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WO2018159562A1 - Membrane de séparation de gaz, module de séparation de gaz, dispositif de séparation de gaz, et procédé de séparation de gaz - Google Patents

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

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Publication number
WO2018159562A1
WO2018159562A1 PCT/JP2018/007051 JP2018007051W WO2018159562A1 WO 2018159562 A1 WO2018159562 A1 WO 2018159562A1 JP 2018007051 W JP2018007051 W JP 2018007051W WO 2018159562 A1 WO2018159562 A1 WO 2018159562A1
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Prior art keywords
gas separation
gas
group
separation membrane
layer
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Japanese (ja)
Inventor
北村　哲
基 原田
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Fujifilm Corp
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Fujifilm Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention relates to a gas separation membrane, a gas separation module, a gas separation device, and a gas separation method.
  • a material composed of a polymer compound has gas permeability specific to each material. Based on the property, a desired gas component can be selectively permeated and separated by a membrane composed of a specific polymer compound.
  • this gas separation membrane gas separation membrane
  • Natural gas, biogas biological waste, organic fertilizer, biodegradable substances, sewage, garbage, gas generated by fermentation and anaerobic digestion of energy crops, etc.
  • Patent Document 1 mentions the use of a fluorine-containing cellulose derivative having a specific structure as a separation membrane.
  • a polymer compound is made into an asymmetric membrane by a phase separation method, and a portion contributing to separation is made into a thin layer called a dense layer or a skin layer.
  • a portion other than the dense layer is allowed to function as a support layer that bears the mechanical strength of the membrane.
  • a composite membrane is also known. In this composite membrane, the gas separation layer responsible for the gas separation function and the support layer responsible for the mechanical strength are made of different materials, and the gas separation layer having gas separation ability is formed in a thin layer on the gas permeable support layer. .
  • the present invention realizes both high gas permeability and excellent gas separation selectivity at a sufficient level even when used under high pressure conditions, and enables high-speed and high-selective gas separation. It is an object of the present invention to provide a gas separation membrane that can maintain good gas separation selectivity even when in contact with a plasticizing component. 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.
  • a cellulose compound in a form in which at least a part of the hydrogen atoms constituting the hydroxyl group of cellulose is substituted with a group having active hydrogen and fluorine atoms is used as a gas.
  • this gas separation membrane When used as a gas separation layer of a separation membrane, this gas separation membrane exhibits excellent gas separation selectivity even when used under high pressure conditions, has excellent gas permeability, and is plasticized by the influence of impurity components such as toluene. I found out that it is difficult to make it.
  • the present invention has been completed through further studies based on these findings.
  • R 1 to R 3 represent a hydrogen atom or a substituent.
  • at least one of R 1 to R 3 is a substituent T having an active hydrogen and a fluorine atom and having a molecular weight of 100 or more and less than 500.
  • R f represents a group having a fluorine atom. * Indicates a binding site.
  • L f represents a divalent group having a fluorine atom. * Indicates a binding site.
  • the numerical value range represented by “to” means that the numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
  • substituents when there are a plurality of substituents, linking groups, and the like (hereinafter referred to as substituents) indicated by specific symbols, or when a plurality of substituents are specified simultaneously or alternatively, It means that a substituent etc. may mutually be same or different. The same applies to the definition of the number of substituents and the like. Further, when there are repetitions of a plurality of partial structures represented by the same indication in the formula, each partial structure or repeating unit may be the same or different.
  • the term “compound” or “group” is used to mean a compound or group itself, a salt thereof, or an ion thereof. In addition, it means that a part of the structure is changed as long as the desired effect is achieved.
  • the gas separation membrane of the present invention contains a specific cellulose compound in the gas separation layer. A preferred embodiment of the gas separation membrane of the present invention will be described.
  • R 1 to R 3 represent a hydrogen atom or a substituent. At least one of R 1 to R 3 is a substituent having an active hydrogen and a fluorine atom and having a molecular weight of 100 or more and less than 500 (hereinafter referred to as “substituent T”).
  • a hydrogen bond constituting a urethane bond (—O—CO—NH—) or a boric acid group (—B (OH) 2 ), and a hydrogen atom constituting a hydroxyl group, a carboxy group or a urethane bond is preferably More preferably, it is a hydrogen atom which comprises a carboxy group or a urethane bond.
