Ru–Ni bimetallic catalysts for steam reforming of xylene: effects of active metals and calcination temperature of the support

Abstract

A series of Ru and Ni supported catalysts were prepared and their catalytic performance was evaluated in the steam reforming of xylenes. The effects of active metals, active metal loading sequence, and the calcination temperature of the support on the catalyst activity and stability were investigated. The bimetallic 2Ru → 15Ni catalyst shows much higher activity and stability than the monometallic 2Ru and 15Ni catalyst owing to the synergic effect of Ni and Ru. The 2Ru → 15Ni catalyst has the least coke deposition owing to its high conversion performance and much less coke precursor being formed on the catalyst surface. After decoking, most of the small-sized pores cannot be recovered because of the pore collapse under severe hydrothermal conditions. o-Xylene has the lowest reactivity due to electronic and steric effects. Besides the steam reforming reaction, demethylation and C–C cracking are also observed, forming benzene and toluene. The catalyst with a loading sequence of 15Ni → 2Ru shows high activity at low temperatures (550–600 °C), but undergoes an activity drop at high temperatures (625–650 °C) because the Ni sintering at high temperatures greatly affects the state of Ru on the catalyst. The catalyst with a loading sequence of 2Ru → 15Ni has an advantage at high temperatures owing to its better sintering resistance. The simultaneously loaded 2Ru ↔ 15Ni catalyst shows the lowest activity. The high calcination temperature of the support enhances the catalyst stability by eliminating the small-sized pores before reaction; on the other hand, the elimination of pores decreases the dispersion of the active metals. The 2Ru → 15Ni catalyst calcined at 1000 °C balances the active metal dispersion and resistance to sintering under severe hydrothermal conditions, showing the best activity and stability. The catalyst calcined at 1000 °C has the best coke resistance with only 0.166 g g_cat⁻¹ of coke formation after the 24 h durability test. The DTG results indicate that the carbon formed on the catalysts is mainly graphitic carbon.