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Combinations of ozone and chlorine dioxide, in (ZD) or (DZ) stages in replacement of D stages can be very efficient in terms of chemical savings as well as in reducing the AOX generated during ECF bleaching of kraft pulps. (DZ) was superior to (ZD) when applied on an unbleached pulp, whereas the contrary was observed when they were implemented on an oxygen bleached pulp. The chemical structure of the lignin as well as the chemistry of both reagents with this residual lignin could explain these results. Laboratory and pilot trials showed that 1 kg of ozone could substitute up to 3 kg of chlorine dioxide. AOX formation was reduced as a consequence of the decrease in ClO2 charge. Minimum AOX was formed when neutralization was performed between Z and D in (ZD). The choice between (DZ) and (ZD) will depend mainly on the existing installation or on the process.
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