Effect of Fluoride Ions on the Surface Dissolution of Vanadium-Bearing Biotite

In shale vanadium ore, vanadium is mainly formed as a low-V(III) homogeneous phase to partially replace Si and exists in the lattice structure of aluminosilicate minerals such as biotite. During the acid leaching of shale vanadium ore, an activator is needed to effectively extract vanadium. Using biotite as a tetrahedral structure doped with Aluminum-Silicon tetrahedron structure, the interaction between leaching-agent ions (H+), activator ions (F−), and vanadium-containing biotite surface was discussed by DFT quantum chemical calculations. The dissolution behavior of activator fluoride ions on the surface of vanadium-bearing biotite during sulfuric acid leaching was revealed. According to the simulated leaching results, the oxygen on the biotite surface first absorbed hydrogen ions to undergo complete hydroxylation, and then combined with hydrogen ions to form water molecules. However, in the presence of activator (NaF), fluoride ions were adsorbed on the surface cations, which catalyzed the formation of water molecules and promoted the dissolution of surface cations. SEM–EDS analysis showed that the surface of vanadium-bearing minerals became very irregular, and the number of voids and cracks greatly increased. At the same time, XPS showed that the addition of activator fluoride ions destroyed the Al-O tetrahedron structure. Many Al and V atoms dissolved in the solution, which improved the leaching rate of vanadium.