Separating actinide elements from fission products

The mutual separation of actinide elements and the selective isolation of useful actinides from fission products are indispensable for the nuclear fuel cycle and have become important subjects of investigation for the development of advanced nuclear fuel reprocessing and TRU (TRans Uranium elements) waste management [1], A variety of research concerning the separation chemistry of actinides has so far been accumulated [2]. There are, however, only a few theoretical studies on actinides in solution[3-5]. Schreckenbach et a), discussed the stability of uranyl (VI) tetrahydroxide [UO,(OH) ] [3] and Spencer and co-workers calculated the optimized structures of some uranyl and plutonyl hydrates [AcO, nH,0 (Ac = U, Pu and n = 4,5,6)] [4],... 

An extraction process for separating actinide elements (principally uranium, U, and plutonium, Pu) from fission products in an aqueous solution of spent fuel rods is illustrated in Figure 5.31. The extraction solvent is 30% tributyl phosphate (TBP) in kerosene. The most extractable of the fission products are zirconium, niobium and ruthenium. Zirconium, Zr, is used herein to represent the fission products. Determine the number of stages required in the wash section and in the extraction section. Determine the percentage of the Pu in the feed which is recovered in the extract product. V denotes the relative volumetric flowrate. 

A procedure for the rapid separation of berkelium from other actinides, lanthanides, and fission products was developed in order to measure the decay properties of short-lived isotopes [54]. Bk and Ce were separated from other elements using solvent extraction with HDEHP followed by cation-exchange high-pressure liquid chromatography (HPLC) using a-hydroxyisobutyrate as the eluant. The elution curve, showing a clean separation of Bk from Ce, is shown in... 

The lanthanide elements are very difficult to separate because of their highly similar chemistry, but the earlier actinide elements have sufficiently different redox chemistry to allow easy chemical separations. This is important in the nuclear power industry, where separations have to be made of the elements produced in fuel rods of nuclear power stations as fission products, and of the products Np and Pu, which arise from the neutron bombardment of the uranium fuel. 

In tlie PUREX process, the spent fuel and blanket materials are dissolved in nitric acid to form nitrates of plutonium and uranium. These are separated chemically from the other fission products, including the highly radioactive actinides, and then the two nitrates are separated into tv/o streams of partially purified plutonium and uranium. Additional processing will yield whatever purity of the two elements is desired. The process yields purified plutonium, purified uranium, and high-level wastes. See also Radioactive Wastes in the entry1 on Nuclear Power Technology. Because of the yield of purified plutonium, the PUREX process is most undesirable from a nuclear weapons proliferation standpoint,... 

The ZEALEX Process Researchers from KRI have shown that the zirconium salt of dibutyl phosphoric acid (ZS-HDBP) was soluble in Isopar-L in the presence of 30% TBP. This super PUREX solvent, known as ZEALEX, extracts actinides (Np-Am) together with lanthanides and other fission products, such as Ba, Cs, Fe, Mo, and Sr from nitric acid solutions. The extraction yields depend on both the molar ratio between Zr and HDBP in the 30% TBP/Isopar-L mixture and the concentration of HN03 (232). Trivalent transplutonium and lanthanide elements can be stripped together from the loaded ZEALEX solvent by a complexing solution, mixing ammonium carbonate, (NH4)2C03, and ethylenediamine-N.N.N. N -tetraacetic acid (EDTA). An optimized version of the process should allow the separation of... 

One possible application in which large amounts of rare earths and actinides would be processed occurs in some schemes for nuclear waste management. If it should prove to be advantageous to remove transplutonium elements from nuclear waste, for example, the recovery of Am and Cm from the much larger amounts of rare earths would be required. This problem has been investigated by the author in tracer tests with rare earth mixtures typical of fission products, using a heavy rare earth such as holmium as a stand-in for Am and Cm (Fig. 5). It is clear that the bulk of the holmium can be recovered in reasonable purity, and that the bulk of the lighter rare earths is effectively separated from the very small amount of heavy rare earths, Am, and Cm. 

The actinide iodate system is one of considerable interest that has attracted chemists for more than 150 years (vide supra). In fact one of the first forms that was isolated in was as the iodate salt, presumably as 1 0(103)4 [63], The precipitation of iodate compounds of the actinides has been used for decades as a method of separated them from lanthanides and other fission products. The precipitation of thorium iodate is perhaps best known in this regard [64-66], but several patents exist describing selective precipitation of transuranium elements [67-72], Despite the key importance of iodate in actinide chemistry the structures of actinide iodates were not described in detail until approximately 2000. 

Some of the pyrochemical processes have more potential for being proliferation resistant because of the great similarity of the chemistry of uranium, plutonium, and some of the fission products in the chosen systems. Ordinary processes are designed to maximize differences in chemical behavior in order to separate constitutents. For some of the pyrochemical processes the chemical equilibria are such that partial separations are possible but complete separations are thermodynamically limited. For example, excess uranium can be separated from plutonium by precipitation in a molten metal such as zinc only until both are present in about equal quantities in solution, but no further ( 3, 4). Likewise, the solubility of fission products is selectively limited. Only a portion of elements such as ruthenium will stay in solution and be removed 05). The majority of the ruthenium precipitates with the actinides. A complete separation is again thermodynamically limited. As a result only a modest dependence needs to be placed on process equipment and facility design for proliferation resistance. 

The FP-3 fission products are oxidized by MgCl2 or ZnCl2, are transferred to the salt phase, and are finally taken up by an acceptor alloy. The FP-4 elements are too inert to be oxidized by MgCl2 or ZnCl2 and remain with the donor alloy. The actinide elements are then separated from the FP-4 Fission products by salt transport to the acceptor alloy followed by vacuum retorting and conversion of metallic intermediates to suitable products. 

Molten-Tin Process for Reactor Fuels (16). Liquid tin is being evaluated as a reaction medium for the processing of thorium- and uranium-based oxide, carbide, and metal fuels. The process is based on the carbothermic reduction of UO2 > nitriding of uranium and fission product elements, and a mechanical separation of the actinide nitrides from the molten tin. Volatile fission products can be removed during the head-end steps and by distilling off a small portion of the tin. The heavier actinide nitrides are expected to sink to the bottom of the tin bath. Lighter fission product nitrides should float to the top. Other fission products may remain in solution or form compounds with... 

Separation of Actinides from the Samples of Irradiated Nuclear Fuels. For the purpose of chemical measurements of burnup and other parameters such as accumulation of transuranium nuclides in irradiated nuclear fuels, an ion-exchange method has been developed to separate systematically the transuranium elements and some fission products selected for burnup monitors (16) Anion exchange was used in hydrochloric acid media to separate the groups of uranium, of neptunium and plutonium, and of the transplutonium elements. Then, cation and anion exchange are combined and applied to each of those groups for further separation and purification. Uranium, neptunium, plutonium, americium and curium can be separated quantitatively and systematically from a spent fuel specimen, as well as cesium and neodymium fission products. 

The thrust of the experimental program at ICPP was to find a separation procedure that would separate plutonium, americium, and curium from high-level first-cycle raffinate (see Table I) and leave behind the cladding elements, salting agents, and the bulk of the fission products. Fission-product lanthanides, because of their similar valence and ionic size, would be expected to follow americium in nearly any simple separation scheme. Americium and curium are present in ICPP waste as trivalent ions while plutonium is most likely present as both Pu(IV) and Pu(VI). Any separation scheme must be applicable to all these ionic actinide species. 

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