Composition and Cr- and Fe-speciation of dust generated during ferrochrome production in a DC arc furnace

Abstract

A potential hazard associated with ferrochrome production is the unintentional generation of Cr(VI) in the off-gas dusts produced during smelting. Cr(VI) is a well-known environmental toxin and genotoxic carcinogen. Although Cr(VI) has been identified in baghouse dusts associated with submerged-arc furnaces, its occurrence in DC-arc-furnace dusts has not been previously investigated. In this study, we report the bulk composition and phase make-up, as well as the surface and bulk speciation of Cr and Fe of dusts generated during smelting of chromite ore under basic slag conditions in a pilot-scale DC arc smelter. Dusts are captured from both within the DC furnace as well as along the off-gas handling stream, after passing through the afterburner. The dusts primarily comprise feed material (chromite, flux, reductant), aerosolized slag, and glassy spherules, interpreted as off-gas condensates. Dusts collected from within the furnace, known as freeboard dusts, are dominated by feed materials, with elevated amounts of flux (lime) and lesser amounts of slag and spherules. In contrast, spherules dominate dusts collected along the off-gas handling stream by dust separators that capture the increasingly fine-grained fraction of dust, with the highest proportion of spherules occurring in baghouse dusts. Chromite is the primary host of Cr in all dust samples, whereas the spherules have low Cr contents. Cr(VI) was identified by X-ray photoelectron spectroscopy in the surfaces of dust collected from all parts of the smelter system considered, including from the furnace freeboard, despite the overall reducing conditions present therein. Cr(VI) concentrations are sufficiently high in dusts collected from the off-gas handling stream (post-afterburner, cyclone, and baghouse) to be detected in the bulk dust samples by X-ray absorption spectroscopy. The higher concentration of Cr(VI) in the finer-grained off-gas dusts, especially the baghouse dusts, is consistent with the increased abundance of spherules, the major Cr(VI)-hosting phase, in these samples. Fe is similarly more oxidized in dusts collected down the off-gas handling stream compared to dusts collected from within the furnace, which are dominated by Fe(II). Fe(III) hosted by FeOOH is predominate in dusts collected from all locations along the off-gas handling stream. These results demonstrate that there is sufficient oxygen ingress and sufficiently high temperatures in the closed DC furnace for Cr(VI) to be generated in the freeboard off-gas dusts. Cr(VI) is associated with the finest grained fraction of dusts, underlining the importance of ensuring the continual improvement of dust-capture systems, especially in terms of their ability to target increasingly finer fractions of dust. • Cr(VI) can form in a closed DC arc furnace. • Cr(VI) forms up to about one-third of the Cr species present on particle surfaces. • Fine-grained dusts captured by the baghouse host the highest proportion of Cr(VI). • Spherules are the major Cr(VI)-bearing phase in off-gas dust. • Chromite is the major source and host of Cr in smelter dusts.