  • the cellulose compound preferably has methyl or acetyl as R 1 to R 3 .
  • R 1 to R 3 By these forms, it can be set as the form which methoxy or acetyloxy was introduce
  • Methoxy and acetyloxy are compact polar groups, and are preferable because they can increase the solubility of the cellulose compound in a solvent without deteriorating gas separation selectivity.
  • At least one of R 1 to R 3 is a group represented by any one of the following general formulas (2-1) to (2-3) (the following general formulas (2-1) to (2-3) It is preferable that it is the substituent T) represented by either.
  • * indicates a binding site (bonding hand).
  • the aryl group having a fluorine atom is preferably phenyl having a fluorine atom.
  • R f is preferably an aryl group having a fluorine atom as a substituent and / or an aryl group having a fluorinated alkyl group (preferably trifluoromethyl).
  • the aryl group preferably has active hydrogen, and the aryl group having active hydrogen is preferably an aryl group having a hydroxyl group or a carboxy group. Preferred specific examples of R f are shown below.
  • R 1 to R 3 is a group represented by any one of the following general formulas (3-1) to (3-3) (the following general formulas (3-1) to (3-3) It is also preferred that it is a substituent T) represented by any one of
  • L f represents a divalent group having a fluorine atom.
  • L f is preferably an alkylene group or an arylene group having a fluorine atom, and more preferably an arylene group having a fluorine atom.
  • the alkylene group having a fluorine atom which can be taken as L f , preferably has 1 to 8 carbon atoms, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 to 3.
  • the substituent T is a group represented by any one of the above general formulas (3-1) to (3-3), gas separation selectivity or plasticization resistance tends to be further improved.
  • the substituent T is a group represented by any one of the general formulas (3-1) to (3-3), the general formula is used from the viewpoint of membrane rigidity that affects gas separation selectivity and plasticization resistance.
  • a group represented by (3-1) is more preferable.
  • the cellulose compound used in the present invention is a group represented by any one of general formulas (2-1) to (2-3) and general formulas (3-1) to (3-3) as R 1 to R 3. May have two or more groups.
  • the cellulose compounds used in the present invention have groups represented by general formulas (2-1) to (2-3) as R 1 to R 3 , the general formulas (3-1) to (3- 3)
  • the general formula (2-1) ) To (2-3) are preferred.
  • the ratio of the total number of groups is preferably 25 to 100%, more preferably 50 to 100%, and further preferably 75 to 100%.
  • the cellulose compound preferably has a degree of substitution with a substituent T of 0.5 or more and 3.0 or less from the viewpoint of solubility in a solvent necessary for film formation and gas permeability.
  • substitution degree of the cellulose compound will be described.
  • the ⁇ -1,4-bonded glucose unit constituting cellulose has a total of three hydroxyl groups at the 2nd, 3rd and 6th positions.
  • the degree of substitution of the cellulose compound indicates the degree of substitution of hydrogen atoms in these hydroxyl groups with other groups. For example, when all of the hydrogen atoms constituting the 2nd, 3rd, and 6th hydroxyl groups of all glucose units are substituted with other groups, the degree of substitution is 3.
  • the cellulose compound has a degree of substitution by a substituent T of 1.0 or more and 2.75 or less from the viewpoint of enhancing solubility in a solvent while imparting desired gas separation selectivity and gas permeability to the gas separation layer. It is preferable that it is 1.5 or more and 2.5 or less.
  • the degree of substitution with the substituent T is preferably 1.0 to 2.5, and more preferably 1.0 to 2.0.
  • the cellulose compound preferably has a degree of substitution (including substitution with a substituent T) of more than 2.5, preferably more than 2.8, more preferably more than 2.9. That is, it is preferable that the cellulose compound has a smaller amount of hydroxyl groups. When the amount of hydroxyl groups is large, gas permeability tends to decrease.
  • the molecular weight of the cellulose compound is preferably a number average molecular weight (Mn) in the range of 5 ⁇ 10 3 to 1000 ⁇ 10 3 , more preferably in the range of 10 ⁇ 10 3 to 500 ⁇ 10 3 , and 10 ⁇ 10 3 to 200 ⁇ . 10 3 ranges are most preferred.
