WO2020241565A1 - Composition, membrane de séparation de gaz et son procédé de production, et dispositif de séparation de gaz - Google Patents

Composition, membrane de séparation de gaz et son procédé de production, et dispositif de séparation de gaz Download PDF

Info

Publication number
WO2020241565A1
WO2020241565A1 PCT/JP2020/020533 JP2020020533W WO2020241565A1 WO 2020241565 A1 WO2020241565 A1 WO 2020241565A1 JP 2020020533 W JP2020020533 W JP 2020020533W WO 2020241565 A1 WO2020241565 A1 WO 2020241565A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
gas separation
separation membrane
acid
permeation
Prior art date
Application number
PCT/JP2020/020533
Other languages
English (en)
Japanese (ja)
Inventor
健祐 川良
史哲 松岡
亜由美 青木
Original Assignee
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Publication of WO2020241565A1 publication Critical patent/WO2020241565A1/fr

Links

Images

Classifications

    • 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
    • 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
    • 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
    • B01D69/1213—Laminated layers
    • 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
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • 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
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B01D71/381—Polyvinylalcohol
    • 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
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • 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
    • 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
    • B01D71/60—Polyamines
    • 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
    • B01D71/60—Polyamines
    • B01D71/601—Polyethylenimine
    • 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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the present invention relates to a composition, a gas separation membrane using this composition, a method for producing the same, and a gas separation device provided with the gas separation membrane.
  • Polymer membranes using polymeric compounds are known to be used for the selective separation of specific components contained in fluids such as liquids, gases, solids and mixtures containing at least two of them.
  • fluids such as liquids, gases, solids and mixtures containing at least two of them.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2001-517711
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2010-202872
  • Patent Document 3 describe polymers for forming a separation membrane for separating CO 2 gas from a gas mixture. It is described that a composition containing the above is used.
  • the present invention provides a composition, a gas separation membrane and a method for producing the same, and a gas separation device for providing a gas separation membrane having high gas permeation performance and excellent durability.
  • the present invention provides the following compositions, gas separation membranes, gas separation devices, and methods for producing gas separation membranes.
  • the alkali metal element contained in the alkali metal compound contains at least one of rubidium and cesium.
  • the ratio (NC / NB) of the number of nitrogen atoms (NB) [mol] contained in the total amount of the basic polymer to the number of nitrogen atoms (NC) [mol] contained in the total amount of the amino acids is 0.1 or more.
  • the hydrophilic resin is poly (meth) acrylic acid, polyvinyl alcohol, vinyl alcohol- (meth) acrylic acid copolymer, alkylaldehyde modified product of polyvinyl alcohol, polyethylene oxide having a hydroxyl group at the main chain terminal, and main components. It is selected from the group consisting of polypropylene oxide having a hydroxyl group at the end of the chain, ethylene oxide-propylene oxide copolymer having a hydroxyl group at the end of the main chain, polyvinyl sulfonic acid, polystyrene sulfonic acid, polyvinyl pyrrolidone, and polyhydroxyalkyl (meth) acrylate.
  • the composition according to [1] which is at least one kind.
  • the basic polymer is polyallylamine, polyvinylamine, polyamidine, polyimidazoline, dicyandiamide-based condensate, polydialylamine, vinylamine-vinyl alcohol copolymer, polyethyleneimine, ethylene oxide adduct of polyethyleneimine, and polyethyleneimine.
  • amino acids are glycine, 3- (methylamino) propionic acid, N- (2-aminoethyl) glycine, N- (3-aminopropyl) glycine, N- (4-cyanophenyl) glycine, and dimethylglycine.
  • a gas separation membrane that selectively permeates a specific gas component A gas separation membrane containing a gas separation functional layer containing the composition according to any one of [1] to [5] and a first porous layer.
  • the gas separation membrane according to [6] which contains a second porous layer on the side of the gas separation functional layer opposite to the first porous layer.
  • the gas separation membrane according to [6] or [7] wherein the specific gas component is an acid gas.
  • a gas separation device provided with the gas separation membrane according to any one of [6] to [8].
  • a permeation side supply port for supplying the sweep gas inert to the gas separation functional layer to the permeation side space, and A permeation gas containing the specific gas component that has permeated the gas separation membrane and a permeation side outlet for discharging the sweep gas from the permeation side space.
  • a sweep gas supply unit for supplying the sweep gas provided on the upstream side of the permeation side supply port, and a sweep gas supply unit.
  • a supply-side space and a transmission-side space separated from each other by the gas separation membrane A supply-side inlet for supplying a raw material gas containing at least the specific gas component to the supply-side space, A non-permeable side outlet for discharging the raw material gas that did not permeate the gas separation membrane from the supply side space, A permeation side supply port for supplying a sweep gas inert to the gas separation functional layer to the permeation side space, A permeation gas containing the specific gas component that has permeated the gas separation membrane and a permeation side outlet for discharging the sweep gas from the permeation side space.
  • a method for producing a gas separation membrane that selectively permeates a specific gas component. A step of preparing a coating solution containing the composition according to any one of [1] to [5], and A method for producing a gas separation membrane, which comprises a step of applying the coating liquid onto the first porous layer.
  • composition The composition of the present embodiment is referred to as a hydrophilic resin (hereinafter, may be referred to as “hydrophilic resin (A)”) and a basic polymer containing a nitrogen atom (hereinafter, referred to as “basic polymer (B)”). It may include), amino acids (hereinafter, may be referred to as “amino acid (C)”), and alkali metal compounds (hereinafter, may be referred to as “alkali metal compound (D)”).
  • the alkali metal element contained in the alkali metal compound (D) contains at least one of rubidium and cesium, and the number of nitrogen atoms (NB) [mol] and amino acids (C) contained in the total amount of the basic polymer (B).
  • the ratio (NC / NB) to the number of nitrogen atoms (NC) [mol] contained in the total amount of) is in the range of 0.1 or more and 2 or less.
  • the above composition can be used, for example, to form a gas separation membrane described later.
  • the separation device can have good separation performance.
  • the ratio (NC / NB) of the number of nitrogen atoms (NB) contained in the total amount of the basic polymer (B) to the number of nitrogen atoms (NC) contained in the total amount of amino acids (C) is 0.1 or more and 2 or less. Is within the range of.
  • the ratio (NC / NB) is preferably 0.2 or more, more preferably 0.3 or more, may be 0.5 or more, and is preferably 1.8 or less. , 1.5 or less, more preferably 1.2 or less, and particularly preferably 0.8 or less.
  • the calculation method of the number of nitrogen atoms (NB) and the number of nitrogen atoms (NC) will be described later.
  • the gas separation device provided with the gas separation membrane formed by using the above composition can have good separation performance. Further, when gas separation is performed using a gas separation device having a gas separation membrane, a low humidity raw material gas or a sweep gas may be used, or the gas flowing in the gas separation device may have a locally low humidity. is there. Even when the gas separator is operated under the condition that such a low humidity gas (hereinafter, may be referred to as “low humidity gas”) flows, the ratio (NC / NB) is within the above range. By being present, excellent durability can be exhibited.
  • the above composition can be suitably used as a composition for a gas separation membrane for forming a gas separation functional layer of the gas separation membrane described later, and can also be used as an acid gas absorber or the like.
  • hydrophilic resin (A) Since the hydrophilic resin (A) is contained in the composition, it is possible to impart appropriate water retention to the gas separation functional layer when forming the gas separation functional layer of the gas separation membrane described later. Further, when the coating liquid containing the composition is applied to form the gas separation functional layer, the viscosity of the coating liquid can be easily adjusted by having an appropriate water retention property, so that the coatability is improved. Can be done. Further, even when a low-humidity raw material gas or sweep gas is supplied to the gas separation device provided with the gas separation membrane, good separation performance can be exhibited.
  • the hydrophilic resin (A) refers to a polymer which is a hydrophilic functional group and has a functional group other than the basic functional group in the polymer chain.
  • Hydrophilic functional groups include acidic functional groups such as carboxy group, sulfo group and phosphono group; alkali metal salt of acidic functional group; hydroxyl group; cyano group; oxyalkylene group; butyral group; acetyl group; amide group; silanol group.
  • An ammonium group; an isocyanate group and the like can be mentioned.
  • the hydrophilic resin (A) has a property of being dissolved in or uniformly dispersed in a polymer that swells in an aqueous medium such as water or a medium containing water as a main component (containing 50% by weight or more of water) or an aqueous medium. It is preferable that the polymer has.
