A FIRST STUDY OF THE PYROLYSIS OF A HALOGENATED ESTER: METHYL CHLOROACETATE

The pyrolysis of a halogenated ester, methyl chloroacetate (MC), under dilute atmosphere and quasi-atmospheric 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 the methyl chloroacetate to ethyl bromoac...