Elucidating the low temperature chemistry of o-xylene enhanced by the reaction pool of dimethyl ether

Abstract

The branched aromatic hydrocarbon with short side chains, such as o-xylene, has weak low temperature oxidation reactivity, while it could proceed low temperature chain recycling reactions by blending a fuel component with higher oxidation reactivity. However, the study of low temperature oxidation kinetics of o-xylene is very scarce. Therefore, this work investigated the low temperature oxidation process of o-xylene in an atmospheric jet stirred reactor by adding a biofuel with higher low temperature oxidation reactivity, i.e. dimethyl ether (DME). A series of characteristic low temperature intermediates, such as phenyl hydroperoxides and ketohydroperoxide from the oxidation of o-xylene, were detected by using the synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). The chemical structures of representative low temperature intermediates were determined by comparing the ionization thresholds from measured photoionization efficiency curves with calculated ionization energies. A kinetic model for o-xylene and DME mixture was developed and verified by literature and present experimental data. Rate of production (ROP) and sensitivity analyses were performed, which indicate that the low temperature oxidation chemistry of o-xylene, such as the negative temperature coefficient behavior, is enhanced by the reaction pool of DME. According to the classical low temperature oxidation mechanism of n-alkanes, the low temperature reactions of o-xylene were proposed. In particular, phenyl hydroperoxides and ketohydroperoxides were revealed to be key indicators for the occurrence of first and second O2 addition reactions during the oxidation of o-xylene, respectively. In addition, the sensitivity analysis uncovers the interaction kinetics between the reaction pools of o-xylene and DME, as well as their effects on fuel consumption and products formation. In summary, present evidence elucidates the low temperature chemistry of a representative branched aromatic, which could contribute to the development of future engines and control of combustion pollutants.