  • the structural unit constituting the hydrophilic resin (A) may be one type or two or more types.
  • the above-mentioned hydrophilic functional group may be contained in any of the structural units and may be contained in all the structural units. ..
  • the above-mentioned hydrophilic functional groups may be contained in one or more in one structural unit, and when two or more functional groups are contained, the above-mentioned hydrophilic functional groups may be the same or 2 It may contain more than a species of functional group.
  • the hydrophilic resin (A) is preferably a polymer having a hydroxyl group, a polymer having an acidic dissociation group, or a polymer having both a hydroxyl group and an acidic dissociation group.
  • the polymer having a hydroxyl group is not particularly limited.
  • the polymer having a hydroxyl group may be composed of a structural unit having one kind of hydroxyl group, may be composed of a structural unit having two or more kinds of hydroxyl groups, and has a structural unit having a hydroxyl group and a structural unit having no hydroxyl group. It may be composed of a combination with a unit.
  • polystyrene resin examples include polyvinyl alcohol, polyhydroxyethyl (meth) acrylate, polyhydroxypropyl (meth) acrylate, polyhydroxybutyl (meth) acrylate, and the like, and polyvinyl alcohol is preferable.
  • (meth) acrylate refers to at least one selected from the group consisting of acrylates and methacrylates. The same applies to the notation such as "(meth) acrylic".
  • a copolymer containing polyvinyl alcohol or a vinyl alcohol unit can be obtained by saponifying at least a part of the constituent units derived from the vinyl ester of fatty acid.
  • Polyvinyl alcohol can usually be obtained by hydrolyzing polyvinyl acetate. Examples of polyvinyl alcohol include "Kuraray Poval (registered trademark)” available from Kuraray Co., Ltd. and "J-Poval (registered trademark)” available from Japan Vam & Poval Co., Ltd.
  • Polyhydroxyethyl (meth) acrylate, polyhydroxypropyl (meth) acrylate, polyhydroxybutyl (meth) acrylate and the like can be obtained by polymerizing a monomer having a hydroxyl group.
  • the monomer having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
  • the polymer having an acidic dissociative group means a polymer having an acidic functional group capable of releasing a proton (H + ) in a medium, and is not particularly limited.
  • the monovalent acidic dissociable group include a carboxy group (-COOH), a sulfo group (-S (O) 2 (OH)), and a phenolic hydroxyl group
  • examples of the divalent acidic dissociable group include a divalent acidic dissociable group.
  • a phosphono group (-P (O) (OH) 2 ) and a phosphonooxy group (-OP (O) (OH) 2 ) can be mentioned.
  • the hydrophilic resin (A) may have only one type of acidic dissociative group or two or more types.
  • the acidic dissociative group is preferably a monovalent acidic dissociative group, more preferably a carboxy group.
  • Polymers having an acidic dissociative group include poly (meth) acrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, phenol-formalin resin, resorcin-formalin resin, polyvinylphosphonic acid, polystyrene phosphonic acid, polyhydroxystyrene, polyvinylphenol and the like. , Which is preferably poly (meth) acrylic acid.
  • the hydrophilic resin (A) may be crosslinked, or a crosslinked polymer and a non-crosslinked polymer may be mixed and used.
  • crosslinked polymer means a polymer that is chemically crosslinked.
  • Chemical cross-linking means intermolecular or intramolecular cross-linking by covalent bonds (excluding coordination bonds).
  • the cross-linking form is not particularly limited, for example, cross-linking with a cross-linking agent having a vinyl group or an epoxy group that reacts with the cross-linking group of the hydrophilic polymer, or generating a radical in the carbon chain (main chain) of the hydrophilic polymer to generate carbon.
  • -Crosslinking method for forming carbon covalent bonds can be mentioned.
  • crosslinked polymer examples include a (meth) acrylic acid-based water-absorbent crosslinked polymer, a (meth) acrylamide-based water-absorbent crosslinked polymer, a vinyl alcohol-based water-absorbent crosslinked polymer, and an ethylene oxide-based water-absorbent crosslinked polymer.
  • sulfonic acid-based water-absorbent cross-linked polymer aspartic acid-based water-absorbent cross-linked polymer, glutamate-based water-absorbent cross-linked polymer, alginate-based water-absorbent cross-linked polymer, starch-based water-absorbent cross-linked polymer, Examples thereof include cellulose-based water-absorbent crosslinked polymers.
  • the crosslinked polymer is preferably a (meth) acrylic acid-based water-absorbent crosslinked polymer having a carboxy group or a vinyl alcohol-based water-absorbent crosslinked polymer.
  • the (meth) acrylic acid-based crosslinked polymer having a carboxy group may further have another acidic dissociative group different from the carboxy group.
  • Other acidic dissociative groups include, for example, sulfo groups, phosphono groups, and phosphonooxy groups.
  • a monomer having this group is polymerized together with the above-mentioned (meth) acrylic acid or the like, or the water-absorbent crosslinked polymer obtained by the polymerization has another acidic dissociable group. It can be introduced into a crosslinked polymer by adding a monomer or a polymer.
  • a preferable example of the (meth) acrylic acid-based crosslinked polymer having a carboxy group is crosslinked poly (meth) acrylic acid having a carboxy group.
  • the crosslinked poly (meth) acrylic acid means a polymer having a chemically crosslinked structure derived from (meth) acrylic acid and a covalent bond and capable of forming a hydrogel.
  • the cross-linked structure by covalent bond may be composed of a structural unit derived from a cross-linking monomer or a cross-linking agent.
  • crosslinkable monomer which is one of the raw materials of chemically crosslinked poly (meth) acrylic acid
  • examples of the crosslinkable monomer which is one of the raw materials of chemically crosslinked poly (meth) acrylic acid include 1,3-butylene glycol di (meth) acrylate and 1,4-butanediol di (meth) acrylate, 1.
  • crosslinked poly (meth) acrylic acid examples include “Akpec (registered trademark)” obtained from Sumitomo Seika and “Sunfresh (registered trademark)” obtained from Sanyo Chemical Industries.
  • the (meth) acrylic acid-based crosslinked polymer having a carboxy group includes maleic acid, fumaric acid, crotonic acid and salts thereof, vinyl alcohol, pyrrolidone, and ( It may contain a structural unit derived from at least one selected from the group consisting of meta) acrylamide.
  • the non-crosslinked polymer is not particularly limited as long as it is the above-mentioned hydrophilic resin (A) that is not crosslinked, but is preferably a (meth) acrylic acid-based polymer or a vinyl alcohol-based polymer having a carboxy group. is there.
  • the (meth) acrylic acid-based non-crosslinked polymer having a carboxy group may further have another acidic dissociative group different from the carboxy group.
  • Other acidic dissociative groups include, for example, sulfo groups, phosphono groups, and phosphonooxy groups.
  • a monomer having this group is polymerized together with the above-mentioned (meth) acrylic acid or the like, or the water-absorbent crosslinked polymer obtained by the polymerization has another acidic dissociable group. It can be introduced into a crosslinked polymer by adding a monomer or a polymer.
  • the (meth) acrylic acid-based non-crosslinked polymer having a carboxy group includes maleic acid, fumaric acid, crotonic acid and salts thereof, vinyl alcohol, and (meth) in addition to the structural units derived from (meth) acrylic acid. ) It may contain a structural unit derived from at least one selected from the group consisting of acrylamide.
  • the non-crosslinked polymer having an acidic dissociation group is more preferably a non-crosslinked poly (meth) acrylic acid having a carboxy group.
  • hydrophilic resin (A) in addition to the above-mentioned polymer having a hydroxyl group and the polymer having an acidic dissociation group, a copolymer having a hydroxyl group and an acidic dissociation group may be used.
  • a copolymer having a hydroxyl group and an acidic dissociation group examples include a vinyl alcohol- (meth) acrylic acid copolymer and the like.
  • the copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer and a graft copolymer.
  • hydrophilic resin (A) examples include poly (meth) acrylic acid, polyvinyl alcohol, vinyl alcohol- (meth) acrylic acid copolymer, alkylaldehyde-modified product of polyvinyl alcohol (for example, polyvinyl butyral), and main chain.
  • Polyethylene oxide having a hydroxyl group at the end polypropylene oxide having a hydroxyl group at the end of the main chain, ethylene oxide-propylene oxide copolymer having a hydroxyl group at the end of the main chain, polyvinyl sulfonic acid, polystyrene sulfonic acid, polyvinyl pyrrolidone, and polyhydroxyalkyl (meth).
  • the main chain is a chain in which repeating structural units of a polymer are connected.
  • the composition may contain only one type of hydrophilic resin (A) and may contain two or more types.
  • the hydrophilic resin (A) shall be distinguished based on the difference in chemical structure, and the two or more kinds of hydrophilic resins (A) shall be different from the functional group species, the number of functional groups, the crosslinked structure, the degree of crosslinking, and the degree of crosslinking. It means that two or more hydrophilic resins (A) having different presence / absence, molecular weight distribution, etc. are contained.
  • the total content of the hydrophilic resin (A) in the composition is preferably 0.5% by weight or more, preferably 1% by weight or more, when the solid content concentration in the composition is 100% by weight. Is more preferably 2% by weight or more, and usually 30% by weight or less, 25% by weight or less, 20% by weight or less, or 10% by weight or less. It may be 5% by weight or less.
  • Base polymer (B) Since the basic polymer (B) is contained in the composition, when the coating liquid containing the composition is applied to form the gas separation functional layer of the gas separation membrane described later, appropriate water retention is provided. By having it, it becomes easy to adjust the viscosity of the coating liquid, so that the coating property can be improved. It is also good when a low-humidity raw material gas or sweep gas is supplied to a gas separation device provided with a gas separation membrane using a composition containing a basic polymer (B) and an amino acid (C) described later. Separation performance can be demonstrated.
