WO2024014285A1 - Membrane de séparation et son procédé de fabrication - Google Patents

Membrane de séparation et son procédé de fabrication Download PDF

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Publication number
WO2024014285A1
WO2024014285A1 PCT/JP2023/023867 JP2023023867W WO2024014285A1 WO 2024014285 A1 WO2024014285 A1 WO 2024014285A1 JP 2023023867 W JP2023023867 W JP 2023023867W WO 2024014285 A1 WO2024014285 A1 WO 2024014285A1
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Prior art keywords
separation
separation membrane
functional layer
porous support
carbon dioxide
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PCT/JP2023/023867
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English (en)
Japanese (ja)
Inventor
俊亮 佐山
和也 吉村
伶哉 日野
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日東電工株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • 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
    • 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
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out

Definitions

  • the present invention relates to a separation membrane and a method for manufacturing the same.
  • Membrane separation methods have been developed as a method for separating acidic gases from mixed gases containing acidic gases such as carbon dioxide. Membrane separation methods can efficiently separate acidic gases while reducing operating costs, compared to absorption methods in which acidic gases contained in a gas mixture are absorbed by an absorbent and separated.
  • separation membranes used in membrane separation methods include composite membranes in which a separation functional layer is formed on a porous support.
  • the material for the separation functional layer include resins such as polyimide resin and polyether block amide resin.
  • Patent Document 1 discloses a separation membrane containing a polyimide resin.
  • the present invention a separation functional layer; a porous support directly in contact with the separation functional layer; Equipped with Each of the separation functional layer and the porous support contains polyimide,
  • the polyimide provides a separation membrane containing a structural unit derived from a tetracarboxylic dianhydride having a six-membered acid anhydride structure.
  • a new separation membrane suitable for separating acidic gas from a mixed gas containing acidic gas can be provided.
  • FIG. 1 is a cross-sectional view schematically showing a separation membrane according to an embodiment of the present invention.
  • FIG. 3 is a diagram for explaining a method for manufacturing a separation membrane.
  • FIG. 3 is a diagram for explaining a method for manufacturing a separation membrane.
  • 1 is a schematic cross-sectional view of a membrane separation device equipped with a separation membrane of the present invention.
  • FIG. 3 is a perspective view schematically showing a modified example of a membrane separation device equipped with the separation membrane of the present invention.
  • 1 is a scanning electron microscope (SEM) image of a cross section of the separation membrane of Example 1.
  • 3 is a SEM image of a cross section of the separation membrane of Example 2.
  • 3 is a SEM image of a cross section of the separation membrane of Example 3.
  • 3 is a SEM image of a cross section of the separation membrane of Example 4.
  • 3 is a SEM image of a cross section of the separation membrane of Example 5.
  • 3 is a SEM image of a cross section of the separation membrane of Example 6.
  • 3 is a SEM image of a cross section of the separation membrane of Example 7.
  • the separation membrane according to the first aspect of the present invention is a separation functional layer; a porous support directly in contact with the separation functional layer; Equipped with Each of the separation functional layer and the porous support contains polyimide,
  • the polyimide includes a structural unit derived from a tetracarboxylic dianhydride having a six-membered acid anhydride structure.
  • the porous support has continuous pores.
  • the separation functional layer and the porous support are integrated.
  • the material of the separation functional layer is the same as the material of the porous support.
  • the total thickness of the separation functional layer and the thickness of the porous support is 10 ⁇ m or more. It is.
  • the structural unit is represented by the following formula (A1).
  • R 1a to R 4a each independently represent a hydrogen atom or an arbitrary substituent.
  • a mixed gas consisting of carbon dioxide and nitrogen is supplied to a space adjacent to one surface of the separation membrane.
  • the permeation rate of carbon dioxide passing through the separation membrane is 100 GPU or more.
  • the concentration of carbon dioxide in the mixed gas is 50 vol% in a standard state, and the mixed gas supplied to the space adjacent to the one surface has a temperature of 30°C and a pressure of 0. 1 MPa, and the space adjacent to the other surface is reduced in pressure so that the pressure in the space is 0.1 MPa lower than the atmospheric pressure in the measurement environment.
  • a mixed gas consisting of carbon dioxide and nitrogen is supplied to a space adjacent to one surface of the separation membrane.
  • the separation coefficient ⁇ of carbon dioxide with respect to nitrogen is 20 or more.
  • the concentration of carbon dioxide in the mixed gas is 50 vol% in a standard state, and the mixed gas supplied to the space adjacent to the one surface has a temperature of 30°C and a pressure of 0. 1 MPa, and the space adjacent to the other surface is reduced in pressure so that the pressure in the space is 0.1 MPa lower than the atmospheric pressure in the measurement environment.
  • the method for manufacturing a separation membrane according to the ninth aspect of the present invention includes: Forming a coating film using a coating solution containing polyimide, a solvent, and a porosity agent; removing the porosity agent from the coating film; including.
  • the polyimide includes a structural unit derived from a tetracarboxylic dianhydride having a six-membered acid anhydride structure.
  • the boiling point of the porosity-forming agent is 50° C. or more higher than the boiling point of the solvent.
  • the porosity-forming agent includes at least one selected from the group consisting of an ether compound and a phosphoric acid compound. .
  • the solvent contains at least one selected from the group consisting of an amide compound and a lactone compound.
  • the coating film may be dried and/or the coating film may be washed with a cleaning liquid.
  • the porosity agent is removed from the coating film.
  • the separation membrane according to the fifteenth aspect of the present invention is A separation membrane comprising a separation functional layer and a porous support directly in contact with the separation functional layer,
  • the material of the separation functional layer is the same as the material of the porous support,
  • the total value of the thickness of the separation functional layer and the thickness of the porous support is 10 ⁇ m or more,
  • the concentration of carbon dioxide in the mixed gas is 50 vol% in a standard state
  • the mixed gas supplied to the space adjacent to the one surface has a temperature of 30°C and a pressure of 0. 1 MPa, and the space adjacent to the other surface is reduced in pressure so that the pressure in the space is 0.1 MPa lower than the atmospheric pressure in the measurement environment.
