Separation method for halogenated unsaturated carbon compound

Patent metadata

Field	Value
Publication number	US-10654775-B2
Application number	US-201615748362-A
Country	US
Kind code	B2
Filing date	Jun 15, 2016
Priority date	Aug 17, 2015
Publication date	May 19, 2020
Grant date	May 19, 2020

Abstract

The method according to this disclosure is a method for separating an unsaturated hydrocarbon having 2 or 3 carbon atoms and a halogenated unsaturated carbon compound formed by replacing at least one of hydrogen atoms included in the unsaturated hydrocarbon with a fluorine atom, from each other and is a method for selectively adsorbing either the unsaturated hydrocarbon or the halogenated unsaturated carbon compound by a porous coordination polymer that includes a metallic ion having a valence of 2 to 4 and an aromatic anion having 1 to 6 aromatic ring(s).

First claim

The invention claimed is:

1. A method for separating an unsaturated hydrocarbon having 2 or 3 carbon atoms and a halogenated unsaturated carbon compound having 2 or 3 carbon atoms from each other, the method comprising:
contacting a porous coordination polymer with a mixture including both the unsaturated hydrocarbon having 2 or 3 carbon atoms and the halogenated unsaturated carbon compound having 2 or 3 carbon atoms, wherein
either the unsaturated hydrocarbon or the halogenated unsaturated carbon compound is selectively adsorbed to the porous coordination polymer, and
the porous coordination polymer is represented by a composition formula [Cr 3 O(OH)(bdc) 3 ] where bdc is 1,4-benzenedicarboxylate, [Zr 6 O 4 (OH) 4 (bpdc) 6 ] where bpdc is 4,4′-biphenyldicarboxylate, or [Ni 2 (dhtp)] where dhtp is 2,5-dihydroxyterephthalate.

2. A method for purifying a halogenated unsaturated carbon compound having 2 or 3 carbon atoms by use of the method for separating the unsaturated hydrocarbon and the halogenated unsaturated carbon compound according to claim 1 , the method comprising:
selectively adsorbing either the unsaturated hydrocarbon or the halogenated unsaturated carbon compound to the porous coordination polymer; and
taking out another one of the unsaturated hydrocarbon and the halogenated unsaturated carbon compound.

3. The method according to claim 1 , wherein
the unsaturated hydrocarbon is ethylene, and wherein
the halogenated unsaturated carbon compound is one or more compound(s) selected from a group consisting of difluoroethylene, trifluoroethylene, tetrafluoroethylene, and hexafluoropropylene.

4. The method according to claim 1 , wherein
the porous coordination polymer is [Ni 2 (dhtp)],
a specific surface area of the porous coordination polymer is 1,000 to 2,000 m 2 /g, and wherein
either the unsaturated hydrocarbon or the halogenated unsaturated carbon compound is selectively adsorbed to the porous coordination polymer under a condition of an adsorption gas pressure of 50 kPa, that is an absolute pressure, or lower.

5. The method according to claim 1 , wherein the porous coordination polymer is [Cr 3 O(OH)(bdc) 3 ] or [Zr 6 O 4 (OH) 4 (bpdc) 6 ],
a specific surface area of the porous coordination polymer is 2,000 to 3,000 m 2 /g, and wherein
either the unsaturated hydrocarbon or the halogenated unsaturated carbon compound is selectively adsorbed to the porous coordination polymer under a condition of an adsorption gas pressure of 50 to 250 kPa that is an absolute pressure.

6. A method for separating a plurality of halogenated unsaturated carbon compounds from each other that are different from each other and that each have 2 or 3 carbon atoms, the method comprising:
contacting a porous coordination polymer with a mixture including the plurality of halogenated unsaturated carbon compounds, wherein
any one of the plurality of halogenated unsaturated carbon compounds is selectively adsorbed to the porous coordination polymer, and
the porous coordination polymer is represented by a composition formula [Cr 3 O(OH)(bdc) 3 ] where bdc is 1,4-benzenedicarboxylate, [Zr 6 O 4 (OH) 4 (bpdc) 6 ] where bpdc is 4,4′-biphenyldicarboxylate, or [Ni 2 (dhtp)] where dhtp is 2,5-dihydroxyterephthalate.

7. A method for purifying a halogenated unsaturated carbon compound having 2 or 3 carbon atoms by use of the method for separating a plurality of halogenated unsaturated carbon compounds from each other according to claim 6 , the method comprising:
selectively adsorbing any one of the plurality of halogenated unsaturated carbon compounds to the porous coordination polymer; and
taking out the other halogenated unsaturated carbon compound.

8. The method according to claim 6 , wherein
the plurality of halogenated unsaturated carbon compounds comprise tetrafluoroethylene, and vinylidene fluoride or trifluoroethylene, and wherein
vinylidene fluoride or trifluoroethylene is selectively adsorbed to the porous coordination polymer.

9. A method of adsorbing or storing a halogenated unsaturated carbon compound having 2 or 3 carbon atoms, the method comprising:
contacting a porous coordination polymer with the halogenated unsaturated carbon compound, and
the porous coordination polymer is represented by a composition formula [Cr 3 O(OH)(bdc) 3 ] where bdc is 1,4-benzenedicarboxylate, [Zr 6 O 4 (OH) 4 (bpdc) 6 ] where bpdc is 4,4′-biphenyldicarboxylate, or [Ni 2 (dhtp)] where dhtp is 2,5-dihydroxyterephthalate.

10. The method according to claim 9 , wherein
the halogenated unsaturated carbon compound is one or more compound(s) selected from a group consisting of difluoroethylene, trifluoroethylene, tetrafluoroethylene, and hexafluoropropylene.

11. The method according to claim 9 , wherein
the porous coordination polymer is [Ni 2 (dhtp)],
a specific surface area of the porous coordination polymer is 1,000 to 2,000 m 2 /g, and wherein
the halogenated unsaturated carbon compound is adsorbed under a condition of an adsorption gas pressure of 100 kPa, that is an absolute pressure, or lower.

12. The method according to claim 9 , wherein
the porous coordination polymer is [Cr 3 O(OH)(bdc) 3 ] or [Zr 6 O 4 (OH) 4 (bpdc) 6 ],
a specific surface area of the porous coordination polymer is 2,000 to 3,000 m 2 /g, and wherein
the halogenated unsaturated carbon compound is adsorbed under a condition of an adsorption gas pressure of 100 to 800 kPa that is an absolute pressure.

Assignees

• Daikin Ind Ltd
• Univ Kyoto

Inventors

• Morikawa Tatsuya
• Shimokawa Mana
• Fujiwara Katsuki
• Tokuno Satoshi
• Higuchi Masakazu
• Kitagawa Susumu

Classifications

• C07C65/03

  monocyclic and having all hydroxy or O-metal groups bound to the ring · CPC title

• C07C63/28

  Salts thereof · CPC title

• B01J20/0237

  Compounds of Cu · CPC title

• B01J20/226 Primary

  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

• B01J20/0211

  Compounds of Ti, Zr, Hf · CPC title