Advances in Chemical Oxidation of Total Reduced Sulfur from Kraft Mills Atmospheric Effluents

Abstract

Chemical oxidation techniques in use for the reduction of malodorous total reduced sulfur (TRS) emissions in the kraft mills atmospheric effluents were reviewed with an emphasis on recent industrial improvements in chlorine dioxide (ClO2) oxidation of TRS as well as on laboratory developments of an iron-based chemistry process. The ClO2 approach was implemented successfully at the industrial scale in two Québec kraft mills. The approach consisted in mixing the non-condensable gases (NCG) containing the TRS with gaseous chlorine dioxide obtained either as a residue from a bleach plant vent stream or through vaporization of fresh solution. Full-scale tests have shown that the amount of chlorine dioxide injected or mixed in the NCG was sufficient to reduce the TRS load below the 10 ppmv-regulated levels in a cost efficient way as compared with incineration. A prospective approach validated in laboratory conditions and using the iron redox chemistry for alkaline oxidative scrubbing of TRS is being investigated at Laval University to reduce the odor pollution and to convert TRS into valuable sulfur. Two configurations were evaluated, one consisting of homogeneous Fe(III) sequestered in trans-1,2-diaminocyclohexanetetraacetic acid (cdta) chelates and another of heterogeneous Fe(III) as Fe/Ce oxides-hydroxides mixtures. The relative performances, advantages and weaknesses of the various chemical oxidation processes were discussed. In addition, the fundamentals of the alkaline oxidative scrubbing of TRS using the iron-based alkaline approach were summarized in terms of the gas-liquid thermodynamic equilibria and of the homogeneous and heterogeneous iron redox reactions.