Thermal formation and chlorination of dioxins and dioxin-like compounds

Sammanfattning: This thesis contributes to an increased understanding of the formation of dioxins and dioxin-like compounds in combustion processes. Although emissions to air from waste incineration facilities have been greatly reduced by the use of efficient air pollution control measures, the resulting residues (ashes and filters) are highly toxic and are classified as hazardous waste. The main objective of the work underlying this thesis was to elucidate the formation and chlorination pathways of dioxins and dioxin-like compounds in waste combustion flue gases in the temperature range 640-200°C in a representative, well-controlled laboratory-scale reactor using artificial municipal solid waste. This could contribute to the reduction of harmful emissions to air and also reduce the toxicity of waste incineration residues, thus reducing or even eliminating the need for costly and potentially hazardous after-treatment.A comparison of four different quenching profiles showed that the formation of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) was rapid and mainly occurred in the 640-400°C temperature region, with high dependency on sufficient residence time within a specific temperature region. Prolonged residence time at high temperatures (450/460°C) reduced the PCDD yields, even at lower temperatures along the post-combustion zone. PCDD, PCDF and PCN (polychlorinated naphthalene) isomer distribution patterns indicated contributions from chlorophenol condensation as well as chlorination reactions for all three classes of compounds. The formation of PCDDs was largely influenced by chlorophenol condensation and to some extent by chlorination reactions. For the PCDFs, chlorine substitution adjacent to the oxygen bridges was unfavoured, as demonstrated by the notably lower abundance of 1,9-substituted congeners. This was supported by bidirectional orthogonal partial least squares (O2PLS) modelling. The variable with the greatest influence on the distribution of PCDD congeners was the relative free energy (R?Gf). The O2PLS models displayed distinct clusters, dividing most of the homologues into two or three sub-groups of congeners which seemed to correspond to the probability of origination from chlorophenol condensation.The effects of injection of aromatic structures into the flue gas differed for each class of compounds. Injection of naphthalene increased the formation of monochlorinated naphthalene but the remaining homologues appeared to be unaffected. This was probably due to insufficient residence time at temperatures necessary for further chlorination. Injected dibenzo-p-dioxin was decomposed, chlorinated and re-condensated into PCDDs and PCDFs, whereas injection of dibenzofuran and fluorene reduced the PCDD levels in the flue gas.