WO2013084826A1 - Complexe métallique, et matériau adsorbant, matériau de stockage et matériau de séparation contenant chacun le premier - Google Patents

Complexe métallique, et matériau adsorbant, matériau de stockage et matériau de séparation contenant chacun le premier Download PDF

Info

Publication number
WO2013084826A1
WO2013084826A1 PCT/JP2012/081123 JP2012081123W WO2013084826A1 WO 2013084826 A1 WO2013084826 A1 WO 2013084826A1 JP 2012081123 W JP2012081123 W JP 2012081123W WO 2013084826 A1 WO2013084826 A1 WO 2013084826A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal complex
gas
acid compound
carbon dioxide
acid
Prior art date
Application number
PCT/JP2012/081123
Other languages
English (en)
Japanese (ja)
Inventor
康貴 犬伏
知嘉子 池田
堀　啓志
Original Assignee
株式会社クラレ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社クラレ filed Critical 株式会社クラレ
Publication of WO2013084826A1 publication Critical patent/WO2013084826A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—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
    • B01J20/223—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
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • 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
    • B01J20/3007—Moulding, shaping or extruding
    • 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
    • B01J20/34—Regenerating or reactivating
    • B01J20/3491—Regenerating or reactivating by pressure treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/007—Use of gas-solvents or gas-sorbents in vessels for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]
    • 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
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/102—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/104—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/108—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/11—Noble gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B01D2257/2064—Chlorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/406—Ammonia
    • 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
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/55—Compounds of silicon, phosphorus, germanium or arsenic
    • 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
    • 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
    • B01D2257/7025—Methane
    • 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
    • B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4566—Gas separation or purification devices adapted for specific applications for use in transportation means
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/08—Copper compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • Y02P20/156—Methane [CH4]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals

Definitions

  • the present invention relates to a metal complex, and an adsorbent, an occlusion material and a separation material comprising the same. More specifically, the present invention relates to a metal complex containing a polyvalent carboxylic acid compound, at least one metal ion, and an aliphatic monocarboxylic acid compound having 4 to 11 carbon atoms.
  • the metal complex of the present invention comprises an adsorbent for adsorbing a gas such as carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, a hydrocarbon having 1 to 4 carbon atoms, a rare gas, hydrogen sulfide, ammonia or organic vapor, It is preferable as a storage material for storing the gas and a separation material for separating the gas.
  • Activated carbon is a representative example, and is widely used in various industries such as air purification, desulfurization, denitration, and removal of harmful substances by utilizing the excellent adsorption performance of activated carbon.
  • the demand for nitrogen has increased for semiconductor manufacturing processes, etc., and as a method for producing such nitrogen, a method of producing nitrogen from air by pressure swing adsorption method or temperature swing adsorption method using molecular sieve charcoal is used.
  • Molecular sieve charcoal is also applied to various gas separation and purification such as hydrogen purification from methanol cracked gas.
  • polymer metal complexes have been developed as adsorbents that give better adsorption performance.
  • the polymer metal complex has features such as (1) a large surface area and high porosity, (2) high designability, and (3) dynamic structural changes due to external stimuli. Expected characteristics.
  • Non-Patent Document 1 In practical use, not only further improvement of adsorption performance, storage performance and separation performance but also improvement of durability against water contained in actual gas is required (for example, see Non-Patent Document 1).
  • Non-Patent Document 2 After synthesizing a polymer metal complex consisting of 2-aminoterephthalic acid and a metal ion, an acid anhydride is reacted with the amino group at the 2-position of terephthalic acid constituting the polymer metal complex to form a polymer via an amide bond. It is known that water resistance is improved by introducing an alkyl chain into a metal complex (see Non-Patent Document 2).
  • the method described in Non-Patent Document 2 requires two steps of a polymer metal complex production process and an alkyl chain introduction process, which complicates the production process. There is a problem that the shape (morphology) cannot be controlled.
  • Non-Patent Document 2 does not mention any gas adsorption performance, occlusion performance, and separation performance of the metal complex.
  • a gas-adsorbing metal complex in which at least one organic acid selected from formic acid, acetic acid, trifluoroacetic acid and propionic acid is added as an additive to a copper biphenyldicarboxylate complex (see Patent Document 1).
  • organic acid selected from formic acid, acetic acid, trifluoroacetic acid and propionic acid is added as an additive to a copper biphenyldicarboxylate complex.
  • Patent Document 1 the purpose of use of the organic acid is not described in Patent Document 1, and only formic acid is described in the examples, and no mention is made of the effect of the monocarboxylic acid compound on water resistance.
  • a first object of the present invention is to provide a metal complex that can be used as a gas adsorbent, gas occlusion material, or gas separation material, which has higher water resistance than before and is excellent in adsorption performance.
  • the second object of the present invention is to provide the metal complex having a controlled particle size and particle shape.
  • the present inventors have intensively studied and found that the above object can be achieved by a metal complex containing a polyvalent carboxylic acid compound, at least one metal ion, and an aliphatic monocarboxylic acid compound having 4 to 11 carbon atoms.
  • the present invention has been reached.
  • a metal comprising a polyvalent carboxylic acid compound, at least one metal ion selected from ions of metals belonging to groups 2 to 13 of the periodic table, and an aliphatic monocarboxylic acid compound having 4 to 11 carbon atoms Complex.
  • An adsorbent comprising the metal complex according to (1) or (2).
  • the adsorbent is carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane or organic vapor.
  • the adsorbent according to (3) which is an adsorbent for adsorbing water.
  • An occlusion material comprising the metal complex according to (1) or (2).
  • the occlusion material is an occlusion material for occluding carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia or organic vapor ( The occlusion material according to 5).
  • a gas storage device including a pressure-resistant container that can be kept airtight and provided with a gas inlet / outlet, and provided with a gas storage space inside the pressure-resistant container, wherein the storage material according to (5) is provided in the gas storage space.
  • Internal gas storage device (8)
  • a gas vehicle provided with an internal combustion engine that obtains driving force from the fuel gas supplied from the gas storage device according to (7).
  • a separating material comprising the metal complex according to (1) or (2).
  • the separator is carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane, or organic vapor
  • the separation material is for separating methane and carbon dioxide, hydrogen and carbon dioxide, nitrogen and carbon dioxide, ethylene and carbon dioxide, methane and ethane, ethane and ethylene, propane and propene, or air and methane.
  • a polycarboxylic acid compound at least one metal ion selected from ions of metals belonging to Groups 2 to 13 of the periodic table, and an aliphatic monocarboxylic acid compound having 4 to 11 carbon atoms are included.
  • Metal complexes can be provided.
  • the metal complex of the present invention has high water resistance, easy control of particle size and particle shape, and high gas adsorption performance.
  • the metal complex of the present invention is excellent in the adsorption performance of various gases, carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, sulfur oxidation It can be used as an adsorbent for adsorbing gases, nitrogen oxides, siloxanes or organic vapors.
  • the metal complex of the present invention is excellent in the occlusion performance of various gases, carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia or It can also be used as a storage material for storing gases such as organic vapor.
  • the metal complex of the present invention is excellent in the separation performance of various gases, carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons having 1 to 4 carbon atoms, rare gas, hydrogen sulfide, ammonia, It can also be used as a separating material for separating gases such as sulfur oxides, nitrogen oxides, siloxanes or organic vapors.
  • FIG. 4 is a SEM photograph of the metal complex obtained in Synthesis Example 1.
  • 1 is a 1H NMR spectrum measured by dissolving the metal complex obtained in Synthesis Example 1 in deuterated aqueous ammonia.
  • FIG. 4 is a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 2.