  • the separation membrane 10 of the present embodiment includes a separation functional layer 1 and a porous support 2, and is composed of only the separation functional layer 1 and the porous support 2, for example.
  • the porous support 2 is in direct contact with the separation functional layer 1 and supports the separation functional layer 1. It is preferable that the separation functional layer 1 and the porous support 2 are integrated. As used herein, "integrated" means that the members cannot be separated from each other non-destructively.
  • the separation functional layer 1 and the porous support 2 each contain polyimide.
  • the polyimide contained in the separation functional layer 1 is typically the same as the polyimide contained in the porous support 2.
  • the material of the separation functional layer 1 is preferably the same as the material of the porous support 2.
  • the separation membrane 10 may be made of only polyimide, or may be made of a single material.
  • the polyimide is typically a polyimide P containing a structural unit A1 derived from a tetracarboxylic dianhydride a1 having a six-membered acid anhydride structure S.
  • Polyimide P further includes a structural unit B derived from a diamine. Note that, depending on the case, each of the separation functional layer 1 and the porous support 2 may contain a polyimide other than polyimide P.
  • the structural unit A1 is a structural unit suitable for improving the permeation rate of acidic gas passing through the separation membrane 10.
  • Tetracarboxylic dianhydride a1 has, for example, one or more, preferably two, acid anhydride structures S.
  • the 6-membered acid anhydride structure S is typically a glutaric anhydride structure represented by the following formula (1).
  • the tetracarboxylic dianhydride a1 may have a condensed ring, and the condensed ring may include an acid anhydride structure S.
  • the condensed ring may include an aromatic ring together with the acid anhydride structure S.
  • the aromatic ring contained in the condensed ring may be composed only of carbon atoms, or may be a heteroaromatic ring containing heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms.
  • the aromatic ring may be polycyclic or monocyclic. The number of carbon atoms in the aromatic ring is not particularly limited, and is, for example, 4 to 14.
  • aromatic ring examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a furan ring, a pyrrole ring, a pyridine ring, and a thiophene ring.
  • the fused ring may or may not have a substituent.
  • Substituents on the condensed ring are not particularly limited, and include halogen groups, hydrocarbon groups, and the like.
  • the halogen group include a fluoro group, a chloro group, a bromo group, and an iodo group.
  • the number of carbon atoms in the hydrocarbon group is not particularly limited, and is, for example, 1 to 15.
  • the hydrocarbon group is, for example, an alkyl group such as a methyl group, an ethyl group, or a propyl group.
  • the hydrocarbon group may be a halogenated hydrocarbon group in which a hydrogen atom is substituted with a halogen group.
  • Tetracarboxylic dianhydride a1 is represented by the following formula (a1), for example.
  • R 1a to R 4a are each independently a hydrogen atom or an arbitrary substituent.
  • the optional substituents are not particularly limited, and include halogen groups, hydrocarbon groups, and the like. Examples of the halogen group and hydrocarbon group include those mentioned above.
  • the structural unit A1 derived from the tetracarboxylic dianhydride a1 is represented by the following formula (A1), for example.
  • the structural unit A1 represented by the formula (A1) is derived from the tetracarboxylic dianhydride a1 represented by the above formula (a1).
  • the nitrogen atom contained in the imide group originates from the diamine reacted with the tetracarboxylic dianhydride a1.
  • R 1a to R 4a are the same as in formula (a1) and independently represent a hydrogen atom or an arbitrary substituent.
  • a specific example of the structural unit A1 represented by the formula (A1) is the following formula (A1-1).
  • the ratio p1 of the amount of the above structural unit A1 to the amount of all the structural units A derived from tetracarboxylic dianhydride is, for example, 50 mol% or more, 70 mol% or more, 90 mol% or more , 95 mol% or more, or even 99 mol% or more.
  • Polyimide P may contain only the above structural unit A1 as the structural unit A derived from tetracarboxylic dianhydride. However, in addition to the structural unit A1, the polyimide P may further contain a structural unit A2 derived from a tetracarboxylic dianhydride a2 having a five-membered acid anhydride structure.
  • the tetracarboxylic dianhydride a2 is not particularly limited, and examples thereof include pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, and the like.
  • polyimide P further includes structural unit B derived from diamine.
  • Diamines are compounds with two primary amino groups.
  • the diamine may or may not contain a functional group other than the primary amino group. Examples of other functional groups include carboxyl groups, hydroxyl groups, thiol groups, and sulfonyl groups.
  • the diamine may have at least one functional group f selected from the group consisting of a carboxyl group, a hydroxyl group, and a thiol group.
  • the diamine may further have an aromatic ring.
  • the aromatic ring include those mentioned above for the tetracarboxylic dianhydride a1.
  • the substituent on the aromatic ring includes, for example, a primary amino group.
  • the aromatic ring may have a substituent other than the substituent containing the primary amino group, or may have no other substituent.
  • Other substituents are not particularly limited, and include groups containing the above functional group f, halogen groups, hydrocarbon groups, and the like.
  • the halogen group and hydrocarbon group include those mentioned above for the tetracarboxylic dianhydride a1.
  • other substituents may include a photopolymerizable functional group (for example, a vinyl group).
  • the diamine is represented by, for example, the following formula (b1), formula (b2), formula (b3), formula (b4), or formula (b5).
  • R 1b to R 30b are each independently a hydrogen atom or an arbitrary substituent.
  • the optional substituent include a group containing a functional group f, a halogen group, and a hydrocarbon group.
  • the halogen group and hydrocarbon group include those mentioned above for the tetracarboxylic dianhydride a1.
