The Mineralogy of Dross Produced During the Slow Cooling of Missouri Lead Bullion

One of the steps in the extractive metallurgy of lead is a refining process called drossing. Hot dross is mixture of impurity compounds that form on the surface during the cooling of lead blast furnace bullion, and in Missouri, the main impurities are copper and sulfur. The slow cooling of bullion throws out of solution all other minor impurity elements (or their compounds) which are much less soluble at lower temperatures (mainly nickel, arsenic, iron, and zinc). The transfer of bullion from the blast furnace to the refinery and the subsequent hot drossing step cause fugitive emission of lead-containing fume and dust, which creates a plant hygiene problem. One cause of the emissions is the high vapor pressure of lead and its compounds during transmission of = 1000 °C bullion to the drossing kettle. Another cause is the lifting of dross dust during manual skimming of dross. The environmental problems associated with the traditional hot drossing process provided an incentive to investigate a new drossing process that avoids contact between plant air and hot bullion or dross. A key aspect of the process development was a detailed mineralogical examination of dross from two different bullions. The bullion samples were cooled at different rates, and the dross filtered out and examined. The morphology, phase identification, and composition of the dross was examined by optical and SEM microscopy. The principal dross phases were copper and cuprous sulfide, galena, a complex sulfide containing copper, nickel and lead, and speiss (containing nickel, cobalt, iron, copper, lead, and arsenic compounds). The copper was acicular, with nickel and arsenic in solid solution. The cuprous sulfide was largely digenite in a granular or dendritic form. A substantial part of the dross was solidified matte with a eutectic microstructure, consisting mainly of CU2S and PbS. Small particles (some of which had a eutectic microstructure) never floated to the surface of the lead during the slowest cooling rate, thus indicating that flotation of tiny matte droplets and dross crystals is exceedingly slow. The success in separating dross and lead by centrifugal filtration suggests its application in industry as a replacement for traditional hot drossing.