  • FIG. 4 is a SEM photograph of the metal complex obtained in Synthesis Example 2.
  • 3 is a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 3.
  • FIG. 4 is a SEM photograph of the metal complex obtained in Synthesis Example 3.
  • 3 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 1.
  • FIG. 3 is a SEM photograph of the metal complex obtained in Comparative Synthesis Example 1.
  • 4 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 2.
  • FIG. 4 is a SEM photograph of the metal complex obtained in Comparative Synthesis Example 2.
  • FIG. 4 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 3.
  • FIG. 4 is a SEM photograph of the metal complex obtained in Comparative Synthesis Example 3.
  • 6 is a powder X-ray diffraction pattern of an intermediate of a metal complex obtained in Comparative Synthesis Example 4.
  • 6 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 4.
  • FIG. 4 is a SEM photograph of the metal complex obtained in Comparative Synthesis Example 4. It is a photograph at the time of water contact angle measurement of the metal complex obtained in Synthesis Example 1.
  • 4 is a photograph of the metal complex obtained in Comparative Synthesis Example 1 when measuring the water contact angle.
  • the horizontal axis represents the diffraction angle (2 ⁇ ) and the vertical axis represents the diffraction intensity (Intensity) represented by cps (Counts per Second) (FIGS. 5, 8, 10, 12, 14, 16). , 18 and 19).
  • the horizontal axis is the equilibrium pressure (Pressure) expressed in MPa
  • the vertical axis is the equilibrium adsorption amount (Amount Adsorbed) expressed in mL (STP) / g (FIG. 25-27).
  • STP standard state, Standard Temperature and Pressure indicates a state of a temperature of 273.15 K and a pressure of 1 bar (10 5 Pa).
  • the metal complex of the present invention includes a polyvalent carboxylic acid compound, at least one metal ion selected from ions of metals belonging to Groups 2 to 13 of the periodic table, and an aliphatic monocarboxylic acid compound having 4 to 11 carbon atoms. Including.
  • the polyvalent carboxylic acid compound used in the present invention is not particularly limited, and dicarboxylic acid compounds, tricarboxylic acid compounds, tetracarboxylic acid compounds, and the like can be used.
  • a dicarboxylic acid compound or a tricarboxylic acid compound is preferable, a tricarboxylic acid compound is more preferable, and an aromatic tricarboxylic acid compound is more preferable.
  • the polyvalent carboxylic acid compound may be a mixture of two or more polyvalent carboxylic acid compounds.
  • the metal complex of the present invention may be a mixture of two or more metal complexes composed of a single polyvalent carboxylic acid compound.
  • the polyvalent carboxylic acid compound may be used in the form of an acid anhydride or an alkali metal salt.
  • the polyvalent carboxylic acid compound may further have a substituent in addition to the carboxyl group.
  • the terephthalic acid may be 2-nitroterephthalic acid.
  • the number of substituents may be 1, 2 or 3.
  • the substituent is not particularly limited.
  • the substituent may be linear or branched such as an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group).
  • alkyl group having 1 to 5 carbon atoms halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group (methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, Isobutoxy group, tert-butoxy group, etc.), amino group, monoalkylamino group (such as methylamino group), dialkylamino group (such as dimethylamino group), formyl group, epoxy group, acyloxy group (acetoxy group, n-propanoyl) Oxy group, n-butanoyloxy group, pivaloyloxy group, benzoyloxy group, etc.), alcohol Aryloxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.
  • n- butoxycarbonyl group a nitro group, a cyano group, a hydroxyl group, an acetyl group, and a trifluoromethyl group.
  • metal ions belonging to groups 2 to 13 of the periodic table used in the present invention include magnesium ion, calcium ion, scandium ion, zirconium ion, vanadium ion, chromium ion, molybdenum ion, manganese ion, iron ion, and cobalt. Ions, nickel ions, copper ions, zinc ions, cadmium ions, aluminum, and the like can be used.
  • the metal ion is preferably a single metal ion, but may be a mixed metal complex containing two or more kinds of metal ions.
  • the metal complex of the present invention may be a mixture of two or more metal complexes composed of a single metal ion.
  • the metal ion may be used in the form of a metal salt.
  • the metal salt include magnesium salt, calcium salt, scandium salt, zirconium salt, vanadium salt, chromium salt, molybdenum salt, manganese salt, iron salt, cobalt salt, nickel salt, copper salt, zinc salt, cadmium salt, aluminum A salt or the like can be used, among which a manganese salt, a cobalt salt, a nickel salt, a copper salt and a zinc salt are preferable, and a copper salt is more preferable.
  • the metal salt is preferably a single metal salt, but two or more metal salts may be mixed and used. Further, as these metal salts, organic acid salts such as acetates and formates, inorganic acid salts such as sulfates, nitrates, hydrochlorides, hydrobromides and carbonates can be used.
  • the aliphatic monocarboxylic acid compound having 4 to 11 carbon atoms used in the present invention may be linear, branched or cyclic.
  • butyric acid, isobutyric acid, enanthic acid, and octylic acid are more preferable.
  • Formic acid (carbon number 1), acetic acid (carbon number 2) and propionic acid (carbon number 3) having 3 or less carbon atoms do not exhibit sufficient water resistance.
  • carbon number 1 carbon number 1
  • acetic acid (carbon number 2) and propionic acid (carbon number 3) having 3 or less carbon atoms do not exhibit sufficient water resistance.
  • the number of carbon atoms is 12 or more, the proportion of the portion (alkyl chain) that does not contribute to gas adsorption increases, so the adsorption amount per unit weight or unit volume decreases.
  • the proportion of the aliphatic monocarboxylic acid compound having 4 to 11 carbon atoms in the metal complex of the present invention is not particularly limited as long as the effects of the present invention are not impaired.
  • the composition ratio of the polyvalent carboxylic acid compound and the monocarboxylic acid compound is preferably in the range of 5: 1 to 5,000: 1, and more preferably in the range of 5: 1 to 2,500: 1. 7: 1 to 1,500: 1 is particularly preferable.
  • composition ratio of the polycarboxylic acid compound and the monocarboxylic acid compound constituting the metal complex of the present invention is analyzed using gas chromatography, high performance liquid chromatography, or NMR after decomposing the metal complex into a uniform solution.
  • the present invention is not limited to these.
  • the metal complex of the present invention may further contain an organic ligand capable of multidentate coordination with a metal ion in addition to the above.
  • the multidentate organic ligand used in the present invention means a neutral ligand having at least two sites coordinated to a metal ion by an unshared electron pair. Examples of the site coordinated to the metal ion by the lone pair include a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom.
