Tributyl phosphate solvent

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 solvents used vary with die nature of the products involved. Widely used are water, hexane, acetone, isopropyl alcohol, furfural, xylene, liquid sulfur dioxide, and tributyl phosphate. Solvent extraction is an important method of both producing and purifying such products as lubrication and vegetable oils, pharmaceuticals, and nonferrous metals,... 

Brewer, K.N., Herbst, R.S., Todd, T.A., Christian, J.D. 1998. Zirconium extraction into octyl-(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide and tributyl phosphate. Solvent Extr. IonExch. 16 (4) 1047-1066. 

Zhang, P., Kimura, T. 2006. Complexation of Eu(III) with dibutyl phosphate and tributyl phosphate. Solvent Extr. lonExch. 24 149-163. 

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 solvent extraction of a tetravalent vanadium oxyvanadium cation, the leach solution is acidified to ca pH 1.6—2.0 by addition of sulfuric acid, and the redox potential is adjusted to —250 mV by heating and reaction with iron powder. Vanadium is extracted from the blue solution in ca six countercurrent mixer—settler stages by a kerosene solution of 5—6 wt % di-2-ethyIhexyl phosphoric acid (EHPA) and 3 wt % tributyl phosphate (TBP). The organic solvent is stripped by a 15 wt % sulfuric acid solution. The rich strip Hquor containing ca 50—65 g V20 /L is oxidized batchwise initially at pH 0.3 by addition of sodium chlorate then it is heated to 70°C and agitated during the addition of NH to raise the pH to 0.6. Vanadium pentoxide of 98—99% grade precipitates, is removed by filtration, and then is fused and flaked. 

Ce(IV) extracts more readily iato organic solvents than do the trivalent Ln(III) ions providing a route to 99% and higher purity cerium compounds. Any Ce(III) content of mixed lanthanide aqueous systems can be oxidi2ed to Ce(IV) and the resultiag solutioa, eg, of nitrates, contacted with an organic extractant such as tributyl phosphate dissolved in kerosene. The Ce(IV) preferentially transfers into the organic phase. In a separate step the cerium can be recovered by reduction to Ce(III) followed by extraction back into the aqueous phase. Cerium is then precipitated and calcined to produce the oxide. 

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. 

Spectrophotometric methods may often be applied directly to the solvent extract utilising the absorption of the extracted species in the ultraviolet or visible region. A typical example is the extraction and determination of nickel as dimethylglyoximate in chloroform by measuring the absorption of the complex at 366 nm. Direct measurement of absorbance may also be made with appropriate ion association complexes, e.g. the ferroin anionic detergent system, but improved results can sometimes be obtained by developing a chelate complex after extraction. An example is the extraction of uranyl nitrate from nitric acid into tributyl phosphate and the subsequent addition of dibenzoylmethane to the solvent to form a soluble coloured chelate. 

A particularly interesting system for the epoxidation of propylene to propylene oxide, working under pseudo-heterogeneous conditions, was reported by Zuwei and coworkers [61]. The catalyst, which was based on the Venturello anion combined with long-chained alkylpyridinium cations, showed unique solubility properties. I11 the presence of hydrogen peroxide the catalyst was fully soluble in the solvent, a 4 3 mixture of toluene and tributyl phosphate, but when no more oxidant was left, the tungsten catalyst precipitated and could simply be removed from the... 

Solvent Extraction. A modified, one-cycle PUREX process is used at Rocky Flats to recover plutonium from miscellaneous Pu-U residues (11). The process utilizes the extraction of uranium (VI) into tributyl phosphate (TBP), leaving plutonium (III) in the raffinate. The plutonium is then sent to ion exchange for... 

The effect of irradiation on the extractability of sulfoxides towards plutonium, uranium and some fission products were studied by Subramanian and coworkers . They studied mainly the effect of irradiation on dihexyl sulfoxide (DHSO) and found that irradiation did not change the distribution coefficient for Ru, Eu and Ce but increases the distribution coefficient for Zr and Pu. When comparing DHSO and tributyl phosphate (TBP), the usual solvent for the recovery and purification of plutonium and uranium from spent nuclear fuels, the effect of irradiation to deteriorate the extraction capability is much larger in TBP. Lan and coworkers studied diphenyl sulfoxides as protectors for the gamma radiolysis of TBP. It was found that diphenyl sulfoxide can accept energy from two different kinds of excited TBP and thus inhibits the decomposition of the latter. 

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. 

Cecolene, see Trichloroethylene Cekiuron, see Diuron Cekubaryl, see Carbaryl Cekusan, see Dichlorvos Celanex, see Lindane Celfume, see Methyl bromide Cellon, see 1,1,2,2-Tetrachloroethane Cellosolve, see 2-Ethoxyethanol Cellosolve acetate, see 2-Ethoxyethyl acetate Cellosolve solvent, see 2-Ethoxyethanol Celluflex DOP, see Di-rr-octyl phthalate Celluflex DPB, see Di-rr-butyl phthalate Celluflex TPP, see Triphenyl phosphate Celluphos 4, see Tributyl phosphate Celmide, see Ethylene dibromide Celthion, see Malathion... 

Fuel. The nuclear fuel cycle starts with mining of the uranium ore, chemical leaching to extract the uranium, and solvent extraction with tributyl phosphate to produce eventually pure uranium oxide. If enriched uranium is required, the uranium is converted to the gaseous uranitim hexafluoride for enrichment by gaseous diffusion or gas centrifuge techniques, after which it is reconverted to uranium oxide. Since the CANDU system uses natural uranium, I will say no more about uranium enrichment although, as I m sure you appreciate, it is a major chemical industry in its own right. 

Thorium sulfate, being less soluble than rare earth metals sulfates, can be separated by fractional crystallization. Usually, solvent extraction methods are applied to obtain high purity thorium and for separation from rare earths. In many solvent extraction processes, an aqueous solution of tributyl phosphate is the extraction solvent of choice. 

Finely-ground monazite is treated with a 45% NaOH solution and heated at 138°C to open the ore. This converts thorium, uranium, and the rare earths to their water-insoluble oxides. The insoluble residues are filtered, dissolved in 37% HCl, and heated at 80°C. The oxides are converted into their soluble chlorides. The pH of the solution is adjusted to 5.8 with NaOH. Thorium and uranium are precipitated along with small quantities of rare earths. The precipitate is washed and dissolved in concentrated nitric acid. Thorium and uranium are separated from the rare earths by solvent extraction using an aqueous solution of tributyl phosphate. The two metals are separated from the organic phase by fractional crystallization or reduction. 

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