Decomposition of Dibenzo-p-Dioxin in Fires

S.L. Summoogum1,a, B.Z. Dlugogorski1, M. Altarawneh2, J.C. Mackie1,3 and E.M. Kennedy1

1Process Safety and Environmental Protection Research Group, School of Engineering, The University of Newcastle, NSW 2308, Australia.

2Chemical Engineering Department, Al-Hussein Bin Talal University, Ma'an, Jordan

3School of Chemistry, The University of Sydney, NSW 2006, Australia


The oxidation of dibenzo-p-dioxin (DD) has been studied experimentally. The objective was to identify the decomposition pathways of DD and to gain an understanding of the reactions leading to the formation of toxic species, including those that may behave in fires and combustion systems as precursors for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F). The experiments were performed in a tubular reactor equipped with sampling systems for condensable and gaseous products. The reaction conditions were characterised by a residence time of 5 s, a temperature range of 400–800 °C (673–1073K) and a total flow rate of 19 cm3 min-1. The ratio of N2 to O2 was 20:1.0. DD slowly vaporised at a rate of 0.07 mg min-1 at a temperature of 100 °C. The flow rates of DD and oxygen corresponded to the fuel equivalence ratio of 0.39. The volatile organic compounds (VOC) were trapped in an activated charcoal cartridge. Performed on a high resolution gas chromatograph-quadrupole mass spectrometer (GCMS), the analyses of VOC identified nine products, namely benzene, toluene, 2-methyl benzofuran, naphthalene, benzofuran, dibenzofuran (a suspected carcinogen), styrene, benzaldehyde and 2,3-dihydro-2-methylenebenzofuran. The first six products were confirmed by the injection of authentic standards. Gas analysis involved the application of Fourier transform infrared (FTIR) spectroscopy and micro gas chromatography (μGC). While the decomposition of DD commenced at around 450°C into 2-methylbenzofuran and 2,3-dihydro-2-methylenebenzofuran, the temperature for complete oxidation was 800 °C .

Keywords: Dibenzo-p-dioxin, Oxidation, Polychlorinated dibenzo-p-dioxins, Polychlorinated dibenzofurans, Volatile organic compounds.

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