WO2024071229A1 - 酸性ガス吸着材シートの製造方法及び酸性ガス吸着材シート - Google Patents

酸性ガス吸着材シートの製造方法及び酸性ガス吸着材シート Download PDF

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WO2024071229A1
WO2024071229A1 PCT/JP2023/035227 JP2023035227W WO2024071229A1 WO 2024071229 A1 WO2024071229 A1 WO 2024071229A1 JP 2023035227 W JP2023035227 W JP 2023035227W WO 2024071229 A1 WO2024071229 A1 WO 2024071229A1
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gas adsorbent
sheet
acidic gas
compound
adsorbent sheet
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French (fr)
Japanese (ja)
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優衣 南
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to EP23872451.2A priority Critical patent/EP4596100A1/en
Priority to JP2024550404A priority patent/JPWO2024071229A1/ja
Priority to US19/113,757 priority patent/US20260102757A1/en
Publication of WO2024071229A1 publication Critical patent/WO2024071229A1/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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/82—Solid phase processes with stationary reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
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    • B01J20/3064—Addition of pore forming agents, e.g. pore inducing or porogenic agents
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    • B01J20/3204—Inorganic carriers, supports or substrates
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    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
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    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
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    • B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/3276—Copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/328—Polymers on the carrier being further modified
    • B01J20/3282—Crosslinked polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3297—Coatings in the shape of a sheet
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/36—Epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • C08G59/502—Polyalkylene polyamines
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    • B01D2253/202—Polymeric adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2257/00—Components to be removed
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    • B01D2257/504—Carbon dioxide
    • 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

Definitions

  • the present invention relates to a method for producing an acidic gas adsorbent sheet and an acidic gas adsorbent sheet.
  • CCS carbon capture and storage
  • CCU carbon capture and utilization
  • an adsorption method As a method for separating acidic gases such as carbon dioxide from the atmosphere, an adsorption method has been developed in which the acidic gas is adsorbed onto an adsorbent.
  • the adsorbent used in the adsorption method can adsorb acidic gases, for example, by coming into contact with the atmosphere.
  • Patent Document 1 discloses an adsorbent containing an amine compound.
  • a dense layer (skin layer) tends to form on its surface.
  • the skin layer affects the diffusion of acidic gases into the adsorbent, and depending on the thickness of the skin layer, the ability to adsorb and desorb acidic gases tends to decrease. Therefore, there is room for improvement in the manufacturing method of sheet-shaped adsorbents.
  • the present invention aims to provide a method for producing an acid gas adsorbent sheet suitable for adsorption and desorption of acid gases, and an acid gas adsorbent sheet.
  • the present invention relates to a step (I) of reacting a compound C1 having a primary amino group with a compound C2 having an epoxy group in a mixed solution containing the compound C1 having a primary amino group, a compound C2 having an epoxy group, and a porogen, the compound C1 having a primary amino group being greater in equivalent than the epoxy group, to obtain a reaction product; (II) cooling the mixture containing the reactant, adding the compound C2 to the mixture, and reacting the reactant with the compound C2 to obtain a reaction solution; A step (III) of curing the reaction liquid to obtain a sheet-like cured product; (IV) removing the porogen from the sheet-like cured body;
  • the present invention provides a method for producing an acidic gas adsorbent sheet, comprising the steps of:
  • the present invention relates to An acidic gas adsorbent sheet comprising a polymer having an amino group,
  • An acidic gas adsorbent sheet is provided which, when subjected to the following desorption test B1, has a carbon dioxide desorption rate of more than 80%.
  • Adsorption test A1 A mixed gas composed of carbon dioxide, nitrogen and water vapor is continuously fed into a container containing the acidic gas adsorbent sheet for 15 hours, where the concentration of carbon dioxide in the mixed gas is 400 vol ppm, the temperature of the mixed gas is 20° C., and the humidity of the mixed gas is 50% RH.
  • Desorption test B1 While continuing to feed the mixed gas into the container, the acidic gas adsorbent sheet after the adsorption test A1 is heated at 50° C. for 15 hours.
  • the present invention provides a method for producing an acidic gas adsorbent sheet suitable for adsorption and desorption of acidic gases, and an acidic gas adsorbent sheet.
  • FIG. 1 is a diagram for explaining a method for measuring the amount of carbon dioxide adsorbed and the desorption rate by an acidic gas adsorbent sheet.
  • FIG. 2 is a cross-sectional view that illustrates an example of an acidic gas adsorbent sheet according to a second embodiment of the present invention.
  • FIG. 3 is a cross-sectional view that typically shows a modified example of the acidic gas adsorbent sheet according to the second embodiment of the present invention.
  • FIG. 4A is a perspective view that illustrates an example of a structure including an acidic gas adsorbent sheet.
  • FIG. 4B is a perspective view that illustrates a modified example of a structure including an acidic gas adsorbent sheet.
  • FIG. 1 is a diagram for explaining a method for measuring the amount of carbon dioxide adsorbed and the desorption rate by an acidic gas adsorbent sheet.
  • FIG. 2 is a cross-sectional view that illustrates an example of an acidic gas adsorb
  • FIG. 5 is an SEM image of the surface of the acidic gas adsorbent sheet of Example 1.
  • FIG. 6 is an SEM image of a cross section of the acidic gas adsorbent sheet of Example 1.
  • FIG. 7 is an SEM image of the surface of the acidic gas adsorbent sheet of Example 2.
  • FIG. 8 is an SEM image of a cross section of the acidic gas adsorbent sheet of Example 2.
  • FIG. 9 is an SEM image of the surface of the acidic gas adsorbent sheet of Example 3.
  • FIG. 10 is an SEM image of a cross section of the acidic gas adsorbent sheet of Example 3.
  • FIG. 11 is an SEM image of the surface of the acidic gas adsorbent sheet of Example 4.
  • FIG. 12 is an SEM image of a cross section of the acidic gas adsorbent sheet of Example 4.
  • FIG. 13 is an SEM image of the surface of the acidic gas adsorbent sheet of Example 5.
  • FIG. 14 is an SEM image of a cross section of the acidic gas adsorbent sheet of Example 5.
  • FIG. 15 is an SEM image of the surface of the acidic gas adsorbent sheet of Comparative Example 1.
  • FIG. 16 is an SEM image of a cross section of the acidic gas adsorbent sheet of Comparative Example 1.
  • FIG. 17 is an SEM image of the surface of the acidic gas adsorbent sheet of Comparative Example 2.
  • FIG. 18 is an SEM image of a cross section of the acidic gas adsorbent sheet of Comparative Example 2.
  • FIG. 19 is an SEM image of the surface of the acidic gas adsorbent sheet of Comparative Example 3.
  • FIG. 20 is an SEM image of a cross section of the acidic gas adsorbent sheet of Comparative Example 3.
  • FIG. 21 is an SEM image of the surface of the acidic gas adsorbent sheet of Comparative Example 4.
  • FIG. 22 is an SEM image of a cross section of the acidic gas adsorbent sheet of Comparative Example 4.
  • a method for producing an acidic gas adsorbent sheet according to the first aspect of the present invention includes the steps of: a step (I) of reacting a compound C1 having a primary amino group with a compound C2 having an epoxy group in a mixed solution containing the compound C1 having a primary amino group, a compound C2 having an epoxy group, and a porogen, the compound C1 having a primary amino group being greater in equivalent than the epoxy group, to obtain a reaction product; (II) cooling the mixture containing the reactant, adding the compound C2 to the mixture, and reacting the reactant with the compound C2 to obtain a reaction solution; A step (III) of curing the reaction liquid to obtain a sheet-like cured product; (IV) removing the porogen from the sheet-like cured body; including.
  • the cooling is performed to a temperature of 10°C or less.
  • the compound C1 includes an amine monomer.
  • the ratio E/A of the equivalent (E) of the epoxy group to the equivalent (A) of the active hydrogen of the primary amino group is 0.3 or less.
  • the ratio E/A of the epoxy group equivalent (E) to the primary amino group active hydrogen equivalent (A) is greater than 0.3 and less than 1 for the compounds C1 and C2 used up to the step (II).
  • the viscosity of the mixture containing the reactants at 25°C is 10,000 mPa ⁇ s or less.
  • the step (III) involves contacting the reaction liquid with a sheet-shaped substrate, and then curing the reaction liquid in contact with the substrate to obtain the sheet-shaped cured body.
  • the substrate includes a fiber structure.
  • the method for producing an acidic gas adsorbent sheet according to the eighth aspect includes contacting the reaction liquid with the substrate, thereby allowing the reaction liquid to permeate the substrate.
