Study On Ultrasonic Enhanced Chlorination Leaching Of Germanium Concentrat

Germanium is a key material in the high-tech industry and its role is irreplaceable.With the rapid development of strategic emerging industries,the demand for germanium has been increasing year by year.Germanium ore refers to raw materials containing germanium with a germanium content of more than 2%.Germanium is extracted through processes such as chlorination,distillation,purification,and hydrolysis.In response to the problem of germanium leaching and distillation from germanium ore,this paper proposes a study on the enhancement of leaching rate through ultrasonic waves.Based on germanium ore from a company in Yunnan,China,hydrochloric acid is used as the leaching medium and ultrasonic external field technology is combined to mainly study the effects of ultrasonic enhancement and conventional methods on germanium leaching rates in order to improve the leaching efficiency of germanium.Through optimization experiments of and purification,the reaction activation energy and the relationship between the initial concentration of hydrochloric acid and the reaction rate constant of conventional conditions and ultrasonic enhanced leaching experiments were explored.The main research results are as follows:（1）The content of germanium and arsenic in the germanium ore were 25.10%and1.55%,respectively.The main phase composition of the raw material is Zn₂Ge O₄,Zn Ge O₃,and As₂O₃.Approximately 97.58%of the germanium ore raw material particles are smaller than 60μm.The germanium ore raw material has three types of morphologies:spherical particles,strip-like,and flocculent.The main component of the flocculent morphology is zinc germanate.（2）Conventional leaching experiments were carried out on germanium ore.The leaching rates of germanium and arsenic were 92.25%and 87.95%,respectively,at an initial hydrochloric acid concentration of 6 mol/L,a liquid-to-solid ratio of 7 m L/g,a conventional chloride leaching temperature of 70°C,and a leaching time of 50 min.Ultrasonic-enhanced germanium ore leaching experiments were carried out at an initial hydrochloric acid concentration of 8 mol/L,a liquid-to-solid ratio of 6 m L/g,a leaching temperature of 60°C,a leaching time of 30 min,a stirring speed of 300 r/min,and an ultrasonic power of 400 W.The leaching rates of germanium and arsenic reached 96.79%and 93.83%,respectively.Compared with the optimal leaching rate under conventional conditions,the leaching rate of germanium increased by 4.54%,and the leaching rate of arsenic increased by 5.88%.This indicates that ultrasonic-enhanced leaching can improve the leaching rate of metals.（3）The process parameters for distillation and enrichment of the leaching solution were optimized.The distillation temperature for Ge Cl₄ enrichment should be between 380K and 390K under atmospheric pressure,a distillation time of 20 min,and a rotation speed of150 r/min.The product of hydrolysis is Ge O₂ with a quartz-like structure and high crystallinity.（4）The kinetic study of the leaching process showed that the hydrochloric acid leaching reaction kinetics of germanium ore under conventional and ultrasonic enhanced conditions conform to the mixed control model,and ultrasonic leaching reactions can reduce the activation energy of the germanium leaching system.Under the same leaching time,the concentration of hydrochloric acid has a significant effect on the leaching rate of germanium.The reaction order of germanium in the leaching reaction is 4.32.Compared with the reaction order of 4.24 under conventional conditions,the n value is larger under ultrasonic enhancement conditions.Therefore,under ultrasonic enhancement conditions,due to the more thorough leaching reaction process,a higher concentration of hydrochloric acid is required.