WO2013115033A1 - Feuille d'adsorption et élément d'adsorption utilisé pour celle-ci - Google Patents

Feuille d'adsorption et élément d'adsorption utilisé pour celle-ci Download PDF

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WO2013115033A1
WO2013115033A1 PCT/JP2013/051308 JP2013051308W WO2013115033A1 WO 2013115033 A1 WO2013115033 A1 WO 2013115033A1 JP 2013051308 W JP2013051308 W JP 2013051308W WO 2013115033 A1 WO2013115033 A1 WO 2013115033A1
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group
carbon atoms
adsorption
metal complex
porous metal
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PCT/JP2013/051308
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English (en)
Japanese (ja)
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増森　忠雄
靖子 西口
祐介 西谷
小林　真申
賢広 渡邉
圭輔 岸田
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東洋紡株式会社
昭和電工株式会社
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Priority claimed from JP2012017193A external-priority patent/JP2013154302A/ja
Priority claimed from JP2012017192A external-priority patent/JP5935354B2/ja
Application filed by 東洋紡株式会社, 昭和電工株式会社 filed Critical 東洋紡株式会社
Publication of WO2013115033A1 publication Critical patent/WO2013115033A1/fr

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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
    • 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
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0233—Compounds of Cu, Ag, Au
    • B01J20/0237—Compounds of Cu
    • 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
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • 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
    • 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
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • 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
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • 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
    • B01D53/047—Pressure swing adsorption
    • 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 an adsorbent sheet that can be used as an adsorbent, an occlusion material, and a separation material. It is related with the form provision at the time of using.
  • the present invention also relates to an adsorption sheet for efficiently separating / collecting or adsorbing / removing moisture, organic solvents, and malodorous components in the air, and an adsorption element using the same.
  • Porous materials such as activated carbon, silica gel, and zeolite are used for deodorization, air and water purification, and gas separation and purification.
  • a porous material obtained by self-assembly by combining a metal ion capable of various coordination forms and a bridging ligand having two or more coordination sites that is, a porous metal complex (MOF)
  • a porous coordination polymer (PCP) a new porous material called a porous coordination polymer (PCP)
  • these porous metal complexes have characteristics not found in conventional porous materials such as activated carbon, silica gel, zeolite, That is, it has features such as a high specific surface area, a sharp pore distribution, and a high structural design, and has attracted attention.
  • Patent Document 1 discloses a gate-type polymer complex that exhibits gas adsorption as a gate and a gas that is I-type. Porous metal complexes have been reported in which the properties of both type I complexes vary with the switching material. Patent Documents 2 and 3 report a porous metal complex that selectively adsorbs only a specific gas with a change in pore structure and size. Furthermore, in Patent Document 3 and Non-Patent Document 1, a flexible porous metal complex whose structure is changed depending on the type of gas in contact with it and a gas separation method using the same are also reported.
  • Patent Document 4 discloses a specific dicarboxylic acid metal complex as a porous metal complex, and discloses that this is suitable as a gas storage material, particularly a gas storage material mainly composed of methane.
  • Patent Document 5 discloses a porous complex synthesized from copper ions and trimesic acids, and an adsorbent is disclosed as an example of its use.
  • Patent Document 6 discloses that a porous coordination polymer obtained from metal chromium or a chromium salt and trimesic acid is particularly excellent as a water vapor adsorbent, and has a high porous coordination polymer. It is disclosed that in order to use molecules as adsorbents for various substances, it is preferable to remove the solvent by heating under reduced pressure.
  • Patent Documents 4 to 6 do not specifically describe an adsorbing sheet composed of these porous metal complexes and a manufacturing method for an adsorbing element using the adsorbing sheet.
  • Patent Document 7 discloses a corrugated sheet containing powdered activated carbon and a self-consolidating fibrous clay mineral and heat-resistant artificial fibers as main components as a sheet made by mixing powdered activated carbon.
  • a processable adsorbent sheet is disclosed.
  • powdered activated carbon is used as an adsorbent, there is a problem that the adsorption performance is not sufficient.
  • Patent Document 8 discloses an adsorption sheet containing zeolite and moisture minerals, clay mineral fibers having self-consolidating properties, glass fibers, and an organic binder. Yes. Since this adsorbing sheet contains clay mineral fibers and glass fibers, it has excellent heat resistance, and since it contains an organic binder, it exhibits excellent adsorbent supportability and sheet flexibility. .
  • a porous material when using zeolite or molecular sieve charcoal as an adsorbent for pressure swing adsorption, the adsorbent is compressed into a pellet using a tablet molding machine or the like. Is common. However, when a porous metal complex having a flexible structure that changes its structure with gas adsorption like the porous metal complex described above is pelletized by general tableting molding, If it is molded to have sufficient strength, there is a problem that the adsorption performance decreases.
  • adsorbents such as zeolite and organic binders are mixed to form an adsorbent sheet
  • the side chains of the organic binder are adsorbed in the pores of the adsorbent zeolite, resulting in sufficient adsorption performance.
  • the same problem is expected when a porous metal complex is used as an adsorbent.
  • the organic binder adsorbed in the pores of the adsorbent (zeolite) can be removed by calcination at a temperature of 400 ° C. to 800 ° C. for 30 minutes or more.
  • the adsorbent is zeolite. Therefore, the adsorption performance is not sufficient.
  • firing under the above conditions destroys the pore structure of the porous metal complex, resulting in insufficient adtitled performance. It was.
  • heat resistance means that the strength is not significantly reduced in the adsorption sheet and the adsorption element using the same under a temperature condition of 80 ° C. or higher.
  • the present invention has been made by paying attention to such circumstances, and its purpose is to absorb absorption derived from the porous metal complex even when the structure of the porous metal complex changes due to gas adsorption / desorption. It is an object of the present invention to provide an adsorption sheet that can sufficiently exhibit the desorption performance.
  • Another object of the present invention is an adsorbent sheet that is excellent in heat resistance, porous metal complex support, and sheet flexibility and has sufficient adsorbing performance, and adsorbing using the same To provide an element.
  • the adsorbing sheet of the present invention includes a porous metal complex (A) and an organic fiber (B) that form a porous structure with metal ions and organic ligands that can bind to the metal ions. Has characteristics.
  • the inventors of the present invention have made a porous metal by gas adsorption / desorption by forming a sheet-like molded body in which a porous metal complex (A) is supported on an organic fiber (B).
  • a molded article containing a porous metal complex (A) capable of following the structural change of the complex and sufficiently exhibiting the excellent adsorption / desorption performance possessed by the porous metal complex (A) can be obtained, and the present invention has been completed. did.
  • the adsorbing sheet of the present invention preferably contains 50% to 90% by mass of the porous metal complex (A).
  • the porous metal complex (A) has hysteresis in the adsorption / desorption isotherm for at least one gas selected from the group consisting of hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide and hydrocarbons having 1 to 4 carbon atoms. It preferably represents a loop.
  • the organic ligand is preferably at least one organic compound selected from the group consisting of the following (1) to (3).