  • the acidic gas adsorbent sheet according to the tenth aspect of the present invention is An acidic gas adsorbent sheet comprising a polymer having an amino group,
  • Adsorption test A1 A mixed gas composed of carbon dioxide, nitrogen and water vapor is continuously fed into a container containing the acidic gas adsorbent sheet for 15 hours, where the concentration of carbon dioxide in the mixed gas is 400 vol ppm, the temperature of the mixed gas is 20° C., and the humidity of the mixed gas is 50% RH.
  • Desorption test B1 While continuing to feed the mixed gas into the container, the acidic gas adsorbent sheet after the adsorption test A1 is heated at 50° C. for 15 hours.
  • the acid gas adsorbent sheet according to the tenth aspect has a porous structure.
  • the thickness of the skin layer on the surface of the acid gas adsorbent sheet is 0.48 ⁇ m or less.
  • the acid gas adsorbent sheet according to any one of the tenth to twelfth aspects further includes a substrate.
  • the substrate includes a fiber structure.
  • the manufacturing method of the acidic gas adsorbent sheet according to the first embodiment of the present invention includes the steps of: (I) reacting compound C1 and compound C2 in a mixed liquid containing compound C1 having a primary amino group, compound C2 having an epoxy group, and a porogen, and in which the equivalent of the primary amino group is greater than the equivalent of the epoxy group, to obtain a reaction product; (II) cooling the mixed liquid containing the obtained reaction product, adding compound C2 to the mixed liquid, and reacting the reaction product obtained in step (I) with compound C2 to obtain a reaction liquid; (III) curing the reaction liquid to obtain a sheet-like cured body; and (IV) removing the porogen from the sheet-like cured body.
  • the mixed solution contains a compound C1 having a primary amino group, a compound C2 having an epoxy group, and a porogen, and the equivalent of the primary amino group is greater than the equivalent of the epoxy group.
  • the compound C1 contains, for example, an amine monomer.
  • the mixed solution may be referred to as "mixed solution L".
  • the amine monomer is a monomer containing at least one primary amino group.
  • the number of primary amino groups contained in the amine monomer is preferably 2 or more, may be 3 or more, or may be 4 or more.
  • the upper limit of the number of primary amino groups is not particularly limited, and may be, for example, 100 or 10.
  • the amine monomer may contain secondary amino groups or tertiary amino groups in addition to the primary amino groups.
  • the molecular weight of the amine monomer is not particularly limited, and may be, for example, 100 or more, 200 or more, 300 or more, 500 or more, 1000 or more, or even 1500 or more.
  • the upper limit of the molecular weight of the amine monomer is not particularly limited, and may be, for example, 10000 or more, or 5000.
  • the molecular weight of the amine monomer is less than 1000, and preferably 500 or less, depending on the case.
  • the ratio of the number of primary amino groups to the number of all amino groups is not particularly limited, and may be, for example, 10% or more, preferably 20% or more, more preferably 30% or more, or 40% or more. The upper limit of this ratio is not particularly limited, and may be, for example, 80% or 60%.
  • the molecular weight of the amine monomer is not particularly limited, and may be, for example, less than 5000, preferably 3000 or less, may be 1000 or less, or may be 500 or less.
  • the molecular weight of the amine monomer is, for example, 50 or more, preferably 100 or more, and more preferably 150 or more.
  • Amine monomers include, for example, aliphatic amines such as ethylamine, ethylenediamine, 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, bis(hexamethylene)triamine, 1,3,6-trisaminomethylhexane, tris(2-aminoethyl)amine, N,N'-bis(3-aminopropyl)ethylenediamine, polymethylenediamine, trimethylhexamethylenediamine, and polyetherdiamine.
  • aliphatic amines such as ethylamine, ethylenediamine, 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-o
  • amines such as isophoronediamine, menthanediamine, piperazine, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro(5,5)undecane adduct, bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane, and modified products thereof; aliphatic polyamines such as polyethyleneimine and polyalkylenepolyamines; (meth)acrylic polymers having amino groups such as aminoethylated acrylic polymers; aliphatic polyamidoamines formed by the reaction of polyamines with dimer acids, and the like.
  • the amine monomer preferably contains an aliphatic amine, particularly triethylenetetramine (TETA), or an aliphatic polyamine, particularly polyethyleneimine (PEI).
  • TETA triethylenetetramine
  • PEI
  • Compound C2 includes, for example, an epoxy monomer.
  • the epoxy monomer contains at least one epoxy group.
  • the number of epoxy groups contained in the epoxy monomer is preferably 2 or more, may be 3 or more, or may be 4 or more.
  • the upper limit of the number of epoxy groups contained in the epoxy monomer is not particularly limited, and may be, for example, 100 or 10.
  • the molecular weight of the epoxy monomer is not particularly limited, and may be, for example, less than 1000, and preferably 500 or less. In some cases, the molecular weight of the epoxy monomer may be 1000 to 50000.
  • Epoxy monomers include, for example, monofunctional epoxy compounds such as n-butyl glycidyl ether, higher alcohol glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, and t-butylphenyl glycidyl ether; diepoxy alkanes such as 1,5-hexadiene diepoxide, 1,7-octadiene diepoxide, and 1,9-decadiene diepoxide; (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, and Ether group-containing polyfunctional epoxy compounds such as glycidyl ether, 1,4-butanediol diglycidyl ether
  • the epoxy monomer may be an aromatic epoxy resin, a non-aromatic epoxy resin, or the like.
  • aromatic epoxy resins include polyphenyl-based epoxy resins, epoxy resins containing a fluorene ring, epoxy resins containing triglycidyl isocyanurate, and epoxy resins containing a heteroaromatic ring (e.g., a triazine ring).
  • polyphenyl-based epoxy resins examples include bisphenol A-type epoxy resins, brominated bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol AD-type epoxy resins, stilbene-type epoxy resins, biphenyl-type epoxy resins, bisphenol A novolac-type epoxy resins, cresol novolac-type epoxy resins, diaminodiphenylmethane-type epoxy resins, and tetrakis(hydroxyphenyl)ethane-based epoxy resins.
  • non-aromatic epoxy resins examples include aliphatic glycidyl ether-type epoxy resins, aliphatic glycidyl ester-type epoxy resins, alicyclic glycidyl ether-type epoxy resins, alicyclic glycidyl amine-type epoxy resins, and alicyclic glycidyl ester-type epoxy resins.
  • the epoxy monomers may be used alone or in combination of two or more.
  • the epoxy monomer preferably contains at least one selected from the group consisting of diepoxyalkanes, ether group-containing polyfunctional epoxy compounds, and amino group-containing polyfunctional epoxy compounds.
  • diepoxyalkanes or ether group-containing polyfunctional epoxy compounds may be used in combination with amino group-containing polyfunctional epoxy compounds.
  • Specific examples of preferred epoxy monomers include 1,7-octadiene diepoxide (ODE), ethylene glycol diglycidyl ether (EDE), 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-m-xylylenediamine.
  • a monofunctional epoxy compound When a monofunctional epoxy compound is used, it is preferable to use it in combination with other epoxy monomers containing two or more epoxy groups.
  • the monofunctional epoxy compound can also be used as a reactive diluent for adjusting the viscosity of the mixed liquid L.
  • the porogen is, for example, a solvent capable of dissolving the monomer contained in the mixed liquid L and further capable of causing reaction-induced phase separation after the reaction of compound C1 and compound C2.
  • the porogen include cellosolves such as methyl cellosolve and ethyl cellosolve, esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, glycols such as polyethylene glycol, polypropylene glycol and polyoxyalkylene glycol, and ethers such as polyoxyethylene monomethyl ether and polyoxyethylene dimethyl ether.
  • polyoxyalkylene glycol examples include poly(1,2-butanediol)-6 propylene glycol and polyoxypropylene diglyceryl ether.
  • the porogen may be a polar solvent such as ethyl acetate, N,N-dimethylformamide (DMF), acetonitrile, ethanol, isopropanol, or a non-polar solvent such as toluene, or a mixture of these.
  • the porogens may be used alone or in combination of two or more kinds.
  • step (I) the mixed liquid L has a primary amino group equivalent greater than the epoxy group equivalent.
  • step (I) the compounding ratio of compound C1 and compound C2 in mixed liquid L is adjusted so that the primary amino group equivalent is greater than the epoxy group equivalent.
  • the ratio E/A of the equivalent (E) of the epoxy group to the equivalent (A) of the active hydrogen of the primary amino group in the mixed liquid L may be 0.3 or less.
