a silicone resin.
  • alkenyl group in polyorganosiloxane P5 examples include vinyl and hexenyl groups.
  • the number of alkenyl groups in polyorganosiloxane P5 is, for example, 2 or more.
  • the alkenyl groups are located, for example, at the ends of polyorganosiloxane P5.
  • Polyorganosiloxane P5 may have alkyl groups such as methyl and ethyl groups, or phenyl groups introduced as side chain substituents.
  • Polyorganosiloxane P5 is, for example, a polyorganosiloxane in which a substituent having a double bond, such as an alkenyl group or an acryloyl group, has been introduced into the polyorganosiloxane described above for polyorganosiloxane P1.
  • a substituent having a double bond such as an alkenyl group or an acryloyl group
  • the weight average molecular weight of polyorganosiloxane P5 is, for example, 1,000 or more, and may be 10,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or even 400,000 or more.
  • the upper limit of the weight average molecular weight of polyorganosiloxane P5 is not particularly limited, and is, for example, 1,000,000.
  • a functional group capable of radical addition contained in compound P6 undergoes radical addition to a double bond contained in an alkenyl group or acryloyl group of polyorganosiloxane P5. This causes a radical addition reaction to proceed, forming a silicone resin.
  • the functional groups capable of radical addition are, for example, thiol groups and alkylthiol groups.
  • alkylthiol groups include mercaptomethyl groups and mercaptoethyl groups.
  • the number of functional groups capable of radical addition in compound P6 is, for example, 2 or more.
  • Compound P6 may be a polyorganosiloxane containing a functional group capable of radical addition.
  • the functional group is, for example, located at the end of the polyorganosiloxane.
  • the polyorganosiloxane may have alkyl groups, such as methyl groups or ethyl groups, or phenyl groups, introduced as side chain substituents.
  • Compound P6 is, for example, the polyorganosiloxane P1 described above to which a functional group capable of radical addition, such as a thiol group, has been introduced.
  • the weight-average molecular weight of compound P6 is, for example, 1,000 or more, and may be 10,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or even 400,000 or more.
  • the upper limit of the weight-average molecular weight of compound P6 is not particularly limited, and is, for example, 1,000,000.
  • a UV-curable silicone resin composition in which the curing reaction proceeds through ionic polymerization, for example, catalytically active species that catalyze ionic polymerization are generated by UV irradiation, and an ionic polymerization reaction proceeds between functional groups capable of ionic polymerization contained in polyorganosiloxane P7. This allows the formation of a silicone resin.
  • the functional group capable of ionically polymerizing is, for example, an epoxy group.
  • substituents containing an epoxy group include the epoxy group itself, a glycidyl group, and a glycidyloxypropyl group.
  • the number of functional groups capable of ionically polymerizing in polyorganosiloxane P7 is, for example, 2 or more.
  • the functional group capable of ionically polymerizing is, for example, located at the end of polyorganosiloxane P7.
  • Polyorganosiloxane P7 may have alkyl groups such as methyl groups and ethyl groups, or phenyl groups introduced as substituents in the side chains.
  • Polyorganosiloxane P7 is, for example, the polyorganosiloxane described above for polyorganosiloxane P1 to which functional groups capable of ionic polymerization, such as epoxy groups, have been introduced.
  • the weight average molecular weight of polyorganosiloxane P7 is, for example, 1,000 or more, and may be 10,000 or more, 100,000 or more, 200,000 or more, 300,000 or more, or even 400,000 or more.
  • the upper limit of the weight average molecular weight of polyorganosiloxane P7 is not particularly limited, and is, for example, 1,000,000.
  • the UV-curable silicone resin composition may further contain an organic solvent in addition to the above-mentioned components.
  • organic solvent include hydrocarbon solvents such as cyclohexane, n-hexane, and n-heptane; aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and methyl acetate; ketone solvents such as acetone and methyl ethyl ketone; and alcohol solvents such as methanol, ethanol, and butanol.
  • the organic solvent may be used alone or in combination of two or more.
  • the UV-curable silicone resin composition may be a solvent-free type that does not substantially contain any solvent such as an organic solvent.
  • the separation functional layer 1 may contain silicone resin as a main component, or may be composed essentially of silicone resin alone. "Main component” refers to the component that is contained in the largest amount by weight in the separation functional layer 1.
  • the separation functional layer 1 contains a (meth)acrylic resin.
  • the (meth)acrylic resin is formed, for example, from a monomer group containing a (meth)acrylic monomer and/or a (meth)acrylic resin composition containing a (meth)acrylic polymer.
  • the (meth)acrylic resin composition may be of a UV-curable type or a heat-curable type.
  • the (meth)acrylic monomers included in the monomer group include, for example, alkyl (meth)acrylates.
  • (meth)acrylate means acrylate and/or methacrylate.
  • the alkyl group contained in the alkyl (meth)acrylate is not particularly limited, and may be, for example, a linear, branched, or cyclic alkyl group having 2 to 14 carbon atoms.
  • alkyl (meth)acrylates include alkyl acrylate esters having an alkyl group with 2 to 14 carbon atoms, preferably alkyl acrylate esters having an alkyl group with 4 to 9 carbon atoms.
  • alkyl acrylate esters include n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, nonyl acrylate, and isononyl acrylate.
  • the alkyl (meth)acrylate may be, for example, a methacrylic acid alkyl ester having an alkyl group with 2 to 14 carbon atoms, preferably an alkyl methacrylic acid ester having an alkyl group with 2 to 10 carbon atoms.
  • methacrylic acid alkyl ester examples include ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, bornyl methacrylate, and isobornyl methacrylate.
  • alkyl (meth)acrylates mentioned above can be used alone or in combination of two or more.
  • the content of alkyl (meth)acrylate in the monomer group is not particularly limited, and is, for example, 70 to 100 wt%, preferably 85 to 99 wt%, and more preferably 87 to 99 wt%.
  • the monomer group may further include a copolymerizable monomer that is copolymerizable with the alkyl (meth)acrylate.
  • the copolymerizable monomer include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; alkyl (meth)acrylates having an alkyl group of 1 or 15 or more carbon atoms; (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; vinyl esters such as vinyl acetate and vinyl propionate; styrene-based monomers such as styrene; epoxy group-containing monomers such as glycidyl (meth)acrylate and methyl glycidyl (meth)acrylate; hydroxyl group-containing (meth)acrylates such as 2-hydroxye
  • nitrogen atom-containing monomers such as N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, (meth)acryloylmorpholine, aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and t-butylaminoethyl (meth)acrylate; alkoxy group-containing monomers such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; functional monomers such as 2-methacryloyloxyethyl isocyanate; olefin-based monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; vinyl ether-based monomers such as vinyl ether; halogen atom-containing mono
  • the (meth)acrylic polymer may be a polymer of the above monomer group.
  • the (meth)acrylic polymer preferably has a structural unit derived from an alkyl (meth)acrylate as a main component.
  • Examples of the alkyl (meth)acrylate include those mentioned above.
  • the content of the structural unit derived from an alkyl (meth)acrylate in the (meth)acrylic polymer is not particularly limited, and is, for example, 70 to 100 wt%, preferably 85 to 99 wt%, and more preferably 87 to 99 wt%.
  • the (meth)acrylic polymer may further contain a structural unit derived from a copolymerizable monomer copolymerizable with the alkyl (meth)acrylate.
  • Examples of the copolymerizable monomer include those described above.
  • the (meth)acrylic resin composition may further contain additives and organic solvents in addition to the monomer group and (meth)acrylic polymer.
