WO2016047351A1 - Membrane de séparation de gaz, module de séparation de gaz, séparateur de gaz et procédé de séparation de gaz - Google Patents

Membrane de séparation de gaz, module de séparation de gaz, séparateur de gaz et procédé de séparation de gaz Download PDF

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Publication number
WO2016047351A1
WO2016047351A1 PCT/JP2015/074001 JP2015074001W WO2016047351A1 WO 2016047351 A1 WO2016047351 A1 WO 2016047351A1 JP 2015074001 W JP2015074001 W JP 2015074001W WO 2016047351 A1 WO2016047351 A1 WO 2016047351A1
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gas separation
group
gas
layer
separation membrane
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PCT/JP2015/074001
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English (en)
Japanese (ja)
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幸治 弘中
史織 木原
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富士フイルム株式会社
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Priority to JP2016550052A priority Critical patent/JP6355058B2/ja
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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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—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
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • B01D71/16—Cellulose acetate
    • 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

Definitions

  • the present invention relates to a gas separation membrane, a gas separation module, a gas separation apparatus, and a gas separation method.
  • Materials made of polymer compounds have gas permeability that is unique to each material. Based on its properties, a desired gas component can be selectively permeated and separated by a membrane composed of a specific polymer compound.
  • a membrane composed of a specific polymer compound.
  • separation and recovery of carbon dioxide from large-scale carbon dioxide sources in thermal power plants, cement plants, steel mill blast furnaces, etc. in relation to the problem of global warming It is being considered. And this membrane separation technology is focused as a solution to environmental problems that can be achieved with relatively small energy.
  • the membrane is plasticized due to high pressure conditions and the effects of impurities (for example, benzene, toluene, xylene) present in natural gas, and this causes a problem of reduction in separation selectivity.
  • impurities for example, benzene, toluene, xylene
  • it is known that it is effective to introduce a cross-linked structure or a branched structure into the polymer compound constituting the film (for example, Patent Documents 3 to 8).
  • the gas separation layer should be made thin to ensure sufficient gas permeability.
  • a method for that purpose there is a method of making a portion contributing to separation into a thin layer called a dense layer or a skin layer by making the polymer compound into an asymmetric membrane by a phase separation method.
  • the dense layer is used as a gas separation layer, and the portion other than the dense layer is made to function as a support layer responsible for the mechanical strength of the membrane.
  • a form of a composite membrane is also known in which a material having a gas separation function and a material having mechanical strength are different materials.
  • the composite membrane has, on a gas permeable support carrying the mechanical strength, has a structure in which the gas separation layer of the thin layer of polymer compound is formed.
  • the present invention is a gas separation membrane having excellent gas permeability as well as excellent gas separation selectivity, which exhibits excellent gas separation performance even when used under high pressure conditions, and is present in natural gas. It is an object of the present invention to provide a gas separation membrane which is less susceptible to the influence of impurity components such as Another object of the present invention is to provide a gas separation module, a gas separation apparatus, and a gas separation method using the gas separation membrane.
  • the present inventors diligently studied in view of the above problems. As a result, when an additive having a specific structure having a pentafluorophenyl group or a tetrafluorophenylene group is added to a polymer having gas separation ability, and a gas separation layer is formed using this, a thin layer gas free of membrane defects is obtained.
  • a gas separation membrane capable of forming a separation layer and further having this gas separation layer is excellent in both gas permeability and gas separation selectivity even under high pressure conditions, and is highly resistant to impurities such as toluene. Was found to indicate.
  • the present invention has been completed based on these findings.
  • a gas separation membrane comprising a gas separation layer comprising a polymer having gas separation ability, comprising:
  • the gas separation layer contains a nonionic compound having a molecular weight of 300 to 5000 represented by any one of the following general formulas (a-1) to (a-4), and the above nonionic in the gas separation layer Separation membrane, wherein the content of the organic compound is 0.01 to 30% by mass.
  • X represents an n-valent group, and n is an integer of 1 or more.
  • L 21 , L 22 , L 31 , L 32 , L 41 and L 42 each represent a substituent other than a fluorine atom.
  • substituents and the like when there are a plurality of substituents, linking groups and the like (hereinafter referred to as substituents and the like) represented by specific symbols, or when a plurality of substituents and the like are defined simultaneously or alternatively,
  • the substituents and the like mean that they may be the same or different. The same applies to the definition of the number of substituents and the like.
  • or repeating unit may be same or different.
  • a substituent which does not specify substitution or non-substitution means that the group may have any substituent within a range that produces a desired effect. . This is also the same as for compounds in which no substitution or substitution is specified.
  • a substituent is referred to in the present specification, unless otherwise specified, a group selected from Substituent Group Z described below is taken as its preferred range.
  • the gas separation membrane, the gas separation module, and the gas separation apparatus of the present invention have excellent gas permeability as well as excellent gas separation selectivity, and have excellent gas separation performance even when used under high pressure conditions. Furthermore, the gas separation membrane, the gas separation module, and the gas separation apparatus of the present invention are not easily affected by impurity components such as toluene present in natural gas.
  • the gas can be separated with excellent gas permeability and excellent gas separation selectivity, and the gas can be separated efficiently even under high pressure conditions. Furthermore, excellent gas separation performance is maintained even if impurities such as toluene are present in the gas.
  • FIG. 1 is a cross-sectional view schematically showing an embodiment of a gas separation composite membrane of the present invention. It is sectional drawing which shows typically another embodiment of the gas-separation composite film of this invention.
  • the gas separation membrane of the present invention uses a composition containing a specific amount of a polymer having gas separation ability and a nonionic compound having a specific structure (hereinafter, may be simply referred to as "nonionic compound"). And a gas separation layer formed. In the gas separation layer, it is preferable that the polymer and the nonionic compound be present homogeneously.
  • Nonionic compound used in the present invention is represented by any one of the following general formulas (a-1) to (a-4).
  • non-ionic when the compound was dissolved in a solvent, means having no charged groups are ionized.
  • X represents an n-valent group.
  • n is an integer of 1 or more, preferably 2 or more, more preferably 2 to 4, and still more preferably 4.
  • X does not contain either a pentafluorophenyl group (—C 6 F 5 ) or a tetrafluorophenylene group (—C 6 F 4 —).
  • X preferably has an aromatic ring.
  • the aromatic ring includes a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring and a quinoline ring.
  • R c1 , R c2 and R c3 are a hydrogen atom or a group selected from a hydroxy group, a carboxy group and an alkyl group.
  • the alkyl group is an alkyl group having a linear or branched structure, preferably a linear alkyl group.
