Metals electrorefining

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). 

The purification of the galHum salt solutions is carried out by solvent extraction and/or by ion exchange. The most effective extractants are dialkyl-phosphates in sulfate medium and ethers, ketones (qv), alcohols, and trialkyl-phosphates in chloride medium. Electrorefining, ie, anodic dissolution and simultaneous cathodic deposition, is also used to purify metallic galHum. 

Electrometallurgy. A term covering the various electrical processes for the working of metals, eg, electro deposition, electrorefining and electro winning, and operations in electric furnaces. 

Electrorefining. Electrolytic refining is a purification process in which an impure metal anode is dissolved electrochemicaHy in a solution of a salt of the metal to be refined, and then recovered as a pure cathodic deposit. Electrorefining is a more efficient purification process than other chemical methods because of its selectivity. In particular, for metals such as copper, silver, gold, and lead, which exhibit Htfle irreversibHity, the operating electrode potential is close to the reversible potential, and a sharp separation can be accompHshed, both at the anode where more noble metals do not dissolve and at the cathode where more active metals do not deposit. 

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. 

Preparation of Plutonium Metal from Fluorides. Plutonium fluoride, PuF or PuF, is reduced to the metal with calcium (31). Although the reactions of Ca with both fluorides are exothermic, iodine is added to provide additional heat. The thermodynamics of the process have been described (133). The purity of production-grade Pu metal by this method is ca 99.87 wt % (134). Metal of greater than 99.99 wt % purity can be produced by electrorefining, which is appHcable for Pu alloys as well as to purify Pu metal. The electrorefining has been conducted at 740°C in a NaCl—KCl electrolyte containing PuCl [13569-62-5], PuF, or PuF. Processing was done routinely on a 4-kg Pu batch basis (135). 

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 ... 

Manufacture and Recovery. Electrolytic copper refinery slimes are the principal source of selenium and its sister element, tellurium, atomic numbers 34 and 52, respectively. Electrolytic copper refinery slimes are those constituents in the copper anode which are not solubilized during the refining process and ultimately accumulate in the bottom of the electrorefining tank. These slimes are periodically recovered and processed for their metal values. Slimes generated by the refining of primary copper, copper produced from ores and concentrates, generally contain from 5—25% selenium and 2—10% tellurium. 

Commercial electrorefining of beryUium has been carried out to obtain a purer metal than the magnesium-reduced beryUium. The most notable purification obtained with respect to iron was specified as 300 ppm maximum, and typicaUy between 100 and 200 ppm Fe as contrasted with the 500—1000 ppm, found in the Mg-reduced beryUium metal. There is, however, no metaUurgical advantage to having a metal of improved purity. 

Air emissions for processes with few controls may be of the order of 30 kilograms lead or zinc per metric ton (kg/t) of lead or zinc produced. The presence of metals in vapor form is dependent on temperature. Leaching processes will generate acid vapors, while refining processes result in products of incomplete combustion (PICs). Emissions of arsine, chlorine, and hydrogen chloride vapors and acid mists are associated with electrorefining. 

In the field of electrowinning and electrorefining of metals, titanium has an advantage as a cathode, upon which copper particularly can be deposited with finely balanced adhesion that allows the electrodeposited metal to strip easily when required. Titanium anodes are also being employed as a replacement for lead or graphite in the production of electrolytic manganese dioxide. 

The enormous scope of the subject of corrosion follows from the definition which has been adopted in the present work. Corrosion will include all reactions at a metal/environment interface irrespective of whether the reaction is beneficial or detrimental to the metal concerned —no distinction is made between chemical or electropolishing of a metal in an acid and the adventitious deterioration of metal plant by acid attack. It follows, therefore, that a comprehensive work on the subject of corrosion should include an account of batteries, electrorefining, chemical machining, chemical and electrochemical polishing, etc. 

Plutonium metal is prepared by two methods--direct reduction of the oxide by calcium (DOR)U,2J, and reduction of PuF by calcium in our metal preparation line (MPL)(3) (see Figure 1). In the DOR process, the plutonium contenF of the reduction slag is so low that the slag can be sent to retrievable storage without further processing. Metal buttons that are produced are no purer than the oxide feed and/or the calcium chloride salt. Los Alamos purifies the buttons by electrorefin-ing(4i,5 ), yielding metal rings that are > 99.96 percent plutonium. 

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. 

Electrorefining. Impure plutonium metal from MSE and Direct Oxide Reduction (DOR) is sent to an electrorefining operation (J3). In plutonium electrorefining, impure plutonium... 

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 basic electrorefining process is now being used on a production scale for the purification of non-specification plutonium metal. The technology is sufficiently well developed to permit 24-hour unattended operation of the electrorefining cells, and the quality of the product metal is highly consistent. This technology is rapidly replacing aqueous chemistry for plutonium metal purification. 

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. Bjorkland, C.W. "Large Scale Preparation of High Purity Plutonium Metal by Electrorefining", Los Alamos Nat. Lab. report LAMS-2441 (1960). 

Mullins, L.J. Morgan, A.M. Apgar, S.A. Ill and Christensen, D.C. "Six-Kilogram Scale Electrorefining of Plutonium Metal", Los Alamos National Laboratory Report LA-9469-MS (1982). 

The production of plutonium metal by both fluoride and oxide reduction is well established at Los Alamos. The subsequent purification of this metal by electrorefining is now being performed in production on a 6-kg batch scale. The objective is the production of high-purity plutonium metal. 

Recent process development efforts have been devoted to more expeditious and less costly pyrochemical reprocessing of residues created by the metal preparation and purification process. We intend to establish an internal recycle which yields either reusable or discardable residues and recovers all plutonium for feed to the electrorefining purification system. This internal recycle is to be performed in a more timely and less costly operation than in the present reprocessing mode. 

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