Extractive Metallurgy Division - A Basket Cathode Electrolytic Cell for Production of Titanium Metal

By confining the electrolytic reduction of TiCl4 to the interior of a porous basket-cathode the electrolyte between the anode and the cathode can be kept free of reduced chlorides of titanium eliminating undesirable reactions of reduced titanium chlorides with brickwork or oxygen in the cell atmosphere. Semiwalls are not needed. Operating conditions are given and discussed. Titanium yields based on TiCl4 introduced are 93 pct. Cell voltage and amperage characteristics are adaptable to multiple cathode-series cell urmngements. EXPERIMENTS conducted in the National Lead Co., Titanium Division, Research Laboratories showed that titanium metal could be deposited in an electrolytic cell in which titanium tetrachloride was introduced through a tubular cathode.' The reduced chlorides as formed were confined to the vicinity of the cathode. They were reduced to form a cocoon-shaped growth of sponge titanium metal at the end of the cathodic tube below the surface of a sodium chloride-strontium chloride electrolyte. No diaphragm was needed.' Although high-purity, coarse crystalline metal was produced in the cocoon growth, the yields of metal removed from the cell, based on the amount of titanium introduced as TiCl4, were usually only 40 to 60 pct. The growth of the cocoon deposits was away from the cathodic tube for introduction of TiC14 toward the anode following the flu lines. The reduced chlorides of titanium diffused through the deposit and were reduced to titanium electrolytically within the deposit or on the outer surfaces. Deposition within the pores of the cocoon was detrimental to further deposition because it plugged the passages used by the reduced chlorides to diffuse away from the point of titanium introduction. As plugging due to deposition in the pores proceeded, the reduced chlorides in the center of the cocoon would force their way out by forming a channel and would escape from the vicinity of the cathode without being reduced to metal. Some work had been done previously1, 2 which indicated that if the end of the cathodic tube for introducing TiC14 was surrounded by a screen connected to the tube so that it too was cathodic, growth could be made to occur within the screen. Direction of growth was observed to be from the screen toward the point of TiCl4 introduction. Through a series of design modifications a cathode evolved which consisted of an introduction tube surrounded by a perforated metal basket as shown in Fig. 1. Modifications of this design are described in Refs. 3, 4, and 5. This basic cathode designa" was incorporated in electrolytic cells containing graphite anodes and constructed of high-silica brick refractory for containing the electrolyte (see Fig. 2). The inner crucible was surrounded by insulating brick and the entire unit contained in a welded steel shell. Suitable cooling chambers with inert gas atmospheres were devised so that the cathode could be removed from the cell without exposing the deposit to air while hot. Various alkali and alkaline earth chlorides were used as electrolytes.