  • the carbon number of the alkyl group is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, and still more preferably an integer of 1 to 3.
  • n is 1, the molecular weight of X is preferably 150 to 500, and more preferably 150 to 300.
  • R c1 to R c5 has the same meaning as R c1 described for X when n is 1.
  • X may have a ring structure.
  • R s1 and R s2 represent a group selected from an alkyl group and an alkoxy group.
  • the alkyl group is an alkyl group having a linear or branched structure, and a linear alkyl group is preferable.
  • the carbon number of the alkyl group is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, and still more preferably an integer of 1 to 3.
  • Specific examples of this alkyl group include methyl, ethyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl and octyl, preferably methyl or ethyl, more preferably methyl.
  • Preferred examples of the moiety of an alkyl group linked to O when R s1 and R s2 are alkoxy groups are the same as the preferred examples when R s1 and R s2 are alkyl groups.
  • the molecular weight of X is preferably 14 to 100, and more preferably 25 to 50.
  • the density of fluorine is increased, and the action of extending the polymer chains can be enhanced.
  • X is a trivalent group composed of two or more atoms selected from a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom Is preferred.
  • X preferably has an oxygen atom at its constituent atom, more preferably an ether bond, and still more preferably an ester bond. It is also preferable that X have a hydroxy group.
  • the molecular weight of X is preferably 14 to 500, and more preferably 25 to 200.
  • X is a tetravalent linking group.
  • X preferably contains a ring structure, and more preferably contains an aromatic ring (which may be an aromatic hydrocarbon ring or an aromatic heterocycle; hereinafter the same).
  • the aromatic ring possessed by X is preferably a single ring.
  • the number of aromatic rings in X is preferably 1 to 10, more preferably 1-6, more preferably 1-4, 2-4 is more preferable.
  • X is a macrocyclic ring structure (preferably a porphyrin ring structure) containing a plurality of (preferably 4 or more, more preferably 4 to 10) aromatic rings.
  • the nonionic compound may have a compact structure, but it is preferable that X has a large rigid structure.
  • X has a large rigid structure, the effect of extending polymer chains can be further enhanced without impairing the gas separation performance, and the gas permeability of the gas separation layer can be effectively improved.
  • the molecular weight of X is preferably 25 to 1,000, more preferably 100 to 700, and still more preferably 200 to 500.
  • L 21 and L 22 each represent a substituent other than a fluorine atom. It is preferable that at least any one of L 21 and L 22 has a pentafluorophenyl group. In this case, the sum of the molecular weight of L 21 and the molecular weight of L 22 is preferably 25 to 500.
  • the compound represented by the formula (a-2) is also preferably represented by the following formula (a-2-a).
  • L 1 and L 2 are a single bond or a divalent linking group.
  • R a1 , R a2 and R a3 represent a hydrogen atom or a substituent.
  • the sum of the molecular weight of L 1 and the molecular weight of L 2 is preferably 25 to 500, and more preferably 100 to 300.
  • L 31 and L 32 each represent a substituent other than a fluorine atom.
  • L 31 and L 32 preferably have an aromatic ring, more preferably one aromatic ring.
  • the aromatic ring is not particularly limited, but is preferably a single ring, more preferably a benzene ring.
  • the benzene ring preferably has a halogen atom as a substituent, and in particular, it preferably has 1 to 5, more preferably 2 to 5, and more preferably 3 to 5 fluorine atoms as a substituent.
  • L 31 and L 32 have a pentafluorophenyl group or a tetrafluorophenylene group.
  • Each of R c1 , R c2 and R c3 has the same meaning as R c1 described for X when n is 1.
  • the sum of the molecular weight of L 31 and the molecular weight of L 32 is preferably 100 to 1000, and more preferably 200 to 500. When L 31 and L 32 have an aromatic ring, L 31 and L 32 are preferably the same.
  • L 41 and L 42 each represent a substituent other than a fluorine atom.
  • L 41 and L 42 preferably have an aromatic ring, more preferably one aromatic ring.
  • a benzene ring is preferable.
  • the benzene ring preferably has a fluorine atom as a substituent, more preferably 1 to 5 fluorine atoms, still more preferably 2 to 5 fluorine atoms, and more preferably 3 to 5 fluorine atoms.
  • L 41 and L 42 have a pentafluorophenyl group or a tetrafluorophenylene group.
  • the molecular weight of L 41 and the molecular weight of L 42 are preferably 155 to 1000 in total, more preferably 200 to 500. When L 41 and L 42 have an aromatic ring, L 41 and L 42 are preferably the same.
  • the nonionic compound used in the present invention is not a photoacid generator capable of generating an acid upon irradiation with light, or a photoradical generator generating radicals upon irradiation with light. That is, the non-ionic compound used in the present invention generates acid or radical by light irradiation using an ultraviolet lamp, an ultraviolet light emitting diode or the like having an emission wavelength of 200 nm to 400 nm, and advances photo cationic polymerization or photo radical polymerization. It is not a photoacid generator or a photoradical generator used to It is preferable that the nonionic compound used in the present invention does not contain a boron atom.
  • the nonionic compound used in the present invention functions to improve gas permeability while maintaining gas separation selectivity by penetrating between polymer chains forming the gas separation layer and pushing the polymer chains moderately well. It is considered to have However, even if the photoacid generator or the photoradical generator represented by any one of the formulas (a-1) to (a-4) is contained in the gas separation layer, the above-mentioned action is hardly obtained. Although the reason is not clear, it is presumed that the properties such as polarity possessed by the structures of the photoacid generator and the photoradical generator affect the interaction with the polymer chain.
  • the molecular weight of the nonionic compound used in the present invention is 300 to 5,000, preferably 300 to 3,000, more preferably 300 to 2,000, still more preferably 500 to 2,000, and still more preferably 500 to 2,000. It is preferably 1,500, and more preferably 600 to 1,200.
  • the molecular weight is less than 300, the effect of pushing the polymer chains apart is small, and the gas separation performance of the gas separation layer is difficult to improve.
  • the molecular weight exceeds 5,000, it is difficult to improve the gas separation performance of the gas separation layer. The reason for this is not clear, but is presumed to be because nonionic compounds are less likely to intercalate between polymer chains.
  • the content of the non-ionic compound in the gas separation layer is 0.01 to 30% by mass, preferably 0.02 to 20% by mass, and 0.05 to 15% by mass. Is more preferably 0.1 to 10% by mass, still more preferably 0.5 to 5% by mass, and still more preferably 0.5 to 4% by mass.
  • content of the nonionic compound in a gas separation layer is content of the nonionic compound in gas separation layer solid content.
