Artículos SCI

A new approach for understanding PrOx reaction over gold catalysts is proposed in this work. The competition between H-2 and CO oxidation has been studied over a series of Au/MOx/Al2O3 (M = Ce and Co) catalysts in simulated post-reforming gas stream, containing H2O and CO2 for H-2 cleanup goals. The catalysts' behavior is correlated to their oxygen storage capacity, redox behavior, and oxidation ability. The estimation of the reaction rates reveals that in these solids the H-2 combustion, the selectivity limiting factor in the PrOx process, is mainly controlled by the support and not by the gold presence. The possible use of the hydrogen oxidation reaction as a catalyst selection criterion is discussed. 

FEBEX clay is considered a reference material in engineered barriers for safe storage of nuclear waste and uranium is a minor component of high-level radioactive waste (HLRW) and a main component of the spent nuclear fuel (SNF). Here, the kinetics of reaction of uranium with FEBEX was investigated in addition to the uranium immobilisation ability and the structural analysis of the reaction products. Hydrothermal treatments were accomplished with UO22+ and tetravalent actinide simulator ZrO2+, also present in HLRW. The quantification of the reaction was performed through gamma spectrometry of uranium. Two mechanisms for UO22+ retention by FEBEX were detected: adsorption and formation of stable and insoluble new phases. The structural analyses performed using ZrO2+, confirmed the uranium adsorption and the presence of new phases, ZrO2 and Zr(SiO4), that emphasise the existence of a chemical reaction with the bentonite. The analysis of the velocity of reaction uranium-clay minerals revealed temperature dependence. An exponential fitting suggested that the removal of uranium from solution at temperatures over 200 °C could be completed in less than a year. For lower temperatures, several years are needed. Milliequivalents of UO22+ immobilised by the clay depended on temperature and time and were over cation exchange capacity (CEC) of FEBEX even at 100 °C (reaching 600% of CEC). The reaction with steel, also temperature dependent, was finally analysed. At 200 °C 40–70% of uranium reacted with steel. But only 30–15% reacted at 300 °C and 100 °C. The reactions provide a stable immobilisation mechanism for uranium even when its sorption and swelling capacities fail. Our experiments will be of particular interest for very deep borehole disposals were higher temperatures and pressures are expected.