JP2015027954A - Metal complex, and adsorbent material, occlusion material and separation material composed thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal complex having excellent gas adsorption performance, gas occlusion performance and gas separation performance.SOLUTION: There is provided a metal complex which comprises a polycarboxylic acid compound, at least one metal ion selected from ions of metals belonging to Groups 2 to 13 in the periodic table and an aromatic monocarboxylic acid compound having 4 to 14 carbon atoms in the base skeleton. The metal complex has excellent adsorption, occlusion and separation abilities of gas, has excellent durability and is stably present under high temperature and high humidity and can retain a high adsorption performance.

Description

  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 aromatic monocarboxylic acid compound having 4 to 14 carbon atoms in the mother skeleton.

  So far, various adsorbents have been developed in fields such as deodorization and exhaust gas treatment. 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. In recent years, 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. Has been. Molecular sieve charcoal is also applied to various gas separation and purification such as hydrogen purification from methanol cracked gas.

  When separating mixed gas by pressure swing adsorption method or temperature swing adsorption method, generally, molecular sieve charcoal or zeolite is used as the separation adsorbent, and separation is performed by the difference in the equilibrium adsorption amount or adsorption rate. . However, when separating the mixed gas based on the difference in the amount of equilibrium adsorption, the conventional adsorbents cannot selectively adsorb only the gas to be removed, so the separation factor becomes small, and the size of the apparatus is inevitable. . In addition, when separating the mixed gas based on the difference in adsorption speed, only the gas to be removed can be adsorbed depending on the type of gas, but it is necessary to perform adsorption and desorption alternately, and in this case, the apparatus still has to be large. I didn't get it.

  On the other hand, 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.

  However, the present situation is that cost reduction by further downsizing of the apparatus is required, and in order to achieve this, further improvement in adsorption performance, storage performance and separation performance is required.

  A metal complex composed of an aluminum ion and an aromatic carboxylic acid is disclosed (see Patent Document 1 and Patent Document 2). However, as a result of evaluating the gas adsorption behavior of the metal complexes described in Patent Document 1 and Patent Document 2, it was found that the performance is not satisfactory and there is room for improvement.

JP 2009-96722 A JP 2010-209042 A

  Accordingly, an object of the present invention is to provide a metal complex that is superior in gas adsorption performance, occlusion performance, and separation performance as compared with conventional ones, and also excellent in weather resistance, and can be used as a gas adsorption material, gas storage material, or gas separation material. Is to provide.

  The present inventors have intensively studied and achieved the above object by using a metal complex comprising a polyvalent carboxylic acid compound, at least one metal ion, and an aromatic monocarboxylic acid compound having 4 to 14 carbon atoms in the mother skeleton. As a result, the inventors have found out that the present invention can be achieved.

That is, according to the present invention, the following is provided.
(1) 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 aromatic monocarboxylic acid compound having 4 to 14 carbon atoms in the mother skeleton Containing a metal complex.
(2) The composition ratio between the polyvalent carboxylic acid compound constituting the metal complex and the aromatic monocarboxylic acid compound having 4 to 14 carbon atoms of the mother skeleton is a polyvalent carboxylic acid compound: 4 to 14 carbon atoms of the mother skeleton. The metal complex according to (1), wherein the aromatic monocarboxylic acid compound is in the range of 3: 1 to 5,000: 1.
(3) The metal complex according to (1) or (2), wherein the polyvalent carboxylic acid compound is a tricarboxylic acid compound.
(4) The metal complex according to any one of (1) to (3), wherein the aromatic monocarboxylic acid compound is an aromatic monocarboxylic acid compound having 6 carbon atoms in the mother skeleton.
(5) The metal complex is in any shape selected from pellets, films, sheets, plates, pipes, tubes, rods, granules, heterogeneous shapes, fibers, hollow fibers, woven fabrics, knitted fabrics and non-woven fabrics. The metal complex according to any one of (1) to (4).
(6) An adsorbent comprising the metal complex according to any one of (1) to (5).
(7) 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, water vapor or The adsorbent according to (6), which is an adsorbent for adsorbing organic vapor.
(8) A canister in which the adsorbent according to (6) is provided.
(9) An occlusion material comprising the metal complex according to any one of (1) to (5).
(10) 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, water vapor or organic vapor. The storage material according to (9).
(11) A gas storage device in which a gas storage space is provided on the inner side of a pressure vessel that can be kept airtight and provided with a gas inlet / outlet, and the gas storage space includes the storage material described in (9). Some gas storage devices.
(12) A gas vehicle including an internal combustion engine that obtains a driving force by the fuel gas supplied from the gas storage device according to (11).
(13) A separating material comprising the metal complex according to any one of (1) to (5).
(14) 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, water vapor or The separating material according to (13), which is a separating material for separating organic vapor.
(15) The separation method using the separation material according to (13), including a step of bringing the metal complex and the mixed gas into contact in a pressure range of 0.01 to 10 MPa.
(16) The separation method according to (15), wherein the separation method is a pressure swing adsorption method or a temperature swing adsorption method.
(17) 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 aromatic monocarboxylic acid compound having 4 to 14 carbon atoms in the mother skeleton The method for producing a metal complex according to (1), wherein the reaction is performed while stirring in a solvent to cause precipitation.