  • the weight average molecular weight (Mw) is preferably in the range of 7 ⁇ 10 3 to 10000 ⁇ 10 3 , more preferably in the range of 15 ⁇ 10 3 to 5000 ⁇ 10 3 , and in the range of 100 ⁇ 10 3 to 3000 ⁇ 10 3 . Is most preferred.
  • the manufacturing method of the cellulose compound used for this invention is not specifically limited, It can obtain by introduce
  • the etherification reaction for example, by reacting cellulose with various alkyl halides, various aryl halides, various epoxies and the like in the presence of a base, a target cellulose compound can be obtained.
  • the target cellulose compound can be obtained by making a cellulose react with various acid chlorides, various acid anhydrides, etc., for example.
  • the raw material cellulose is not particularly limited.
  • substituted celluloses such as ethyl cellulose can also be used. Details of these raw material celluloses can be found in, for example, Marusawa and Uda, “Plastic Materials Course (17) Fibrous Resin”, Nikkan Kogyo Shimbun (published in 1970), and Japan Institute of Invention and Technology Publication No. 2001-2001. 1745 (pages 7 to 8).
  • FIG. 1 is a longitudinal sectional view schematically showing a gas separation composite membrane 10 which is a preferred embodiment of the present invention. 1 is a gas separation layer, 2 is a support layer. FIG. 2 is a cross-sectional view schematically showing a gas separation composite membrane 20 which is another preferred embodiment of the present invention.
  • the nonwoven fabric layer 3 is added as a further support body. 1 and 2 show a mode in which carbon dioxide is selectively permeated from a mixed gas of carbon dioxide and methane.
  • upper support layer means that another layer may be interposed between the support layer and the gas separation layer.
  • the side on which the gas to be separated is supplied is “upper”, and the side on which the separated gas (permeate gas) is emitted is “lower”.
  • a gas separation layer is formed on at least the surface of the gas permeable support layer.
  • a composite membrane having both gas separation selectivity and gas permeability and mechanical strength can be obtained.
  • the layer thickness of the gas separation layer is preferably a thin film as much as possible within the range showing high gas permeability while having desired mechanical strength and separation selectivity.
  • the thickness of the gas separation layer is preferably 0.01 to 5.0 ⁇ m, and more preferably 0.05 to 2.0 ⁇ m.
  • the support layer is not particularly limited as long as it has the purpose of meeting mechanical strength and high gas permeability, and may be either organic or inorganic material.
  • An organic polymer porous film is preferable, and the thickness thereof is 1 to 3000 ⁇ m, preferably 5 to 500 ⁇ m, and more preferably 5 to 150 ⁇ m.
  • the pore structure of this porous membrane 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 support layer has “gas permeability” means that carbon dioxide is supplied to the support layer (a film composed of only the support layer) at a temperature of 40 ° C.
  • the permeation rate of carbon dioxide is 1 ⁇ 10 ⁇ 5 cm 3 (STP) / cm 2 ⁇ sec ⁇ cmHg (10 GPU) or more.
  • the gas permeability of the support layer is such that when carbon dioxide is supplied at a temperature of 40 ° C. and the total pressure on the gas supply side is 4 MPa, the carbon dioxide permeation rate is 3 ⁇ 10 ⁇ 5 cm 3 (STP) / It is preferably cm 2 ⁇ sec ⁇ cmHg (30 GPU) or more, more preferably 100 GPU or more, further preferably 200 GPU or more, and further preferably 500 GPU or more.
  • the material for the support layer examples include 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, Polyacrylonitrile, polyphenylene oxide, polysulfone, polyethersulfone, polyimide, polyaramid and the like can be mentioned.
  • the shape of the support layer can be any shape such as a flat plate shape, a spiral shape, a tubular shape, and a hollow fiber shape.
  • the gas separation membrane of the present invention is not limited to the above-described composite membrane, but is preferably an asymmetric membrane as described later.
  • the gas separation membrane of the present invention is preferably in the form of a composite membrane in which a gas separation layer is provided on a gas-permeable support layer (porous support layer).
  • the gas separation membrane of the present invention can be in the form of an asymmetric membrane in which the support and the gas separation layer are integrally formed of the same cellulose compound.
  • the composite membrane of the present invention preferably includes forming a gas separation layer by applying a coating liquid containing the cellulose compound on a gas permeable support layer and drying the coating membrane.