  • Organic compound having two or more carboxyl groups and / or hydroxyl groups in the molecule, having no heterocyclic ring, and capable of bidentate coordination with metal ions (2) In the molecule, N, O or S A monocyclic or polycyclic saturated or unsaturated heterocyclic ring having one heteroatom selected from the following: an organic compound having a carboxyl group or a hydroxyl group and capable of bidentate coordination to a metal ion (3) Intramolecular And a bidentate organic compound having a monocyclic or polycyclic saturated or unsaturated heterocycle having 2 or more heteroatoms selected from the group consisting of N, O and S
  • the organic ligand includes an alkylene dicarboxylic acid compound having 4 to 20 carbon atoms, an alkenylene dicarboxylic acid compound having 4 to 20 carbon atoms, and a dicarboxylic acid represented by the following general formulas (I) to (III). Acid compounds;
  • R 1 s are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a formyl group, carbon
  • an acylamino group having 1 to 4 carbon atoms, and two or more R 1 groups may be cyclic, or two or more R 1 groups may be condensed cyclically.
  • R 2 s are the same or different and each represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent
  • X represents a hydrogen atom or a substituent.
  • R 3 are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms) Or an alkoxy group having 1 to 4 carbon atoms
  • R 3 are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms) Or an alkoxy group having 1 to 4 carbon atoms), and organic compounds represented by the following general formulas (IX) to (XII);
  • Y is the same or different and represents an oxygen atom, a sulfur atom, —CH 2 —, —CH (OH) —, —CO—, —NH—, —C 2 N 4 —, —C ⁇ C—, —C 2 H 2 — or —C 6 H 4 —, wherein R 4 s are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, carbon An alkoxy group having 1 to 4 carbon atoms, a formyl group, an acyloxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group, a carboxyl group, an amino group, 1 to carbon atoms 4 monoalkylamino groups, dialkylamino groups having 1 to 4 carbon atoms or acylamino groups having 1 to 4 carbon atom
  • the organic fiber (B) is preferably cellulose.
  • the adsorbing sheet of the present invention is preferably produced by a wet papermaking method.
  • the present invention also includes an adsorption sheet characterized by containing a porous metal complex (A) and a heat-resistant fiber (D).
  • the adsorbing sheet preferably contains clay mineral fibers having self-consolidating properties.
  • the said adsorption sheet contains an organic binder.
  • the adsorption element using the adsorption sheet of the present invention is a preferred embodiment of the present invention.
  • the adsorption sheet of the present invention it can be reproduced without impairing the adsorption performance of the porous metal complex (A). Moreover, the adsorption
  • the organic solvent as used in this specification refers to the organic compound which has the property to melt
  • aldehydes such as formaldehyde and acetaldehyde
  • carboxylic acids such as acetic acid and isovaleric acid
  • nitrogen-containing compounds such as ammonia
  • hydrogen sulfide, methyl disulfide, methyl And sulfur-containing compounds such as mercaptans.
  • FIG. 3 is a graph showing an adsorption / desorption isotherm of carbon dioxide at 298 K of the blue powder obtained in Experimental Example 1-1.
  • FIG. 4 is a graph showing an adsorption and desorption isotherm of carbon dioxide at 298 K of the adsorption sheet obtained in Experimental Example 1-1.
  • FIG. 3 is a graph showing ethylene adsorption / desorption isotherms at 273 K of the blue powder obtained in Experimental Example 1-1.
  • FIG. 3 is a graph showing an adsorption / desorption isotherm of ethylene at 273 K of the adsorption sheet obtained in Experimental Example 1-1.
  • FIG. 3 is a graph showing an adsorption / desorption isotherm of carbon dioxide at 298 K of the white powder obtained in Experimental Example 1-2. It is a figure which shows the adsorption-and-desorption isotherm of a carbon dioxide in 298K of the adsorption sheet obtained in Experimental example 1-2.
  • FIG. 3 is a graph showing the adsorption and desorption isotherm of carbon dioxide at 298 K of the blue powder obtained in Experimental Example 1-3. It is a figure which shows the adsorption-desorption isotherm of a carbon dioxide in 298K of the adsorption sheet obtained in Experimental example 1-3.
  • FIG. 3 is a graph showing an adsorption / desorption isotherm of carbon dioxide at 298 K of the white powder obtained in Experimental Example 1-2. It is a figure which shows the adsorption-and-desorption isotherm of a carbon dioxide in 298K of the adsorption sheet obtained in Experimental example 1-2.
  • FIG. 3 is a graph showing
  • FIG. 3 is a graph showing adsorption / desorption isotherms of carbon dioxide at 298 K of the pellets obtained in Experimental Example 1-4.
  • FIG. 4 is a graph showing ethylene adsorption / desorption isotherms at 273 K of the pellets obtained in Experimental Example 1-4.
  • FIG. 7 is a graph showing adsorption / desorption isotherms of carbon dioxide at 298 K of the pellets obtained in Experimental Example 1-5. It is a model figure in case the adsorption-desorption isotherm of a porous metal complex shows a hysteresis loop. It is a figure which shows the X-ray-diffraction pattern of a porous metal complex (A1-1). It is a figure which shows the X-ray-diffraction pattern of a porous metal complex (A1-2).
  • Adsorption sheet The adsorption sheet of the present invention comprises (i) a porous metal complex (A) having a porous structure composed of a metal ion and an organic ligand capable of binding to the metal ion, and an organic fiber (B). (Hereinafter sometimes referred to as “first adsorbing sheet”) or (ii) a porous metal complex (A) and a heat-resistant fiber (D) (hereinafter referred to as “second”). However, the first and second suction sheets may be collectively referred to as “the suction sheet of the present invention”). First, the first suction sheet will be described.
  • the 1st adsorption sheet of this invention is a porous metal complex (A) which comprises a porous structure by the metal ligand and the organic ligand which can be couple
  • the thickness of the first adsorption sheet of the present invention is preferably 0.01 mm to 2 mm. More preferably, it is 0.1 mm to 0.5 mm, and further preferably 0.1 mm to 0.3 mm. If the thickness of the adsorbing sheet is too thin, it is difficult to increase the amount of the porous metal complex (A) supported. On the other hand, if the adsorbing sheet is too thick, the workability of the adsorbing element such as a gas separation device may be reduced.
  • the basis weight of the first adsorbing sheet of the present invention is preferably 50 g / m 2 to 200 g / m 2 .
  • the basis weight is 130 g / m 2 to 170 g / m 2 . If the basis weight is too small, the structure of the adsorption sheet becomes sparse, and the amount of the porous metal complex (A) supported becomes small, so that sufficient adsorption performance may not be exhibited, while the basis weight is large. If it is too large, the adsorbing sheet becomes thick, and there is a possibility that problems such as cracking are likely to occur when the adsorbing element is processed.
  • Porous metal complex (A) The porous metal complex (A) contained in the first adsorbing sheet of the present invention has a porous structure formed by metal ions and organic ligands that can bind to the metal ions. Therefore, the porous metal complex (A) has pores, and gas molecules can be accommodated in the pores.