  • the ratio E/A in the mixed liquid L is preferably 0.2 or less, and may be 0.16 or less, 0.12 or less, or even 0.05 or less. There is no lower limit, and it is, for example, 0.01 or more.
  • step (I) compound C1 and compound C2 in mixed liquid L are reacted to obtain a reactant.
  • the reactant obtained in step (I) may be referred to as "reactant P1."
  • reactant P1 is formed in mixed liquid L.
  • An example of reactant P1 is an amine polymer that includes a structural unit derived from an epoxy monomer.
  • reactant P1 may be a polymer of a monomer group including an amine monomer and an epoxy monomer (particularly a polymer of an amine monomer and an epoxy monomer).
  • the equivalent weight of the primary amino group is greater than the equivalent weight of the epoxy group, and preferably the ratio E/A is 0.3 or less. Note that one primary amino group contains two active hydrogens. Therefore, when the ratio E/A is 0.3 or less, reactant P1 usually contains a large number of primary amino groups.
  • the reaction of compound C1 and compound C2 can be carried out by adding energy to the mixed liquid L.
  • the energy added to the mixed liquid L is preferably thermal energy.
  • the reaction of step (I) can be promoted by heating the mixed liquid L. That is, step (I) is preferably carried out under heating.
  • the heating temperature of the mixed liquid L is not particularly limited, and may be, for example, 40°C to 100°C, or 50°C to 80°C.
  • the heating time of the mixed liquid L is not particularly limited, and is, for example, 30 minutes to 5 hours.
  • the mixed liquid L may be heated while being stirred.
  • the energy added to the mixed liquid L may be light energy. In step (I), it is preferable to completely react compound C1 and compound C2 in the mixed liquid L.
  • the viscosity of the mixed liquid L containing the reactant P1 at 25°C may be 10000 mPa ⁇ s or less.
  • the viscosity of the mixed liquid L containing the reactant P1 is preferably 7500 mPa ⁇ s or less, and may be 5000 mPa ⁇ s or less, 4200 mPa ⁇ s or less, 4000 mPa ⁇ s or less, 3500 mPa ⁇ s or less, 3000 mPa ⁇ s or less, or even 2700 mPa ⁇ s or less.
  • the lower limit is not limited, and may be, for example, 500 mPa ⁇ s or more, or 1000 mPa ⁇ s or more.
  • the viscosity is measured by stirring the mixed liquid L containing the reactant P1 at a shear rate of 1 s -1 .
  • the reaction of the step (I) is carried out by heating to, for example, 60°C, the mixed liquid L containing the reactant P1 after the reaction is cooled to 25°C, and the viscosity is measured.
  • the mixed liquid L may further contain components other than the compound C1, the compound C2, and the porogen.
  • the other components include reaction accelerators.
  • the reaction accelerators include tertiary amines such as triethylamine and tributylamine; and imidazoles such as 2-phenol-4-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenol-4,5-dihydroxyimidazole. These reaction accelerators can promote the reaction for synthesizing the reactant P1. It is preferable that the mixed liquid L does not contain, for example, porous particles such as alumina, or a binder for binding the porous particles together, as other components.
  • Step (II) the mixed solution L containing the reactant P1 is cooled, and then the compound C2 is further added to the mixed solution L to react the reactant P1 with the compound C2 to obtain a reaction solution.
  • reaction solution P2 the reaction solution obtained in step (II) may be referred to as "reaction solution P2".
  • the mixed solution L containing the reactant P1 may be cooled to 10°C or less, preferably 4°C or less.
  • step (II) the active hydrogen of the primary amine remaining in the reactant P1 reacts with the compound C2.
  • the reaction between the reactant P1 and the compound C2 may be a crosslinking reaction of the reactant P1 with an epoxy monomer.
  • step (III) the reactant contained in the reaction liquid P2 reacts with the remaining compound C2.
  • Reaction liquid P2 contains, for example, an amine polymer containing a constituent unit derived from an epoxy monomer.
  • reaction liquid P2 may contain a polymer of a monomer group including an amine monomer and an epoxy monomer (particularly a polymer of an amine monomer and an epoxy monomer).
  • Compound C2 may be added in multiple batches.
  • the compound C2 to be added may be cooled to 10°C or lower, preferably 4°C or lower.
  • the reaction in step (II) may be carried out by stirring the mixed liquid L to which compound C2 has been added.
  • the temperature of the mixed liquid L at the start of step (II) may be lower than room temperature, for example, 10°C or lower.
  • the ratio E/A of the compounds C1 and C2 used up to the step (II) may be greater than 0.3 and less than 1. That is, the ratio E/A of the compounds C1 and C2 used up to the step of obtaining the reaction liquid P2 may be greater than 0.3 and less than 1.
  • the ratio E/A may be preferably 0.4 or more, more preferably 0.5 or more.
  • the ratio E/A may be preferably 0.8 or less, 0.7 or less, more preferably 0.6 or less, and even more preferably 0.5 or less.
  • the ratio E/A of the compounds C1 and C2 used up to the step (II) may be 0.5.
  • the reactants contained in the reaction liquid P2 usually have secondary amino groups.
  • the secondary amino groups are functional groups suitable for appropriately adjusting the adsorption and desorption properties of the adsorbent sheet for acidic gases.
  • Step (III) the reaction liquid P2 is cured to obtain a sheet-shaped cured body.
  • the cured body obtained in step (III) may be referred to as "cured body B.”
  • the curing of the reaction liquid P2 proceeds by the reaction of the reactant contained in the reaction liquid P2 with the remaining compound C2.
  • step (III) the reaction liquid P2 may be brought into contact with a sheet-shaped substrate, and then the reaction liquid P2 may be cured to obtain a sheet-shaped cured body B.
  • step (II) as the reaction between reactant P1 and compound C2 progresses, the temperature of reaction liquid P2 tends to increase.
  • step (III) when the temperature of reaction liquid P2 reaches 20°C to 35°C in step (II), reaction liquid P2 is brought into contact with a sheet-shaped substrate.
  • the substrate may be, for example, a fiber structure containing fiber, a mesh, a foam, a non-porous sheet, or a foil.
  • the fiber include glass fiber; natural fibers such as wood pulp, cotton, and hemp (e.g., Manila hemp); and chemical fibers (synthetic fibers) such as polyester fiber, rayon, vinylon, acetate fiber, polyvinyl alcohol (PVA) fiber, polyamide fiber, polyolefin fiber, and polyurethane fiber.
  • Examples of the fiber structure include woven fabric, nonwoven fabric, and paper. A specific example of a fiber structure is glass paper.
  • the substrate may include a fiber structure.
  • the thickness of the substrate is not particularly limited and may be, for example, 1 ⁇ m to 500 ⁇ m, or 100 ⁇ m to 300 ⁇ m.
  • step (III) the reaction liquid P2 may be brought into contact with a substrate containing a fiber structure, so that the reaction liquid P2 permeates the substrate, and then the reaction liquid P2 may be cured to obtain a sheet-like cured body B.
  • the reaction liquid P2 may come into contact with the substrate by impregnating the substrate with the reaction liquid P2, or by applying the reaction liquid P2 onto the substrate by a roll coating method, a spin coating method, or the like.
  • Cured body B contains a polymer and a porogen resulting from the reaction of compound C1 and compound C2.
  • the polymer and the porogen are phase-separated to form a co-continuous structure.
  • step (IV) the porogen is removed from the sheet-shaped cured body B.
  • the method for removing the porogen from the sheet-shaped cured body B is not particularly limited.
  • the porogen may be extracted and removed from the cured body B by immersing the cured body B in a solvent.
  • a solvent for extracting the porogen, water, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, an aliphatic alcohol solvent, an ether solvent, a halogen-containing organic solvent, an ester solvent, etc. can be used.
  • aliphatic hydrocarbon solvent n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, isooctane, petroleum ether, benzine, etc.
  • aromatic hydrocarbon solvent toluene, xylene, mesitylene, benzene, etc. can be used.
  • aliphatic alcohol solvent methanol, ethanol, isopropanol, butanol, cyclohexanol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol, etc. can be used.
  • ether solvent examples include diethyl ether, diisopropyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, and anisole.
  • halogen-containing organic solvent examples include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, and chlorobenzene.
  • ester solvent examples include ethyl acetate. These solvents can be used alone or in combination of two or more.
  • step (IV) the porogen is removed from the sheet-like cured body B, thereby obtaining, for example, an acidic gas adsorbent sheet having a porous structure.
