Revisiting low temperature oxidation chemistry of n-heptane

Cheng Xie (1) , Maxence Lailliau (2) , Gani Issayev (3) , Qiang Xu (1) , Weiye Chen (1) , Philippe Dagaut (2) , Aamir Farooq (3) , S. Mani Sarathy (3) , Lixia Wei (4) , Zhandong Wang (1)

1 NSRL - National Synchrotron Radiation Laboratory
2 ICARE - Institut de Combustion, Aérothermique, Réactivité et Environnement
3 KAUST - King Abdullah University of Science and Technology [Saudi Arabia]
4 aDalian NationalLaboratoryforCleanEnergy

Benefitting from the rapid development of instrumental analysis methods, intermediate products that were difficult to probe in the past can now be measured and quantified in complex reaction systems. To understand low temperature reactions of interest for combustion applications, and reduce the deviations between model predictions and experimental measurements, constant advancement in understanding low temperature oxidation process is necessary. This work examines the oxidation of n-heptane in jet-stirred reactors at atmospheric pressure, with an initial n-heptane mole fraction of 0.005, equivalence ratio of 0.5, a residence time of 1s, and over a temperature range of 500-800 K. Reaction products were analyzed using synchrotron ultra-violet photoionization mass spectrometry, gas chromatography, and Fourier-transform infrared spectroscopy. Ignition delay times of n-heptane/O2/CO2 mixture were measured in a rapid compression machine at 20 and 40 bar over a 600-673 K temperature range. Based on the experimental results, a comprehensive kinetic model of n-heptane low temperature oxidation was developed by considering the sub-mechanisms of keto-hydroperoxide, cyclic ether, heptene isomers, and the third O2 addition reaction, and by updating the rate constants of keto-hydroperoxide decomposition and second oxygen addition reactions. The combination of reaction mechanism development and evaluation of the rate constants of key reactions enabled the model to effectively predict the species concentrations and ignition delay times of n-heptane low temperature oxidation, providing additional insight into alkane low temperature oxidation chemistry.

Mots clés: kinetic modeling; low temperature oxidation; Korcek reaction; ignition delay time; third oxygen addition; jet-stirred reactor

Domaines: Chimie théorique et/ou physique; Milieux fluides et réactifs

Cheng Xie, Maxence Lailliau, Gani Issayev, Qiang Xu, Weiye Chen, et al.. Revisiting low temperature oxidation chemistry of n-heptane. Combustion and Flame, 2022, 242, pp.112177. ⟨10.1016/j.combustflame.2022.112177⟩. ⟨hal-03684380⟩