Controlled Hydrothermal Precipitation of Alunite and Natroalunite in High-Aluminum Vanadium-Bearing Aqueous System

Abstract

During the acid leaching process of black shale, with the destruction of the aluminosilicate mineral structure, a large amount of aluminum (Al) is leached, accompanied by the release of vanadium (V). To separate aluminum from the vanadium-containing solution, the precipitation behavior of aluminum ions (Al3+) was investigated under hydrothermal conditions with the formation of alunite and natroalunite. In the solution environment, alunite and natroalunite are able to form stably by the Al3+ hydrolysis precipitation process at a temperature of 200 °C, a pH value of 0.4 and a reaction time of 5 h. When Al3+ was precipitated at a K/Al molar ratio of 1, the aluminum precipitation efficiency and the vanadium precipitation efficiency were 64.77% and 1.72%, respectively. However, when Al3+ was precipitated at a Na/Al molar ratio of 1, the precipitation efficiency of the aluminum decreased to 48.71% and the vanadium precipitation efficiency increased to 4.36%. The thermodynamics and kinetics results showed that alunite forms more easily than natroalunite, and the reaction rate increases with increasing temperature, and the precipitation is controlled by the chemical reaction. Vanadium loss increases as the pH value increases. It can be deduced that the ion state of tetravalent vanadium (VO2+) was transformed into the ion state of pentavalent vanadium (VO2+) in the hydrothermal environment. The VO2+ can be adsorbed on the alunite or natroalunite as a result of their negative surface charges, ultimately leading to vanadium loss.