Insights in the Phenomena Involded in Deactivation of Industrial Hydrocracking Catalysts Through an Accelerated Deactivation Protocol

July Vivas-Báez (1, 2) , Alberto Servia (1) , Gerhard Pirngruber (1) , Anne-Claire Dubreuil (1) , David J Pérez-Martínez (2)

1 IFPEN - IFP Energies nouvelles
2 ECOPETROL

A representative accelerated experimental deactivation procedure was developed to understand the activity loss of bifunctional vacuum gasoil (VGO) hydrocracking catalysts over time. Experiments were performed in an up-flow fixed-bed pilot unit with a typical vacuum gas oil feedstock. The deactivation was measured by tracking the decrease of VGO conversion (370 °C+) with time on stream. The catalyst consisted of nickel-molybdenum sulfide particles dispersed on a carrier containing USY zeolite. The impact of temperature, liquid hourly space velocity (LHSV), hydrogen to hydrocarbon (H2/HC) ratio and organic nitrogen (Norg) on the catalyst deactivation rate was first studied. The variables with the most significant impact on conversion loss were temperature and space velocity. Temperature directly influences the production rate of coke precursors, whereas space velocity affects the local concentration of feed contaminants along the reactor. Based on these results, the following operating conditions were selected to establish the final accelerated deactivation experimental protocol: T = 418 °C, LHSV = 3 h−1, H2/HC = 1500NL/L, P = 14 MPa, organic nitrogen content (Norg) = 150 ppm weight, total nitrogen content = 2500 ppm weight and a total time on stream of 30 days. Spent samples from this procedure presented similar properties to some industrial catalysts submitted to cycle lengths between 12 and 18 months. Both types of samples yield similar values of surface area and pore volume loss as well as a similar amount and nature of coke deposits. These results led to the qualitative validation of the protocol representativeness. This experimental procedure was then used to get more insight into the deactivation phenomenon. It was found that the organic nitrogen content of the feedstock is crucial, as it determines the ratio between available metal and acid sites. This ratio determines the reactions that take place and, therefore, the type of coke produced.

Mots clés: Deactivation; Hydrocracking; Coking; Vacuum gasoil

Domaines: Catalyse; Sciences de l'environnement

July Vivas-Báez, Alberto Servia, Gerhard Pirngruber, Anne-Claire Dubreuil, David J Pérez-Martínez. Insights in the Phenomena Involded in Deactivation of Industrial Hydrocracking Catalysts Through an Accelerated Deactivation Protocol. Fuel, 2021, 303, pp.120681. ⟨10.1016/j.fuel.2021.120681⟩. ⟨hal-03432383⟩