  • the cellulose compound content in the coating solution is not particularly limited, but is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass.
  • the content of the cellulose compound is too small, when the film is formed on the porous support, it easily penetrates into the lower layer, and there is a high possibility that defects will occur in the surface layer that contributes to separation.
  • the cellulose compound content is too high, the pores are filled at a high concentration when a film is formed on the porous support, and sufficient permeability may not be obtained.
  • the organic solvent used as a medium for the coating solution is not particularly limited, but hydrocarbons such as n-hexane and n-heptane, esters such as methyl acetate, ethyl acetate and butyl acetate; methanol, ethanol, n- Alcohols such as propanol, isopropanol, n-butanol, isobutanol, tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerin, propylene glycol; acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, cyclopentanone, cyclohexanone, etc.
  • hydrocarbons such as n-hexane and n-heptane, esters such as methyl acetate, ethyl acetate and butyl acetate
  • methanol, ethanol, n- Alcohols such as
  • Aliphatic ketones ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tri Lopylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol phenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, dibutyl ether, tetrahydrofuran, methylcyclopentyl ether,
  • Examples include ethers such as dioxane; N-methylpyrrolidone, 2-pyrrolidone, dimethylformamide, dimethylimidazolidinone, dimethyl sulfoxide, and dimethylacetamide, and one or more of these can be used.
  • another layer may exist between the support layer and the gas separation layer.
  • a preferred example of the other layer is a siloxane compound layer.
  • the siloxane compound layer By providing the siloxane compound layer, the unevenness on the outermost surface of the support can be smoothed, and the separation layer can be easily thinned.
  • the siloxane compound forming the siloxane compound layer include those having a main chain made of polysiloxane and compounds having a siloxane structure and a non-siloxane structure in the main chain.
  • siloxane compound means an organopolysiloxane compound unless otherwise specified.
  • siloxane compound having a main chain made of polysiloxane examples include one or more polyorganosiloxanes represented by the following formula (1) or (2). Moreover, 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 The compound of the form is mentioned.
  • R S is a non-reactive group and is an alkyl group (preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 6 carbon atoms). 15, more preferably an aryl group having 6 to 12 carbon atoms, and still more preferably phenyl).
  • X S is a reactive group selected from a hydrogen atom, a halogen atom, a vinyl group, a hydroxyl group, and a substituted alkyl group (preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group 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 group having 1 to 18 carbon atoms.
  • the number of carbon atoms of the alkyl group constituting the hydroxyalkyl group is preferably an integer of 1 to 10, for example, —CH 2 CH 2 CH 2 OH.
  • the preferable number of carbon atoms of the epoxy cyclohexyl alkyl group having 7 to 16 carbon atoms is an integer of 8 to 12.
  • a preferable carbon number of the (1-oxacyclobutan-3-yl) alkyl group having 4 to 18 carbon atoms is an integer of 4 to 10.
  • a preferable carbon number of the alkyl group constituting the methacryloxyalkyl group is an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 —OOC—C (CH 3 ) ⁇ CH 2 .
  • a preferable carbon number of the alkyl group constituting the mercaptoalkyl group is an integer of 1 to 10, and examples thereof include —CH 2 CH 2 CH 2 SH.
  • m and n are preferably numbers that give a molecular weight of 5,000 to 1,000,000.
  • a reactive group-containing siloxane unit (wherein the number is a structural unit represented by n) and a siloxane unit having no reactive group (wherein the number is m)
  • the distribution of the structural unit represented by That is, in the formulas (1) and (2), the (Si (R S ) (R S ) —O) units and the (Si (R S ) (X S ) —O) units may be randomly distributed. .
  • 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 the 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 synonymous with m and n in Formula (1), respectively.
  • m and n have the same meanings as m and n in formula (1), respectively.
  • m and n are synonymous with m and n in Formula (1), respectively. It is preferable that the both ends of Formula (6) have 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 bonded thereto.
  • m and n are synonymous with m and n in formula (1), respectively. 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 unit and the non-siloxane structural unit may be randomly distributed.
  • the compound having a siloxane structure and a non-siloxane structure in the main chain preferably contains 50 mol% or more of siloxane structural units, more preferably 70 mol% or more, based on the total number of moles of all repeating structural units. .
