Kinetic modeling study of benzene and PAH formation in laminar methane flames

Jin, Hanfeng; Frassoldati, Alessio; Wang, Yizun; Zhang, Xiaoyuan; Zeng, Meirong; Li, Yuyang; Qi, Fei; Cuoci, Alberto; Faravelli, Tiziano

doi:10.1016/j.combustflame.2014.11.031

“…Despite their potential in synthesizing PA Hs in extreme environments,both the HAVA and HACA mechanisms have come under scrutiny,since flame data and recent models infer that astepwise addition of acetylene is too slow to reproduce the quantified mass fractions of PA Hs in combustion flames and in circumstellar environments. [14] Koshi et al [15] along with Li et al [16] postulated that an overlooked phenyladdition/dehydrocyclization (PAC)m echanism may result in ar apid synthesis of PA Hs.T his hypothetical PACr oute involves an addition of phenyl to an aromatic hydrocarbon. This is followed by hydrogen loss and successive dehydrogenation succeeded by cyclization along with another hydrogen atom loss accompanied by aromatization ( Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Polycyclic Aromatic Hydrocarbons by Phenyl Addition–Dehydrocyclization: The Third Way

Zhao

¹

,

Prendergast

²

,

Kaiser

³

et al. 2019

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Polycyclic aromatic hydrocarbons (PAHs) represent the link between resonance‐stabilized free radicals and carbonaceous nanoparticles generated in incomplete combustion processes and in circumstellar envelopes of carbon rich asymptotic giant branch (AGB) stars. Although these PAHs resemble building blocks of complex carbonaceous nanostructures, their fundamental formation mechanisms have remained elusive. By exploring these reaction mechanisms of the phenyl radical with biphenyl/naphthalene theoretically and experimentally, we provide compelling evidence on a novel phenyl‐addition/dehydrocyclization (PAC) pathway leading to prototype PAHs: triphenylene and fluoranthene. PAC operates efficiently at high temperatures leading through rapid molecular mass growth processes to complex aromatic structures, which are difficult to synthesize by traditional pathways such as hydrogen‐abstraction/acetylene‐addition. The elucidation of the fundamental reactions leading to PAHs is necessary to facilitate an understanding of the origin and evolution of the molecular universe and of carbon in our galaxy.

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“…The development of the kinetic model of 1,3butadiene/propyne co-pyrolysis originates from our recent aromatic hydrocarbon models [10,[19][20][21][22]. The sub-mechanism of 1,3-butadiene developed in this work mainly contains the isomerization, unimolecular decomposition, addition, H-atom abstraction reactions.…”

Section: Kinetic Model and Numerical Simulation Methodsmentioning

confidence: 99%

“…The rate constant of the two reactions are adopted from the theoretical investigation of Matsugi et al [32]. The presentsub-mechanism of aromatic hydrocarbons has been validated from a lot of experimental data [10,[19][20][21][22]. The final model consists of 278 species and 1705 reactions.…”

Section: Kinetic Model and Numerical Simulation Methodsmentioning

confidence: 99%

Numerical Investigation on 1,3-Butadiene/Propyne Co-pyrolysis and Insight into Synergistic Effect on Aromatic Hydrocarbon Formation

Li

¹

,

Zou

²

,

Zhang

³

et al. 2017

Chinese Journal of Chemical Physics

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A numerical investigation on the co-pyrolysis of 1,3-butadiene and propyne is performed to explore the synergistic effect between fuel components on aromatic hydrocarbon formation. A detailed kinetic model of 1,3-butadiene/propyne co-pyrolysis with the sub-mechanism of aromatic hydrocarbon formation is developed and validated on previous 1,3-butadiene and propyne pyrolysis experiments. The model is able to reproduce both the single component pyrolysis and the co-pyrolysis experiments, as well as the synergistic effect between 1,3butadiene and propyne on the formation of a series of aromatic hydrocarbons. Based on the rate of production and sensitivity analyses, key reaction pathways in the fuel decomposition and aromatic hydrocarbon formation processes are revealed and insight into the synergistic effect on aromatic hydrocarbon formation is also achieved. The synergistic effect results from the interaction between 1,3-butadiene and propyne. The easily happened chain initiation in the 1,3-butadiene decomposition provides an abundant radical pool for propyne to undergo the H-atom abstraction and produce propargyl radical which plays key roles in the formation of aromatic hydrocarbons. Besides, the 1,3-butadiene/propyne co-pyrolysis includes high concentration levels of C3 and C4 precursors simultaneously, which stimulates the formation of key aromatic hydrocarbons such as toluene and naphthalene.

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“…Despite their potential in synthesizing PAHs in extreme environments, both the HAVA and HACA mechanisms have come under scrutiny, since flame data and recent models infer that a stepwise addition of acetylene is too slow to reproduce the quantified mass fractions of PAHs in combustion flames and in circumstellar environments . Koshi et al .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Polycyclic Aromatic Hydrocarbons by Phenyl Addition–Dehydrocyclization: The Third Way

Zhao

¹

,

Prendergast

²

,

Kaiser

³

et al. 2019

View full text Add to dashboard Cite

Polycyclic aromatic hydrocarbons (PAHs) represent the link between resonance‐stabilized free radicals and carbonaceous nanoparticles generated in incomplete combustion processes and in circumstellar envelopes of carbon rich asymptotic giant branch (AGB) stars. Although these PAHs resemble building blocks of complex carbonaceous nanostructures, their fundamental formation mechanisms have remained elusive. By exploring these reaction mechanisms of the phenyl radical with biphenyl/naphthalene theoretically and experimentally, we provide compelling evidence on a novel phenyl‐addition/dehydrocyclization (PAC) pathway leading to prototype PAHs: triphenylene and fluoranthene. PAC operates efficiently at high temperatures leading through rapid molecular mass growth processes to complex aromatic structures, which are difficult to synthesize by traditional pathways such as hydrogen‐abstraction/acetylene‐addition. The elucidation of the fundamental reactions leading to PAHs is necessary to facilitate an understanding of the origin and evolution of the molecular universe and of carbon in our galaxy.

show abstract

Kinetic modeling study of benzene and PAH formation in laminar methane flames

Cited by 77 publications

References 134 publications

Synthesis of Polycyclic Aromatic Hydrocarbons by Phenyl Addition–Dehydrocyclization: The Third Way

Synthesis of Polycyclic Aromatic Hydrocarbons by Phenyl Addition–Dehydrocyclization: The Third Way

Numerical Investigation on 1,3-Butadiene/Propyne Co-pyrolysis and Insight into Synergistic Effect on Aromatic Hydrocarbon Formation

Synthesis of Polycyclic Aromatic Hydrocarbons by Phenyl Addition–Dehydrocyclization: The Third Way

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