Part XII – December 1968 – Papers - Determination of the Absolute Short-Term Current Efficiency of an Aluminum Electrolytic Cell

The current ejyiciency of aluminum cells was derived from the metal produced over a period of time and the theoretical faradaic yield. The difference in the actual amount of aluminum in the cathode at the beginning and end of the period must be determined. The weight of aluminum in the cathode was calculated from the dilution of an added quantity of impurity metal. Use of multiple indicator metals, copper, manganese, and titanium, demonstrated that the weight of aluminum in cells can be determined to within 1 pct with routine but careful chemical analyses. Over intervals of the order of 30 days, current efficiencies reliable to within 1 pct can be obtained. INVESTIGATIONS beginning with those of Pearson and waddington ,' through the most recent published work of Georgievskii,9-11 illustrate the direct relationship between the composition of the anode gas and the applicability of analysis of anode gases to the control of alumina reduction cells. McMinn12 noted the lack of an independent method for measuring cell production efficiency over the short term. There is no doubt that changes in the current efficiency are immediately reflected in the composition of anode gases. However, the accuracy of faradaic yields calculated from gas analyses depends upon the degree of interaction between primary anode gas and Carbon.6 A conventional industrial practice of obtaining long-term current efficiency for production units from mass balances and quantity of electricity is generally insensitive to the impact of planned control of any one or more of the influential reduction cell parameters such as temperature, alumina concentration, and mean interelectrode distance. Consequently, there is a real need in the aluminum industry for a procedure to obtain the absolute cell current efficiency over a short term—10 to 30 days—both for the calibration of values obtained from gas analysis6 and for evaluating the effect of controlling specific parameters in the reduction process. The amount of aluminum produced may be determined by considering the cathode pool as a reduction of an impurity metal in aluminum. Analyses over a period will show a decreasing concentration of the impurity due to the accumulation of aluminum solvent. The increase in aluminum inferred from analyses is the amount produced by the cell during the period. Combining weights of the cell aluminum in the cathode at the beginning and end of a specific period, weights of aluminum tapped and the quantity of electricity passed during the interval will yield the current efficiency. Smart,I3 Lange;4 Rempel,15 Beletskii and Mashovets,16 and winkhaus17 have used dilution techniques to determine aluminum inventory in alumina reduction cells. A technique for determining the weight of aluminum in production cells by addition of small amounts of copper to the aluminum cathode was described by smart.13 The precision in values of the aluminum reservoir through dilution of copper in the cathode ranged from about 1 to 3 pct depending upon the quantity of copper added in the range 0.2 to 0.01 wt pct, respectively. Because the method appears so direct and apparently simple, one would not anticipate difficulties in application to industrial cells. The objective of this study was to resolve this problem associated with the trace metal dilution technique for determining the amount of aluminum in a cell. The approach in evaluating trace metal dilution as a basic factor in determining the weight of aluminum in the cell reservoir, and the absolute current efficiency of the Hall-Heroult cell, was to dilute more than one trace metal in the aluminum cathode so that we could discriminate among complications arising from physical mixing, the possibility of separation of intermetallic compounds, loss of the added elements, and chemical detection. EXPERIMENTAL METHODS These experiments are not complex but require standardized procedures. The technique involves addition of the trace metals to the cathode, knowing when these metals are homogeneously distributed in the liquid cathode, timing of the sampling, employing accurate and precise analytical methods, using reliable procedures for monitoring the amount of electricity passed through the cell, and accurate weighing of aluminum removed from the cell during the particular period. More accurate results might be obtained if the increment in concentration of the added indicator metals were of the order of 0.1 to 0.2 wt pct. The method must be applicable to production units and, hence, the contamination of the aluminum minimized. For this reason, the concentration of trace metals in the cathode was kept below 0.07 wt pct and generally at 0.04 wt pct level. Trace quantities of copper, manganese, titanium, and silicon are already present in virgin aluminum and are suitable as additives from electrochemical and analytical points of view. Concentration of silicon is quite dependent upon the characteristics of the raw materials and was not used extensively in this work. Chemical Analyses. All instrumental analyses require calibration against an absolute technique such as a gravimetric, volumetric, or spectrophotometric method which represents the ultimate in sensitivity, precision, and accuracy. On review, the best methods for copper appeared to be optical absorption without