The Oscillatory Behaviour of Cu-ZSM-5 Catalysts for N2O Decomposition: Investigation of Cu Species by Complementary Techniques.

Copper-exchanged ZSM-5 (Cu-ZSM-5) is a promising catalyst thanks to the Cu redox pair. A particular feature of this material consists in the presence of spontaneous isothermal oscillations which take place during N2O decomposition reaction, depending on the operating conditions. In the present work, a set of five Cu-ZSM-5 catalysts was synthesised by three procedures and three different copper precursor concentrations: i) wet impregnation, ii) single ion exchange, and iii) double ion exchange. Catalytic tests revealed that the ion-exchanged samples exhibit a low catalytic activity and no oscillatory behaviour, except for the twice-exchanged sample which achieves an average N2O conversion of 26 % at 400 °C. Conversely, the impregnated samples reach higher levels of N2O conversion (66 % for Cu5ZSM5_WI and 72 % for Cu10ZSM5_WI) and demonstrate a similar oscillating pattern. Further investigations disclosed that the most active catalysts, characterised by the presence of oscillatory behaviour, have more abundant and easily reducible copper species (ICP, EDX and H2-TPR) which interact better with the zeolitic support (FT-IR). Catalytic tests under a long time on stream (TOS) suggest that either self-organised patterns or deterministic chaos can be achieved during the reaction, depending on the operating conditions, such as temperature and contact time.

Understanding the effect of heating rate on hydrothermal liquefaction: A comprehensive investigation from model compounds to a real food waste.

Hydrothermal liquefaction (HTL) emerges as an efficient technology for converting food waste into biocrude. Among HTL parameters, the impact of heating rate is understudied. This study systematically explores its variation (5-115 K/min) on HTL performance using actual food waste and model compounds representing its constituents. Results revealed that an increase in heating rates significantly impacts HTL performances (+63 % biocrude and -34 % solid with food waste) with short residence times, as slower heating rates imply a longer overall time and a higher kinetic advancement of the reaction. Conversely, with longer residence times, the influence of heating rates becomes negligible, as kinetics during heating times are overshadowed by those at operating temperatures. A subtle effect of heating variation at extended residence time was observed only with carbohydrates. This research emphasizes the utility of a kinetic severity factor (KSF) as a valuable tool for simultaneously considering heating rates, operating times, and temperatures.