Adsorption competition effects in hydroconversion of alkane mixtures on zeolites

In the present work, molecular competition effects in the hydroconversion of alkane mixtures in vapor and liquid phase were studied. The influence of the pore size was investigated by performing catalytic experiments with equimolar heptane/nonane mixtures on a series of bifunctional zeolite catalysts (Pt/H-Y, Pt/H-USY, Pt/H-Beta, Pt/H-MCM-22). Vapor phase catalytic experiments were performed at a total pressure of 4.5 bar, while a total pressure of 100 bar was applied in the liquid phase experiments. The experimental results were analyzed using a lumped adsorption-reaction model. In vapor phase, the longest chain is preferentially converted on all studied catalysts. In liquid phase, the differences in conversion rate were less pronounced. On Pt/H-MCM-22, with active pockets on the surface, and Pt/H-USY having large mesopores, the competition between short and long alkanes in liquid phase reflect the intrinsic reactivities of the reacting molecules. In zeolites with smaller pores (Pt/H-Y, Pt/H-Beta), an inversion of the reactivity order of alkanes of different chain length was observed when increasing the pressure from 4.5 bar and vapor phase to 100 bar and liquid phase. The inversion of apparent reactivity orders is due to changes in physisorption at high pressure, favoring uptake of the smallest molecules