Resurrection of the spent NiMo/Al2O3 catalyst for diesel hydrofining

Abstract

Spent catalysts from the hydrofining process are hazardous wastes, while their appropriate utilization can also bring enormous environmental and economic benefits. Herein, a chemical resurrection method was developed to resurrect and recycle the industrial spent NiMo/Al2O3 hydrofining catalyst. The spent catalysts are calcined to remove the carbon deposit followed by the treatment with citric acid (CA) and ethylene glycol (EG). The results show that the calcination can also accelerate the aggregation and inerting of the active phase. However, the redispersion and reactivation of the inactive phases over the spent catalysts are realized through formation of metal complex with the citric acid, which weaken the interaction between Mo species and support. It increases reducibility of the Mo species and then improve the sulfurization degree of the resurrected catalyst. Besides, the average length of MoS2 is reduced while the stacking number is increased. The ethylene glycol further regulates the reducibility of Ni and Mo species to promote the formation of NiMoS phase with high activity instead of Ni3S2. Consequently, the average length of the MoS2 is reduced while the average stacking number of MoS2 and content of the NiMoS phase are increased over the resurrected catalyst compared with the spent catalyst. It recovers the hydrodesulfurization activity of the resurrected catalyst to a level higher than that over the spent and industrially regenerated catalyst.