  • siloxane compound which comprises a siloxane compound layer is enumerated 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 further preferably 1000 GPU or more in terms of 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 change method using a solution containing a cellulose compound.
  • the phase inversion method is a known method for forming a film while bringing a polymer solution into contact with a coagulation liquid to cause phase conversion.
  • a so-called dry / wet method is suitably used.
  • the dry and wet method evaporates the solution on the surface of the polymer solution in the form of a film to form a thin dense layer, and then immerses it in a coagulation liquid (solvent that is compatible with the solvent of the polymer solution and the polymer is insoluble),
  • a coagulation liquid solvent that is compatible with the solvent of the polymer solution and the polymer is insoluble
  • the thickness of the surface layer contributing to gas separation called a dense layer or skin layer is not particularly limited.
  • the thickness of the surface layer is preferably 0.01 to 5.0 ⁇ m and more preferably 0.05 to 1.0 ⁇ m from the viewpoint of imparting practical gas permeability.
  • the porous layer below the dense layer lowers the gas permeability resistance and at the same time plays a role of imparting mechanical strength, and its thickness is particularly limited as long as it is self-supporting as an asymmetric membrane. It is not limited.
  • This thickness is preferably 5 to 500 ⁇ m, more preferably 5 to 200 ⁇ m, and even 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 and wet spinning method.
  • the dry-wet spinning method is a method for producing an asymmetric hollow fiber membrane by applying a dry-wet method to a polymer solution that is discharged from a spinning nozzle to have a hollow fiber-shaped target shape. More specifically, the polymer solution is discharged from a nozzle into a hollow fiber-shaped target shape, and after passing through an air or nitrogen gas atmosphere immediately after discharge, the polymer is not substantially dissolved and is compatible with the solvent of the polymer solution.
  • an asymmetric structure is formed by dipping in a coagulating liquid having a gas, then dried, and further heat-treated as necessary to produce a gas separation asymmetric membrane.
  • the solution viscosity of the solution containing the cellulose compound 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 (for example, 10 ° C.). This is preferable because the shape after discharge can be stably obtained.
  • the film is immersed in the primary coagulation liquid and solidified to such an extent that the shape of the hollow fiber or the like can be maintained, wound on a guide roll, and then immersed in the secondary coagulation liquid to fully saturate the entire film. It is preferable to solidify. It is efficient to dry the coagulated film after replacing the coagulating liquid with a solvent such as hydrocarbon.
  • the heat treatment for drying is preferably performed at a temperature lower than the softening point or secondary transition point of the cellulose compound used.
  • a siloxane compound layer may be provided on the gas separation layer as a protective layer in contact with the gas separation layer.
  • the surfactant include alkylbenzene sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfonate of higher fatty acid ester, sulfate ester of higher alcohol ether, sulfonate of higher alcohol ether, higher alkyl
  • Anionic surfactants such as alkyl carboxylates of sulfonamides, alkyl phosphates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, ethylene oxide adducts of acetylene glycol,
  • Nonionic surfactants such as ethylene oxide adducts of glycerin and polyoxyethylene sorbitan fatty acid esters, and other amphoteric boundaries such as alkyl betaines and amide betaines
  • 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. Of these, polyvinylpyrrolidone 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 particularly preferably 5 to 50 ° C.
  • a gas such as air or oxygen may coexist at the time of forming the film, but it is preferably in an inert gas atmosphere.
  • the content of the cellulose compound in the gas separation layer is not particularly limited as long as desired gas separation performance can be obtained. From the viewpoint of further improving the gas separation performance, the content of the cellulose compound 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. Is preferable, and it is more preferable that it is 70 mass% or more.
  • the content of the polyimide compound 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 as a gas separation recovery method and gas separation purification method.
  • gas separation membrane capable of efficiently separating a specific gas from a gas mixture containing a gas such as perfluorohydrocarbon.
  • a gas separation membrane that selectively permeates carbon dioxide from a gas mixture containing carbon dioxide and hydrocarbon (preferably methane) is preferable.
  • the permeation rate of carbon dioxide at 40 ° C. and 5 MPa is preferably 20 GPU or more, and 30 GPU or more. More preferably, it is 35 to 500 GPU.
  • the permeation rate ratio between carbon dioxide and methane (R CO2 / R CH4 ) is preferably 15 or more, and more preferably 20 or more.