  • the basic polymer (B) refers to a polymer containing a nitrogen atom and having a basic functional group in the polymer chain, and is a polymer having a nitrogen atom in the main chain, the side chain, or both of them. Is preferable.
  • the basic functional group include an amide group, a primary to tertiary amino group, and the like, and these amino groups also include a heterocyclic group containing a nitrogen atom as a heteroatom.
  • heterocyclic group containing a nitrogen atom as a heteroatom examples include aziridine, azirin, azetidine, pyrrolidine, pyrrole, piperidine, pyridine, azepan, imidazole, pyrazole, oxazole, thiazole, imidazoline, morpholine, thiazine, triazole, tetrazole and pyrimidine.
  • the basic polymer (B) may contain a functional group other than the basic one.
  • the molar ratio of non-basic functional groups / basic functional groups in the basic polymer (B) is preferably less than 10, more preferably 5 or less, still more preferably 3 or less, even more preferably 1 or less. Most preferably, it is 0.5 or less.
  • the basic polymer (B) is not particularly limited, but for example, polyallylamine, polyvinylamine, polyamidine, polyimidazoline, dicyandiamide-based condensate, polydialylamine, vinylamine-vinyl alcohol copolymer, polyethyleneimine, ethylene oxide of polyethyleneimine. It is preferably at least one selected from the group consisting of an adduct and a propylene oxide adduct of polyethyleneimine.
  • the basic polymer (B) contains amino groups such as polyallylamine, polyvinylamine, polyamidine, polyimidazoline, dicyandiamide-based condensate, vinylamine-vinyl alcohol copolymer, polyethyleneimine, and ethyleneoxide adduct of polyethyleneimine. It is more preferable that the polymer is a basic polymer, and more preferably at least one of polyallylamine, polyethyleneimine, an ethylene oxide adduct of polyethyleneimine, and a propylene oxide adduct of polyethyleneimine.
  • the basic polymer (B) may be crosslinked, or a crosslinked polymer and a non-crosslinked polymer may be mixed and used.
  • the crosslinked form is not particularly limited, and is reactive such as isothiocyanate, isocyanate, acyl azide, NHS ester, sulfonyl chloride, aldehyde, glyoxal, epoxide, oxylane, carbonate, aryl halide, imide ester, carbodiimide, anhydride, fluoroester.
  • Examples thereof include cross-linking with a cross-linking agent having a functional group and a cross-linking method in which a radical is generated in the carbon chain (main chain) of the basic polymer to form a carbon-carbon covalent bond.
  • the number of nitrogen atoms (NB) contained in the total amount of the basic polymer (B) in the composition can be, for example, 10 or more, 100 or more, or 1,000 or more. Also, it is usually 50,000 or less, may be 30,000 or less, or may be 20,000 or less.
  • the number of nitrogen atoms (NB) contained in the total amount of the basic polymer (B) is determined by repeating the addition amount [g] of the basic polymer (B) in the composition in terms of the molar mass [g / mol] of the structural unit. It can be calculated as the amount of substance [mol] by dividing and multiplying by the number of nitrogen atoms contained in the repeating structural unit.
  • the number of nitrogen atoms (NB) is calculated as the sum of the number of nitrogen atoms calculated by the above method for each basic polymer (B). be able to.
  • the composition may contain only one type of the basic polymer (B) and may contain two or more types.
  • the basic polymer (B) shall be distinguished based on the difference in chemical structure, and the two or more basic polymers (B) shall be referred to as a functional group species, the number of functional groups, a crosslinked structure, and a degree of crosslinkage. It means that two or more basic polymers (B) having different crosslinks, molecular weight distributions, etc. are contained.
  • the total content of the basic polymer (B) in the composition is preferably 5% by weight or more, preferably 15% by weight or more, when the solid content concentration in the composition is 100% by weight. It is more preferably 20% by weight or more, and usually 70% by weight or less, 60% by weight or less, or 50% by weight or less.
  • amino acid (C) Since the amino acid (C) is contained in the composition, the gas separation device provided with the gas separation membrane formed by using the above composition can have good separation performance. Further, by using the amino acid (C) in combination with the basic polymer (B), it is possible to improve the durability when the gas separation device is operated under the condition that a low humidity gas flows. By using the amino acid (C) in combination with the alkali metal compound (D) described later, it can be expected that good separation performance will be exhibited at various operating temperatures of the gas separator.
  • the amino acid (C) may be one that is converted to the amino acid (C) in the composition by adding a precursor of the amino acid (C) when obtaining the composition.
  • Amino acid (C) refers to a compound having both functional groups of an amino group and a carboxy group.
  • the amino group may be any of a primary to tertiary amino group, but is preferably a primary amino group or a secondary amino group, and more preferably a secondary amino group. ..
  • the amino acid (C) is not particularly limited as long as it has an amino group and a carboxy group.
  • Examples of the amino acid (C) include glycine, 3- (methylamino) propionic acid, N- (2-aminoethyl) glycine, N- (3-aminopropyl) glycine, N- (4-cyanophenyl) glycine, and the like.
  • At least one selected from the group consisting of isomers of these compounds At least one selected from the group consisting of isomers of these compounds.
  • amino acids (C) at least one selected from the group consisting of glycine, sarcosine, iminodiacetic acid, ethylenediaminediacetic acid, ethylenediaminediacpropionic acid, lysine, arginine, serine, and isomers of these compounds. It is preferable to have.
  • the amino acid (C) is preferably an ⁇ -amino acid in which an amino group is bonded to a carbon atom to which a carboxy group is bonded. , And at least one selected from the group consisting of isomers of these compounds, more preferably glycine or sarcosin.
  • the number of nitrogen atoms (NC) contained in the total amount of amino acids (C) in the composition can be, for example, 1 or more, 10 or more, 100 or more, and usually 100. It may be 000 or less, 60,000 or less, or 40,000 or less.
  • the number of nitrogen atoms (NC) contained in the total amount of the amino acid (C) is the value obtained by dividing the addition amount [g] of the amino acid (C) in the composition by the molar mass [g / mol], and the amino acid (C). It can be calculated as the amount of substance [mol] by multiplying the number of nitrogen atoms contained in the structural formula of.
  • the number of nitrogen atoms (NC) can be calculated as the sum of the number of nitrogen atoms calculated by the above method for each amino acid (C).
  • the composition may contain only one type of amino acid (C) and may contain two or more types.
  • the total content of the amino acid (C) in the composition is preferably 10% by weight or more, more preferably 15% by weight or more, when the solid content concentration in the composition is 100% by weight. It is more preferably 20% by weight or more, and usually 50% by weight or less, 40% by weight or less, or 30% by weight or less.
  • the number of moles (MC) of the amino acid (C) can be, for example, 0.001 mol or more, 0.01 mol or more, 0.1 mol or more, and also. Usually, it is 100 mol or less, 50 mol or less, or 10 mol or less.
  • the molar ratio (MC / MD) of the number of moles (MC) of the amino acid (C) to the number of moles (MD) of the alkali metal compound (D) described later is preferably 0.1 or more, preferably 0.3 or more. It is more preferably 0.5 or more, and it is preferably 1.1 or less, more preferably 1.0 or less, and it may be 0.8 or less. When the molar ratio (MC / MD) is within the above range, good separation performance can be exhibited at various operating temperatures of the gas separation device.
  • Alkali metal compound (D) Since the alkali metal compound (D) is contained in the composition, the gas separation device provided with the gas separation membrane formed by using the above composition can have good separation performance. When the alkali metal compound (D) is used in combination with the amino acid (C), good separation performance can be exhibited at various operating temperatures of the gas separation device.
  • the alkali metal element contained in the alkali metal compound (D) contains at least one of rubidium and cesium.
  • the alkali metal compound (D) may contain both rubidium and cesium, but preferably contains either one.
  • alkali metal compound (D) examples include alkali metal carbonate, alkali metal hydrogen carbonate, alkali metal hydroxide, alkali metal phosphate, and alkali metal alkoxide.
  • the alkali metal compound (D) is preferably at least one selected from the group consisting of alkali metal carbonate, alkali metal hydrogen carbonate, and alkali metal hydroxide, and is preferably cesium carbonate, cesium hydrogen carbonate, or hydroxide. It is preferably at least one selected from the group consisting of cesium, rubidium carbonate, rubidium hydrogencarbonate, and rubidium hydroxide.
  • the composition may contain only one kind of alkali metal compound (D) and may contain two or more kinds.
  • the total content of the alkali metal compound (D) in the composition is the basic polymer (B), the amino acid (C), and the alkali metal compound (D) when the solid content concentration in the composition is 100% by weight.
  • it depends on the type, it is preferably 25% by weight or more, more preferably 35% by weight or more, further preferably 40% by weight or more, and usually 70% by weight or less, 60% by weight. It may be less than%, and may be less than 50% by weight.
  • the number of moles (MD) of the alkali metal compound (D) can be, for example, 0.001 mol or more, 0.01 mol or more, or 0.1 mol or more. Further, it is usually 10 mol or less, may be 5 mol or less, or may be 1 mol or less.
