Detailed kinetic modeling of autocatalysis in methane pyrolysis

Journal Article · Thu Feb 22 04:00:00 EST 1990 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100367a043· OSTI ID:6729150

Dean, A M ^[1]

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1. Exxon Research and Engineering Co., Annandale, NJ (USA)

A detailed kinetic model is developed to explain the observed acceleration in rates of product formation during the pyrolysis of methane at 0.58 atm and 1038 K. This model, obtained by a systematic simplification of a much larger one, consists of 44 reactions involving 25 species. The model includes a number of reactions involving chemically activated complexes formed by radical addition and recombination reactions, with rates for unimolecular reaction and bimolecular stabilization of these energized complexes evaluated with a QRRK formalism. A combination of reaction rate analysis as well as sensitivity analysis is used to show that these chemically activated reactions lead to surprisingly rapid production of cyclopentadiene at very low extents of conversion ({approx} 0.1%) and that dissociation of cyclopentadiene accounts for the acceleration in rate. An optimization procedure was used to obtain an accurate description of the observed kinetics without compromising the theoretical plausibility of the rate constants.

• OSTI ID: 6729150
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:4; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400800* -- Combustion
Pyrolysis
& High-Temperature Chemistry
ALKANES
CALCULATION METHODS
CATALYSIS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMBUSTION KINETICS
DATA
DATA ANALYSIS
DECOMPOSITION
HYDROCARBONS
INFORMATION
KINETICS
MATHEMATICAL MODELS
METHANE
NUMERICAL DATA
ORGANIC COMPOUNDS
PYROLYSIS
REACTION KINETICS
THEORETICAL DATA
THERMOCHEMICAL PROCESSES
VERY HIGH TEMPERATURE