Method for producing olefin
The present invention provides a method for producing an olefin from a carboxylic acid having a β-hydrogen atom or an anhydride thereof in the presene of a catalyst containing at least one metal element selected from metals of Group 8, Group 9 and Group 10 and bromine element at a reaction temperature of 120° C. to 270° C.
1. A method for producing an olefin, comprising converting a carboxylic acid having a β-hydrogen atom or an anhydride thereof to an olefin in the presence of a catalyst, at a reaction temperature of 120° C. to 270° C.,
wherein said catalyst is selected from the group consisting of NiBr 2 , RhBr 3 , FeBr 2 , [Rh(CO) 2 Br] 2 , and a mixture of KBr and [Rh(CO) 2 Cl] 2 .
2. The method for producing an olefin according to claim 1 , wherein said catalyst is selected from the group consisting of NiBr 2 , RhBr 3 , and FeBr 2 .
3. The method for producing an olefin according to claim 2 , wherein said catalyst is NiBr 2 and an amount of said NiBr 2 is 0.00001 to 0.2 mol as Ni to one mole of the carboxylic acid having a β-hydrogen atom or an anhydride thereof.
4. The method for producing an olefin according to claim 2 , wherein said catalyst is NiBr 2 and an amount of said NiBr 2 is 0.001 to 0.04 mol as Ni to one mole of the carboxylic acid having a β-hydrogen atom or an anhydride thereof.
5. The method for producing an olefin according to claim 1 , wherein said catalyst is a mixture of KBr and [Rh(CO) 2 Cl] 2 .
6. The method for producing an olefin according to claim 5 , wherein an amount of said [Rh(CO) 2 Cl] 2 is 0.00001 to 0.2 mol as Rh to one mole of the carboxylic acid having a β-hydrogen atom or an anhydride thereof.
7. The method for producing an olefin according to claim 5 , wherein an amount of said [Rh(CO) 2 Cl] 2 is 0.001 to 0.03 mol as Rh to one mole of the carboxylic acid having a β-hydrogen atom or an anhydride thereof.
8. The method for producing an olefin according to claim 5 , wherein an amount of said KBr is 0.001 to 10 mol to one mole of said carboxylic acid having a β-hydrogen atom or an anhydride thereof.
9. The method for producing an olefin according to claim 5 , wherein an amount of said KBr is 0.05 to 2 mol to one mole of said carboxylic acid having a β-hydrogen atom or an anhydride thereof.
10. The method for producing an olefin according to claim 1 , wherein the catalyst further comprises an organophosphorous compound as a ligand compound.
11. The method for producing an olefin according to claim 10 , wherein the content of the ligand compound is 0.3 to 100 mol to one mole of a metal atom of Group 8, Group 9, and Group 10 in said catalyst.
12. The method for producing an olefin according to claim 1 , wherein the carboxylic acid having a β-hydrogen atom and the anhydride thereof are, respectively, represented by formula (i) and (ii):
wherein, R 1 represents a saturated or unsaturated hydrocarbon group having a β-hydrogen atom and 11 to 17 carbon atoms, and R 2 represents a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 17 carbon atoms.
13. The method for producing an olefin according to claim 1 , wherein said converting is conducted in the presence of a solvent which is selected from the group consisting of an aromatic hydrocarbon, an aliphatic hydrocarbon, an alicyclic hydrocarbon, an alcohol, an ether, maleic anhydride, phthalic anhydride, acetic anhydride, and acetic acid.
14. The method for producing an olefin according to claim 13 , wherein a weight ratio of a starting material/(a starting material+the solvent) is 1/26 to 1/1, wherein the starting material is the carboxylic acid having a β-hydrogen atom or an anhydride thereof.
15. The method for producing an olefin according to claim 2 , wherein said catalyst is RhBr 3 and an amount of said RhBr 3 is 0.00001 to 0.2 mol as Rh to one mole of the carboxylic acid having a β-hydrogen atom or an anhydride thereof.
16. The method for producing an olefin according to claim 2 , wherein said catalyst is RhBr 3 and an amount of said RhBr 3 is 0.001 to 0.04 mol as Rh to one mole of the carboxylic acid having a β-hydrogen atom or an anhydride thereof.
17. The method for producing an olefin according to claim 2 , wherein said catalyst is FeBr 2 and an amount of said FeBr 2 is 0.00001 to 0.2 mol as Fe to one mole of the carboxylic acid having a β-hydrogen atom or an anhydride thereof.
18. The method for producing an olefin according to claim 2 , wherein said catalyst is FeBr 2 and an amount of said FeBr 2 is 0.001 to 0.04 mol as Fe to one mole of the carboxylic acid having a β-hydrogen atom or an anhydride thereof.
19. The method for producing an olefin according to claim 1 , wherein said catalyst is [Rh(CO) 2 Br] 2 .