WO2024070575A1 - 浸透気化膜 - Google Patents

浸透気化膜 Download PDF

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Publication number
WO2024070575A1
WO2024070575A1 PCT/JP2023/032766 JP2023032766W WO2024070575A1 WO 2024070575 A1 WO2024070575 A1 WO 2024070575A1 JP 2023032766 W JP2023032766 W JP 2023032766W WO 2024070575 A1 WO2024070575 A1 WO 2024070575A1
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Prior art keywords
filler
silicone resin
group
pervaporation membrane
resin composition
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PCT/JP2023/032766
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English (en)
French (fr)
Japanese (ja)
Inventor
威 矢野
武史 仲野
知哉 小川
晋平 村上
暁恵 池永
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to CN202380068400.3A priority Critical patent/CN119947820A/zh
Priority to US19/114,839 priority patent/US20260008017A1/en
Priority to JP2024549970A priority patent/JPWO2024070575A1/ja
Priority to EP23871812.6A priority patent/EP4596092A1/en
Publication of WO2024070575A1 publication Critical patent/WO2024070575A1/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
    • 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
    • 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
    • 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
    • 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
    • B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
    • 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
    • B01D71/024—Oxides
    • B01D71/027—Silicium oxide
    • 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
    • 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
    • B01D71/701—Polydimethylsiloxane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1216—Three or more layers

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.
  • One example of a method for separating volatile organic compounds from an aqueous solution containing the compounds is the pervaporation method using a pervaporation membrane.
  • the pervaporation method is suitable for separating volatile organic compounds from an aqueous solution containing various substances. Compared to distillation, the pervaporation method also tends to reduce energy consumption and carbon dioxide emissions.
  • a specific example of the material of the pervaporation membrane used in the pervaporation method is silicone resin (for example, Patent Document 1).
  • the present invention relates to A pervaporation membrane having a separation functional layer,
  • the separation functional layer provides a pervaporation membrane having a matrix containing a silicone resin and a filler containing silica and dispersed in the matrix.
  • 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.
  • 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 pervaporation membrane having a separation functional layer,
  • the separation functional layer has a matrix containing a silicone resin, and a filler containing silica and dispersed in the matrix.
  • the filler has a Hansen solubility parameter of 20 MPa 1/2 to 27 MPa 1/2 .
  • the filler has a surface modified with a modifying group that includes a hydrocarbon group.
  • the modifying group includes at least one selected from the group consisting of an organosilyl group and a polyorganosiloxane group.
  • the pH of the filler dispersion measured by the following test is 4.0 to 9.0. Test: Mix water, methanol, and the filler to prepare a dispersion, and measure the pH of the dispersion, where the content of the filler in the dispersion is 4 wt%, the weight ratio of water to methanol is 1:1, and the temperature of the dispersion is 25°C.
  • the average particle size of the filler is 1 ⁇ m or less.
  • the content of the filler in the separation functional layer is less than 70 wt%.
  • the silicone resin is formed from an addition type silicone resin composition, a condensation type silicone resin composition, or a UV-curable silicone resin composition.
  • a pervaporation membrane according to any one of the first to eighth 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.
  • the pervaporation membrane 10 is typically a membrane (separation membrane) that preferentially transmits an organic compound C from an aqueous solution S containing a volatile organic compound C.
  • the pervaporation membrane 10 may further include a porous support 5 that supports the separation functional layer 1.
  • the separation functional layer 1 has, for example, a surface 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 of only the separation functional layer 1 and the porous support 5.
  • 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 has a matrix 2 containing a silicone resin and a filler 3 that is dispersed in the matrix 2 and contains silica. All or a part of the filler 3 is embedded in the matrix 2. Within the matrix 2, all of the fillers 3 may be spaced apart from one another, or may be partially aggregated.
  • the matrix 2 contains a silicone resin.
  • the silicone resin is formed, for example, from a silicone resin composition.
  • the silicone resin is formed from an addition type silicone resin composition, a condensation type silicone resin composition, or a UV-curable silicone resin composition, and is preferably formed from an addition type 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. It is preferable that the addition type silicone resin composition 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 more likely it is that the separation characteristics of pervaporation membrane 10 will improve.
  • 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.
