Kroll Process - History and Subsequent Developments

History and Subsequent Developments

Many methods have been applied to the production of titanium metal, beginning with a report in 1887 by Nilsen and Pettersen using sodium, which was optimized into the commercial Hunter process. In the 1920s van Arkel had described the thermal decomposition of titanium tetraiodide to give highly pure titanium. Titanium tetrachloride was found to reduce with hydrogen at high temperatures to give hydrides that can be thermally processed to the pure metal. With this background, Kroll developed both new reductants and new apparatus for the reduction of titanium tetrachloride. Its high reactivity toward trace amounts of water and other metal oxides presented challenges. Significant success came with the use of calcium as a reductant, but the resulting still contained significant oxide impurities. Major success using magnesium at 1000 °C using a molybdenum clad reactor, as reported to the Electrochemical Society in Ottawa. Kroll's titanium was highly ductile reflecting its high purity. The Kroll process displaced the Hunter process and continues to be the dominant technology for the production of titanium metal, as well as driving the majority of the world's production of magnesium metal.

Other technologies are competing with the Kroll process. One process involves electrolysis of a molten salt. Problems with this process include "redox recycling," the failure of the diaphragm, and dendritic deposition in the electrolyte solution. Another process, the FFC Cambridge process, has been patented for a solid electrolytic solution, and its implementation would eliminate the titanium-sponge processing. Also in development is a pyrometallurgical route that involves the reduction of an intermediate form of titanium with aluminium. It combines the advantages of pyrometallurgy and a cheap reductant.