Oxidation of automotive primary reference fuels at elevated pressures

Automotive engine knock limits the maximum operating compression ratio and ultimate thermodynamic efficiency of spark-ignition (SI) engines. In compression-ignition (CI) or diesel cycle engines, the premixed burn phase, which occurs shortly after injection, determines the time it takes for autoignition to occur. In order to improve engine efficiency and to recommend more efficient, cleaner-burning alternative fuels, we must understand the chemical kinetic processes that lead to autoignition in both SI and CI engines. These engines burn large molecular-weight blended fuels, a class to which the primary reference fuels (PRF) n-heptane and iso-octane belong. In this study, experiments were performed under enginelike conditions in a high-pressure flow reactor using both the pure PRF fuels and their mixtures in the temperature range 550–880 K and at 12.5 atm pressure. These experiments not only provide information on the reactivity of each fuel but also identify the major intermediate products formed during the oxidation process. A detailed chemical kinetic mechanism is used to simulate these experiments, and comparisons of experimentally measured and model predicted profiles for O₂, CO, CO₂, H₂O and temperature rise are presented. Intermediates identified in the flow reactor are compared with those present in the computations, and the kinetic pathways leading to their formation are discussed. In addition, autoignition delay times measured in a shock tube over the temperature range 690–1220 K and at 40 atm pressure were simulated. Good agreement between experiment and simulation was obtained for both the pure fuels and their mixtures. Finally, quantitative values of major intermediates measured in the exhaust gas of a cooperative fuels research engine operating under motored engine conditions are presented together with those predicted by the detailed model.