  • the organic ligand capable of multidentate coordination is preferably a heteroaromatic ring compound, and more preferably a heteroaromatic ring compound having a nitrogen atom at a coordination site.
  • multidentate organic ligand examples include 1,4-diazabicyclo [2.2.2] octane, pyrazine, 2,5-dimethylpyrazine, 4,4′-bipyridyl, 2,2 ′.
  • the organic ligand capable of multidentate coordination may be used alone, or two or more organic ligands capable of multidentate coordination may be mixed and used.
  • the metal complex of the present invention may be a mixture of two or more metal complexes composed of a single multidentate organic ligand.
  • the metal complex of the present invention may further contain a monodentate organic ligand as long as the effects of the present invention are not impaired.
  • the monodentate organic ligand means a neutral ligand having one site coordinated to a metal ion by an unshared electron pair.
  • the monodentate organic ligand for example, furan, thiophene, pyridine, quinoline, isoquinoline, acridine, trimethylphosphine, triphenylphosphine, triphenylphosphite, methylisocyanide and the like can be used, and pyridine is particularly preferable.
  • the monodentate organic ligand may have a hydrocarbon group having 1 to 23 carbon atoms as a substituent.
  • the ratio is not particularly limited as long as the effect of the present invention is not impaired, but the composition ratio of the polyvalent carboxylic acid and the monodentate organic ligand Is preferably in a molar ratio range of 1: 5 to 1: 1,000, and more preferably in a range of 1:10 to 1: 100.
  • the composition ratio can be determined by analysis using gas chromatography, high performance liquid chromatography, NMR, or the like, but is not limited thereto.
  • the metal complex includes a polyvalent carboxylic acid compound, at least one metal salt selected from salts of metals belonging to Groups 2 to 13 of the periodic table, an aliphatic monocarboxylic acid compound having 4 to 11 carbon atoms, and Can be produced by reacting an organic ligand capable of multidentate coordination with a metal ion in either the gas phase, liquid phase, or solid phase. It is preferable to make it react and to precipitate a metal complex. For example, an aqueous solution or organic solvent solution of a metal salt and an aqueous solution or organic solvent solution containing a polyvalent carboxylic acid compound and an aliphatic monocarboxylic acid compound having 4 to 11 carbon atoms are mixed and reacted. A metal complex can be obtained. At this time, the reaction may be performed under ultrasonic wave or microwave irradiation.
  • the metal complex of the present invention can also be produced by electrolytic synthesis without using a metal salt.
  • the aliphatic monocarboxylic acid compound having 4 to 11 carbon atoms may coexist from the initial stage of the reaction or may be added at the late stage of the reaction.
  • an aliphatic monocarboxylic acid compound is allowed to coexist when reacting a polyvalent carboxylic acid compound and a metal ion, the particle size and particle shape can be easily controlled, and the production process can be simplified.
  • the molar concentration of the polyvalent carboxylic acid compound in the mixed solution for producing the metal complex is preferably 0.01 to 5.0 mol / L, and more preferably 0.05 to 2.0 mol / L. Even if the reaction is performed at a concentration lower than this, the desired metal complex can be obtained, but this is not preferable because the yield decreases.
  • the molar concentration of the metal salt in the mixed solution for producing the metal complex is preferably 0.01 to 5.0 mol / L, and more preferably 0.05 to 2.0 mol / L. Even if the reaction is performed at a concentration lower than this, the desired metal complex can be obtained, but this is not preferable because the yield decreases.
  • an organic solvent, water, or a mixed solvent thereof can be used as the solvent used for the production of the metal complex.
  • the reaction temperature may be appropriately selected according to the solvent to be used, but is preferably 253 to 463 K, more preferably 298 to 423 K.
  • the completion of the reaction can be confirmed by quantifying the remaining amount of the raw material by gas chromatography or high performance liquid chromatography. After completion of the reaction, the obtained mixed solution is subjected to suction filtration to collect a precipitate, washed with an organic solvent, and then vacuum dried at about 373 K for several hours to obtain the metal complex of the present invention.
  • the metal complex of the present invention does not adsorb gas when the solvent is adsorbed. Therefore, when used as the adsorbent, occlusion material, or separation material of the present invention, it is necessary to vacuum dry the previously obtained metal complex to remove the solvent in the pores. Usually, vacuum drying may be performed at a temperature at which the metal complex is not decomposed (for example, 298 K to 523 K or less), but the temperature is preferably lower (for example, 298 K to 393 K or less).
  • the metal complex of the present invention has a one-dimensional, two-dimensional, or three-dimensional integrated structure depending on the type of polyvalent carboxylic acid compound and metal ion used.
  • An example of a metal complex having a one-dimensional integrated structure is a metal complex composed of 2,3-pyrazinedicarboxylic acid and copper ion
  • an example of a metal complex having a two-dimensional integrated structure is terephthalic acid and copper ion.
  • Examples of metal complexes in which the metal complex has a three-dimensional integrated structure include metal complexes composed of trimesic acid and copper ions.
  • the metal complex has a unit called a paddle wheel structure (Fig. 1) in which two hexacoordinate copper ions are bridged with four trimesic acid carboxylate ions. (FIG. 2), and the octahedral structures are bonded to each other to form a three-dimensional pore (FIG. 3).
  • the metal complex has the above-mentioned structure can be confirmed by, for example, single crystal X-ray structure analysis, powder X-ray crystal structure analysis, but is not limited thereto.
  • the aliphatic monocarboxylic acid compound having 4 to 11 carbon atoms is coordinated to a metal ion.
  • the particle size and particle shape of the metal complex can be controlled.
  • the long-chain alkyl group of the aliphatic monocarboxylic acid compound appears on the crystal surface of the metal complex, so that the hydrophobic effect and steric effect of the alkyl chain impede water access to the metal ion and improve water resistance. .
  • the aliphatic monocarboxylic acid compound is present at the end of crystal growth, that is, the crystal surface, the alkyl chain derived from the aliphatic monocarboxylic acid compound is exposed on the crystal surface of the metal complex. And since the approach of water to a metal ion is inhibited by the hydrophobic effect and steric effect of the alkyl chain, the decomposition reaction of the metal complex accompanied by the dissociation of the coordination bond is suppressed, and the water resistance is improved. The presence of an aliphatic monocarboxylic acid compound on the crystal surface of the metal complex can be confirmed by, for example, time-of-flight secondary ion mass spectrometry.
  • the water resistance of the metal complex of the present invention can be evaluated by measuring the water contact angle.