  According to the present invention, there are provided a metal complex containing a polyvalent carboxylic acid compound, at least one metal ion, and an aromatic monocarboxylic acid compound having 4 to 14 carbon atoms in the mother skeleton, and a method for producing the metal complex. Can do.

  Since 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 substances, nitrogen oxides, siloxanes, water vapor, organic vapors and the like.

  Moreover, since the metal complex of the present invention is excellent in the occlusion 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 storage material for storing water vapor or organic vapor.

  Furthermore, since 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 sulfur oxides, nitrogen oxides, siloxanes, water vapor or organic vapors.

It is a paddle wheel skeleton composed of a carboxylate ion of trimesic acid and a copper ion. It is a schematic diagram of the octahedral structure which consists of trimesic acid and a copper ion. It is a three-dimensional integrated structure of a metal complex composed of trimesic acid and copper ions. It is a conceptual diagram of the gas vehicle provided with the gas storage apparatus. 3 is a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 1. FIG. 2 is a ¹ H-NMR spectrum measured by dissolving the metal complex obtained in Synthesis Example 1 in a 4 wt% sodium hydroxide-d heavy aqueous solution. 4 is a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 2. FIG. 3 is a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 1. FIG. 4 is a powder X-ray diffraction pattern 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. It is an adsorption isotherm of butane at 298 K of the metal complexes obtained in Synthesis Example 1, Synthesis Example 2, Comparative Synthesis Example 1, Comparative Synthesis Example 2 and Comparative Synthesis Example 3. 2 is an adsorption / desorption isotherm of methane at 298 K of the metal complex obtained in Synthesis Example 1. FIG. 2 is an adsorption / desorption isotherm of methane at 298 K of the metal complex obtained in Comparative Synthesis Example 1. FIG. 2 is an adsorption / desorption isotherm of carbon dioxide and hydrogen at 313 K of the metal complex obtained in Synthesis Example 1. FIG.

  The metal complex of the present invention comprises 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 aromatic monocyclic compound having 4 to 14 carbon atoms in the mother skeleton. A carboxylic acid compound.

  Although it does not specifically limit as a polyvalent carboxylic acid compound used for this invention, A dicarboxylic acid compound, a tricarboxylic acid compound, a tetracarboxylic acid compound, etc. can be used. Examples of the dicarboxylic acid compound include succinic acid, 1,4-cyclohexanedicarboxylic acid, fumaric acid, muconic acid, 2,3-pyrazinedicarboxylic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6 -Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2,5-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,5-thiophenedicarboxylic acid, 2,2 ' -Dithiophene dicarboxylic acid etc. are mentioned. Examples of the tricarboxylic acid compound include trimesic acid, trimellitic acid, biphenyl-3,4 ', 5-tricarboxylic acid, 1,3,5-tris (4-carboxyphenyl) benzene, 1,3,5-tris ( 4'-carboxy [1,1'-biphenyl] -4-yl) benzene and the like. Examples of the tetracarboxylic acid compound include pyromellitic acid, [1,1 ′: 4 ′, 1 ″] terphenyl-3,3 ″, 5,5 ″ -tetracarboxylic acid, 1,2,4. , 5-tetrakis (4-carboxyphenyl) benzene and the like.

  Among these, tricarboxylic acid compounds are preferable, and aromatic tricarboxylic acid compounds (for example, trimesic acid, trimellitic acid, biphenyl-3,4 ', 5-tricarboxylic acid, 1,3,5-tris (4-carboxyphenyl) benzene 1,3,5-tris (4′-carboxy [1,1′-biphenyl] -4-yl) benzene, etc.) is more preferable. The polyvalent carboxylic acid compound may be used alone, or two or more polyvalent carboxylic acid compounds 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 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 polyvalent carboxylic acid having a substituent is preferably an aromatic polyvalent carboxylic acid, and the substituent is preferably bonded to the aromatic ring of the aromatic polyvalent carboxylic acid. The number of substituents may be 1, 2 or 3. Although it does not specifically limit as a substituent, For example, 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, etc.). Having a C1-C5 alkyl group), 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 (methylamino group etc.), dialkylamino group (dimethylamino group etc.), 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. Specifically, 2-nitroterephthalic acid, 2-fluoroterephthalic acid, 1,2,3,4-tetrafluoroterephthalic acid, 2,4,6-trifluoro-1,3,5-benzenetricarboxylic acid, etc. Examples thereof include polyvalent carboxylic acid compounds having a substituent.

