Gas separation material using metal complex and gas separation method

1. A gas separating material that selectively separates a target gas defined as a hydrocarbon gas having a carbon-carbon double bond and having 2 or 4 carbon atoms from a mixed gas containing the target gas and a hydrocarbon gas having the same number of carbon atoms as the target gas, comprising a metal complex of:

2,3-pyrazinedicarboxylic acid;

at least one metal M ion selected from the group consisting of copper, zinc, and cadmium;

an organic ligand (B) capable of bidentate coordination to the metal ion, represented by the following general formula (2):

wherein the organic ligand (B) capable of bidentate coordination is 1,2-di(4-pyridyl)ethane represented by the general formula (2) wherein all of R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are hydrogen atoms, and X is —CH 2 —CH 2 —, or 1,3-di(4-pyridyl)propane represented by the general formula (2) wherein all of R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are hydrogen atoms, and X is —CH 2 —CH 2 —CH 2 —; and

the composition thereof is the following composition formula (I):

M 2+ 2 A 2− 2 B  (I)

wherein M 2+ is an ion of the metal M, A 2− is 2,3-pyrazinedicarboxylate dianion, and B is an organic ligand (B) capable of bidentate coordination to the metal ion, and wherein the target gas is ethylene or 1,3-butadiene.

2. A method for separating a hydrocarbon gas having a carbon-carbon double bond and having 2 or 4 carbon atoms, the method comprising an adsorption step of bringing a mixed gas containing a target gas defined as a hydrocarbon gas having a carbon-carbon double bond and having 2 or 4 carbon atoms and a hydrocarbon gas having the same number of carbon atoms as the target gas into contact with a separating material to selectively adsorb the target gas on the separating material, and a subsequent regeneration step of desorbing the target gas adsorbed to the separating material from the separating material and collecting the target gas desorbed to separate the hydrocarbon gas having a carbon-carbon double bond and having 2 or 4 carbon atoms from the mixed gas, wherein the separating material comprises a metal complex of:

2,3-pyrazinedicarboxylic acid;

at least one metal M ion selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, titanium, vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, zinc, and cadmium;

an organic ligand (B) capable of bidentate coordination to the metal ion, represented by the following general formula (1):

or the following general formula (2):

wherein X is any of —CH 2 —, —CH 2 —CH 2 —, —CH 2 —CH 2 —CH 2 —, —CH═CH—, —C≡C—, —O—, —S—, —S—S—, —N═N—, or —NHCO—, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 each of which may be the same or different, and are any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms that may have a substituent, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a formyl group, an acyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group, a cyano group, an amino group, a monoalkyl amino group having 1 to 4 carbon atoms, a dialkyl amino group having 2 to 4 carbon atoms, an acylamino group having 2 to 4 carbon atoms, or a halogen atom; and

the composition thereof is the following composition formula (I):

M 2+ 2 A 2− 2 B  (I)

wherein M 2+ is an ion of the metal M, A 2− is 2,3-pyrazinedicarboxylate dianion, and B is an organic ligand (B) capable of bidentate coordination to the metal ion.

3. The separation method according to claim 2 , wherein the target gas is ethylene, and the hydrocarbon gas having the same number of carbon atoms as the target gas is ethane.

4. The separation method according to claim 2 , wherein the target gas is 1,3-butadiene, and the hydrocarbon gas having the same number of carbon atoms as the target gas is 1-butene, normal butane, or a mixture thereof.

