The selectivity of the full wet leaching process for vanadium extraction using H2SO4 is low, resulting in a high impurity content in vanadium extracted from vanadium-bearing shale. This study focused on vanadium extraction and iron separation from vanadium-bearing shale, involving the coordination of H3PO4 in an H2SO4 leaching system. The effects of the ratio and quantity of H2SO4-H3PO4, leaching time, leaching temperature, and liquid-to-solid ratio on vanadium-bearing shale leaching were investigated. The dissolution processes of various minerals and the mechanism of iron coordination precipitation were analyzed. Results showed that vanadium leaching efficiency was 91.07% and iron leaching efficiency decreased from 84% to 23.86% under optimal leaching conditions-H2SO4-to-H3PO4 ratio of 2 : 1, H+ content of 8 mol kg-1, liquid-to-solid ratio of 0.8 L kg-1, and leaching time of 12 h at 95 °C. Leaching kinetics showed that the leaching process of vanadium shale was a mixed-control process in the H3PO4-H2SO4 leaching system; additionally, the leaching process was mainly controlled by a chemical reaction with an activation energy of 67 kJ mol-1. The preferential dissolution order of minerals in the vanadium-bearing shale was calcite, apatite, magnetite, muscovite, and pyrite. Under the H2SO4-H3PO4 leaching system, the iron content was reduced by inhibiting the dissolution of pyrite and coordination precipitation of Fe3+ with PO4 3-, thus separating iron and vanadium from the source. This provides guidance for vanadium extraction and impurity separation from vanadium-bearing shale using an all-wet method.
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