  • the metal complex of the present invention preferably has a water contact angle of 90 ° or more, and more preferably 150 ° or more.
  • the metal complex of the present invention is excellent in various gas adsorption performance, occlusion performance, and separation performance. Therefore, the metal complex of the present invention is useful as an adsorbent, occlusion material, and separation material for various gases, and these are also included in the scope of the present invention.
  • Examples of the adsorbent, occlusion material, and separation material of the present invention include carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, and hydrocarbons having 1 to 4 carbon atoms (methane, ethane, ethylene, acetylene, propane, propene, methyl Acetylene, propadiene, butane, 1-butene, isobutene, 1-butyne, 2-butyne, 1,3-butadiene, methylallene, etc.), noble gases (such as helium, neon, argon, krypton, xenon), hydrogen sulfide, ammonia , Sulfur oxides, nitrogen oxides, siloxanes (hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, etc.), water vapor or organic vapor can be suitably used to adsorb, occlude, and separate gases.
  • 1 to 4 carbon atoms methane, ethan
  • the separation material of the present invention in particular, carbon dioxide in methane, carbon dioxide in hydrogen, carbon dioxide in nitrogen, carbon dioxide in ethylene, ethane in methane, ethane in ethylene, and propene in propane It is suitable for separating acetylene in ethylene, methane in nitrogen, methane in air, or the like by a pressure swing adsorption method or a temperature swing adsorption method.
  • the organic vapor means a vaporized organic substance that is liquid at normal temperature and pressure.
  • organic substances examples include alcohols such as methanol and ethanol; amines such as trimethylamine; aldehydes such as acetaldehyde; pentane, isoprene, hexane, cyclohexane, heptane, methylcyclohexane, octane, 1-octene, cyclooctane, C5-C16 aliphatic hydrocarbons such as cyclooctene, 1,5-cyclooctadiene, 4-vinyl-1-cyclohexene, 1,5,9-cyclododecatriene; aromatics such as benzene, toluene and xylene Hydrocarbons; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; halogenated hydrocarbons such as methyl chloride and chloroform.
  • alcohols such as methanol and ethanol
  • the adsorbent, occlusion material, and separation material of the present invention are cellulose acetate, polyamide, polyester, polycarbonate, polysulfone, polyethersulfone, polyolefin, polytetrafluoro, if necessary, as long as the effects of the present invention are not impaired. They may be combined with natural or synthetic fibers such as ethylene derivatives or paper, or inorganic fibers such as glass or alumina.
  • the usage form of the adsorbent, occlusion material and separation material in the present invention is not particularly limited.
  • the metal complex may be used as a powder, pellets, films, sheets, plates, pipes, tubes, rods, granules, various deformed shapes, fibers, hollow fibers, woven fabrics, knitted fabrics, non-woven fabrics, etc. You may shape
  • the method for producing the pellet containing the adsorbent, occlusion material or separation material of the present invention there is no particular limitation on the method for producing the pellet containing the adsorbent, occlusion material or separation material of the present invention, and any of the conventionally known pelletization methods can be adopted, but the density of the pellet can be increased. A tableting method is preferred.
  • the method for producing a sheet containing the adsorbent, occlusion material or separation material of the present invention is not particularly limited, and any conventionally known sheeting method can be adopted, but the density of the sheet can be further increased.
  • Wet paper making is preferred.
  • the wet papermaking method is a manufacturing method in which raw materials are dispersed in water, filtered through a net, and dried.
  • a honeycomb shape can be given. Any of the conventionally known processing methods can be adopted as a method for forming a sheet containing the adsorbent, occlusion material or separation material of the present invention into a honeycomb shape.
  • the honeycomb shape refers to a continuous hollow column body such as a square, sinusoidal, or roll-shaped hollow polygonal column or a cylinder in addition to a hexagonal cross section.
  • the sheet in order to make a sheet containing the adsorbent, occlusion material or separation material of the present invention into a sinusoidal honeycomb shape, the sheet is first shaped into a waveform through a shaping roll, and one side of the corrugated sheet or Join flat sheets on both sides. This is laminated to form a sinusoidal honeycomb filter.
  • it is normal to attach and fix an adhesive at the top of the corrugation, but when the corrugated sheets are laminated, the flat sheet between them is necessarily fixed, so it is not always necessary to apply the adhesive Absent.
  • attaching an adhesive agent it is necessary to use what does not impair the adsorption capacity of the sheet.
  • the adhesive for example, corn starch, vinyl acetate resin, acrylic resin, or the like can be used.
  • the pitch is preferably 0.5 to 8 mm, and the peak height is preferably 0.4 to 5 mm.
  • the metal complex of the present invention (or the storage material of the present invention) can also be used in a gas storage device taking advantage of its storage performance.
  • a gas storage device a pressure-resistant container that can be kept airtight and has a gas inlet / outlet is provided.
  • a gas storage device By press-fitting a desired gas into the gas storage device, the gas can be adsorbed and stored in the internal storage material.
  • the gas When taking out the gas from the gas storage device, the gas can be desorbed by opening the pressure valve and reducing the internal pressure in the pressure vessel.
  • the metal complex of the present invention may be embedded in powder form, but from the viewpoint of handleability, etc., a pellet shaped product obtained by molding the metal complex of the present invention is used. May be.
  • FIG. 4 shows an example of a gas vehicle equipped with the gas storage device of the present invention described above.
  • the gas storage device can store fuel gas in the gas storage space 3, and can be suitably used as the fuel tank 1 of a gas vehicle or the like.
  • This gas vehicle includes the gas storage device in which the metal complex of the present invention is incorporated as a fuel tank 1, obtains natural gas stored in the tank from the fuel tank 1, and generates a combustion oxygen-containing gas (for example, air) ) And an engine as an internal combustion engine that obtains a driving force by combustion.
  • the fuel tank 1 includes a pressure vessel 2 and includes a pair of outlets 5 and 6 as inlets and outlets through which gas to be stored can enter and exit the container 2.
  • a pair of valves 7 constituting an airtight holding mechanism that can be maintained in a pressure state are provided at each of the entrances and exits.
  • Natural gas as fuel is filled into the fuel tank 1 in a pressurized state at a gas station.