  • the pores have a flexible structure capable of selectively adsorbing only a specific kind of gas with a change in structure or size by an external stimulus (pressure or the like). With such pores, a specific type of gas can be selectively adsorbed in the pores. Therefore, the porous metal complex (A) according to the present invention can be used as an adsorbent that adsorbs a specific gas in accordance with the purpose of adsorption, occlusion, and separation. Therefore, the size of the pores of the porous metal complex (A) according to the present invention is not particularly limited, but is preferably 2 to 50 mm, more preferably 2 to 30 mm, and still more preferably 2 to 20 mm. It is.
  • the specific gas include at least one gas selected from the group consisting of hydrogen, nitrogen, oxygen, carbon monoxide, carbon dioxide, and hydrocarbons having 1 to 4 carbon atoms.
  • the hydrocarbon having 1 to 4 carbon atoms include methane, ethane, propane and butane.
  • the adsorption / desorption isotherm with respect to the above-mentioned specific gas preferably exhibits a hysteresis loop.
  • “the adsorption / desorption isotherm shows a hysteresis loop” means that when the adsorption / desorption isotherm for a specific gas is created for the porous metal complex (A), as shown in FIG. It means that the adsorption / desorption isotherm at the time and the desorption isotherm at the time of gas desorption take different trajectories.
  • FIG. 12 is a model example when the adsorption / desorption isotherm of the porous metal complex (A) shows a hysteresis loop.
  • the locus of the adsorption / desorption isotherm during adsorption coincides with the locus of the desorption isotherm during desorption.
  • the adsorption amount A1 at the pressure P1 at which the adsorption amount at the time of gas adsorption starts to increase greatly the adsorption amount A2 at the pressure P1 at the time of desorption, and at the time of gas desorption. Since the adsorption amount A3 at the pressure P2 at which the adsorption amount starts to decrease greatly and the adsorption amount A4 at the pressure P2 at the time of adsorption are different from each other, the adsorption and desorption isotherms at the time of adsorption and desorption become different trajectories.
  • the porous metal complex (A) in which the adsorption / desorption isotherm shows a hysteresis loop as shown in FIG. 12 can arbitrarily perform gas adsorption / desorption by controlling the pressure. It is useful because it can also be used in a gas separator utilizing this characteristic.
  • the metal ion constituting the porous metal complex (A) of the present invention is not particularly limited as long as it can form pores capable of accommodating a specific molecule by organization with an organic ligand.
  • Elements and transition metal elements can be used, but preferably at least one metal selected from the group consisting of magnesium, calcium, aluminum, vanadium, manganese, iron, cobalt, nickel, copper, zinc, cadmium, lead and palladium. Cations. More preferably, it is at least one metal ion selected from magnesium, aluminum, copper and zinc.
  • the organic ligand constituting the porous metal complex (A) according to the present invention has two or more sites capable of coordinate bonding with a metal ion in the molecule, and a specific molecule is formed by organization with the metal ion.
  • the organic compound is not particularly limited as long as it can form a porous structure having a plurality of pores that can be accommodated, but at least one of the organic compounds is selected from the following groups (1) to (3): preferable.
  • Organic compound having two or more carboxyl groups and / or hydroxyl groups in the molecule, having no heterocyclic ring, and capable of bidentate coordination with metal ions (2) N, O or S in the molecule
  • organic compound (1) As an organic compound having two or more carboxyl groups and / or hydroxyl groups in the molecule, having no heterocyclic ring and capable of bidentate coordination with a metal ion (hereinafter referred to as organic compound (1)) Is an alkylene dicarboxylic acid compound having 4 to 20 carbon atoms (the carbon number includes carbon constituting a carboxy group), an alkenylene dicarboxylic acid compound having 4 to 20 carbon atoms (the carbon number is a carboxy group). And carbon atoms constituting), dicarboxylic acid compounds represented by the following general formulas (I) to (III), dicarboxylic acid compounds represented by the following general formula (IV), and the following general formula (V) An organic compound is mentioned.
  • each R 1 is the same or different and is a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an alkoxy having 1 to 4 carbon atoms.
  • the dialkylamino group the two alkyl groups may be the same or different (the same applies hereinafter).
  • the alkyl group may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.
  • the alkoxy group includes a methoxy group. , An ethoxy group, a propoxy group, and a butoxy group.
  • Examples of the acyloxy group include those substituted with a linear or branched alkyl group having 1 to 4 carbon atoms (for example, an acetoxy group, a propionyloxy group).
  • Group, isopropionyloxy group, etc.) and alkoxycarbonyl group include those substituted with a linear or branched alkyl group having 1 to 4 carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group).
  • Group, isopropoxycarbonyl group, butoxycarbonyl group, etc.) and monoalkylamino group include straight-chain Examples include those substituted with a branched alkyl group (for example, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, etc.).
  • Examples thereof include those having 1 to 4 linear or branched alkyl groups substituted (for example, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, s-butylamino group, etc.), and acylamino group Includes those substituted with a linear or branched alkyl group having 1 to 4 carbon atoms (for example, acetylamino group, propionylamino group, etc.).
  • R 1 is preferably a hydrogen atom.
  • R 2 s are the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms which may have a substituent
  • X represents a hydrogen atom or a substituent.
  • R 2 is preferably a hydrogen atom.
  • each R 3 is the same or different and is a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkyl group having 2 to 4 carbon atoms.
  • R 3 is preferably a hydrogen atom.
  • organic compound (2) Two or more metal ions having a monocyclic or polycyclic saturated or unsaturated heterocycle having one heteroatom selected from N, O or S and a carboxyl group or a hydroxyl group in the molecule.
  • organic compound (2) examples include organic compounds represented by the following general formulas (VI) to (VIII)).
  • R 3 s are the same or different and each represents a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, carbon An alkynyl group having 2 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
  • R 3 is preferably a hydrogen atom.
  • organic compounds (3) bidentate coordination to a metal ion having a monocyclic or polycyclic saturated or unsaturated heterocycle having two or more heteroatoms selected from the group consisting of N, O and S in the molecule
  • organic compounds (3) include organic compounds represented by the following general formulas (IX) to (XII).
  • Y is the same or different and represents an oxygen atom, a sulfur atom, —CH 2 —, —CH (OH) —, —CO—, —NH—, —C 2 N 4 — ( 1,2,4,5-tetrazine-3,6-diyl group), —C ⁇ C—, —C 2 H 2 — or —C 6 H 4 —, preferably —C 2 H 2 — or — C 6 H 4 —.
  • R 4 s are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a formyl group, or 1 to 4 carbon atoms.
  • a dialkylamino group having 1 to 4 carbon atoms is the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a formyl group, or 1 to 4 carbon atoms.
  • acyloxy group alkoxycarbonyl group, mono- or di-alkylamino group, and acylamino group are the same as those for R 1 of the organic compound (1).
  • R 4 is preferably a hydrogen atom.
  • n is an integer of 0 to 3, preferably 0 or 1.
  • organic ligands may be used alone or in combination of two or more, and may be appropriately selected according to the type of gas to be adsorbed.