  • the molar ratio (MC / MD) of the number of moles (MC) of the amino acid (C) to the number of moles (MD) of the alkali metal compound (D) is 0.1 or more and 1.1 or less. Is preferable. When the molar ratio (MC / MD) is within the above range, good separation performance can be exhibited at various operating temperatures of the gas separation device.
  • the composition of the present embodiment may contain other components other than the above-mentioned hydrophilic resin (A), basic polymer (B), amino acid (C), and alkali metal compound (D).
  • Other components may include, as an additive, a medium for dissolving or dispersing the composition, a surfactant, a catalyst that promotes permeation of the gas separation functional layer by a hydration reaction with a specific gas component, and the like. Good.
  • Other components may include alkali metal salts of lithium or potassium. Examples of the alkali metal salt include alkali metal carbonate, alkali metal hydrogen carbonate, and alkali metal hydroxide.
  • Examples of the medium include protic polar solvents such as water, methanol, ethanol, alcohols such as 1-propanol and 2-propanol; non-polar solvents such as toluene, xylene and hexane; and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. , N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and other aprotic polar solvents; and the like.
  • One type of medium may be used alone, or two or more types may be used in combination as long as they are compatible with each other.
  • a medium containing at least one selected from the group consisting of alcohols such as water, methanol, ethanol, 1-propanol and 2-propanol is preferable, and a medium containing water is more preferable.
  • the surfactant is not particularly limited, but for example, polyoxyethylene polyoxypropylene glycols, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, fluorine-based surfactants, silicone-based surfactants, betaine.
  • Conventionally known surfactants such as based surfactants, amino acid based surfactants, and sulfonic acid based surfactants can be used.
  • One type of surfactant may be used alone, or two or more types may be used in combination.
  • the hydration reaction catalyst that promotes the hydration reaction when the specific gas component is an acidic gas preferably contains an oxoacid compound, and is selected from the group consisting of Group 14 elements, Group 15 elements, and Group 16 elements. It is more preferable to contain an oxoacid compound of at least one element to be used, and it is possible to contain at least one selected from the group consisting of a tellurous acid compound, a selenous acid compound, a arsenic compound, and an orthosilicic acid compound. More preferred.
  • the gas separation membrane selectively permeates a specific gas component.
  • the specific gas component is preferably an acid gas.
  • the acidic gases carbon dioxide (CO 2), hydrogen sulfide (H 2 S), carbonyl sulfide, sulfur oxides (SO x), nitrogen oxides (NO x), include hydrogen halides such as hydrogen chloride, and ..
  • the specific gas component is preferably carbon dioxide.
  • the shape of the gas separation membrane may be a sheet shape, a tube shape, and preferably a sheet shape.
  • a sheet-shaped gas separation membrane will be described as an example.
  • the gas separation membrane includes a gas separation functional layer containing the above composition and a first porous layer, and the gas separation functional layer is supported by the first porous layer.
  • the gas separation functional layer can be, for example, a gel-like resin layer.
  • the gas separation membrane may have a second porous layer on the side opposite to the first porous layer of the gas separation functional layer.
  • the first porous layer and the second porous layer do not serve as diffusion resistance of the raw material gas supplied to the gas separation functional layer, particularly the gas component that selectively permeates the gas separation functional layer among the components contained in the raw material gas.
  • it is preferably one having high gas permeability and porosity.
  • first porous layer and the second porous layer each contain a resin material.
  • the resin materials contained in the first porous layer and the second porous layer are, for example, polyolefin resins such as polyethylene (PE) and polypropylene (PP); polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVF), and polyvinylidene fluoride.
  • Fluorine-containing resin such as vinylidene (PVDF); polyester resin such as polyethylene terephthalate (PET) and polyethylene naphthalate; polystyrene (PS), polyethersulfone (PES), polyphenylene sulfide (PPS), polysulfone (PSF), polyacrylonitrile ( Resin materials such as PAN), polyvinylidene oxide (PPO), polyamide (PA), polyimide (PI), polyetherimide (PEI), polyetheretherketone (PEEK), high molecular weight polyester, heat-resistant polyamide, aramid, polycarbonate, etc. Can be mentioned.
  • PVDF vinylidene
  • polyester resin such as polyethylene terephthalate (PET) and polyethylene naphthalate
  • PS polystyrene
  • PES polyethersulfone
  • PPS polyphenylene sulfide
  • PSF polysulfone
  • Resin materials such as PAN), polyvinylidene oxide
  • a polyolefin resin or a fluorine-containing resin is preferable from the viewpoint of water repellency.
  • examples of the materials contained in the first porous layer and the second porous layer include inorganic materials such as metal, glass, and ceramics, and both these inorganic materials and the above resin materials can be used. It may be included.
  • the material forming the first porous layer and the material forming the second porous layer may be the same material or different materials.
  • porous body Even if the porous body is further laminated on the surface of the first porous layer and the second porous layer that does not come into contact with the gas separation functional layer for the purpose of additionally imparting strength to the first porous layer and the second porous layer.
  • a resin material and an inorganic material exemplified as the first porous layer and the second porous layer, and a non-woven fabric or a woven fabric containing both of these materials can be preferably used.
  • the method for producing the gas separation membrane is a step of preparing a coating liquid containing the above composition (hereinafter, may be referred to as a “preparation step”) and a step of applying the coating liquid on the first porous layer (hereinafter, may be referred to as a “preparation step”).
  • preparation step a step of preparing a coating liquid containing the above composition
  • preparation step a step of applying the coating liquid on the first porous layer
  • the preparation step is a step of preparing a coating liquid to be applied on the first porous layer using the above composition.
  • the above composition and the medium can be mixed to prepare a coating liquid.
  • the medium the above-mentioned medium can be used.
  • the composition may be used as a coating liquid.
  • the preparatory step may include a defoaming step for removing air bubbles contained in the prepared coating liquid. Examples of the defoaming step include a method of applying shear by stirring or filtering the coating liquid, a method of vacuum degassing or degassing the coating liquid under reduced pressure, a method of heating the coating liquid to degas, and the like. Can be done.
  • the coating step is a step of applying the coating liquid prepared in the preparation step onto the first porous layer.
  • the coating process is by slot die coating, spin coating method, bar coating, die coating, blade coating, air knife coating, gravure coating, roll coating coating, spray coating, dip coating, comma roll method, kiss coating method, screen printing, inkjet printing, etc. It can be carried out.
  • the coating step preferably includes a step of removing the medium from the coating liquid film formed by applying the coating liquid on the first porous layer.
  • Examples of the step of removing the medium include a method of evaporating and removing the medium from the film of the coating liquid by heating or the like.
  • the second porous layer is on the opposite side of the coating liquid membrane from the first porous layer. It may have a step of laminating the porous layer. After laminating the second porous layer, a step of further removing the medium in the film of the coating liquid may be performed.
  • the gas separation membrane can be used for known gas separation membrane elements (separation membrane elements) such as spiral type, flat membrane type, hollow fiber type, tube type, pleated type, and plate and frame type.
  • FIGS. 1A and 1B are schematic perspective views provided with a partially developed portion showing an example of a gas separation membrane element using the gas separation membrane described above.
  • the spiral type gas separation membrane elements 1, 1a are as shown in FIGS. 1A and 1B.
  • An element laminate in which at least one or more of the supply-side flow path member 3, the gas separation membrane 10, and the transmission-side flow path member 4 are laminated can be provided with a wound body wound around a central tube 5. ..
  • the winding body may have an arbitrary shape such as a cylindrical shape or a square tubular shape.
  • the central tube 5 has a plurality of holes 50 on the outer peripheral surface thereof that communicate the flow path space of the permeated gas formed by the permeation side flow path member 4 and the hollow space inside the central tube 5.
  • the gas separation membrane element 1a may further include a fixing member such as an outer peripheral tape or a telescope prevention plate 55 shown in FIG. 1B in order to prevent unwinding or unwinding of the winding body, and gas separation may be provided.
  • a fixing member such as an outer peripheral tape or a telescope prevention plate 55 shown in FIG. 1B in order to prevent unwinding or unwinding of the winding body, and gas separation may be provided.
  • An outer wrap (reinforcing layer) may be provided on the outermost circumference of the wound body in order to secure the strength against the load due to the internal pressure and the external pressure applied to the membrane element.
  • the gas separation membrane element can be used in the gas separation membrane module.
  • the gas separation membrane module has one or more gas separation membrane elements.
  • the gas separation membrane module is for discharging the raw material gas supply port for supplying the raw material gas to the gas separation membrane (the portion communicating with the supply side end portion 51 shown in FIG. 1B) and the permeated gas that has passed through the gas separation membrane.