  Examples of ions of metals belonging to Groups 2 to 13 of the periodic table used in the present invention include magnesium ions, calcium ions, scandium ions, lanthanoid ions (such as lanthanum ions, terbium ions, and lutetium ions), and actinoid ions (actinium ions). ), Zirconium ion, vanadium ion, chromium ion, molybdenum ion, manganese ion, iron (II) ion, iron (III) ion, cobalt ion, nickel ion, copper ion, zinc ion, cadmium ion, aluminum ion Among them, scandium ions, lanthanoid ions, chromium ions, iron (III) ions, copper ions and aluminum ions are preferable, and aluminum ions are more preferable. Arbitrariness. The metal ion is preferably a single metal ion, but two or more kinds of metal ions 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 metal ion.

  The metal ion may be used in the form of a metal salt. Examples of metal salts include magnesium salts, calcium salts, scandium salts, lanthanoid salts (such as lanthanum salts, terbium salts, and lutetium salts), actinoid salts (such as actinium salts and lauren salts), zirconium salts, vanadium salts, chromium salts, Molybdenum salt, manganese salt, iron (II) salt, iron (III) salt, cobalt salt, nickel salt, copper salt, zinc salt, cadmium salt, aluminum salt, etc. can be used, among which scandium salt, lanthanoid salt, Chromium salts, iron (III) salts, copper salts and aluminum salts are preferred, and aluminum salts are more preferred. 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 aromatic monocarboxylic acid compound used in the present invention has 4 to 14 carbon atoms in the mother skeleton. The aromatic monocarboxylic acid compound may be a heteroaromatic monocarboxylic acid compound. Here, the “carbon number of the mother skeleton” means the carbon number of only the ring structure excluding the carbon number of the substituent (including the carboxyl group). For example, 2-thiophenecarboxylic acid (4 carbon atoms in the mother skeleton), 3-pyridinecarboxylic acid (5 carbon atoms in the mother skeleton), 4-pyridinecarboxylic acid (5 carbon atoms in the mother skeleton), benzoic acid (of the mother skeleton) Carbon number 6), 2-naphthalene carboxylic acid (mother skeleton carbon number 10), 9-anthracene carboxylic acid (mother skeleton carbon number 14), and the like can be used. Among these, an aromatic monocarboxylic acid compound having 4 to 10 carbon atoms in the mother skeleton is preferable, 4 to 6 is more preferable, and 6 (benzoic acid) is particularly preferable. The aromatic monocarboxylic acid compound may be used alone, or two or more aromatic monocarboxylic acid compounds 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 aromatic monocarboxylic acid compound.

  The aromatic monocarboxylic acid compound may further have a substituent in addition to the carboxyl group. The number of substituents may be 1, 2 or 3. Examples of the substituent include, for example, an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, etc. 5 alkyl group), aryl group (such as phenyl group), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group (methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n- Butoxy, isobutoxy, tert-butoxy, etc.), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, etc.), nitro, cyano, hydroxyl, acetyl, tri A fluoromethyl group etc. are mentioned. The aromatic monocarboxylic acid compound may be used in the form of an alkali metal salt.

  Although the composition ratio of the polyvalent carboxylic acid compound constituting the metal complex of the present invention and the aromatic monocarboxylic acid compound having 4 to 14 carbon atoms of the mother skeleton is not particularly limited, the polyvalent carboxylic acid compound: aromatic Group monocarboxylic acid compound = preferably within the range of 3: 1 to 5,000: 1, polyvalent carboxylic acid compound: aromatic monocarboxylic acid compound = within the range of 3: 1 to 2,500: 1 More preferably, it is more preferably in the range of 5: 1 to 1,000: 1.

  The composition ratio between the polyvalent carboxylic acid compound constituting the metal complex of the present invention and the aromatic monocarboxylic acid compound having 4 to 14 carbon atoms of the mother skeleton is determined by gas chromatography after decomposing the metal complex to obtain a uniform solution. It can be determined by analysis using high performance liquid chromatography, NMR or the like, but is not limited thereto.

  The metal complex of the present invention comprises 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 aromatic monocyclic compound having 4 to 14 carbon atoms in the mother skeleton. It can be produced by reacting a carboxylic acid compound in a solvent for several tens of minutes to several days and depositing it. At this time, it is preferable to carry out the reaction while stirring the reaction solution. Moreover, you may react under an ultrasonic wave or a microwave irradiation. For example, an aqueous solution or organic solvent solution of a metal salt containing the above metal ion and an aqueous solution or organic solvent solution containing a polyvalent carboxylic acid compound and an aromatic monocarboxylic acid compound are mixed under normal pressure and stirred. The metal complex of this invention can be obtained by making it react. Further, the aromatic monocarboxylic acid compound having 4 to 14 carbon atoms of the mother skeleton may be present at the beginning of the reaction or may be added at the later stage of the reaction, but is preferably present at the beginning of the reaction.

  As a solvent used for producing the metal complex, an organic solvent, water, or a mixed solvent thereof can be used. Specifically, methanol, ethanol, propanol, diethyl ether, butanol, dimethoxyethane, tetrahydrofuran, hexane, cyclohexane, heptane, benzene, toluene, methylene chloride, chloroform, acetone, ethyl acetate, acetonitrile, N, N-dimethylformamide, N, N-diethylformamide, water or a mixed solvent thereof can be used.

