Chemical kinetic modeling of de novo synthesis of PCDD/F in municipal waste incinerators.

A kinetic model is developed for de novo synthesis of PCDD/F from carbon in incinerator fly ash. The main mechanistic steps considered in the model are carbon gasification, PCDD/F formation, desorption and degradation. Rate equations are derived which can relate PCDD/F formation with process variables including carbon concentration of fly ash, partial pressure of oxygen, reaction temperature and time. The kinetic model has been verified using laboratory de novo synthesis data reported in the literature. When the model is applied to industrial incinerator conditions, PCDD/F formation levels of 0.1-0.5 microg/N m3 in the gas phase and 0.1-1.2 microg/g in the solid phase are calculated, and both are in good agreement with incinerator measurements.