Residue hydrodesulfurization, catalyst deactivation

Those deactivation models accounting for both coke and metal sulfides are rather simple. Coke and metals foul residue hydrodesulfurization catalysts simultaneously via different processes, and decrease both intrinsic reaction rate and effective diffusivity. They never uniformly distribute in the commercial reactors. We have examined the activity and diffusivity of the aged and regenerated catalysts which were used at the different conditions as well as during the different periods. This paper describes the effects of vacuum residue conversion, reactor position, and time on-stream on the catalyst deactivation. Two mechanisms of the catalyst deactivation, depending on residue conversion level and reactor position, are also proposed. 

A study on the residue hydrodesulfurization catalysts used in the commercial reactors has suggested that there exists two deactivation mechanism such as metal-controlled deactivation and coke-controlled deactivation, depending on a residue conversion level. In the second and third bed, the deactivation is controlled by metal deposition. However, in the fourth bed, a coke-controlled deactivation appears at a high residue conversion. We also have proposed that there exist two stages in the metal-controlled deactivation. During the first stage, metal sulfides partially poison the active sites and... 

Feed properties and operation conditions determine catalyst life in the residue hydrodesulfurization. In a high conversion operation of vacuum residue, catalyst deactivation due to coke is as important as the one due to metals. Though many researchers have worked on understanding and modelling deactivation of residue hydrodesulfurization catalysts, there has still been a controversy in a coke deactivation mechanism [2, 3]. Very few publications are available discussing an effect of a bed temperature profile on catalyst deactivation in large scale adiabatic commercial reactors. Most of the studies on deactivation of residue hydrodesulfiirization catalysts have been done with small-scale isothermal reactors [2,3,4,5]. The activity tests of the used catalysts were conducted to study the catalyst deactivation in the commercial reactors. This paper also describes an effect of a bed temperature profile on coke deactivation, which was tested in the commercial reactors. 

In a study of the deactivation by coking of an atmospheric residue HDM catalyst, we have been able to obtain coked catalysts almost free from metal deposits in batch reactor and coked catalysts containing small amounts of metal sulfide deposits in continuous flow reactor using a Safaniya atmospheric residue under similar experimental conditions (30). We report in this paper a study of the deactivating effects of the deposits using toluene hydrogenation, cyclohexane isomerization and thiophene hydrodesulfurization reactions. 

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. 

A Catalyst Deactivation Model for Residual Oil Hydrodesulfiirization and Application to Deep Hydrodesulfurization of Diesel Fuel... 

The activity tests of the catalysts used in the commercial reactors were conducted in the bench-scale reactor. The aged catalyst samples were taken from the second bed through the fourth, where the hydrodesulfurization catalyst was packed. The aged catalysts were Soxhlet-extracted with toluene followed by drying. The activity tests were conducted for the fresh and aged catalysts with Arabian Heavy atmospheric residue at a temperature of 360 °C and pressure of 12 MPa. A detail of the study on the catalyst deactivation in the commercial reactors will be discussed elsewhere [9]. 

Effective solutions to the problems of the vacuum residue hydrodesulfurization unit equipped with the fixed bed reactors, such as a hot spot, pressure-drop buildup, and catalyst deactivation by coke fouling, were discussed. Improving liquid distribution can prevent hot spot occurrence. Dispersing inorganic solids throughout the reactors can control a pressure-drop increase in the first bed. For a high conversion operation, controlling the conversion in each bed can minimize the coke deactivation in the fourth bed. 

The catalyst which has a larger pore diameter tends to show a lower deactivation rate, as well as lower HDS activity. Figure 1 shows one example of the results of residual hydrodesulfurization experiments testing three kinds of catalysts which have different pore diameters. The micro-reactors were operated under the same conditions, as shown in Figure 1. Catalyst A, Catalyst B and Catalyst C were the test catalysts which have the same properties with different pore diameters ( C > B > A). The activity and deactivation rate of each catalyst were shown to depend strongly on pore diameter, as shown in Figure 1. 

A major problem in the catalytic hydrodesulfurization of residual oils is the deactivation of the catalyst by metal-containing asphaltenic species in the feed. As can be seen from the results of a typical desulfurization experiment presented in Fig. 1, the catalyst shows a rapid initial decline which is attended with a fast build-up of coke on the catalyst. At a relatively low catalyst age 0, as defined in Section IV, a stationary coke level is reached. In contrast, the deposition of the inorganic remnants of the hydro-cracked asphaltenes (mainly vanadium and nickel sulfides) continues and gradually clogs the pores in the outer zone of the catalyst particles, as confirmed by electron microprobe analyses of spent catalyst samples (see Fig. 2). This causes a slow further loss in desulfurization activity over a longer period of time. Ultimately, the catalyst becomes totally inactive for desulfurization because the - still active - inner core has become completely inaccessible to the sulfur-bearing molecules. 

---