  • Matrix 2 may contain silicone resin as a main component, or may be composed essentially of silicone resin. "Main component” refers to the component that is contained in the largest amount by weight in matrix 2.
  • the content of the matrix 2 in the separation functional layer 1 is not particularly limited, and may be, for example, 30 wt% to 99 wt%, or 30 wt% to 90 wt%.
  • the filler 3 contains silica.
  • the filler 3 containing silica tends to have better hydrolysis resistance than the filler containing zeolite. Furthermore, the filler 3 containing silica tends to increase the free volume of the silicone resin contained in the matrix 2.
  • the separation characteristics of the pervaporation membrane 10, in particular, the separation coefficient ⁇ of BuOH relative to water tends to improve.
  • the free volume of the silicone resin is not particularly limited, and may be, for example, 0.260 nm 3 or more, 0.280 nm 3 or more, 0.300 nm 3 or more, 0.320 nm 3 or more, 0.330 nm 3 or more, or even 0.340 nm 3 or more.
  • the upper limit of the free volume of the silicone resin is, for example, 0.400 nm 3 or less, 0.380 nm 3 or less, or even 0.360 nm 3 or less.
  • the free volume of the silicone resin may be 0.300 nm 3 to 0.400 nm 3 .
  • the free volume of the silicone resin can be determined by the method described below.
  • Silica usually means silicon dioxide.
  • Filler 3 may be a silica filler containing silicon dioxide as a main component. Silica filler does not have a crystalline structure, for example. Silica filler can be produced, for example, by reacting metal silicon with oxygen. Silica filler can also be produced by the sol-gel method, the precipitation method, the aqueous solution wet method, or the like. Filler 3 may be substantially composed of silicon dioxide only.
  • the filler 3, particularly the silica filler does not have micropores with a diameter of, for example, 2 nm or less.
  • the filler 3 may have mesopores with a diameter of 2 nm to 50 nm and macropores with a diameter of 50 nm or more.
  • the filler 3 preferably has a surface modified with a modifying group that includes a hydrocarbon group.
  • the filler 3 is preferably surface-modified with a modifying group.
  • the surface-modified filler 3 has high dispersibility in the silicone resin and is 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 3 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 3 is sufficiently surface-modified with a modifying group. In other words, it is preferable that the number of hydroxyl groups present on the surface of the filler 3 is small. Whether the filler 3 is sufficiently surface-modified with a modifying group can be determined, for example, from the pH of the dispersion liquid of the filler 3 or the Hansen solubility parameter (HSP value) of the filler 3.
  • 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 dispersion of the filler 3 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 3 is sufficiently surface-modified with the modifying group, and the number of hydroxyl groups present on the surface is small.
  • the content of filler 3 is 4 wt %
  • the weight ratio of water to methanol is 1:1
  • the temperature of the dispersion is 25° C.
  • the HSP value of the filler 3 is, for example, 30 MPa 1/2 or less, and may be 27 MPa 1/2 or less, 26 MPa 1/2 or less, 25 MPa 1/2 or less, or even 24 MPa 1/2 or less.
  • the lower limit of the HSP value of the filler 3 is, for example, 20 MPa 1/2 .
  • the HSP value of the filler 3 may be 20 MPa 1/2 to 27 MPa 1/2 , or may be 20 MPa 1/2 to 25 MPa 1/2 .
  • the HSP value of the filler 3 can be specified by the following method. First, 20 types of solvents with known HSP values are prepared.
  • acetone acetone, methanol, ethanol, butanol, acetonitrile, dimethyl sulfoxide, dipropylene glycol, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, tetrahydrofuran, aniline, acetic acid, benzyl alcohol, ethylene glycol, glycerin, 1-methylimidazole, N-methylformamide, pyridine, salicylaldehyde, and 2-aminoethanol can be used.
  • filler 3 is added to 20 mL of the prepared solvent, and ultrasonic treatment is performed for 10 minutes. For each solvent, it is visually determined whether or not the filler 3 is dispersed. In particular, when the solvent to which the filler 3 is added is transparent and insoluble matter cannot be visually confirmed, it is determined that the filler 3 is dispersed in the solvent.
  • the solvent in which the filler 3 is dispersed is plotted on a three-dimensional graph with the dispersion term ⁇ D, the polarization term ⁇ P, and the hydrogen bond term ⁇ H as axes, and a dissolution sphere containing the solvent is created.
