Uranium, solvent extraction

Tertiary amines are susceptible to oxidation (RsNiO), and some evidence has been found to suggest that oxidation does indeed occur after several months recycling in a uranium solvent extraction circuit [A. W. Ashbrook, unpublished data]. 

Bakshani, N. Maurer, E. E. Alien, M. P. Degenhart, A. L. Crud at the Sohio uranium solvent extraction circuit. Paper at AIME Annual Meeting, New Orleans, February 1979. 

Fujii, T., Yamana, H., Watanabe, M., Moriyama, H. 2002. Extraction study for TRUEX process using short-lived radionuclides produced by neutron irradiation of uranium. Solvent Extraction and Ion Exchange 20(2) 151-175. 

Fig. 21.14. Uranium solvent extraction process for purification of ore concentrate and scrap slurry feed eliminates clarification cost and losses. (Courtesy USDOE.)...

Movsowitz, R. L., Kleinberger, R., Buchalter, E. M., Grinbaum, B., and Hall, S. 2001. Comparison of the performance of full-scale pulsed columns versus mixer-settlers for uranium solvent extraction. In Proceedings international solvent extraction conference, vol. 2, eds. M. Cox, M. Hidalgo, and M. Valiente, 1455-1460. London Society of Chemical Industry. 

The wastes from uranium and plutonium processing of the reactor fuel usually contain the neptunium. Precipitation, solvent extraction, ion exchange, and volatihty procedures (see Diffusion separation methods) can be used to isolate and purify the neptunium. 

The development of the novel Davy-McKee combined mixer—settler (CMS) has been described (121). It consists of a single vessel (Fig. 13d) in which three 2ones coexist under operating conditions. A detailed description of units used for uranium recovery has been reported (122), and the units have also been studied at the laboratory scale (123). AppHcation of the Davy combined mixer electrostatically assisted settler (CMAS) to copper stripping from an organic solvent extraction solution has been reported (124). 

Solvent Extraction. Liquid—hquid extractioa, well known ia the chemical iadustry, was first used ia extractive metallurgy for the processiag of uranium. When a dilute solution of uranium is contacted with an extractant such as di(2-ethylhexyl) phosphoric acid (D2EHPA) or R2HPO4, dissolved ia... 

U02(C02) 3. The pregnant solution is concentrated and purified by ion exchange or solvent extraction, yielding a stripping solution of ca 50 kg/m U Og. Uranium is then precipitated chemically. Pure U Og is obtained by calcination (see Uraniumand URANIUM COMPOUNDS). 

An improved solvent extraction process, PUREX, utilizes an organic mixture of tributyl phosphate solvent dissolved in a hydrocarbon diluent, typically dodecane. This was used at Savannah River, Georgia, ca 1955 and Hanford, Washington, ca 1956. Waste volumes were reduced by using recoverable nitric acid as the salting agent. A hybrid REDOX/PUREX process was developed in Idaho Falls, Idaho, ca 1956 to reprocess high bum-up, fuUy enriched (97% u) uranium fuel from naval reactors. Other separations processes have been developed. The desirable features are compared in Table 1. 

The rate (kinetics) and the completeness (fraction dissolved) of oxide fuel dissolution is an inverse function of fuel bum-up (16—18). This phenomenon becomes a significant concern in the dissolution of high bum-up MO fuels (19). The insoluble soHds are removed from the dissolver solution by either filtration or centrifugation prior to solvent extraction. Both financial considerations and the need for safeguards make accounting for the fissile content of the insoluble soHds an important challenge for the commercial reprocessor. If hydrofluoric acid is required to assist in the dissolution, the excess fluoride ion must be complexed with aluminum nitrate to minimize corrosion to the stainless steel used throughout the facility. Also, uranium fluoride complexes are inextractable and formation of them needs to be prevented. 

Solvent Extraction Reagents. Solvent extraction is a solution purification process that is used extensively in the metallurgical and chemical industries. Both inorganic (34,35) and organic (36) solutes are recovered. The large commercial uses of phosphine derivatives in this area involve the separation of cobalt [7440-48-4] from nickel [7440-02-0] and the recovery of acetic acid [61-19-7] and uranium [7440-61-1]. 

