Molded article for hydrocarbon adsorption

Patent metadata

Field	Value
Publication number	US-9475032-B2
Application number	US-201414906818-A
Country	US
Kind code	B2
Filing date	Jul 1, 2014
Priority date	Jul 26, 2013
Publication date	Oct 25, 2016
Grant date	Oct 25, 2016

Abstract

Provided is a molded article for hydrocarbon adsorption, in which a porous metal complex, the structure of which may vary with adsorption and desorption of gases, can exhibit to a sufficient degree the adsorption and desorption capabilities inherent to the complex. This molded article for hydrocarbon adsorption is characterized by including (A) a metal complex constituted by metal ions, and organic ligands capable of bonding to the metal ions, and (B) a polymer binder component containing within its molecules a total of 0.3 mmol/g to 8.0 mmol/g, inclusive, of at least one functional group selected from group consisting of the carboxyl group, the hydroxyl group, amino groups, the mercapto group, epoxy groups, and the sulfo group.

First claim

The invention claimed is:

1. A molded article for hydrocarbon adsorption comprising a metal complex (A), composed of metal ions and organic ligands capable of bonding with the metal ions; and a polymer binder component (B), which contains at least one functional group selected from the group consisting of a carboxyl group, hydroxyl group, amino group, mercapto group, epoxy group and sulfo group at a total of 0.3 mmol/g to 8.0 mmol/g in a molecule thereof.

2. The molded article for hydrocarbon adsorption according to claim 1 , wherein a functional group of the polymer binder component (B) is a hydroxyl group or carboxyl group.

3. The molded article for hydrocarbon adsorption according to claim 1 , wherein the polymer binder component (B) is an ethylenic hydrocarbon polymer, polyester, polyamide or polyether.

4. The molded article for hydrocarbon adsorption according to claim 1 , wherein the polymer binder component (B) is a copolymer of a (meth)acrylic acid ester having 1 to 10 carbon atoms and (meth)acrylic acid.

5. The molded article for hydrocarbon adsorption according to claim 1 , which contains 50% by weight to 97% by weight of the metal complex (A).

6. The molded article for hydrocarbon adsorption according to claim 1 , wherein the organic ligands are at least one organic compound selected from the group consisting of the following (1) to (3):
organic ligand (1): an organic compound having two or more carboxyl groups and/or hydroxyl groups, not having a heterocyclic ring, and capable of bidentate coordination with the metal ions;
organic ligand (2): a saturated or unsaturated, monocyclic or polycyclic heterocyclic compound having a carboxyl group or hydroxyl group, having one heteroatom selected from N, O or S in a ring thereof, and capable of bidentate coordination with the metal ions; and
organic ligand (3): a saturated or unsaturated, monocyclic or polycyclic heterocyclic compound having two or more heteroatoms selected from the group consisting of N, O and S in one or a plurality of rings thereof, and capable of bidentate coordination with the metal ions.

7. The molded article for hydrocarbon adsorption according to claim 6 , wherein the organic ligand (1) is at least one type selected from the group consisting of an alkylene dicarboxylic acid compound having 4 to 20 carbon atoms, an alkenylene dicarboxylic acid compound having 4 to 20 carbon atoms, a dicarboxylic acid compound represented by the following general formulas (I) to (IV), and a hydroxycarboxylic acid compound represented by the following general formula (V):

wherein R 1 respectively and independently represents a hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, formyl group, acyloxy group having 1 to 4 carbon atoms, alkoxycarbonyl group having an alkoxy group having 1 to 4 carbon atoms, nitro group, cyano group, carboxyl group, amino group, monoalkylamino group having 1 to 4 carbon atoms, dialkylamino group having an alkyl group having 1 to 4 carbon atoms or acylamino group having 1 to 4 carbon atoms, and two or more of R 1 may condense to form a ring;

wherein R 2 respectively and independently represents a hydrogen atom, halogen atom or alkyl group having 1 to 4 carbon atoms, X represents a hydrogen atom, alkyl group having 1 to 4 carbon atoms, alkenyl group having 2 to 4 carbon atoms, alkynyl group having 2 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, nitro group, carboxyl group, hydroxyl group or amino group; and

wherein R 3 respectively and independently represents a hydrogen atom, alkyl group having 1 to 4 carbon atoms, alkenyl group having 2 to 4 carbon atoms, alkynyl group having 2 to 4 carbon atoms or alkoxy group having 1 to 4 carbon atoms.

8. The molded article for hydrocarbon adsorption according to claim 6 , wherein the organic ligand (2) is at least one type selected from the group consisting of compounds represented by the following general formulas (VI) to (VIII):

wherein R 3 respectively and independently represents a hydrogen atom, alkyl group having 1 to 4 carbon atoms, alkenyl group having 2 to 4 carbon atoms, alkynyl group having 2 to 4 carbon atoms or alkoxy group having 1 to 4 carbon atoms.

9. The molded article for hydrocarbon adsorption according to claim 6 , wherein the organic ligand (3) is at least one type selected from the group consisting of compounds represented by the following general formulas (IX) to (XII):

wherein Y represents an oxygen atom, sulfur atom, —CH 2 —, —CH(OH)—, —CO—, —NH—, —C 2 N 4 —, —C≡C—, —C 2 H 2 — or —C 6 H 4 —, R 4 respectively and independently represents a hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, formyl group, acyloxy group having 1 to 4 carbon atoms, alkoxycarbonyl group having an alkoxy group having 1 to 4 carbon atoms, nitro group, cyano group, carboxyl group, amino group, monoalkylamino group having 1 to 4 carbon atoms, dialkylamino group having an alkyl group having 1 to 4 carbon atoms or acylamino group having 1 to 4 carbon atoms, and n is an integer of 0 to 3.

10. The molded article for hydrocarbon adsorption according to claim 1 , wherein the metal ions are a copper ion or zinc ion.

11. The molded article for hydrocarbon adsorption according to claim 1 , wherein the hydrocarbon targeted for adsorption is a hydrocarbon having 2 to 5 carbon atoms.

12. The molded article for hydrocarbon adsorption according to claim 11 , wherein the hydrocarbon having 2 to 5 carbon atoms is 1,3-butadiene.

13. The molded article for hydrocarbon adsorption according to claim 1 , which is produced by a tableting method.

14. A method for producing a molded article for hydrocarbon adsorption, comprising annealing the molded article according to claim 1 obtained by tableting at a temperature equal to or higher than the glass transition temperature (Tg) of the polymer binder (B).

Assignees

• Showa Denko Kk

Inventors

• Watanabe Yoshihiro
• Kishida Keisuke
• Okumura Yoshikuni

Classifications

• B01J20/2803

  Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products · CPC title

• B01J20/3007

  Moulding, shaping or extruding · CPC title

• B01J20/226

  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) · CPC title

• C07F1/08

  Copper compounds · CPC title

• C07F3/06

  Zinc compounds · CPC title