  • the ⁇ D (MPa 1/2 ), ⁇ P (MPa 1/2 ), and ⁇ H (MPa 1/2 ) at the center of the dissolution sphere are substituted into the following formula, and the obtained calculated value ⁇ T (MPa 1/2 ) can be regarded as the HSP value of the filler 3.
  • ⁇ T ( ⁇ D 2 + ⁇ P 2 + ⁇ H 2 ) 1/2
  • the shape of the filler 3 is, for example, particulate.
  • "particulate” includes spherical, ellipsoidal, scaly, and fibrous.
  • the filler 3 may be powdered.
  • the average particle size of the filler 3 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 filler 3 with a small average particle size tends to disperse stress applied to the separation functional layer 1 and has a tendency to have high adhesion to the porous support 5.
  • the lower limit of the average particle size of the separation functional layer 1 and the filler 3 is not particularly limited and may be, for example, 1 nm or 5 nm.
  • the average particle size of filler 3 can be determined, for example, by the following method. First, a cross section of separation functional layer 1 is observed with a transmission electron microscope. In the obtained electron microscope image, the area of a specific filler 3 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 3. The particle size of an arbitrary number of fillers 3 (at least 50 particles) is calculated, and the average of the calculated values is regarded as the average particle size of filler 3.
  • the content of the filler 3 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 content of the filler 3 in the separation functional layer 1 is not particularly limited, and may be, for example, less than 70 wt% or less than 50 wt%. When the content of the filler 3 is less than 50 wt%, there is a tendency that the occurrence of defects such as cracks can be sufficiently suppressed during the preparation of the separation functional layer 1.
  • the separation functional layer 1 does not substantially contain any filler (e.g., zeolite particles) other than the filler 3 containing, for example, silica.
  • the surface area D1 of the filler 3 per weight of the matrix 2 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 3 by nitrogen gas adsorption, the weight W1 (g) of the matrix 2 contained in the separation functional layer 1, and the weight W2 (g) of the filler 3 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 includes, for example, a main body portion 6 and a microporous layer 7 disposed on the main body portion 6.
  • the microporous layer 7 is located between the main body portion 6 and the separation functional layer 1, and is in direct contact with both the main body portion 6 and the separation functional layer 1.
  • the porous support 5 is typically an ultrafiltration membrane.
  • the main body 6 is, for example, a fiber structure such as a woven fabric or a nonwoven fabric, and is typically a nonwoven fabric.
  • fibers contained in the fiber structure include 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 main body 6 is, for example, a nonwoven fabric made of polyester fibers.
  • the main body 6 has an average pore size of, for example, 1 ⁇ m to 50 ⁇ m.
  • microporous layer 7 examples include fluororesins such as polyvinylidene fluoride and polytetrafluoroethylene; polyarylethersulfones such as polysulfone and polyethersulfone; and polyimides.
  • the microporous layer 7 has an average pore size of, for example, 0.01 ⁇ m to 0.4 ⁇ 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 may be, for example, 300 ⁇ m or less, or 200 ⁇ m or less.
  • the pervaporation membrane 10 can be prepared, for example, by forming a separation functional layer 1 on the microporous layer 7 of the porous support 5.
  • a coating liquid containing the material of the separation functional layer 1 is prepared.
  • the coating liquid is, for example, a mixture of a silicone resin composition (an addition type silicone resin composition, a condensation type silicone resin composition, or a UV-curable silicone resin composition) and a filler.
  • the mixture of the silicone resin composition and the filler may also be simply referred to as a silicone resin composition.
  • a coating film is obtained by applying the coating liquid onto the porous support 5.
  • the separation functional layer 1 is formed by curing the coating film.
  • 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 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 silicone resin composition used.
  • the pervaporation membrane 10 of this embodiment is suitable for separating an organic compound C from an aqueous solution S containing a volatile organic compound C.
  • the organic compound C is not particularly limited as long as it has volatility.
  • the "volatile organic compound” means, 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, or the like, 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 pervaporation membrane 10 of the present embodiment tends to have a high separation factor of the organic compound C relative to water.
