Perflourocarbon Generation during Electrolysis in Molten Fluoride

"The anode process of carbon electrode in fluoride melt was studied by voltammetry and chronoamperometry. Anode gases were analyzed by gas chromatography on-line during controlled-potential electrolysis. Two peaks were observed on the cyclic voltammograms. According to the results of gas chromatography, the first peak was corresponded to the discharge of residual oxide ions, with the formation of CO and CO2. Discharge of fluoride ions occurred at 4.1 V vs. Li+/Li, and leading to the anode effect. With the occurrence of anode effect, small amount of CF4 was detected. As the potential reached 4.5 V, CF4 and C2F6 gas evolution occurred, and the current increased to form the second peak.1.IntroductionIn the primary production of Aluminum and some rare earth metals like neodymium, a departure from normal cell operation known as anode effect results in the generation of perfluorocarbons (PFCs), which have high global warming potentials [1]. Owing to the pressure of environmental protection, considerable research has been carried out to clarify the mechanism of anode effect and PFC generation of industry and laboratory cells in the aluminum electrolysis system [2-9]. The common result on PFC generation is that the PFCs are emitted from Hall-Heroult cells only when they are on anode effect. In this article, we selected LiF, the main electrolyte for the neodymium electrolysis [10-11], to perform further investigation on the underlying kinetics of PFC generation and the nature of the reactions at the electrode.2. ExperimentalAll experiments were carried out in an alumina tube reactor, which was filled with high purity helium atmosphere. Spectrographic graphite crucibles were used, which played the dual role of molten fluoride container and the counter electrode. Lithium fluoride was analytical grade. The experiments were carried out at 900 °C."