Extraction of uranium from

For extraction of uranium from sulfate leach Hquors, alkyl phosphoric acids, alkyl phosphates, and secondary and tertiary alkyl amines are used in an inert diluent such as kerosene. The formation of a third phase is suppressed by addition of modifiers such as long-chain alcohols or neutral phosphate esters. Such compounds also increase the solubihty of the amine salt in the diluent and improve phase separation. 

Ryon, Daley, and Lowrie [Chem. Eng. Ftog., 55(10), 70, (1959), U.S. AFC ORNL-2951, I960]. Continuous extraction of uranium from sulfate-ore-leach liquors and kerosine -t- trihiityl phosphate and di(2-ethylhexyl)-phosphoric acid baffled vessels, turbine agitated. There is strong evidence of the influence of a slow chemical reaction. 

Ryon and Lowrie (U.S. AEC ORNL-3.381, 1960). Batch and continuous extraction of uranium from aqueous sulfate solutions into kerosine -t- amines, stripping of extract with aqueous sodium carbonate baffled vessels, turbine agitated. A detailed process study. 

Simard et al. [Can. J. Chem. Eng., 39, 229 (1961)]. Continuous extraction of uranium from aqueous nitrate solutions into kerosine -t- trihiityl phosphate and from sulfate solutions containing tricaprylamine unbaffled vessel, propeller agitated. Process details for high recovery and low reagent costs. 

As the parent of actinium in this series it was named protoactinium, shortened in 1949 to protactinium. Because of its low natural abundance its chemistry was obscure until 1960 when A. G. Maddock and co-workers at the UK Atomic Energy Authority worked up about 130g from 60 tons of sludge which had accumulated during the extraction of uranium from UO2 ores. It is from this sample, distributed to numerous laboratories throughout the world, that the bulk of our knowledge of the element s chemistry was gleaned. 

The extraction of metals by liquid amines has been widely investigated and depends on the formation of anionic complexes of the metals in aqueous solution. Such applications are illustrated by the use of Amberlite LA.l for extraction of zirconium and hafnium from hydrochloric acid solutions, and the use of liquid amines for extraction of uranium from sulphuric acid solutions.42,43... 

AMEX [Amine extraction] A process for the solvent extraction of uranium from sulfuric acid solutions using an amine extractant ... 

Dapex [Di-alkylphosphoric acid extraction] A process for the solvent extraction of uranium from sulfuric acid solutions using di-(2-ethylhexyl) phosphoric acid (HDEHP). The HDEHP is dissolved in kerosene containing 4 percent of tributyl phosphate. The uranium is stripped from the organic phase by aqueous sodium carbonate and precipitated as uranyl peroxide (yellow cake). The process was no longer in use in 1988. See also Amex. 

Uses Denaturant for ethyl alcohol solvent for paints, varnishes, cellulose acetate, nitrocellulose lacquers, resins, fats, oils, and waxes preparation of methyl amyl alcohol in hydraulic fluids and antifreeze extraction of uranium from fission products organic synthesis. 

Amine extraction is used also in another important industrial process, the extraction of uranium from sulphuric acid leached ores, which uses trilauryl amine (TLA). In that case, the extraction reaction is... 

High-grade pitchblende ores are leached with nitric acid to recover uranium. Extraction of uranium from nitrate solutions is usually performed with TBP. TBP-based solvents are used in several areas of the nuclear industry, especially for reprocessing of spent nuclear fuels and for refining the uranium product of the Amex and Dapex processes. Extraction of uranium by TBP solvents is described in sections 12.3.4 and 12.5. 

As noted earlier (see section 12.3.1), the Amex process, which uses long-chain amines, is preferred over the Dapex process, which uses HDEHP, for solvent extraction of uranium from H2SO4 leach solutions. Because the surfactant properties of amine sulfates are conducive to formation of objectionable emulsions, the Amex process is very sensitive to the presence of solids in the H2SO4 leachate. For acceptable phase coalescence in the Amex process, feeds should contain no more than 20 ppm solids. The Dapex process can tolerate feeds containing as much as 100 ppm solids. 

Concentration/purification by solvent extraction usually involves four steps (a) extraction of uranium from the leach liquor in a solvent, (b) scrubbing to remove impurities from the solvent, (c) stripping to remove uranium from the solvent, and (d) regeneration of the solvent. The solvent phase in solvent extraction will contain the extractant that complexes uranium to make it soluble in the organic phase, a diluent, an inexpensive material to dilute the extractant, and a modifier to improve the solubility of the extractant in the diluent. Typical extractants are amines with isode-canol acting as a modifier to improve the amine solubility in a diluent such as kerosene. The typical chemistry of the extraction would involve the reactions... 