  • the separation factor ⁇ of the pervaporation membrane 10 for n-butanol (BuOH) relative to water is, for example, 25 or more, and may be 30 or more, 35 or more, or even 40 or more.
  • the upper limit of the 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 in contact 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)
  • 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
  • 15 hPa the space adjacent to the other side of the pervaporation membrane 10
  • 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 brought into contact 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 ⁇ (Y A /Y B )/(X A /X B )
  • the flux of BuOH permeating through pervaporation membrane 10 is not particularly limited and is, for example, 0.01 (g/min/m 2 ) to 10.0 (g/min/m 2 ).
  • the pervaporation membrane 10 of this embodiment there is a tendency for there to be a strong adhesive force between the separating functional layer 1 and the porous support 5.
  • the pervaporation membrane 10 has, for example, a peel strength A of 0.15 N/20 mm or more 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 to 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 peel strength A.
  • the initial chuck distance in the tensile testing machine is 150 mm. The test is performed in an atmosphere of 25°C.
  • the peel strength A 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, or even 0.6 N/20 mm or more.
  • the upper limit of the peel strength A is not particularly limited, and is, for example, 20 N/20 mm.
  • 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, 10.5 g of silica filler (AEROSIL RX50, manufactured by Nippon Aerosil Co., Ltd.), 77.1 g of toluene (Fujifilm Wako Pure Chemical Industries, special grade) as a dilution solvent, and 0.65 g of platinum catalyst (CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) as a curing catalyst were added to 65 g of a silicone resin composition (KS-847T, manufactured by Shin-Etsu Chemical Co., Ltd.), to prepare a coating liquid (addition type silicone resin composition).
  • the silica filler had a surface modified with a trimethylsilyl (TMS) group.
  • a coating film (thickness 500 ⁇ m) was obtained by coating the coating liquid on a porous support.
  • a porous support RS-50 (a laminate of a PVDF microporous layer and a PET nonwoven fabric) manufactured by Nitto Denko Corporation was used.
  • the coating film was formed on the PVDF microporous layer of RS-50.
  • 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.
  • the filler content in the separation functional layer was 35 wt %. This resulted in the pervaporation membrane of Example 1.
  • Example 2 The pervaporation membrane of Example 2 was obtained in the same manner as in Example 1, except that the type of filler was changed as shown in Table 2.
  • Example 3 A pervaporation membrane of Example 3 was obtained by the same method as in Example 1, except that a coating liquid (addition type silicone resin composition) was prepared by adding 15 g of silica filler (AEROSIL RX50, manufactured by Nippon Aerosil Co., Ltd.), 87 g of toluene (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a dilution solvent, and 0.5 g of a platinum-based catalyst (CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) as a curing catalyst to 50 g of a silicone resin composition (KS-847T, manufactured by Shin-Etsu Chemical Co., Ltd., toluene solution, solid content 30 wt%).
  • silica filler AEROSIL RX50, manufactured by Nippon Aerosil Co., Ltd.
  • 87 g of toluene special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • Example 4 A pervaporation membrane of Example 4 was obtained by the same method as in Example 1, except that a coating liquid (condensation type silicone resin composition) was prepared by adding 10.5 g of silica filler (AEROSIL RX50, manufactured by Nippon Aerosil Co., Ltd.), 82.3 g of toluene (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a dilution solvent, and 1.95 g of a tin-based catalyst (YC6831, manufactured by Momentive Performance Materials Japan Co., Ltd.) as a curing catalyst to 65 g of a silicone resin composition (YSR3022, manufactured by Momentive Performance Materials Japan Co., Ltd.).
  • silica filler AEROSIL RX50, manufactured by Nippon Aerosil Co., Ltd.
  • 82.3 g of toluene special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • a tin-based catalyst YC6831, manufactured by Momentive Performance
  • Example 5 The pervaporation membrane of Example 5 was obtained in the same manner as in Example 4, except that the type of filler was changed as shown in Table 2.
  • Example 6 A pervaporation membrane of Example 6 was obtained by the same method as in Example 1, except that a coating liquid (condensation type silicone resin composition) was prepared by adding 15 g of silica filler (AEROSIL RX50, manufactured by Nippon Aerosil Co., Ltd.), 91.0 g of toluene (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a dilution solvent, and 1.5 g of a tin-based catalyst (YC6831, manufactured by Momentive Performance Materials Japan Co., Ltd.) as a curing catalyst to 50 g of a silicone resin composition (YSR3022, manufactured by Momentive Performance Materials Japan Co., Ltd.).
