Ce-Mn oxides for high-temperature gasifier effluent desulfurization

We examined Ce-Mn mixed oxides as high-temperature desulfurization materials, exploring various Mn/Ce ratios and the effects of admixing other rare earth oxides. The sulfur capacities at temperatures from 900 to 1025 K with simple air regeneration were measured for repeat cycles until a stable, reversible capacity was obtained. The measured sulfur capacities with a realistic model syngas containing H S, H , N , CO, H O, and CO were compared to thermodynamically possible maximum sulfur capacities. The oxidized and sulfided (reduced) sorbents were characterized by X-ray diffraction (XRD), X-ray absorption near-edge spectroscopy (XANES), X-ray absorption fine structure (XAFS), temperature-programmed reduction (TPR), and Brunauer-Emmett-Teller (BET) surface area. Density functional theory calculations are used to aid in interpreting characterization data and in explaining the enhanced S adsorption capacities. There is a large synergistic effect on sulfur adsorption and reaction resulting from the intimate admixing of Mn with CeO and CeO /La O rare earth oxides. However, while these materials are stable at temperatures near 900 K, even using air regeneration, the observed stable sulfur capacities fall far short of predictions based on thermodynamic equilibrium. The differences are attributed to (a) inhibition by CO and H O; (b) formation of some irreversible sulfates upon air regeneration; (c) inability of sulfur to diffuse into larger, sintered crystals of the mixed oxides; (d) gradual dissolution of Mn in an underlying support such as Al O (when present). © 2012 American Chemical Society. 2 2 2 2 2 2 2 2 3 2 2 2