A comparative kinetic study on ultra-deep hydrodesulfurization of pre-treated gas oil over nanosized MoS2, CoMo-sulfide, and commercial CoMo/Al2O3 catalysts

Unsupported nanosized MoS2 and CoMo-sulfide catalysts were synthesized, and their catalytic performances for the deep hydrodesulfurization (HDS) of treated gas oil were investigated as compared with that of a CoMo/Al2O3 catalyst. The HDS reactions were carried out in a batch autoclave reactor at 340 °C and 3 MPa H2. The CoMo-sulfide catalyst shows the highest activity and can reduce the sulfur content to less than 10 ppm. The decrease in total sulfur content as a function of reaction time was found to follow pseudo-second order kinetics (empirical form). The change in the concentration of some individual representative sulfur-containing species in gas oil as a function of time was found to follow pseudo-first-order kinetics. However, the change in combined concentration of these species in the gas oil during HDS with the reaction time was found to corroborate pseudo-second-order kinetics. A kinetic model approach was proposed from which an estimation of the intrinsic kinetic data can be achieved. The model fitted the obtained data reasonably well, suggesting its potential for better assessment of the catalytic activity in the HDS of real feedstock. The study reveals that ranking of catalyst activities using model refractory sulfur-containing compounds does not necessarily imply a typical rank in case of investigating the real feedstocks.

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► Synthesis of nanosized MoS2 and Co-promoted MoS2 catalysts.
► Kinetics of gas oil hydrodesulfurization.
► Nanosized catalysts show higher hydrodesulfurization activity than the commercial CoMo/Al2O3 catalyst.
► HDS results of sulfur-containing compounds do not necessarily be typical to that for real feedstock.