Experimental and Computational Investigation of the Influence of Ethanol on Auto-ignition of n-Heptane in Non-Premixed Flows

TL;DR

This study combines experimental and computational methods to examine how ethanol addition affects n-heptane auto-ignition in counterflow flames, revealing ethanol's inhibitory effect on low-temperature chemistry and auto-ignition delay.

Contribution

It provides new insights into the chemical pathways and elementary steps involved in ethanol's inhibition of n-heptane auto-ignition through combined experiments and detailed reaction mechanism analysis.

Findings

Ethanol addition inhibits low-temperature chemistry in n-heptane.

Auto-ignition is promoted by high-temperature chemistry at high strain rates.

Ethanol competes for O2, delaying auto-ignition in n-heptane/ethanol mixtures.

Abstract

Experimental and computational investigations are carried out to elucidate the influence of ethanol addition on n-heptane auto-ignition in counterflows. An axisymmetric stream of air, temperature gradually increased, is directed onto the surface of an evaporating pool of a liquid fuel. The air-stream temperature at auto-ignition is measured at various strain rates for n-heptane, ethanol, and various n-heptane/ethanol mixtures. Critical conditions for auto-ignition are predicted employing San Diego Mechanism for both fuels and fuel mixtures, and the results are compared with measurements. Measurements and predictions show that low-temperature chemistry (LTC) plays a significant role in promoting auto-ignition of n-heptane at low strain rates, but there is insufficient residence time at high strain rates for LTC to take place, so auto-ignition is promoted by high-temperature chemistry. Experimental and computational results show addition of ethanol inhibits LTC of n-heptane. To identify the responsible elementary steps, computations are performed to identify those dominate O2 consumption and contribute to the temperature rise in the reaction zone for n-heptane and n-heptane/ethanol mixtures at low strain rates. For n-heptane, O2 is consumed primarily by the low-temperature steps that result in ketohydroperoxide; the temperature rise is produced by subsequent LTC steps. For the mixtures, a key step consuming O2 is O2 + CH3CHOH = HO2 + CH3CHO, and the heat release occurs through the classical high-temperature reaction mechanism. Thus, the inhibition of auto-ignition that is observed to occur when ethanol is added to n-heptane arises from the competition for O2 between this step and the LTC addition of O2 to the heptyl radical and to the radical arising from the subsequent isomerization, for n-heptane.