  • silica filler AEROSIL RX50, manufactured by Nippon Aerosil Co., Ltd.
  • 91.0 g of toluene special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • a tin-based catalyst YC6831, manufactured by Momentive Performance Materials Japan
  • Example 7 The pervaporation membrane of Example 7 was obtained in the same manner as in Example 6, except that the type of filler was changed as shown in Table 2.
  • Example 8 A pervaporation membrane of Example 8 was obtained by the same method as in Example 1, except that 54 g of toluene (manufactured by Fujifilm Wako Pure Chemical Industries, special grade) as a dilution solvent and 1 g of a platinum-based catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T) as a curing catalyst were added to 100 g of a silicone resin composition (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847T, toluene solution, solid content 30 wt%) to prepare a coating liquid (addition type silicone resin composition).
  • toluene manufactured by Fujifilm Wako Pure Chemical Industries, special grade
  • a platinum-based catalyst manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T
  • Example 9 A pervaporation membrane of Example 9 was obtained by the same method as in Example 1, except that 3.75 g of silica filler (AEROSIL RX200, manufactured by Nippon Aerosil Co., Ltd.), 42.0 g of toluene (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a dilution solvent, and 0.5 g of a platinum-based catalyst (CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) as a curing catalyst were added to 50 g of a silicone resin composition (KS-847T, manufactured by Shin-Etsu Chemical Co., Ltd., toluene solution, solid content 30 wt%) to prepare a coating liquid (addition type silicone resin composition).
  • silica filler AEROSIL RX200, manufactured by Nippon Aerosil Co., Ltd.
  • toluene special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • CAT-PL-50T manufactured by
  • Example 10 The pervaporation membrane of Example 10 was obtained in the same manner as in Example 9, except that the type of filler was changed as shown in Table 2.
  • Example 11 A pervaporation membrane of Example 11 was obtained by the same method as in Example 1, except that 1.15 g of silica filler (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.), 31.6 g of toluene (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a dilution solvent, and 0.5 g of a platinum-based catalyst (CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) as a curing catalyst were added to 50 g of a silicone resin composition (KS-847T, manufactured by Shin-Etsu Chemical Co., Ltd., toluene solution, solid content 30 wt%) to prepare a coating liquid (addition type silicone resin composition).
  • silica filler AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.
  • toluene special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • CAT-PL-50T platinum-based catalyst
  • the free volume of silicone resin contained in the pervaporation membranes of Examples 1 to 3 and 8 to 11 was determined by the following method. First, a layer having the same composition and thickness as the separation functional layer of the pervaporation membrane was prepared on a release liner. A release-treated polyethylene terephthalate (PET) film (Mitsubishi Chemical Corporation, MRE38) was used as the release liner. The above layer was prepared on the release surface of the release liner. Next, the release liner was removed to prepare a free-standing membrane of the separation functional layer.
  • PET polyethylene terephthalate
  • a positron source was sandwiched between the above-mentioned free-standing film, and the positron lifetime spectrum of the free-standing film was measured.
  • a sealed source of 22 Na was used as the positron source, and a high-speed response photomultiplier tube (BaF 2 scintillator) was used as the detector. Furthermore, the count number was set to about 6 Mcount, and the measurement time was set to 24 hours (i.e., about 70 counts/sec).
  • the lifetime value of orthopositronium correlated with the free volume of the silicone resin was analyzed. For the analysis, software (PALSfit 3.171) was used.
  • the above-mentioned lifetime value was converted into the free volume pore diameter (the diameter of the sphere when the free volume is assumed to be a sphere), and the free volume was calculated.
  • the separation functional layer of Example 8 is composed of only silicone resin
  • the separation functional layer of Examples 1 to 3 and 9 to 11 is composed of silicone resin and silica filler. Therefore, according to the above measurement method, for Examples 1 to 3 and 9 to 11, the total value of the free volume of the silicone resin and the free volume of the silica filler is obtained. Therefore, in Examples 1 to 3 and 9 to 11, the above measurement method was also performed on the silica filler itself used, and the free volume of the silica filler was identified. Based on the obtained results and the content (vol%) of the silica filler in the separation functional layer, the free volume of the silicone resin was identified. In addition, the content (vol%) of the silica filler in the separation functional layer can be calculated from the content (wt%) of the silica filler and the density (g/cm 3 ) of the silica filler.