  • a permeated gas discharge port (a portion communicating with the discharge port 52 shown in FIG. 1B) and a non-permeated gas discharge port for discharging the raw material gas that did not permeate the gas separation membrane sheet (discharge side end portion 53 shown in FIG. 1B). It has a part that communicates with).
  • the raw material gas supply port, the non-permeated gas discharge port, and the permeated gas discharge port may be provided in the main body of the gas separation membrane element, and may be referred to as a container for accommodating the gas separation membrane element (hereinafter, referred to as “housing”). .) May be provided.
  • the housing can form a space for enclosing the raw material gas flowing in the gas separation membrane module.
  • a tubular member such as stainless steel and a closing member for closing both ends of the tubular member in the axial direction. And may have.
  • the housing may have an arbitrary cylindrical shape such as a cylindrical shape or a square tubular shape, but since the gas separation membrane element is usually cylindrical, it is preferably cylindrical.
  • a partition is provided inside the housing to prevent mixing of the raw material gas supplied to the supply side end portion 51 and the non-permeable gas provided in the gas separation membrane element that has not penetrated the gas separation membrane. Can be provided.
  • the raw material gas supplied to each gas separation membrane element may be supplied in parallel or in series.
  • supplying the raw material gas in parallel means at least distributing the raw material gas and introducing it into a plurality of gas separation membrane elements
  • supplying the raw material gas in series means discharging at least from the gas separation membrane element in the previous stage. It means to introduce the permeated gas and / or non-permeated gas to the gas separation membrane element in the subsequent stage.
  • Gas separator 2 and 3 are schematic views showing an example of the gas separation device of the present embodiment.
  • the gas separation device has the above-mentioned gas separation membrane, and can include at least one gas separation membrane module including the gas separation membrane.
  • the arrangement and number of gas separation membrane modules provided in the gas separation device can be selected according to the required processing amount, the recovery rate of a specific gas component, the size of the place where the gas separation device is installed, and the like.
  • the gas separator is as shown in FIG.
  • a supply side chamber 62 supply side space
  • a permeation side chamber 63 permeation side space
  • a supply side inlet for supplying a raw material gas containing at least a specific gas component to the supply side chamber 62
  • a non-permeable side outlet for discharging the raw material gas that did not permeate the gas separation membrane 10 from the supply side chamber 62
  • a permeation side outlet for discharging a permeated gas containing a specific gas component that has permeated the gas separation membrane 10 from the permeation side chamber 63, and a permeation side outlet.
  • a decompression pump 71 (decompression unit) for depressurizing the permeated gas provided on the downstream side of the permeation side outlet can be provided.
  • the downstream side and the upstream side of the gas separation device are determined based on the direction in which the raw material gas, the permeated gas, etc. flow in the gas separation device.
  • the humidity of the permeation side chamber 63 is lower than that of the supply side chamber 62, and the humidity of the permeation side surface of the gas separation membrane 10 is lower.
  • Cheap Since the gas separation membrane 10 is formed by using the above-mentioned composition, it can exhibit excellent durability even when the humidity of the surface on the permeation side is lowered. In addition, high gas permeation performance under high humidity conditions can be exhibited.
  • the gas separator is as shown in FIG.
  • a supply side chamber 62 supply side space
  • a permeation side chamber 63 permeation side space
  • a supply side inlet for supplying a raw material gas containing at least a specific gas component to the supply side chamber 62
  • a non-permeable side outlet for discharging the raw material gas that did not permeate the gas separation membrane 10 from the supply side chamber 62
  • a permeation side supply port for supplying a sweep gas (for example, Ar or the like) inert to the gas separation functional layer included in the gas separation membrane 10 to the permeation side chamber 63.
  • a sweep gas for example, Ar or the like
  • a permeation side outlet for discharging a permeation gas and a sweep gas containing a specific gas component that has permeated the gas separation membrane 10 from the permeation side chamber 63, and a permeation side outlet.
  • a sweep gas supply unit for supplying sweep gas provided on the upstream side of the permeation side supply port can be provided.
  • Sweep gas is supplied in the gas separation device shown in FIG.
  • the humidity of the permeation side chamber 63 is lower than that of the supply side chamber 62, and the humidity of the permeation side surface of the gas separation membrane 10 is likely to be lower.
  • the gas separation membrane 10 is formed by using the above-mentioned composition, it can exhibit excellent durability even when the humidity of the surface on the permeation side is lowered. In addition, high gas permeation performance under high humidity conditions can be exhibited.
  • the gas separation device shown in FIG. 3 may include a permeation side supply port, a permeation side outlet, and a sweep gas supply unit shown in FIG.
  • the gas separation device shown in FIG. 2 may include the decompression pump 71 shown in FIG.
  • the gas separation method of the present embodiment is a method of selectively separating a specific gas component from a raw material gas by using the gas separation device provided with the gas separation membrane described above.
  • the gas separation method of the present embodiment can realize high gas permeation performance under high humidity conditions and high durability under low humidity conditions.
  • the raw material gas supplied to the gas separation device is not particularly limited as long as it contains a specific gas component.
  • the humidity of the raw material gas supplied to the supply side inlet of the gas separator may be high humidity or low humidity, for example, 60 RH% or more, 80% RH or more, 90 RH%. It may be more than or equal to 50 RH% or less, 30 RH% or less, 20 RH% or less, or 0 RH%.
  • the humidity at the inlet of the supply side is the partial pressure of water calculated based on the moisture content in the raw material gas supplied to the gas separator and the pressure at the inlet of the supply side, and is the saturated water vapor pressure at the evaluation temperature (temperature of the raw material gas). It can be calculated by dividing.
  • the supply-side inlet referred to here is an inlet for the raw material gas in the supply-side chamber 62 of the gas separator shown in FIGS. 2 and 3.
  • the gas separation method of the present embodiment is also suitable under low humidity conditions where the humidity at the permeation side outlet of the gas separation device is 45 RH% or less.
  • the humidity of the permeation side outlet when operating under low humidity conditions is preferably 40 RH% or less, may be 35 RH% or less, 25 RH% or less, or 10 RH% or less. , 0 RH% or less.
  • the humidity of the permeation side outlet is the amount of condensed water obtained by condensing the gas discharged from the permeation side outlet of the gas separator by a cooling trap provided in the middle of the discharge path on the downstream side of the permeation side outlet, and the amount of condensed water after the cooling trap.
  • the permeation side outlet referred to here is a gas outlet in the permeation side chamber 63 of the gas separation device shown in FIGS. 2 and 3.
  • the amount of membrane separation processed is determined by the amount of permeated gas that permeates the gas separation membrane.
  • the pressure of the raw material gas supplied to the gas separation device is increased by a compressor or the like, so that the gas partial pressure at the supply side inlet of the gas separation membrane is permeated through the gas separation membrane.
  • a method of increasing the gas partial pressure at the side outlet (the side where the permeated gas of the gas separation membrane is discharged); by depressurizing the permeation side outlet of the gas separation membrane, the gas partial pressure at the supply side inlet of the gas separation membrane Is higher than the gas partial pressure at the permeation side outlet of the gas separation membrane; a method of increasing the permeated gas amount by supplying a sweep gas for discharging together with the permeated gas to the permeation side outlet of the gas separation membrane; It is preferable to use a method in which two or more of these are combined.
  • the gas separation method can further include a step of supplying the sweep gas to the permeation side inlet of the gas separation device.
  • the sweep gas may be selected according to the type of the raw material gas, the specific gas component that permeates the gas separation membrane, and the like.
  • the acid gas separation device is a form of the gas separation device described above, and is particularly used for separating acid gas. Therefore, the acid gas separation device includes an acid gas separation membrane which is a gas separation membrane for separating the acid gas. Specifically, in the acid gas separation device, the acid gas separation membrane is in the form of a gas separation membrane element (hereinafter, referred to as "acid gas separation membrane element"), and this acid gas separation membrane element is in the form of a gas separation membrane module. It is equipped with an acid gas separation membrane module.
  • acid gas separation membrane element gas separation membrane element
  • the arrangement and number of acid gas separation membrane modules of the acid gas separation device and the arrangement and number of acid gas separation membrane elements in the acid gas separation membrane module are the required processing amount, acid gas recovery rate, and acid gas separation. It can be selected according to the size of the place where the device is installed.