  • organic compounds alkylene dicarboxylic acid compounds having 4 to 20 carbon atoms, organic compound (I), organic compound (IV), organic compound (IX), and organic compound (X) are preferable, and fumaric acid, Terephthalic acid and its derivatives, isophthalic acid and its derivatives, pyrazine and its derivatives, 4,4′-bipyridine, 1,2-bis (4-pyridyl) ethane, 1,2-bis (4-pyridyl) ethylene, 1, 2-bis (4-pyridyl) acetylene, more preferably 1,3,5-benzenetricarboxylic acid, 5-nitroisophthalic acid, pyrazine, 2,3-pyrazinecarboxylic acid, 1,2-bis (4- Pyridyl) ethylene.
  • a combination of organic ligands selected from each of the organic compound groups; a combination of two or more organic ligands selected from the organic compound group specified in (3) above is preferred, more preferably an organic compound ( I) and a combination of organic compound (IX), a combination of organic compound (IV) and organic compound (IX), a combination of organic compound (X) and organic compound (IX), represented by organic compound (X)
  • the porous metal complex (A) is a salt of the above metal (for example, nitrate, sulfate, formate, acetate, carbonate, hydrochloride, hydrobromide, tetrafluoroborate, phosphorus hexafluoride).
  • Acid salt and the above-mentioned organic ligand are dissolved in water or an organic solvent and reacted for several hours to several days. The organic solvent only needs to dissolve the metal salt and the organic ligand.
  • reaction conditions are not particularly limited, and may be appropriately adjusted according to the progress of the reaction.
  • the reaction temperature is preferably room temperature (25 ° C.) to 150 ° C.
  • Examples of the form of the porous metal complex (A) according to the present invention include various forms such as granular, powdery, fibrous, film-like, and plate-like, preferably powdery or granular, preferably powdery. Is more preferable.
  • the average particle size of the porous metal complex (A) is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, further preferably 5 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 200 ⁇ m or less. More preferably, those having a thickness of 100 ⁇ m or less can be preferably used.
  • the “average particle diameter” is a 50% diameter (median diameter), and can be measured by, for example, a laser diffraction / scattering particle size distribution measuring apparatus.
  • the BET specific surface area of the porous metal complex by the 77K nitrogen adsorption method is not particularly limited, but is preferably 500 m 2 / g or more, for example. If the BET specific surface area is smaller than 500 m 2 / g, it may be difficult to obtain sufficient adsorption performance.
  • the BET specific surface area is more preferably 1000 m 2 / g or more.
  • the upper limit of the BET specific surface area is not particularly limited, but is preferably 6000 m 2 / g or less. If this range is exceeded, the production of the porous metal complex becomes very difficult.
  • an average particle diameter and a BET specific surface area can be measured by the method as described in an Example.
  • the amount of the porous metal complex (A) contained in the first adsorption sheet of the present invention is preferably 50% by mass to 90% by mass.
  • the content of the porous metal complex (A) is more preferably 60% by mass to 80% by mass.
  • the productivity of the adsorption sheet is lowered or the porous metal complex ( There is a tendency for dropout of A) to increase.
  • Organic fiber (B) The organic fiber (B) in the 1st adsorption sheet of this invention is a component which functions as a support
  • the pulp form means a state separated and processed for use in papermaking.
  • Examples of the organic fiber (B) include cellulose fiber, polyester, vinylon, polypropylene, polyamide, rayon, acrylic fiber, polylactic acid fiber, polybenzimidazole, polybenzoxazole, polyimide, polyamideimide, and polyether ketone.
  • fibers made from wholly aromatic polyamides such as aramid and meta-aramid, polybenzimidazole, polybenzoxazole, polyimide, polyamideimide or polyether ketone are used. It is done.
  • the said organic fiber (B) may be used independently, and 2 or more types may be mixed and used for it.
  • the amount of the organic fiber (B) contained in the first adsorption sheet of the present invention is preferably 5% by mass to 20% by mass.
  • the content of the organic fiber (B) is less than 5% by mass, the supporting ability of the porous metal complex tends to be insufficient.
  • the content exceeds 20% by mass the porous metal complex (A) contained in the adsorption sheet Since the amount is relatively small, it may be difficult to obtain a sufficient adsorption effect. More preferably, it is 10% by mass to 20% by mass, and further preferably 15% by mass to 20% by mass.
  • organic binder (C) As a binder for carrying
  • the organic binder (C) is not particularly limited as long as the porous metal complex (A) can be supported on the adsorption sheet at a high ratio during the production of the adsorption sheet.
  • a polyvinyl alcohol polymer, a polyacrylonitrile polymer, a polyethylene polymer, a polyester polymer, a starch binder, a cellulose polymer, or the like can be used as the organic binder (C).
  • PVA polyvinyl alcohol
  • starch polyacrylonitrile, methyl cellulose, carboxymethyl cellulose, and the like.
  • the amount of the organic binder (C) is preferably 5% by mass to 30% by mass with respect to a total of 100% by mass of the constituent components of the adsorption sheet (more preferably 5% by mass to 10% by mass, and even more preferably 5% by mass). Mass% to 7 mass%).
  • the amount of the organic binder (C) is less than 5% by mass, the fixability of the porous metal complex (A) to the fiber component such as the organic fiber (B) and the bonding property between the fiber components tend to be poor. If it exceeds 30% by mass, the amount of the porous metal complex (A) in the adsorbing sheet is relatively small, so that it may be difficult to obtain a sufficient adsorbing effect.
  • the first adsorption sheet of the present invention may contain additives other than the porous metal complex (A), the organic fiber (B), and the organic binder (C) as necessary.
  • the additive include glass fiber, polymer flocculant, and pigment for the purpose of improving the mechanical strength of the adsorption sheet.
  • the amount of these components to be used is preferably 0% by mass to 10% by mass (more preferably 3% by mass to 7% by mass) with respect to a total of 100% by mass of the constituent components of the adsorption sheet.
  • the first adsorbing sheet of the present invention can selectively adsorb only a specific kind of gas while the porous metal complex (A) changes its structure and size, and adsorbs and desorbs the specific gas by changing the pressure. Since it has a porous metal complex (A) that can be used, it has excellent separation performance for separating a specific gas from a mixed gas. Moreover, since the component which comprises a 1st adsorption sheet is comparatively flexible and can follow the structural change of a porous metal complex (A), a porous metal complex (A) has also in an adsorption sheet. Excellent performance can be demonstrated. Therefore, the 1st adsorption sheet of this invention is preferably used as an adsorption sheet which comprises the adsorption element in a pressure swing adsorption method gas separation apparatus, for example.
  • the 2nd adsorption sheet of the present invention contains a porous metal complex (A) and a heat resistant fiber (D).
  • A porous metal complex
  • D heat resistant fiber
  • the thickness of the second suction sheet of the present invention is preferably 0.1 mm to 0.6 mm, more preferably 0.1 mm to 0.5 mm. If the thickness is less than 0.1 mm, the sheet strength is remarkably reduced, and it may be difficult to process the honeycomb-shaped adsorption element in post-processing. Further, if the thickness is larger than 0.6 mm, the pressure loss of the adsorbing element tends to increase when the adsorbing sheet is processed into a honeycomb shape or the like.
