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Oxidation of a model PCB (4-chlorobiphenyl) in catalytic and non-catalytic flow reactors and formation of PCDF

Altarawneh, M.ORCID: 0000-0002-2832-3886, Mackie, J.C., Hou, S., Kennedy, E.M. and Dlugogorski, B.Z. (2013) Oxidation of a model PCB (4-chlorobiphenyl) in catalytic and non-catalytic flow reactors and formation of PCDF. In: Proceedings of the Australian Combustion Symposium, 6 - 8 November, Perth, Western Australia pp. 291-294.

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Oxidation of a model polychlorinated biphenyl (4-chlorobiphenyl) has been studied in three flow reactors: an alumina reactor (1) exhibiting significant catalytic effects including promotion of O2 (1∆) and chlorination-dechlorination reactions at temperatures as low as 350° C; a high purity quartz reactor (2) which produced significantly lower O2 (1∆) and negligible chlorination-dechlorination and a high purity quartz reactor with surfaces passified by a boron oxide coating (3) in which only normal oxidation was observed at elevated temperatures (>600°C). The low temperature phenomena have been studied by quantum chemical techniques and reaction mechanisms to explain products’ formation (including the MCD 3-chlorodibenzofuran) are given. 3-Chlorodibenzofuran (the simplest PCDF) and benzaldehyde are important low temperature products produced by O2 (1∆) in reactors (1) and (2). Both O2 (1∆) and ground state O2 (3 Σ g) can displace Cl atoms from 4-chlorobiphenyl to produce polychlorobenzenes although only O2 (1Δ) produces significant yields of chlorobenzenes at low temperatures. Styrene and naphthalene also arise from O2 displacement of Cl.

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