Tailoring MgO-based supported Rh catalysts for purification of gas streams from phenol

Abstract

The present work is focused on the sol-gel synthesis, characterization and catalytic performance evaluation of novel Mg-Ce-Zr-O-based mixed oxides supported Rh catalysts for the purification of H 2-rich gas streams from phenol through steam reforming in the 575-730°C range. Phenol is used as a model compound of tars, the former being one of the main constituents of tars formed during steam gasification and pyrolysis of biomass. Novel Rh catalysts (0.1wt%) supported on Mg-Ce-Zr-O-based mixed oxides modified by alkaline-earth, rare earth, and transition metal ions, having the general formula Mg-Ce-Zr-X-O (where X stands for La, Sr, Ba, Ca and Zn) were systematically studied. The physicochemical properties of the catalysts were evaluated using complementary bulk and surface characterization techniques, such as BET, XPS, in situ XRD, TEM/SAED and SEM/EDX. Transient techniques including H 2-TPR, TPD-CO 2 and TPD-NH 3 were employed in order to characterize redox behavior, surface basicity, and surface acidity of support, respectively. Among the catalysts examined, a 0.1wt% Rh/40Mg-20Ce-20Zr-20La-O was found to exhibit the highest hydrogen product yield, specific H 2 production rate (μmol/m 2min), and the lowest CO/CO 2 product ratio (575-730°C), even when compared to a Ni-based commercial steam reforming of tars catalyst. At 655°C, a H 2 yield of ∼95% and a specific reaction rate of 100μmolH 2/m 2min were obtained for a feed containing 0.5vol% phenol and 40vol% H 2O at a gas hourly space velocity of ∼80,000h -1. This activity behavior is correlated with the largest concentration of basic sites and labile oxygen species (μmol/m 2), and also with the largest acid/base site ratio present in the 40Mg-20Ce-20Zr-20La-O support composition. Steam was also found to be an efficient reagent for the removal of carbonaceous deposits (e.g., C xH y) formed on the catalyst surface during phenol steam reforming. The H/C atom compositional ratio of the carbonaceous deposits was found to depend on reaction temperature. © 2011 Elsevier B.V.