  • additives include a polymerization initiator, a crosslinking agent, and a filler described below.
  • organic solvents include those described above for the silicone resin composition.
  • the (meth)acrylic resin composition may be a solvent-free type that does not substantially contain a solvent such as an organic solvent.
  • the resin composition preferably contains a photopolymerization initiator as an additive.
  • photopolymerization initiators include benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; substituted benzoin ethers such as anisole methyl ether; substituted acetophenones such as 2,2-diethoxyacetophenone and 2,2-dimethoxy-2-phenylacetophenone; ⁇ -hydroxyalkylphenones such as 1-hydroxycyclohexyl-phenyl ketone; substituted alpha-ketol such as 2-methyl-2-hydroxypropiophenone; aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride; and photoactive compounds such as 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.
  • benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether, and benzil dimethyl ketal
  • oximes such as benzophenone compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s -triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)
  • the (meth)acrylic resin composition may contain one or more photopolymerization initiators.
  • the amount of the photopolymerization initiator in the (meth)acrylic resin composition is, for example, 0.02 to 10 parts by weight, or may be 0.05 to 5 parts by weight, per 100 parts by weight of the monomer group.
  • the resin composition preferably contains a crosslinking agent as an additive.
  • a crosslinking agent is a polyfunctional monomer having two or more polymerizable functional groups in one molecule.
  • polyfunctional monomers include (mono- or poly-)alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylate; esters of (meth)acrylic acid and polyhydric alcohols such as neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; and polyfunctional vinyl compounds such as divinylbenzene.
  • the amount of the crosslinking agent in the (meth)acrylic resin composition is, for example, 5 parts by weight or less, and may be 3 parts by weight or less, 2 parts by weight or less, 1 part by weight or less, or even 0.5 parts by weight or less, based on 100 parts by weight of the monomer group.
  • the lower limit of the amount is, for example, 0.01 parts by weight or more, and may be 0.05 parts by weight or more.
  • the separation functional layer 1 may contain (meth)acrylic resin as a main component, or may be substantially composed of only (meth)acrylic resin.
  • the separation functional layer 1 may have a matrix containing a resin (silicone resin or (meth)acrylic resin) and a filler dispersed in the matrix. In this embodiment, all or part of the filler is embedded in the matrix in the separation functional layer 1. All of the fillers may be separated from one another in the matrix, or may be partially aggregated.
  • a resin silicone resin or (meth)acrylic resin
  • the filler includes inorganic materials such as zeolite, silica, and bentonite.
  • the filler includes at least one selected from the group consisting of zeolite and silica, and preferably includes silica.
  • Fillers containing silica tend to have better hydrolysis resistance than fillers containing zeolite.
  • fillers containing silica tend to increase the free volume of the resin (particularly silicone resin) contained in the matrix. When the free volume of the resin increases, the separation characteristics of the pervaporation membrane 10, particularly the separation coefficient ⁇ of BuOH relative to water, tend to improve.
  • the filler allows the viscosity of the resin composition (particularly the (meth)acrylic resin composition) to be appropriately adjusted, which tends to make it easier to prepare a resin composition suitable for coating.
  • Silica usually means silicon dioxide.
  • the filler may be a silica filler containing silicon dioxide as a main component.
  • the silica filler does not have a crystalline structure, for example.
  • the silica filler can be produced, for example, by reacting metal silicon with oxygen.
  • the silica filler can also be produced by the sol-gel method, the precipitation method, the aqueous solution wet method, etc.
  • the filler may be substantially composed of silicon dioxide only.
  • the filler may contain zeolite.
  • zeolites contained in the filler include high-silica zeolites with a high ratio of silica to alumina, and silicalites that do not contain alumina.
  • fillers that contain high-silica zeolites include HSZ (registered trademark) manufactured by Tosoh Corporation, HiSiv (registered trademark) manufactured by Union Showa Corporation, USKY manufactured by Union Showa Corporation, and Zeoal (registered trademark) manufactured by Nakamura Choukou Co., Ltd.
  • the filler particularly the silica filler, does not have micropores with a diameter of, for example, 2 nm or less.
  • the filler may have mesopores with a diameter of 2 nm to 50 nm and macropores with a diameter of 50 nm or more.
  • the filler particularly the silica filler, preferably has a surface modified with a modifying group that includes a hydrocarbon group.
  • the filler is preferably surface-modified with a modifying group.
  • Surface-modified fillers have high dispersibility in resins and are suitable for suppressing the occurrence of cracks during the preparation of the separation functional layer 1, etc.
  • the number of carbon atoms in the hydrocarbon group contained in the modifying group is not particularly limited, and may be, for example, 1 to 25.
  • the number of carbon atoms in the hydrocarbon group may be 5 or less.
  • the hydrocarbon group may be linear, branched, or cyclic. Examples of the hydrocarbon group include alkyl groups such as methyl and ethyl groups.
  • the modifying group may further contain a silicon atom, and a hydrocarbon group may be bonded to the silicon atom.
  • the modifying group may contain at least one selected from the group consisting of an organosilyl group and a polyorganosiloxane group.
  • organosilyl group include triorganosilyl groups such as a trimethylsilyl group; and diorganosilyl groups such as a dimethylsilyl group.
  • the polyorganosiloxane group include a dimethylpolysiloxane group.
  • Surface modification with a modifying group can be carried out, for example, by reacting the hydroxyl groups present on the surface of the filler with a known silane coupling agent.
  • surface-modified silica fillers include the product names "AEROSIL (registered trademark) RX series” (RX50, RX200, RX300, etc.), “AEROSIL (registered trademark) RY series” (RY50, RY200, RY200S, etc.), “AEROSIL (registered trademark) NY series” (NY50, NY50L, etc.), “AEROSIL (registered trademark) NAX series” (NAX50, etc.), and “AEROSIL (registered trademark) R series” (R972, R974, R976, etc.), all manufactured by Nippon Aerosil Co., Ltd.
  • the filler is sufficiently surface-modified with a modifying group.
  • the number of hydroxyl groups present on the surface of the filler is small.
  • Whether the filler is sufficiently surface-modified with a modifying group can be determined, for example, from the pH of the filler dispersion or the Hansen solubility parameter (HSP value) of the filler.
  • the Hansen solubility parameter is a solubility parameter introduced by Hildebrand divided into three components: a dispersion term ⁇ D, a polarization term ⁇ P, and a hydrogen bond term ⁇ H. Details of the Hansen solubility parameter are disclosed in "Hansen Solubility Parameters; A Users Handbook (CRC Press, 2007)" and the like.
  • the pH of the filler dispersion measured by the following test is, for example, 4.0 to 9.0, and may be 6.0 to 8.0.
  • the pH of the dispersion is preferably neutral (about pH 7.0).
  • the pH of the dispersion is neutral, it can be said that the filler is sufficiently surface-modified with the modifying group, and the number of hydroxyl groups present on the surface is small.
  • the shape of the filler is, for example, particulate.
  • "particulate” includes spherical, ellipsoidal, scaly, and fibrous.
  • the filler may be powdered.
  • the average particle size of the filler is not particularly limited, and may be, for example, 50 ⁇ m or less, 20 ⁇ m or less, 10 ⁇ m or less, 1 ⁇ m or less, 500 nm or less, 100 nm or less, 50 nm or less, 30 nm or less, or even 20 nm or less.
  • a separation functional layer 1 containing a filler with a small average particle size tends to disperse stress applied to the separation functional layer 1 and has a high tendency to have high adhesion to the porous support 5.