  • the basis weight of the second adsorbing sheet of the present invention is preferably 25 g / m 2 to 200 g / m 2 . More preferably, it is 40 g / m 2 to 150 g / m 2 . If the basis weight is less than 25 g / m 2 , the thickness of the sheet may be reduced, and the sheet strength may be significantly reduced, which may make it difficult to process the honeycomb-shaped adsorption element in post-processing. On the other hand, if the basis weight exceeds 200 g / m 2 , the thickness of the sheet becomes too large, and the pressure loss of the adsorption element when processed into a honeycomb or the like may increase.
  • Porous metal complex (A) The porous metal complex (A) according to the present invention is a porous material composed of a metal ion and a compound having a ligand. As a porous metal complex (A), the same thing as the thing used with a 1st adsorption sheet can be used.
  • transition metal such as typical metal elements, such as aluminum ion, iron ion, copper ion, and zinc ion Elements.
  • preferred compounds having a ligand include, for example, 2-methylimidazole, terephthalic acid and trimesic acid.
  • porous metal complex (A) constituting the second adsorbing sheet for example, a porous metal complex composed of zinc ions and 2-methylimidazole (manufactured by BASF, Basolite (registered trademark, the same applies hereinafter) Z1200), porous metal complex composed of aluminum ion and terephthalic acid (BASF, Basolite A100), porous metal complex composed of copper ion and trimesic acid (BASF, Basolite C300), iron ion And a porous metal complex composed of trimesic acid (BASF Corp., Basolite F300) is preferred.
  • a highly hydrophobic porous metal complex is a porous metal complex that has been subjected to a vacuum heat treatment at a temperature of 200 ° C. for 48 hours or more under vacuum conditions in a nitrogen atmosphere at 30 ° C. and a relative humidity of 60% RH. It refers to a porous metal complex having a mass increase rate of less than 10% by mass obtained by dividing the mass increase when left standing for 3 days or more by the mass of the porous metal complex immediately after the vacuum heat treatment.
  • Specific examples of the highly hydrophobic porous metal complex (A) include a porous metal complex composed of zinc ions and 2-methylimidazole (Basolite Z1200, manufactured by BASF).
  • the content of the porous metal complex (A) is preferably 50% by mass to 85% by mass, more preferably 60% by mass to 80% by mass. If the content is less than 50% by mass, it may be difficult to obtain sufficient adsorption performance. On the other hand, when the content exceeds 85% by mass, it becomes difficult to sufficiently support the porous metal complex on the adsorption sheet, and the amount of dropping off increases. In addition, the sheet strength may be significantly reduced.
  • the heat resistant fiber (D) contained in the second adsorbing sheet of the present invention is a component that ensures the heat resistance of the adsorbing sheet.
  • the heat-resistant fiber (D) is a calorimeter measuring device (Q50, manufactured by TA Instruments Japan Co., Ltd.) using 30 mg of a sample dried in advance at 150 ° C. under vacuum for 12 hours. It means a fiber having a weight loss rate of 5% or less when the temperature is raised from room temperature to 300 ° C. at an air flow rate of 60 mL / min and a temperature increase rate of 20 ° C./min.
  • Such a heat-resistant fiber (D) is less likely to cause a significant decrease in strength under a temperature condition of 80 ° C. or higher, and is preferable as a component that imparts heat resistance to the adsorption sheet.
  • the significant decrease in strength means that when the second adsorbing sheet of the present invention is bent at 90 degrees in a heated atmosphere of 80 ° C. or higher, the adsorbing sheet is not easily cracked or cracked.
  • the heat resistant fiber (D) include inorganic fibers such as glass fiber, ceramic fiber, rock wool fiber, etc .; among the organic fibers (B) exemplified in the first adsorption sheet, those having heat resistance, specifically Include organic fibers such as aramid fiber, meta-aramid fiber, polybenzimidazole fiber, polybenzoxazole fiber, polyimide fiber, polyamide fiber, polyamideimide fiber, polyetherketone fiber; and fibers obtained by fibrillating them; Of these, it is preferable to use one or more of them.
  • the fiber diameter of the heat resistant fiber (D) is preferably 1 ⁇ m to 15 ⁇ m, and more preferably 1 ⁇ m to 10 ⁇ m.
  • the fiber length is preferably 1 mm to 10 mm, more preferably 2 mm to 5 mm.
  • the heat resistant fiber (D) contains glass fibers having a fiber diameter of 1 ⁇ m to 10 ⁇ m and a fiber length of 2 mm to 5 mm. Is preferred.
  • the content of the heat resistant fiber (D) in the second adsorption sheet is preferably 5% by mass to 30% by mass, more preferably 10% by mass to 25% by mass, and further preferably 10% by mass to 20% by mass. It is. If the amount of the heat-resistant fiber (D) is too large, the amount of the porous metal complex (A) contained in the adsorption sheet is relatively small, so that it may be difficult to obtain a sufficient adsorption effect. If the amount of the conductive fiber (D) is too small, it may be difficult to obtain sufficient heat resistance.
  • the 2nd adsorption sheet in this invention contains the clay mineral fiber (E) which has self-consolidating property.
  • the self-consolidating property represents a property of consolidating only by itself. Therefore, by using the clay mineral fiber (E) having self-consolidating properties, the heat resistance of the adsorption sheet and the supportability of the porous metal complex (A) can be improved.
  • the adsorption sheet strength can be further improved by the self-consolidating property of (E).
  • a magnesium silicate fiber or a calcium silicate fiber is preferable.
  • the fiber diameter and fiber length of the clay mineral fiber (E) are not particularly limited, but the fiber diameter is preferably 0.1 ⁇ m to 0.5 ⁇ m, more preferably 0.1 ⁇ m to 0.2 ⁇ m.
  • the length is preferably 1 ⁇ m to 50 ⁇ m, more preferably 1 ⁇ m to 30 ⁇ m.
  • the fiber diameter is less than 0.1 ⁇ m and the fiber length is less than 1 ⁇ m, the fiber is too fine, so that not only the support property of the porous metal complex (A) tends to be lowered, but also the strength of the adsorption sheet is lowered. Furthermore, it may be difficult to handle the clay mineral fiber (E) during sheet production.
  • the fiber diameter is larger than 0.5 ⁇ m and the fiber length is longer than 50 ⁇ m, heating at a high temperature for a long time is required to develop sufficient self-consolidation properties, and the porous metal complex (A) The pore structure may be broken.
  • the content of the clay mineral fiber (E) in the second adsorption sheet is preferably 5% by mass to 35% by mass, more preferably 5% by mass to 25% by mass.
  • the content of the clay mineral fiber (E) is less than 5% by mass, the supportability of the porous metal complex (A) is insufficient.
  • the content exceeds 35% by mass the porous metal complex (A) becomes the clay mineral fiber. It may be covered with (E) and it may be difficult to obtain sufficient adsorption performance.
  • Organic binder (C) It is preferable that the 2nd adsorption sheet in this invention contains an organic binder (C). This is because the flexibility and strength of the adsorption sheet can be improved.
  • the organic binder (C) is not particularly limited as long as it can join the porous metal complex (A) (adsorbent) and the heat-resistant fiber (D).
  • the same organic binder as that of the first adsorption sheet such as a polyvinyl alcohol polymer, a polyacrylonitrile polymer, a polyethylene polymer, and a polyester polymer, can be used. From the viewpoint of handleability, polyvinyl alcohol polymers are preferred.
