Kinetic Modeling of Quinoline Hydrodenitrogenation over a NiMo(P)/Al₂O₃ Catalyst in a Batch Reactor

Abstract

A kinetic study of the hydrodenitrogenation of quinoline is performed in a batch reactor, over a NiMo(P)/γ-Al 2 O 3 sulfide catalyst, in the range of temperature of 340−360 °C and concentration of 1−2 wt % of quinoline. Liquid−vapor mass transfer is considered in the reactor model, and the kinetic expression using Langmuir−Hinshelwood model considers competitive adsorption of reactants, products, and solvents. The activation energies of every elementary reaction and adsorption enthalpies of nitrogen compounds are calculated. The kinetic modeling shows that the hydrogenation of 1,2,3,4tetrahydroquinoline into decahydroquinoline is the rate-determining step of the principal reaction pathway. The self-inhibition effect due to competitive adsorption of nitrogen-containing compounds is confirmed. The adsorption constants of nitrogen compounds decrease in the order saturated amines > NH 3 > aromatic amines, showing that their adsorption strength is related to the basicity of molecules. Moreover, the kinetic model is validated by an additional experiment using ammonia as an inhibitor.

Copper-Organic Framework-Derived Porous Nanorods for Chemoselective Hydrogenation of Quinoline Compounds at an Aqueous/Oil Interface

“…The catalytic hydrogenation of quinoline has been reported to be a pseudo-first order with respect to quinoline concentration. 52 At first, the initial reaction rate constants (k) of Cu/C-600 at different reaction temperatures of 383, 393, and 403 K were calculated by plotting the values of ln(C/ C 0 ) (C = unconverted quinoline, initial quinoline) against variable reaction times (t) in the range of 1−3 h (Figure 9a). From an Arrhenius plot of the data (Figure 9b), the apparent activation energy (E a ) was estimated to be 49.55 kJ/mol, which is comparable to and even lower than previously reported E a values using precious metal catalysts for the same reaction, e.g., supported Pd NPs: 41.1 kJ/mol, 53 RuCl 2 (PPh 3 ) 3 : 79.1 kJ/ mol, 54 and AuPd: 20−55 kJ/mol.…”

Promotion of C-S Bond Scission over Solid Catalytic Sulfides by Aromatics and Nitrogen Heterocycles

“…The second hypothesis is that the hydrogenation-dehydrogenation equilibrium established in the first step of the hydrotreating reaction sequence for the naphthalene 8,23 , indole 24 , and quinoline 25,26 could supply additional surface hydrogen for the C-S bond scission reaction. The reactions networks of the hydrogenations of quinoline, indole, and naphthalene are presented in the Supporting Information (Section S3).…”

Promotion of C-S Bond Scission over Solid Catalytic Sulfides by Aromatics and Nitrogen Heterocycles

“…The second hypothesis is that the hydrogenation-dehydrogenation equilibrium established in the first step of the hydrotreating reaction sequence for the naphthalene 8,23 , indole 24 , and quinoline 25,26 could supply additional surface hydrogen for the C-S bond scission reaction. The reactions networks of the hydrogenations of quinoline, indole, and naphthalene are presented in the Supporting Information (Section S3).…”