  • a filler may actually reduce the adhesion between the separation functional layer 1 and the porous support 5.
  • the lower limit of the average particle size of the filler is not particularly limited and may be, for example, 1 nm or 5 nm.
  • the average particle size of the filler can be determined, for example, by the following method. First, a cross section of the separation functional layer 1 is observed with a transmission electron microscope. In the obtained electron microscope image, the area of a specific filler is calculated by image processing. The diameter of a circle having the same area as the calculated area is regarded as the particle size (particle diameter) of that specific filler. The particle size of an arbitrary number of fillers (at least 50) is calculated, and the average of the calculated values is regarded as the average particle size of the filler.
  • the filler content in the separation functional layer 1 is, for example, 1 wt% or more, and may be 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, or even 40 wt% or more.
  • the upper limit of the filler content in the separation functional layer 1 is not particularly limited, and may be, for example, 70 wt% or less, and may be less than 50 wt%. When the filler content is less than 50 wt%, there is a tendency that the occurrence of defects such as cracks can be sufficiently suppressed during the production of the separation functional layer 1.
  • the matrix content in the separation functional layer 1 is not particularly limited, and may be, for example, 30 wt% to 99 wt%, and may be 30 wt% to 90 wt%.
  • the surface area D1 of the filler per weight of the matrix is not particularly limited, and may be, for example, 5 m 2 /g or more, 10 m 2 /g or more, 20 m 2 /g or more, 30 m 2 /g or more, 40 m 2 /g or more, or even 50 m 2 /g or more.
  • the upper limit of the surface area D1 is not particularly limited, and may be, for example, 100 m 2 /g or less.
  • the surface area D1 can be calculated by the following formula based on the BET specific surface area D2 (m 2 /g) of the filler by nitrogen gas adsorption, the weight W1 (g) of the matrix contained in the separation functional layer 1, and the weight W2 (g) of the filler contained in the separation functional layer 1.
  • D1( m2 /g) D2( m2 /g) ⁇ W2(g)/W1(g)
  • the thickness of the separation functional layer 1 is, for example, 200 ⁇ m or less, and may be 100 ⁇ m or less, or even 80 ⁇ m or less.
  • the thickness of the separation functional layer 1 may be 1.0 ⁇ m or more, 10 ⁇ m or more, or even 30 ⁇ m or more.
  • the porous support 5 has, for example, only a main body portion and does not have a microporous layer.
  • the porous support 5 is preferably a fiber structure.
  • the fiber structure include a woven fabric, a nonwoven fabric, and a stretched porous membrane containing fibrils.
  • the fiber structure is typically a nonwoven fabric or a stretched porous membrane.
  • the fibers contained in the fiber structure include, for example, natural fibers such as wood pulp, cotton, and hemp (e.g., Manila hemp); and chemical fibers (synthetic fibers) such as polyester fibers, rayon, vinylon, acetate fibers, polyvinyl alcohol (PVA) fibers, polyamide fibers, polyolefin fibers, and polyurethane fibers.
  • the porous support 5 is, for example, a nonwoven fabric made of polyester fibers.
  • the fiber structure When the fiber structure is an expanded porous membrane, it is preferable that the fiber structure contains a fluororesin.
  • fluororesins include polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), perfluoroalkoxy fluororesin (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP), with PTFE being preferred.
  • expanded PTFE porous membranes are formed by stretching a paste extrudate or cast film containing PTFE particles. Expanded PTFE porous membranes are composed of fine fibrils of PTFE and may have nodes where the PTFE is in an aggregated state compared to the fibrils.
  • the separation functional layer 1 is in direct contact with, for example, a fiber structure (specifically, a nonwoven fabric or an expanded porous membrane).
  • the separation functional layer 1 contains a (meth)acrylic resin and is in direct contact with the porous support 5, which is a fiber structure, during operation of a membrane separation device equipped with a pervaporation membrane 10, a portion of the separation functional layer 1 may enter the opening H1 of the porous support 5, reducing the flux of the permeating fluid passing through the pervaporation membrane 10.
  • the separation functional layer 1 contains a (meth)acrylic resin, if an expanded porous membrane is used as the porous support 5, the separation functional layer 1 is less likely to enter the opening H1, and the reduction in the flux of the permeating fluid tends to be sufficiently suppressed.
  • the porous support 5 (main body) has an average pore size of, for example, 1 ⁇ m to 50 ⁇ m.
  • the thickness of the porous support 5 is not particularly limited and may be, for example, 10 ⁇ m or more, 50 ⁇ m or more, or even 100 ⁇ m or more.
  • the thickness of the porous support 5 is, for example, 300 ⁇ m or less, and may be 200 ⁇ m or less.
  • the porous support 5 has a large average diameter L1 of the openings H1 on the surface A1, and therefore tends to have high breathability by itself.
  • the porous support 5 has a thickness-wise air permeability expressed as an air permeability (Gurley air permeability) determined in accordance with the air permeability measurement method B (Gurley type method) defined in JIS L1096:2010, which may be, for example, 50 seconds/100 mL or less, 30 seconds/100 mL or less, 10 seconds/100 mL or less, or even 5 seconds/100 mL or less.
  • the lower limit of the Gurley air permeability of the porous support 5 is not particularly limited, and is, for example, 0.1 seconds/100 mL.
  • the surface A1 of the porous support 5 may be treated with a molecular bonding agent.
  • the molecular bonding agent contains a molecular bonding compound (hereinafter referred to as "compound C1") and, if necessary, a solvent such as an organic solvent or water.
  • Compound C1 has a reactive group F1 capable of reacting with the surface A1 of the porous support 5, and a reactive group F2 capable of reacting with a resin (particularly a silicone resin) contained in the separation functional layer 1.
  • the reactive group F2 may be capable of reacting not only with the silicone resin, but also with the surface A1 of the porous support 5.
  • the reactive group F1 is, for example, at least one selected from the group consisting of an amino group, an azide group, a mercapto group, an isocyanate group, a ureido group, and an epoxy group, and is typically an azide group.
  • the reactive group F2 is, for example, at least one selected from the group consisting of a silanol group and a group G that generates a silanol group by a hydrolysis reaction.
  • a specific example of the group G is an alkoxysilyl group.
  • Compound C1 is represented, for example, by the following formula (1).
  • R A represents a reactive group F1 or a monovalent substituent having one or more reactive groups F1
  • R B represents a reactive group F2
  • Z represents a divalent organic group.
  • Z may be an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent, an alkynylene group having 2 to 20 carbon atoms which may have a substituent, an arylene group having 6 to 20 carbon atoms which may have a substituent, etc.
  • alkylene groups having 1 to 20 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups, with methylene, ethylene, and propylene being preferred, and propylene being more preferred.
  • alkenylene groups having 2 to 20 carbon atoms include vinylene, propenylene, butenylene, and pentenylene groups.
  • alkynylene groups having 2 to 20 carbon atoms include ethynylene and propynylene groups.
  • arylene groups having 6 to 20 carbon atoms include o-phenylene, m-phenylene, p-phenylene, 2,6-naphthylene, and 1,5-naphthylene groups.
  • Examples of the substituents that the above alkylene, alkenylene, and alkynylene groups may have include halogen atoms such as fluorine and chlorine atoms; alkoxy groups such as methoxy and ethoxy groups; alkylthio groups such as methylthio and ethylthio groups; and alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups.
