Partial oxidation of jet fuels over Rh/Al2O3: design and reaction kinetics of sulfur-containing surrogates

The conversion of logistic fuels via catalytic partial oxidation (CPOX) on Rh/Al2O3 at short contact times is an efficient method for generating hydrogen-rich synthesis gas. Depending on the inlet conditions, fuel, and catalyst, high syngas yields, low by-product formation, and rates of high fuel conversion can be achieved. CPOX is relevant for mobile hydrogen generation, e. g., on board of airplanes in order to increase the fuel efficiency via fuel cell-based auxiliary power units. Jet fuels contain hundreds of different hydrocarbons and a significant amount of sulfur. The hydrocarbon composition and sulfur content of a jet fuel vary depending on distributor, origin, and refinement of the crude oil. Little is known about the influence of the various compounds on the synthesis-gas yield and the impact of sulfur on the product yield. In this work, the influence of three main chemical compounds of a jet fuel (aromatics, alkanes, and sulfur compounds) on syngas selectivity, the catalyst deactivation process, and reaction sequence is unraveled. As representative components of alkanes and aromatics, n-dodecane and 1,2,4-trimethylbenzene were chosen for ex-situ and in-situ investigations on the CPOX over Rh/Al2O3, respectively. Additionally, for a fixed paraffin-to-aromatics ratio, benzothiophene or dibenzothiophene were added as a sulfur component in three different concentrations. The knowledge gained about the catalytic partial oxidation of jet fuels and their surrogates is used to identify requirements for jet fuels in mobile applications based on CPOX and to optimize the overall system efficiency. The results show an influence of the surrogate composition on syngas selectivity. The tendency for syngas formation increases with higher paraffin contents. A growing tendency for by-product formation can be observed with increasing aromatics contents in the fuel. The impact of sulfur on the reaction system shows an immediate change in the product distribution. An increase in water selectivity and decrease in hydrogen selectivity are observed. The carbon-based main product distribution does not change. Concerning the deactivation process in the presence of sulfur, adding sulfur leads to an immediate decline in the reaction rate of steam reforming. These conclusions gained in the ex-situ study are confirmed by in-situ studies, in which a more detailed insight into the reaction sequence of the CPOX of higher hydrocarbons is provided. The reaction sequence of catalytic partial oxidation of the pure substances n-dodecane and 1,2,4-trimethylbenzene as well as the surrogate blend shows a more complex reaction network compared to methane. Decomposition reactions of the hydrocarbons and their limited diffusion rate lead to the deployment of three reaction zones and a delayed oxygen consumption. Sulfur deactivation very likely occurs in the part of the catalyst in which oxygen is completely consumed, leading to the observed shift in water-to-hydrogen product ratio and the smaller reaction rate of steam reforming.