Modeling of aromatics formation in fuel-rich methane oxy-combustion with an automatically generated pressure-dependent mechanism
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Author(s)
Oßwald, Patrick
Chu, Te-Chun
Buras, Zachary
Liu, Mengjie
Goldman, Mark Jacob
Green Jr, William H
Date Issued
January 2019
Journal
Physical Chemistry Chemical Physics
Publisher
Royal Society of Chemistry (RSC)
Citation
Chu, Te-Chun, Zachary J. Buras, Patrick Oßwald, Mengjie Liu, Mark Jacob Goldman, and William H. Green. “Modeling of Aromatics Formation in Fuel-Rich Methane Oxy-Combustion with an Automatically Generated Pressure-Dependent Mechanism.” Physical Chemistry Chemical Physics 21, no. 2 (2019): 813–832.
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Final published version
Abstract
With the rise in production of natural gas, there is increased interest in homogeneous partial oxidation (POX) to convert methane to syngas (CO + H2), ethene (C2H4) and acetylene (C2H2). In POX, polycyclic aromatic hydrocarbons (PAH) are important undesired byproducts. To improve the productivity of such POX processes, it is necessary to have an accurate chemical mechanism for methane-rich combustion including PAH. A new mechanism was created to capture the chemistry from C0 to C12, incorporating new information derived from recent quantum chemistry calculations, with help from the Reaction Mechanism Generator (RMG) software. For better estimation of kinetics and thermochemistry of aromatic species, including reactions through carbene intermediates, new reaction families and additional data from quantum chemistry calculations were added to RMG-database. Many of the rate coefficients in the new mechanism are significantly pressure-dependent at POX conditions. The new mechanism was validated against electron-ionization molecular beam mass spectrometry (EI-MBMS) data from a high-temperature flow reactor reported by Kohler et al. In this work quantification of additional species from those experiments is reported including phenylacetylene (C8H6), indene (C9H8), naphthalene (C10H8) and acenaphthylene (C12H8) at many temperatures for several feed compositions. Comparison of the experimental species concentration data and the new kinetic model is satisfactory; the new mechanism is generally more accurate than other published mechanisms. Moreover, because the new mechanism is composed of elementary chemical reaction steps instead of global fitted kinetics, pathway analysis of species could be investigated step-by-step to understand PAH formation. For methane-rich combustion, the most important routes to key aromatics are propargyl recombination for benzene, reactions of the propargyl radical with the phenyl radical for indene, and hydrogen abstraction acetylene addition (HACA) for naphthalene.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
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Creative Commons Attribution 4.0 International license
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DOI of Published Version
https://doi.org/10.1039/c8cp06097e
