Dehydrogenation of ethane to ethylene by CO2 over highly dispersed Cr on large‐pore mesoporous silica catalysts

Abstract

A series of large‐pore mesoporous silica (LPMS)‐supported CrOx catalysts were synthesized by hydrothermal and impregnation methods and tested for ethane dehydrogenation in the presence of CO2 as an oxidant. To assess the effect of hydrothermal temperature treatment on the characteristics of LPMS support, different hydrothermal temperatures (100–160 °C) were studied and optimized. The optimum support was then loaded with different amounts of chromium (0, 2, 4, 8, and 11 wt % Cr). The obtained catalysts were characterized by different techniques such as XRD, BET, TEM, SEM, XPS, FTIR, and diffuse reflectance UV‐Vis spectroscopy. The characterization results indicated that the sample hydrothermally treated at 130 °C exhibited the highest pore volume, a narrow pore size distribution, and a moderate BET surface area. Chromium species with various oxidation states including Cr3+, Cr6+, and α‐Cr2O3 were detected in all synthesized Cr(y)/LPMS‐130 catalysts. A lower Cr content resulted in the formation of Cr6+, whereas a higher Cr content dominated the α‐Cr2O3 on the surface of the catalyst. Among the synthesized catalysts, the Cr(4)/LPMS‐130 catalyst showed the highest Cr6+/Cr3+ ratio, indicating a good dispersion of chromium species along with a fine particle size. The ethane conversion and ethylene selectivity were 50.5 and 91.1% for Cr(4)/LPMS‐130, respectively. Carbon dioxide was believed to supply enough lattice oxygen to maintain the Cr species at a higher oxidation state and to consume the hydrogen resulting from ethane cracking by a reverse water gas shift reaction.