Oxidation reaction behavior of Cr-hosting spinels during heating of solid wastes containing Cr

Cr-hosting spinels are frequently formed during heating of solid wastes containing multiple metals, and its oxidation reaction (Cr(III) → Cr(VI)) is closely related with the toxicity of products. This study examined the reaction behaviors of Cr-hosting spinels (ZnCr2O4, CuCr2O4 and NiCr2O4) at high temperature and proposed possible oxidation mechanism. Cr-hosting spinels alone usually exhibit good thermal stability at high temperature. However, CaO can trigger the oxidation of Cr(III) in Cr-hosting spinels at 500–900 °C and ZnCr2O4 is easier to be oxidized than NiCr2O4 and CuCr2O4 at same condition. The oxidation of Cr-hosting spinels is accompanied with the formation of CaCrO4 and divalent metal oxides (ZnO, NiO and CuO). The broken and rebuilding of CrO bonds are key steps for Cr-hosting spinels oxidation, blocking the combination of free Cr with Ca and O atoms maybe more effective approach for suppressing Cr(III) oxidation. Furthermore, CaO can trigger the reduction of CaCrO4 into a new Cr(V) compound (Ca5(CrO4)3O0.5) at 900–1200 °C. As the temperature rising to 1300 °C, CuO reacts with CaCrO4 to form CuCrO2, in which Cu(II) and Cr(VI) are reduced into Cu(I) and Cr(III) respectively. This study provided some new knowledge for the reaction behavior of Cr-hosting spinels when solid wastes containing Cr were treated at high temperature.