  • Examples of the substituents that the arylene group may have include a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; an alkyl group such as a methyl group or an ethyl group; an alkoxy group such as a methoxy group or an ethoxy group; and an alkylthio group such as a methylthio group or an ethylthio group.
  • substituents may be bonded to any position in the alkylene group, alkenylene group, alkynylene group, arylene group, or other group, and multiple substituents may be bonded to the same element or different elements.
  • R A examples include groups represented by the following formulas (2) to (4).
  • R 1 represents a divalent hydrocarbon group having 1 to 10 carbon atoms.
  • R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • R 4 and R 5 each independently represent a reactive group F1 or a group represented by the above formula (2).
  • * in formula (2) represents a bond to a carbon atom constituting a triazine ring in formula (4).
  • R 6 represents a single bond or a divalent group represented by -N(R 7 )-.
  • R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • R 1 is preferably a divalent hydrocarbon group having 2 to 6 carbon atoms.
  • R 1 include alkylene groups or arylene groups having 1 to 10 carbon atoms, specifically, alkylene groups such as an ethylene group or a trimethylene group; and arylene groups such as an o-phenylene group, an m-phenylene group, or a p-phenylene group.
  • R 2 and R 3 are preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
  • R 2 and R 3 include an alkyl group, alkynyl group, or aryl group having 1 to 20 carbon atoms, and specific examples thereof include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group; alkenyl groups such as a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 3-butenyl
  • R 4 and R 5 are preferably the same reactive group F1.
  • R6 represents a single bond or a divalent group represented by -N( R7 )-.
  • Examples of the hydrocarbon group for R7 include the same as those described above as the hydrocarbon groups for R2 and R3 . It is preferable that R6 represents -NH-.
  • R A is preferably a group represented by formula (4), and more preferably a group represented by formula (4) in which R 4 or R 5 is an azide group or a group represented by the above formula (2).
  • R A examples include a group represented by the following formula (5).
  • * represents a bond to Z in formula (1).
  • R 1 to R 3 and R 6 are the same as those described above for formulas (2) and (4).
  • R 1 to R 3 may be the same or different.
  • R B may be a group represented by the following formula (6). -Si(X) a (Y) 3-a (6)
  • X represents a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms
  • Y represents a hydrocarbon group having 1 to 20 carbon atoms
  • a represents an integer of 1 to 3.
  • X is, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, etc., and is preferably an ethoxy group.
  • Y is, for example, the hydrocarbon group described above for R2 and R3 in formula (2).
  • R B is preferably one in which X represents a hydroxy group or an alkoxy group having 1 to 10 carbon atoms and a is 3, and more preferably one in which X represents a hydroxy group or an ethoxy group and a is 3.
  • Examples of the compound C1 in which R is an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, [3-(N,N-dimethylamino)propyl]trimethoxysilane, [3-(phenylamino)propyl]trimethoxysilane, trimethyl[3-(triethoxysilyl)propyl]ammonium chloride, and trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride.
  • Examples of the compound C1 in which R A is an azide group include (11-azidoundecyl)trimethoxysilane and (11-azidoundecyl)triethoxysilane.
  • Examples of the compound C1 in which R A is a mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane.
  • Examples of the compound C1 in which R A is an isocyanate group include 3-(trimethoxysilyl)propyl isocyanate and 3-(triethoxysilyl)propyl isocyanate.
  • Examples of the compound C1 in which R A is a ureido group include 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane.
  • Examples of the compound C1 in which R A is an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane.
  • Examples of the compound C1 in which R is a monovalent substituent having one or more reactive groups F1 include 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and compounds represented by the following formulas (1-1) to (1-9).
  • Compound C1 is preferably a compound represented by the above formulas (1-1) to (1-9), and more preferably a compound represented by formula (1-1) or (1-9).
  • the pervaporation membrane 10 can be produced, for example, by the following method. First, as shown in FIG. 1B, a separation functional layer 1 is produced on a release liner 12.
  • the separation functional layer 1 can be produced by applying a coating liquid containing the material of the separation functional layer 1 onto the release liner 12 and curing the resulting coating film.
  • the coating liquid is, for example, a silicone resin composition or a (meth)acrylic resin composition.
  • the coating film can be cured at room temperature or in a heated environment.
  • the coating film can also be cured by irradiation with active energy rays such as UV.
  • the coating film may be cured while the coating film is sandwiched between two release liners 12.
  • the heating conditions for the coating film are not particularly limited.
  • the heating temperature for the coating film may be 80°C or higher, 90°C or higher, 100°C or higher, or even 120°C or higher.
  • the upper limit for the heating temperature for the coating film is not particularly limited, and is, for example, 200°C.
  • the heating time for the coating film can be adjusted as appropriate depending on the composition of the resin composition used.
  • the surface 1a of the separation functional layer 1 may be subjected to a surface modification treatment.
  • the surface modification treatment include corona treatment, plasma treatment, excimer treatment, and frame treatment, with corona treatment being preferred.
  • the surface modification treatment is performed, for example, by irradiating the surface 1a of the separation functional layer 1 with active energy rays.
  • active energy rays include electron beams, ion beams, plasma beams, and ultraviolet rays.
  • Examples of the release liner 12 include films containing resin; paper; and sheets containing metal materials such as aluminum and stainless steel. Sheets containing metal materials tend to have high heat resistance.
  • the release liner 12 is preferably a film containing resin because of its excellent surface smoothness.
  • examples of the polymer contained in the resin include polyolefins such as polyethylene, polypropylene, polybutene, polybutadiene, and polymethylpentene; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyvinyl chloride, vinyl chloride copolymers; polyurethane; and ethylene-vinyl acetate copolymers, with polyester, particularly polyethylene terephthalate, being preferred.
  • the surface of the release liner 12 may be subjected to a release treatment.
  • the release treatment may be performed, for example, by applying a release treatment agent to the surface of the release liner 12.
  • the release treatment agent include silicone-based release treatment agents, long-chain alkyl-based release treatment agents, fluorine-based release treatment agents, and molybdenum sulfide-based release treatment agents.
  • the release treatment agents may be used alone or in combination of two or more types.
  • the release liner 12 is preferably a film made of polyethylene terephthalate (PET) that has been subjected to a release treatment.
  • PET polyethylene terephthalate
  • the thickness of the release liner 12 is not particularly limited, but is, for example, 5 to 100 ⁇ m, and preferably 10 to 50 ⁇ m.
  • a molecular bonding agent (coating liquid) containing the above-mentioned compound C1 is prepared.
  • the molecular bonding agent is coated on the surface A1 of the porous support 5.
  • Compound C1 reacts with surface A1, thereby bonding with surface A1.
  • reactive groups F2 are present on surface A1.
  • reactive groups F2 can be introduced into surface A1 of the porous support 5 by treatment with the molecular bonding agent.
  • the porous support 5 is placed on the separation functional layer 1 so that the surface A1 of the porous support 5 coated with the molecular adhesive is in contact with the separation functional layer 1 ( Figure 1C), and then heated and dried. This causes a reaction between the reactive group F2 present on the surface A1 and the resin (particularly silicone resin) contained in the separation functional layer 1 to proceed.
  • the drying temperature of the molecular adhesive is, for example, 40 to 150°C, and may be 60°C or higher, or even 70°C or higher.
  • the drying temperature of the molecular adhesive may be 150°C or lower, or may be 90°C or lower.
  • the molecular adhesive may be heated and dried at the stage where the molecular adhesive is applied to the surface A1 of the porous support 5.
