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Rare Earth/Transition Metal Oxides For Syngas Cleanup, Rui Li
Rare Earth/Transition Metal Oxides For Syngas Cleanup, Rui Li
LSU Doctoral Dissertations
Syngas from gasification of biomass or biomass and coal is a potential source of renewable energy. However, byproducts such as H2S and tars must be removed before further utilization or processing of syngas. Rare earth oxides (REOs, e.g., Ce/LaOx (1.7< x <2)) mixed with transition metals (e.g., Mn, Fe) were synthesized by various methods, and in some cases supported on a thermally stable alumina. Both desulfurization and tar reforming experiments were conducted at high temperatures under similar conditions with synthetic effluents in order to achieve better heat integration and higher yield to desired products CO and H2. The sulfur capacities at temperatures from 900-1025 K with air regeneration were measured for repeat cycles until a stable, reversible capacity was obtained. The oxidized and sulfided (reduced) sorbents were characterized by XRD, XANES, XAFS, TPR and BET. Density functional theory calculations were used to aid in interpreting characterization data and in explaining the enhanced S adsorption capacities. The results showed that mixed REOs, such as Ce/Tb, and Ce/La synthesized by a templated sol-gel approach do not have high sulfur capacities. The presence of either CO2 or H2O inhibits the adsorption of H2S. However, addition of Mn to REOs effectively increased the sulfur capacity, and Mn-REO sorbents are regenerable even in the presence of air, although there is some sulfate formation. The formation of elemental sulfur during regeneration could be related to the oxygen vacancies promoted by doping Mn into the ceria lattice. DFT calculations suggested doping Mn into CeO2 decreased the vacancy formation energies and lowered the H2S adsorption energy. In contrast, for MnO-doped REOs supported on ã-Al2O3, although their surface areas remained high after multi-cycle usage, the probable formation of MnAl2O4 as observed by XANES reduces the sulfur capacities. Reforming experiments were carried out using synthetic syngas mixtures with C10H8 as a tar model compound, both with and without H2S. The results showed that CO2 and H2O inhibit the reforming activities to some extent. Fe- or Mn-doped supported REOs are promising tar cleanup catalysts. They exhibited higher sulfur tolerance, less coking, and less methanation than typical Ni-based high temperature reforming catalysts. This behavior is in part attributed to enhanced generation of oxygen vacancies in the doped REOs.
Ceria-Zirconia Oxide High Temperature Desulfurization Sorbent, Kwang Bok Yi
Ceria-Zirconia Oxide High Temperature Desulfurization Sorbent, Kwang Bok Yi
LSU Doctoral Dissertations
High temperature desulfurization of highly reducing coal-derived gases using ceria and ceria-zirconia sorbents is the primary object of this dissertation research. If H2S concentration is reduced to less than 1 ppmv the product gas may be used with fuel cells and downstream catalytic process. CeO2 is reduced to a non-stoichiometric oxide, which is superior to CeO2 in removing H2S. Moreover, ZrO2 addition to CeO2 to form a solid solution, Ce1-xZrxO2, increases the reducibility of CeO2. This should also result in improved desulfurization performance. Pure CeO2 and sorbents, both commercially available and prepared at LSU, were tested. XRD analysis indicated that …