Characterization of the Manganese Oxide Scales Formed on a Grooved Cast Pb-Ag Anode from a Zinc Electrowinning Operation

"Grooved cast Pb-Ag anodes are used by some zinc refineries to improve current efficiency. It was found that the manganese oxide scale formed on a grooved Pb-0.75% Ag anode consists mainly of MnO2, which occurs characteristically in rhythmically banded colloform structures and adheres to a layer of ""Pb02+PbS04"" that oxidized from the anode. The relatively homogeneous and nearly fracture-free morphology of the ""Pb02+PbS04"" layer suggests the relatively uniform corrosion of the anode. Deposition of the Mn oxide initially follows the contours of the anode surface, but the grooves eventually become filled with Mn oxide and gypsum. Hydrous Mn oxides and amorphous Mn oxides are believed to be also present in the manganese oxide scale. Tiny particles of PbS04 and SrS04, together with gypsum, other impurities and micro-pores, tend to concentrate in the grooves.IntroductionManganese is a common impurity in hydrometallurgical zinc processing circuits. The manganese originates from sphalerite (Zn,Fe,Mn)S and from the Mn02 added to the leaching circuit to oxidize ferrous ions [1]. Manganese in the sphalerite follows Zn through the roasting, leaching and purification processes, and is present as Mn(II) in the purified ZnS04 solution. The Mn in the added Mn02 is reduced to Mn(II) during the oxidation of the ferrous ions present in the leach solutions. In both cases, MnS04 is generated, and the MnS04 accumulates in the purified solution. In the cellhouse, Zn is plated at the cathodes to produce high quality metal. The Mn(II) is partly oxidized at the anode surface to Mn(IV), and the Mn(IV) precipitates as a scale on the surface of the anode and as a sludge on the bottom of the electrolysis cells. The presence of a thin layer of manganese oxide scale on the surface of the Pb-Ag anode can minimize the corrosion of lead and, accordingly, reduce the contamination of the electrodeposited zinc. However, a heavy manganese scale build-up can cause ""staining"" of the zinc deposits and reduced current efficiencies. Consequently, periodic anode cleaning to remove excess manganese oxide scale is carried out routinely in commercial operations."