Products, Pathways, and Kinetics for Catalytic Hydrodenitrogenation of
Quinoline in Hydrothermal Condition
Abstract
This study focuses on mechanism and kinetics in catalytic
hydrodenitrogenation(HDN) of quinoline under hydrothermal conditions
(300, 350 and 400°C), in which 30% Ni-Ru/γ-Al2O3 serves as catalyst and
formic acid(FA) is used for in-situ H2 generation. The major products
were 1,2,3,4 tetrahydroquinoline, dehydroquinoline, aniline, methyl
aniline, 2-hexene, toluene. The quinoline conversion rate followed
first-order kinetics, and the activation energy was 41.72 kJ/mol. A
kinetic model based on the reaction network of hydrodenitrogenation of
quinoline clearly captures all of the trends in the data and fits the
temporal variation of all major products. Results reveal that
1,2,3,4-tetrahydroquinoline→dehydroquinoline→2-hexene is the main
quinoline HDN route. Reaction rate analysis illustrates deamination is
the main denitrogenation pathway. Sensitivity analysis demonstrated that
the production of aniline derivatives inhibits yield of quinoline
derivatives. TEM characterization indicates that nickel and ruthenium
metal are uniformly distributed on the supporter, which was confirmed by
XRD and XPS characterization as well.