화학공학소재연구정보센터
Industrial & Engineering Chemistry Research, Vol.36, No.3, 846-853, 1997
Kinetic-Study of High-Temperature Removal of H2S by Novel Metal-Oxide Sorbents
The behavior of different mixed oxides, including zinc titanates (ZT) and zinc ferrites modified with CuO (ZFC) or TiO2 (ZFT), as hot gas desulfurizing sorbents was investigated. The sorbents were prepared by calcination at 650 degrees C of a mixture of bulk oxides in three different stoichiometries in order to form new phases and modify their textural properties. Tests of stability against reduction were obtained by thermoprogrammed reduction, and kinetic studies of the sulfidation reaction were carried out in a thermobalance in the temperature range of 550-650 degrees C. Kinetic parameters of the intrinsic reaction were obtained assuming a grain model. The sulfidation behavior of the sorbents as extrudates was investigated in a fixed-bed reactor in terms of breakthrough curves. Fresh and sulfided samples were characterized by Hg porosimetry, X-ray diffraction, and SEM-EDX. The study shows that the addition of TiO2 or CuO to zinc ferrite based sorbents calcined at 650 degrees C has little effect on the stability against reduction but markedly influences their textural properties. The stabilizing effect of Ti is observed in samples calcined at higher temperature or in non-iron-containing sorbents. The calculated kinetic constants indicate that the Zn content and the incorporation of Cu have an enhancing effect on the kinetics of the sulfidation process. Including H-2 in the feed gas decreases the reactivity and increases the activation energy. Extrudated sorbents showed a good performance as desulfurizing agents and maintained the H2S concentration in the outlet gas below 20 ppm. ZT sorbent exhibited a poor efficiency, which makes the addition of Ti questionable.