Identifier

etd-05192014-150835

Degree

Doctor of Philosophy (PhD)

Department

Chemical Engineering

Document Type

Dissertation

Abstract

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.

Date

2014

Document Availability at the Time of Submission

Release the entire work immediately for access worldwide.

Committee Chair

Dooley, Kerry M.

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