Amine salts represent the only commercially important class of extractants of the anion-exchange type. Their most widespread use is in the extraction of uranium from sulfate leach liquors, but they have found application in the recovery of cobalt, zinc and copper from chloride solutions, as well as in the extraction of metals that readily form oxyanions, such as vanadium, molybdenum and tungsten. 

Some authors consider that the extracted complex is best formulated as an adduct, such as [(RjNH)2S04]2, U02S04(H20)3, which is the stoichiometry suggested by Sato on the basis of the analysis of solutions of tri- -octylamine saturated with uranium.204 Further studies of the extraction of uranium from sulfate media by amine salts have been reviewed by Cattrall and... 

Shimada, T., Ogumo, S., Sawada, K., Enokida, Y., Yamamoto, I. 2006. Selective extraction of uranium from a mixture of metal or metal oxides by a tri-n-butyl- phosphate complex with HN03 and H20 in supercritical C02. Anal. Sci. 22 (11) 1387-1391. 

Kumar, R. Sivaraman, N. Srinivasan, T.G. VasudevaRao, RR. Studies on the supercritical fluid extraction of uranium from tissue matrix, Radiochim. Acta 90 (2002) 141-145. 

Solvent extraction plays an important role in many commercial processes for the extraction of uranium from ore. In this case, the radioactivity levels are quite low compared with those in spent fuel extraction. The liquors from hy-drometallurgical leaching of ores are typically fairly dilute in uranium (0.5-5 g/L) and contain iron and other metals in solution. Depending on conditions, solvent extraction or ion exchange may be used to separate and concentrate the uranium from the leach liquor. 

Uranyl carbonate complexes have attracted considerable interest in recent years as they are intermediates in the processing of mixed oxide reactor fuels and in extraction of uranium from certain ores using carbonate leaching more topically they can be formed when uranyl ores react with carbonate or bicarbonate ions underground, and can be present in relatively high amounts in groundwaters. The main complex formed in carbonate leaching of uranyl ores is 8 coordinate [1102(003)3], but around pH 6 a cyclic trimer [(002)3(003)6] has been identified. 

The levels of uranium in aquatic organisms decline with each successive trophic level because of very low assimilation efficiencies in higher trophic animals. Bioconcentration factors measured in fish were low (Mahon 1982 Poston 1982 Waite et al. 1988) and were thought to arise from the extraction of uranium from the water or simply from the accumulation of uranium on gill surfaces (Ahsanullah and Williams 1989). In plants, uptake of uranium may be restricted to the root system and may actually... 

Arden et al. (A7) used the jigged-bed ion exchange technique for the extraction of uranium from acid-leached pulps. This method treats de-sandcd pulp containing 2(M0% by weight of solids with the -1-300 mesh particles removed by classification in single hydrocycloncs. The volume of the slime pulp is 1.2-2.0 times the volume of the leach solution compared to 2-3 times if conventional filtration is used. 

Fundamental studies have been reported using the cationic liquid ion exchanger di(2-ethylhexyl) phosphoric acid in the extraction of uranium from wet-process phosphoric acid (H34), yttrium from nitric acid solution (Hll), nickel and zinc from a waste phsophate solution (P9), samarium, neodymium, and cerium from their chloride solutions (12), aluminum, cobalt, chromium, copper, iron, nickel, molybdenum, selenium, thorium, titanium, yttrium, and zinc (Lll), and in the formation of iron and rare earth di(2-ethylhexyl) phosphoric acid polymers (H12). Other cationic liquid ion exchangers that have been used include naphthenic acid, an inexpensive carboxylic acid to separate copper from nickel (F4), di-alkyl phosphate to recover vanadium from carnotite type uranium ores (M42), and tributyl phosphate to separate rare earths (B24). 

The early experiments on solvent extraction directly from leached pulp were beset with problems such as losses of solvent in the aqueous phase and the formation of emulsions. The use of mixer-settler, pump mixer, and internal mixer-settler type contactors on a laboratory scale (Gil) has demonstrated the feasibility of uranium extraction from desanded slurries with 5-1. )% solids and from high-density slurries with 48-60% percent solids. The deemulsification rate of a synthetic slurry as a function of the temperature of the system and the pH of the slurries (T12) and the effect of extractant entrainment in the aqueous effluent on solvent extraction of uranium from slurries containing more than 40% solids (E6) have been studied. 

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