Phase formation characteristics during the thermochemical reduction of metals from natural coltan using aluminum and calcium–aluminum alloy at 1400–1450 °C were investigated to develop methods for extracting niobium and tantalum from rare metal raw materials. The studied coltan sample consists of a columbite–tantalite solid solution with the composition (Mn,Fe)(Nb,Ta)2O6, cassiterite Sn0.9O2, tapiolite (Ta,Nb)2(Mn,Fe)O6, and calcioolivine Ca2SiO4. This study established that the choice of reducing agent determines the sequence of oxide phase transformations. During the aluminothermic process, orthorhombic columbite–tantalite is completely reduced, while tetragonal tapiolite persists even at 1400 °C. The use of a calcium–aluminum alloy containing 69.4 wt.% Ca results in a reversal of this trend: tapiolite is reduced at the early stages (800–1250 °C) through an intermediate (Ta,Nb)O2 phase, whereas the columbite–tantalite solid solution remains up to 1250 °C. Calcium, having a high affinity for oxygen, forms intermediate perovskite-type oxide phases that act as diffusion barriers, limiting the access of the reducing agent to residual mineral inclusions (mainly Nb-Ta minerals of the orthorhombic crystal system). A temperature rise to 1450 °C initiates the redistribution of oxide components: the content of CaNbO3 decreases, the Ca2(Nb,Ta)AlO6 phase disappears, and its components are involved in the formation of Ca(Nb,Ta)0.25MnO2.74 and Ca4Nb2O9. Diffusion constraints are reduced, and the residual columbite–tantalite solid solution is reduced, as confirmed by its complete absence in the products at 1450 °C. In the metallic phase, solid solutions of tantalum and niobium, Ta-Nb-Sn intermetallic compounds (Ta,Nb)3Sn, titanium aluminide, and ferroalloys with an increased (Ta,Nb)/(Fe,Mn) ratio are formed. The phase transformations elucidated during metallothermic reduction of coltan using different reducing agents, together with the formation of metallic and intermetallic phases, establish a scientific foundation for the development of advanced rare metal extraction processes.
Pikulin et al. (Fri,) studied this question.