Molten salt applications in materials processing

The science of molten salt electrochemistry for electrowinning of reactive metals, such as calcium, and its in situ application in pyroreduction has been described. Calcium electrowinning has been performed in a 5-10 wt% calcium oxide-calcium chloride molten salt by the electrolytic dissociation of calcium oxide. This electrolysis requires the use of a porous ceramic sheath around the anode to keep the cathodically deposited calcium and the anodic gases separate. Stainless steel cathode and graphite anode have been used in the temperature range of 850-950 degrees C. This salt mixture is produced as a result of the direct oxide reduction (DOR) of reactive metal oxides by calcium in a calcium chloride bath. The primary purpose of this process is to recover the expensive calcium reductant and to recycle calcium chloride. Experimental data have been included to justify the suitability as well as limitations of the electrowinning process. Transport of oxygen ions through the sheath is found to be the rate controlling step. Under the constraints of the reactor design, a calcium recovery rate of approx. 150 g/h was achieved. Feasibility of a process to produce metals by pyrometallurgical reduction, using the calcium reductant produced electrolytically within the same reactor, has been shown in a hybrid process. Several processes are currently under investigation to use this electrowon calcium for in situ reduction of metal oxides. (c) 2004 Elsevier Ltd. All rights reserved.