  • X 1 and X 2 are a single bond or an arbitrary linking group.
  • the optional linking group is, for example, a divalent hydrocarbon group.
  • the divalent hydrocarbon group include alkylene groups such as methylene group, ethylene group, propane-1,3-diyl group, and propane-2,2-diyl group.
  • the divalent hydrocarbon group may be a halogenated hydrocarbon group in which a hydrogen atom is substituted with a halogen group.
  • the divalent hydrocarbon group may further have an aromatic ring. Examples of the aromatic ring include those mentioned above for the tetracarboxylic dianhydride a1.
  • the divalent hydrocarbon group may be a fluorenediyl group.
  • X 1 and X 2 may contain a functional group such as an ether group or an ester group together with or in place of the divalent hydrocarbon group.
  • the structural unit B derived from diamine may have at least one functional group F selected from the group consisting of carboxyl groups, hydroxyl groups, thiol groups, and metal salts thereof.
  • the metal contained in the metal salt as the functional group F is not particularly limited, and includes, for example, Li, Na, K, Be, Mg, Ca, Ba, Sc, Y, Ti, Zr, V, Cr, Mo, and Mn. , Fe, Co, Ni, Cu, Ag, Zn, B, Al, Ga, In, Pb, etc.
  • the metal salt as functional group F the metal is specifically present as a cation.
  • the valence of this metal cation is, for example, 1 or more, preferably 2 or more, and more preferably 3 or more.
  • the structural unit B contains a metal salt as the functional group F
  • a plurality of polyimides P can be coordinated to the metal cation contained in the metal salt via a functional group such as a carboxyl group.
  • the plurality of polyimides P are crosslinked with each other via the metal cations. Formation of such a crosslinked structure suppresses physical aging of the polyimide P, which tends to suppress deterioration of the separation performance of the separation functional layer 1 over time.
  • the polyimide P contains a metal salt as the functional group F
  • the separation performance of the separation functional layer 1 also tends to improve.
  • the metal salt as the functional group F is, for example, a functional group f contained in a polyimide P obtained from a monomer group containing tetracarboxylic dianhydride a1 and a diamine, by exchanging a dissociative proton with a metal cation.
  • a functional group f contained in a polyimide P obtained from a monomer group containing tetracarboxylic dianhydride a1 and a diamine by exchanging a dissociative proton with a metal cation.
  • the structural unit B derived from diamine is represented by, for example, the following formula (B1), formula (B2), formula (B3), formula (B4), or formula (B5).
  • the structural units B represented by formulas (B1) to (B5) are derived from diamines represented by formulas (b1) to (b5) above, respectively.
  • R 1b to R 4b are each independently a hydrogen atom or an arbitrary substituent.
  • the arbitrary substituent is, for example, a group containing the above-mentioned functional group F, a halogen group, a hydrocarbon group, or the like. Examples of the halogen group and hydrocarbon group include those mentioned above for the tetracarboxylic dianhydride a1.
  • R 5b to R 8b are each independently a hydrogen atom or an arbitrary substituent.
  • arbitrary substituents include, for example, a group containing a functional group F, a halogen group, a hydrocarbon group, and the like.
  • the halogen group and hydrocarbon group include those mentioned above for the tetracarboxylic dianhydride a1.
  • a specific example of the structural unit B represented by formula (B2) is the following formula (B2-1).
  • R 9b to R 16b are each independently a hydrogen atom or an arbitrary substituent, and X 1 is a single bond or an arbitrary linking group.
  • arbitrary substituents include, for example, a group containing a functional group F, a halogen group, a hydrocarbon group, and the like. Examples of the halogen group and hydrocarbon group include those mentioned above for the tetracarboxylic dianhydride a1.
  • the arbitrary linking group is, for example, a divalent hydrocarbon group.
  • the divalent hydrocarbon group include those mentioned above.
  • X 1 may contain a functional group such as an ether group or an ester group together with or in place of the divalent hydrocarbon group.
  • R 17b to R 24b are each independently a hydrogen atom or an arbitrary substituent, and X 2 is a single bond or an arbitrary linking group.
  • arbitrary substituents include, for example, a group containing a functional group F, a halogen group, a hydrocarbon group, and the like. Examples of the halogen group and hydrocarbon group include those mentioned above for the tetracarboxylic dianhydride a1.
  • the arbitrary linking group is, for example, a divalent hydrocarbon group.
  • the divalent hydrocarbon group include those mentioned above.
  • X 2 may contain a functional group such as an ether group or an ester group together with or in place of the divalent hydrocarbon group.
  • R 25b to R 30b are each independently a hydrogen atom or an arbitrary substituent.
  • the arbitrary substituent is, for example, a group containing a functional group F, a halogen group, a hydrocarbon group, or the like. Examples of the halogen group and hydrocarbon group include those mentioned above for the tetracarboxylic dianhydride a1.
  • the structural unit B represented by formula (B5) is suitable for improving the rigidity of the polyimide P. Polyimide P, which has excellent rigidity, tends to suppress plasticization of the separation membrane 10 even when the pressure of the gas mixture to be separated is high.
  • structural unit B represented by the formula (B5) include the following formulas (B5-1) to (B5-2).
  • polyimide P structural units A derived from tetracarboxylic dianhydride and structural units B derived from diamine are arranged alternately.
  • examples of combinations of adjacent structural units A and B include the following formulas (A1-B1) and (A1-B5).
  • R 1a to R 4a , R 1b to R 4b , and R 25b to R 30b are the same as those described above for formula (A1), formula (B1), and formula (B5). .
  • the weight average molecular weight (Mw) of the polyimide P is, for example, 30,000 or more, preferably 50,000 or more, and more preferably 75,000 or more, from the viewpoint of the mechanical strength of the separation membrane 10.
  • the upper limit of the weight average molecular weight of polyimide P is not particularly limited, and is, for example, 1 million.