  • the acidic gas separator preferably includes, in addition to at least one acidic gas separation membrane module, a decompression unit for depressurizing the permeated gas on the downstream side of the permeation side outlet of the acidic gas separator, and a permeation of the acidic gas separator. It further includes at least one of the sweep gas supply parts for supplying the sweep gas discharged together with the permeated gas to the side inlet, and the decompression part communicates with the permeate gas discharge part of the acidic gas separation membrane module.
  • the sweep gas supply unit communicates with the sweep gas supply unit further provided in the acidic gas separation membrane module.
  • the sweep gas is a gas for suppressing a decrease in the differential pressure of the acid gas (gas to be separated) between the supply side space and the permeation side space of the acid gas separation device and using it as a driving force for gas permeation.
  • the acid gas separation film can remove water vapor from the raw material gas containing CO 2 and water vapor at the same time as CO 2, so that the acid gas separation film and acid gas described above can be removed.
  • the separation membrane module and acid gas separation device can be used to remove CO 2 and water vapor from various gases.
  • gases include, for example, a reformed gas obtained by reforming hydrocarbons and used for producing hydrogen, etc .; electricity containing hydrogen generated from the reformed gas as a raw material in a fuel cell or the like. Examples include chemical oxidation reaction gas; biogas obtained by methane fermentation of biomass, etc .; combustion exhaust gas generated in a boiler, etc.
  • the acid gas separation membrane module can be used in a hydrogen production apparatus.
  • the acid gas separation membrane module can selectively permeate the gas component containing carbon dioxide gas from the raw material gas containing at least hydrogen and carbon dioxide.
  • the acid gas separation membrane module provided in the hydrogen production apparatus may be provided as an acid gas separation membrane module including the acid gas separation membrane module.
  • the hydrogen contained in the raw material gas supplied to the acid gas separation membrane module may be contained in the reformed gas generated by the reforming reaction of the hydrocarbon.
  • Crude purified hydrogen (hydrogen) can be produced by removing CO 2 and water vapor from this reformed gas using an acid gas separation membrane. Reforming reaction of hydrocarbons can be carried out CO 2 reforming with CO 2, steam reforming using water vapor, by any combination of these two reforming. Therefore, when producing crude hydrogen, the mixed gas containing CO 2 and water vapor recovered by removal using an acid gas separation membrane can be reused for the hydrocarbon modification reaction. This makes it possible to reduce the amount of raw materials used in the hydrocarbon modification reaction.
  • the amount of acid gas membrane separation processed is determined by the amount of permeated gas that permeates the acid gas separation membrane.
  • the pressure of the raw material gas supplied to the supply side of the acidic gas separation film via the mixed gas supply unit provided in the acidic gas separation film module is increased by a compressor or the like. By doing so, the gas partial pressure on the supply side is made higher than the gas partial pressure on the permeation side (the side on which the permeated gas of the acidic gas separation membrane is discharged); via the permeated gas discharge portion provided in the acidic gas separation membrane module.
  • a method in which the gas partial pressure on the supply side is made higher than the gas partial pressure on the permeation side by depressurizing the permeation side of the acidic gas separation membrane (hereinafter, may be referred to as “decompression method”); acid gas separation.
  • compression method A method of increasing the amount of permeated gas by supplying a sweep gas for discharging together with the permeated gas to the permeation side of the acidic gas separation membrane via the sweep gas supply unit provided in the membrane module (hereinafter, "sweep method”). ”); A method in which two or more of these are combined can be mentioned.
  • the decompression method A method of increasing the amount of permeated gas by supplying a sweep gas for discharging together with the permeated gas to the permeation side of the acidic gas separation membrane via the sweep gas supply unit provided in the membrane module.
  • the number of nitrogen atoms (NB) contained in the total amount of the basic polymer (B) in the composition is determined by repeating the addition amount [g] of the basic polymer (B) in terms of the molar mass [g / mol] of the structural unit. It was calculated as the amount of substance [mol] by dividing and multiplying by the number of nitrogen atoms contained in the repeating structural unit.
  • the number of nitrogen atoms (NC) contained in the total amount of amino acids (C) in the composition is the value obtained by dividing the amount [g] of the amino acid (C) added by the molar mass [g / mol], and the amino acid (C). It was calculated as the amount of substance [mol] by multiplying the number of nitrogen amino acids contained in the structural formula of.
  • the ratio (NC / NB) was calculated based on the calculated number of nitrogen atoms.
  • Material gas (CO 2: 13.6 vol%, the He: 26.8 vol%, H 2 O: 59.6% by volume) supplied to the supply side chamber 62 of the gas separation membrane cell 61 at a flow rate of 40.9NL / h and sweep gas (Ar: 34.5 vol%, H 2 O: 65.5% by volume) was fed to the permeation side chamber 63 of the gas separation membrane cell 61 at a flow rate of the 4.8NL / h.
  • water was fed by the fixed-quantity liquid feed pumps 68 and 70, heated and evaporated to adjust the mixing ratio of H 2 O.
  • the pressure in the supply side chamber 62 was adjusted to 125 kPaA (absolute pressure) by a back pressure regulator provided on the downstream side of the cooling trap 64 in the middle of the non-permeated gas discharge path. Further, a back pressure regulator 69 and a pressure reducing pump 71 are provided between the cooling trap 66 and the gas chromatograph 67, whereby the pressure in the permeation side chamber 63 is adjusted to atmospheric pressure. After starting the operation of the gas separator, when the steady state is reached, the water vapor contained in the permeated gas discharged from the permeation side chamber 63 is removed by the cooling trap 66, and then this permeated gas is analyzed by the gas chromatograph 67, and CO.
  • a back pressure regulator provided on the downstream side of the cooling trap 64 in the middle of the non-permeated gas discharge path.
  • a back pressure regulator 69 and a pressure reducing pump 71 are provided between the cooling trap 66 and the gas chromatograph 67, whereby the pressure in the permeation
  • the CO 2 permeance of the gas separation membrane of Example 6 was measured using the gas separation device provided with the gas separation membrane cell 61 (housing) shown in FIG.
  • the same members as those of the gas separator shown in FIG. 2 are designated by the same reference numerals.
  • the prepared gas separation membrane is cut into an appropriate size to form a flat membrane shape, which is formed into a supply side chamber 62 (supply side space) and a transmission side chamber 63 (permeation side) of the stainless steel gas separation membrane cell 61. It was fixed between the space).
  • the temperature of the gas separation membrane cell 61 was set to 93 ° C. by a constant temperature bath.
  • Material gas (CO 2: 17.1 vol%, the He: 34.9 vol%, H 2 O: 73.0% by volume) supplied to the supply side chamber 62 of the gas separation membrane cell 61 at a flow rate of 3.8NL / h did.
  • water was fed at Metering pump 81, heated and evaporated, H 2 O was adjusted to the mixing ratio.
  • the pressure in the supply side chamber 62 was adjusted to 125 kPaA (absolute pressure) by a back pressure regulator 65 provided on the downstream side of the cooling trap 64 in the middle of the non-permeated gas discharge path.
  • a back pressure regulator 69 and a pressure reducing pump 71 are provided between the cooling trap 66 and the gas chromatograph 67, whereby the pressure in the permeation side chamber 63 is adjusted to 20 kPaA.
  • the water vapor contained in the permeated gas discharged from the permeation side chamber 63 is removed by the cooling trap 66, and then this permeated gas is analyzed by the gas chromatograph 67. Then, the CO 2 permit [mol / (m 2 ⁇ sec ⁇ kPa)] after long-term operation was calculated.
  • the gas separation membrane 10 obtained in Examples 1 to 5 and Comparative Examples 1 to 5 was used using a gas separation device provided with the gas separation membrane cell 83 shown in FIG. was subjected to a durability test. Specifically, the prepared gas separation membrane 10 was cut into a size of 20 cm 2 to form a flat membrane shape, which was fixed between the supply side chamber 81 and the transmission side chamber 82 of the stainless steel gas separation membrane cell 83. The temperature of the gas separation membrane cell 83 was not particularly maintained, and the measurement was performed under room temperature (25 ° C.) conditions.
  • the gas separation membrane was fixed to the gas separation membrane cell 83, and the durability test He gas was supplied at 100 kPa / min so that the pressure in the supply side chamber 81 was 500 kPa, and held for 10 minutes from the time when it reached 500 kPa. Subsequently, the same procedure was repeated, and the pressure was increased to 700 kPa and 900 kPa in order. In the process of increasing the pressure and maintaining the pressure, the presence or absence of leakage in the permeation side chamber 82 was detected by the flow meter 84.
  • Example 1 6.67 parts by weight of water, 5.06 parts by weight of a 15% by weight aqueous solution of polyvinyl alcohol (PVA) as a hydrophilic resin (A) (trade name "Poval 217", manufactured by Kuraray Co., Ltd.), and a basic polymer.
  • PVA polyvinyl alcohol
  • A hydrophilic resin
  • the coating liquid obtained above was used as a first porous layer of a hydrophobic PTFE porous membrane (trade name "Poreflon HP-010-50" (thickness: 50 ⁇ m, average pore size: 0.1 ⁇ m, pore ratio: 73 volume%), The contact angle of water at a temperature of 25 ° C.: 113 ° C.) was applied to one side of Sumitomo Electric Fine Polymer Co., Ltd.) at a temperature of 20 to 25 ° C. Subsequently, the above-mentioned hydrophobic PTFE porous film as the second porous layer is laminated on the opposite side of the coating liquid film formed on the first porous layer from the first porous layer, and this is placed in the dryer.