  • the reaction of compounds C1 and C2 can be moderately advanced before the sheet-shaped cured body B is prepared, so that the polymerization rate at which phase separation is possible is reached even near the surface of the sheet-shaped cured body B, where heat is more easily transferred, and phase separation is more likely to occur. Therefore, by removing the porogen, an acidic gas adsorbent sheet having a porous structure up to the surface can be obtained. According to the manufacturing method of this embodiment, an acidic gas adsorbent sheet can be obtained in which there is no dense layer on the surface or the dense layer on the surface is thin.
  • the acidic gas adsorbent sheet obtained by the manufacturing method according to the first embodiment of the present invention may have a porous structure including pores derived from a three-dimensional mesh skeleton, and the three-dimensional mesh skeleton may include a polymer having an amino group.
  • the acidic gas adsorbent sheet according to the second embodiment of the present invention is an acidic gas adsorbent sheet containing a polymer having an amino group.
  • Adsorption test A1 A mixed gas composed of carbon dioxide, nitrogen and water vapor is continuously fed into a container containing an acidic gas adsorbent sheet for 15 hours.
  • the concentration of carbon dioxide in the mixed gas is 400 vol ppm
  • the temperature of the mixed gas is 20° C.
  • the humidity of the mixed gas is 50% RH.
  • Desorption test B1 While continuing to feed the mixed gas into the container, the acidic gas adsorbent sheet after the adsorption test A1 is heated at 50° C. for 15 hours.
  • polymer P the polymer having an amino group
  • Polymer P Details of polymer P will be described later.
  • the acidic gas adsorbent sheet according to the second embodiment may further include a substrate.
  • the substrate include those described above in the first embodiment.
  • the substrate may include a fiber structure.
  • FIG. 2 is a cross-sectional view showing an example of an acidic gas adsorbent sheet according to the second embodiment.
  • the acidic gas adsorbent sheet 10 is a laminate of a resin sheet 1 containing a polymer P and a substrate 2.
  • the resin sheet 1 may be substantially composed of the polymer P.
  • the acidic gas adsorbent sheet 10 may include a substrate 2 made of a fiber structure and a polymer P penetrating into the voids of the substrate 2.
  • the acidic gas adsorbent sheet 10 may be a laminate of a resin sheet 1 containing a polymer P and a substrate 2 made of a fiber structure, and at least a part of the resin sheet 1 may penetrate into the voids of the substrate 2 made of a fiber structure.
  • the resin sheet 1 and the substrate 2 may be composite.
  • the acidic gas adsorbent sheet 10 may include a plurality of resin sheets 1.
  • FIG. 3 is a cross-sectional view showing a modified example of the acidic gas adsorbent sheet according to the second embodiment.
  • the acidic gas adsorbent sheet 11 is a laminate of a resin sheet 1 containing a polymer P, a substrate 2, and a resin sheet 3 containing a polymer P. At least a portion of the resin sheet 1 and the resin sheet 3 may penetrate into the voids in the substrate 2 made of a fiber structure. In other words, the resin sheet 1 and the substrate 2, and the resin sheet 3 and the substrate 2 may each be composited.
  • resin sheet 3 may be the same as or different from that of resin sheet 1.
  • resin sheet when simply referring to a "resin sheet,” the resin sheet includes both resin sheet 1 and resin sheet 3.
  • the acidic gas adsorbent sheet according to the second embodiment may have a porous structure.
  • the porous structure may include pores derived from a three-dimensional mesh skeleton.
  • the acidic gas adsorbent sheet according to the second embodiment is an acidic gas adsorbent sheet having a porous structure including pores derived from a three-dimensional mesh skeleton, and the three-dimensional mesh skeleton may include a polymer having an amino group.
  • the pores derived from the three-dimensional mesh skeleton are large enough to be observed, for example, when observed at a magnification of 5,000 times using a scanning electron microscope (SEM).
  • the thickness of the skin layer on the surface of the acidic gas adsorbent sheet according to the second embodiment may be 0.48 ⁇ m or less. That is, the thickness of the skin layer on the surface of the resin sheet may be 0.48 ⁇ m or less.
  • the skin layer is a dense layer on the surface of the acidic gas adsorbent sheet, and means a layer in which no holes can be confirmed when, for example, a cross section of the acidic gas adsorbent sheet is observed at a magnification of 5000 times using an SEM.
  • the thickness of the skin layer is preferably 0.4 ⁇ m or less, and may be 0.3 ⁇ m or less, 0.2 ⁇ m or less, 0.1 ⁇ m or less, or even 0 ⁇ m.
  • the lower limit of the thickness of the skin layer is not particularly limited, and is, for example, 0 ⁇ m or more.
  • the acidic gas adsorbent sheet according to the second embodiment may not have a skin layer on its surface.
  • the acidic gas adsorbent sheet according to the second embodiment has a thin skin layer or no skin layer, so that the acidic gas can easily diffuse into the adsorbent sheet, and the ability to adsorb and desorb the acidic gas can be improved. In particular, the acidic gas can be rapidly adsorbed.
  • the thickness of the acidic gas adsorbent sheet according to the second embodiment is, for example, 1000 ⁇ m or less, preferably 500 ⁇ m or less, and more preferably 300 ⁇ m or less.
  • the lower limit of the thickness of the acidic gas adsorbent sheet according to the second embodiment is not particularly limited, and is, for example, 10 ⁇ m.
  • the polymer P contains, for example, at least one amino group selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group. From the viewpoint of the adsorption of acidic gases, the polymer P preferably contains at least one selected from the group consisting of a primary amino group and a secondary amino group, and particularly preferably contains a secondary amino group. In other words, the amino group possessed by the polymer P preferably contains a secondary amino group. According to the polymer P having a secondary amino group, there is also a tendency that the adsorbed acidic gas can be easily desorbed.
  • the regeneration treatment of the acidic gas adsorbent sheet 10 can be performed under relatively mild conditions.
  • the polymer P may contain a tertiary amino group, but may not contain a tertiary amino group.
  • the weight ratio of the nitrogen element in the polymer P is, for example, 5 wt% or more, and preferably 10 wt% or more. The higher this weight ratio, the more the acid gas adsorption ability of the acid gas adsorbent sheet 10 tends to improve.
  • the upper limit of the weight ratio of the nitrogen element in the polymer P is not particularly limited, and is, for example, 30 wt%. Note that when all the nitrogen elements contained in the polymer P are derived from amino groups, the above weight ratio of the nitrogen element can be regarded as the weight ratio of the amino groups in the polymer P.
  • the density of the amino groups in the polymer P is, for example, 1 mmol/g or more, preferably 5 mmol/g or more, and more preferably 10 mmol/g or more.
  • the upper limit of the density of the amino groups is not particularly limited, and is, for example, 30 mmol/g.
  • the density of the amino groups in the polymer P means the amount of amino groups contained in 1 g of the polymer P.
  • the polymer P may contain other functional groups besides amino groups. Examples of other functional groups include hydroxyl groups, ether groups, ester groups, and amide groups. It is preferable that the polymer P contains an ether group as the other functional group.
  • the polymer P is, for example, an amine polymer containing a structural unit U1 derived from an epoxy monomer.
  • This amine polymer contains, for example, at least one selected from the group consisting of reactants of a compound group containing an amine monomer and an epoxy monomer, and is preferably the above reactant.
  • the above reactant not only tends to have a high density of nitrogen elements, but also tends to have high heat resistance and moist heat resistance.
  • the group of monomers for forming the polymer includes amine monomers and epoxy monomers, and is preferably composed only of these monomers.
  • the polymer is preferably a polymer of amine monomers and epoxy monomers.
  • Examples of the amine monomer include those described above in the first embodiment.
  • Examples of the epoxy monomer include those described above in the first embodiment.
  • polymer P as an amine polymer contains a structural unit U1 derived from an epoxy monomer.
  • polymer P further contains a structural unit U2 derived from an amine monomer.
  • the content of structural unit U1 in polymer P, particularly in a polymer is, for example, 20 wt % to 70 wt %.
  • the content of structural unit U2 in polymer P, particularly in a polymer is, for example, 30 wt % or more, preferably 50 wt % or more.
  • the upper limit of the content of structural unit U2 is not particularly limited, and is, for example, 80 wt %.
  • the glass transition temperature Tg of the polymer P is not particularly limited, and is, for example, 40° C. or less, preferably 30° C. or less, more preferably 20° C. or less, and even more preferably 15° C. or less, and may be 10° C. or less, 5° C. or less, or may be 0° C. or less.
  • the rate at which the acidic gas is adsorbed in the acidic gas adsorbent sheet tends to be high.
