Long-term stability at fuel processing of diesel and kerosene

Abstract

The long-term stability at autothermal reforming of diesel fuel and kerosene was studied using Juelich's autothermal reformer ATR 9.2, which is equipped with a commercial proprietary RhPt/Al2O3–CeO2 catalyst. The experiment was run for 10,000 h of time on stream at constant reaction conditions with an O2/C molar ratio of 0.47, a H2O/C molar ratio of 1.9, and a gas hourly space velocity of 30,000 h−1. Kerosene produced via the gas-to-liquid process and diesel fuel synthesized via the bio-to-liquid route were used. Both fuels were almost free of mass fractions of sulfur and aromatics. The trends for the desired main products of autothermal reforming H2, CO, CO2, and CH4 were almost stable when kerosene was used. When the fuel mass flow was switched to diesel fuel however, different modes of catalyst deactivation occurred (active sites blocked by carbonaceous deposits, sintering processes), leading to a decrease in the concentrations of H2 and CO2 with a simultaneous increase in the CO content. This paper defines carbon conversion as the decisive criterion for evaluating the long-term stability during autothermal reforming of kerosene and diesel fuel. Carbon conversion was diminished via three different pathways during the long-term experiment. Undesired byproducts found in the gas phase leaving the reactor had the strongest impact on carbon conversion. These byproducts included ethene, propene, and benzene. Furthermore, a liquid oily residue was detected floating on the condensed unconverted mass flow of water. This happened once during the whole experiment. Finally, undesired organic byproducts were dissolved in the mass flow of unconverted water. These were found to be straight-chain and branched paraffins, esters, alcohols, acids, aldehydes, ketones, etc. Nevertheless, at the end of the long-term experiment, carbon conversion still amounted to more than 98.2%.