  • the process of applying the molecular adhesive and drying it may be repeated multiple times. This makes it possible to increase the density of the reactive groups F2 on the surface A1.
  • different types of molecular adhesives may be used for each process.
  • the reaction between the reactive group F1 and the surface A1 of the porous support 5 tends to proceed easily by irradiating the surface A1 with ultraviolet light.
  • the reactive group F2 is reacted with the resin, and then the release liner 12 is removed to obtain the pervaporation membrane 10.
  • the adhesion between the separation functional layer 1 and the porous support 5 may be sufficiently large even if the surface A1 of the porous support 5 is not treated with a molecular adhesive.
  • the separation functional layer 1 contains a (meth)acrylic resin, it tends to be easy to adjust the peel strength between the separation functional layer 1 and the porous support 5 to 0.15 N/20 mm or more even without using a molecular adhesive.
  • the pervaporation membrane 10 of the present embodiment is suitable for use in separating an organic compound C from an aqueous solution S containing a volatile organic compound C, for example.
  • the organic compound C is not particularly limited as long as it is volatile.
  • the term "volatile organic compound” refers to, for example, an organic compound having a boiling point of 20°C to 260°C under atmospheric pressure (101.325 kPa). Note that, when the organic compound C has a high concentration in an aqueous solution, for example, it generates an aqueous phase containing water as a main component and an organic phase having a higher content of the organic compound C than the aqueous phase. However, the organic compound C may not generate an aqueous phase and an organic phase.
  • the number of carbon atoms in the organic compound C is not particularly limited, and may be, for example, 10 or less, 8 or less, 6 or less, or even 4 or less.
  • the lower limit of the number of carbon atoms in the organic compound C may be 1 or 2.
  • the organic compound C has a functional group containing an oxygen atom, such as, for example, a hydroxyl group, a carbonyl group, an ether group, or an ester group. In the organic compound C, the number of functional groups containing an oxygen atom is typically one.
  • the organic compound C may be, for example, an alcohol, a ketone, an ester, etc., and is typically an alcohol.
  • the alcohol may be an alkyl alcohol composed only of an alkyl group and a hydroxyl group, or an aryl alcohol containing an aryl group and a hydroxyl group.
  • the alkyl alcohol may be linear, branched, or cyclic. Examples of the alkyl alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, and n-pentanol. Examples of the aryl alcohol include phenol.
  • the ketone may be a dialkyl ketone consisting of only alkyl and carbonyl groups.
  • dialkyl ketones include methyl ethyl ketone (MEK) and acetone.
  • the ester may be a fatty acid alkyl ester composed only of alkyl groups and ester groups.
  • fatty acid alkyl esters include ethyl acetate.
  • the organic compound C is not limited to those mentioned above.
  • the organic compound C may be an aromatic hydrocarbon such as benzene, toluene, or xylene.
  • the aqueous solution S may contain one type of organic compound C, or may contain two or more types of organic compounds C.
  • the content of organic compound C in the aqueous solution S is, for example, 0.5 wt% or more, and may be 1 wt% or more, 2 wt% or more, or even 5 wt% or more.
  • the upper limit of the content of organic compound C is not particularly limited, and is, for example, 50 wt%.
  • the organic compound C may be a fermentation product produced by a microorganism fermenting a carbon source, or may be alcohol (bioalcohol) produced by a microorganism.
  • the aqueous solution S may be a fermentation liquid containing the organic compound C as a fermentation product.
  • the aqueous solution S is not limited to a fermentation liquid, and may be waste liquid or wastewater discharged from a chemical plant, etc.
  • the aqueous solution S may further contain other components such as a microorganism that produces a fermentation product, a carbon source, a nitrogen source, and inorganic ions in addition to water and the organic compound C.
  • a microorganism that produces the fermentation product is typically a fungus.
  • carbon sources include polysaccharides such as starch and monosaccharides such as glucose.
  • the separation factor of organic compound C relative to water in pervaporation membrane 10.
  • the separation factor ⁇ of n-butanol (BuOH) relative to water in pervaporation membrane 10 is, for example, 10 or more, and may be 15 or more, 20 or more, 25 or more, 30 or more, or even 40 or more.
  • the upper limit of separation factor ⁇ is, for example, 100.
  • the separation factor ⁇ can be measured by the following method.
  • a mixed liquid consisting of BuOH and water is contacted with one side of the pervaporation membrane 10 (for example, the main surface 10a of the pervaporation membrane 10 on the separation function layer side), and the space adjacent to the other side of the pervaporation membrane 10 (for example, the main surface 10b of the pervaporation membrane 10 on the porous support side) is depressurized.
  • the weight ratio of water and the weight ratio of BuOH in the permeated fluid are measured.
  • the content of BuOH in the mixed liquid is 1.0 wt%.
  • the mixed liquid that is contacted with the pervaporation membrane 10 has a temperature of 30° C.
  • the space adjacent to the other side of the pervaporation membrane 10 is depressurized to 15 hPa.
  • the separation factor ⁇ can be calculated from the following formula.
  • X A and X B are the weight ratio of BuOH and the weight ratio of water in the mixed liquid, respectively.
  • Y A and Y B are the weight ratio of BuOH and the weight ratio of water, respectively, in the permeating fluid that permeates the pervaporation membrane 10 .
  • Separation factor ⁇ ( YA / YB )/( XA / XB )
  • the flux of BuOH passing through the pervaporation membrane 10 is not particularly limited and is, for example, 0.01 (g/min/ m2 ) to 10.0 (g/min/ m2 ) (i.e., 0.0006 (kg/ m2 /hr) to 0.6 (kg/ m2 /hr)).
  • pervaporation membranes are produced by applying a coating solution containing the material of the separation functional layer onto a porous support and drying the resulting coating film. At this time, the average diameter of the openings on the surface of the porous support facing the separation functional layer tends to be adjusted to a low value to prevent the coating solution from penetrating into the porous support.
  • a pervaporation membrane is produced using, as a porous support, a laminate in which a microporous layer with an average diameter of openings smaller than that of a main body part such as a fiber structure is arranged on the main body part (for example, Patent Document 1).
  • the porous support 5 is adjusted so that the average diameter L1 of the openings H1 on the surface A1 is 0.5 ⁇ m or more. Because the average diameter L1 of the openings H1 is large, the pervaporation membrane 10 tends to have good separation performance (particularly the flux of the permeating fluid that permeates the pervaporation membrane).
  • the membrane separation device 20 of this embodiment includes a pervaporation membrane 10 and a tank 22.
  • the tank 22 has a first chamber 23 and a second chamber 24.
  • the first chamber 23 functions as a supply space to which a supply fluid (specifically, the above-mentioned aqueous solution S) is supplied.
  • the second chamber 24 functions as a permeation space to which a permeation fluid S1 is supplied.
  • the permeation fluid S1 is obtained by permeating the aqueous solution S through the pervaporation membrane 10.
  • the pervaporation membrane 10 is disposed inside the tank 22. Inside the tank 22, the pervaporation membrane 10 separates the first chamber 23 and the second chamber 24. The pervaporation membrane 10 extends from one of the pair of walls of the tank 22 to the other.
  • the first chamber 23 has an inlet 23a and an outlet 23b.
  • the second chamber 24 has an outlet 24a.
  • the inlet 23a is an opening for supplying the aqueous solution S to the supply space (first chamber 23).
  • the outlet 24a is an opening for discharging the permeated fluid S1 from the permeated space (second chamber 24).
