AN EQUILIBRIUM-ANALYSIS OF SOME CHLORINATED HYDROCARBONS IN STOICHIOMETRIC TO FUEL-RICH POST-FLAME COMBUSTION ENVIRONMENTS

The equilibrium composition of product gases from the combustion of chlorinated hydrocarbons (CHC) has been studied for varying ratios of C, H, Cl, and O under stoichiometric to fuel-rich conditions. An interactive, PC-compatible FORTRAN program, STANJAN, was utilized in conjunction with thermochemical data sources to calculate equilibrium compositions of gas mixtures as a function of temperature. The predicted results, when judiciously interpreted, assist in the understanding of the potential for formation of residual organic substance emissions (ROSEs) in post-flame environments of an incinerator. Arguments are presented for the potential formation of chlorinated species, which are stable at ambient temperature, if locally fuel-rich mixtures penetrate into the lower temperature zones of an incinerator. ROSEs that have been observed in field tests of incinerators burning chlorinated compounds are predicted to form under the fuel-rich condition. Furthermore, when the equivalence ratio is greater than unity by even a slight amount, the degree of chlorination of product gases increases markedly when the Cl/H ratio also exceeds unity. In that case, time, temperature, turbulence and an overall fuel-lean stoichiometry may not be sufficient to guarantee elimination of measurable levels of chlorinated products. Possible implications of the equilibrium calculations are discussed. Further systematic studies with additional CHCs, nitrogen-, sulfur-, and heavy metal-bearing compounds are recommended as well as continued efforts to carry out kinetic studies.