  • the lower limit of the glass transition temperature Tg of the polymer P is, for example, ⁇ 100° C., preferably ⁇ 50° C., and more preferably ⁇ 10° C., from the viewpoint of sufficiently ensuring the adsorption and desorption of the acidic gas in the acidic gas adsorbent sheet and from the viewpoint of heat resistance.
  • the glass transition temperature Tg means the midpoint glass transition temperature (T mg ) obtained in accordance with the provisions of JIS K7121:1987.
  • the polymer P usually corresponds to a thermosetting resin.
  • the polymer P is solid, for example, at 25° C., preferably in the range of 25° C. to 80° C.
  • the weight average molecular weight of polymer P is not particularly limited, and is, for example, 500 or more, preferably 1000 or more, more preferably 10000 or more, and even more preferably 100000 or more.
  • the upper limit of the weight average molecular weight of polymer P is, for example, 10,000,000.
  • the resin sheet contains, for example, polymer P as a main component.
  • main component means the component contained most in the resin sheet by weight ratio.
  • the content of polymer P in the resin sheet is, for example, 50 wt% or more, preferably 70 wt% or more, more preferably 90 wt% or more, and may be 95 wt% or more, or may be 99 wt% or more.
  • the resin sheet may be substantially composed of only polymer P. The higher the content of polymer P, the more the acid gas adsorption property of the acid gas adsorbent sheet tends to improve.
  • the resin sheet may contain materials other than the polymer P.
  • the other materials include reaction accelerators, plasticizers, fillers, pigments, dyes, antioxidants, conductive materials, antistatic agents, UV absorbers, flame retardants, and antioxidants.
  • reaction accelerators include those described above in the first embodiment.
  • Fillers include fibers and fiber-containing fiber structures.
  • fibers include glass fibers; natural fibers such as wood pulp, cotton, and hemp (e.g., Manila hemp); and chemical fibers (synthetic fibers) such as polyester fibers, rayon, vinylon, acetate fibers, polyvinyl alcohol (PVA) fibers, polyamide fibers, polyolefin fibers, and polyurethane fibers.
  • fiber structures include woven fabrics, nonwoven fabrics, and paper. A specific example of a fiber structure is glass paper.
  • the resin sheet may have a porous structure, and the porous structure may include holes derived from a three-dimensional mesh skeleton.
  • the three-dimensional mesh skeleton includes a polymer P having an amino group.
  • the resin sheet may be a porous resin sheet including a polymer P.
  • the above three-dimensional mesh skeleton is typically composed of only the polymer P.
  • the above three-dimensional mesh skeleton extends continuously.
  • the holes included in the resin sheet are, for example, continuous holes formed continuously in a three-dimensional shape.
  • the resin sheet may have independent holes, or may have through holes penetrating the resin sheet.
  • the porous structure of the resin sheet may further include holes derived from the fiber structure.
  • the resin sheet preferably does not include, for example, a fiber including the polymer P, and is preferably not a nonwoven fabric including the fiber. That is, in the second embodiment, the resin sheet excludes, for example, a nonwoven fabric having a fiber including the polymer P.
  • the three-dimensional mesh skeleton containing polymer P and the fiber structure may exist independently in the resin sheet.
  • the porous structure of the resin sheet has, for example, holes originating from the three-dimensional mesh skeleton containing polymer P as well as holes originating from the fiber structure.
  • the resin sheet can be considered to have a composite of the three-dimensional mesh skeleton containing polymer P and the fiber structure.
  • the thickness of the resin sheet 1 is, for example, 500 ⁇ m or less, preferably 200 ⁇ m or less, and more preferably 100 ⁇ m or less.
  • the lower limit of the thickness of the resin sheet 1 is not particularly limited, and is, for example, 10 ⁇ m.
  • the thickness of the resin sheet 3 is the same as that of the resin sheet 1. The smaller the thickness of the resin sheet, the larger the cross-sectional area of the ventilation path of, for example, a structure, particularly a honeycomb structure, made using the acidic gas adsorbent sheet 10 can be adjusted. A structure with a large cross-sectional area of the ventilation path is suitable for reducing pressure loss that occurs when it comes into contact with acidic gas.
  • the specific surface area of the resin sheet is not particularly limited, and is, for example, 0.1 m 2 /g or more, preferably 1.0 m 2 /g or more, and more preferably 2.0 m 2 /g or more.
  • the upper limit of the specific surface area of the resin sheet is not particularly limited, and is, for example, 10 m 2 /g.
  • the specific surface area of the resin sheet means the BET (Brunauer-Emmett-Teller) specific surface area by nitrogen gas adsorption.
  • the BET specific surface area can be measured by a method conforming to the provisions of JIS Z8830:2013.
  • the porosity of the resin sheet is, for example, 20% or more, preferably 30% or more, and more preferably 40% or more.
  • the upper limit of the porosity of the resin sheet is not particularly limited, and may be, for example, 80% or 60%.
  • the porosity of the resin sheet can be calculated by the following formula based on the volume V (cm 3 ), weight W (g) and true density D (g/cm 3 ) of the resin sheet.
  • the true density D means the specific gravity of the material constituting the resin sheet.
  • Porosity (%) 100 ⁇ (V - (W / D)) / V
  • the adsorption test A1 and the desorption test B1 will be described in detail below.
  • the adsorption test A1 and the desorption test B1 can be measured, for example, using a measuring device 200 shown in FIG. 1.
  • the measuring device 200 includes a first tank 230 and a second tank 231.
  • the first tank 230 stores dry nitrogen
  • the second tank 231 stores a mixed gas of dry nitrogen and dry carbon dioxide.
  • the concentration of carbon dioxide in the mixed gas in the second tank 231 is, for example, 5 vol%.
  • the measuring device 200 further includes a first container 240 containing water 270, and a first path 260 for sending nitrogen from the first tank 230 to the first container 240.
  • the first path 260 has one end connected to the gas outlet of the first tank 230 and the other end disposed in the water 270 of the first container 240.
  • the nitrogen sent from the first tank 230 to the first container 240 is humidified by contact with the water 270.
  • a mass flow controller 235 for adjusting the flow rate of nitrogen sent from the first tank 230 to the first container 240 is disposed in the first path 260.
  • the measuring device 200 further includes a second container 241, a second path 262, and a bypass path 261.
  • the second path 262 connects the first container 240 and the second container 241.
  • the humidified nitrogen sent to the first container 240 is sent to the second container 241 through the second path 262.
  • the bypass path 261 branches off from the first path 260 at a position between the first tank 230 and the mass flow controller 235, and connects to the second path 262.
  • a portion of the nitrogen sent from the first tank 230 flows into the bypass path 261 and is sent to the second container 241 through the second path 262.
  • a mass flow controller 236 is disposed in the bypass path 261 to adjust the flow rate of the nitrogen sent from the first tank 230 to the bypass path 261.
  • the measuring device 200 further includes a third path 263 for sending the mixed gas from the second tank 231 to the second path 262.
  • the third path 263 has one end connected to the gas outlet of the second tank 231 and the other end connected to the second path 262.
  • a mass flow controller 237 is disposed in the third path 263 for adjusting the flow rate of the mixed gas sent from the second tank 231 to the second path 262.
  • the mixed gas sent to the second path 262 is sent to the second container 241 via the second path 262.
  • the measuring device 200 further includes a third container 242 and a fourth path 264.
  • the third container 242 contains water 271 and an adsorption section 221 disposed in the water 271.
  • the temperature of the water 271 is maintained at 20°C.
  • the adsorption section 221 has a gas inlet 222 and a gas outlet 223.
  • the adsorption section 221 functions as a container that contains an acid gas adsorbent sheet therein.
  • the adsorption section 221 is configured so that the water 271 does not penetrate into the inside.
  • the adsorption section 221 is typically a tube made of a hydrophobic resin, for example, a fluororesin such as tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA).
  • a fluororesin such as tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA).
  • the tube serving as the adsorption section 221 has an inner diameter of 4 mm and an outer diameter of 6 mm.
  • the adsorption section 221 is configured to be detachable from the measuring device 200.
  • the measuring device 200 can also be used as an acid gas adsorption device equipped with an adsorption section 221.
  • the present invention provides an acid gas adsorption device equipped with an adsorption section 221 having a gas inlet 222 and a gas outlet 223, the adsorption section 221 housing an acid gas adsorbent sheet.
  • the fourth path 264 connects the second container 241 and the third container 242.
  • the fourth path 264 is connected to the gas inlet 222 of the adsorption section 221 in the third container 242.
