Thiocyanate-extraction process zirconium-hafnium separation

In the initial thiocyanate-complex Hquid—Hquid extraction process (42,43), the thiocyanate complexes of hafnium and zirconium were extracted with ether from a dilute sulfuric acid solution of zirconium and hafnium to obtain hafnium. This process was modified in 1949—1950 by an Oak Ridge team and is stiH used in the United States. A solution of thiocyanic acid in methyl isobutyl ketone (MIBK) is used to extract hafnium preferentially from a concentrated zirconium—hafnium oxide chloride solution which also contains thiocyanic acid. The separated metals are recovered by precipitation as basic zirconium sulfate and hydrous hafnium oxide, respectively, and calcined to the oxide (44,45). This process is used by Teledyne Wah Chang Albany Corporation and Western Zirconium Division of Westinghouse, and was used by Carbomndum Metals Company, Reactive Metals Inc., AMAX Specialty Metals, Toyo Zirconium in Japan, and Pechiney Ugine Kuhlmann in France. 

Solvent extraction has proved to be the most effective method for the separation of zirconium and hafnium, which invariably occur in nature in close association, owing to their almost identical chemical properties. These metals have found considerable use in the nuclear-power industry on account of their unusually high (hafnium) and low (zirconium) neutron-capture cross-sections. It is evident that the mutual separation of the two metals must be of a high degree to make them suitable for such applications. Two different solvent-extraction processes are known to be used on a commercial scale in one process, zirconium is selectively extracted from nitrate media into TBP in the second process, hafnium is selectively extracted from thiocyanate solutions into methyl isobutyl ketone (MIBK). 

Chlorination of zircon has been the process mainly used in the United States because it produces ZrCU, which is used in the Kroll process for making zirconium metal (Sec. 8.3), and because ZrCU was the feed material for the first process developed for separating hafnium from zirconium, using thiocyanate extraction (Sec. 7.3). 

Most LWR fuel rod cladding is made of Zircaloy (and its derivatives), which is an alloy of primarily zirconium and tin. Other alloying elements include niobium, iron, chromium, and nickel. Zircaloy was chosen because it has a very low cross section for thermal neutrons. Naturally occurring zirconium contains about l%-5% hafnium. The hafnium must be removed because it has a very high thermal neutron cross section and is often used in making control rods for reactors. The separation process used in the United States is a liquid-liquid extraction process. It is based on the difference in solubility of the metal thiocyanates in methyl isobutyl ketone. In Europe, a process known as extractive distillation is used to purify zirconium. This method employs a separation solvent that interacts differently with the zirconium and hafnium, causing their relative volatilities to change. This enables them to be separated by a normal distillation process. The separated zirconium is then alloyed with the required constituents. 

The reasons for the selective extraction of hafnium over zirconium from thiocyanate solutions by solvating extractants are not well understood. Hence, a recent review of the chemistry of these metals described the separation process but offered no explanation for the observed selectivity.306 There is no evidence that differences in the stabilities of the thiocyanate complexes of hafnium(IV) and zirconium(IV) are responsible for the selective extraction of the former, since the formation constants of the respective complexes are essentially identical for both metals.307 However, there is some indication that the hafnium thiocyanates are more readily solvated by the extractant than are the corresponding complexes of zirconium. 

Although the solvent purification process is adequate for the production of say reactor-grade zirconium, it is possible to modify it so that pure hafnium may also be obtained. Distribution data are available for various solutions containing thiocyanate, sulphate and chloride from which it is possible, for example, to deduce that both hafnium and zirconium will extract into hexone provided the aqueous phase has a high thiocyanate concentration and a low chloride concentration. The zirconium may then be selectively backwashed in a second extractor using say an aqueous phase of high thiocyanate concentration and moderate sulphate concentration, where the separation factor of the system is high. The hafnium can then... 

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