Experimental and computational investigations of ethane and ethylene kinetics with copper oxide particles for Chemical Looping Combustion

In this work, reaction pathways for the oxidation of methane, ethane, and ethylene with CuO was obtained by ReaxFF Molecular Dynamics (MD) simulations between temperatures of 1000 K and 2000 K. Experiments in a fixed-bed flow reactor were preformed with methane, ethane, and ethylene at temperatures ranging from 500 K to 1000 K with time-dependent species measurements from an Electron-Ionization Molecular Beam Mass Spectrometer (MBMS), and species validation with Gas Chromatography (GC) for detection of complete and intermediate combustion products. The MBMS and GC allow for the detection of oxygenated species and larger species produced from radical reformation. The simulation and experiment agree on the production of such species as CH3CHO, CH2O, CO, and H2O, which allow for the creation of simple C1 and C2 reaction pathways, which can be used in kinetic models of C2 species and larger fuels such as biofuels, which inherently depend on C1 and C2 kinetics and reaction pathway. The simulation and experiment disagree on the formation of C2H2, CH3OH, and CO2, with large amounts of C2H2 being measured in the ethylene oxidation simulations and CH3OH being formed in methane oxidation simulations, while neither species were experimentally found. In the case of CO2, large amounts of CO2 are rapidly produced in experiments with C2 fuels at 800 K, while little-to-no CO2 was observed in simulations. This is believed to be resulting from the extremely short timescale of the simulations, preventing total oxidation of the fuel. The differences in products produced between simulation and experiment allow for the potential to modify the ReaxFF potential functions to more accurately model the experimental products of Cu-H-O-C reaction kinetics. (C) 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Automated summary

In this study, reaction pathways for the oxidation of methane, ethane, and ethylene with CuO were investigated using ReaxFF Molecular Dynamics simulations. Experimental results confirmed some of the simulated products but discrepancies were observed, indicating the potential for modifying the potential functions to accurately model experimental products.