Deep hydrodesulfurization （HDS） is an important process to produce high quality liquid fuels with ultra-low sul- fur. Process intensification for deep HDS could be implemented by developing new active catalysts and/...Deep hydrodesulfurization （HDS） is an important process to produce high quality liquid fuels with ultra-low sul- fur. Process intensification for deep HDS could be implemented by developing new active catalysts and/or new types of reactors. In this work, the kinetics of dibenzothiophene （DBT） hydrodesulfurization over Ni-P/SBA-15/ cordierite catalyst was investigated at 340-380 ℃ and 3.0-5.0 MPa. The first-order reaction model with respect to both DBT and H2 was used to fit the kinetics data in a batch recycle operation system. It is found that both the activation energy and rate constant over the Ni-P monolithic catalyst under our operating conditions are close to those over conventionally used HDS catalysts. Comparative performance studies of two types of reactors, i.e., trickle bed reactor and monolithic reactor, were performed based on reactor modeling and simulation. The results indicate that the productivity of the monolithic reactor is 3 times higher than that of the trickle bed reactor on a catalyst weight basis since effective utilization of the catalyst is higher in the monolithic reactor, but the volumetric productivity of the monolithic reactor is lower for HDS of DBT. Based on simulation results, a two- reactor-in-series configuration for hydrodesulfurization is proposed, in which a monolithic reactor is followed by a tickled bed reactor so as to attain intensified performance of the system converting fuel oil of different sulfur-containing compounds. It is illustrated that the two reactor scheme outperforms the trickle bed reactor both on reactor volume and catalyst mass bases while the content of sulfur is reduced from 200 μg·g-1 to about 10 μ·g-1.展开更多
Diatomite-dispersed NiMoW catalyst was prepared and characterized,and the activity of catalyst samples was tested during the HDS reaction of FCC diesel.Sulfur compounds in the feedstock and the hydrogenated products o...Diatomite-dispersed NiMoW catalyst was prepared and characterized,and the activity of catalyst samples was tested during the HDS reaction of FCC diesel.Sulfur compounds in the feedstock and the hydrogenated products obtained over different catalysts were determined by GC-PFPD.The test results showed that the diatomite-dispersed NiMoW catalyst had high hydrodesulfurization activity for FCC diesel,which could be contributed to the excellent hydrogenation performance of the said catalyst.Characterization of catalyst by TEM and XRD indicated that the diatomite-dispersed NiMoW catalyst possessed higher layer stacking,larger curvature of MoS2or WS2,and segregated Ni3S2crystals relative to the supported catalyst.This kind of structure leads to high hydrogenation activity of the diatomite-dispersed NiMoW catalyst.展开更多
基金Supported by the State Key Development Program for Basic Research of China(2006CB202503)
文摘Deep hydrodesulfurization （HDS） is an important process to produce high quality liquid fuels with ultra-low sul- fur. Process intensification for deep HDS could be implemented by developing new active catalysts and/or new types of reactors. In this work, the kinetics of dibenzothiophene （DBT） hydrodesulfurization over Ni-P/SBA-15/ cordierite catalyst was investigated at 340-380 ℃ and 3.0-5.0 MPa. The first-order reaction model with respect to both DBT and H2 was used to fit the kinetics data in a batch recycle operation system. It is found that both the activation energy and rate constant over the Ni-P monolithic catalyst under our operating conditions are close to those over conventionally used HDS catalysts. Comparative performance studies of two types of reactors, i.e., trickle bed reactor and monolithic reactor, were performed based on reactor modeling and simulation. The results indicate that the productivity of the monolithic reactor is 3 times higher than that of the trickle bed reactor on a catalyst weight basis since effective utilization of the catalyst is higher in the monolithic reactor, but the volumetric productivity of the monolithic reactor is lower for HDS of DBT. Based on simulation results, a two- reactor-in-series configuration for hydrodesulfurization is proposed, in which a monolithic reactor is followed by a tickled bed reactor so as to attain intensified performance of the system converting fuel oil of different sulfur-containing compounds. It is illustrated that the two reactor scheme outperforms the trickle bed reactor both on reactor volume and catalyst mass bases while the content of sulfur is reduced from 200 μg·g-1 to about 10 μ·g-1.
基金support of National Natural Science Foundation of China(Grant No.21306106)the Specialized Research Fund for the Doctoral Program of Higher Education of China(Grant No.2012371812012)China Postdoctoral Science Foundation(Grant No.2012M541941)
文摘Diatomite-dispersed NiMoW catalyst was prepared and characterized,and the activity of catalyst samples was tested during the HDS reaction of FCC diesel.Sulfur compounds in the feedstock and the hydrogenated products obtained over different catalysts were determined by GC-PFPD.The test results showed that the diatomite-dispersed NiMoW catalyst had high hydrodesulfurization activity for FCC diesel,which could be contributed to the excellent hydrogenation performance of the said catalyst.Characterization of catalyst by TEM and XRD indicated that the diatomite-dispersed NiMoW catalyst possessed higher layer stacking,larger curvature of MoS2or WS2,and segregated Ni3S2crystals relative to the supported catalyst.This kind of structure leads to high hydrogenation activity of the diatomite-dispersed NiMoW catalyst.