  • the free volume fraction of the gas separation layer is about 0.1 to 0.3, and the free volume vacancy radius is about 5 to 10 ⁇ . If the balance of the structure of this free volume, the number of pentafluorophenyl group and tetrafluorophenylene group in the nonionic compound to be added, the molecular weight of the nonionic compound and the addition amount of the nonionic compound influences the gas separation performance Conceivable.
  • the pentafluorophenyl group and tetrafluorophenylene group possessed by the nonionic compound used in the present invention have a weak intermolecular force.
  • the nonionic compound used in the present invention when added to the polymer in a specific amount, becomes compatible with the polymer while suppressing the aggregation of the polymer and exerting an effect of appropriately spreading the polymer chains. It is believed that this action can improve the gas permeability without impairing the gas separation selectivity of the gas separation membrane.
  • the nonionic compounds used in the present invention can be synthesized according to known methods, and commercially available products can also be used. Examples of nonionic compounds which can be used in the present invention are shown below, but the present invention is not limited thereto.
  • the gas separation membrane of the present invention comprises a gas separation layer containing a polymer.
  • the polymer which comprises a gas separation layer does not have a restriction
  • the gas separation layer may be a polyimide compound, a polybenzoxazole compound, a polyethersulfone compound, a polyether ketone compound, a polycarbonate compound, a polysulfone compound, a polystyrene compound, a polyaniline compound, a PIM (Polymer of Intrinsic Microporosity) compound, an alkylcellulose and cellulose acetate It can form using 1 type, or 2 or more types selected from.
  • a polyimide compound it is preferable to use a polyimide compound, a polyether ketone compound, a polycarbonate compound or cellulose acetate from the viewpoint of gas separation performance, it is more preferable to use a polyimide compound or cellulose acetate, and it is more preferable to use a polyimide compound.
  • a polymer having gas separation ability forms a 10 ⁇ m thick film made of a polymer, and for the obtained film, the total pressure on the gas supply side is 0.5 MPa at a temperature of 40 ° C.
  • the polymer constituting the gas separation layer preferably has a ring structure from the viewpoint of exhibiting high gas permeability, more preferably has an aromatic ring, and further preferably has a benzene ring.
  • the aromatic ring may be a single ring or a multiple ring structure.
  • the proportion of the benzene ring in the polymer is preferably 20 to 75% by mass, and more preferably 30 to 60% by mass.
  • the proportion of the benzene ring occupied in the polymer is the proportion of the total of the mass of carbon atom and hydrogen atom which the benzene ring in the polymer has in the polymer.
  • the benzene ring When the benzene ring has a substituent on its ring carbon atom, it means the proportion of the structure excluding the substituent. For example, if a benzene ring is present as phenylene in the polymer, the mass of one benzene ring is that of C 6 H 4 . Also, for example, when a benzene ring is present as phenylene having one substituent on a ring-constituting carbon atom, the mass of one benzene ring is a mass of C 6 H 3 .
  • a benzene ring is present as a divalent linking group (a divalent group consisting of two benzene rings) in which two hydrogen atoms are removed from a naphthalene ring
  • this divalent linking group has The mass of the benzene ring is the mass of C 10 H 6 .
  • this divalent linking group is mass benzene ring having is the mass of the C 6 H 3.
  • the polymerization average molecular weight of the polymer used for the gas separation layer is preferably 10,000 to 100,000, and more preferably 30,000 to 500,000.
  • the molecular weight and the degree of dispersion are values measured by GPC (gel filtration chromatography) unless otherwise specified, and the molecular weight is a polystyrene-equivalent weight average molecular weight.
  • the gel packed in the column used in the GPC method is preferably a gel having an aromatic compound as a repeating unit, and examples thereof include a gel composed of a styrene-divinylbenzene copolymer. It is preferable to use 2 to 6 columns connected.
  • the solvent to be used examples include ether solvents such as tetrahydrofuran and amide solvents such as N-methyl pyrrolidinone.
  • the measurement is preferably performed at a solvent flow rate in the range of 0.1 to 2 mL / min, and most preferably in the range of 0.5 to 1.5 mL / min. By performing the measurement within this range, the load on the device is not applied, and the measurement can be performed more efficiently.
  • the measurement temperature is preferably 10 to 50 ° C., and most preferably 20 to 40 ° C.
  • the column and carrier to be used can be appropriately selected according to the physical properties of the polymer compound to be measured.
  • the preferable aspect of the said polyimide compound used for a gas separation layer is demonstrated below.
  • the polyimide compound used for the gas separation layer comprises at least one structural unit represented by the following formula (I) and the following formulas (II-a), (II-b), (III-a) and (III-b) And at least one structural unit represented by the following formula (II-a) or (II-b), and the following formula (III-a) or (III-) It is more preferable to include at least one of the structural units represented by b).
  • the polyimide compound used for the gas separation layer can contain structural units other than the above-mentioned structural units, and the number of moles thereof is 100, where the sum of the number of moles of each repeating unit represented by the above-mentioned formula is 100. And 20 or less, and more preferably 0 to 10. It is particularly preferable that the polyimide resin used in the present invention comprises only each repeating unit represented by each of the above formulas.
  • R represents a group having a structure represented by any one of the following formulas (I-1) to (I-28). * Indicates a binding site to a carbonyl group in formula (I).
  • R is preferably a group represented by the formula (I-1), (I-2) or (I-4), and a group represented by (I-1) or (I-4) Is more preferable, and a group represented by (I-1) is particularly preferable.
  • X 1 to X 3 each represent a single bond or a divalent linking group.
  • this divalent linking group -C (R x ) 2- (R x represents a hydrogen atom or a substituent.
  • R x represents a substituent
  • substituent group Z an alkyl group (a preferred range is the same as the alkyl group shown in the substituent group Z below) is preferable.
  • An alkyl group having a halogen atom as a substituent is more preferable, and trifluoromethyl is particularly preferable.
  • X 3 is linked to any one of the two carbon atoms described on the left and one of the two carbon atoms described on the right.
  • R 1 and R 2 each represent a hydrogen atom or a substituent.
  • substituent groups listed in Substituent Group Z described later can be mentioned.
  • R 1 and R 2 may be bonded to each other to form a ring.
  • R 1 and R 2 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom.
  • the carbon atoms shown in formulas (I-1) to (I-28) may further have a substituent.
  • a postscript Substituent Group Z can be mentioned, and in particular, an alkyl group or an aryl group is preferable.
  • R 3 represents an alkyl group or a halogen atom.