  • the outlet 23b is an opening for discharging the aqueous solution S that has not permeated the pervaporation membrane 10 (non-permeated fluid S2) from the supply space (first chamber 23).
  • Each of the inlet 23a, outlet 23b, and outlet 24a is formed, for example, on the wall surface of the tank 22.
  • the membrane separation device 20 is suitable for a flow-through (continuous) membrane separation method. However, the membrane separation device 20 may also be used for a batch-type membrane separation method.
  • the membrane separation device 20 is operated, for example, as follows: First, the aqueous solution S is supplied to the first chamber 23 of the membrane separation device 20 through the inlet 23a. This allows the aqueous solution S to come into contact with one surface (e.g., the main surface 10a) of the pervaporation membrane 10.
  • the space adjacent to the other surface of the pervaporation membrane 10 (e.g., the main surface 10b) is depressurized.
  • the pressure in the second chamber 24 is depressurized through the outlet 24a.
  • the pressure in the second chamber 24 can be depressurized, for example, by a depressurization device such as a vacuum pump.
  • the pressure in the second chamber 24 is, for example, 50 kPa or less, and may be 20 kPa or less, 10 kPa or less, 5 kPa or less, 3 kPa or less, or even 2 kPa or less.
  • pressure means absolute pressure.
  • a permeated fluid S1 having a high content of organic compound C can be obtained on the other side of the pervaporation membrane 10.
  • the permeated fluid S1 is supplied to the second chamber 24.
  • the permeated fluid S1 is typically a gas.
  • the permeated fluid S1 is discharged to the outside of the membrane separation device 20 through the outlet 24a.
  • the content of organic compounds C in the aqueous solution S gradually decreases from the inlet 23a to the outlet 23b of the first chamber 23.
  • the aqueous solution S (non-permeated fluid S2) treated in the first chamber 23 is discharged to the outside of the membrane separation device 20 through the outlet 23b.
  • the non-permeated fluid S2 is typically a liquid.
  • the pervaporation membrane 10 allows preferential permeation of the organic compound C contained in the aqueous solution S. Therefore, the permeated fluid S1 obtained by operating the membrane separation device 20 has a higher content of organic compound C than the aqueous solution S supplied to the membrane separation device 20.
  • the membrane separation device 20 may be a spiral membrane element, a hollow fiber membrane element, a disk-tube membrane element in which a plurality of pervaporation membranes are stacked, a plate-and-frame membrane element, or the like.
  • Fig. 3 shows a spiral membrane element.
  • the membrane separation device 25 in Fig. 3 includes a central tube 26 and a stack 27.
  • the stack 27 includes the pervaporation membrane 10.
  • the central tube 26 has a cylindrical shape. A plurality of holes or slits are formed on the surface of the central tube 26 to allow the permeation fluid S1 to flow into the interior of the central tube 26.
  • materials for the central tube 26 include resins such as acrylonitrile butadiene styrene copolymer resin (ABS resin), polyphenylene ether resin (PPE resin), and polysulfone resin (PSF resin); and metals such as stainless steel and titanium.
  • the inner diameter of the central tube 26 is, for example, in the range of 20 to 100 mm.
  • the laminate 27 further includes a supply-side flow path material 28 and a permeation-side flow path material 29.
  • the laminate 27 is wound around the central tube 26.
  • the membrane separation device 25 may further include an exterior material (not shown).
  • the supply-side flow passage material 28 and the permeate-side flow passage material 29 can be, for example, a resin net, woven fabric, or knitted fabric made of polyethylene, polypropylene, polyethylene terephthalate (PET), polyphenylene sulfide (PPS), or ethylene-chlorotrifluoroethylene copolymer (ECTFE).
  • PET polyethylene terephthalate
  • PPS polyphenylene sulfide
  • ECTFE ethylene-chlorotrifluoroethylene copolymer
  • the membrane separation device 25 can be operated, for example, in the following manner. First, the aqueous solution S is supplied to one end of the wound stack 27. The space inside the central tube 26 is depressurized. As a result, the permeated fluid S1 that has permeated the pervaporation membrane 10 of the stack 27 moves into the interior of the central tube 26. The permeated fluid S1 is discharged to the outside through the central tube 26. The aqueous solution S (non-permeated fluid S2) that has been treated in the membrane separation device 25 is discharged to the outside from the other end of the wound stack 27.
  • the membrane separation system 100 of the present embodiment includes the above-mentioned membrane separation device 20.
  • the membrane separation system 100 may include the membrane separation device 25 described in Fig. 3 instead of the membrane separation device 20.
  • the membrane separation system 100 further includes a tank 30 in addition to the membrane separation device 20.
  • the tank 30 stores the aqueous solution S to be supplied to the membrane separation device 20.
  • the tank 30 may be a fermenter for producing an organic compound C by fermentation of a carbon source by microorganisms.
  • the membrane separation system 100 further includes an aqueous solution supply path 70, a non-permeated fluid discharge path 71, and a permeated fluid discharge path 72.
  • the aqueous solution supply path 70 is a path for supplying the aqueous solution S from the tank 30 to the membrane separation device 20 during operation, and is connected to the outlet 31 of the tank 30 and the inlet 23a of the membrane separation device 20.
  • a pump 50 for controlling the flow rate of the aqueous solution S is disposed in the aqueous solution supply path 70.
  • the non-permeated fluid discharge path 71 is a path for discharging the non-permeated fluid S2 from the membrane separation device 20 during operation, and is connected to the outlet 23b of the membrane separation device 20.
  • a pump 51 for controlling the flow rate of the non-permeated fluid S2 is disposed in the non-permeated fluid discharge path 71.
  • the pump 51 may not be disposed in the non-permeated fluid discharge path 71.
  • the non-permeated fluid discharge path 71 may be connected to the inlet 32 of the tank 30 and configured to send the non-permeated fluid S2 to the tank 30 during operation.
  • the non-permeated fluid S2 may be mixed with the aqueous solution S in the tank 30 and circulated through the aqueous solution supply path 70 and the non-permeated fluid discharge path 71.
  • the non-permeated fluid S2 is sent to the tank 30, the aqueous solution S and the non-permeated fluid S2 are mixed in the tank 30, and the content of the organic compound C in the aqueous solution S decreases.
  • the tank 30 is a fermentation tank, the decrease in the content of the organic compound C in the aqueous solution S can prevent the fermentation by the microorganisms from stopping, thereby allowing the production of the fermented product to be carried out continuously.
  • the permeate fluid discharge path 72 is a path for discharging the permeate fluid S1 from the membrane separation device 20 during operation, and is connected to the outlet 24a of the membrane separation device 20.
  • a pressure reducing device 52 is arranged in the permeate fluid discharge path 72.
  • the pressure reducing device 52 can reduce the pressure inside the permeation space of the membrane separation device 20.
  • the pressure reducing device 52 is preferably a vacuum device such as a vacuum pump.
  • the vacuum pump is typically a gas transport type vacuum pump, and examples of the vacuum pump include a reciprocating vacuum pump and a rotary vacuum pump. Examples of the reciprocating vacuum pump include a diaphragm type and a rocking piston type vacuum pump.
  • the rotary vacuum pump examples include a liquid ring pump; an oil rotary pump (rotary pump); a mechanical booster pump; and various dry pumps such as a roots type, a claw type, a screw type, a turbo type, and a scroll type.
  • the pump as the pressure reducing device 52 may be equipped with a variable speed mechanism for changing the rotation speed, etc.
  • An example of the variable speed mechanism is an inverter that drives the motor of the pump. By controlling the pump speed and other parameters with the variable speed mechanism, the pressure in the permeation space of the membrane separation device 20 can be appropriately adjusted.