  • R CO2 represents the permeation rate of carbon dioxide
  • R CH4 represents the permeation rate of methane.
  • 1 GPU is 1 ⁇ 10 ⁇ 6 cm 3 (STP) / (cm 2 ⁇ sec ⁇ cmHg).
  • the gas separation method of the present invention is a method for separating a specific gas from a mixed gas of two or more components using the gas separation membrane of the present invention.
  • the gas separation method of the present invention preferably includes selectively allowing carbon dioxide to permeate from a mixed gas containing carbon dioxide and methane.
  • the pressure during gas separation is preferably 0.5 to 10 MPa, more preferably 1 to 10 MPa, and further preferably 2 to 7 MPa.
  • the gas separation temperature is preferably ⁇ 30 to 90 ° C., more preferably 15 to 70 ° C.
  • a gas separation membrane module can be prepared using the gas separation membrane of the present invention.
  • modules include spiral type, hollow fiber type, pleated type, tubular type, plate & frame type and the like.
  • a gas separation apparatus having means for separating and recovering or purifying gas can be obtained using the gas separation membrane or gas separation membrane module of the present invention.
  • the gas separation composite membrane of the present invention may be applied to, for example, a gas separation and recovery device as a membrane / absorption hybrid method used in combination with an absorbing solution as described in JP-A-2007-297605.
  • This solid was reslurried four times with a mixed solution of isopropanol (40 mL) / hexane (160 mL), and vacuum dried to obtain 3.10 g of cellulose compound 1 as a white powder.
  • the obtained cellulose compound 1 the type of functional groups substituting for the hydrogen atom constituting a hydroxyl group contained in the cellulose raw material (R 1 in the general formula (1), R 2, and R 3), as well as cellulose compound 1
  • the degree of substitution was observed and determined by 1 H-NMR using the method described in Cellulose Communication 6, 73-79 (1999).
  • the weight average molecular weight Mw of the cellulose compound 1 was measured using the gel permeation chromatography (GPC).
  • N-methylpyrrolidone was used as a solvent
  • a polystyrene gel was used
  • a molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene was used.
  • the GPC apparatus HLC-8220 GPC (manufactured by Tosoh Corporation) was used.
  • the weight average molecular weight of the cellulose compound 1 was 406000.
  • cellulose compound 6 was synthesized in the same manner as in the synthesis of cellulose compound 1 except that tetrafluorosuccinic anhydride (manufactured by Tokyo Chemical Industry) was used instead of 4- (trifluoromethyl) phenyl isocyanate. did.
  • the weight average molecular weight of the cellulose compound 6 was 255000.
  • Comparative compound 1 is acetylcellulose (acetyl substitution degree 2.4, manufactured by Daicel), comparative compound 2 is a cellulose compound described in Example 1 of JP-A-59-55307, and comparative compound 3 is Japanese Patent Publication No. 58-24161.
  • the structure of the substituent corresponding to R 1 to R 3 in the general formula (1) and the degree of substitution thereof for each comparative compound (cellulose compound) are shown below. The parenthesis indicates the molecular weight.
  • the gas separation composite membrane shown in FIG. 2 was produced (the smooth layer is not shown in FIG. 2).
  • 0.08 g of cellulose compound 1 and 9.92 g of tetrahydrofuran were mixed and stirred for 30 minutes, and then spin coated on the PAN porous membrane provided with the above smooth layer to form a gas separation layer.
  • a composite membrane of Example 1 was obtained.
  • the thickness of the layer of the cellulose compound 1 was about 70 nm
  • the thickness of the PAN porous film was about 180 ⁇ m including the nonwoven fabric.
  • These polyacrylonitrile porous membranes had a molecular weight cut-off of 100,000 or less.
  • the permeability of carbon dioxide at 40 ° C. and 5 MPa of this porous membrane was 25000 GPU.
  • Example 2 Production of composite membranes
  • Example 3 Cellulose Compound 3
  • Example 4 Cellulose Compound 4
  • Example 5 Cellulose Compound 5
  • Example 6 Cellulose Compound 6
  • Example 7 Cellulose Compound 7
  • Example 8 Cellulose compound 8
  • Comparative Examples 1 to 5 Preparation of Composite Membrane Composite membranes of Comparative Examples 1 to 5 in the same manner as in Example 1 except that Comparative Compound 1 to 5 was used instead of Cellulose Compound 1 in Example 1 above. Was made.