  • the preferable thing of this alkyl group and a halogen atom is synonymous with the preferable range of the alkyl group and halogen atom which were prescribed by the postscript substituent group Z.
  • L1 indicating the number of R 3 is an integer of 0 to 4, preferably 1 to 4 and more preferably 3 to 4.
  • R 3 is preferably an alkyl group, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.
  • R 4 and R 5 each represent an alkyl group or a halogen atom, or a group which forms a ring with X 2 in combination with each other.
  • the preferable thing of this alkyl group and a halogen atom is synonymous with the preferable range of the alkyl group and halogen atom which were prescribed by the postscript substituent group Z.
  • the structure in which R 4 and R 5 are linked is not particularly limited, but a single bond, -O- or -S- is preferable. But R 4 R m1, n1 indicating the number of 5 is an integer of 0 to 4, preferably 1-4, 3-4 is more preferable.
  • R 4 and R 5 are alkyl groups, methyl or ethyl is preferred, and trifluoromethyl is also preferred.
  • R 6 , R 7 and R 8 each represent a substituent.
  • R 7 and R 8 may be bonded to each other to form a ring.
  • l2, m2 and n2 are integers of 0 to 4, preferably 0 to 2, and more preferably 0 to 1.
  • J 1 represents a single bond or a divalent linking group.
  • R b R c R d -** R b to R d each represents a hydrogen atom, an alkyl group or an aryl group, and the preferable range thereof will be described in Substituent Group Z below
  • * -SO 3 - N + R e R f R g -** R e to R g each represents a hydrogen atom, an alkyl group or an aryl group, the preferred range of which is described later in Substituent Group Z And alkylene groups (preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), or arylene groups (preferably 6 to 20 carbon atoms, and more preferably 6 to 6 carbon atoms). 15).
  • J 1 is preferably a single bond, a methylene group or a
  • a 1 is preferably -COOH or -OH.
  • Substituent group Z An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, iso-propyl, tert-butyl and n-octyl And n-decyl, n-hexadecyl, etc.), a cycloalkyl group (preferably having 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and particularly preferably 3 to 10 carbon atoms.
  • an alkyl group preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, iso-propyl, tert-butyl and n-octyl And n-decyl, n-hexadecyl
  • cyclopropyl, cyclopentyl, cyclohexyl etc. alkenyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms; And vinyl, allyl, 2-butenyl, 3-pentenyl and the like), an alkynyl group (preferably having a carbon number of 2 to 6).
  • Acyl group (preferably an acyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl and the like), and alkoxy A carbonyl group (preferably an alkoxycarbonyl group having a carbon number of 2 to 30, more preferably 2 to 20, particularly preferably 2 to 12, and examples thereof include methoxycarbonyl and ethoxycarbonyl), and aryloxy A carbonyl group (preferably an aryloxycarbonyl group having 7 to 30, more preferably 7 to 20, and particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl and the like), an acyloxy group (for example, phenyloxycarbonyl).
  • Preferably it has 2 to 30 carbons, more preferably 2 to 20 carbons, especially It is preferably an acyloxy group having 2 to 10 carbon atoms, and examples thereof include acetoxy, benzoyloxy and the like), an acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably carbon And 2 to 10 acylamino groups, such as acetylamino and benzoylamino).
  • Alkoxycarbonylamino group preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.
  • aryl An oxycarbonylamino group preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino and the like).
  • a sulfonylamino group (preferably having a carbon number of 1 to 30, more preferably a carbon number of 1 to 20, particularly preferably a carbon number of 1 to 12, and examples include methanesulfonylamino, benzenesulfonylamino and the like), sulfamoyl group (Preferably having a carbon number of 0 to 30, more preferably 0 to 20 carbon atoms, particularly preferably a sulfamoyl group having 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and the like phenylsulfamoyl.),
  • a carbamoyl group (preferably having a carbon number of 1 to 30, more preferably having a carbon number of 1 to 20, and particularly preferably having a carbon number of 1 to 12), such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like.
  • An alkylthio group preferably an alkylthio group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio
  • an arylthio group is preferably an arylthio group having a carbon number of 6 to 30, more preferably 6 to 20, particularly preferably 6 to 12, and examples thereof include phenylthio and the like, a heterocyclic thio group (preferably having a carbon number of 1).
  • a heterocyclic thio group e.g. pyridylthio, 2-benzoxazolyl thio, and 2-benzthiazolylthio the like.
  • a sulfonyl group (preferably a sulfonyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl), and sulfinyl groups (preferably)
  • the hetero atom may be a non-aromatic hetero ring, and examples of the hetero atom constituting the hetero ring include a nitrogen atom, an oxygen atom and a sulfur atom, preferably having 0 to 30 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • silyl group preferably, Is preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms.
  • silyloxy group preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms.
  • trimethylsilyloxy, triphenylsilyloxy and the like can be mentioned.
  • substituents may be further substituted by any one or more substituents selected from the above-mentioned Substituent Group Z.
  • substituents when there is a plurality of substituents in one structural site, those substituents are linked to each other to form a ring, or condensed with a part or all of the above structural sites to be aromatic. It may form a ring or an unsaturated heterocyclic ring.
  • the ratio of each repeating unit represented by the above formulas (I), (II-a), (II-b), (III-a) and (III-b) is particularly preferably.
  • it is appropriately adjusted in consideration of gas permeability and separation selectivity according to the purpose (recovery rate, purity, etc.) of gas separation.
  • the ratio (E II / E III ) of the total number of moles of (E III ) is preferably 5/95 to 95/5, more preferably 10/90 to 80/20, and preferably 20/80 to More preferably, it is 60/40.
  • the weight average molecular weight of the polyimide compound used in the present invention is preferably 10,000 to 1,000,000, more preferably 15,000 to 500,000, and still more preferably 20,000 to 200. , 000.
  • the polyimide compound which can be used in the present invention can be synthesized by condensation polymerization of a specific bifunctional acid anhydride (tetracarboxylic acid dianhydride) and a specific diamine.
  • a specific bifunctional acid anhydride tetracarboxylic acid dianhydride
  • a specific diamine for example, a general book (for example, Ikuo Imai and Takuo Yokota, “Latest Polyimide-Basics and Applications-”, NTS Co., Ltd., August 25, 2010, p. 3 to 49 , Etc.) can be appropriately selected.
  • At least one kind of tetracarboxylic acid dianhydride as a raw material is represented by the following formula (VI). It is preferable that all the tetracarboxylic dianhydrides used as a raw material are represented by following formula (VI).
  • R has the same meaning as R in the above formula (I).
