Langmuir-Hinshelwood kinetics catalytic reaction rate data

The reaction progress is monitored ofF-Une by HPLC. Flow rates, residence times and initial concentrations of 4-chlorophenol are varied and kinetic parameters are calculated from the data obtained. It can be shown that the photocatalytic reaction is governed by Langmuir-Hinshelwood kinetics. The calculation of Damkohler numbers shows that no mass transfer limitation exists in the microreactor, hence the calculated kinetic data really represent the intrinsic kinetics of the reaction. Photonic efficiencies in the microreactor are still somewhat lower than in batch-type slurry reactors. This finding is indicative of the need to improve the catalytic activity of the deposited photocatalyst in comparison with commercially available catalysts such as Degussa P25 and Sachtleben Hombikat UV 100. The illuminated specific surface area in the microchannel reactor surpasses that of conventional photocatalytic reactors by a factor of 4-400 depending on the particular conventional reactor type. 

Langmuir-Hinshelwood rate expressions of all the reactions of the network were used in the kinetic modeling of the HDN of quinoline by Satterfield et al. (80, 81, 88). Their assumption that there is a single catalytic site for all reactions is too simple. Nevertheless, they collected an impressive body of kinetic data and pinpointed the reactions that were close to equilibrium and those which were kinetically significant. Gioia and Lee (100) extended these studies to higher pressures (up to 15 MPa H2). Only one model survived their regression analysis of the kinetic data. In this model, it was necessary to assume that 1,2,3,4-THQ reacted directly not only to o-propylaniline but also to propylbenzene (PB) and propylcyclohexene (PCHE). Their analysis does not appear to be very reliable, however. First,... 

The pre-exponentials and the apparent activation energies corresponding to the rate coefficients ki, k2 and ks had to be estimated from the experimental data sets from fovir batch reactor and ten CSTR experiments. The initial concentration of reactant A and the temperature were varied. The kinetic rate equations of the catalytic reactions can be described by using the following so-called Langmuir-Hinshelwood Hougen-Watson equations. 

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