Kinetic modeling of the hydrotreatment of light cycle oil and heavy gas oil using the structural contributions approach

The kinetics of the hydrodesulfurization of light cycle oil (LCO) and heavy gas oil (HGO) over a CoMo/Al2O3 catalyst were investigated in a perfectly mixed flow reactor with stationary basket of the Robinson-Mahoney type at temperatures of 330, 310 and 290 °C, H2/HC molar ratios of 2.8, 3.6 and 7.2 and a pressure of 65 bar. Hougen-Watson type rate equations were derived for the conversion of dibenzothiophene, substituted (di)benzothiophene and their products. To avoid having to deal with a huge number of model parameters, a methodology based upon structural contributions was applied. In the absence of own kinetic data on key components a number of kinetic and adsorption parameters were taken from published work on a very similar catalyst. For a given value of H2/HC only a small number of experiments was required to determine the value of the very complex denominators DENσ and DENτ appearing in the rate equations for the hydrodesulfurization of LCO and of HGO and of their evolution with the conversion of the feedstock. With the rate equations constructed in this way the calculated total conversion of DBT, its conversion into biphenyl and into cyclohexylbenzene were in excellent agreement with the experimental values.