  • At least one kind of diamine compound as a raw material is any one of the following formulas (VII-a), (VII-b), (VIII-a) and (VIII-b) It is preferable to be represented by the formula Furthermore, at least one kind of diamine compound as a raw material is represented by the following formula (VII-a) or (VII-b), and at least one kind is represented by the following formula (VIII-a) or (VIII-b) Is preferred. It is preferable that all of the diamine compounds used as the raw materials are represented by any of the following formulas (VII-a), (VII-b), (VIII-a) and (VIII-b).
  • each symbol in the formulas (VII-a) and (VII-b) has the same meaning as the symbol in the above formulas (II-a) and (II-b), respectively. Further, each symbol in the formulas (VIII-a) and (VIII-b) is the same as the symbol in the above formulas (III-a) and (III-b), respectively.
  • diamine compound which can be used for this invention, the following can be mentioned, for example.
  • a polybenzoxazole compound a polyether sulfone compound, a polyether ketone compound, a polycarbonate compound, a polysulfone compound, a polystyrene compound, a polyaniline compound, a PIM (Polymer of Intrinsic Microporosity) compound, an alkyl cellulose or cellulose acetate
  • a polybenzoxazole compound a polyether sulfone compound, a polyether ketone compound, a polycarbonate compound, a polysulfone compound, a polystyrene compound, a polyaniline compound, a PIM (Polymer of Intrinsic Microporosity) compound, an alkyl cellulose or cellulose acetate
  • PIM Polymer of Intrinsic Microporosity
  • FIG. 1 is a longitudinal sectional view schematically showing a gas separation composite membrane 10 according to a preferred embodiment of the present invention.
  • FIG. 1 is a gas separation layer
  • 2 is a support layer (gas permeable support layer) composed of a porous layer.
  • FIG. 2 is a cross-sectional view schematically showing a gas separation composite membrane 20 according to a preferred embodiment of the present invention.
  • a non-woven fabric layer 3 is added as a support layer.
  • support layer upper side means that another layer may be interposed between the support layer and the gas separation layer.
  • the gas separation layer may be formed and disposed on the surface or the inner surface of the porous support (support layer), and at least on the surface, it is easily formed into a composite membrane. be able to.
  • a composite membrane having the advantage of combining high separation selectivity with high gas permeability and mechanical strength can be obtained.
  • the film thickness of the separation layer is preferably as thin as possible under the conditions of imparting high gas permeability while maintaining mechanical strength and separation selectivity.
  • the thickness of the gas separation layer is not particularly limited, but is preferably 0.01 to 5.0 ⁇ m, and more preferably 0.05 to 2.0 ⁇ m.
  • the porous support (porous layer) preferably applied to the gas permeable support layer is not particularly limited as long as it is for the purpose of meeting the mechanical strength and the high gas permeability. Either inorganic material may be used.
  • the porous layer is preferably a porous film of an organic polymer, and its thickness is 1 to 3000 ⁇ m, preferably 5 to 500 ⁇ m, more preferably 5 to 150 ⁇ m.
  • the pore structure of the porous layer usually has an average pore diameter of 10 ⁇ m or less, preferably 0.5 ⁇ m or less, more preferably 0.2 ⁇ m or less.
  • the porosity is preferably 20 to 90%, more preferably 30 to 80%.
  • the molecular weight cut-off of a porous layer is 100,000 or less.
  • the support layer has “gas permeability” means that carbon dioxide is supplied to the support layer (a film consisting of only the support layer) at a temperature of 40 ° C. with the total pressure on the gas supply side being 4 MPa. It means that the permeation rate of carbon dioxide is at least 1 ⁇ 10 ⁇ 5 cm 3 (STP) / cm 2 ⁇ sec ⁇ cmHg (10 GPU). Furthermore, the gas permeability of the support layer is such that the carbon dioxide permeation rate is 3 ⁇ 10 -5 cm 3 (STP) / when carbon dioxide is supplied at a total pressure of 4 MPa at the gas supply side at a temperature of 40 ° C.
  • porous membrane As materials for the porous membrane, conventionally known polymers such as polyolefin resins such as polyethylene and polypropylene, fluorine-containing resins such as polytetrafluoroethylene, polyvinyl fluoride and polyvinylidene fluoride, polystyrene, cellulose acetate, polyurethane And various resins such as polyacrylonitrile, polyphenylene oxide, polysulfone, polyether sulfone, polyimide and polyaramid.
  • the shape of the porous membrane may be any shape such as a flat plate, a spiral, a tube, and a hollow fiber.
  • a support is formed in order to further impart mechanical strength to the lower part of the support layer forming the gas separation layer.
  • a support include woven fabric, non-woven fabric, net and the like, but non-woven fabric is preferably used from the viewpoint of film forming property and cost.
  • the non-woven fabric fibers made of polyester, polypropylene, polyacrylonitrile, polyethylene, polyamide or the like may be used alone or in combination.
  • the non-woven fabric can be produced, for example, by forming main fibers and binder fibers uniformly dispersed in water with a circular net or a long net, and drying with a dryer.
  • it is also preferable to perform pressure heat processing by sandwiching the non-woven fabric between two rolls for the purpose of removing fluff and improving mechanical properties.
  • the method for producing a composite membrane of the present invention preferably includes applying a coating solution containing the above-mentioned polymer and a nonionic compound on a support to form a gas separation layer.
  • a coating liquid is a composition which contains the said polymer and a nonionic compound homogeneously.
  • the content of the polymer in the coating solution is not particularly limited, but is preferably 0.1 to 30% by mass, and more preferably 0.5 to 10% by mass. If the content of the polymer is too low, there is a high possibility that defects may occur in the surface layer contributing to separation when forming a film on a porous support, because the layer easily penetrates the lower layer.
  • the pores may be filled with a high concentration, and the permeability may be lowered.
  • the gas separation membrane of the present invention can be appropriately produced by adjusting the molecular weight, structure, composition and solution viscosity of the polymer of the separation layer.
  • the organic solvent used as the medium of the coating solution is not particularly limited, but hydrocarbon organic solvents such as n-hexane and n-heptane, ester organic solvents such as methyl acetate, ethyl acetate and butyl acetate, Lower alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, aliphatic ketones such as diacetone alcohol, cyclopentanone, cyclohexanone, ethylene glycol , Diethylene glycol, triethylene glycol, glycerin, propylene glycol, ethylene glycol monomethyl or monoethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripez Ethers such as pyren
  • organic solvents are suitably selected in the range that they do not adversely affect the support etc., but preferably they are ester (preferably butyl acetate), alcohol (preferably methanol, ethanol, isopropanol) , Isobutanol), aliphatic ketones (preferably, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, cyclopentanone, cyclohexanone), ethers (ethylene glycol, diethylene glycol monomethyl ether, methylcyclopentyl ether) are preferable, more preferably fat Family ketone type, alcohol type and ether type. Moreover, these can be used combining 1 type or 2 types or more.