  The reaction temperature may be appropriately selected according to the solvent to be used, but is preferably from 253 to 463K, more preferably from 298 to 423K.

  The mixing ratio of the metal salt and the polyvalent carboxylic acid compound when producing the metal complex is preferably in the range of a molar ratio of metal salt: polyvalent carboxylic acid compound = 1: 5 to 8: 1, and 1: 3 to 6 A molar ratio in the range of 1 is more preferable.

  The mixing ratio of the polyvalent carboxylic acid compound and the aromatic monocarboxylic acid compound having 4 to 14 carbon atoms of the mother skeleton is: polyvalent carboxylic acid compound: aromatic monocarboxylic acid compound = 1: 1,000 to 5,000: 1. Is preferably within the range of the molar ratio of 1: 100 to 1,000: 1.

  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. Further, the molar concentration of the metal salt is preferably 0.01 to 5.0 mol / L, and the molar concentration of the aromatic monocarboxylic acid compound having 4 to 14 carbon atoms of the mother skeleton is preferably 0.01 to 150 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 completion of the reaction can be confirmed by quantifying the remaining amount of the raw material by an absorptiometric method, gas chromatography, high performance liquid chromatography or the like, but is not limited thereto. 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.

  Since the metal complex of the present invention is a porous body and can adsorb and desorb low molecules such as gas in its pores, it can be used as an adsorbent, occlusion material and separation material for various gases. . However, gas is not adsorbed in a state where the solvent used in the production 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, 298K to 523K or less), and the temperature is preferably lower (for example, 298K to 393K or less). This operation can be replaced by cleaning with supercritical carbon dioxide, and is more effective.

  The metal complex of the present invention has a one-dimensional, two-dimensional, or three-dimensional integrated structure depending on the polyvalent carboxylic acid compound used, the metal ion, and the type of organic ligand that can be multidentately coordinated with the metal ion.

  An example of a metal complex having a one-dimensional integrated structure is a metal complex composed of 2,3-pyrazinedicarboxylic acid and a copper ion, and an example of a metal complex having a two-dimensional integrated structure is from terephthalic acid and a 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.

  In the metal complex of the present invention, the particle size and morphology can be controlled by the type and amount of the monocarboxylic acid compound used. The particle size of the metal complex can be confirmed by, for example, a laser diffraction method, a dynamic light scattering method, an image imaging method, a gravity sedimentation method, or the like, but is not limited thereto.

  As an example, a metal complex having trimesic acid as a polyvalent carboxylic acid compound and copper ions as metal ions will be described in detail. 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 fact that the metal complex has three-dimensional pores can be confirmed by, for example, single crystal X-ray structure analysis, powder X-ray crystal structure analysis, single crystal neutron structure analysis, but is not limited thereto.

  When the polyvalent carboxylic acid compound is reacted with the metal ion, the reaction between the metal ion and the polyvalent carboxylic acid compound and the reaction between the metal ion and the aromatic monocarboxylic acid compound are allowed to coexist with the aromatic monocarboxylic acid compound. The reaction will be competitive. When the aromatic monocarboxylic acid compound is coordinated to a metal ion, since there is only one coordination site of the aromatic monocarboxylic acid compound, crystal growth stops at that coordination site, so the aromatic monocarboxylic acid The compound can be regarded as a terminator in the crystal growth reaction. On the other hand, since the reaction between the metal ion and the aromatic monocarboxylic acid compound is reversible, the crystal nucleation rate and crystal growth rate are controlled, and the metal complex has few crystal defects as well as control of the particle size and particle shape. Can be obtained. The metal complex of the present invention having few crystal defects is excellent in, for example, gas adsorption performance, gas storage performance, or gas separation performance.

  The performance improvement mechanism is an estimation, but even if it does not follow the mechanism, it is included in the technical scope of the present invention as long as it satisfies the requirements defined in the present invention.

  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, adsorbent and separator 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 (helium, neon, argon, krypton, xenon, etc.), 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. In the separation material of the present invention, in particular, methane and carbon dioxide, hydrogen and carbon dioxide, nitrogen and carbon dioxide, ethylene and carbon dioxide, methane and ethane, ethylene and ethane, nitrogen and oxygen, oxygen and argon, nitrogen and It is suitable for separating methane, air and methane by pressure swing adsorption method or temperature swing adsorption method.

  The organic vapor means a vaporized organic substance that is liquid at normal temperature and pressure. Examples of such organic substances include alcohols such as methanol and ethanol; amines such as trimethylamine; aldehydes such as formaldehyde and acetaldehyde; pentane, isoprene, hexane, cyclohexane, heptane, methylcyclohexane, octane, 1-octene, cyclohexane C5-C16 hydrocarbons such as octane, cyclooctene, 1,5-cyclooctadiene, 4-vinyl-1-cyclohexene, 1,5,9-cyclododecatriene; aromatic hydrocarbons such as benzene and toluene Ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; halogenated hydrocarbons such as methyl chloride and chloroform.

