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    Evolution of oxygenated polycyclic aromatic hydrocarbon chemistry at flame temperatures

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    Name:
    OPAH Manuscript.pdf
    Size:
    1.586Mb
    Format:
    PDF
    Description:
    Accepted Manuscript
    Embargo End Date:
    2021-08-24
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    Type
    Article
    Authors
    Liu, Peng cc
    Chen, Bingjie
    Li, Zepeng cc
    Bennett, Anthony cc
    Sioud, Salim
    Sarathy, Mani cc
    Roberts, William L. cc
    KAUST Department
    Chemical Engineering Program
    Clean Combustion Research Center
    Combustion and Pyrolysis Chemistry (CPC) Group
    Mechanical Engineering Program
    Organics
    Physical Science and Engineering (PSE) Division
    high-pressure combustion (HPC) Research Group
    Date
    2019-08-24
    Online Publication Date
    2019-08-24
    Print Publication Date
    2019-11
    Permanent link to this record
    http://hdl.handle.net/10754/656736
    
    Metadata
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    Abstract
    Oxygenated polycyclic aromatic hydrocarbons (OPAH) have received increasing attention due to their toxic effect on human health. This study comprehensively investigates the evolution of OPAH chemistry at flame temperatures. Jet-stirred reactor (JSR) experiments with benzene/phenol/C2H2/N2 and benzene/C2H2/O2/N2 revealed that OPAH with oxygenated heterocycle can be formed by the addition of C2H2 at 1400 K. To further clarify the evolution of OPAH chemistry in soot systems, OPAH formation and decomposition reaction pathways and kinetic parameters have been theoretically investigated. The potential energy surfaces of 1-naphtholate and 2-naphtholate growth, and thermal decomposition reactions, were calculated by combining the density functional theory B3LYP/6–311+G(d,p) and CCSD(T)/cc-pvdz methods. The reaction rate coefficients in the temperature range of 800–2500 K and pressure range of 0.1–100 atm were calculated using RRKM theory by solving the master equations. The potential energy surface of C2H2+1-naphtholate and C2H2+2-naphtholate growth reactions showed that the O atom could be locked in a naphthofuran molecule with the formation of a C[sbnd]O[sbnd]C oxygenated heterocycle; and the reaction rates were determined by adding the C2H2 elementary step with the energy barrier of 26.0 and 19.9 kcal/mol, respectively. Thermal decomposition reactions of 1-naphtholate and 2-naphtholate yielded an indenyl radical and CO. The thermal decomposition reaction rates were significantly sensitive to the zig-zag site structure next to the C[dbnd]O bond. The decomposition rate of 1-naphtholate at 1500 K, with a zig-zag site near the C[dbnd]O bond, was 14.8 times lower than that of 2-naphtholate with no zig-zag site near the C[dbnd]O bond. Rate comparison results indicate that the C[dbnd]O functional group rapidly converts to a C[sbnd]O[sbnd]C functional group with the addition of C2H2. The formation, growth and thermal decomposition reactions of 1-naphtholate and 2-naphtholate were added to a detailed PAH mechanism to check the effect of OPAH reactions on PAH formation chemistry. The concentration profile of naphthalene predicted by the updated PAH mechanism was lower than current PAH mechanism predictions by 29%, indicating that the OPAH reactions had a significant effect on PAH formation chemistry, and should be included in the PAH mechanism. However, due to the relatively low concentration of OPAH compared to PAH, it is possible to ignore the correlation between OPAH and soot nucleation at flame temperatures; therefore an OPAH evolution pathway (PAH → incipient soot → OPAH formation on soot particle → selective thermal decomposition of OPAH), is proposed to explain the high content of OPAH molecules (e.g., 9,10-anthraquinone, benz(a)anthracene-7,12-dione, and benzanthrone) adsorbed on the soot particle.
    Citation
    Liu, P., Chen, B., Li, Z., Bennett, A., Sioud, S., Sarathy, S. M., & Roberts, W. L. (2019). Evolution of oxygenated polycyclic aromatic hydrocarbon chemistry at flame temperatures. Combustion and Flame, 209, 441–451. doi:10.1016/j.combustflame.2019.08.018
    Sponsors
    This research was supported by the Clean Combustion Research Center at the King Abdullah University of Science and Technology (KAUST). The calculations were run with the support of KAUST Supercomputing lab (Shaheen & Ibex).
    Publisher
    Elsevier
    Journal
    Combustion and Flame
    DOI
    10.1016/j.combustflame.2019.08.018
    Additional Links
    https://linkinghub.elsevier.com/retrieve/pii/S0010218019303815
    ae974a485f413a2113503eed53cd6c53
    10.1016/j.combustflame.2019.08.018
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Engineering Program; Mechanical Engineering Program; Clean Combustion Research Center

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