Electrolytic Recovery of Metallic Iron and Chlorine Gas from Chloride Waste

"Titanium dioxide pigment plants using the so-called “chloride process” produce considerable amounts of chloride waste, which contains predominantly iron chloride. In most cases, this waste is dissolved in a weak hydrochloric acid solution and then neutralised. The metal content of the waste is dumped as hydroxide sludge, while its chloride content is lost in an effluent.Rio Tinto Iron & Titanium has developed a new proprietary process whereby pure metallic iron and chlorine gas are recovered from chloride waste by electrolysis. This process uses a two compartment cell separated by an anion exchange membrane to prevent iron cycling between its trivalent and divalent valence. The cathode is made of titanium Grade 7, while the anode is a dimensionally stable one of the type “metal–mixed metal oxide” (MMO) for the evolution of chlorine gas. The catholyte is concentrated and pH-adjusted iron-rich chloride solution originating from chloride waste. The anolyte is recirculating solution containing alkali or alkali earth chlorides such as MgCl2, NaCl, etc. Current efficiencies above 90% can be achieved at temperatures about 80°C using catholyte solutions almost saturated in iron chloride and other chlorides.In this paper, we discuss the details of this process, and how this could be integrated within a chloride pigment plant for the treatment of chloride wastes."