  • the permeated fluid discharge path 72 may further include a heat exchanger for cooling the permeated fluid S1.
  • the heat exchanger can condense the gaseous permeated fluid S1.
  • the heat exchanger is, for example, a gas-liquid heat exchanger that causes heat exchange between a cooling medium such as antifreeze and the gaseous permeated fluid S1.
  • the heat exchanger may be located between the membrane separation device 20 and the pressure reducing device 52 (upstream of the pressure reducing device 52), or between the pressure reducing device 52 and the recovery section 40 (downstream of the pressure reducing device 52), which will be described later.
  • the membrane separation system 100 further includes a recovery section 40.
  • the recovery section 40 recovers the permeated fluid S1 sent from the membrane separation device 20, and can store the permeated fluid S1, for example.
  • the recovery section 40 is, for example, a tank that stores the permeated fluid S1.
  • a permeated fluid discharge path 72 is connected to an inlet 41 of the recovery section 40.
  • the membrane separation system 100 may further include a controller 60 that controls each component of the membrane separation system 100.
  • the controller 60 is, for example, a DSP (Digital Signal Processor) that includes an A/D conversion circuit, an input/output circuit, an arithmetic circuit, a memory device, etc.
  • the controller 60 stores a program for appropriately operating the membrane separation system 100.
  • each of the paths in the membrane separation system 100 is composed of, for example, metal or plastic piping.
  • Example 1 First, 54 g of toluene (Fujifilm Wako Pure Chemical Industries, special grade) as a dilution solvent and 1 g of platinum catalyst (Shin-Etsu Chemical Industry, CAT-PL-50T) as a curing catalyst were added to 100 g of a silicone resin composition (KS-847T, toluene solution, solid content 30 wt%) to prepare a coating liquid (addition type silicone resin composition). Next, the coating liquid was applied onto a release liner (Diafoil MRE38, Mitsubishi Chemical Corporation) to obtain a coating film (thickness 500 ⁇ m).
  • a silicone resin composition KS-847T, toluene solution, solid content 30 wt%
  • the coating film was heated at 90 ° C for 20 minutes and cured to prepare a separation function layer with a thickness of 50 ⁇ m.
  • the surface of the prepared separation function layer was subjected to corona treatment.
  • the corona treatment was performed under the conditions of output 0.16 kW, table moving speed 3 m / min, and discharge amount 200 W ⁇ min / m 2 .
  • a PET nonwoven fabric was prepared as a porous support.
  • An aqueous solution containing a molecular bonding compound (N,N'-bis(2-aminoethyl)-6-(3-trihydroxysilylpropyl)amino-1,3,5-triazine-2,4-diamine, manufactured by Io Chemical Laboratory) at a content of 0.5 wt% was applied to the surface of the porous support, and the porous support was placed on the separation functional layer so that the surface treated with the aqueous solution was in contact with the separation functional layer, and heated at 90°C for 10 minutes. This caused the surface of the porous support to bond with the silicone resin contained in the separation functional layer via the molecular bonding compound.
  • the release liner was removed to obtain the pervaporation membrane of Example 1.
  • Example 2 First, a laminate of a microporous layer made of polysulfone and a nonwoven fabric made of PET was prepared as a porous support. Next, 50 g of a silicone resin composition (KE-1935B, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 50 g of a silicone resin composition (KE-1935A, manufactured by Shin-Etsu Chemical Co., Ltd.) to prepare a coating liquid (addition type silicone resin composition). This coating liquid was a solventless type that did not contain a solvent. Next, a coating film (thickness 70 ⁇ m) was obtained by coating the coating liquid on the microporous layer of the porous support.
  • a silicone resin composition KE-1935B, manufactured by Shin-Etsu Chemical Co., Ltd.
  • the coating film was heated at 150°C for 10 minutes to harden it, producing a separation functional layer with a thickness of 50 ⁇ m. This resulted in the pervaporation membrane of Example 2.
  • Example 3 First, RS-50 (a laminate of a PVDF microporous layer and a PET nonwoven fabric) manufactured by Nitto Denko Corporation was prepared as a porous support. Next, 54 g of toluene (manufactured by Fujifilm Wako Pure Chemical Industries, special grade) was added as a dilution solvent to 100 g of a silicone resin composition (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847T, toluene solution, solid content 30 wt%), and 1 g of a platinum-based catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T) was added as a curing catalyst to prepare a coating liquid (addition type silicone resin composition). This coating liquid was applied onto the microporous layer of the porous support to obtain a coating film (thickness 500 ⁇ m).
  • a silicone resin composition manufactured by Shin-Etsu Chemical Co., Ltd., KS-8
  • the coating film was heated at 90°C for 20 minutes to harden it, producing a separation functional layer with a thickness of 50 ⁇ m. This resulted in the pervaporation membrane of Example 3.
  • Example 4 First, 1.8 g of silica filler (AEROSIL RX200, manufactured by Nippon Aerosil Co., Ltd.) was added to 18.2 g of 2-ethylhexyl acrylate (2EHA, manufactured by Toa Gosei Co., Ltd.), and the mixture was stirred (2000 rpm, 3 minutes) and degassed (2200 rpm, 1 minute) using a Thinky Mixer.
  • silica filler AEROSIL RX200, manufactured by Nippon Aerosil Co., Ltd.
  • 2EHA 2-ethylhexyl acrylate
  • 0.017 g of 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added as a crosslinking agent, and the mixture was stirred (2000 rpm, 1 minute) and degassed (2200 rpm, 1 minute).
  • 0.017 g of 1-hydroxycyclohexyl-phenyl ketone (Omnirad184, manufactured by IGM Resins BV) was added as a photopolymerization initiator, and the mixture was stirred (2000 rpm, 3 minutes) and degassed (2200 rpm, 1 minute) to prepare a coating liquid (acrylic resin composition).
  • the coating liquid was applied between two release liners (Mitsubishi Chemical Corporation, Diafoil MRE38, MRF38) to prepare a coating film sandwiched between the two release liners.
  • the coating liquid was applied by applicator coating so that the thickness of the coating film was about 20 ⁇ m.
  • UV was irradiated from one release liner (MRF38) side to harden the coating film to prepare a separation functional layer. UV irradiation was performed using a black light under the conditions of illuminance 2.5 mW/cm 2 , discharge amount 2400 mJ/cm 2 , and irradiation time 16 minutes. The distance between the black light and the surface of the coating film was adjusted to 30 mm.
  • one of the release liners was peeled off to expose the surface of the separation functional layer.
  • the exposed surface of the separation functional layer was placed on the porous support, and a 2 kg roller was moved back and forth once to press them together.
  • a PTFE expanded porous membrane NVF1122, manufactured by Nitto Denko Corporation was used as the porous support.
  • the other release liner was removed to obtain the pervaporation membrane of Example 4.
  • Example 5 The pervaporation membrane of Example 5 was obtained in the same manner as in Example 4, except that RS-50 (a laminate of a PVDF microporous layer and a PET nonwoven fabric) manufactured by Nitto Denko Corporation was used as the porous support, and the surface of the porous support on the PVDF microporous layer side was overlapped with a separation functional layer.
  • RS-50 a laminate of a PVDF microporous layer and a PET nonwoven fabric manufactured by Nitto Denko Corporation was used as the porous support, and the surface of the porous support on the PVDF microporous layer side was overlapped with a separation functional layer.