  • the fuel tank 1 includes a storage material 4 made of the metal complex of the present invention, and the storage material 4 adsorbs natural gas (such as a gas containing methane as a main component) at room temperature and under pressure. . Then, when the valve 7 on the outlet side is opened, the gas in the adsorbed state is desorbed from the occlusion material 4 and sent to the engine side for combustion to obtain travel driving force.
  • the gas compression ratio can be increased with respect to the apparent pressure as compared with the fuel tank not filled with the occlusion material.
  • the thickness of the tank can be reduced and the weight of the entire gas storage device can be reduced, which is useful for gas vehicles and the like.
  • the fuel tank 1 is normally in a normal temperature state, and is not particularly cooled.
  • the temperature of the fuel tank 1 is relatively high, for example, in summer, when the temperature rises. Even in such a high temperature range (about 298 to 333 K), the occlusion material of the present invention can keep its adsorption capacity high and is useful.
  • the separation method includes a step of bringing the gas into contact with the metal complex of the present invention (or the separation material of the present invention) under conditions that allow the gas to be adsorbed to the metal complex.
  • the adsorption pressure and the adsorption temperature which are conditions under which the gas can be adsorbed on the metal complex, can be appropriately set according to the type of substance to be adsorbed.
  • the adsorption pressure is preferably from 0.01 to 10 MPa, more preferably from 0.1 to 3.5 MPa.
  • the adsorption temperature is preferably 195K to 343K, and more preferably 273 to 313K.
  • the separation method can be a pressure swing adsorption method or a temperature swing adsorption method.
  • the separation method further includes a step of increasing the pressure from the adsorption pressure to a pressure at which gas can be desorbed from the metal complex.
  • the desorption pressure can be appropriately set according to the type of substance to be adsorbed.
  • the desorption pressure is preferably 0.005 to 2 MPa, more preferably 0.01 to 0.1 MPa.
  • the separation method is a temperature swing adsorption method
  • the separation method further includes a step of raising the temperature from the adsorption temperature to a temperature at which the gas can be desorbed from the metal complex.
  • the desorption temperature can be appropriately set according to the type of substance to be adsorbed.
  • the desorption temperature is preferably 303 to 473K, and more preferably 313 to 373K.
  • the separation method is a pressure swing adsorption method or a temperature swing adsorption method
  • the step of bringing the gas into contact with the metal complex and the step of changing the pressure to a temperature or a temperature at which the gas can be desorbed from the metal complex are repeated as appropriate. Can do.
  • the water contact angle was measured using a contact angle meter (based on JIS R3257). At this time, prior to the measurement, the sample was filled without applying force to the powder X-ray diffraction sample holder, and the upper surface of the sample was smoothed with a glass plate. Details of the analysis conditions are shown below.
  • the powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. From the comparison between FIG. 5 and FIG. 8, it is clear that the obtained metal complex has the same structure as the metal complex obtained in Synthesis Example 1. Moreover, the SEM photograph of the obtained metal complex is shown in FIG. 9 (magnification: 3,000 times).
  • trimesic acid: isobutyric acid 28: 1.
  • the powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. From comparison between FIG. 5 and FIG. 10, it is clear that the obtained metal complex has the same structure as the metal complex obtained in Synthesis Example 1. Moreover, the SEM photograph of the obtained metal complex is shown in FIG. 11 (magnification: 3,000 times).
  • trimesic acid: heptanoic acid 10: 1.
  • FIG. 19 shows a powder X-ray diffraction pattern of the obtained metal complex. Moreover, the SEM photograph of the obtained metal complex is shown in FIG. 20 (magnification: 3,000 times).
  • Example 1 For the metal complex obtained in Synthesis Example 1, an attempt was made to measure the water contact angle, but the water repellency was high and the contact angle could not be measured. A photograph at the time of measurement is shown in FIG. From FIG. 21, it is clear that the water contact angle is 150 ° or more, and the metal complex obtained in Synthesis Example 1 was super water-repellent.
  • Example 2 As a result of measuring the water contact angle for the metal complex obtained in Synthesis Example 2, the metal complex obtained in Synthesis Example 2 was super-water-repellent as in Example 1.
  • Example 3 As a result of measuring the water contact angle for the metal complex obtained in Synthesis Example 3, the metal complex obtained in Synthesis Example 3 was super-water-repellent as in Example 1.
  • Example 4 About the metal complex obtained by the synthesis example 1, the adsorption amount of the carbon dioxide in 195K was measured by the capacitance method, and the adsorption isotherm was created. The results are shown in FIG. 25 (Example 4).
  • FIG. 6, FIG. 9 and FIG. 11 show that the metal complexes obtained in Synthesis Examples 1 to 3 that satisfy the constituent requirements of the present invention have uniform particle sizes, and the particle size and particle shape can be controlled. .
  • Example 5 For the metal complex obtained in Synthesis Example 1, the adsorption / desorption amount of methane at 195 K was measured by a volumetric method, and an adsorption / desorption isotherm was prepared. The results are shown in FIG.
  • the metal complex obtained in Synthesis Example 1 adsorbs and desorbs methane as the pressure increases, it is clear that the metal complex of the present invention can be used as a storage material for methane.
  • the metal complex obtained in Synthesis Example 1 selectively adsorbs and desorbs carbon dioxide as the pressure increases, it is clear that the metal complex of the present invention can be used as a separator for carbon dioxide and hydrogen.
  • the metal complexes obtained in Synthesis Examples 1 to 3 that satisfy the constituent requirements of the present invention are excellent not only in adsorption performance but also in occlusion performance and separation performance, and also have water resistance. It is useful as a gas adsorbent, occlusion material, and separation material.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Cooling, Air Intake And Gas Exhaust, And Fuel Tank Arrangements In Propulsion Units (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un complexe métallique présentant une résistance élevée à l'eau et des performances élevées d'adsorption. Le complexe métallique comprend un composé de polyacide carboxylique, au moins un ion métallique choisi parmi des ions de métaux appartenant aux groupes 2 à 13 du tableau périodique, et un composé de monoacide carboxylique aliphatique comportant 4 à 11 atomes de carbone.
PCT/JP2012/081123 2011-12-07 2012-11-30 Complexe métallique, et matériau adsorbant, matériau de stockage et matériau de séparation contenant chacun le premier WO2013084826A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011268191 2011-12-07
JP2011-268191 2011-12-07