  • the weight average molecular weight of polyimide P can be determined by measuring the molecular weight distribution of polyimide P using, for example, a gel permeation chromatograph (GPC) equipped with a differential refractive index detector (RID), and from the obtained chromatogram (chart). It can be calculated using a standard polystyrene calibration curve.
  • GPC gel permeation chromatograph
  • RID differential refractive index detector
  • Polyimide P can be produced, for example, by the following method. First, diamine is dissolved in a solvent to obtain a solution.
  • the solvent include polar organic solvents such as N-methyl-2-pyrrolidone and 1,3-dioxolane.
  • the tetracarboxylic dianhydride group containing the above-mentioned tetracarboxylic dianhydride a1 is gradually added to the obtained solution.
  • the monomer group containing the tetracarboxylic dianhydride a1 and the diamine react to form a polyamic acid.
  • the addition of the tetracarboxylic dianhydride group is carried out, for example, under stirring conditions in a heating environment of 140° C. or higher for 3 to 20 hours.
  • polyimide P can be obtained by imidizing the polyamic acid.
  • the imidization method include a chemical imidization method and a thermal imidization method.
  • the chemical imidization method is a method of imidizing polyamic acid using a dehydration condensation agent, for example, under room temperature conditions.
  • Examples of the dehydration condensation agent include acetic anhydride, pyridine, and triethylamine.
  • the thermal imidization method is a method of imidizing polyamic acid by heat treatment. The temperature of the heat treatment is, for example, 180° C. or higher.
  • the separation functional layer 1 is, for example, a layer that can preferentially transmit acidic gas contained in a mixed gas, and is typically observed at a magnification of 5000 times using a scanning electron microscope (SEM). It is a dense layer (non-porous layer) in which no pores can be seen.
  • SEM scanning electron microscope
  • the content of polyimide in the separation functional layer 1 is, for example, 50 wt% or more, and may be 60 wt% or more, 70 wt% or more, 80 wt% or more, 90 wt% or more, or even 95 wt% or more.
  • the separation functional layer 1 may be substantially composed only of polyimide.
  • the thickness of the separation functional layer 1 is, for example, 50 ⁇ m or less, and may be 25 ⁇ m or less, 15 ⁇ m or less, 10 ⁇ m or less, 8 ⁇ m or less, 5 ⁇ m or less, 3 ⁇ m or less, or even 1 ⁇ m or less.
  • the lower limit of the thickness of the separation functional layer 1 may be 0.05 ⁇ m or 0.1 ⁇ m.
  • the thickness of the separation functional layer 1 can be determined by the following method. First, a cross section of the separation membrane 10 is observed using a scanning electron microscope. Using the obtained electron microscope image, the distance between a pair of mutually opposing principal surfaces of the separation functional layer 1 is measured at a plurality of arbitrary points (at least four points). The average value of the obtained values can be regarded as the thickness of the separation functional layer 1.
  • the porous support 2 is in direct contact with the separation functional layer 1 and supports the separation functional layer 1.
  • the porous support 2 has a porous structure. From the viewpoint of improving the permeability coefficient and permeation rate of acidic gases passing through the separation membrane 10, it is preferable that the porous support 2 has continuous pores that are continuously formed in a three-dimensional shape. However, the porous support 2 may have independent pores, or may have both continuous pores and independent pores. The porous support 2 may have through holes passing through the porous support 2.
  • the content of polyimide in the porous support 2 is, for example, 50 wt% or more, and may be 60 wt% or more, 70 wt% or more, 80 wt% or more, 90 wt% or more, or even 95 wt% or more.
  • the porous support 2 may be substantially composed only of polyimide.
  • the polyimide content in the porous support 2 may be the same as the polyimide content in the separation functional layer 1.
  • the thickness of the porous support 2 is, for example, 10 ⁇ m or more, and may be 20 ⁇ m or more, 30 ⁇ m or more, 40 ⁇ m or more, or even 50 ⁇ m or more.
  • the upper limit of the thickness of the porous support 2 may be 300 ⁇ m or 100 ⁇ m.
  • the thickness of the porous support 2 can be determined by the method described above for the separation functional layer 1.
  • the total value V of the thickness of the separation functional layer 1 and the thickness of the porous support 2 is, for example, 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, It may be 40 ⁇ m or more, 50 ⁇ m or more, or even 60 ⁇ m or more.
  • the upper limit of the total value V may be 300 ⁇ m or 100 ⁇ m.
  • the method for manufacturing the separation membrane 10 includes, for example, forming a coating film 6 using a coating liquid L containing polyimide, a solvent, and a porosity-forming agent, and forming a porous film from the coating film 6. and removing the agent.
  • the coating liquid L can be prepared, for example, by mixing polyimide, a solvent, and a porosity-forming agent.
  • the polyimide is typically the above-mentioned polyimide P containing a structural unit A1 derived from a tetracarboxylic dianhydride a1 having a six-membered acid anhydride structure S.
  • polyimide P is more easily dissolved in a solvent than other polyimides, and is therefore suitable for the manufacturing method of this embodiment.
  • the content of polyimide in the coating liquid L can be adjusted as appropriate depending on the solubility of the polyimide, and is, for example, 1 wt% to 30 wt%.
  • the solvent is typically a good solvent that can dissolve the polyimide.
  • the solvent preferably contains at least one selected from the group consisting of an amide compound and a lactone compound, and more preferably an amide compound.
  • the amide compound include N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), and N,N-dimethylacetamide (DMAc).
  • the lactone compound include ⁇ -butyrolactone.
  • the boiling point of the solvent is not particularly limited, and is, for example, 100°C to 250°C.
  • the content of the solvent in the coating liquid L is, for example, 30 wt% to 95 wt%.
  • the porosity agent is typically a poor solvent that hardly dissolves polyimide P.
