Chromium-containing ferroalloy wastes represent an important secondary resource; however, chromium is mainly bound in thermodynamically stable spinel phases, which complicates its reduction. Unlike previous studies focusing on pure oxide systems, this work demonstrates the enhanced destabilization and subsequent reduction of MgCr2O4 spinel in real ferroalloy wastes under SHS conditions, revealing a non-monotonic relationship between activation time and reduction efficiency. A critical activation threshold (~30 min) was identified, beyond which particle agglomeration suppresses reaction kinetics. Powder mixtures based on HShP and KEK wastes with Al–C–Si reducing agents were mechanically activated for 10–120 min and subsequently subjected to SHS at 950 °C. The combustion parameters, phase composition (XRD), microstructure (SEM), and elemental composition (EDS) were analyzed. The results show a pronounced non-monotonic dependence of combustion temperature and front velocity on activation time, with maximum values at ~30 min (1920 °C and 1.10 mm/s for HShP; 1765 °C and 0.98 mm/s for KEK). XRD analysis indicates that MgCr2O4 was not detected within the XRD detection limits and that the highest relative amount of metallic chromium phase (~8% for HShP and ~6.8% for KEK) was observed at the same activation time. SEM observations reveal the formation of a more dispersed and porous structure, while EDS indicates an increase in chromium content up to ~15 wt.% in local regions. At longer activation times, overgrinding and agglomeration reduce process efficiency. Mechanical activation enhances chromium reduction through improved mass transfer, with an optimal activation time of ~30 min. The chromium reduction efficiency was evaluated using a semi-quantitative approach based on XRD phase analysis and supported by EDS data, allowing comparative assessment of reduction efficiency rather than absolute extraction values. These results highlight the existence of a critical mechanochemical activation threshold governing the balance between enhanced reactivity and agglomeration effects.
Толендиулы et al. (Tue,) studied this question.