Reuse of Spent Hydrotreating Catalyst of the Middle Petroleum Fractions

Abstract

Reuse of spent hydrodesulphurization (HDS) of middle petroleum fractions catalyst CoMo/γAl2O3 was accomplished via removal of coke and contaminants such as vanadium, Iron, Nickel, and sulfur. Three processes were adopted; extraction, leaching, decoking. Soluble and insoluble coke was removed. Leaching step used three different solvents (oxalic acid, ammonium peroxydisulfate and oxalic acid + H2O2) in separate in order to remove contaminant metals (V, S, Ni and Fe). The effect of soluble coke removal on leaching step was studied. It was found that the removal of soluble coke significantly enhances the leaching of contaminants and barely affected the removal of active metals (Co and Mo). It was found that the best route (sequence) was soluble coke extraction followed by contaminants leaching then decoking process and the best leaching solvent was oxalic acid. According to this determination, the removed contaminants were 79.9 % for sulfur, 13.69% for vanadium, 82.27 % for iron, and 76.34 % for nickel. The active components loss accompanied with this process were 5.08 % for cobalt and 6.88% for molybdenum. Leaching process conditions (leaching solvent concentration, temperature and leaching time) were studied to determine the best-operating conditions. The rejuvenated catalyst activity was examined by a pilot scale HDS unit of naphtha. Sulfur content removal of naphtha was found to be 85.56 % for single pass operation under typical operating conditions of refinery HDS unit of naphtha which are 1 ml/min feed flow rate, 200 H2/HC ratio, 32 bar operating pressure and 320 °C operating temperature.

Keywords

• Catalyst rejuvenation, spent catalyst, Hydrodesulphurization, Extraction, Leaching, Catalyst activity.