It has been proposed that, as an increase in the conversion of vacuum residue in the commercial fixed-bed reactors, a coke-controlled catalyst deactivation regime appears in the last bed, where coke blocks the active sites as well as decreases the diffusivity. The activity and diffusivity tests were conducted for aged and regenerated catalysts, which were used in the commercial reactors, to investigate mechanisms of the deactivation by coke and metal deposition. The effects of residue conversion, reactor position, and time on-stream on the deactivation were investigated, comparing the catalysts aged at different conditions.The Mizushima Oil Refinery of Japan Energy Corporation first implemented a high conversion operation of vacuum residue, versus a constant desulfurization operation, in the commercial residue hydrodesulfurization unit equipped with fixed-bed reactors, to produce more middle distillates as well as fuel oil with lower viscosity. The catalysts will be replaced when the sulfur content in the product oil reaches the allowable limit. Since we have believed that an increase in the residue conversion decreases the catalyst activity by coke deposition, we have been interested in controlling the coke deactivation to maximize the residue conversion during a scheduled operating period.Though a number of researchers have proposed deactivation mechanisms and models of the residue hydrodesulfurization catalysts, most of them are correlated with the amount and distribution of Ni and V deposited on the catalyst surface (1,2, 3, 4). Newson has proposed a semi-quantitative deactivation model accounting for pore plugging by both coke and metal sulfides (5). Bartholdy and Cooper studied the catalyst deactivation at a constant desulfurizarion operation and a high temperature operation (6). They suggest that a high temperature operation causes an initial larger activity loss due to coke deposition. Meyers et al. examined the effects of coke and metal sulfides on residue catalyst deactivation in three-stage expanded-bed reactors with a high residue conversion operation, and observed the largest deactivation in the
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