Metal complex, adsorbent, separating material, and 1, 3-butadiene separation method
View Patent ↗A separating material superior to conventional separating materials, and a separation method are provided, with which 1,3-butadiene is selectively separated and recovered from a mixed gas including 1,3-butadiene and C4 hydrocarbons other than 1,3-butadiene. A metal complex, which comprises a dicarboxylic acid compound (I) (see (I) below) represented by general formula (I), an ion of a metal such as beryllium, and a dipyridyl compound (II) represented by general formula (II), namely L-Z-L (II) (see L below), is characterized by including, as the dipyridyl compound (II), at least two different dipyridyl compounds (II). The metal complex is used as a 1,3-butadiene separating material. Formula (I) L is represented by any of the compounds below.
1. A metal complex consisting of:
a dicarboxylic acid compound (I) represented by the following general formula (I):
wherein X represents a carbon atom or nitrogen atom, Y represents a hydrogen atom, optionally substituted alkyl group having 1 to 4 carbon atoms, alkenyl group having 2 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, formyl group, acyloxy group having 2 to 4 carbon atoms, hydroxyl group, alkoxycarbonyl group having 2 to 4 carbon atoms, nitro group, cyano group, amino group, monoalkylamino group having 1 to 4 carbon atoms, dialkylamino group having 2 to 4 carbon atoms, acylamino group having 2 to 4 carbon atoms, sulfo group, sulfonate group or halogen atom in the case X represents a carbon atom or Y is not present in the case X represents a nitrogen atom, and R 1 , R 2 and R 3 respectively and independently represent a hydrogen atom, optionally substituted alkyl group having 1 to 4 carbon atoms or halogen atom;
an ion of at least one type of metal 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; and,
a dipyridyl compound (II) represented by the following general formula (II):
L-Z-L (II)
wherein L is represented by any of the following formulas:
wherein R 4 , R 5 , R 6 and R 7 respectively and independently represent a hydrogen atom, alkyl group having 1 to 4 carbon atoms or a halogen atom, and Z represents —CR 8 R 9 —CR 10 R 11 — (wherein R 8 , R 9 , R 10 and R 11 respectively and independently represent a hydrogen atom, alkyl group having 1 to 4 carbon atoms, hydroxyl group or halogen atom), an alkylene group having 3 to 4 carbon atoms, —CH═CH—, —C≡C—, —S—S—, —N═N—, —O—CH 2 —, —NH—CH 2 —or —NHCO—);
wherein two or more different types of the dipyridyl compound (II) are contained as the dipyridyl compound (II), and only one type of the dicarboxylic acid compound (I) is contained as the dicarboxylic acid compound (I), and
wherein the metal complex has a three-dimensional structure that is a multiply interpenetrating pseudo-diamondoid framework.
2. The metal complex according to claim 1 , wherein Z in the general formula (II) is —CR 8 R 9 —CR 10 R 11 —(wherein R 8 , R 9 , R 10 and R 11 respectively and independently represent a hydrogen atom, alkyl group having 1 to 4 carbon atoms, hydroxyl group or halogen atom), an alkylene group having 3 to 4 carbon atoms, —CH═CH—, —S—S— or —NHCO—.
3. The metal complex according to claim 1 , wherein a combination of the dipyridyl compound (II) is any of 1,2-di(4-pyridyl)ethylene and 1,2-di(4-pyridyl)ethane, 1,2-di(4-pyridyl)ethylene and 1,2-di(4-pyridyl)ethylene glycol, 1,2-di(4-pyridyl)ethylene and 4,4′-dipyridyl disulfide or 1,2-di(4-pyridyl)ethylene and 1,3-di(4-pyridyl)propane.
4. The metal complex according to claim 1 , wherein the dicarboxylic acid compound (I) is one selected from the group consisting of isophthalic acid, 5-methylisophthalic acid and 5-nitroi sophthalic acid.
5. The metal complex according to claim 1 , wherein the metal ion is at least one selected from the group consisting of a cobalt ion, nickel ion and zinc ion.
6. An adsorbent comprising the metal complex according to claim 1 .
7. The adsorbent according to claim 6 , wherein the adsorbent is an adsorbent for adsorbing carbon dioxide, hydrogen gas, carbon monoxide, oxygen gas, nitrogen gas, hydrocarbons having 1 to 5 carbon atoms, rare gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane, water vapor or organic vapor.
8. A separating material comprising the metal complex according to claim 1 .
9. The separating material according to claim 8 , wherein the separating material selectively separates 1,3-butadiene from a mixed gas containing 1,3-butadiene and a hydrocarbon having four carbon atoms other than 1,3-butadiene.
10. The separating material according to claim 9 , wherein the hydrocarbon having four carbon atoms other than 1,3-butadiene is at least one selected from the group consisting of 1-butene, isobutene, trans-2-butene, cis-2-butene, isobutane and n-butane.
11. The separating material according to claim 8 , wherein the separating material is a separating material for separating carbon dioxide, hydrogen gas, carbon monoxide, oxygen gas, nitrogen gas, hydrocarbons having 1 to 5 carbon atoms, rare gas, hydrogen sulfide, ammonia, sulfur oxide, nitrogen oxide, siloxane, water vapor or organic vapor.
12. A separation membrane comprising a porous support and the separating material according to claim 8 attached to the surface of the porous support.
13. A separation membrane comprising a polymeric material and the separating material according to claim 8 kneaded and dispersed in the polymeric material.
14. A method for producing the metal complex according to claim 1 , comprising reacting a salt of at least one type of metal 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, the dicarboxylic acid compound (I), and two or more types of the dipyridyl compound (II) and precipitating a metal complex, wherein wet grinding is carried out during the reaction.
15. A 1,3-butadiene separation method comprising: an adsorption step for contacting a separating material with a mixed gas containing 1,3-butadiene and a hydrocarbon having four carbon atoms other than 1,3-butadiene and selectively adsorbing 1,3-butadiene onto the separating material, followed by a regeneration step for desorbing the 1,3-butadiene adsorbed onto the separating material from the separating material and capturing the released 1,3-butadiene, wherein the separating material is the separating material according to claim 8 .
16. The metal complex according to claim 2 , wherein a combination of the dipyridyl compound (II) is any of 1,2-di(4-pyridyl)ethylene and 1,2-di(4-pyridyl)ethane, 1,2-di(4-pyridyl)ethylene and 1,2-di(4-pyridyl)ethylene glycol, 1,2-di(4-pyridyl)ethylene and 4,4′-dipyridyl disulfide or 1,2-di(4-pyridyl)ethylene and 1,3-di(4-pyridyl)propane.