Plutonium ions Purex process

Ammonium ions, tetradecyldimethylbenzyl-liquid—Liquid extraction, 1, 548 Ammonium molybdate, 3,1257 Ammonium nitrate, hydroxyl-as plutonium(IV) reductant Purex process, 6, 949 Amphotericin B metal complexes, 2, 973 a-Amylase zinc, 6, 607 Anabaena spp. 

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... 

A primary goal of chemical separation processes in the nuclear industry is to recover actinide isotopes contained in mixtures of fission products. To separate the actinide cations, advantage can be taken of their general chemical properties [18]. The different oxidation states of the actinide ions lead to ions of charges from +1 (e.g., NpOj) to +4 (e.g., Pu" " ) (see Fig. 12.1), which allows the design of processes based on oxidation reduction reactions. In the Purex process, for example, uranium is separated from plutonium by reducing extractable Pu(IV) to nonextractable Pu(III). Under these conditions, U(VI) (as U02 ) and also U(IV) (as if present, remain in the... 

The control of the actinide metal ion valence state plays a pivotal role in the separation and purification of uranium and plutonium during the processing of spent nuclear fuel. Most commercial plants use the plutonium-uranium reduction extraction process (PUREX) [58], wherein spent fuel rods are initially dissolved in nitric acid. The dissolved U and Pu are subsequently extracted from the nitric solution into a non-aqueous phase of tributyl phosphate (TBP) dissolved in an inert hydrocarbon diluent such as dodecane or odourless kerosene (OK). The organic phase is then subjected to solvent extraction techniques to partition the U from the Pu, the extractability of the ions into the TBP/OK phase being strongly dependent upon the valence state of the actinide in question. 

The Purex process will continue to be the main method for the reprocessing of nuclear reactor fuels. The inherent flexibility of this process allows for modifications needed to accomodate a large range of fuel compositions and product specifications. Among the several plutonium partitioning methods developed, those avoiding the introduction of extraneous metal ions... 

In the Purex process, plutonium and uranium are coextracted into an organic phase and partitioned by reducing plutonium(IV) to the aqueous-favoring plutonium(III). This has been achieved chemically by use of a suitable reductant such as ferrous sulfamate ( 1) or uranium(IV). (2, 3, 4, 5) The use of ferrous sulfamate results in accelerated corrosion of the stainless steel, due to the presence of ferric ions and sulfuric acid, and in an increase in the volume of wastes. The use of natural uranium(IV) can cause dilution of the 235U in slightly enriched uranium, thus lowering the value of the recovered uranium. 

The hot run was made with the feed solution obtained by dissolving highly irradiated Pu-Al alloy in HNO3 with mercuric ion catalyst. Uranium was added to the solution to produce a typical Purex feed. Uranium and most of the plutonium were recovered by the normal Purex process. The aqueous waste containing Am, Cm, Cf, fission products, Al, and Hg was evaporated and acid was stripped to produce the feed (Table 2). The results are as expected from the laboratory tests excellent recovery of Pu, Am, and Cm but low decontamination factors (DF). 

Ions of different valences of a metal behave like different elements with respect to extract-ability. The difference between Ce and Ce in Table 4.2 is one example. Another is afforded by Pu and Pu 02, which are readily extracted by TBP in kerosene, whereas Pu has a very low distribution coefficient [G31. Consequently, by adjusting the oxidation-reduction potential of the aqueous phase to control the proportion of an element in different valence states, it is possible to vary its distribution coefficient between wide limits. This is the mearts by which plutonium is stripped from aqueous solutions containing plutonium and uranium in sections C and D of Fig. 4.5 illustrating the Purex process. Addition of a reducing... 

Process selection. The processes just described recovered neptunium only partially and in variable yield because of the difficulty in controlling the distribution of neptunium valence between 5 and 6 in the primary extraction step with nitrite-catalyzed HNO3 and the incomplete reduction of neptunium from valence 5 to 4 in the partitioning step with feirous ion. This section describes a modified Purex process that could be used if more complete recovery of neptunium were required. It is based on process design studies by Tajik [Tl]. The principal process steps are shown in the material flow sheet Fig. 10.32. In the primary decontamination step, pentavalent vanadium oxidizes neptunium to the extractable hexavalent state. In the partitioning step, tetravalent uranium reduces plutonium to the inextractable trivalent state while converting neptunium to the still-extractable tetravalent state. 

Americium and curium can be obtained from the aqueous waste of the Purex process. This americium is a mixture of Am and " Am. Isotopically pure Am, the decay product of " Pu, can be obtained from aged plutonium. Solvent extraction and ion-exchange procedures are used to recover americium from waste streams. Americium metal is produced by lanthanum reduction of the oxide, followed by vacuum distillation of the americium at 1400°C. 

Evidence foi the anionic complex PuCP is the precipitation of complex halides such as Cs2PuClg from concentrated HCl (aq). The ability of Pu(IV) to form stable nitrate complexes provides the basis for the Purex and ion-exchange (qv) process used in the chemical processing of Pu (107). Pu(VI) is similar to Pu(IV) in its abihty to form complex ions. Detailed reviews of complex ion formation by aqueous plutonium are available (23,94,105). 

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