  • ester preferably butyl acetate
  • alcohol preferably methanol, ethanol, isopropanol
  • aliphatic ketones preferably, methyl ethyl ketone, methyl isobutyl ketone, diace
  • another layer may be present between the support layer and the gas separation layer.
  • a siloxane compound layer is mentioned as a preferable example of another layer.
  • the irregularities on the outermost surface of the support can be smoothed, and the separation layer can be easily thinned.
  • a siloxane compound which forms a siloxane compound layer the thing in which a principal chain consists of polysiloxane, and the compound which has a siloxane structure and a non-siloxane structure in a principal chain are mentioned.
  • -Siloxane compound whose main chain is composed of polysiloxane-
  • a siloxane compound which the principal chain consists of polysiloxane which can be used for a siloxane compound layer 1 type (s) or 2 or more types of polyorganosiloxane represented by following formula (1) or (2) are mentioned.
  • these polyorganosiloxanes may form a crosslinking reaction product.
  • a cross-linking reaction for example, a compound represented by the following formula (1) is crosslinked by a polysiloxane compound having a group capable of linking by reacting with the reactive group X S of the formula (1) at both ends And other forms of compounds.
  • R S is a non-reactive group and is preferably an alkyl group (preferably having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms) or an aryl group (preferably 6 to carbon atoms 15, more preferably an aryl group having 6 to 12 carbon atoms, still more preferably phenyl).
  • X S is a reactive group and is selected from a hydrogen atom, a halogen atom, a vinyl group, a hydroxyl group, and a substituted alkyl group (preferably having 1 to 18 carbon atoms, more preferably having 1 to 12 carbon atoms) It is preferably a group.
  • Y S and Z S are the above R S or X S.
  • m is a number of 1 or more, preferably 1 to 100,000.
  • n is a number of 0 or more, preferably 0 to 100,000.
  • X S, Y S, Z S, R S, m and n are X S of each formula (1), Y S, Z S, R S, and m and n synonymous.
  • non-reactive group R S when the non-reactive group R S is an alkyl group, examples of the alkyl group include methyl, ethyl, hexyl, octyl, decyl and octadecyl. .
  • examples of the fluoroalkyl group include —CH 2 CH 2 CF 3 and —CH 2 CH 2 C 6 F 13 .
  • examples of the alkyl group include a hydroxyalkyl group having 1 to 18 carbon atoms and an aminoalkyl having 1 to 18 carbon atoms.
  • a carboxyalkyl group having 1 to 18 carbon atoms a chloroalkyl group having 1 to 18 carbon atoms, a glycidoxyalkyl group having 1 to 18 carbon atoms, a glycidyl group, an epoxycyclohexylalkyl group having 7 to 16 carbon atoms, Examples thereof include (1-oxacyclobutane-3-yl) alkyl groups having 4 to 18 carbon atoms, methacryloxyalkyl groups, and mercaptoalkyl groups.
  • the number of carbon atoms of the alkyl group constituting the hydroxyalkyl groups is an integer of 1 to 10, for example, -CH 2 CH 2 CH 2 OH.
  • the preferred carbon number of the alkyl group constituting the above aminoalkyl group is preferably an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 NH 2 .
  • the preferred carbon number of the alkyl group constituting the carboxyalkyl group is preferably an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 COOH.
  • the preferred carbon number of the alkyl group constituting the above chloroalkyl group is preferably an integer of 1 to 10, and preferred examples include -CH 2 Cl.
  • the preferred carbon number of the alkyl group constituting the glycidoxyalkyl group is an integer of 1 to 10, and a preferred example is 3-glycidyloxypropyl.
  • the preferred carbon number of the epoxycyclohexylalkyl group having 7 to 16 carbon atoms is an integer of 8 to 12.
  • the preferred carbon number of the (1-oxacyclobutan-3-yl) alkyl group having 4 to 18 carbon atoms is an integer of 4 to 10.
  • the carbon number of the alkyl group constituting the mercaptoalkyl group is preferably an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 SH.
  • m and n are numbers such that the molecular weight of the compound is 5,000 to 1,000,000.
  • a siloxane unit (wherein the number is m) having no reactive group and a reactive group-containing siloxane unit (wherein the structural unit is represented by the number represented by n)
  • the structural unit is represented by the number represented by n
  • Examples of the compound having a siloxane structure and a non-siloxane structure in the main chain that can be used for the siloxane compound layer include compounds represented by the following formulas (3) to (7).
  • R S, m and n are respectively the same as R S, m and n in formula (1).
  • R L is -O- or -CH 2-
  • R S1 is a hydrogen atom or methyl. Both ends of Formula (3) are preferably an amino group, a hydroxyl group, a carboxy group, a trimethylsilyl group, an epoxy group, a vinyl group, a hydrogen atom, or a substituted alkyl group.
  • n and n are respectively synonymous with m and n in Formula (1).
  • n and n are respectively synonymous with m and n in Formula (1).
  • m and n are respectively synonymous with m and n in Formula (1). It is preferable that an amino group, a hydroxyl group, a carboxy group, a trimethylsilyl group, an epoxy group, a vinyl group, a hydrogen atom, or a substituted alkyl group is bonded to both ends of the formula (6).
  • m and n are respectively synonymous with m and n in Formula (1). It is preferable that an amino group, a hydroxyl group, a carboxy group, a trimethylsilyl group, an epoxy, a vinyl group, a hydrogen atom or a substituted alkyl group is bonded to both ends of the formula (7).
  • the siloxane structural units and the non-siloxane structural units may be distributed randomly.
  • the compound having a siloxane structure and a non-siloxane structure in the main chain preferably contains 50 mol% or more, and more preferably 70 mol% or more of siloxane structural units based on the total number of moles of all repeating structural units. .
  • the weight average molecular weight of the siloxane compound used in the siloxane compound layer is preferably 5,000 to 1,000,000 from the viewpoint of achieving both thin film formation and durability.
  • the method of measuring the weight average molecular weight is as described above.
  • siloxane compound constituting the siloxane compound layer are listed below.
  • the thickness of the siloxane compound layer is preferably 0.01 to 5 ⁇ m, and more preferably 0.05 to 1 ⁇ m from the viewpoint of smoothness and gas permeability.
