Plutonium processing anionic

Figure 3 shows a flowsheet for plutonium processing at Rocky Flats. Impure plutonium metal is sent through a molten salt extraction (MSE) process to remove americium. The purified plutonium metal is sent to the foundry. Plutonium metal that does not meet foundry requirements is processed further, either through an aqueous or electrorefining process. The waste chloride salt from MSE is dissolved then the actinides are precipitated with carbonate and redissolved in 7f1 HN03 and finally, the plutonium is recovered by an anion exchange process. 

Acid waste streams are sent through a nitric acid recovery process, and then to a secondary plutonium recovery anion exchange process. The acid waste streams are then sent to waste treatment. 

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). 

Impure plutonium oxide residues are dissolved in 12M HN03-0.1M HF under refluxing conditions, and then the plutonium is recovered and purified by anion exchange. Plutonium is leached from other residues, such as metal and glass, and is also purified by anion exchange. The purified plutonium eluate from the anion exchange process is precipitated with hydrogen peroxide. The plutonium peroxide is calcined to the oxide, and the plutonium oxide is fluorinated. The plutonium tetrafluoride is finally reduced to the metal with calcium. 

Acid waste streams are processed through nitric acid recovery and then sent to a secondary plutonium recovery process which uses anion exchange. Acid, basic, and laundry waste streams are sent to waste treatment. A discussion of the process steps shown on Figure 1 follows. 

Molten salt extraction residues are processed to recover plutonium by an aqueous precipitation process. The residues are dissolved in dilute HC1, the actinides are precipitated with potassium carbonate, and the precipitate redissolved in nitric acid (7M) to convert from a chloride to a nitrate system. The plutonium is then recovered from the 7M HNO3 by anion exchange and the effluent sent to waste or americium recovery. We are studying actinide (III) carbonate chemistry and looking at new... 

D. B. James, Anion Exchange Processing of Plutonium, LA-3499, Los Alamos Scientific Laboratory, N.M., 1966. 

The process sequence currently used for waste salts (except those containing aluminum for which no process currently exists) is shown in Figure 1. The process includes (1) dilute hydrochloric acid dissolution of residues (2) cation exchange to convert from the chloride to the nitrate system and to remove gross amounts of monovalent impurities (3) anion exchange separation of plutonium (4) oxalate precipitation of americium and (5) calcination of the oxalate at 600°C to yield americium oxide. 

A continuing problem with the cation exchange process as used in production operations is that it has not been sufficiently selective and therefore allows considerable carryover of the MSE salt constituents and impurities with the plutonium and americium. This isn t serious with plutonium since plutonium can be subsequently purified by anion exchange. For americium, however, the subsequent recovery process is oxalate precipitation which is less selective and carries some of the impurities into the final product. 

Separation and Purification. In the Purex process discussed here, the uranium, plutonium, and fission products are separated by solvent extraction into three different streams (Fig. 21.20). The plutonium stream goes through anion exchange (discussed later) to reduce traces of ruthenium, and the uranium stream goes through silica gel sorption to reduce traces of zirconium. The fission-product stream, which contains the fission products... 

Plutonium peroxide was investigated by Hamaker and Koch, (0 Hopkins, (2) and Koshland, et al. (3) in the 19 0 s and Leary (h) in the early 1950 s. This work showed that the composition of the precipitate varied and often incorporated anions from the solution from which it was precipitated. These investigations, as well as other work (5), also showed that the peroxide precipitate exists in both hexagonal and cubic crystalline forms. Although both forms are compounds of Pu(lV), they have slightly different O /Pu ratios (6). The cubic form can be colloidal and therefore is less suitable for process application than the hexagonal form. The acidity of the solution has an effect on the... 

A more radical modification of the Purex process, the Aquafluor process, developed by General Electric for its Midwest Fuel Recovery Plant, retained only a single TBP co-decontamina-tion cycle followed by a continuous anion exchange contactor in which plutonium was to be removed from the U-Pu nitrate solution. The performance of this plant was never tested with plutonium, since General Electric decided to forego operation of the plant after technical difficulties developed during the "cold" checkout trials. 

No definite reason for these fluctuations could be identified, but it is known that neptunium, due to its complicated redox chemistry, reacts in a very sensitive way to even minor process variations (7,8). Based on these results the proposal was made (J5) to recover the "co-extracted" portion of the neptunium by running the second plutonium and uranium purification cycles under conditions where the Np is directed into the aqueous raffinates (2AW and 2DW streams). In the Pu purification cycle, this can be done by adding sufficient nitrous acid to keep the Np pentavalent, while in the U purification cycle (which is run under slightly reducing conditions) a low acidity and a high loading help to reject Np into the aqueous 2DW stream. The two raffinate streams are combined in WAK in the 3W evaporator, and the Np is thus collected in the concentrate from this unit (3WW stream). Consequently the proposal was made to recover the Np from this 3WW stream by use of the well-known anion exchange process (9,J ). 

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