  • the comparative compounds used in Comparative Examples 1 to 5 are as follows. Comparative Example 1: Comparative Compound 1, Comparative Example 2: Comparative Compound 2, Comparative Example 3: Comparative Compound 3, Comparative Example 4: Comparative Compound 4, Comparative Example 5: Comparative Compound 5
  • Test Example 1 Evaluation of CO 2 Permeation Rate and Gas Separation Selectivity of Gas Separation Membrane Gas separation performance was evaluated as follows using the gas separation membranes (composite membranes) of the above Examples and Comparative Examples. The gas separation membrane was cut to a diameter of 5 cm together with the porous support (support layer) to prepare a permeation test sample.
  • a mixed gas of carbon dioxide (CO 2 ): methane (CH 4 ) of 13:87 (volume ratio) is used, and the total pressure on the gas supply side is 5 MPa (minus CO 2 The pressure was adjusted to 0.65 MPa), the flow rate was 500 mL / min, and 40 ° C., and the gas was supplied from the gas separation layer side.
  • the permeated gas was analyzed by gas chromatography. The gas permeability of the membrane was compared by calculating the gas permeation rate as gas permeability (Permeance).
  • the gas separation selectivity was calculated as the ratio of the CO 2 permeation rate R CO2 to the CH 4 permeation rate R CH4 of this membrane (R CO2 / R CH4 ).
  • the evaluation criteria of gas permeability and gas separation selectivity were as follows.
  • R CO2 is 60 or more
  • B R CO2 is 45 or more and less than 60
  • C R CO2 is 30 or more and less than 45
  • D R CO2 is less than 30
  • R CO2 / R CH4 is 20 or more

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  • Engineering & Computer Science (AREA)
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  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne une membrane de séparation de gaz comprenant une couche de séparation de gaz qui contient un composé cellulosique en tant que matériau constitutif, et le composé cellulosique ayant une unité répétitive représentée par la formule générale (1). L'invention concerne aussi un module de séparation de gaz qui utilise cette membrane de séparation de gaz, un dispositif de séparation de gaz, et un procédé de séparation de gaz. Dans la formule générale (1), chacune des fractions R11-R3 représente un atome d'hydrogène ou un substituant, à condition qu'au moins l'une des fractions R1-R3 représente un substituant T qui comprend un hydrogène actif et un atome de fluor, tout en ayant un poids moléculaire supérieur ou égal à 100 mais inférieur à 500.
PCT/JP2018/007051 2017-02-28 2018-02-26 Membrane de séparation de gaz, module de séparation de gaz, dispositif de séparation de gaz, et procédé de séparation de gaz Ceased WO2018159562A1 (fr)

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JP7751826B2 (ja) * 2020-10-30 2025-10-09 国立大学法人東京農工大学 修飾多糖、ガス分離膜形成用材料、フィルム、ガス分離膜、ガス分離膜モジュールおよびガス分離方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02212501A (ja) * 1989-02-10 1990-08-23 Daikin Ind Ltd 含フッ素セルロース誘導体
JP2005315668A (ja) * 2004-04-28 2005-11-10 Daicel Chem Ind Ltd 光学異性体用分離剤
WO2008102920A1 (fr) * 2007-02-23 2008-08-28 Daicel Chemical Industries, Ltd. Charge de séparation d'isomère optique
WO2016047351A1 (fr) * 2014-09-22 2016-03-31 富士フイルム株式会社 Membrane de séparation de gaz, module de séparation de gaz, séparateur de gaz et procédé de séparation de gaz

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02212501A (ja) * 1989-02-10 1990-08-23 Daikin Ind Ltd 含フッ素セルロース誘導体
JP2005315668A (ja) * 2004-04-28 2005-11-10 Daicel Chem Ind Ltd 光学異性体用分離剤
WO2008102920A1 (fr) * 2007-02-23 2008-08-28 Daicel Chemical Industries, Ltd. Charge de séparation d'isomère optique
WO2016047351A1 (fr) * 2014-09-22 2016-03-31 富士フイルム株式会社 Membrane de séparation de gaz, module de séparation de gaz, séparateur de gaz et procédé de séparation de gaz

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