Publications (1)

Publication Number Publication Date
WO2013084826A1 true WO2013084826A1 (fr) 2013-06-13

Family

ID=48574193

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/081123 WO2013084826A1 (fr) 2011-12-07 2012-11-30 Complexe métallique, et matériau adsorbant, matériau de stockage et matériau de séparation contenant chacun le premier

Country Status (2)

Country Link
JP (1) JPWO2013084826A1 (fr)
WO (1) WO2013084826A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015117202A (ja) * 2013-12-18 2015-06-25 新日鐵住金株式会社 ふっ素を含有する配位高分子錯体、ガス吸着材、これを用いたガス分離装置およびガス貯蔵装置
JP2015117203A (ja) * 2013-12-18 2015-06-25 新日鐵住金株式会社 ふっ素を含有する配位高分子錯体、ガス吸着材、これを用いたガス分離装置およびガス貯蔵装置
JP2017057439A (ja) * 2015-09-14 2017-03-23 新日鐵住金株式会社 金属−多孔性高分子金属錯体複合材料の製造方法および金属−多孔性高分子金属錯体複合材料
JP2020528043A (ja) * 2018-06-11 2020-09-17 南京工▲業▼大学 二次元シート状Ｃｕ−ＭＯＦ材料を調製する方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08217811A (ja) * 1995-02-13 1996-08-27 Osaka Gas Co Ltd 高分子合成方法
JP2008208110A (ja) * 2007-01-31 2008-09-11 Nissan Motor Co Ltd 多孔性金属錯体、多孔性金属錯体の製造方法、吸着材、分離材、ガス吸着材及び水素吸着材
US20090263656A1 (en) * 2006-10-11 2009-10-22 Byung-Joon Chae Organic-inorganic hybrid structures having nanoparticles adhering thereon and method for preparing the same
JP2009544646A (ja) * 2006-07-27 2009-12-17 ビーエーエスエフ ソシエタス・ヨーロピア 銅含有金属有機骨格材料の製造方法
JP2011517309A (ja) * 2007-09-25 2011-06-02 ザ レジェンツ オブ ザ ユニヴァースティ オブ カリフォルニア 食用に適した生体適合性金属有機構造体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08217811A (ja) * 1995-02-13 1996-08-27 Osaka Gas Co Ltd 高分子合成方法
JP2009544646A (ja) * 2006-07-27 2009-12-17 ビーエーエスエフ ソシエタス・ヨーロピア 銅含有金属有機骨格材料の製造方法
US20090263656A1 (en) * 2006-10-11 2009-10-22 Byung-Joon Chae Organic-inorganic hybrid structures having nanoparticles adhering thereon and method for preparing the same
JP2008208110A (ja) * 2007-01-31 2008-09-11 Nissan Motor Co Ltd 多孔性金属錯体、多孔性金属錯体の製造方法、吸着材、分離材、ガス吸着材及び水素吸着材
JP2011517309A (ja) * 2007-09-25 2011-06-02 ザ レジェンツ オブ ザ ユニヴァースティ オブ カリフォルニア 食用に適した生体適合性金属有機構造体