  • Gurley air permeability For the porous support used in producing the pervaporation membrane, the Gurley air permeability was measured by a method based on the air permeability measurement method B (Gurley type method) specified in JIS L1096:2010.
  • aperture ratio For the porous support used in producing the pervaporation membrane, the aperture ratio R1 of the surface A1 facing the separating functional layer and the aperture ratio R2 of the surface A2 facing surface A1 were measured by the method described above.
  • the average diameter L1 of the openings on the surface A1 facing the separation functional layer and the average diameter L2 of the openings on the surface A2 facing surface A1 were determined using the method described above.
  • Example 1 The above test was carried out on the prepared pervaporation membrane to measure the peel strength.
  • the tensile tester used was an autograph AGS-50NX manufactured by Shimadzu Corporation.
  • the separation functional layer was sufficiently fixed to the porous support, and the separation functional layer could not be peeled off from the porous support by hand, and when an attempt was made to peel it off forcefully, the separation functional layer broke. Therefore, in Example 1, the breaking strength of the separation functional layer was measured by the above-mentioned method. As described above, the peel strength can be considered to be equal to or greater than the breaking strength.
  • the separation functional layer was soft and difficult to grip directly with a zipper. Therefore, for these, the peel strength was measured using an evaluation sheet (PET film) by the method described above.
  • the separation factor ⁇ of n-butanol (BuOH) with respect to water was measured for the pervaporation membrane prepared by the following method. First, the pervaporation membrane was cut into a size of 74 mm in diameter to prepare a flat membrane-shaped test piece. This test piece was set in a batch-type membrane separation device (cell). A mixed liquid consisting of n-butanol (BuOH) and water was supplied to the supply space of this cell. The content of BuOH in the mixed liquid was 1.0 wt%.
  • the cell was immersed in a water bath, and the temperature of the mixed liquid was adjusted to 30°C.
  • the pressure in the permeation space was reduced to 15 hPa while stirring the mixed liquid using a stirrer placed in the cell.
  • the gaseous permeation fluid was cooled by a cooling trap using liquid nitrogen, and the permeation fluid was condensed.
  • the composition of the liquid permeation fluid was analyzed using gas chromatography, and the separation factor ⁇ and the flux (kg/m 2 /hr) of BuOH permeated through the pervaporation membrane were calculated based on the obtained results.
  • KS847T Silicone resin composition (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847T)
  • KE1935 Silicone resin composition (manufactured by Shin-Etsu Chemical Co., Ltd., KE-1935)
  • RX200 Silica filler (AEROSIL RX200, manufactured by Nippon Aerosil Co., Ltd., surface modification group: trimethylsilyl (TMS) group)
  • Example 1 the average diameter L1 of the openings on the surface A1 of the porous support facing the separation functional layer was 0.5 ⁇ m or more. Furthermore, the peel strength between the separation functional layer and the porous support was 0.15 N/20 mm or more. The pervaporation membrane of Example 1 had better PV performance than Examples 2 and 3.
  • Example 4 the average diameter L1 of the openings on the surface A1 of the porous support facing the separation functional layer was 0.5 ⁇ m or more. Furthermore, the peel strength between the separation functional layer and the porous support was 0.15 N/20 mm or more. The pervaporation membrane of Example 4 had better PV performance than Example 5.
  • the pervaporation membrane of the present embodiment is suitable for separating volatile organic compounds from an aqueous solution containing the organic compounds.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
PCT/JP2023/030397 2022-09-26 2023-08-23 浸透気化膜 Ceased WO2024070355A1 (ja)

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US19/115,323 US20260022036A1 (en) 2022-09-26 2023-08-23 Pervaporation membrane
CN202380068351.3A CN119947819A (zh) 2022-09-26 2023-08-23 渗透气化膜
JP2024549882A JPWO2024070355A1 (https=) 2022-09-26 2023-08-23
EP23871596.5A EP4596090A1 (en) 2022-09-26 2023-08-23 Pervaporation membrane

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57136905A (en) * 1981-02-18 1982-08-24 Kuraray Co Ltd Separation of mixed liquid
JPS62286503A (ja) * 1986-06-03 1987-12-12 Sumitomo Electric Ind Ltd 多孔性中空糸複合膜及びその製造方法
JPS63116705A (ja) * 1986-07-29 1988-05-21 ゲ−エフテ−　ゲゼルシヤフト　フユア　トレンテヒニク　ミツト　ベシユレンクテル　ハフツング パ−ベ−パレ−ション法及びそれに用いる膜
JPH0824604A (ja) * 1994-07-18 1996-01-30 Asahi Glass Co Ltd 溶存揮発性物質の分離方法および溶存揮発性物質の分離膜
JP2005087882A (ja) * 2003-09-17 2005-04-07 National Institute Of Advanced Industrial & Technology 発酵アルコール含有水溶液から高濃度アルコールを製造する多機能多層構造型分離膜。
JP2005525224A (ja) 2002-02-26 2005-08-25 クレアヴィス ゲゼルシャフト フュア テヒノロギー ウント イノヴェイション ミット ベシュレンクテル ハフツング ハイブリッド膜、その製造方法および膜の使用
JP2006150323A (ja) * 2004-11-01 2006-06-15 Japan Gore Tex Inc 隔膜およびその製法、並びに該隔膜を備えた熱交換器
JP2014094501A (ja) * 2012-11-09 2014-05-22 Daicel Corp 多孔膜積層体及びその製造方法
WO2014115687A1 (ja) * 2013-01-25 2014-07-31 住友ベークライト株式会社 浸透気化膜およびフェノール濃縮方法
JP2018023955A (ja) * 2016-08-12 2018-02-15 セーレン株式会社 積層体およびこれを備える膜構造体

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57136905A (en) * 1981-02-18 1982-08-24 Kuraray Co Ltd Separation of mixed liquid
JPS62286503A (ja) * 1986-06-03 1987-12-12 Sumitomo Electric Ind Ltd 多孔性中空糸複合膜及びその製造方法
JPS63116705A (ja) * 1986-07-29 1988-05-21 ゲ−エフテ−　ゲゼルシヤフト　フユア　トレンテヒニク　ミツト　ベシユレンクテル　ハフツング パ−ベ−パレ−ション法及びそれに用いる膜
JPH0824604A (ja) * 1994-07-18 1996-01-30 Asahi Glass Co Ltd 溶存揮発性物質の分離方法および溶存揮発性物質の分離膜
JP2005525224A (ja) 2002-02-26 2005-08-25 クレアヴィス ゲゼルシャフト フュア テヒノロギー ウント イノヴェイション ミット ベシュレンクテル ハフツング ハイブリッド膜、その製造方法および膜の使用
JP2005087882A (ja) * 2003-09-17 2005-04-07 National Institute Of Advanced Industrial & Technology 発酵アルコール含有水溶液から高濃度アルコールを製造する多機能多層構造型分離膜。
JP2006150323A (ja) * 2004-11-01 2006-06-15 Japan Gore Tex Inc 隔膜およびその製法、並びに該隔膜を備えた熱交換器
JP2014094501A (ja) * 2012-11-09 2014-05-22 Daicel Corp 多孔膜積層体及びその製造方法
WO2014115687A1 (ja) * 2013-01-25 2014-07-31 住友ベークライト株式会社 浸透気化膜およびフェノール濃縮方法
JP2018023955A (ja) * 2016-08-12 2018-02-15 セーレン株式会社 積層体およびこれを備える膜構造体

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JPWO2024070355A1 (https=) 2024-04-04

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