  • a hydrophobic PTFE porous membrane trade name "Poreflon HP-010-50" (thickness: 50 ⁇ m, average pore size: 0.1 ⁇ m, pore ratio: 73 volume%)
  • Example 2 5.22 parts by weight of water, 3.96 parts by weight of a 15% by weight aqueous solution of polyvinyl alcohol (PVA) as the hydrophilic resin (A), and 50% by weight polyethyleneimine (PEI) as the basic polymer (B). After mixing 10.80 parts by weight of the aqueous solution, 4.88 parts by weight of glycine (Gly) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as the amino acid (C) and 50% by weight cesium hydroxide aqueous solution as the alkali metal compound (D).
  • PVA polyvinyl alcohol
  • PEI polyethyleneimine
  • Gas separation having a thickness of 42 ⁇ m was obtained in the same manner as in Example 1 except that 19.50 parts by weight and 0.03 part by weight of a 10% by weight aqueous surfactant solution were added and mixed to obtain a mixed solution.
  • a gas separation film having a functional layer was obtained.
  • the same PVA, PEI aqueous solution, cesium hydroxide, and surfactant aqueous solution as those used in Example 1 were used.
  • Table 1 shows the results of calculating the ratio (NC / NB) of the number of nitrogen atoms contained in the total amount of each of the basic polymer (B) and the amino acid (C) contained in the mixed solution.
  • the obtained gas separation membrane was evaluated for CO 2 gas permeation performance (Test Example 1: sweep method) and membrane durability by a durability test. The results are shown in Table 1.
  • Example 3 10.98 parts by weight of water, a 3.85% by weight aqueous solution of polyacrylic acid (PAA (1)) as a hydrophilic resin (A) (trade name "Akpec HV-501E", manufactured by Sumitomo Seika Co., Ltd.) 21.43 After mixing 1.65 parts by weight by weight and 1.65 parts by weight of a 50% by weight polyethyleneimine (PEI) aqueous solution as the basic polymer (B), 1.64 parts by weight of sarcosin (Sar) as the amino acid (C) and alkali.
  • PAA (1) polyacrylic acid
  • A hydrophilic resin
  • PI polyethyleneimine
  • Sar sarcosin
  • Example 1 Except that 5.53 parts by weight of a 50% by weight cesium hydroxide aqueous solution as a metal compound (D) and 0.15 parts by weight of a 10% by weight surfactant aqueous solution were added and mixed to obtain a mixed solution. , A gas separation film having a gas separation functional layer having a thickness of 39 ⁇ m was obtained in the same manner as in Example 1. As the PEI aqueous solution, Sar, cesium hydroxide, and the surfactant aqueous solution, the same ones used in Example 1 were used. Table 1 shows the results of calculating the ratio (NC / NB) of the number of nitrogen atoms contained in the total amount of each of the basic polymer (B) and the amino acid (C) contained in the mixed solution. In addition, the obtained gas separation membrane was evaluated for CO 2 gas permeation performance (Test Example 1: sweep method) and membrane durability by a durability test. The results are shown in Table 1.
  • Example 4 40.00 parts by weight of water, 21.43 parts by weight of a 3.85% by weight aqueous solution of polyacrylic acid (PAA (1)) as the hydrophilic resin (A), 50% by weight polyethylene as the basic polymer (B) After mixing 1.65 parts by weight of imine (PEI), 0.75 parts by weight of glycine (Gly) as amino acid (C) and 2.98 parts by weight of 50% by weight cesium hydroxide aqueous solution as alkali metal compound (D). , And 0.15 parts by weight of a 10% by weight aqueous surfactant solution were added and mixed to obtain a mixed solution, but a gas having a gas separation functional layer having a thickness of 34 ⁇ m was obtained in the same manner as in Example 1.
  • PAA (1) polyacrylic acid
  • a separation film was obtained.
  • the PAA (1), the PEI aqueous solution, Gly, cesium hydroxide, and the surfactant aqueous solution were the same as those used in Examples 1 to 3.
  • Table 1 shows the results of calculating the ratio (NC / NB) of the number of nitrogen atoms contained in the total amount of each of the basic polymer (B) and the amino acid (C) contained in the mixed solution.
  • the obtained gas separation membrane was evaluated for CO 2 gas permeation performance (Test Example 1: sweep method) and membrane durability by a durability test. The results are shown in Table 1.
  • Example 5 41.31 parts by weight of water, polyacrylic acid as hydrophilic resin (A) and sodium polyacrylate (PAA (2)) (trade name "Akpek HV-501E", trade name “Acpana AP-40", both (Manufactured by Sumitomo Seika)) 1.30 parts by weight (1.08 parts by weight of polyacrylic acid, 0.22 parts by weight of sodium polyacrylate.
  • This sodium polyacrylate was partially saponified, that is, A mixture of 6.72 parts by weight of polyacrylic acid in the form of sodium polyacrylate) and a 15% by weight polyallylamine aqueous solution (trade name "PAA15C", manufactured by Nittobo Medical Co., Ltd.) as a basic polymer (B).
  • Table 1 shows the results of calculating the ratio (NC / NB) of the number of nitrogen atoms contained in the total amount of each of the basic polymer (B) and the amino acid (C) contained in the mixed solution.
  • the obtained gas separation membrane was evaluated for CO 2 gas permeation performance (Test Example 1: sweep method) and membrane durability by a durability test. The results are shown in Table 1.
  • Table 1 shows the results of calculating the ratio (NC / NB) of the number of nitrogen atoms contained in the total amount of each of the basic polymer (B) and the amino acid (C) contained in the mixed solution.
  • the obtained gas separation membrane was evaluated for CO 2 gas permeation performance (Test Example 1: sweep method) and membrane durability by a durability test. The results are shown in Table 1.
  • a gas separation function having a thickness of 29 ⁇ m was obtained in the same manner as in Example 1 except that 0.42 parts by weight and 0.15 parts by weight of a 10% by weight aqueous surfactant solution were added and mixed to obtain a mixed solution.
  • a gas separation film having a layer was obtained.
  • the PAA (1), the PEI aqueous solution, Sar, the lithium hydroxide monohydrate, and the surfactant aqueous solution were the same as those used in Examples 1, 3 and Comparative Example 1.
  • Table 1 shows the results of calculating the ratio (NC / NB) of the number of nitrogen atoms contained in the total amount of each of the basic polymer (B) and the amino acid (C) contained in the mixed solution.
  • the obtained gas separation membrane was evaluated for CO 2 gas permeation performance (Test Example 1: sweep method) and membrane durability by a durability test. The results are shown in Table 1.
  • the PAA (1), the PEI aqueous solution, Gly, the lithium hydroxide monohydrate, and the surfactant aqueous solution were the same as those used in Examples 1 to 3 and Comparative Example 1.
  • Table 1 shows the results of calculating the ratio (NC / NB) of the number of nitrogen atoms contained in the total amount of each of the basic polymer (B) and the amino acid (C) contained in the mixed solution.
  • the obtained gas separation membrane was evaluated for CO 2 gas permeation performance (Test Example 1: sweep method) and membrane durability by a durability test. The results are shown in Table 1.
  • Example 1 A separation film was obtained.
  • the PAA (1), PEI aqueous solution, Sar, cesium hydroxide, and surfactant aqueous solution used were the same as those used in Examples 1 and 3.
  • Table 1 shows the results of calculating the ratio (NC / NB) of the number of nitrogen atoms contained in the total amount of each of the basic polymer (B) and the amino acid (C) contained in the mixed solution.
  • the obtained gas separation membrane was evaluated for CO 2 gas permeation performance (Test Example 1: sweep method) and membrane durability by a durability test. The results are shown in Table 1.
  • a separation film was obtained.
  • the PAA (1), the PEI aqueous solution, Gly, cesium hydroxide, and the surfactant aqueous solution were the same as those used in Examples 1 to 3.
  • Table 1 shows the results of calculating the ratio (NC / NB) of the number of nitrogen atoms contained in the total amount of each of the basic polymer (B) and the amino acid (C) contained in the mixed solution.
  • the obtained gas separation membrane was evaluated for CO 2 gas permeation performance (Test Example 1: sweep method) and membrane durability by a durability test. The results are shown in Table 1.
  • Example 6 A gas separation membrane was obtained in the same procedure as in Example 1. The obtained gas separation membrane was evaluated for the selective permeation performance of CO 2 gas (Test Example 2: Decompression method). The results are shown in Table 2.
  • 1,1a Gas separation membrane element 1,1a Gas separation membrane element, 3 Supply side flow path member, 4 Permeation side flow path member, 5 Central tube, 10 Gas separation membrane, 50 holes, 51 Supply side end, 52 Discharge port, 53 Discharge side end, 55 Telescope prevention plate, 61 Gas separation membrane cell, 62 Supply side chamber (supply side space), 63 Permeation side chamber (permeation side space), 64 Cooling trap, 65 Back pressure regulator, 66 Cooling trap, 67 Gas chromatograph, 68 Quantitative Liquid feed pump, 69 back pressure regulator, 70 fixed quantity liquid feed pump, 71 decompression pump (decompression part), 81 supply side chamber, 82 permeation side chamber, 83 gas separation membrane cell, 84 flow meter.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette composition contient une résine hydrophile, un polymère basique contenant un atome d'azote, un acide aminé et un composé de métal alcalin. L'élément de métal alcalin contenu dans le composé de métal alcalin comprend du rubidium et/ou du césium. Le rapport du nombre d'atomes d'azote (NC mol) contenu dans l'acide aminé entier au nombre d'atomes d'azote (NB mol) contenu dans l'ensemble du polymère basique, à savoir NC/NB se situe dans la plage de 0,1 à 2 (inclus).
PCT/JP2020/020533 2019-05-29 2020-05-25 Composition, membrane de séparation de gaz et son procédé de production, et dispositif de séparation de gaz WO2020241565A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019100351A JP7264722B2 (ja) 2019-05-29 2019-05-29 組成物、ガス分離膜及びその製造方法、並びにガス分離装置
JP2019-100351 2019-05-29