  • the pore forming agent preferably contains at least one selected from the group consisting of an ether compound and a phosphoric acid compound, and more preferably contains an ether compound.
  • ether compounds include diethylene glycol, diethylene glycol monomethyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol, tetraethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, and tripropylene.
  • glycol compounds such as glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, and polyethylene glycol.
  • Examples of the phosphoric acid compound include phosphoric ester compounds such as trimethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, and triethyl phosphate.
  • the boiling point of the porosity-forming agent is preferably higher than the boiling point of the solvent.
  • the boiling point of the pore-forming agent may be, for example, 50°C or more higher than the boiling point of the solvent, 80°C or more, or even 100°C or more higher.
  • the boiling point of the pore-forming agent is, for example, 200°C to 350°C.
  • the content of the porosity agent in the coating liquid L is, for example, 10 wt% to 50 wt%.
  • the content of the porosity-forming agent is preferably higher than the content of polyimide.
  • the coating film 6 can be formed, for example, by applying the coating liquid L onto the base material 5 (FIG. 2A).
  • Substrate 5 is typically a release liner.
  • the release liner include a film containing resin; paper; and a sheet containing a metal material such as aluminum or stainless steel. Sheets containing metallic materials tend to have high heat resistance.
  • the release liner is preferably a film containing resin from the viewpoint of excellent surface smoothness.
  • the polymers 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; ethylene-vinyl acetate copolymer, etc., and polyester, particularly polyethylene terephthalate, is preferred.
  • 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
  • ethylene-vinyl acetate copolymer etc.
  • polyester particularly polyethylene terephthalate
  • the surface of the release liner may be subjected to release treatment.
  • the release treatment can be performed, for example, by applying a release treatment agent to the surface of the release liner.
  • the release agent include a silicone release agent, a long-chain alkyl release agent, a fluorine release agent, and a molybdenum sulfide release agent.
  • the release agent may be used alone or in combination of two or more.
  • the release liner is preferably a release-treated polyethylene terephthalate (PET) film.
  • the thickness of the base material 5 is not particularly limited, and is, for example, 5 to 100 ⁇ m, preferably 10 to 50 ⁇ m.
  • the method of applying the coating liquid L to the substrate 5 is not particularly limited, and for example, a spin coating method, a dip coating method, etc. can be used.
  • the coating liquid L may be applied to the base material 5 using an applicator, a wire bar, or the like.
  • pores are formed due to the porosity-forming agent, and a dense layer (skin layer) is formed near the surface of the coating film 6 that is exposed to the outside.
  • a porous support 2 having pores caused by the porosity-forming agent and a separation functional layer 1 corresponding to a skin layer are formed (FIG. 2B).
  • the porosity agent is removed from the coating film 6 so that the separation functional layer 1 and the porous support 2 are formed from the coating film 6.
  • the porosity agent can be removed from the coating film 6 by, for example, drying the coating film 6 and/or washing the coating film 6 with a cleaning liquid.
  • drying the coating film 6 the drying temperature is, for example, 50° C. to 300° C., and the drying time is, for example, 1 to 20 hours.
  • the coating film 6 may be dried in a reduced pressure atmosphere or a vacuum atmosphere.
  • the coating film 6 When cleaning the coating film 6 with a cleaning liquid, it is preferable to use a cleaning liquid that has high compatibility with the porosity-forming agent.
  • a cleaning liquid for example, water or alcohol such as methanol can be used.
  • the coating film 6 may be cleaned by immersing the coating film 6 in a cleaning liquid.
  • the solvent when removing the porosity agent from the coating film 6, the solvent is also removed from the coating film 6.
  • the solvent before removing the porosity agent from the coating film 6, the solvent may be removed from the coating film 6 in advance.
  • the solvent can be removed from the coating film 6 in advance by pre-drying the coating film 6.
  • the pre-drying conditions are, for example, a temperature of 50° C. to 150° C. and a time of 10 minutes to 5 hours.
  • the base material 5 is removed from the laminate of the separation functional layer 1 and the porous support 2. Thereby, the separation membrane 10 can be obtained.
  • Conventional methods for producing separation membranes include a direct method in which a coating solution containing a material for the separation functional layer is applied onto a porous support and the resulting coating film is dried to form a separation functional layer; Examples include a transfer method in which a separation functional layer formed on a base material is transferred to a porous support.
  • the separation functional layer 1 and the porous support 2 are manufactured by removing the porosity agent and the solvent from the coating film 6. That is, in the manufacturing method of this embodiment, the porous support 2 does not come into contact with the solvent originating from the coating film 6 after the porous support 2 is formed. Therefore, the separation membrane 10 produced by the production method of this embodiment tends to have higher separation performance than a separation membrane produced by a direct method.
  • the transfer method for example, when a thin separation functional layer with a thickness of about 1 ⁇ m or less is transferred to a porous support, defects are likely to occur in the separation functional layer. Furthermore, since the surface of the separation functional layer is in contact with the base material before transfer, impurities derived from the base material may adhere to the surface of the separation functional layer, which may reduce the separation performance. In contrast, in the manufacturing method of this embodiment, since there is no transfer operation, defects are less likely to occur in the separation functional layer 1. In addition, in the manufacturing method of the present embodiment, the separation functional layer 1 is usually formed near the surface of the coating film 6 on the opposite side to the surface of the coating film 6 that is in contact with the base material 5. Also, impurities derived from the base material 5 tend to be less likely to adhere.
  • Japanese Patent No. 4947989 discloses a method in which a porous film containing a polyimide precursor (polyamic acid) is produced and then polyimide is formed from the precursor by a thermal imidization method.
  • the porous film tends to shrink and deform due to the heat treatment of the thermal imidization method.
  • the coating liquid L containing polyimide since the coating liquid L containing polyimide is used, there is no need to perform thermal imidization on the coating film 6, etc., and the separation film of the desired shape and thickness is formed. 10 can be easily produced.
