71669-25-5Relevant articles and documents
Role of copper chloride in the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans during incineration
Hatanaka, Takeshi,Kitajima, Akio,Takeuchi, Masao
, p. 73 - 79 (2007/10/03)
Combustion experiments in a laboratory-scale fluidized-bed reactor were performed to elucidate the role of copper chloride in formation of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) during model waste incineration. The amounts of PCDDs and PCDFs formed, the homologue profiles, and the isomer distributions were measured in the flue gas from incineration of model wastes containing various levels of copper. A correlation was found between the Cu content of the waste and the proportion of each congener. An increase in copper enhanced the formation of certain congeners, showing that copper acts as a catalyst for formation of PCDDs and PCDFs. An increase in the copper content of the waste decreased the CO concentration in the flue gas and reduced the formation of PCDDs and PCDFs during incineration. This indicates that copper also works as an oxidation catalyst to promote combustion, leading to lower concentrations of products of incomplete combustion. It is indispensable to consider both roles of the catalyst, i.e., enhancement and suppression, in the formation of PCDDs and PCDFs during waste incineration, which are estimated separately from the isomer distributions and the amounts of PCDDs and PCDFs formed.
Isomer distributions of polychlorinated dibenzo-p-dioxins/dibenzofurans formed during de novo synthesis on incinerator fly ash
Addink, Ruud,Govers, Harrie A. J.,Olie, Kees
, p. 1888 - 1893 (2007/10/03)
Polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) emitted from municipal waste incinerators appear to have a chlorination pattern that is quite constant across various samples and conditions. This suggested that these patterns may be controlled by thermodynamic properties of the individual PCDD/F congeners, such as the free Gibbs energy of formation (Δg°(f,T)). This would make prediction of the isomer composition of a particular sample (and hence its TEQ value) possible, based on values of ΔG°(f,T). A laboratory scale study was carried out with activated carbon on fly ash as the source of PCDD/F formation. Although it was found that the isomer distributions within homologues were independent of the reaction time (proof of thermodynamic control), other observations (lack of equilibrium/isomerization between isomers and lack of similarity between isomer distributions measured and predicted by ΔG°(f,T)) contradicted the possibility of thermodynamic control. Hence, this study could not confirm that de novo formation of PCDD/F could explain thermodynamically controlled isomer distributions in incinerators. Some recommendations for further work- time-based studies with precursors, isomerization studies with single congeners, and more data on ΔG°(f,T) values of PCDD/F-were made. Polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) emitted from municipal waste incinerators appear to have a chlorination pattern that is quite constant across various samples and conditions. This suggested that these patterns may be controlled by thermodynamic properties of the individual PCDD/F congeners, such as the free Gibbs energy of formation (ΔG°f,T). This would make prediction of the isomer composition of a particular sample (and hence its TEQ value) possible, based on values of ΔG°f,T. A laboratory scale study was carried out with activated carbon on fly ash as the source of PCDD/F formation. Although it was found that the isomer distributions within homologues were independent of the reaction time (proof of thermodynamic control), other observations (lack of equilibrium/isomerization between isomers and lack of similarity between isomer distributions measured and predicted by ΔG°f,T) contradicted the possibility of thermodynamic control. Hence, this study could not confirm that de novo formation of PCDD/F could explain thermodynamically controlled isomer distributions in incinerators. Some recommendations for further work - time-based studies with precursors, isomerization studies with single congeners, and more data on ΔG°f,T values of PCDD/F - were made.
High-resolution gas chromatography of the 22 tetrachlorodibenzo-p-dioxin isomers
Buser,Rappe
, p. 2257 - 2262 (2007/10/02)
The 22 tetrachlorodibenzo-p-dioxins (TCDDs) were synthesized in microgram quantities by a simple pyrolysis procedure from different potassium chlorophenates. The separation of these TCDD isomers was studied on high-resolution glass capillary columns with different stationary phases (Silar 10c, OV-17, OV-101) and by use of mass spectrometric detection. Conditions were found that allowed the unambiguous assignment of many of these isomers, including the very toxic 2378-TCDD. The determination of the various TCDD isomers is illustrated in the analysis of samples from known contaminated areas in Seveso, Italy, and in eastern Missouri, and the method is also applied to the analysis of fish from the Tittabawassee River in Michigan and fly ash samples from municipal incinerators in Switzerland.