  • a first concentration meter 250 for measuring the concentration of carbon dioxide in the gas supplied to the adsorption section 221 is disposed in the fourth path 264.
  • a CO 2 /H 2 O gas analyzer, LI-850-3, manufactured by LI-COR Corporation can be used as the first concentration meter 250.
  • the measuring device 200 further includes a fifth path 265 that is connected to the gas outlet 223 of the adsorption section 221 and is used to discharge gas from the adsorption section 221 to the outside of the measuring device 200.
  • a back pressure valve 255 and a second concentration meter 251 are disposed in the fifth path 265.
  • the back pressure valve 255 can adjust the pressure in the adsorption section 221 to a constant value.
  • the second concentration meter 251 can measure the concentration of carbon dioxide in the gas discharged from the adsorption section 221.
  • a CO 2 /H 2 O gas analyzer LI-850-3, manufactured by LI-COR Corporation can be used.
  • Each path of the measuring device 200 is made of, for example, metal or resin piping.
  • an acidic gas adsorbent sheet is prepared and dried.
  • the drying process is performed, for example, by treating the acidic gas adsorbent sheet for 2 hours or more under conditions of a vacuum atmosphere and 60° C.
  • the acidic gas adsorbent sheet after the drying process is loaded into the adsorption section 221 in a dry room with a dew point of about ⁇ 60° C.
  • 50 mg of the acidic gas adsorbent sheet is loaded into the adsorption section 221.
  • a fourth path 264 and a fifth path 265 are connected to both ends of the adsorption section 221, and the adsorption section 221 is immersed in the water 271 in the third container 242.
  • nitrogen from the first tank 230 and the mixed gas from the second tank 231 are supplied to the second container 241 through the first path 260, the second path 262, the bypass path 261, and the third path 263 of the measuring device 200.
  • these gases are mixed to obtain a mixed gas G composed of carbon dioxide, nitrogen, and water vapor.
  • the concentration of carbon dioxide in the mixed gas G is adjusted to 400 vol ppm.
  • the mixed gas G has a temperature of 20° C. and a humidity of 50% RH.
  • the mixed gas G is supplied to the adsorption section 221 through the fourth path 264 at a flow rate sufficient for the weight of the acidic gas adsorbent sheet, for example, a flow rate of 300 mL/min for 50 mg of the acidic gas adsorbent sheet.
  • the pressure of the mixed gas G is adjusted to, for example, 107 kPa by the back pressure valve 255.
  • the adsorption section 221 is removed from the third container 242 and immersed in a water bath (not shown) at 80°C for at least two hours.
  • the adsorption section 221 is immersed in the water bath until the carbon dioxide concentration measured by the first concentration meter 250 and the carbon dioxide concentration measured by the second concentration meter 251 become substantially the same value. This completes the pretreatment of the acid gas adsorbent sheet in the adsorption section 221.
  • adsorption test Next, while the mixed gas G is being supplied to the adsorption section 221, the adsorption section 221 is removed from the hot water bath and immersed in the water 271 in the third container 242. This starts a carbon dioxide adsorption test (adsorption test A1) for the acidic gas adsorbent sheet in the adsorption section 221. The adsorption test is continued for 15 hours after it is started. In detail, the mixed gas G is continuously supplied to the adsorption section 221 for 15 hours.
  • the amount of carbon dioxide adsorbed by the acidic gas adsorbent sheet within 1 hour from the start is measured as M1
  • the amount of carbon dioxide adsorbed by the acidic gas adsorbent sheet within 15 hours from the start is measured as M2.
  • the amount of carbon dioxide adsorbed by the acidic gas adsorbent sheet can be calculated from the result of measuring the difference between the concentration of carbon dioxide measured by the first concentration meter 250 and the concentration of carbon dioxide measured by the second concentration meter 251 over time. Based on the amount of substance M1, the amount of carbon dioxide adsorbed by 1 g of the acidic gas adsorbent sheet within 1 hour from the start of the test is calculated, and the calculated value is specified as the amount of adsorption a1.
  • the amount of carbon dioxide adsorbed by 1 g of the acidic gas adsorbent sheet within 15 hours from the start of the test is calculated, and the calculated value is specified as the amount of adsorption a2.
  • the adsorption test is performed for 15 hours, the adsorption of carbon dioxide by the acidic gas adsorbent sheet can usually be considered to have reached equilibrium.
  • the amount of adsorption a2 is the saturated adsorption amount of carbon dioxide of the acidic gas adsorbent sheet. If the inlet and outlet concentration meters are not stable at the same value, it indicates that the adsorption has not yet reached saturation.
  • the saturated adsorption amount at 20°C (adsorption amount a2) can be calculated by using the data up to 15 hours and performing a fitting analysis using the Avrami formula using analysis software (gnuplot) as described in Chemical Engineering Journal 161 (2010) 182-190.
  • the amount of carbon dioxide desorbed from the acidic gas adsorbent sheet for 15 hours from the start is measured as M3.
  • the amount of carbon dioxide desorbed from the acidic gas adsorbent sheet can be calculated from the result of measuring the difference between the concentration of carbon dioxide measured by the first concentration meter 250 and the concentration of carbon dioxide measured by the second concentration meter 251 over time. Based on the amount of substance M3, the amount of carbon dioxide desorbed from 1 g of the acidic gas adsorbent sheet in 15 hours is calculated, and the calculated value is specified as the desorption amount b1.
  • the desorption of carbon dioxide by the acidic gas adsorbent sheet usually reaches equilibrium and can be considered to be desorbed and saturated. That is, in the desorption test B1, the saturated desorption amount of carbon dioxide desorbed from the acidic gas adsorbent is measured, and the desorption amount b1 is the saturated desorption amount of carbon dioxide from the acidic gas adsorbent sheet.
  • the saturated desorption amount at 50°C can also be obtained by performing fitting analysis with the Avrami formula using the method described in Chemical Engineering Journal 161 (2010) 182-190 using analysis software (gnuplot) using data from less than 15 hours from the start, for example up to 1.5 hours, and the obtained value can be regarded as the desorption amount b1 of carbon dioxide desorbed from 1 g of the acidic gas adsorbent sheet up to 15 hours from the start.
  • the amount a1 of carbon dioxide adsorption from the start of the adsorption test A1 until one hour later is preferably 0.5 mmol/g or more, and may be 0.52 mmol/g or more, 0.6 mmol/g or more, 0.62 mmol/g or more, 0.66 mmol/g or more, 0.7 mmol/g or more, or even 0.72 mmol/g or more.
  • the upper limit of the amount a1 of carbon dioxide adsorption is not particularly limited, and is, for example, 5.0 mmol/g or less.
  • the carbon dioxide desorption rate Y when desorption test B1 is performed is preferably 82% or more, and may be 83% or more, 85% or more, or even 86% or more.
  • the upper limit of the carbon dioxide desorption rate Y is not particularly limited, and is, for example, 99% or less.
  • the acidic gas adsorbent sheet according to the second embodiment can be manufactured by, for example, the manufacturing method according to the first embodiment.
  • the acidic gas adsorbent sheet according to the second embodiment can adsorb acidic gases, such as carbon dioxide, hydrogen sulfide, carbonyl sulfide, sulfur oxides (SO x ), hydrogen cyanide, and nitrogen oxides (NO x ), and is preferably carbon dioxide.
  • acidic gases such as carbon dioxide, hydrogen sulfide, carbonyl sulfide, sulfur oxides (SO x ), hydrogen cyanide, and nitrogen oxides (NO x )
  • the acidic gas adsorbent sheet 10 can be used, for example, by the following method. First, a mixed gas containing an acidic gas is brought into contact with the acidic gas adsorbent sheet 10.
  • the mixed gas contains, for example, other gases in addition to the acidic gas. Examples of the other gases include non-polar gases such as hydrogen and nitrogen, and inert gases such as helium, and nitrogen is preferred.
  • the mixed gas is typically air.
  • the mixed gas may be off-gas from a chemical plant or thermal power plant.
  • the temperature of the mixed gas is, for example, room temperature (23°C).
  • the concentration of the acidic gas in the mixed gas is not particularly limited, and is, for example, 0.01 vol% (100 volppm) or more, preferably 0.04 vol% (400 volppm) or more, and may be 1.0 vol% or more, under standard conditions (0°C, 101 kPa).
  • the upper limit of the carbon dioxide concentration in the mixed gas is not particularly limited, and is, for example, 10 vol% under standard conditions.
  • the pressure of the mixed gas is typically equal to the atmospheric pressure in the environment in which the acidic gas adsorbent sheet 10 is used. However, the mixed gas that is brought into contact with the acidic gas adsorbent sheet 10 may be pressurized.
