# US 2014/0190436 A1 · Metal complex and adsorbent material, storage material, and separating material comprising same

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- Number: US 2014/0190436 A1
- Document ID: US20140190436A1
- Status: Published application
- Kind: A1
- Application number: 14/238,662
- Filed: 2012-08-08
- Published: 2014-07-10
- Earliest claimed: 2011-08-17
- Assignees: Kuraray Co., Ltd.
- Inventors: Yasutaka Inubushi; Chikako Ikeda; Takashi Hori
- Web page: https://patentgrep.com/patent/US20140190436A1

## CPC

- B01D 53/0462: {Temperature swing adsorption}
- B01D 53/02: by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)}
- B01D 53/047: Pressure swing adsorption
- B01J 20/223: {containing metals, e.g. organo-metallic compounds, coordination complexes}
- B01J 20/226: {Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F)}
- B01J 20/3085: {Chemical treatments not covered by groups B01J20/3007 - B01J20/3078}
- B01J 20/3425: {of sorbents or filter aids comprising organic materials}
- B01J 20/3483: {by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling}
- B01J 20/3491: {by pressure treatment}
- C01B 3/56: by contacting with solids; Regeneration of used solids
- C07C 63/28: Salts thereof
- C07C 65/21: containing ether groups, [IMAGE cpc-sch-C07C-0958.gif] groups,[IMAGE cpc-sch-C07C-0959.gif] groups, or[IMAGE cpc-sch-C07C-0960.gif] groups
- C07F 3/003: {without C-Metal linkages}
- B01D 2253/204: Metal organic frameworks (MOF's)
- B01D 2256/18: Noble gases
- B01D 2257/102: Nitrogen
- B01D 2257/104: Oxygen
- B01D 2257/304: Hydrogen sulfide
- B01D 2257/406: Ammonia
- B01D 2257/502: Carbon monoxide
- B01D 2257/504: Carbon dioxide
- B01D 2257/702: Hydrocarbons
- B01D 2257/80: Water
- C01B 2203/042: Purification by adsorption on solids
- C01B 2203/043: Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
- C01B 2203/0475: the impurity being carbon dioxide
- Y02C 20/40: of CO2
- Y02P 20/151: Reduction of greenhouse gas [GHG] emissions, e.g. CO2
- Y02P 20/50: Improvements relating to the production of bulk chemicals
- Y02P 30/00: Technologies relating to oil refining and petrochemical industry
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- Y02C: CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The problem of providing a metal complex having excellent gas adsorption performance, gas storage performance, and gas separation performance is solved by a metal complex comprising a dicarboxylic acid compound (I) including 20 to 99 mole % of a dicarboxylic acid compound (I-1) selected from terephthalic acid derivatives having an electron-donating group in the 2nd position such as 2-methoxyterephthalic acid, 2-methylterephthalic acid, and terephthalic acid, and 80 to 1 mole % of a dicarboxylic acid compound (I-2) selected from terephthalic acid derivatives having an electron-withdrawing group in the 2nd position such as 2-nitroterephthalic acid, 2-fluoroterephthalic acid, 2-chloroterephthalic acid, 2-bromoterephthalic acid, and 2-iodoterephthalic acid; at least one kind of metal ion selected from metal ions belonging to Group 2 and Groups 7 to 12 of the periodic table; and an organic ligand capable of bidentate binding to the metal ion.

## Claims

### Claim 1

A metal complex comprising:
two different dicarboxylic acid compounds (I-1) and (I-2) each of which is a dicarboxylic acid compound (I) of formula (I),
wherein
X is a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group, a formyl group, an acyloxy group, an alkoxycarbonyl group, a nitro group, an amino group, a monoalkyl amino group, a dialkyl amino group, an acylamino group, or a halogen atom,
R1, R2, and R3 are the same or different, and are each independently a hydrogen atom, an alkyl group that may have a substituent, or a halogen atom, and
X of the dicarboxylic acid compound (I-1) is an electron-donating group, and X of the dicarboxylic acid compound (I-2) is an electron-withdrawing group;
at least one kind of metal ion selected from metal ions belonging to Group 2 and Groups 7 to 12 of the periodic table; and
an organic ligand capable of bidentate binding to the metal ion, wherein a molar ratio of the dicarboxylic acid compound (I-1) to the dicarboxylic acid compound (I-2) is from 20:80 to 99:1.