  • the separation membrane 10 is typically a flat membrane.
  • the separation membrane 10 may have a shape other than a flat membrane, for example, may be a hollow fiber membrane.
  • the separation membrane 10 of this embodiment tends to have high separation performance against acidic gases due to the separation functional layer 1 and the porous support 2.
  • the separation performance of the separation membrane 10 against acidic gas tends to improve.
  • the permeation rate T of carbon dioxide passing through the separation membrane 10 is, for example, 100 GPU or more, and may be 200 GPU or more, 300 GPU or more, 400 GPU or more, 500 GPU or more, or even 1000 GPU or more.
  • the upper limit of the transmission rate T is not particularly limited, and is, for example, 5000 GPU.
  • GPU means 10 ⁇ 6 ⁇ cm 3 (STP)/(sec ⁇ cm 2 ⁇ cmHg).
  • cm 3 (STP) means the volume of carbon dioxide at 1 atmosphere and 0°C.
  • the permeation rate T can be calculated by the following method. First, a mixed gas consisting of carbon dioxide and nitrogen is supplied to a space adjacent to one surface of the separation membrane 10 (for example, the main surface 11 on the separation functional layer side of the separation membrane 10), and the other surface of the separation membrane 10 is supplied with a gas mixture consisting of carbon dioxide and nitrogen. (For example, the space adjacent to the main surface 12 of the separation membrane 10 on the porous support side) is depressurized. Thereby, a permeated fluid that has passed through the separation membrane 10 is obtained. The weight of the permeate fluid and the volume proportions of carbon dioxide and nitrogen in the permeate fluid are determined. The transmission rate T can be calculated from the measurement results.
  • the concentration of carbon dioxide in the mixed gas is 50 vol% under standard conditions (0° C., 101 kPa).
  • the mixed gas supplied to the space adjacent to one surface of the separation membrane 10 has a temperature of 30° C. and a pressure of 0.1 MPa.
  • the space adjacent to the other surface of the separation membrane 10 is reduced in pressure so that the pressure in the space is 0.1 MPa lower than the atmospheric pressure in the measurement environment.
  • the separation coefficient ⁇ of carbon dioxide to nitrogen of the separation membrane 10 is not particularly limited, and may be, for example, 20 or more, 25 or more, 30 or more, or even 35 or more. .
  • the upper limit of the separation coefficient ⁇ is not particularly limited, and is, for example, 50.
  • the material of the separation functional layer is the same as the material of the porous support, and the total thickness of the separation functional layer and the porous support is 10 ⁇ m or more.
  • a separation membrane having a permeation rate T of 100 GPU or more and a separation coefficient ⁇ of 20 or more has not been known so far.
  • a separation membrane 10 comprising a separation functional layer 1 and a porous support 2 in direct contact with the separation functional layer 1,
  • the material of the separation functional layer 1 is the same as the material of the porous support 2,
  • the total value of the thickness of the separation functional layer 1 and the thickness of the porous support 2 is 10 ⁇ m or more,
  • the permeability coefficient C1 of carbon dioxide in consideration of the thickness of the separation functional layer 1 is, for example, 100 Barrer or more, 500 Barrer or more, 1000 Barrer or more, 1500 Barrer or more, 2000 Barrer or more, and even It may be 2500 Barrer or more.
  • the upper limit of the transmission coefficient C1 is not particularly limited, and is, for example, 5000 Barrer.
  • Barrer means 10 ⁇ 10 ⁇ cm 3 (STP) ⁇ cm/(sec ⁇ cm 2 ⁇ cmHg).
  • the transmission coefficient C1 (Barrer) is a value obtained by multiplying the transmission rate T (GPU) by the thickness ( ⁇ m) of the separation functional layer 1.
  • the above permeability coefficient C1 is approximately the same as the permeability coefficient C2 of carbon dioxide in the self-supporting membrane (single-layer membrane) of the separation functional layer 1.
  • the permeability coefficient C2 can be measured by the same method as the permeability coefficient C1, except that a self-supporting membrane of the separation functional layer 1 is used instead of the separation membrane 10.
  • the self-supporting membrane of the separation functional layer 1 can be produced, for example, by a method similar to the method for producing the separation membrane 10 described above, except that no porosity agent is used.
  • the rate of change R of the transmission coefficient calculated by the following formula (I) is, for example, -90% to 90%, preferably -50% to 50%, and -30% to 30%. Good too.
  • the rate of change R may be 0% or less.
  • the rate of change R tends to be adjusted to -50% or more.
  • the rate of change R tends to be less than -50%. Note that if the rate of change R exceeds 0% and the value of the above-mentioned separation coefficient ⁇ is very small, there is a possibility that a defect exists in the separation functional layer 1 included in the separation membrane 10.
  • Rate of change R 100 x (transmission coefficient C1 - transmission coefficient C2) / transmission coefficient C2 (I)
  • Applications of the separation membrane 10 of this embodiment include applications for separating acidic gas from a mixed gas containing acidic gas.
  • the mixed acidic gas include carbon dioxide, hydrogen sulfide, carbonyl sulfide, sulfur oxides (SOx), hydrogen cyanide, and nitrogen oxides (NOx), with carbon dioxide being preferred.
  • the mixed gas contains gases other than acidic gas.
  • gases include, for example, nonpolar gases such as hydrogen and nitrogen, and inert gases such as helium, with nitrogen being preferred.
  • the separation membrane 10 of this embodiment is suitable for use in separating carbon dioxide from a mixed gas containing carbon dioxide and nitrogen.
  • the use of the separation membrane 10 is not limited to the use of separating acidic gas from the above-mentioned mixed gas.
  • the membrane separation apparatus 100 of this embodiment includes a separation membrane 10 and a tank 20.
  • the tank 20 includes a first chamber 21 and a second chamber 22.