  • an organic binder (C) is not specifically limited, Since a fibrous thing is used, since an adsorption sheet can be produced simply, it is preferable.
  • the content (C) of the organic binder in the second adsorption sheet is preferably 5% by mass to 15% by mass, and more preferably 5% by mass to 10% by mass. If it is less than 5% by mass, the supportability of the porous metal complex (A) is insufficient, and if it exceeds 15% by mass, the porous metal complex (A) is coated with the organic binder (C), and sufficient adsorption performance is obtained. There is a tendency to become difficult to get.
  • the second adsorbing sheet of the present invention may contain a porous material other than the porous metal complex (A), and the porous material contained in the adsorbing sheet of the present invention is not particularly limited.
  • organic polymer porous materials such as activated carbon, zeolite, silica gel, activated alumina, clay mineral (excluding the clay mineral fiber (E) described above), aluminophosphate, silicoaluminophosphoric acid, styrene-divinylbenzene copolymer, etc. Examples include masses.
  • Preferred are activated carbon, zeolite, silica gel and activated alumina, which can be obtained at low cost.
  • the content of other components in the second adsorption sheet is preferably 20% by mass or less.
  • the second adsorbing sheet of the present invention is an indoor, vehicle, wallpaper, furniture, interior material, resin molded body, electrical device, etc., for the purpose of reducing malodorous components, etc., or in the air discharged from factories, etc. It can be widely used for the purpose of solvent separation / recovery or adsorption / removal.
  • Manufacturing method of adsorption sheet The method in particular of manufacturing the adsorption sheet of this invention is not restrict
  • sheet constituent materials such as porous metal complex (A), organic fiber (B) and / or heat resistant fiber (D), and organic binder (C) and clay mineral fiber (E) used as necessary.
  • wet sheeting method There is a wet sheeting method in which a sheet-like material is obtained by dispersing in water, an organic solvent or a mixture thereof, molding, dehydrating and drying.
  • Other components such as mineral fiber (E) are dispersed in water at a predetermined blending ratio (preparation of dispersion slurry).
  • concentration of each component in the dispersed slurry may be appropriately adjusted so that the content in the adsorption sheet is within the above-described range.
  • the obtained dispersion slurry is paper-made with a paper machine to obtain a sheet-like material, which is then dehydrated and dried to obtain an adsorption sheet.
  • the method of dehydration and drying is not particularly limited, for example, a dehydration method such as a method of dehydrating under pressure by passing a sheet-like material between a pair of rolls; hot air is blown on the sheet-like material after sun-drying and dehydration Any conventionally known method such as a method; etc. can be used.
  • the porous metal complex (A) is mixed with the sheet constituent material in a state having solvent molecules in the pores and subjected to a sheet forming step.
  • the organic binder (C) constituting the adsorption sheet may be adsorbed in the pores. In this case, it is difficult to remove the organic binder (C) trapped in the pores of the porous metal complex (A) even if the solvent removal treatment described later is performed after forming the sheet, and the adsorption performance of the adsorption sheet is The result is inferior.
  • the adsorption performance of the adsorption sheet can be secured.
  • solvent molecules are adsorbed in the pores of the porous metal complex (A), but the porous metal complex (A) is solvent molecules in the pores.
  • the organic solvent can be adsorbed in the pores by the method described in the examples described later.
  • numerator here refers to water and a general organic solvent molecule.
  • the porous metal complex (A) is formed into a sheet with solvent molecules in the pores, the porous metal complex (A) is solvent molecules in the pores. In this state, it is difficult to obtain sufficient adsorption performance. Therefore, in order to develop the adsorption performance, it is preferable to perform a solvent removal treatment after the sheet forming step. In addition, if the implementation time of a solvent removal process is after the sheet forming process, it will not be specifically limited.
  • the conditions for the solvent removal treatment are not particularly limited, but the temperature is preferably 80 ° C. to 300 ° C. If it is less than 80 degreeC, there exists a possibility that the removal of a solvent may become incomplete and sufficient adsorption
  • the degree of reduced pressure is not particularly limited, and may be appropriately adjusted according to the physical properties and blending amount of the porous metal complex (A).
  • 10 3 Pa to 10 ⁇ 5 Pa is preferable, and 10 ⁇ 1 Pa. More preferably, it is ⁇ 10 ⁇ 5 Pa.
  • the solvent removal treatment time is not particularly limited, it is preferably, for example, 1 hour to 100 hours, more preferably 3 hours to 48 hours, and further preferably 3 hours to 24 hours.
  • the most preferable solvent removal treatment conditions are 100 to 200 ° C. and 3 to 24 hours under vacuum.
  • the adsorption sheet of the present invention may be used in a planar shape, or may be used in a desired shape by appropriately performing pleating processing, honeycomb processing, corrugating processing, or the like.
  • Adsorption element The adsorption element of the present invention is characterized by being provided with the adsorption sheet of the present invention.
  • the type of the adsorbing element according to the present invention is not particularly limited, and any conventionally known type can be adopted and may be appropriately selected according to the application and purpose.
  • the shape of the suction sheet provided in the suction element of the present invention is not particularly limited, but for example, a suction sheet processed into a flat shape, a pleat shape, a honeycomb shape, or the like can be used.
  • the adsorption sheet processed into a pleat is used as a cross-flow type adsorption element
  • the adsorption sheet processed into a honeycomb is used as a parallel flow type adsorption element
  • contact with the gas to be treated respectively By increasing the area, it is possible to improve the removal efficiency and reduce the pressure loss of the adsorption element at the same time.
  • the parallel flow type adsorption element is superior to the cross flow type adsorption element in terms of prevention of clogging due to mist and dust, low pressure loss, and weight reduction. Therefore, the adsorption sheet provided in the adsorption element is a honeycomb. It is preferable that it is a shape.
  • the adsorbing element using the adsorbing sheet of the present invention is used in indoors, in vehicles, for wallpaper, furniture, interior materials, resin moldings, electrical equipment, etc., for reducing malodorous components, etc. It can be widely used for the purpose of separation / recovery or adsorption / removal of organic solvents.
  • Porous metal complex (A1-1) Synthesis of [Cu 2 (pzdc) 2 (prz)] Copper nitrate trihydrate (1.23 g, 5.0 mmol, 1.0 eq.) was added to an eggplant flask (500 ml), Pyrazine (4.05 g, 50.0 mmol, 10.0 eq.) And pure water (100 ml) were added and mixed. To the obtained blue transparent solution, a mixed solution of an aqueous solution (80 ml) of 2,3-pyrazinedicarboxylic acid (0.84 g, 5.0 mmol, 1.0 eq.) And an aqueous 1N NaOH solution (20 ml) was added dropwise. .
  • the powder X-ray diffraction pattern of the obtained porous metal complex (A1-1) was measured.
  • the measurement results are shown in FIG.
  • the composition of the adsorbent sheet is 70% by mass of the porous metal complex (A1-1), 20% by mass of pulp-like cellulose as the organic fiber (B), 5% by mass of PVA as the organic binder (C), inorganic fiber
  • the adsorbent sheet (1) which is a sheet-like molded body having a thickness of about 0.26 mm and a basis weight of about 150 g / m 2 , was manufactured using a wet papermaking apparatus so that the glass fiber was 5% by mass.