  The metal complex or adsorbent of the present invention, the occlusion material, and the separation material are within a range that does not impair the effects of the present invention, if necessary, titanium dioxide, silicon dioxide, aluminum oxide, montmorillonite, kaolin, bentonite, halloysite, Dickite, nacrite, anaukisite, tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc.), starch, cellulose, cellulose acetate, polyvinyl alcohol, polyamide, polyester, polycarbonate, polysulfone, polyether It can also be molded together with a binder such as sulfone, polyolefin and polytetrafluoroethylene. The concentration of the binder in the molded body is usually 0.1 to 20% by weight. Further, it may be combined with natural or synthetic fibers such as paper, or inorganic fibers such as glass or alumina.

  The usage form of the metal complex or adsorbent, occlusion material and separation material of the present invention is not particularly limited. For example, it may be used as a powder, or formed into pellets, films, sheets, plates, pipes, tubes, rods, granules, various deformed shapes, fibers, hollow fibers, woven fabrics, knitted fabrics, nonwoven fabrics, etc. May be used.

  The method for producing a pellet containing the metal complex or adsorbent, occlusion material or separation material of the present invention is not particularly limited, and any conventionally known pelletization method can be employed. The tableting method is preferable from the viewpoint that the density of the pellet can be increased. Usually, at the time of tableting molding, a metal complex or a composition of the metal complex and the binder is prepared in advance, and this is solidified into a fixed shape under pressure using a commercially available tablet molding machine. At this time, if necessary, a lubricant such as graphite and magnesium stearate may be added to the preparation.

  The method for producing a sheet containing the metal complex or adsorbent, occlusion material or separation material of the present invention is not particularly limited, and any conventionally known sheeting method can be employed. The wet papermaking method is preferable from the viewpoint that the sheet can be densified. 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 as an example of the deformed shape. Any of the conventionally known processing methods can be employed as a method for forming a sheet containing the metal complex or adsorbent, occlusion material or separation material of the present invention into a honeycomb shape. In addition, in the present invention, 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. For example, in order to obtain a sinusoidal honeycomb shape, first, the sheet is passed through a shaping roll and shaped into a corrugated shape, and a flat sheet is bonded to one or both sides of the corrugated sheet. This is laminated to form a sinusoidal honeycomb filter. Here, it is common to fix the apex of the corrugation with an adhesive, but when the sheet containing the corrugated metal complex of the present invention is laminated, the flat sheet in between is necessarily fixed. It is not always necessary to apply an adhesive. In addition, when attaching an adhesive agent, it is necessary to use what does not impair the adsorption | suction ability of a sheet | seat. As the adhesive, for example, corn starch, vinyl acetate resin, acrylic resin, or the like can be used. In order to improve the gas adsorption performance, it is preferable to reduce the adhesion pitch of the corrugated sheet and reduce the peak height. 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 adsorbent of the present invention) can also be used in a canister by taking advantage of its adsorption performance. A canister is widely used as a device for preventing fuel evaporated in a fuel tank in a vehicle from diffusing into the atmosphere. The canister adsorbs the fuel vapor in contact with the surface and has an internal adsorbent having the property of releasing the fuel vapor by the air flow, and the adsorbent made of the metal complex of the present invention includes the adsorbent. It can be suitably used as a material. The canister having the adsorbent made of the metal complex of the present invention has superior adsorption performance and can improve the amount of fuel vapor adsorbed compared to the canister having the activated carbon as an adsorbent. it can. Therefore, the present invention is particularly useful as a canister for a hybrid vehicle that requires a canister with higher adsorption performance.

  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. As an example of the gas storage device, there is a gas storage device in which a gas storage space is provided inside a pressure-resistant container that can be kept airtight and has a gas inlet / outlet, and the storage space includes the storage material made of the metal complex of the present invention. . By press-fitting a desired gas into the gas storage device, the gas can be adsorbed and stored in the internal storage material. 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. When installing the occlusion material in the gas storage space, 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.

  Such a gas storage device 1 can store fuel gas in the storage space 3 and can be suitably used as a fuel tank 1 of a gas vehicle or the like. An example of a gas vehicle equipped with the gas storage device of the present invention is shown in FIG. This gas vehicle includes the gas storage device 1 in which the metal complex of the present invention is housed 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, an engine as an internal combustion engine that is mixed with air and obtains driving power by combustion is provided. The fuel tank 1 includes a pressure-resistant container 2 and includes a pair of outlets and an inlet through which a gas to be stored can enter and exit, and is hermetically maintained so that the gas in the container 2 can be maintained in a pressurized state. A pair of valves constituting the mechanism is 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. . When the valve on the outlet side is opened, the gas in the adsorbed state is desorbed from the occlusion material 4, sent to the engine side, and combusted to obtain travel driving force.