5. The separation method according to claim 2 , wherein the separation method is pressure swing adsorption.

6. The separation method according to claim 2 , wherein the separation method is temperature swing adsorption.

7. A method for separating a hydrocarbon gas having a carbon-carbon double bond and having 2 or 4 carbon atoms, the method comprising a step of bringing a mixed gas containing a target gas defined as a hydrocarbon gas having a carbon-carbon double bond and having 2 or 4 carbon atoms and a hydrocarbon gas having the same number of carbon atoms as the target gas into contact a separation membrane to selectively permeate the target gas through the separation membrane, thereby obtaining a gas with a higher concentration of the target gas than the mixed gas, wherein the separation membrane comprises a porous support and a gas separating material deposited on a surface portion of the porous support,

wherein the separating material comprises a metal complex of:

2,3-pyrazinedicarboxylic acid;

at least one metal M ion selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, titanium, vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, zinc, and cadmium;

an organic ligand (B) capable of bidentate coordination to the metal ion, represented by the following general formula (1):

or the following general formula (2):

wherein X is any of —CH 2 —, —CH 2 —CH 2 —, —CH 2 —CH 2 —CH 2 —, —CH═CH—, —C≡C—, —O—, —S—, —S—S—, —N═N—, or —NHCO—, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 each of which may be the same or different, and are any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms that may have a substituent, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a formyl group, an acyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group, a cyano group, an amino group, a monoalkyl amino group having 1 to 4 carbon atoms, a dialkyl amino group having 2 to 4 carbon atoms, an acylamino group having 2 to 4 carbon atoms, or a halogen atom; and

the composition thereof is the following composition formula (I):

M 2+ 2 A 2− 2 B  (I)

wherein M 2+ is an ion of the metal M, A 2− is 2,3-pyrazinedicarboxylate dianion, and B is an organic ligand (B) capable of bidentate coordination to the metal ion.

8. A method for separating a hydrocarbon gas having a carbon-carbon double bond and having 2 or 4 carbon atoms, the method comprising a step of bringing a mixed gas containing a target gas defined as a hydrocarbon gas having a carbon-carbon double bond and having 2 or 4 carbon atoms and a hydrocarbon gas having the same number of carbon atoms as the target gas into contact a separation membrane to selectively permeate the target gas through the separation membrane, thereby obtaining a gas with a higher concentration of the target gas than the mixed gas, wherein the separation membrane comprises a polymer material and a gas separating material mixed and dispersed in the polymer material,

wherein the separating material comprises a metal complex of:

2,3-pyrazinedicarboxylic acid;

at least one metal M ion selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, titanium, vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, zinc, and cadmium;

an organic ligand (B) capable of bidentate coordination to the metal ion, represented by the following general formula (1):

or the following general formula (2):

wherein X is any of —CH 2 —, —CH 2 —CH 2 —, —CH 2 —CH 2 —CH 2 —, —CH═CH—, —C≡C—, —O—, —S—, —S—S—, —N═N—, or —NHCO—, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 each of which may be the same or different, and are any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms that may have a substituent, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a formyl group, an acyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group, a cyano group, an amino group, a monoalkyl amino group having 1 to 4 carbon atoms, a dialkyl amino group having 2 to 4 carbon atoms, an acylamino group having 2 to 4 carbon atoms, or a halogen atom; and

the composition thereof is the following composition formula (I):

M 2+ 2 A 2− 2 B  (I)

wherein M 2+ is an ion of the metal M, A 2− is 2,3-pyrazinedicarboxylate dianion, and B is an organic ligand (B) capable of bidentate coordination to the metal ion.

9. The separation method according to claim 2 , wherein the target gas is ethylene or 1,3-butadiene.

10. The separation method according to claim 2 , wherein the metal M is at least one selected from the group consisting of copper, zinc, and cadmium.

11. The separation method according to claim 2 , wherein the metal M is copper.

12. The separation method according to claim 2 , wherein the organic ligand (B) capable of bidentate coordination is pyrazine represented by the general formula (1) wherein all of R 1 , R 2 , R 3 , and R 4 are hydrogen atoms.

13. The separation method according to claim 2 , wherein the organic ligand (B) capable of bidentate coordination is 1,2-di(4-pyridyl)ethane represented by the general formula (2) wherein all of R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are hydrogen atoms, and X is —CH 2 —CH 2 —, or 1,3-di(4-pyridyl)propane represented by the general formula (2) wherein all of R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are hydrogen atoms, and X is —CH 2 —CH 2 —CH 2 —.