PoUowing further development (38), a two-cycle process has been adopted by industry. In the first concentration cycle, the clarified feed acid containing 100—200 mg/L U Og [1334-59-8] is oxidized, for example, with hydrogen peroxide or sodium chlorate [7775-09-9] to ensure that uranium is in its 6+ valence state is not extracted. Uranium is extracted with a solvent composed of 0.5 Af D2EHPA and 0.125 Af TOPO dissolved in an aUphatic hydrocarbon diluent. 

Recovery of Uranium from Leach Solutions. The uranium can be recovered from leach solutions using a variety of approaches including ion exchange (qv), solvent extraction, and chemical precipitation. The most common methods in practice are ion exchange and solvent extraction to purify and concentrate the uranium prior to final product precipitation. 

Solvent Extraction. Solvent extraction has widespread appHcation for uranium recovery from ores. In contrast to ion exchange, which is a batch process, solvent extraction can be operated in a continuous countercurrent-fiow manner. However, solvent extraction has a large disadvantage, owing to incomplete phase separation because of solubihty and the formation of emulsions. These effects, as well as solvent losses, result in financial losses and a potential pollution problem inherent in the disposal of spent leach solutions. For leach solutions with a concentration greater than 1 g U/L, solvent extraction is preferred. For low grade solutions with <1 g U/L and carbonate leach solutions, ion exchange is preferred (23). Solvent extraction has not proven economically useful for carbonate solutions. 

Chemical Precipitation. The product of the extraction processes, whether derived from acid or carbonate leach, is a purified uranium solution that may or may not have been upgraded by ion exchange or solvent extraction. The uranium ia such a solution is concentrated by precipitation and must be dried before shipment. Solutions resulting from carbonate leaching are usually precipitated directly from clarified leach Hquors with caustic soda without a concentration step, as shown ia equation 9. 

In practice, uranium ore concentrates are first purified by solvent extraction with tributyl phosphate in kerosene to give uranyl nitrate hexahydrate. The purified uranyl nitrate is then decomposed thermally to UO (eq. 10), which is reduced with H2 to UO2 (eq. 11), which in turn is converted to UF by high temperature hydrofluorination (eq. 12). The UF is then converted to uranium metal with Mg (eq. 19). 

For vanadium solvent extraction, Hon powder can be added to reduce pentavalent vanadium to quadrivalent and trivalent Hon to divalent at a redox potential of —150 mV. The pH is adjusted to 2 by addition of NH, and an oxyvanadium cation is extracted in four countercurrent stages of mixer—settlers by a diesel oil solution of EHPA. Vanadium is stripped from the organic solvent with a 15 wt % sulfuric acid solution in four countercurrent stages. Addition of NH, steam, and sodium chlorate to the strip Hquor results in the precipitation of vanadium oxides, which are filtered, dried, fused, and flaked (22). Vanadium can also be extracted from oxidized uranium raffinate by solvent extraction with a tertiary amine, and ammonium metavanadate is produced from the soda-ash strip Hquor. Fused and flaked pentoxide is made from the ammonium metavanadate (23). 

The separation of basic precipitates of hydrous Th02 from the lanthanides in monazite sands has been outlined in Fig. 30.1 (p. 1230). These precipitates may then be dissolved in nitric acid and the thorium extracted into tributyl phosphate, (Bu"0)3PO, diluted with kerosene. In the case of Canadian production, the uranium ores are leached with sulfuric acid and the anionic sulfato complex of U preferentially absorbed onto an anion exchange resin. The Th is separated from Fe, A1 and other metals in the liquor by solvent extraction. 

Because of the technical importance of solvent extraction, ion-exchange and precipitation processes for the actinides, a major part of their coordination chemistry has been concerned with aqueous solutions, particularly that involving uranium. It is, however, evident that the actinides as a whole have a much stronger tendency to form complexes than the lanthanides and, as a result of the wider range of available oxidation states, their coordination chemistry is more varied. 

In the determination of molybdenum in uranium alloys containing 2.5% molybdenum,20 the uranium had to be removed because its high absorbance made the method insensitive. After a single solvent extraction, the molybdenum could be determined with a standard deviation... 

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