  • Experimental Example 1 the reduced-pressure drying process at the time of creating the adsorption / desorption isotherm corresponds to the desolvation step.
  • the gate-type adsorption behavior was also reproduced. From this result, it is clear that the adsorption sheet of the present invention is excellent as an adsorbent without impairing the adsorption performance of the porous metal complex powder.
  • the composition of the adsorbent sheet is 70% by mass of the porous metal complex (A1-2), 20% by mass of the pulp-like cellulose as the organic fiber (B), 5% by mass of PVA as the organic binder (C), and glass as the inorganic fiber.
  • An adsorption sheet (2) having a thickness of about 0.25 mm and a basis weight of about 150 g / m 2 was produced using a wet papermaking machine so that the fiber content was 5% by mass.
  • the unit mass of the porous metal complex (A1-2) in the case of the porous metal complex (A1-2) (FIG. 5) and the case of the adsorption sheet (2) (FIG. 6) is shown.
  • almost no difference in the CO 2 adsorption amount per adsorption sheet (2) is found to have a CO 2 adsorption amount corresponding to the mass of the porous metal complex (A1-2) carrying. From this result, it is clear that the adsorbing sheet of the present invention is excellent as an adsorbing material without impairing the adsorption performance of the porous metal complex.
  • Example 1-3 Production of Adsorption Sheet Using blue powder of “Basolite (registered trademark) C300” (obtained from Sigma Aldrich Japan Co., Ltd., average particle size 35 ⁇ m) as the porous metal complex (A1-3), the composition in the adsorption sheet is 60% by mass of the porous metal complex (A1-3), 20% by mass of the pulp-like cellulose as the organic fiber (B), 5% by mass of PVA as the organic binder (C), and 5% by mass of glass fiber as the inorganic fiber. Then, using a wet papermaking apparatus, an adsorption sheet (3) having a thickness of about 0.28 mm and a basis weight of about 156 g / m 2 was produced.
  • Example 1-4 The porous metal complex (A1-1) obtained in Experimental Example 1-1 was used as the porous metal complex, and the composition in the pellet was 94% by mass of the porous metal complex (A1-1), the organic binder (C) Pellets (1) having a thickness of about 4 mm and a diameter of 3 mm were molded by a tablet molding apparatus so that 3% by mass of PVA and 3% by mass of graphite as a lubricant were obtained.
  • the porous metal complex (A1-1) and other components are firmly solidified, and the porous metal complex (A1-1) has its structure. It is considered that the original adsorption performance could not be exhibited because it was difficult to change, and the rise of the adsorption amount became unclear. From this result, it is clear that the adsorption performance of the porous metal complex (A1-1) is impaired by molding into pellets.
  • Example 1-5 The porous metal complex (A1-3) used in Experimental Example 1-3 was used as the porous metal complex, the composition in the pellet was 94% by mass of the porous metal complex (A1-3), and 3% of PVA was used as the organic binder component. %, Pellets (2) having a thickness of about 4 mm and a diameter of 3 mm were molded by a tablet molding apparatus so that the lubricant was 3% by mass of graphite.
  • An inorganic adhesive (water glass) is used as a binder, the adsorbing sheet is corrugated by a regular method, and the obtained corrugated board is laminated by using an inorganic adhesive (water glass) to form a honeycomb, 300 A cell / inch 2 honeycomb sample was prepared.
  • a honeycomb sample (60 mm ⁇ , thickness 20 mm) was set in a 60 mm ⁇ glass column, and dry air containing 5 ppm of toluene at a temperature of 25 ° C. was passed through the column at a speed of 2 m / s.
  • the toluene concentration before and after passing through the honeycomb sample was measured every minute, and the toluene removal rate was calculated from the change in concentration before and after the passage. The measurement is continued until the removal rate reaches 20%, and the total removal mass [g] of toluene is calculated from the elapsed time and the removal rate, and the toluene removal amount [g / L] is calculated by dividing it by the volume of the honeycomb sample. Calculated.
  • Example 2-1 As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 ⁇ m. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-1) in which solvent molecules were adsorbed in the pores.
  • Basolite Z1200 manufactured by BASF
  • Example 2-2 As the porous metal complex (A), Basolite A100 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 ⁇ m. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-2) in which solvent molecules were adsorbed in the pores.
  • Basolite A100 manufactured by BASF
  • the adsorbent sheet was prepared using a wet papermaking machine with a mass of basis weight 70 g / m 2 . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
  • the adsorbent sheet was prepared using a wet papermaking machine with a mass of basis weight 70 g / m 2 . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
  • Example 2-5 As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 ⁇ m. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-5) in which solvent molecules were adsorbed in the pores.
  • the porous metal complex sample (A2-5) is 60% by mass, heat-resistant fiber (D), glass fiber (fiber diameter 6 ⁇ m, fiber length 3 mm) is 15% by mass, and clay mineral fiber (E) is magnesium silicate.
  • Fiber fiber diameter 0.2 ⁇ m, fiber length 30 ⁇ m 15 mass%, organic binder (C), polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 ⁇ m, fiber length 3 mm) 10 mass%
  • the adsorbent sheet was prepared using a wet papermaking machine with a mass of basis weight 70 g / m 2 . Further, the solvent removal treatment was performed at 150 ° C. and 1 atm for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
  • Example 2-6 As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 ⁇ m. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-6) in which solvent molecules were adsorbed in the pores.
  • Basolite Z1200 manufactured by BASF
  • Example 2--7 As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was sieved to prepare an average particle size of 10 ⁇ m. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-7) in which solvent molecules were adsorbed in the pores.
  • Basolite Z1200 manufactured by BASF
  • the adsorbent sheet was prepared using a wet papermaking machine with a mass of basis weight 70 g / m 2 . Furthermore, the solvent removal treatment was performed at 150 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
  • Example 2-8 As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was lightly pressed and hardened at a pressure of 10 kgf / cm 2 and sieved to prepare an average particle size of 150 ⁇ m. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-8) in which solvent molecules were adsorbed in the pores.
  • the porous metal complex sample (A2-8) is 60% by mass, heat-resistant fiber (D), glass fiber (fiber diameter 6 ⁇ m, fiber length 3 mm) is 15% by mass, and clay mineral fiber (E) is magnesium silicate.
  • Fiber fiber diameter 0.1 ⁇ m, fiber length 1 ⁇ m 15 mass%, organic binder (C), polyvinyl alcohol (PVA) fiber (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 ⁇ m, fiber length 3 mm) 10 mass%
  • the adsorbent sheet was prepared using a wet papermaking machine with a mass of basis weight 70 g / m 2 . Furthermore, the solvent removal treatment was performed at 150 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
  • Example 2-9 As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 ⁇ m. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-9) in which solvent molecules were adsorbed in the pores.