  • the gas permeability at 40 ° C. and 4 MPa of the siloxane compound layer is preferably 100 GPU or more, more preferably 300 GPU or more, and still more preferably 1000 GPU or more in carbon dioxide transmission rate.
  • the gas separation membrane of the present invention may be an asymmetric membrane.
  • the asymmetric membrane can be formed by a phase conversion method using a solution (polymer solution) containing a polymer having gas separation ability and a nonionic compound.
  • the phase conversion method is a known method in which a polymer solution is brought into contact with a coagulating solution to form a film while phase conversion is performed, and in the present invention, a so-called dry-wet method is suitably used.
  • the solution on the surface of the polymer solution in the form of a film is evaporated to form a thin dense layer (gas separation layer), and then a coagulating solution (a solvent compatible with the solvent of the polymer solution and the polymer is insoluble) And a porous layer is formed by utilizing the phase separation phenomenon occurring at that time to form a porous layer, and proposed by Rob-Slillajan et al. (Eg, US Pat. No. 3,133,132). Specification).
  • the thickness of the surface layer (gas separation layer) contributing to gas separation which is called a dense layer or a skin layer, is not particularly limited, but from the viewpoint of imparting practical gas permeability, 0.
  • the thickness is preferably 01 to 5.0 ⁇ m, and more preferably 0.05 to 1.0 ⁇ m.
  • the porous layer below the dense layer plays a role of lowering mechanical resistance while reducing resistance of gas permeability, and its thickness is particularly large as long as self-supporting property as an asymmetric membrane is given.
  • it is preferably 5 to 500 ⁇ m, more preferably 5 to 200 ⁇ m, and still more preferably 5 to 100 ⁇ m.
  • the gas separation asymmetric membrane of the present invention may be a flat membrane or a hollow fiber membrane.
  • the asymmetric hollow fiber membrane can be produced by a dry-wet spinning method.
  • the dry-wet spinning method is a method of producing an asymmetric hollow fiber membrane by applying the dry-wet method from a spinning nozzle to a polymer solution having a hollow fiber shape.
  • the polymer solution is discharged from a nozzle into a hollow fiber target shape, and after passing through an atmosphere of air or nitrogen gas immediately after the discharge, the polymer is not substantially dissolved and compatible with the solvent of the polymer solution It is a method of immersing in a coagulating solution having the following to form an asymmetric structure, then drying it, and if necessary, heat treatment to produce a separation membrane.
  • the solution viscosity of the polymer solution to be discharged from the nozzle is 2 to 17000 Pa ⁇ s, preferably 10 to 1500 Pa ⁇ s, particularly 20 to 1000 Pa ⁇ s at the discharge temperature (eg 10 ° C.) It is preferable because the shape of can be stably obtained.
  • Immersion in a coagulating solution is performed by immersing in a primary coagulating solution to coagulate to the extent that the shape of a membrane such as hollow fiber can be maintained, then wound on a guide roll, and then immersed in a secondary coagulating solution to sufficiently immerse the entire membrane. It is preferable to coagulate into It is efficient to dry the coagulated membrane after replacing the coagulating solution with a solvent such as hydrocarbon.
  • the heat treatment for drying is preferably carried out at a temperature lower than the softening point or second-order transition point of the polymer used.
  • the content of the polymer in the gas separation layer is not particularly limited as long as the desired gas separation performance can be obtained.
  • the content of the polymer in the gas separation layer is preferably 20% by mass or more, more preferably 40% by mass or more, and 60% by mass or more More preferably, it is particularly preferably 70% by mass or more.
  • the content of the polymer in the gas separation layer may be 100% by mass, but is usually 99% by mass or less.
  • the gas separation membrane (composite membrane and asymmetric membrane) of the present invention can be suitably used for gas separation and recovery, gas separation and purification.
  • gas separation membrane composite membrane and asymmetric membrane
  • the gas separation membrane can efficiently separate a specific gas from a gas mixture containing a gas such as a perfluoro compound of In particular, it is preferable to use a gas separation membrane for selectively separating carbon dioxide from a gas mixture containing carbon dioxide / hydrocarbon (methane).
  • the permeation rate of carbon dioxide at 4 MPa at a temperature of 40 ° C. is preferably more than 20 GPUs, more than 30 GPUs More preferably, 50 to 500 GPU is more preferable, and 100 to 300 GPU is particularly preferable.
  • the permeation rate ratio of carbon dioxide to methane (R CO2 / R CH4 , also referred to as separation selectivity) is preferably 15 or more, more preferably 20 or more, and still more preferably 23 or more, It is particularly preferable that it is 25 to 50.
  • R CO2 indicates the permeation rate of carbon dioxide
  • R CH4 indicates the permeation rate of methane.
  • one GPU is 1 ⁇ 10 ⁇ 6 cm 3 (STP) / cm 2 ⁇ sec ⁇ cmHg.
  • Various polymer compounds can also be added to the gas separation layer of the gas separation membrane of the present invention in order to adjust the membrane physical properties.
  • the polymer compound acrylic polymer, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, vinyl resin, acrylic resin, rubber resin , Waxes and other natural resins can be used. Moreover, two or more of these may be used in combination.
  • nonionic surfactant, cationic surfactant, an organic fluoro compound etc. can also be added for liquid physical-property adjustment.
  • the surfactant examples include alkyl benzene sulfonate, alkyl naphthalene sulfonate, higher fatty acid salt, sulfonate of higher fatty acid ester, sulfate of higher alcohol ether, sulfonate of higher alcohol ether, higher alkyl Sulfonamide alkyl carboxylate, anionic surfactant such as alkyl phosphate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, ethylene oxide adduct of acetylene glycol, Non-ionic surfactants such as ethylene oxide adduct of glycerin, polyoxyethylene sorbitan fatty acid ester, and other amphoteric surfaces such as alkyl betaine and amido betaine Active agents, silicone surface active agent, including a fluorine-based surfactant, can be appropriately selected from surfactants and derivatives thereof
  • a polymer dispersant may be included, and specific examples of the polymer dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, and polyacrylamide. Among them, polyvinyl pyrrolidone is preferably used.
  • the conditions for forming the gas separation membrane of the present invention are not particularly limited, but the temperature is preferably -30 to 100 ° C, more preferably -10 to 80 ° C, and still more preferably 5 to 50 ° C.
  • a gas such as air or oxygen may be allowed to coexist at the time of film formation, but it is desirable to be under an inert gas atmosphere.
  • the gas separation method of the present invention is a method comprising selectively permeating carbon dioxide from a mixed gas containing carbon dioxide and methane using the gas separation membrane of the present invention.
