Molten salt electrorefining

A more recently developed pyrometaHurgical process is that of the proposed integral fast reactor, which would use metallic fuel (U—Pu—Zr alloy) and a molten salt electrorefiner as follows ... 

Choi, S. et al. 2010. Three-dimensional multispecies current density simulation of molten-salt electrorefining. Journal of Alloys and Compounds 503(1) 177-185. 

Figure 7.15 Plotating basket anode in molten salt electrorefining [29].

The electrorefining of many metals can be carried out using molten salt electrolytes, but these processes are usually expensive and have found Httie commercial use in spite of possible technical advantages. The only appHcation on an industrial scale is the electrorefining of aluminum by the three-layer process. The density of the molten salt electrolyte is adjusted so that a pure molten aluminum cathode floats on the electrolyte, which in turn floats on the impure anode consisting of a molten copper—aluminum alloy. The process is used to manufacture high purity aluminum. 

Figure 3 shows a flowsheet for plutonium processing at Rocky Flats. Impure plutonium metal is sent through a molten salt extraction (MSE) process to remove americium. The purified plutonium metal is sent to the foundry. Plutonium metal that does not meet foundry requirements is processed further, either through an aqueous or electrorefining process. The waste chloride salt from MSE is dissolved then the actinides are precipitated with carbonate and redissolved in 7f1 HN03 and finally, the plutonium is recovered by an anion exchange process. 

An overview is presented of plutonium process chemistry at Rocky Flats and of research in progress to improve plutonium processing operations or to develop new processes. Both pyrochemical and aqueous methods are used to process plutonium metal scrap, oxide, and other residues. The pyrochemical processes currently in production include electrorefining, fluorination, hydriding, molten salt extraction, calcination, and reduction operations. Aqueous processing and waste treatment methods involve nitric acid dissolution, ion exchange, solvent extraction, and precipitation techniques. 

Early experimental work in electrorefining at Los Alamos by Mullins et-all ) demonstrated that americium could be partitioned between molten plutonium and a molten NaCl-KCl salt containing Pu+3 ions, and Knighton et-al(8), working at ANL on molten salt separation processes for fuel reprocessing, demonstrated that americium could be extracted from Mg-Zn-Pu-Am alloys with immiscible molten magnesium chloride salts. Work... 

The principle of the electrorefining process is basically simple plutonium is oxidized at a liquid metal anode containing impure metal feed and the resulting Pu+3 ions are transported through molten salt to a cathode where pure metal is produced. 

The very chemically reactive plutonium hydride is usually decomposed in a vacuum-tight furnace capable of attaining a temperature of 700°C. Plutonium hydride that is decomposed under vacuum at temperatures below 400°C forms a very fine (<20y) metallic powder above 500°C the powder begins to sinter into a porous frit which melts at 640°C to form a consolidated metal ingot. This metal typically contains significant oxide slag but is suitable for feed to either molten salt extraction or electrorefining. 

Mullins, L.J. Leary, J.A. "Fused Salt Electrorefining of Molten Plutonium by the LAMEX Process", I and EC Process Design and Development, Vol. 4, Pg. 394, October 1965. 

Americium Extraction (more commonly referred to as Molten Salt Ex-or MSE). This process is specifically designed to reduce the americium content of the plutonium metal. (Am241 spontaneously grows into plutonium as a result of Pu241 decay.) When the impure metal contains more than 1000 ppm of americium, it is run through the MSE process. Otherwise, it bypasses the MSE step and proceeds directly to electrorefining. 

Molten Salt Extraction and Electrorefining Salt Recycle. 

Electrorefining has been used for the purification of many common as well as reactive metals. It has been seen that the emf or the potential required for such a process is usually small because the energy needed for the reduction of the ionic species at the cathode is almost equal to that released by the oxidation of the crude metal at the anode. Some metals, such as copper, nickel, lead, silver, gold, etc., are refined by using aqueous electrolytes whereas molten salt electrolytes are necessary for the refining of reactive metals such as aluminum,... 

Methods have been developed (75) to prepare actinide metals directly from actinide oxides or oxycompounds by electrolysis in molten salts (e.g., LiCl/KCl eutectic). Indeed, the purest U, Np, and Pu metals have been obtained (19, 24) by oxidation of the less pure metal into a molten salt and reduction to purer metal (electrorefining. Section III,D). 

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. 

During the electrorefining of uranium metal in a molten salt eutectic, a low current density favors the formation of large single crystals. Up to 5-cm single crystals of uranium metal have resulted from the large-scale (100 kg of U) electrorefining of uranium metal in molten LiCl/KCl eutectic (17). 

Magnesium chloride and excess magnesium are removed by distillation at reduced pressure. Pure zirconium may be prepared by several methods that include iodide decomposition process, zone refining, and electron beam melting. Also, Zr metal may be electrorefined in a molten salt bath of potassium zirconium fluoride, K2ZrFe... 

Molten salt-based uranium electrochemistry continues to be an important area of research because of the use of pyrochemi-cal processes within the nuclear industry. Previous reviews have covered a large portion of the literature but recent reports have added to the body of knowledge. The recent review by Wdlit etal. on the electrorefining of uranium and plutonium offers comprehensive literature coverage from... 

Recent studies on the electrochemical behavior of plutonium in molten salts have mainly been performed in LiCl— KCl based melts. The electrorefining step in a pyroprocessing procedure for the recycling of nuclear fuel from the Integral Fast Reactor (IFR) Program has been... 

Beryllium chloride, [CAS 7787-47-5], BeCF, with a melting point of 440 C, is used as a component of molten salt baths for electrowinning or electrorefining of the metal. The compound hydrolyzes readily with atmospheric moisture, evolving HO, so protective atmospheres are required during processing. 

Interesting potential applications of molten salts are electroplating and electrorefining of refractory metals and rare earth metals. Electrowinning of titanium has been tested on a pilot scale. Electrodeposition of refractory compounds like TiB2 has also been demonstrated. Due to space limitations these more exotic applications of molten salts will not be treated here. However, short chapters on molten salt batteries and fuel cells are included. 

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