### Claim 2 (depends on 1)

The metal complex according to claim 1, wherein
X of the dicarboxylic acid compound (I-1) is an alkyl group that may have a substituent, an alkoxy group or hydrogen atom, and
X of the dicarboxylic acid compound (I-2) is a formyl group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a hydrogen atom,
unless X of the dicarboxylic acid compound (I-1) and X of the dicarboxylic acid compound (1-2) are hydrogen atoms simultaneously.

### Claim 3 (depends on 1)

The metal complex according to claim 1, wherein a combination of the dicarboxylic acid compound (I-1) and the dicarboxylic acid compound (I-2) is selected from the group consisting of 2-methoxyterephthalic acid and 2-nitroterephthalic acid, 2-methylterephthalic acid and 2-nitroterephthalic acid, 2-methoxyterephthalic acid and terephthalic acid, 2-methylterephthalic acid and terephthalic acid, terephthalic acid and 2-nitroterephthalic acid, terephthalic acid and 2-fluoroterephthalic acid, terephthalic acid and 2-chloroterephthalic acid, terephthalic acid and 2-bromoterephthalic acid, and terephthalic acid and 2-iodoterephthalic acid.

### Claim 4 (depends on 1)

The metal complex according to claim 1, wherein the organic ligand capable of bidentate binding is at least one selected from the group consisting of 4,4′-bipyridyl, 2,2′-dimethyl-4,4′-bipyridine, 1,2-bis(4-pyridyl)ethyne, 1,4-bis(4-pyridyl)butadiyne, 1,4-bis(4-pyridyl)benzene, 3,6-di(4-pyridyl)-1,2,4,5-tetrazine, 2,2′-bi-1,6-naphthyridine, phenazine, diazapyrene, trans-1,2-bis(4-pyridyl)ethene, 4,4′-azopyridine, 1,2-bis(4-pyridyl)ethane, 4,4′-dipyridyl sulfide, 1,3-bis(4-pyridyl)propane, 1,2-bis(4-pyridyl)glycol, N-(4-pyridyl)isonicotinamide, 2,6-di(4-pyridyl)benzo[1,2-c:4,5-c′] dipyrrol-1,3,5,7(2H,6H)-tetrone, 4,4′-bis(4-pyridyl)biphenylene, and N,N′-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide.

### Claim 5 (depends on 1)

The metal complex according to claim 1, wherein the metal ion is a copper ion or a zinc ion.

### Claim 6 (depends on 1)

The metal complex according to claim 1, wherein a ratio of the dicarboxylic acid compound (I) to the organic ligand capable of bidentate binding, both forming the metal complex, is 2:1.

### Claim 7 (depends on 1)

An adsorbent material comprising the metal complex according to claim 1.

### Claim 8 (depends on 7)

The adsorbent material according to claim 7, wherein the adsorbent material is an adsorbent material suitable for adsorbing carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, noble gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane, water vapor, or organic vapor.

### Claim 9 (depends on 1)

A storage material comprising the metal complex according to claim 1.

### Claim 10 (depends on 9)

The storage material according to claim 9, wherein the storage material is a storage material suitable for storing carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, noble gas, hydrogen sulfide, ammonia, water vapor, or organic vapor.

### Claim 11 (depends on 9)

A gas storage device comprising a pressure-resistant container and a gas storage space inside the pressure-resistant container, wherein the pressure-resistant container can be made airtight and has an outlet and an inlet for a gas, and the storage material according to claim 9 is in the gas storage space.

### Claim 12 (depends on 11)

A gas-fueled automobile comprising an internal-combustion engine that obtains a driving force from a fuel gas supplied from the gas storage device according to claim 11.

### Claim 13 (depends on 1)

A separating material comprising the metal complex according to claim 1.

### Claim 14 (depends on 13)

The separating material according to claim 13, wherein the separating material is a separating material suitable for separating carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbon having 1 to 4 carbon atoms, noble gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane, water vapor, or organic vapor.

### Claim 15 (depends on 13)

The separating material according to claim 13, wherein the separating material is a separating material suitable 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, ethylene and acetylene, nitrogen and methane, or air and methane.

### Claim 16 (depends on 13)

A separation method, comprising separating with the separating material according to claim 13, by contacting the metal complex and a mixed gas in a pressure range from 0.01 MPa to 10 MPa.

### Claim 17 (depends on 16)

The separation method according to claim 16, wherein the separation method is a pressure swing adsorption process or a temperature swing adsorption process.

### Claim 18 (depends on 1)

A method for producing the metal complex according to claim 1, comprising reacting, in a solvent, the dicarboxylic acid compound (I), the metal ion, and the organic ligand to precipitate the metal complex.