Industrial & Engineering Chemistry Research, Vol.48, No.7, 3331-3340, 2009
Long-Term Deactivation of a Commercial CoMo/gamma-Al2O3 Catalyst in Hydrodesulfurization of a Naphtha Stream
Long-term deactivation of a commercial CoMo/gamma-Al2O3 catalyst used in the hydrodesulfurization of a naphtha stream was studied using 35 months of operating data of an industrial HDS fixed bed reactor. The major sulfur-containing species of the naphtha feed was identified as 2-ethyl-4-methylthiophene (2E4MT) based on GC-MS analysis. The characterization of the industrial catalysts was performed by BET, XRD, XRF, and HCN Leco analyses. The reaction rate constant of the gas-phase hydrodesulfurization reaction was calculated by fitting the industrial reactor conversion data to the Hougen-Watson rate equation, assuming that the surface reaction between the sulfur-containing species and adsorbed hydrogen is the rate-determining step. The effectiveness factor was similar to 0.91, nearly constant along the catalyst bed, implicitly implying that the HDS reaction is approximately first order in 2E4MT concentration. From the combined kinetics and characterization analyses, it was found that the main mechanisms of deactivation of the commercial HDS catalysts were (1) sulfur loss and coke deposition (recoverable by regeneration) and (2) Co-Mo-S permanent loss of activity. After 7 months of operation (before the first regeneration), the share of each deactivation mechanism in the loss of activity is (1) 81% and (2) 19%. The Co-Mo-S permanent loss of activity is assumed to be caused by arsenic poisoning, Co reaction with the alumina matrix, and decrease in the catalytic active surface area.