Metal molten-salt electrolysis purification

In Fig. 9.13, the heat treatments are necessary to improve the efficiency of the sulphation step. The latter can be engineered in several alternative types of plant. Alternatives are available for the subsequent steps to pure oxide, but usually based upon precipitation and crystallization, as is the one shown in Fig. 9.13. The precipitation of beryllium hydroxide by boiling an alkaline solution of sodium beryllate, is a particularly valuable purification step, and is also used in Fig. 9.14. Chlorination of oxide mixed with carbon is a standard type of operation as used for the preparation of chloride intermediates of other metals. Molten salt electrolysis is one of the two alternative commercial routes to pure beryllium metal, the other being shown in Fig. 9.14. 

The cheapest type of nitrate-to-oxide conversion process, based upon thermal denitration, has been shown in Fig. 9.3. This can be carried out in a simple batch type of pot denitrator or in more elegant continuous plant for larger scale production. If a little iron impurity is introduced, the molten salt electrolysis stage which follows allows an opportunity for purification again before the metal powder is produced. 

Other Metals. AH the sodium metal produced comes from electrolysis of sodium chloride melts in Downs ceUs. The ceU consists of a cylindrical steel cathode separated from the graphite anode by a perforated steel diaphragm. Lithium is also produced by electrolysis of the chloride in a process similar to that used for sodium. The other alkaH and alkaHne-earth metals can be electrowon from molten chlorides, but thermochemical reduction is preferred commercially. The rare earths can also be electrowon but only the mixture known as mischmetal is prepared in tonnage quantity by electrochemical means. In addition, beryIHum and boron are produced by electrolysis on a commercial scale in the order of a few hundred t/yr. Processes have been developed for electrowinning titanium, tantalum, and niobium from molten salts. These metals, however, are obtained as a powdery deposit which is not easily separated from the electrolyte so that further purification is required. 

If an actinide metal is available in sufficient quantity to form a rod or an electrode, very efficient methods of purification are applicable electrorefining, zone melting, and electrotransport. Thorium, uranium, neptunium, and plutonium metals have been refined by electrolysis in molten salts (84). An electrode of impure metal is dissolved anodically in a molten salt bath (e.g., in LiCl/KCl eutectic) the metal is deposited electrochemically on the cathode as a solid or a liquid (19, 24). To date, the purest Np and Pu metals have been produced by this technique. 

After several runs of the electrolysis process, the active metal fission products such as alkali, alkaline earth and rare earth metals are accumulated in the molten salt. The accumulated fission products must be removed from the molten salt because they will affect the recovery efficiency of U and TRU. Periodically, the molten salt is removed from the electrolysis cell, purified using the salt purification process and recycled to the electrolysis cell. However, the molten salt always contains U and TRU with the fission products because the electrolysis is used to recover pure U and TRU without fission products. Therefore, fission products removed from the molten salt are always accompanied by some amount of U and TRU. It is necessary to optimize between the loss of U and TRU and the quantity of fission products removed because an increased removal of the fission products results in an increased contamination by the TRU in the waste stream. 

The salt purification process is illustrated in Fig. XXIV-9. A fraction of the molten salt is removed from the electrolysis cell and is placed in contact with lithium-rich liquid cadmium. By the exchange reaction between Li and salt-borne TRU and the fission products, the less stable species in the molten salt are transferred to the liquid Cd. Generally, U and TRU are less stable than the rare earth metals and are first transferred to the liquid Cd. The Li concentration in the liquid Cd must be increased to decrease the contamination of the molten salt by TRU. Then, concentration of the fission products is also increased in the liquid Cd. After a forward reductive extraction process, the decontaminated salt with the salt-borne fission products passes through zeolite beds that replace nearly all of the alkali, alkaline earth, and rare earth metals with K and Li by ion exchange. The residual actinides in the molten salt are also adsorbed in the zeolite. The molten salt leaving the zeolite is free of actinides and fission product ions. The purified salt is mixed with an oxidizer such as CdCb and is contacted with liquid Cd that contains U and TRU by the forward reductive extraction process. CdCb will contain U and TRU to be oxidized. U and TRU are transferred to the molten salt from the liquid Cd. The molten salt with U and TRU is recycled to the electrolysis cell. The liquid metal is also recycled to the forward reductive extraction process. 

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