Hydrodesulfurization – Heterogeneous
V. Vanrysselberghe
ATOFINA Research SA, Seneffe (Feluy), Belgium
Search for more papers by this authorV. Vanrysselberghe
ATOFINA Research SA, Seneffe (Feluy), Belgium
Search for more papers by this authorAbstract
The article deals with hydrodesulfurization and hydrodearomatization of oil fractions.
In the first part the composition of hydrotreatment catalysts, their preparation, activation, and deactivation, and the nature of their active phase and its interaction with the reaction mixture are reviewed.
In the second part the article concentrates on various levels of kinetic modeling, extending from lumped first- or second-order models to sets of kinetic equations based on detailed reaction schemes of the process, distinguishing between the hydrogenolysis and the hydrogenation routes. A methodology for the kinetic modeling of the hydrodesulfurization of oil fractions is presented, in which the sulfur components are considered individually, instead of lumped. The rate equations of substituted S-containing components of the thiophenic families are related to those of the heads of the families or “parent” molecules through “structural contirbutions” entering into the kinetic and adsorption coefficients of the Hougen–Watson-type kinetic equations. These structural contributions are derived from experimental work on, eg, thiophenic model components such as (substituted) (di)benzothiophene. By way of example, the approach is applied to a complex mixture such as light cycle oil fractions and the extension to other fractions is outlined.
A one-dimensional heterogeneous plug-flow model is applied to the simulation of an adiabatic reactor for diesel hydrodesulfurization and hydrodearomatization. The kinetic equations of the S-removal are of the Hougen–Watson type and are based upon the structural contribution approach. The feasibility of achieving the drastic reduction in S-levels set by the new legislations is discussed.
Finally, flow schemes of industrial hydrotreatment processes are described.
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