  • HSP value of filler The HSP values of the fillers used in Examples 1 to 7 and 9 to 11 were determined by the method described above. HSPiP was used for the analysis of the HSP values. The measurement results of the dispersibility of the fillers in each solvent are shown in Table 1.
  • the separation factor ⁇ of n-butanol (BuOH) relative to water was measured 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 then immersed in a water bath and the temperature of the mixed liquid was adjusted to 30°C. Next, the pressure in the permeation space was reduced to 15 hPa while stirring the mixed liquid using a stirrer placed inside the cell. This caused the mixed liquid to permeate the pervaporation membrane, and a gaseous permeation fluid was obtained. 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 ⁇ was calculated based on the results obtained.
  • peel strength A was measured by the above-mentioned method for the pervaporation membranes of Examples 1 to 3 and 8 to 11.
  • the tensile tester used was an Autograph AGS-50NX manufactured by Shimadzu Corporation.
  • KS847T Silicone resin composition (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847T)
  • YSR3022 Silicone resin composition (YSR3022, manufactured by Momentive Performance Materials Japan, Inc.)
  • RX50 Silica filler (AEROSIL RX50, manufactured by Nippon Aerosil Co., Ltd., surface modification group: trimethylsilyl (TMS) group)
  • RY50 Silica filler (AEROSIL RY50, manufactured by Nippon Aerosil Co., Ltd., surface modification group: dimethylpolysiloxane (PDMS) group)
  • RX200 Silica filler (AEROSIL RX200, manufactured by Nippon Aerosil Co., Ltd., surface modification group: trimethylsilyl (TMS) group)
  • RY200 Silica filler (AEROSIL RX200, manufactured by Nippon Aerosil Co., Ltd., surface modification group: trimethylsilyl (TMS) group)
  • the pervaporation membranes of Examples 1 to 7 and 9 to 11 which have a matrix containing silicone resin and a filler containing silica, had a higher separation coefficient ⁇ for n-butanol from water than Example 8. From these results, it can be said that the pervaporation membranes of Examples 1 to 7 and 9 to 11 are suitable for separating volatile organic compounds from aqueous solutions containing the organic compounds. It can be seen from the results of Examples 1 to 3 and 8 to 11 that the addition of a filler containing silica increases the free volume of the silicone resin. Furthermore, it can be seen from the results of Examples 1 to 3 and 8 to 11 that the addition of a filler improves the adhesion between the separation functional layer and the porous support.
  • 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)
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  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
PCT/JP2023/032766 2022-09-26 2023-09-07 浸透気化膜 Ceased WO2024070575A1 (ja)

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JPS5895524A (ja) * 1981-11-30 1983-06-07 Kuraray Co Ltd 液−液分離膜
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
CN102188914A (zh) * 2011-04-07 2011-09-21 清华大学 一种优先透醇硅橡胶复合膜的制备方法
JP4899122B2 (ja) 2006-08-31 2012-03-21 独立行政法人産業技術総合研究所 有機化合物分離膜及び有機化合物分離方法
WO2021054368A1 (ja) * 2019-09-18 2021-03-25 日東電工株式会社 精製システム、精製方法、膜分離装置、及び溶剤の製造方法
WO2021124011A1 (en) * 2019-12-17 2021-06-24 3M Innovative Properties Company Articles including an isoporous membrane disposed on a porous substrate and methods of making the same

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JPS5895524A (ja) * 1981-11-30 1983-06-07 Kuraray Co Ltd 液−液分離膜
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
JP4899122B2 (ja) 2006-08-31 2012-03-21 独立行政法人産業技術総合研究所 有機化合物分離膜及び有機化合物分離方法
CN102188914A (zh) * 2011-04-07 2011-09-21 清华大学 一种优先透醇硅橡胶复合膜的制备方法
WO2021054368A1 (ja) * 2019-09-18 2021-03-25 日東電工株式会社 精製システム、精製方法、膜分離装置、及び溶剤の製造方法
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