The alkaline decomposition of hexathionate has been investigated by high-performance liquid chromatography monitoring the concentration of polythionates (such as hexathionate, pentathionate, and tetrathionate) and that of thiosulfate simultaneously in buffered medium at a constant ionic strength. As a major final product, unlike in the case of the alkaline decomposition of tetrathionate and pentathionate, a significant amount of sulfur deposition was also observed. Nevertheless, the chromatograms clearly suggested that heptathionate also appears as a key intermediate in a detectable amount during the course of the reaction. On the basis of these observations an 11-step kinetic model with 9 fitted and 4 fixed rate coefficients is suggested to take all of the most important characteristics of the decomposition into account. The proposed model includes the well-known thiosulfate-assisted sulfur chain, increasing pathways for tetrathionate and pentathionate along with their rate coefficients, but among them that of the thiosulfate-assisted rearrangement of pentathionate has not been reported yet. Having these kinetic parameters in hand reveals a reasonable trend of these rate coefficients against the length of the sulfur chain, suggesting that the attack of the nucleophilic agents like hydroxide, thiosulfate, and sulfite ions is determined by the electron density in the vicinity of the given sulfur atom.
Summary
Development of a cost‐effective oxygen carrier (OC) for chemical looping combustion (CLC) technology remains an important task to be accomplished. Bauxite waste red mud from the United States has shown promise as an OC, but bauxite waste from China has not been evaluated extensively although huge quantities of it exists. In comparison, the Chinese bauxite waste usually contains low Fe2O3 and high Na concentration. Hence, the purpose of this study was to evaluate a typical red mud (from Zibo, China) with low Fe2O3/Na mass ratio for its potential as a cost‐effective OC during CLC processing. Parametric reactor testing was accomplished with a focus on OC reactivity during CLC, and evaluations were accomplished of morphologies, elemental concentrations, and mechanical strengths before and after reaction testing; special attention was paid to the stability of Na. These results showed that Zibo red mud (a) used as an OC during CLC had satisfactory reactivity particularly after pre‐calcination at 1250°C, (b) had high contents of Na that were stable and uniformly distributed during reaction testing and formed NaAlSiO4 during sample calcination and reaction testing, and (c) showed high mechanical strengths that were similar to those of other oxygen carriers. Considering that huge amounts of this inexpensive Zibo red mud are located within areas near aluminum processing plants, it may become a promising material as an OC for CLC processing.
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