  • the acid gas adsorbent sheet that comes into contact with the mixed gas adsorbs the acid gas contained in the mixed gas.
  • the operation of bringing the mixed gas into contact with the acid gas adsorbent sheet is continued, for example, until the adsorption of the acid gas by the acid gas adsorbent sheet reaches equilibrium.
  • the acidic gas adsorbent sheet that has adsorbed the acidic gas is regenerated.
  • the regeneration can be performed, for example, by heating the acidic gas adsorbent sheet.
  • the heating temperature of the acidic gas adsorbent sheet is, for example, 50 to 80°C.
  • the acidic gas adsorbent sheet may be heated under a reduced pressure or vacuum.
  • the acidic gas, particularly carbon dioxide, desorbed from the acidic gas adsorbent sheet can be used as a raw material for chemical synthesis or dry ice.
  • the adsorption of acidic gas by the acidic gas adsorbent sheet and the regeneration of the acidic gas adsorbent sheet can be performed using the measurement device 200 (acidic gas adsorption device) described above.
  • the structure 30A of the third embodiment includes the above-mentioned acidic gas adsorbent sheet 10 and has a ventilation path 14.
  • the acidic gas adsorbent sheet 11 shown in Fig. 3 can also be used instead of the acidic gas adsorbent sheet 10.
  • the structure 30A is typically a honeycomb structure having a plurality of ventilation paths 14 extending in the same direction.
  • the structure 30A includes an adsorbent unit U in which, for example, an acidic gas adsorbent sheet 10A having a corrugated shape and an acidic gas adsorbent sheet 10B having a flat shape are laminated.
  • an acidic gas adsorbent sheet 10A a plurality of peaks 12 and a plurality of valleys 13 are alternately arranged.
  • An air passage 14 is formed between the peaks 12 or valleys 13 of the acidic gas adsorbent sheet 10A and the acidic gas adsorbent sheet 10B.
  • the direction x is the direction in which the plurality of peaks 12 and the plurality of valleys 13 of the acidic gas adsorbent sheet 10A are alternately arranged (wave direction).
  • the direction y is the lamination direction of the acidic gas adsorbent sheets 10A and 10B in the adsorbent unit U.
  • the direction z is a direction perpendicular to each of the directions x and y, and is the direction in which the air passage 14 extends.
  • the structure 30A includes, for example, a plurality of adsorbent units U.
  • the number of adsorbent units U in the structure 30A is not particularly limited and may be, for example, 2 to 100.
  • the plurality of adsorbent units U are stacked in the direction y such that the plurality of acidic gas adsorbent sheets 10A and the plurality of acidic gas adsorbent sheets 10B are arranged alternately. By stacking the plurality of adsorbent units U, the structure 30A has a block shape.
  • the ventilation path 14 is a through-hole that penetrates the structure 30A in the direction z.
  • the ventilation path 14 is surrounded by the acidic gas adsorbent sheets 10A and 10B.
  • the acidic gas moves in the direction z through the ventilation path 14 and is efficiently adsorbed by the acidic gas adsorbent sheets 10A and 10B.
  • the structure 30A having a large cross-sectional area of the ventilation path 14 is suitable for reducing pressure loss that occurs when contacting an acidic gas.
  • the structure 30A with reduced pressure loss can reduce the power of a fan used to move the acidic gas, for example. Note that the acidic gas adsorbent sheet 10 tends to have a relatively large amount of amino group substance per unit volume, and therefore tends to be able to sufficiently adsorb acidic gas even when the thickness of the resin sheet 1 is small.
  • the shape of the structure 30A including the acidic gas adsorbent sheet 10 is not limited to that shown in Fig. 4A.
  • the structure 30B shown in Fig. 4B has a shape in which one adsorbent unit U is wound around a central tube 80. Except for this, the configuration of the structure 30B is the same as the configuration of the structure 30A.
  • the structure 30B has a cylindrical shape.
  • the multiple peaks 12 and multiple valleys 13 of the acidic gas adsorbent sheet 10A are arranged alternately in the circumferential direction of the structure 30B.
  • the ventilation paths 14 formed between the peaks 12 or valleys 13 of the acidic gas adsorbent sheet 10A and the acidic gas adsorbent sheet 10B penetrate the structure 30B in the direction in which the central tube 80 extends.
  • the acidic gas moves through the ventilation paths 14 in the direction in which the central tube 80 extends, and is efficiently adsorbed by the acidic gas adsorbent sheets 10A and 10B.
  • Example 1 First, compound C1, compound C2, and porogen were charged into a 300 ml cylindrical container (Tightboy, manufactured by Thinky Corporation). As compound C1, 64.34 g of triethylenetetramine (manufactured by Tosoh Corporation) was used. As compound C2, 10 g of ethylene glycol diglycidyl ether (Denacol EX-810, manufactured by Nagase ChemteX Corporation) and 15 g of pentaerythritol tetraglycidyl ether (Shofree (registered trademark) PETG, manufactured by Showa Denko K.K.) were used.
  • ethylene glycol diglycidyl ether Disacol EX-810, manufactured by Nagase ChemteX Corporation
  • pentaerythritol tetraglycidyl ether Shofree (registered trademark) PETG, manufactured by Showa Denko K.K.
  • porogens 56.69 g of poly(1,2-butanediol)-6 propylene glycol (UNIOL (registered trademark) PB-500, manufactured by NOF Corporation) and 56.69 g of polyoxypropylene diglyceryl ether (UNILUBE (registered trademark) DGP-700, manufactured by NOF Corporation) were used. These were stirred for 5 minutes at 650 rpm and 0.2 kPa in a centrifugal mixer (Thinky Mixer (vacuum)) to obtain a mixture of Compound C1, Compound C2, and porogen. The mixture was heated at 60° C. for 3 hours to produce Reactant P1.
  • a centrifugal mixer Thinky Mixer (vacuum)
  • the ratio (E/A) of the equivalent (A) of the active hydrogen of the primary amino group contained in the amine monomer used in the preparation of the reactant P1 to the equivalent (E) of the epoxy group contained in the epoxy monomer was 0.16.
  • the mixed liquid containing the reactant P1 was cooled, and the viscosity at a shear rate of 1 s at 25°C was measured.
  • the mixture containing reactant P1 was stored in a refrigerator at 4°C.
  • an epoxy solution was prepared by mixing 21.26 g of ethylene glycol diglycidyl ether (Denacol EX-810, manufactured by Nagase ChemteX Corporation) and 31.89 g of pentaerythritol tetraglycidyl ether (Showa Denko K.K., Showfree (registered trademark) PETG), and stored in a refrigerator at 4°C.
  • ethylene glycol diglycidyl ether (Denacol EX-810, manufactured by Nagase ChemteX Corporation)
  • 31.89 g of pentaerythritol tetraglycidyl ether Showa Denko K.K., Showfree (registered trademark) PETG
  • reaction solution P2 The epoxy solution was added to the mixture containing reactant P1. As a result, the ratio (E/A) of the epoxy group equivalent (E) to the active hydrogen equivalent (A) of the primary amino group in all materials used was 0.5. The mixture was then stirred at 310 rpm with a stirring blade at room temperature to obtain reaction solution P2.
  • reaction liquid P2 The temperature of reaction liquid P2 was monitored while stirring, and stirring was stopped when the temperature reached 20°C.
  • a 250 ⁇ m thick glass paper was immersed in reaction liquid P2 with a temperature of 20°C for 10 seconds and removed.
  • the impregnated sheet obtained was left to stand at 120°C for 1 hour to harden. This resulted in a sheet-like hardened body.
  • This hardened body was immersed in ethyl acetate at 60°C for 30 minutes, and the operation was repeated twice with liquid exchange. As a result, the porogen was removed from the hardened body, and a resin sheet with a porous structure was formed.
  • an acid gas adsorbent sheet of Example 1 was obtained, in which the resin sheet was composited within the glass paper sheet.
  • Example 2 The reaction liquid P2 was stirred until the liquid temperature reached 30°C, and the glass paper was impregnated with the reaction liquid P2 having a liquid temperature of 30°C. In the same manner as in Example 1, an acidic gas adsorbent sheet of Example 2 was obtained.
  • Example 3 An acidic gas adsorbent sheet of Example 3 was obtained in the same manner as in Example 1, except that the types and amounts of raw materials were changed as shown in Table 1, and reaction liquid P2 was stirred until the liquid temperature reached 30° C., and the glass paper was impregnated with reaction liquid P2 whose liquid temperature was 30° C. That is, an acidic gas adsorbent sheet of Example 3 was obtained by the same operation as in Example 2, except for the types and amounts of raw materials.