  Since the occlusion material made of the metal complex of the present invention is incorporated, the fuel tank 1 can increase the gas compressibility against the apparent pressure as compared with the fuel tank not filled with the occlusion material. Since the thickness can be reduced and the weight of the entire gas storage device can be reduced, it 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 in summer, for example, when the temperature rises. Even under such a high temperature range (about 298 to 333 K), the occlusion material of the present invention can keep its occlusion ability 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. For example, the adsorption pressure is preferably 0.01 to 10 MPa, and more preferably 0.1 to 3.5 MPa. Further, 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. When the separation method is a pressure 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. For example, the desorption pressure is preferably 0.005 to 2 MPa, and more preferably 0.01 to 0.1 MPa. When 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. For example, the desorption temperature is preferably 303 to 473K, and more preferably 313 to 373K.

  When 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.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Analysis and evaluation in the following examples and comparative examples were performed as follows.

(1) Measurement of powder X-ray diffraction pattern Using an X-ray diffractometer, the range of diffraction angle (2θ) = 2 to 50 ° was scanned at a scanning speed of 1 ° / min and measured by a symmetric reflection method. Details of the analysis conditions are shown below.
<Analysis conditions>
Apparatus: SmartLab, manufactured by Rigaku Corporation
X-ray source: CuKα (λ = 1.5418Å) 45 kV 200 mA
Goniometer: Horizontal goniometer Detector: D / teX Ultra
Step width: 0.02 °
Slit: Divergent slit = 2/3 °
Receiving slit = 0.3mm
Scattering slit = 2/3 °

(2) Determination of C4-C14 aromatic monocarboxylic acid compound of mother skeleton contained in metal complex ¹ H-NMR measurement was performed on a sample in which the metal complex was dissolved in 4 wt% sodium hydroxide-d heavy aqueous solution. It was calculated from the integral ratio of the obtained spectrum. Details of the analysis conditions are described below.
<Analysis conditions>
Device: JNM-LA500 manufactured by JEOL Ltd.
Resonance frequency: 500 MHz
Solvent: 4 wt% sodium hydroxide-d heavy aqueous solution Reference material: sodium 3- (trimethylsilyl) propanoate-d ₄
Temperature: 298K
Integration count: 64 times

(3) Measurement of adsorption isotherm Gas adsorption / desorption amount was measured by a volumetric method using a high-accuracy gas adsorption amount measuring device, and an adsorption isotherm was created (based on JIS Z8831-2). At this time, the sample was dried at 373 K and 0.5 Pa for 5 hours prior to measurement to remove adsorbed water and the like. Details of the analysis conditions are shown below.
<Analysis conditions>
Apparatus: BELSORP-max manufactured by Nippon Bell Co., Ltd.
Equilibrium waiting time: 500 seconds

(4) Measurement of adsorption / desorption isotherm Using a high-pressure gas adsorption amount measuring device, the gas adsorption / desorption amount was measured by the volume method, and an adsorption / desorption isotherm was created (in accordance with JIS Z8831-2). At this time, the sample was dried at 373 K and 0.5 Pa for 5 hours prior to measurement to remove adsorbed water and the like. Details of the analysis conditions are shown below.
<Analysis conditions>
Apparatus: BELSORP-HP manufactured by Nippon Bell Co., Ltd.
Equilibrium waiting time: 500 seconds

<Synthesis Example 1>
Under a nitrogen atmosphere, 1.84 g (4.9 mmol) of aluminum nitrate nonahydrate, 2.15 g (4.9 mmol) of 1,3,5-tris (4-carboxyphenyl) benzene and 0.598 g of benzoic acid (4. 9 mmol) was dissolved in 107 mL of N, N-diethylformamide and stirred at 423 K for 24 hours. The precipitated metal complex was collected by suction filtration, and then washed with ethanol three times. Then, it dried at 373K and 50Pa for 8 hours, and obtained the target metal complex 1.57g. FIG. 5 shows a powder X-ray diffraction pattern of the obtained metal complex.

10 mg of the obtained metal complex was dissolved in 800 mg of 4 wt% sodium hydroxide-d heavy aqueous solution, and ¹ H-NMR measurement was performed. The obtained spectrum is shown in FIG. As a result of analyzing the spectrum, the integration of the peak at 7.736 ppm (d, 6H) attributed to the 3rd and 5th protons of the 4-carboxyphenyl group of 1,3,5-tris (4-carboxyphenyl) benzene. When the value was 1,000, the integrated value of the peak at 7.903 ppm (d, 2H) attributed to protons at the 2nd and 6th positions of benzoic acid was 25.7. The molar ratio of 1,3,5-tris (4-carboxyphenyl) benzene and benzoic acid contained is found to be 1,3,5-tris (4-carboxyphenyl) benzene: benzoic acid = 13: 1. It was.

^From the results of ¹ H-NMR measurement and elemental analysis, the composition formula of the obtained metal complex is [Al (C ₂₇ H ₁₅ O ₆ ) _1-x (C ₆ H ₅ COO) _x ] _n (x = 0. 072). n means an arbitrary natural number. The theoretical yield is [Al (C ₂₇ H ₁₅ O ₆ ) _0.928 (C ₆ H ₅ COO) _0.072 ] _n (aluminum: 1,3,5-tris (4-carboxyphenyl) benzene: benzoic acid = 1 : 0.928: 0.072). As a result, the yield of the obtained metal complex was 73%.

