Mechanism of Calcium Fluoride Acceleration for Vacuum Carbothermic Reduction of Magnesia

Abstract The use of a small amount of calcium fluoride as an additive greatly accelerated the reduction of magnesia during the preparation of magnesium from magnesia using the vacuum carbothermic reduction method. At 1573 K (1300 °C), the magnesia reaction rates of the samples with 1, 3, and 5 pct CaF2 were all approximately 26 pct, three times that of free CaF2, and they were arranged in order of the calcium fluoride weight percentages at 1673 K (1400 °C). The residues were analyzed using chemical analysis, XRD, SEM, EDS, and XRF. The possible acceleration mechanism was discussed. Calcium fluoride combined with magnesia and silicon dioxide to form a eutectic that melted as a channel to aid the solid–solid reaction between carbon and magnesia at approximately 1573 K (1300 °C). Calcium fluoride in the molten state offered free calcium ions and fluorine ions. Fluorine ions entered and distorted the magnesia crystal lattice. The structural strength and chemical stability of the magnesia crystal lattice decreased, which facilitated the magnesia reduction by carbon. Calcium ions were employed to generate the calcium and magnesium silicate. The easyly evaporating fluorides, including magnesium fluoride and silicon tetrafluoride, were regarded as the main reason for the loss of fluorine.