Diene production method
A method for producing diene comprises a step 1 of obtaining a straight chain internal olefin by removing a branched olefin from a raw material including at least the branched olefin and a straight chain olefin; and a step 2 of producing diene from the internal olefin by oxidative dehydrogenation using a first catalyst and a second catalyst, and the first catalyst has a complex oxide including bismuth, molybdenum and oxygen, and the second catalyst includes at least one selected from the group consisting of silica and alumina.
1. A method for producing diene, comprising:
obtaining a straight chain internal olefin by removing a branched olefin from a raw material including at least the branched olefin and a straight chain olefin; and
producing diene from the internal olefin by oxidative dehydrogenation using a dehydrogenation catalyst and an isomerization catalyst,
wherein
the dehydrogenation catalyst has a complex oxide including bismuth, molybdenum and oxygen, and
the isomerization catalyst includes at least one selected from the group consisting of silica-alumina and zeolites, and
a volume ratio between the dehydrogenation catalyst and the isomerization catalyst (volume of the dehydrogenation catalyst/volume of the isomerization catalyst) is 1.5 to 20.
2. The method for producing diene according to claim 1 , wherein
at least a part of the straight chain olefin is a terminal olefin, and
in obtaining the straight chain internal olefin, reactive distillation is performed to remove the branched olefin from the raw material and to isomerize the terminal olefin to the internal olefin.
3. The method for producing diene according to claim 1 , wherein
the isomerization catalyst has a support and an element supported on the support,
the support includes at least one selected from the group consisting of silica and alumina, and
the element supported on the support is at least one selected from the group consisting of Group 10 elements of the periodic table and Group 11 elements of the periodic table, and lanthanoids.
4. The method for producing diene according to claim 3 , wherein Ni is the Group 10 element of the periodic table, Cu, Ag or Au is the Group 11 element of the periodic table, and La is the lanthanoid.
5. The method for producing diene according to claim 3 , wherein Ag is supported on the support as the Group 11 element of the periodic table.
6. The method for producing diene according to claim 1 ,
wherein the isomerization catalyst includes silica and alumina, and
a total acid amount of the isomerization catalyst measured by ammonia temperature programmed desorption is 0.11 mmol/g or less.
7. The method for producing diene according to claim 1 ,
wherein the isomerization catalyst includes silica and alumina, and
the isomerization catalyst has a ratio A 2 /A 1 of 0.03 or more of an amount A 2 of acid sites measured in a temperature range of 600° C. or higher to an amount A 1 of all acid sites measured by ammonia temperature programmed desorption.
8. The method for producing diene according to claim 1 , wherein
the isomerization catalyst includes silica and alumina, and
a molar ratio of Si to Al (Si/Al) in the second catalyst is 100 or more.
9. The method for producing diene according to claim 1 , wherein
assuming that a mass content of the branched olefin in the raw material is C 1 and a mass content of the straight chain olefin in the raw material is C 2 ,
C 2 /C 1 is 0.1 to 5.0.
10. The method for producing diene according to claim 1 , wherein
the straight chain olefin includes butene.
11. The method for producing diene according to claim 1 , wherein
the raw material is obtained by fluid catalytic cracking of a heavy oil fraction, and
a number of carbon atoms of the branched olefin or the straight chain olefin is 4.
12. The method for producing diene according to claim 1 , wherein
the raw material is obtained by thermal decomposition of naphtha, and
a number of carbon atoms of the branched olefin or the straight chain olefin is 4.