A study of chlorobenzene pyrolysis

Vin, Nicolas; Battin‐Leclerc, Frédérique; Gall, Hervé Le; Sebbar, Nadia; Bockhorn, Henning; Trimis, D.; Herbinet, Olivier

doi:10.1016/j.proci.2018.05.067

Cited by 18 publications

(24 citation statements)

References 20 publications

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“…The present experimental procedure was already used to study the pyrolysis of chlorobenzene [14] and bromoéthane [15]. Since this procedure has been already detailed in these previous works, reminders of only the main features are given here.…”

Section: Methodsmentioning

confidence: 99%

First Study of the Pyrolysis of a Halogenated Ester: Methyl Chloroacetate

Vin

Battin‐Leclerc

Herbinet

2019

Ind. Eng. Chem. Res.

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The pyrolysis of a halogenated ester, methyl chloroacetate (MC), under dilute atmosphere and quasiatmospheric pressure was studied at temperatures from 473 to 1048 K using an alumina tubular reactor. MC was chosen as a surrogate to model the thermal decomposition of ethyl bromoacetate, a chemical warfare agent. A maximum MC conversion of 99.8% was observed at a residence time of 2 s, a temperature of 1048 K, and an inlet mole fraction of 0.01. The following products were quantified: CO, CO2, HCl, methane, ethylene, ethane, propene, chloromethane, dichloromethane, vinyl chloride, chloroethane, and dichloroethane. For the first time, a detailed kinetic model of MC pyrolysis was developed and gave a good prediction of the global reactivity and the formation of most of the major products. Flow rate and sensitivity analyses were made to highlight the different pathways of decomposition during the MC pyrolysis. In a first attempt to extrapolate the results obtained with methyl chloroacetate to ethyl bromoacetate, simulations were run with a modified version of the model developed in this study taking into account the differences in bond dissociation energies induced by the change of the chlorine atom by a bromine one. Supplementary MaterialKinetic mechanism used in this work given under CHEMKIN format.Thermodynamic data of all species of the mechanism.Scheme of the experimental setup used for running pyrolysis experiments, measured temperature profile in the TR in absence of reaction, and the carbon, oxygen, and chlorine balances, SCF energy, zero-point corrected electronic energy, frequencies and geometry of molecules, radicals and transition states, calculated at the CBS-QB3 level of theory, comparison of the kinetic parameters of reaction R30 in Table 1 with literature data, experimental mole fractions of species in a tabular form.

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Section: Methodsmentioning

confidence: 99%

First Study of the Pyrolysis of a Halogenated Ester: Methyl Chloroacetate

Vin

Battin‐Leclerc

Herbinet

2019

Ind. Eng. Chem. Res.

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“…As described previously [22], using a heated transfer line maintained at 433 K to avoid product condensation, the gases sampled at the outlet of the reactors were analyzed using: 8  Gas chromatography (GC): methane, ethylene, acetylene and ethane were quantified by a first chromatograph fitted with a PlotQ capillary column, a thermal conductivity detector (TCD) and a flame ionization detector (FID); other types of molecules were quantified using a second chromatograph, fitted with a HP-1 capillary column and a FID. A gas chromatograph equipped with a Plot-Q capillary column and coupled to a mass spectrometer was used to identify the reaction products (mass spectra of the fuel and of species which were not calibrated using standards are given in Figure S4 in SM).…”

Section: Methodsmentioning

confidence: 99%

A study of thermal decomposition of bromoethane

Vin

Battin‐Leclerc

Herbinet

2018

Journal of Analytical and Applied Pyrolysis

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The pyrolysis of bromoethane under dilute atmosphere and quasi-atmospheric pressure was studied at temperatures from 600 to 975 K using a fused silica jet-stirred reactor (JSR) and an alumina tubular reactor (TR). In the JSR, a complete conversion was observed at a residence time of 2 s, a temperature of 975 K and an inlet mole fraction of bromoethane of 0.01. In the TR, the full conversion was observed from 925 K. In both reactors, the following species were quantified: methane, ethylene, acetylene, ethane, 1,3butadiene, vinylacetylene and vinyl bromide. A new detailed kinetic model was developed and gave a good prediction for both reactors of the global reactivity and the major products. Flow rate and sensitivity analyses have been performed to better understand the important reaction pathways during bromoethane pyrolysis. They showed, in contrast to previous studies, that the radical mechanism is far from being negligible and that the sole analysis of reaction products can be misleading as the radical mechanism mainly lead to ethylene and HBr which are also the two products from the molecular decomposition reaction of bromoethane.

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“…The tubular reactor set-up was developed recently in LRGP for kinetic studies at elevated temperatures [40] (up to 1300 K) because this type of reactor is often used in industry for a variety of purposes. It consisted of an alumina tube (recrystallized alumina, volume of 294 cm 3 )…”

Section: Tubular Reactormentioning

confidence: 99%