Comparative study on ethyl butanoate reactivity – Experimental investigation and kinetic modeling of the C6 ethyl ester

Abstract

Ethyl butanoate is a representative for oxygenated hydrocarbons as they are discussed as future liquid fuels from sustainable production pathways. An in-depth understanding of the influence of oxygen on the reactivity of those fuel candidates is mandatory for the molecular design and their application in internal combustion engines. Towards this goal, ignition delay times for ethyl butanoate were measured at conditions relevant to internal combustion engines using a shock tube and a rapid compression machine. These experiments were conducted for stoichiometric mixtures with air-like conditions at pressures of 20, 30 and 40 bar and a total temperature range of 680–1260 K. A negative temperature coefficient regime was found where the ignition delay times increased with increasing temperatures for all covered pressures. To further understand the kinetics of ethyl butanoate and the influence of the ester functional group, a detailed kinetic mechanism was developed and validated against the measured ignition delay times. A good agreement between the measured data and the prediction by the newly developed mechanism was achieved. The findings of this work were then used to compare ethyl butanoate to di-ethyl carbonate, methyl pentanoate and n-heptane, which also show a seven-heavy-atom-membered main chain and have all been kinetically studied before. The differences between the molecular structures and their effect on the kinetic pathways was discussed to extract information for future fuel design. It was found that especially the inhibting effect of oxgen atoms on six-membered internal H-atom migration reactions has a significant impact on the fuel’s reactivity.