  • the pressure at the time of gas separation is preferably 0.5 to 10 MPa, more preferably 1 to 10 MPa, and still more preferably 2 to 7 MPa.
  • the gas separation temperature is preferably -30 to 90 ° C, and more preferably 15 to 70 ° C.
  • a gas separation module can be prepared using the gas separation membrane of the present invention.
  • modules include spiral type, hollow fiber type, pleat type, tubular type, plate & frame type and the like.
  • the gas separation membrane or the gas separation membrane module of the present invention can be used to obtain a gas separation apparatus having means for separating, recovering, or separating and purifying gas.
  • the gas separation membrane of the present invention may be applied to, for example, a gas separation and recovery apparatus as a membrane / absorption hybrid method used in combination with an absorbent as described in JP-A-2007-297605.
  • Nonionic compound Nonionic compounds A-01 to A-10 shown in Table 1 below were prepared. In addition, Comparative Compounds -01 to 05 were prepared as Comparative Compounds.
  • R 7 , R 8 and R 9 each represent a hydrogen atom or an acetyl group.
  • the above-mentioned P-03 is a commercially available product (trade name: L-70, manufactured by Daicel Corporation, having an acetylation degree of 0.55).
  • the degree of acetylation means the weight percentage of bound acetic acid per unit weight.
  • Example 1 Preparation of Composite Membrane ⁇ Preparation of PAN Porous Membrane with Smooth Layer> (Preparation of radiation curable polymer having dialkyl siloxane group)
  • 39 g of UV 9300 manufactured by Momentive
  • 10 g of X-22-162C manufactured by Shin-Etsu Chemical
  • 10 g of DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) 0. 007 g was added, and 50 g of n-heptane was added and dissolved therein. This was maintained at 95 ° C. for 168 hours to obtain a radiation curable polymer solution (viscosity 22.8 mPa ⁇ s at 25 ° C.) having a polysiloxane structure.
  • Comparative Examples 1 to 10 Preparation of Composite Membrane The same as in Example 1 except that the type of polymer, and the type and amount of the non-ionic compound in Example 1 were changed as described in Table 3 below. Then, composite membranes of Comparative Examples 1 to 10 were produced.
  • Example 19 Preparation of asymmetric membrane 2.5 g of methyl ethyl ketone, 2.5 g of N, N-dimethylformamide and 0.6 g of n-butanol were used with respect to 0.5 g of the polymer (P-03) prepared as described above. The mixed solution was added and dissolved, and then filtered through a PTFE microfiltration membrane with a pore diameter of 5.0 ⁇ m, and this was used as a dope solution.
  • a polyester non-woven fabric (manufactured by Awa Paper Co., Ltd., film thickness: 95 ⁇ m) is laid on a clean glass plate, and the above dope solution is developed in a room temperature (20 ° C.) environment and allowed to stand for 30 seconds, then the primary coagulation solution It was immersed in (0 ° C., 75 wt% methanol aqueous solution) for 1 hour. Then, the asymmetric membrane was produced by further immersing in a secondary coagulating solution (0 ° C., 75 wt% methanol aqueous solution) for 1 hour. The resulting asymmetric membrane is washed with methanol, and then methanol is replaced with isooctane, followed by heating at 50 ° C. for 8 hours and heating at 110 ° C. for 6 hours to evaporate and dry the isooctane, so that the dense skin layer is 0.1 ⁇ m or less
  • the total thickness of the polymer layer was 40 ⁇ m.
  • Example 20 Preparation of Asymmetric Membrane An asymmetric membrane was prepared in the same manner as in Example 19 except that the polymer (P-03) was changed to the polymer (P-05) in Example 19 above.
  • Comparative Examples 11 to 13 Preparation of Asymmetric Membrane The same as Example 19 except that the type of polymer, and the type and addition amount of the nonionic compound in Example 19 were changed as described in Table 3. Then, the asymmetric membranes of Comparative Examples 11 to 13 were produced.
  • Test Example 1 Evaluation of CO 2 Permeation Rate of Gas Separation Membrane-1
  • the performance of the gas separation membrane was evaluated as follows using the gas separation membranes (composite membrane and asymmetric membrane) of each of the above Examples and Comparative Examples.
  • the gas separation membrane was cut into a diameter of 47 mm together with the porous support (support layer) to prepare a permeation test sample.
  • the permeated gas was analyzed by gas chromatography.
  • the gas permeability of the membranes was compared by calculating the gas permeation rate as the gas permeability (Permeance).
  • Evaluation 1 in Table 3 relates to the CO 2 permeation rate, and when the same type of polymer is used, the non-CO 2 permeation rate (QA 1) when the non-ionic compound is not added based on the ratio of CO 2 transmission rate in the case of the addition of ionic compound (QA2) (QA2 / QA1) , it was evaluated by the following evaluation criteria.
  • the gas permeation performance is improved without impairing the gas separation selectivity regardless of the type of the polymer. did. Furthermore, by using a specific amount of the non-ionic compound specified in the present invention for the gas separation layer, the gas separation performance is less likely to deteriorate even when exposed to the impurity component toluene, and the durability is also improved.
  • the mixed gas is replaced with a mixed gas of 10:90 (volume ratio) of carbon dioxide (CO 2 ): methane (CH 4 ) in the above-described Test Examples 1 and 2, as in Table 3 above.
  • a result showing superior gas separation performance as compared with the gas separation membrane of the comparative example was obtained.
  • the gas separation membrane of the present invention can provide an excellent gas separation method, a gas separation module, and a gas separation apparatus provided with this gas separation module.

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Abstract

La présente invention concerne une membrane de séparation de gaz qui est pourvue d'une couche de séparation de gaz qui contient un polymère ayant une capacité de séparation de gaz, et la couche de séparation de gaz contenant un composé non ionique représenté par l'une des formules générales (a-1) à (a-4) et ayant une masse moléculaire comprise entre 300 et 5 000 et la teneur en composé non ionique dans la couche de séparation de gaz étant comprise entre 0,01 et 30 % en masse ; et un module de séparation de gaz, un séparateur de gaz et un procédé de séparation de gaz, chacun de ceux-ci utilisant ladite membrane de séparation de gaz. Dans la formule (a-1), X représente un groupe n-valent et n représente un nombre entier supérieur ou égal à 1. Dans les formules (a-2) à (a-4), chacun des L21, L22, L31, L41 et L42 représente un substituant autre qu'un atome de fluor.
PCT/JP2015/074001 2014-09-22 2015-08-26 Membrane de séparation de gaz, module de séparation de gaz, séparateur de gaz et procédé de séparation de gaz WO2016047351A1 (fr)

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