Chemical Engineering Research & Design, Vol.121, 393-406, 2017
Refinery approach of bio-oils derived from fast pyrolysis of lignin to jet fuel range hydrocarbons: Reaction network development for catalytic conversion of cyclohexanone
This study demonstrated that the bio-oil derived from fast pyrolysis of lignin was excellent candidate to be converted into the jet and diesel fuel range hydrocarbons by catalytic upgrading process. This research addresses specifically the kinetic and mechanism of cyclohexanone conversion using sulfided CoMo/gamma-Al2O3 catalyst in a fixed-bed flow reactor. The main routes of cyclohexanone upgrading included hydrodeoxygenations (HDO), dehydrogenation, hydrogenation and coupling. The selectivity-conversion analyses at different operating condition indicate that benzene, cyclohexene, phenol, and 2-cyclohexen-1-one formed as primary products and the other main products, 2-methylphenol, cyclohexylbenzene, biphenyl, 2-phenylphenol, 2-cyclohexylcyclohexan-1-one, 2-cyclohexylidenecyclohexane-1-one and 2-cyclohexylphenol appeared as non-primary products. An approximate reaction network and a first order kinetic model are developed to determine kinetic parameters. Kinetic investigations indicate that among the various reactions on sulfided CoMo/Al2O3, HDO is characterized by the highest rate and that selectivities for oxygen removal are favored by operation at higher temperatures and pressures. The apparent activation energy for the HDO reaction that leads to benzene formation is approximately 35.6 kJ/mol; coupling is the reaction class characterized by the highest apparent activation energy. The pseudo-first-order rate constants for formation of the main products of cyclohexanone conversion decrease in the following order: benzene >2-cyclohexylidenecyclohexane-1-one > cyclohexylbenzene > 2-cyclohexen-1-one > 2-phenylphenol> phenol> cyclohexene > 2-cyclohexylphenol> 2-methylphenol> 2-cyclohexylcyclohexan-1-one > biphenyl. (C) 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.