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
????? B M ET AL.: "?????????? ???????????????? ????? ??? ???????????? ?????????? ?????? ?????? c ???????????????? ????????? ? ?-?????????????.", KOORDINATSIONNAYA KHIMIYA, vol. 3, no. 2, 1977, pages 183 - 192 *
AYAKO UMEMURA ET AL.: "Keisan Kagakuteki Shuho to Gosei Kagakuteki Shuho o Kumiawaseta Sakutai Framework Seisei Kiko no Kaimei", ANNUAL MEETING OF THE CHEMICAL SOCIETY OF JAPAN IN SPRING KOEN YOKOSHU, vol. 92, no. 2, 9 March 2012 (2012-03-09), pages 526 *
AYAKO UMEMURA ET AL.: "Kessho no Size to Katachi o Seigyo suru", GENDAI KAGAKU, 1 April 2012 (2012-04-01), pages 46 - 47 *
AYAKO UMEMURA ET AL.: "Soshika Model ni yoru Takosei Sakutai Framework Seisei Kiko no Rironteki Kenkyu to Kessho Keitai no Sekkei", ANNUAL MEETING OF THE CHEMICAL SOCIETY OF JAPAN IN SPRING KOEN YOKOSHU, vol. 91, no. 2, 11 March 2011 (2011-03-11), pages 461 *
SERGIO J. GARIBAY ET AL.: "Postsynthetic Modification: A Versatile Approach Toward Multifunctional Metal-Organic Frameworks", INORGANIC CHEMISTRY, vol. 48, no. 15, 2009, pages 7341 - 7349, XP055067505 *
SONIA PEREZ-YANEZ ET AL.: "Open-Framework Copper Adeninate Compounds with Three-Dimensional Microchannels Tailored by Aliphatic Monocarboxylic Acids", INORGANIC CHEMISTRY, vol. 50, no. 12, 20 May 2011 (2011-05-20), pages 5330 - 5332, XP055067502 *
TAKAAKI TSURUOKA ET AL.: "Nanoporous Nanorods Fabricated by Coordination Modulation and Oriented Attachment Growth", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 48, no. 26, 2009, pages 4739 - 4743, XP055067497 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015117202A (ja) * 2013-12-18 2015-06-25 新日鐵住金株式会社 ふっ素を含有する配位高分子錯体、ガス吸着材、これを用いたガス分離装置およびガス貯蔵装置
JP2015117203A (ja) * 2013-12-18 2015-06-25 新日鐵住金株式会社 ふっ素を含有する配位高分子錯体、ガス吸着材、これを用いたガス分離装置およびガス貯蔵装置
JP2017057439A (ja) * 2015-09-14 2017-03-23 新日鐵住金株式会社 金属−多孔性高分子金属錯体複合材料の製造方法および金属−多孔性高分子金属錯体複合材料
JP2020528043A (ja) * 2018-06-11 2020-09-17 南京工▲業▼大学 二次元シート状Ｃｕ−ＭＯＦ材料を調製する方法

Also Published As

Publication number Publication date
JPWO2013084826A1 (ja) 2015-04-27

Similar Documents

Publication Publication Date Title
WO2014007181A1 (fr) Complexe métallique, et absorbant, matière d'occlusion et matière de séparation obtenus à partir de celui-ci
JP6270720B2 (ja) 金属錯体、並びにそれからなる吸着材、吸蔵材及び分離材
JP6076255B2 (ja) 金属錯体、並びにそれからなる吸着材、吸蔵材及び分離材
JP5574669B2 (ja) 金属錯体及びそれからなる分離材
WO2010021345A1 (fr) Complexe métallique et son procédé de fabrication
JP5478120B2 (ja) 金属錯体及びその製造方法
JP5677131B2 (ja) 金属錯体、並びにそれからなる吸蔵材及び分離材
WO2013069721A1 (fr) Complexe métallique et adsorbant, absorbant et séparateur formés à partir de ces derniers
US20150361102A1 (en) Method for producing metal complex
JP2012031161A (ja) 金属錯体、並びにそれからなる吸蔵材及び分離材
JP5725784B2 (ja) 金属錯体及びそれからなる分離材
JP5478121B2 (ja) 金属錯体及びその製造方法
JP2012193122A (ja) 金属錯体及びそれからなる分離材
WO2013084826A1 (fr) Complexe métallique, et matériau adsorbant, matériau de stockage et matériau de séparation contenant chacun le premier
JP6242136B2 (ja) 多孔性金属錯体組成物
JP5677132B2 (ja) 金属錯体及びその製造方法
WO2013024888A1 (fr) Matériau de séparation et procédé de séparation utilisant ledit matériau de séparation
WO2014126238A1 (fr) Complexe métallique et adsorbant, absorbant et séparateur, dont chacun est formé du complexe métallique
JP2014028943A (ja) 配位高分子、並びにそれからなる吸着材、吸蔵材及び分離材
JP2015205857A (ja) 金属錯体、並びにそれからなる吸着材、吸蔵材及び分離材
JP2015027954A (ja) 金属錯体、並びにそれからなる吸着材、吸蔵材及び分離材
JP5832197B2 (ja) 金属錯体、並びにそれからなる吸蔵材及び分離材
JP2017048145A (ja) 金属錯体、並びにそれからなる吸着材、吸蔵材および分離材
JP2011037793A (ja) 金属錯体及びその製造方法
JP2014058481A (ja) 金属錯体、並びにそれからなる吸着材、吸蔵材及び分離材

Legal Events

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

Ref document number: 12855155

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013548216

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12855155

Country of ref document: EP

Kind code of ref document: A1