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Oxidation behavior of dodecane and two mixtures of dodecane and m-xylene (90/10 wt.% and 80/20 wt.%) over an Rh catalyst in a meso-scale heat recirculating combustor was examined to isolate the effect of aromatic content on performance. The fuel conversion, product selectivities, and reaction kinetics were calculated, and the global combustion behavior observed. The results showed that increasing the amount of m-xylene in the fuel increased the fuel conversion from 85% (pure dodecane) to 92% (90/10) and further to 98% (80/20). The presence of xylene also significantly increased CO 2 /H 2 O selectivity and decreased CO/H 2 selectivity. Global activation energy increased linearly with increase in xylene content, supporting that addition of aromatic species to fuel lowers the overall reactivity. The non-catalytic reaction was also simulated using Chemkin software to determine the effect of the Rh catalyst on the combustor performance and to analyze the difference in chemical mechanisms. The results revealed that the catalyst promotes total oxidation over partial oxidation, and lowers the global activation energy by up to 70%. [ABSTRACT FROM AUTHOR]

The results obtained from the combustion behavior of propane over platinum and rhodium catalysts in a meso-scale heat recirculating combustor are presented. The extinction limits, conversion, product selectivity/yield, and activation energy using the two catalysts were compared in an effort to predict their performance using a liquid fuel. The extinction limits were also compared to those of non-catalytic combustion in the same combustor. The results showed that the use of a catalyst greatly expanded the range of stable operating conditions, in terms of both extinction limits and flow rates supported. The Rh catalyst was found to exhibit a higher propane conversion rate, reaching a maximum of 90.4% at stoichiometric conditions (as compared to only 61.4% offered by the Pt catalyst under lean conditions), but the Pt catalyst had superior CO 2 selectivity for most of the examined conditions, indicating more of the heat released being used for product formation as opposed to being lost to the environment. However, despite having a higher rate of heat loss, the combustion with the Rh catalyst produced an overall higher amount of enthalpy than the Pt due to its superior fuel conversion. The Pt catalyst also had a significantly smaller activation energy (13.8 kJ/mol) than the Rh catalyst (74.7 kJ/mol), except at equivalence ratios richer than Φ = 1.75 (corresponding to catalyst temperatures below 500 °C), where it abruptly changed to 211.4 kJ/mol, signifying a transition from diffusion-limited reactions to kinetically limited reactions at this point. The results reveal that Rh would be a more suitable catalyst for use in liquid-fueled meso-scale combustors, as fuel conversion has been found to be a limiting factor for combustion stability in these systems, and as its higher output energy allows for greater flexibility of use. [ABSTRACT FROM AUTHOR]

Volcano curves for hydrocarbon total oxidation. • The use of the volcano curve to predict catalysts for an entire homologous series is exploited. • Catalytic activity over seven monometallic and three Ag-Pd/Al 2 O 3 bimetallic catalysts is evaluated experimentally. • Hysteresis in activity, with three distinct kinetic regimes, with varying oxygen concentration is found. • Hydrocarbons with two or more carbon atoms are good surrogates of the alkane homologous series whereas methane is not. • The feed composition controls the catalyst oxidation state and potentially impacts the optimal catalyst properties. Volcano curves are typically developed and used for predicting new catalysts for a single reaction and one substrate. The concept of using the volcano curve to predict catalysts for an entire homologous series of reactions has been unexplored. Herein the catalytic activity of seven monometallic catalysts (Pt, Pd, Rh, Ag, Ni, Cu, and Co/Al 2 O 3) and three Ag-Pd/Al 2 O 3 bimetallic catalysts is evaluated in the total oxidation of small alkanes (methane, ethane, propane, and isobutane) in the 280–400 °C temperature range under fuel lean and rich conditions. We show that hysteresis in activity, with three distinct kinetic regimes, is a common phenomenon of alkane oxidation over all catalysts studied when varying the oxygen concentration, and the size of the hysteresis loop depends on the oxophilicity of the catalyst and the reducing ability of the hydrocarbon. Expectedly, the concept of the universality of the volcano curve for a homologous series is valid but only when a suitable surrogate substrate is chosen. Hydrocarbons with two or more carbon atoms can serve as surrogates of the alkane homologous series, whereas methane is not. Interestingly and consistent with the hysteresis, the feed composition controls the catalyst oxidation state and potentially impacts the optimal catalyst descriptors used to determine new catalysts. The predicted 1:3 Ag-Pd catalyst is indeed superior to single metals for the homologous series under fuel lean conditions for ethane and larger alkanes. It is inferior to Pt under fuel rich conditions and better than Pd and Pt for methane rich conditions. A method for qualitative inference of the catalyst structure, based on the volcano curve and the oxidation state of the catalyst, is proposed. [ABSTRACT FROM AUTHOR]