The Kinetics of Hydrocarbon Cracking

A general kinetic model which describes the catalytic cracking of pure hydrocarbons is presented. The model includes a monomolecular cracking path based on the Langmuir adsorption isotherm as well as a bimolecular path, following Rideal kinetics, which accounts for the possibility of a chain cracking mechanism being involved. Catalyst decay is accounted for using the time-on-stream-decay function. Fitting of experimental data from n-nonane cracking on USHY at 673 K, combined with Monte Carlo simulations indicates that, in that case, the total catalytic activity could include between 0 and 90% of activity due to chain processes. This large margin of error stems from the combined effects of a large decay rate, forcing the experimenter to use average conversion data, and of experimental error. Fitting of the model to previously published cracking data for 2-methylpentane on USHY showed that the model lacks a suitable parameter to account for thermal reactions which were not accounted for in the original data set. This observation supports the impression that the model is sensitive to departures from the postulated mechanism. The above kinetic model has also been fitted to the results of n-nonane cracking at three temperatures as well as to previously published data for various other linear paraffins. 32 refs., 17 figs., 6 tabs.