Shock-tube and plug-flow reactor study of the oxidation of fuel-rich CH4/O2 mixtures enhanced with additives

Partial oxidation of hydrocarbons under well-controlled conditions opens a path to higher-value chemicals from natural gas with small exergy losses if the chemical conversion proceeds in an internal combustion engine as a polygeneration process (Gossler et al., 2015). For the relevant reaction conditions, kinetics models are not sufficiently validated due to the atypical reaction conditions, e.g., high equivalence ratios and pressures. The purpose of this study is to obtain experimental validation data for chemical reaction mechanisms that can be used to predict polygeneration processes in practical applications. In case of methane these processes proceed under fuel-rich conditions and yield primarily syngas (CO/H-2). In this study, the partial oxidation of methane was investigated for an equivalence ratio of phi =2 in a shock tube and a plug-flow reactor (PFR) in order to cover a wide temperature range. Time-resolved CO mole fractions were measured in shock-heated mixtures between 1600 and 2100 K at similar to 1 bar. Good agreement was found between the experiment and the models (Yasunaga et al., 2010; Burke et al., 2015; Zhao et al., 2008). Stable reaction products were monitored by time-of-flight mass spectrometry between 532 and 992 K at 6 bar in a tubular flow reactor at reaction times >4s. The influence of dimethyl ether (DME) and n-heptane addition on methane reactivity and conversion was investigated. The additives significantly lower the initial reaction temperature by producing significant amounts of OH. The results were compared to simulations and serve as validation data for the development of reaction mechanisms for these atypical reaction conditions. Good agreement was found between the experiment and the models for most of species. (C) 2016 The Combustion Institute. Published by Elsevier Inc. All rights reserved.