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UBC Theses and Dissertations

The enhancing effect of pyrite on the kinetics of ferrous iron oxidation by dissolved oxygen Littlejohn, Patrick Oliver Leahy


The oxidation of ferrous in acidic sulfate media by dissolved oxygen is an important reaction in any sulfide mineral leach process that uses ferric as a surrogate oxidant. Ferric is reduced as it oxidizes metal sulfides, and the resulting ferrous is re-oxidized by dissolved oxygen. The oxidation of ferrous to ferric by dissolved oxygen is quite slow outside of elevated pressure-temperature autoclaves. However, pyrite in solution has been found to have a catalytic effect on the reaction, speeding it up significantly. This effect is particularly significant in the context of the Galvanox™ acidic sulphate atmospheric leach process. To quantify the kinetics of this reaction and the effect of pyrite, tests were run in an atmospheric batch reactor with constant tracking of pH and redox potential. The kinetics of this reaction were quantified with respect to primary variables such as acidity, pyrite pulp density, temperature, and total iron concentration. Secondary factors such as copper concentration, gas liquid mixing rate and the source of pyrite mineral were also considered. Redox potential is a logarithmic function of the ratio of the activity of free ferric to free ferrous and is complicated by speciation within the Fe(III)-Fe(II)-H₂SO₄-H₂O system. Correlating redox potential data with extent of reaction was achieved by using permanganate redox titration and the isokinetic technique to link redox potential data directly to the fraction of ferrous reacted. This technique is effective over the potential range of interest – 360 to 510 mV vs Ag/AgCl. Under these conditions the leaching rate of pyrite is appreciable, so the rate of pyrite dissolution was predicted with the shrinking sphere model developed by Bouffard et al. Ferrous oxidation in solution was simulated with an adjusted version of the model of Dreisinger and Peters, which also accounts for the catalytic effect of dissolved copper. Oxygen solubility was predicted using the model of Tromans. Experimental data show a clear enhancing effect of pyrite on ferrous oxidation. A mathematical model of this effect applicable to the conditions of Galvanox™ leaching is presented.

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