Publications (1)

Publication Number Publication Date
WO2020241565A1 true WO2020241565A1 (fr) 2020-12-03

Family

ID=73547882

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/020533 WO2020241565A1 (fr) 2019-05-29 2020-05-25 Composition, membrane de séparation de gaz et son procédé de production, et dispositif de séparation de gaz

Country Status (2)

Country Link
JP (1) JP7264722B2 (fr)
WO (1) WO2020241565A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005059448A (ja) * 2003-08-15 2005-03-10 Oji Paper Co Ltd インクジェット記録用シート
JP2010202870A (ja) * 2009-02-27 2010-09-16 General Electric Co <Ge> アミノ酸可動キャリアを含むメンブレン
JP2013049048A (ja) * 2011-08-01 2013-03-14 Renaissance Energy Research:Kk Ｃｏ２促進輸送膜及びその製造方法
JP2018172563A (ja) * 2017-03-31 2018-11-08 住友化学株式会社 相互貫入網目構造を有するゲル

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005059448A (ja) * 2003-08-15 2005-03-10 Oji Paper Co Ltd インクジェット記録用シート
JP2010202870A (ja) * 2009-02-27 2010-09-16 General Electric Co <Ge> アミノ酸可動キャリアを含むメンブレン
JP2013049048A (ja) * 2011-08-01 2013-03-14 Renaissance Energy Research:Kk Ｃｏ２促進輸送膜及びその製造方法
JP2018172563A (ja) * 2017-03-31 2018-11-08 住友化学株式会社 相互貫入網目構造を有するゲル

Also Published As

Publication number Publication date
JP2020193288A (ja) 2020-12-03
JP7264722B2 (ja) 2023-04-25

Similar Documents

Publication Publication Date Title
US10507434B2 (en) Composition for CO2 gas separation membrane, CO2 gas separation membrane and method for producing same, and CO2 gas separation membrane module
TWI724504B (zh) 分離膜片、分離膜元件、分離膜模組及分離膜片的製造方法
JP7089356B2 (ja) 酸性ガス分離膜シートの製造方法及び製造装置
WO2017175656A1 (fr) Membrane de séparation de gaz acide et procédé de séparation de gaz acide utilisant celle-ci, module de séparation de gaz acide et dispositif de séparation de gaz acide
WO2020241565A1 (fr) Composition, membrane de séparation de gaz et son procédé de production, et dispositif de séparation de gaz
WO2022014302A1 (fr) Composition de résine pour membrane de séparation de gaz et membrane de séparation de gaz
WO2020241563A1 (fr) Composition, film de séparation de gaz et son procédé de production, et dispositif de séparation de gaz
WO2021039309A1 (fr) Membrane de séparation de gaz acide, dispositif de séparation de gaz acide, procédé de production d&#39;une membrane de séparation de gaz acide, et procédé de séparation de gaz acide
CN112739449B (zh) 对于制造酸性气体分离膜有用的组合物
WO2022014301A1 (fr) Membrane de séparation de gaz et son procédé de production
WO2021117362A1 (fr) Procédé de séparation de gaz et dispositif de séparation de gaz
EP4331713A1 (fr) Membranes de mélange de polymères acide-basique pour séparation sélective de gaz

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20814273

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20814273

Country of ref document: EP

Kind code of ref document: A1