Anodic electrochemical behavior was studied on graphite anode at 1000 ℃ in cryolite-alumina molten salt by means of cyclic voltammetry. The high current peak in a typical cyclic voltammogram was discussed. It is considered that a type of oxyfluoroaliminate complex anions reacts with carbon to form a high-resistance CF film on the anode surface at a high potential. The passivation potential is 3.28 V in 0.5% alumina-containing electrolyte, and the passivation potential increases with alumina content increasing which indicates that the alumina content determines the anodic process in the cryolite-alumina molten salt system.
By using cyclic and linear sweep voltammetry,the electrochemical deposition behaviors of Mg^2+ and B^3+ in fluorides molten salts of KF-MgF2 and KF-KBF4 at 880℃ were investigated,respectively.The results show that the electrochemical reduction of Mg^2+ is a one-step reaction as Mg^2++2e-→Mg in KF-1%MgF2 molten salt,and the electrochemical reduction of B^3+ is also a one-step reaction as B^3++3e-→B in KF-KBF4 (1%,2% KBF4) molten salts.Both the cathodic reduction reactions of Mg^2+ and B^3+ are controlled by diffusion process.The diffusion coefficients of Mg^2+ in KF-MgF2 molten salts and B^3+ in KF-KBF4 molten salts are 6.8×10^-7 cm^2/s and 7.85×10^-7 cm^2/s,respectively.Moreover,the electrochemical synthesis of MgB2 by co-deposition of Mg and B was carried out in the KF-MgF2-KBF4 (molar ratio of 6:1:2) molten salt at 750℃.The X-ray diffraction analysis indicates that MgB2 can be deposited on graphite cathode in the KF-MgF2-KBF4 molten salt at 750℃.
A two-step alkaline-acidic leaching process was conducted to separate the cryolite from spent pot lining and to purify the carbon. The influencing factors of temperature, time, and the ratio of liquid to solid in alkaline and acidic leaching were investigated. The results show that the recovery of soluble compounds of Na3AlF6 and Al2O3 dissolving into the solution during the NaOH leaching is 65.0%,and the purity of carbon reaches 72.7%. During the next step of HCl leaching, the recovery of soluble compounds of CaF2 and NaAl11O17 dissolving into the HCl solution is 96.2%, and the carbon purity increases to 96.4%. By mixing the acidic leaching solution and the alkaline leaching solution, the cryolite precipitates under a suitable conditions of pH value 9 at 70 °C for 2 h. The cryolite precipitating rate is 95.6%, and the purity of Na3AlF6 obtained is 96.4%.
SHI Zhong-ningLI WeiHU Xian-weiREN Bi-junGAO Bing-liangWANG Zhao-wen