  • Basolite Z1200 manufactured by BASF
  • porous metal complex sample A2-9), heat-resistant fiber (D), 10% by mass of glass fiber (fiber diameter 6 ⁇ m, fiber length 3 mm), and clay mineral fiber (E), magnesium silicate 5% by mass of fibers (fiber diameter 0.1 ⁇ m, fiber length 1 ⁇ m) and 5% by mass of polyvinyl alcohol (PVA) fibers (manufactured by Kuraray Co., Ltd., VPB105, fiber diameter 11 ⁇ m, fiber length 3 mm) as organic binder (C)
  • PVA polyvinyl alcohol
  • the adsorbent sheet was prepared using a wet papermaking machine with a mass of basis weight 70 g / m 2 . Furthermore, the solvent removal treatment was performed at 200 ° C. under vacuum for 24 hours to obtain an adsorption sheet sample, and the obtained sample was measured for heat resistance, supportability, flexibility, and adsorption performance.
  • Example 2-11 As the porous metal complex (A), Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and then sieved to prepare an average particle size of 1 ⁇ m. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-11) in which solvent molecules were adsorbed in the pores.
  • Basolite Z1200 manufactured by BASF
  • HSZ-390HUA (Y-type zeolite manufactured by Tosoh Corporation) was pulverized in a mortar and sieved to prepare an average particle size of 1 ⁇ m.
  • the obtained zeolite sample was 70% by mass, heat-resistant fiber (D), glass fiber (fiber diameter 6 ⁇ m, fiber length 3 mm) 15% by mass, clay mineral fiber (E), magnesium silicate fiber (fiber diameter 0.
  • adsorption sheet was prepared using a wet papermaking machine at a mass of basis weight 70 g / m 2 . Furthermore, it processed in 200 degreeC and vacuum conditions for 24 hours, and the adsorption sheet sample was obtained. The obtained samples were measured for heat resistance, supportability, flexibility, and adsorption performance.
  • Basolite Z1200 manufactured by BASF was pulverized in a mortar and sieved to prepare an average particle size of 1 ⁇ m. Further, the sample was immersed in N, N-dimethylformamide for 24 hours and then filtered to obtain a porous metal complex sample (A2-12) in which solvent molecules were adsorbed in the pores.
  • Example 2-14 Basolite Z1200 (manufactured by BASF) was pulverized in a mortar and sieved to prepare an average particle size of 1 ⁇ m. Further, the sample was subjected to solvent removal treatment at 200 ° C. under vacuum for 24 hours to obtain a porous metal complex sample (A2-13).
  • the porous metal complex sample (A2-13) was 70% by mass
  • the polybutylene terephthalate fiber (fiber diameter 6 ⁇ m, fiber length 3 mm) was 15% by mass
  • the clay mineral fiber (E) was magnesium silicate fiber (fiber diameter 0.
  • Basolite Z1200 manufactured by BASF was pulverized in a mortar and sieved to prepare an average particle size of 1 ⁇ m. Further, the sample was subjected to solvent removal treatment at 200 ° C. under vacuum for 24 hours to obtain a porous metal complex sample (A2-14).
  • Table 1 or 2 shows the results of measuring the heat resistance, supportability, flexibility, and adsorption performance of the samples of Experimental Examples 2-1 to 2-15.
  • the adsorbent is not the porous metal complex (A) (Experimental Example 2-12)
  • the heat resistant fiber It can be seen that heat resistance, supportability, flexibility, and adsorption performance are superior to those in the case where (D) is not included (Experimental Examples 2-13, 2-14, and 2-15).
  • the clay mineral fiber (E) is not included (Experimental Example 2-10)
  • the organic binder (C) is not included (Experimental Example 2-11)
  • the heat resistance A tendency to be slightly inferior in supportability or flexibility was observed.
  • the first adsorption sheet of the present invention can be reproduced without impairing the adsorption behavior of the porous metal complex (A) in which a hysteresis loop is seen in the adsorption / desorption isotherm depending on the type of gas. Moreover, since the content ratio of a porous metal complex (A) can also be raised by setting it as the shape of an adsorption sheet, the 1st adsorption sheet of this invention has the outstanding adsorption / desorption characteristic.
  • the first adsorbing sheet of the present invention can be used in applications such as adsorbents, occlusion materials, and separating materials, and the adsorbent can be desorbed by placing the first adsorbing sheet of the present invention under reduced pressure. Since the regeneration of the adsorption performance is easy, it is extremely meaningful in the industry.
  • the second adsorbing sheet or adsorbing element of the present invention it becomes possible to efficiently separate / recover or adsorb / remove moisture, organic solvents, and malodorous components in the air. It can be expected to greatly contribute to the world.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

La présente invention a pour but de proposer une feuille d'adsorption et un élément d'adsorption l'utilisant, qui peuvent fournir une performance d'adsorption et de désorption suffisante provenant d'un complexe métallique poreux même dans un cas où la structure du complexe métallique poreux change suite à une adsorption et désorption de gaz, et qui est résistant à la chaleur, a d'excellentes propriétés de support de complexe métallique poreux et une flexibilité de feuille en plus d'une performance d'adsorption suffisante. Cette feuille d'adsorption comprend un complexe métallique poreux (A) qui comprend une structure poreuse résultant de la liaison d'ions métalliques et de ligands organiques qui peuvent se lier avec les ions métalliques, et des fibres organiques (B), ou comprend le complexe métallique poreux (A) et des fibres résistant à la chaleur (D).
PCT/JP2013/051308 2012-01-30 2013-01-23 Feuille d'adsorption et élément d'adsorption utilisé pour celle-ci WO2013115033A1 (fr)

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JPWO2021039273A1 (fr) * 2019-08-23 2021-03-04
WO2021200072A1 (fr) * 2020-03-31 2021-10-07 ダイキン工業株式会社 Système d'ajustement de la qualité de l'air
JP7461850B2 (ja) 2020-10-20 2024-04-04 大陽日酸株式会社 検知素子、検知素子の製造方法及びガス濃度測定ユニット

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JP2004074026A (ja) * 2002-08-19 2004-03-11 Nippon Steel Corp ガス吸着材ならびにこれを用いたガス分離装置およびガス貯蔵装置
JP2007014880A (ja) * 2005-07-07 2007-01-25 Toyobo Co Ltd 吸着シート、吸着エレメント及びその製造方法
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JPWO2021039273A1 (fr) * 2019-08-23 2021-03-04
WO2021039273A1 (fr) * 2019-08-23 2021-03-04 昭和電工株式会社 Procédé de récupération d'oléfine
CN113906001A (zh) * 2019-08-23 2022-01-07 昭和电工株式会社 烯烃的回收方法
JP7375822B2 (ja) 2019-08-23 2023-11-08 株式会社レゾナック オレフィンの回収方法
WO2021200072A1 (fr) * 2020-03-31 2021-10-07 ダイキン工業株式会社 Système d'ajustement de la qualité de l'air
JP2021159830A (ja) * 2020-03-31 2021-10-11 ダイキン工業株式会社 空気質の調整システム
JP7104339B2 (ja) 2020-03-31 2022-07-21 ダイキン工業株式会社 空気質の調整システム
JP7461850B2 (ja) 2020-10-20 2024-04-04 大陽日酸株式会社 検知素子、検知素子の製造方法及びガス濃度測定ユニット

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