Preparation and characterization of SBA-1–supported chromium oxide catalysts for CO2 assisted dehydrogenation of propane

Abstract

A series of Crx/SBA-1 cubic mesoporous catalysts with 1, 3, 5, 7, 10, and 15wt.% content of Cr (Crtotal) were obtained by incipient wetness impregnation of SBA-1. The obtained catalysts were characterized with various physicochemical techniques (chemical composition, low-temperature adsorption of N2, H2–TPR, XRD, UV–vis DRS, Raman, and EPR) and tested in dehydrogenation of propane to propene in the presence of CO2. Various chromium species including Cr6+, dispersed Cr5+, and crystalline Cr2O3 were found in the calcined Crx/SBA-1 samples. Cr6+ species were present mainly in the form of mono- and dichromates, despite the Cr loading. The presence of dispersed Cr5+ species and crystalline α-Cr2O3 in the calcined catalysts depended on the total Crtotal content. Cr5+ species were found in the samples containing below 7wt.% of Crtotal, while particles of crystalline α-Cr2O3 were detected in the catalyst with Crtotal content above 5wt.%. All of the Crx/SBA-1 catalysts exhibited excellent catalytic activity and high selectivity in the dehydrogenation of propane to propene in the presence of CO2 with the maximum propane conversion (37.7% at 550°C) for ∼7wt.% of Crtotal. For higher Cr contents the conversion of propane remained almost constant which was connected with the formation of crystalline Cr2O3 which was inactive in the test reaction. Operando UV–vis DRS measurements performed during the dehydrogenation of propane, both in the presence and absence of CO2 at 550°C, indicated that the Cr6+ species (main redox sites) were reduced rapidly to Cr2+/Cr3+ species already at the beginning of the process. The dispersed Cr2+/Cr3+ ions were the main sites available to the reactants under the dehydrogenation conditions in all of the studied feed compositions.