<Synthesis Example 2>
Under a nitrogen atmosphere, 1.84 g (4.9 mmol) of aluminum nitrate nonahydrate, 2.15 g (4.9 mmol) of 1,3,5-tris (4-carboxyphenyl) benzene and 1.79 g (15 mmol) of benzoic acid Was dissolved in 107 mL of N, N-diethylformamide and stirred at 423 K for 24 hours. The precipitated metal complex was collected by suction filtration, and then washed with ethanol three times. Then, it dried at 373K and 50Pa for 8 hours, and obtained the objective metal complex 1.72g. FIG. 7 shows a powder X-ray diffraction pattern of the obtained metal complex.

As a result of ¹ H-NMR measurement performed in the same manner as in Synthesis Example 1, the molar ratio of 1,3,5-tris (4-carboxyphenyl) benzene and benzoic acid contained in the metal complex was 1,3,5- It was found that tris (4-carboxyphenyl) benzene: benzoic acid = 4.5: 1.

  The yield of the obtained metal complex calculated in the same manner as in Synthesis Example 1 was 87%.

<Comparative Synthesis Example 1>
Under a nitrogen atmosphere, 1.84 g (4.9 mmol) of aluminum nitrate nonahydrate and 2.15 g (4.9 mmol) of 1,3,5-tris (4-carboxyphenyl) benzene were added to 107 mL of N, N-diethylformamide. Dissolved and stirred at 423K for 24 hours. The precipitated metal complex was collected by suction filtration, and then washed with ethanol three times. Then, it dried at 373K and 50Pa for 8 hours, and obtained the target metal complex 1.71g (yield 76%). The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Comparative Synthesis Example 2>
Based on the description in Patent Document 1 and Patent Document 2, a metal complex was synthesized as follows. Under a nitrogen atmosphere, 1.84 g (4.9 mmol) of aluminum nitrate nonahydrate and 2.15 g (4.9 mmol) of 1,3,5-tris (4-carboxyphenyl) benzene were added to 107 mL of N, N-diethylformamide. Dissolved and left at 423K for 24 hours without stirring. The precipitated metal complex was collected by suction filtration, and then washed with ethanol three times. Then, it dried at 373K and 50Pa for 8 hours, and obtained the target metal complex 1.71g (yield 76%). The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

<Comparative Synthesis Example 3>
Under a nitrogen atmosphere, 1.84 g (4.9 mmol) of aluminum nitrate nonahydrate, 2.15 g (4.9 mmol) of 1,3,5-tris (4-carboxyphenyl) benzene and 0.882 g (15 mmol) of acetic acid were added. The resultant was dissolved in 107 mL of N, N-diethylformamide and stirred at 423 K for 24 hours. The precipitated metal complex was collected by suction filtration, and then washed with ethanol three times. Then, it dried at 373K and 50Pa for 8 hours, and obtained 1.62g of the target metal complexes. The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG.

¹ H-NMR measurement was conducted in the same manner as in Synthesis Example 1 and the spectrum was analyzed. As a result, the protons at the 3-position and 5-position of the 4-carboxyphenyl group of 1,3,5-tris (4-carboxyphenyl) benzene were analyzed. When the integrated value of the peak of 7.736 ppm (d, 6H) assigned is 1,000, the integrated value of the peak of 1.963 ppm (s, 3H) assigned to the proton of the methyl group of acetic acid is 16 The molar ratio of 1,3,5-tris (4-carboxyphenyl) benzene and acetic acid contained in the metal complex was 1,3,5-tris (4-carboxyphenyl) benzene: acetic acid. = 29: 1.

  The yield of the obtained metal complex calculated in the same manner as in Synthesis Example 1 was 74%.

<Example 1>
For the metal complex obtained in Synthesis Example 1, the adsorption amount of butane at 298 K was measured by the volumetric method, and an adsorption isotherm was created. The results are shown in FIG.

<Example 2>
For the metal complex obtained in Synthesis Example 2, the amount of butane adsorbed at 298 K was measured by the volumetric method, and an adsorption isotherm was prepared. The results are shown in FIG.

<Comparative Example 1>
For the metal complex obtained in Comparative Synthesis Example 1, the amount of butane adsorbed at 298 K was measured by the volumetric method, and an adsorption isotherm was prepared. The results are shown in FIG.

<Comparative example 2>
With respect to the metal complex obtained in Comparative Synthesis Example 2, the amount of butane adsorbed at 298 K was measured by a volumetric method, and an adsorption isotherm was prepared. The results are shown in FIG.

<Comparative Example 3>
For the metal complex obtained in Comparative Synthesis Example 3, the adsorption / desorption amount of methane at 298 K was measured by the volume method, and an adsorption / desorption isotherm was prepared. The results are shown in FIG.

