Premium
Oxidative pyrolysis of CH 2 Cl 2 , CHCl 3 , and CCl 4 ‐I: Incineration implications
Author(s) -
Taylor Philip H.,
Dellinger Barry,
Tirey Debra A.
Publication year - 1991
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550231202
Subject(s) - chemistry , chloroform , pyrolysis , carbon tetrachloride , decomposition , chloride , olefin fiber , carbon fibers , toluene , radical , methylene , oxygen , inorganic chemistry , organic chemistry , catalysis , materials science , composite number , composite material
The oxidative pyrolysis of methylene chloride, chloroform, and carbon tetrachloride has been investigated using a micro‐bore, fused silica, tubular flow reactor operating under laminar flow conditions coupled to in‐line GC‐MS detection. Data were obtained over the temperature range 573–1273 K for the following conditions: chlorocarbon/oxygen equivalence ratios of 3.0, chlorocarbon concentrations of 2.7 ± 0.1 × 10 −5 mols/L, gas‐phase residence times of 2.0 s, and reactor pressures of 1.15 ± 0.05 atm. The parent stability (defined by the temperature required for 99% destruction) was evaluated as:\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_2 {\rm Cl}_2 :1028{\rm\, K, CHCl}_3 :873{\rm\, K,}\,{\rm CCl}_{\rm 4} :1153{\rm\, K} $$\end{document}Chemically activated recombination of chlorinated C 1 radicals are proposed as important pathways to chlorinated ethane and olefin products. The most significant finding from analysis of product distributions containing ≥2 carbon atoms was the observation of ca. 1 mol% yields of higher‐molecular‐weight perchlorinated aromatic species from the decomposition of chloroform and carbon tetrachloride. Implications with respect to the controlled high‐temperature incineration of these chlorinated methanes are briefly discussed.