  • Separation membrane 10 is arranged inside tank 20. Inside the tank 20, the separation membrane 10 separates a first chamber 21 and a second chamber 22.
  • the separation membrane 10 extends from one of the pair of wall surfaces of the tank 20 to the other.
  • the first chamber 21 has an inlet 21a and an outlet 21b.
  • the second chamber 22 has an outlet 22a.
  • Each of the inlet 21a, the outlet 21b, and the outlet 22a is an opening formed in the wall surface of the tank 20, for example.
  • Membrane separation using the membrane separation device 100 is performed, for example, by the following method.
  • a mixed gas 30 containing an acidic gas is supplied to the first chamber 21 through the inlet 21a.
  • the concentration of acidic gas in the mixed gas 30 is not particularly limited, and in a standard state is, for example, 0.01 vol% (100 ppm) or more, preferably 1 vol% or more, more preferably 10 vol% or more, and even more preferably is 30 vol% or more, particularly preferably 50 vol% or more.
  • the upper limit of the concentration of acidic gas in the mixed gas 30 is not particularly limited, and is, for example, 90 vol% in a standard state.
  • the pressure inside the first chamber 21 may be increased by supplying the mixed gas 30.
  • the membrane separator 100 may further include a pump (not shown) for pressurizing the mixed gas 30.
  • the pressure of the mixed gas 30 supplied to the first chamber 21 is, for example, 0.1 MPa or more, preferably 0.3 MPa or more.
  • the pressure inside the second chamber 22 may be reduced while the mixed gas 30 is supplied to the first chamber 21.
  • the membrane separator 100 may further include a pump (not shown) for reducing the pressure inside the second chamber 22.
  • the pressure in the second chamber 22 may be reduced so that the space within the second chamber 22 is, for example, 10 kPa or more, preferably 50 kPa or more, more preferably 100 kPa or more smaller than the atmospheric pressure in the measurement environment.
  • the permeate fluid 35 By supplying the mixed gas 30 into the first chamber 21, it is possible to obtain a permeate fluid 35 having a higher content of acidic gas than the mixed gas 30 on the other side of the separation membrane 10. That is, the permeate fluid 35 is supplied to the second chamber 22 .
  • the permeate fluid 35 contains, for example, acidic gas as a main component. However, the permeate fluid 35 may contain a small amount of gas other than acidic gas. Permeate fluid 35 is discharged to the outside of tank 20 through outlet 22a.
  • the concentration of acidic gas in the mixed gas 30 gradually decreases from the inlet 21a of the first chamber 21 toward the outlet 21b.
  • the mixed gas 30 (non-permeable fluid 36) treated in the first chamber 21 is discharged to the outside of the tank 20 through the outlet 21b.
  • the membrane separation apparatus 100 of this embodiment is suitable for a flow type (continuous type) membrane separation method.
  • the membrane separation apparatus 100 of this embodiment may be used in a batch-type membrane separation method.
  • the membrane separation device 100 may be a spiral membrane element, a hollow fiber membrane element, or the like.
  • Figure 4 shows a spiral-shaped membrane element.
  • the membrane separation device 110 in FIG. 4 includes a central tube 41 and a stacked body 42.
  • the laminate 42 includes the separation membrane 10.
  • the central tube 41 has a cylindrical shape. A plurality of holes are formed on the surface of the center tube 41 to allow the permeate fluid 35 to flow into the center tube 41 .
  • Examples of materials for the center tube 41 include resins such as acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polyphenylene ether resin (PPE resin), and polysulfone resin (PSF resin); metals such as stainless steel and titanium. It will be done.
  • the inner diameter of the central tube 41 is, for example, in the range of 20 to 100 mm.
  • the laminate 42 further includes a supply side channel material 43 and a permeate side channel material 44.
  • the laminate 42 is wound around the central tube 41.
  • the membrane separation device 110 may further include an exterior material (not shown).
  • a resin net made of polyphenylene sulfide (PPS) or ethylene-chlorotrifluoroethylene copolymer (ECTFE) can be used.
  • Membrane separation using the membrane separation device 110 is performed, for example, by the following method.
  • the permeated fluid 35 that has passed through the separation membrane 10 of the laminate 42 moves into the center tube 41 .
  • the permeate fluid 35 is discharged to the outside through the central pipe 41.
  • the mixed gas 30 (non-permeable fluid 36) processed by the membrane separator 110 is discharged to the outside from the other end of the wound stack 42. Thereby, the acidic gas can be separated from the mixed gas 30.
  • Example 1 Polyimide was synthesized using an automatic polymerization device (manufactured by METTLER TOLEDO, EasyMax402).
  • a separable flask (volume 400 mL) attached to the apparatus was equipped with a Dimroth, stirring rod, internal thermometer, nitrogen inlet tube, and flat stopper.
  • a coolant set at 10°C was circulated through the Dimroth chiller.
  • N 2 gas was passed through the flask at a flow rate of 100 mL/min.
  • the stirring speed was set at 300 rpm.
  • naphthalene-1,4,5,8-tetracarboxylic dianhydride NTDA
  • 9.11 g (75 mmol) of benzoic acid were further added as tetracarboxylic dianhydride.
  • the jacket temperature of the apparatus was raised to 180°C and stirred for 8 hours. At this time, the internal temperature of the flask was 172 to 175°C. After stirring, the internal temperature of the flask was cooled to 25° C. and left overnight.
  • polyimide, N,N-dimethylformamide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a solvent, and polyethylene glycol monomethyl ether 400 (manufactured by NOF Corporation) as a porosity agent were added in the weight ratios shown in Table 1. Added to a cup with a lid. Next, the obtained mixture was stirred for 25 minutes at 2000 rpm using a stirring device (Awatori Rentaro manufactured by Thinky), and further defoamed for 5 minutes at 2200 rpm. As a result, a coating liquid in which the polyimide was uniformly dissolved in the solvent was obtained.