  From FIG. 11, the metal complexes obtained in Synthesis Example 1 and Synthesis Example 2 that satisfy the constituent requirements of the present invention adsorb butane as the pressure increases, and the amount of adsorption does not contain an aromatic monocarboxylic acid compound. Since it is more than the metal complexes obtained in Comparative Synthesis Example 1, Comparative Synthesis Example 2 and Comparative Synthesis Example 3 that do not satisfy the constituent requirements of the invention, it is clear that the metal complex of the present invention can be used as an adsorbent for butane. The reason why such a difference has occurred is not necessarily clear, but when a metal complex is produced without using an aromatic monocarboxylic acid compound having 4 to 14 carbon atoms of the mother skeleton, crystal generation and crystallization occur when stirring in the production process. Since the growth proceeds rapidly, it is thought that the number of defects increased in the resulting metal complex and the performance was greatly reduced. In addition, since the metal complexes obtained in Synthesis Example 1 and Synthesis Example 2 have a large amount of butane adsorbed at 50 kPa, application to a canister for preventing diffusion of fuel vapor and the like can be expected.

<Example 3>
For the metal complex obtained in Synthesis Example 1, the adsorption and desorption amount of methane at 298 K was measured by the volumetric method, and an adsorption isotherm was created. The results are shown in FIG.

<Comparative Example 4>
For the metal complex obtained in Comparative Synthesis Example 1, the adsorption / desorption amount of methane at 298 K was measured by a volumetric method, and an adsorption isotherm was prepared. The results are shown in FIG.

  From the comparison between FIG. 12 and FIG. 13, the metal complex obtained in Synthesis Example 1 that satisfies the constituent requirements of the present invention adsorbs methane as the pressure increases, and the amount of adsorption does not contain an aromatic monocarboxylic acid compound. It is clear that the metal complex of the present invention can be used as a methane occlusion material because it is more than the metal complex obtained in Synthesis Example 1 and releases methane as the pressure decreases. Application can be expected.

  For the metal complex obtained in Synthesis Example 1, the adsorption and desorption amounts of carbon dioxide and hydrogen at 313 K were measured by the volume method, and adsorption and desorption isotherms were created. The results are shown in FIG.

  As shown in FIG. 14, the metal complex obtained in Synthesis Example 1 that satisfies the constituent requirements of the present invention selectively adsorbs carbon dioxide as the pressure increases and releases carbon dioxide as the pressure decreases. It is clear that the complex is excellent as a separator for carbon dioxide and hydrogen, and application to a separator used in the pressure swing adsorption method can be expected.

1 Gas storage device (fuel tank)
2 Pressure vessel 3 Gas storage space 4 Storage material

Claims (17)

  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 aromatic monocarboxylic acid compound having 4 to 14 carbon atoms in the mother skeleton Complex. The composition ratio between the polyvalent carboxylic acid compound constituting the metal complex and the aromatic monocarboxylic acid compound having 4 to 14 carbon atoms in the mother skeleton is polyvalent carboxylic acid compound: aromatic having 4 to 14 carbon atoms in the mother skeleton. The metal complex according to claim 1, wherein the monocarboxylic acid compound is in the range of 3: 1 to 5,000: 1.   The metal complex according to claim 1 or 2, wherein the polyvalent carboxylic acid compound is a tricarboxylic acid compound.   The metal complex according to any one of claims 1 to 3, wherein the aromatic monocarboxylic acid compound is an aromatic monocarboxylic acid compound having 6 carbon atoms in the mother skeleton.   The metal complex is in any shape selected from pellets, films, sheets, plates, pipes, tubes, rods, granules, heteromorphs, fibers, hollow fibers, woven fabrics, knitted fabrics and non-woven fabrics. The metal complex in any one of 1-4.   An adsorbent comprising the metal complex according to claim 1.   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, water vapor or organic vapor. The adsorbent according to claim 6, which is an adsorbent for adsorbing. A canister in which the adsorbent according to claim 6 is internally provided.   The occlusion material which consists of a metal complex in any one of Claims 1-5.   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, water vapor or organic vapor. 9. The occlusion material according to 9.   A gas storage device in which a gas storage space is provided on the inner side of a pressure vessel that can be kept airtight and has a gas inlet / outlet, wherein the gas storage space includes the storage material according to claim 9. apparatus. A gas vehicle comprising an internal combustion engine that obtains driving force from fuel gas supplied from the gas storage device according to claim 11.   The separating material which consists of a metal complex in any one of Claims 1-5. The separator is carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, a hydrocarbon having 1 to 4 carbon atoms,
The separation material according to claim 13, which is a separation material for separating rare gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane, water vapor or organic vapor. The separation method using the separation material according to claim 13, comprising a step of contacting the metal complex and the mixed gas in a pressure range of 0.01 to 10 MPa. The separation method according to claim 15, wherein the separation method is a pressure swing adsorption method or a temperature swing adsorption method. 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 aromatic monocarboxylic acid compound having 4 to 14 carbon atoms in the mother skeleton in a solvent The method for producing a metal complex according to claim 1, wherein the reaction is performed while stirring and precipitation is performed.

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