Dioxins degradation and reformation during mechanochemical treatment

- The chloride ions contained in fly ash negatively influence upon PCDD/Fs-degradation during MCD.
- A novel additive, a mix of calcium oxide and aluminium metal, was proposed.
- Dechlorination is the major mechanism for PCDD/Fs degradation and CaO-Al promotes the degradation of PCDD.

Mechanochemical dechlorination and destruction of polychlorinated dibenzo-p-dioxins and -furans (PCDD/F) on fly ash from Municipal Solid Waste Incineration was tested with and without additives (CaO and CaO/aluminium powder). The first results disappointed because of obvious PCDD/F-reformation and a second test series was conducted after removing soluble salts (NaCl, KCl …) by thorough two-stage water washing. This second test series was successful and demonstrated good destruction results, especially with combined CaO/aluminium powder as additive. In a third test series salt was again added to the water-washed fly ash, and the first, poor results were largely reconstituted. For all tests a fairly complete (94 out of 136 congeners) isomer-specific analysis was conducted and analysed, allowing to differentiate between, e.g., 2,3,7,8-substituted PCDD/F and congeners formed following the chlorophenol route. The first became more important in the samples series Fly Ash, Milled Fly Ash, milling with added CaO, and milling with CaO/aluminium-addition. The second follow the opposite trend. This isomer-specific analysis will form the basis for further study using Principal Component Analysis.