  • a coating liquid was applied onto a base material (75SG2 manufactured by Panac) to form a coating film with a thickness of 300 ⁇ m.
  • the coating film was dried at 60° C. for 30 minutes using an oven. The coated film was once taken out of the oven and further dried at 130° C. for 30 minutes.
  • the coating film was peeled off from the base material and immersed in methanol for 30 minutes. As a result, the porosity-forming agent was removed from the coating film, and a separation functional layer and a porous support were formed.
  • the separation membrane of Example 1 was obtained by vacuum drying at 60° C. for 1 hour and further drying at 300° C. for 30 minutes.
  • the thicknesses of the separation functional layer and porous support were determined by the method described above.
  • a gas permeation test was conducted on the separation membrane produced in the example by the following method. First, a separation membrane was set in a metal cell and sealed with an O-ring to prevent leakage. Next, the mixed gas was injected into the metal cell so that the mixed gas came into contact with the main surface of the separation membrane on the separation functional layer side.
  • the gas mixture consisted essentially of carbon dioxide and nitrogen. The concentration of carbon dioxide in the gas mixture was 50 vol% under standard conditions.
  • the mixed gas injected into the metal cell had a temperature of 30° C. and a pressure of 0.1 MPa. Next, the pressure in the space (permeation side space) in the metal cell adjacent to the main surface of the separation membrane on the porous support side was reduced using a vacuum pump.
  • the pressure in the permeation side space was reduced so that the pressure in the space was 0.1 MPa lower than the atmospheric pressure in the measurement environment.
  • a permeate fluid was obtained from the main surface of the separation membrane on the porous support side. Based on the composition of the obtained permeate fluid, the weight of the permeate fluid, etc., the permeation rate T of carbon dioxide, the separation coefficient ⁇ of carbon dioxide with respect to nitrogen ⁇ (CO 2 /N 2 ), and the permeation coefficient C1 of carbon dioxide were calculated. .
  • the permeability coefficient C2 of carbon dioxide in the separation functional layer was determined.
  • the transmission coefficient C2 was 1743 Barrer.
  • the rate of change R of the transmission coefficient was calculated using the above formula (I).
  • the separation membrane of the example has high values for both the carbon dioxide permeation rate T and the carbon dioxide separation coefficient ⁇ , and is suitable for separating acidic gas from a mixed gas containing acidic gas. I can say that there is. From the results of Examples 1 to 7, it can be seen that when the porous support has continuous pores, the rate of change R of the permeability coefficient tends to be a relatively high value.
  • the separation membrane of this embodiment is suitable for separating acidic gas from a mixed gas containing acidic gas.
  • the separation membrane of this embodiment is suitable for separating carbon dioxide from off-gas of chemical plants or thermal power generation.

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Abstract

La présente invention concerne une nouvelle membrane de séparation qui est appropriée pour séparer un gaz acide d'un mélange gazeux contenant le gaz acide. Une membrane de séparation (10) selon la présente invention est pourvue d'une couche à fonction de séparation (1) et d'un support poreux (2) qui est en contact direct avec la couche à fonction de séparation (1). La couche à fonction de séparation (1) et le support poreux (2) contiennent chacun un polyimide. Le polyimide comprend une unité structurale (A1) dérivée d'un dianhydride tétracarboxylique (a1) qui présente une structure d'anhydride d'acide S ayant un cycle à six chaînons. Par exemple, le support poreux (2) présente des trous continus.
PCT/JP2023/023867 2022-07-15 2023-06-27 Membrane de séparation et son procédé de fabrication WO2024014285A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002355938A (ja) * 2001-05-30 2002-12-10 Tonen Chem Corp 複合膜、その製造方法及びそれを用いた電池用セパレータ又はフィルター
JP2003236352A (ja) * 2002-02-15 2003-08-26 Ube Ind Ltd 新規分離膜およびその製造方法
JP2008086903A (ja) * 2006-10-02 2008-04-17 Ube Ind Ltd Ｓｉ原子含有ポリイミドによって形成された非対称膜、ガス分離膜、及びガス分離方法
JP2013530820A (ja) * 2010-05-13 2013-08-01 エア プロダクツ アンド ケミカルズ インコーポレイテッド ポリマー、ポリマー膜及びその製造方法
JP2014184424A (ja) * 2012-09-25 2014-10-02 Ube Ind Ltd 非対称中空糸ガス分離膜、及びガス分離方法
CN108043232A (zh) * 2017-12-06 2018-05-18 上海交通大学 一种六元环聚酰亚胺共聚物分离膜及其制备方法和用途
JP2020084155A (ja) * 2018-11-30 2020-06-04 ダイキン工業株式会社 樹脂組成物、樹脂膜及び気体透過膜

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002355938A (ja) * 2001-05-30 2002-12-10 Tonen Chem Corp 複合膜、その製造方法及びそれを用いた電池用セパレータ又はフィルター
JP2003236352A (ja) * 2002-02-15 2003-08-26 Ube Ind Ltd 新規分離膜およびその製造方法
JP2008086903A (ja) * 2006-10-02 2008-04-17 Ube Ind Ltd Ｓｉ原子含有ポリイミドによって形成された非対称膜、ガス分離膜、及びガス分離方法
JP2013530820A (ja) * 2010-05-13 2013-08-01 エア プロダクツ アンド ケミカルズ インコーポレイテッド ポリマー、ポリマー膜及びその製造方法
JP2014184424A (ja) * 2012-09-25 2014-10-02 Ube Ind Ltd 非対称中空糸ガス分離膜、及びガス分離方法
CN108043232A (zh) * 2017-12-06 2018-05-18 上海交通大学 一种六元环聚酰亚胺共聚物分离膜及其制备方法和用途
JP2020084155A (ja) * 2018-11-30 2020-06-04 ダイキン工業株式会社 樹脂組成物、樹脂膜及び気体透過膜

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