  • Example 4 An acidic gas adsorbent sheet of Example 4 was obtained in the same manner as in Example 1, except that the types and amounts of raw materials were changed as shown in Table 1, and reaction liquid P2 was stirred until the liquid temperature reached 30° C., and the glass paper was impregnated with reaction liquid P2 whose liquid temperature was 30° C. That is, an acidic gas adsorbent sheet of Example 4 was obtained by the same operation as in Example 2, except for the types and amounts of raw materials.
  • Example 5 First, compound C1, compound C2, and porogen were charged into a 300 ml cylindrical container (Tightboy, manufactured by Thinky Corporation). 82.51 g of polyethyleneimine (Epomin SP-012, manufactured by Nippon Shokubai Co., Ltd.) was used as compound C1. 6.2 g of ethylene glycol diglycidyl ether (Denacol EX-810, manufactured by Nagase Chemtex Corporation) was used as compound C2.
  • 51.63 g of poly(1,2-butanediol)-6 propylene glycol (UNIOL (registered trademark) PB-500, manufactured by NOF Corporation) and 51.63 g of a copolymer of butylene glycol and propylene glycol (UNIOL (registered trademark) PB-700, manufactured by NOF Corporation) were used as porogens. These were stirred for 5 minutes at 1000 rpm and 0.2 kPa in a centrifugal mixer (Thinky Mixer (vacuum)) to obtain a mixture of Compound C1, Compound C2, and porogen. The mixture was heated at 60° C. for 3 hours to produce Reactant P1. The mixture containing Reactant P1 was cooled, and the viscosity at a shear rate of 1 s at 25° C. was measured.
  • the ratio (E/A) of the equivalents (A) of the active hydrogen of the primary amino group to the equivalents (E) of the epoxy group of the material used to prepare reactant P1 was 0.05.
  • the resulting mixture containing reactant P1 was stored in a refrigerator at 4°C.
  • reaction solution P2 The above ethylene glycol diglycidyl ether was added to the mixture containing reactant P1. As a result, the ratio (E/A) of the epoxy group equivalent (E) to the primary amino group active hydrogen equivalent (A) in all materials used was 0.5. The mixture was then stirred at room temperature at 310 rpm using a stirring blade to obtain reaction solution P2.
  • reaction liquid P2 The temperature of reaction liquid P2 was monitored while stirring, and stirring was stopped when the temperature reached 25°C.
  • a 250 ⁇ m thick glass paper was immersed in reaction liquid P2 at a temperature of 25°C for 10 seconds and removed.
  • the impregnated sheet obtained was left to stand at 120°C for 10 minutes to harden. This resulted in a sheet-like hardened body.
  • This hardened body was immersed in ethyl acetate at 60°C for 30 minutes, and the operation was repeated twice with liquid exchange. As a result, the porogen was removed from the hardened body, and a resin sheet with a porous structure was formed.
  • an acid gas adsorbent sheet of Example 5 was obtained, in which the resin sheet was composited within the glass paper sheet.
  • a mixture of compound C2 and porogen was obtained.
  • the mixture was stored in a refrigerator at 4°C.
  • 64.34 g of triethylenetetramine manufactured by Tosoh Corporation
  • the mixed liquid and compound C1 were then mixed.
  • the ratio (E/A) of the epoxy group equivalent (E) to the primary amino group active hydrogen equivalent (A) in all materials used was 0.5.
  • the mixture was stirred at 310 rpm with a stirring blade at room temperature to carry out the reaction.
  • the temperature of the reaction solution was monitored while stirring, and stirring was stopped when the temperature reached 25°C.
  • a 250 ⁇ m thick glass paper was immersed in the reaction solution at 25°C for 10 seconds and removed.
  • the impregnated sheet obtained was left to stand at 120°C for 1 hour to harden. This resulted in a sheet-like hardened body.
  • This hardened body was immersed in ethyl acetate at 60°C for 30 minutes, and the operation was repeated twice with liquid exchange. As a result, the porogen was removed from the hardened body, and a resin sheet with a porous structure was formed.
  • an acid gas adsorbent sheet of Comparative Example 1 was obtained, in which the resin sheet was composited within the glass paper sheet.
  • Comparative Example 2 The reaction liquid was stirred until the temperature of the reaction liquid reached 35°C, and an acidic gas adsorbent sheet of Comparative Example 2 was obtained in the same manner as Comparative Example 1, except that the glass paper was impregnated with the reaction liquid at a temperature of 35°C.
  • the mixture was stored in a refrigerator at 4° C. Separately, 58.1 g of ethylene glycol diglycidyl ether (Denacol EX-810, manufactured by Nagase ChemteX Corp.) was stored in a refrigerator at 4° C. as compound C2. The mixture and compound C2 were mixed. The ratio (E/A) of the epoxy group equivalent (E) to the primary amino group active hydrogen equivalent (A) in all materials used was 0.5. The mixture was stirred at room temperature at 310 rpm using a stirring blade to carry out the reaction.
  • the temperature of the reaction solution was monitored while stirring, and the stirring was stopped when the temperature reached 25°C.
  • a 250 ⁇ m thick glass paper was immersed in the reaction solution at 25°C for 10 seconds and removed.
  • the impregnated sheet obtained was left to stand at 120°C for 10 minutes to harden. This resulted in a sheet-like hardened body.
  • This hardened body was immersed in ethyl acetate at 60°C for 30 minutes, and the operation was repeated twice with liquid exchange. As a result, the porogen was removed from the hardened body, and a resin sheet with a porous structure was formed.
  • an acid gas adsorbent sheet of Comparative Example 3 was obtained, in which the resin sheet was composited within the glass paper sheet.
  • Comparative Example 4 The reaction liquid was stirred until the temperature of the reaction liquid reached 35°C, and the glass paper was impregnated with the reaction liquid at a temperature of 35°C. In the same manner as in Comparative Example 3, an acidic gas adsorbent sheet of Comparative Example 4 was obtained.
  • the saturated adsorption amount obtained by performing fitting analysis using the Avrami formula on the data up to 15 hours after the start of the adsorption test was regarded as the adsorption amount a2.
  • the saturated desorption amount obtained by performing fitting analysis using the Avrami formula on the data up to 1.5 hours after the start of the desorption test was regarded as the desorption amount b1.
  • the test results are shown in Table 3.
  • TETA Triethylenetetramine (manufactured by Tosoh Corporation)
  • PEI1200 Polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., Epomin SP-012, weight average molecular weight approximately 1200)
  • EDE Ethylene glycol diglycidyl ether (Nagase Chemtex Corporation, EX-810)
  • PETG Pentaerythritol tetraglycidyl ether (Showa Denko K.K., Showfree (registered trademark) PETG)
  • PB500 Poly(1,2-butanediol)-6 propylene glycol (NOF Corporation, Uniol (registered trademark) PB-500)
  • DGP700 Polyoxypropylene diglyceryl ether (NOF Corporation, Unilube (registered trademark) DGP-700)
  • PB700 copolymer of butylene glycol and propylene glycol (NOF Corporation,
  • the acid gas adsorbent sheets of Examples 1 to 5 had a three-dimensional mesh skeleton composed of a polymer and had holes on their surface. In other words, the acid gas adsorbent sheets of Examples 1 to 5 did not have a skin layer. As can be seen from Figures 15 to 20, the acid gas adsorbent sheets of Comparative Examples 1 to 3 did not have holes on their surface but had a skin layer. The thicknesses of the skin layers of the acid gas adsorbent sheets of Comparative Examples 1 to 3 are shown in Table 3.
  • Example 1 to 5 The 60-minute adsorption rate of Examples 1 to 5 was improved over that of Comparative Examples 1 to 4. In other words, Examples 1 to 5 adsorbed carbon dioxide more quickly than Comparative Examples 1 to 4. Comparative Example 4, although it did not have a skin layer, had a lower 60-minute adsorption rate than Examples 1 to 5. In Comparative Example 4, phase separation had progressed too far before it was made into a sheet-shaped hardened body, resulting in a coarse porous structure, which is thought to result in a lower adsorption capacity than Examples 1 to 5. Therefore, it can be seen that the acidic gas adsorbent sheet produced by the manufacturing method of the present invention is suitable for improving the adsorption capacity of acidic gases.
  • the acid gas adsorbent sheet produced by the manufacturing method of this embodiment is suitable for adsorbing and desorbing acid gases.

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