Plutonium processing PUREX process

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,... 

Jenkins, J.A., Mills, A.L., Thompson, P.J., Jubin, R.T. 1993. Performance of centrifugal contactors on uranium and plutonium active PUREX flowsheets. In Solvent Extraction in the Process Industries ISEC 93, York, UK, September 16-21. Logsdail, D.H., Slater, M.J. Eds. Elsevier Applied Science, London and New York. 

Pandey, N.K. Koganti, S.B. Simulation of electro-mixer-settler for the partitioning of uranium and plutonium in PUREX process, Ind. J. Chem. Technol. 11 (2004) 535-547. 

These variations permit the separation of other components, if desired. Additional data on uranium, plutonium, and nitric acid distribution coefficients as a function of TBP concentration, solvent saturation, and salting strength are available (24,25). Algorithms have also been developed for the prediction of fission product distributions in the PUREX process (23). 

Uranium. The uranium product from the PUREX process is in the form of uranyl nitrate which must be converted to some other chemical depending on anticipated use. One route to MO fuel is to mix uranium and plutonium nitrates and perform a coprecipitation step. The precipitate is... 

By-Products. The PUREX process is efficient at separating uranium and plutonium from everything else in the spent fuel. Within the high level waste stream are a number of components which have, from time to time, been sufficiendy interesting to warrant their recovery. The decision to recover a particular isotope is usually based on a combination of market incentives and desired waste reduction. 

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). 

The plutonium extracted by the Purex process usually has been in the form of a concentrated nitrate solution or symp, which must be converted to anhydrous PuF [13842-83-6] or PuF, which are charge materials for metal production. The nitrate solution is sufficientiy pure for the processing to be conducted in gloveboxes without P- or y-shielding (130). The Pu is first precipitated as plutonium(IV) peroxide [12412-68-9], plutonium(Ill) oxalate [56609-10-0], plutonium(IV) oxalate [13278-81-4], or plutonium(Ill) fluoride. These precipitates are converted to anhydrous PuF or PuF. The precipitation process used depends on numerous factors, eg, derived purity of product, safety considerations, ease of recovering wastes, and required process equipment. The peroxide precipitation yields the purest product and generally is the preferred route (131). The peroxide precipitate is converted to PuF by HF—O2 gas or to PuF by HF—H2 gas (31,132). 

Then the fuel elements are dissolved in 7m HNO3 to give a solution containing U and Pu which, in the widely used plutonium-uranium-reduction, or Purex process, are extracted into 20% tributyl phosphate (TBP) in kerosene leaving most of the fission products... 

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. 

Irradiated Fuel A historically important and continuing mission at the Hanford site is to chemically process irradiated reactor fuel to recover and purify weapons-grade plutonium. Over the last 40 years, or so, several processes and plants— Bismuth Phosphate, REDOX, and PUREX—have been operated to accomplish this mission. Presently, only the Hanford PUREX Plant is operational, and although it has not been operated since the fall of 1972, it is scheduled to start up in the early 1980 s to process stored and currently produced Hanford -Reactor fuel. Of nine plutonium-production reactors built at the Hanford site, only the N-Reactor is still operating. 

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... 

Navratil, J. D. Leebl, R. G. "Modified Purex Processes for the Separation and Recovery of Plutonium-Uranium Residues," U.S. DOE Rept. RFP-2675, Rockwell International, Golden, Colorado, July 1978. 

Purex [Plutonium and uranium recovery by extraction] A process for the solvent extraction of plutonium from solutions of uranium and fission products, obtained by dissolving spent nuclear fuel elements in nitric acid. The solvent is tri-n-butyl phosphate (TBP) in... 

Redox [Reduction oxidation] A process for separating the components of used nuclear fuel by solvent extraction. It was the first process to be used and was brought into operation at Hanford, United States, in 1951, but was superseded in 1954 by the Purex process. The key to the process was the alternate reduction and oxidation of the plutonium, hence the name. The solvent was Hexone (4-methyl-2-pentanone, methyl isobutyl ketone), so the process was also known as the Hexone process. The aqueous phase contained a high... 

The solvent extraction process that uses TBP solutions to recover plutonium and uranium from irradiated nuclear fuels is called Purex (plutonium uranium extraction). The Purex process provides recovery of more than 99% of both uranium and plutonium with excellent decontamination of both elements from fission products. The Purex process is used worldwide to reprocess spent reactor fuel. During the last several decades, many variations of the Purex process have been developed and demonstrated on a plant scale. 

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... 

Figure 12.5 illustrates the basic components of the Purex process three purification cycles for both uranium and plutonium are shown. High levels of beta and gamma radioactivity are present only in the first cycle, in which 99.9% of the fission products are separated. The other two cycles, based upon the same chemical reactions as the first cycle, obtain additional decontamination and overall purity of the uranium and plutonium products. 

Uranium stripping Dilute HNO3 solutions at 45-50°C are used to remove uranium from the TBP phase. Traces of the fission products ruthenium and zirconium are eliminated in the second and third cycles of the Purex process. Also, in the second and third cycles, neptunium and the last traces of plutonium are removed from the uranium product. 

Long-lived ty = 2.1 x 10 years) Tc, present as TCO4 in Purex process HNO3 feed solutions, is partially coextracted with uranium and plutonium in the first cycle. Unless separated in the Purex process, Tc contaminates the uranium product subsequent processing of the U02(N03)2 solution to UO2 can release some of the technetium to the environment. The presence of technetium in the purification steps as well as in the uranium product causes several other complications. Thus it is desirable to route all Tc into the high-level waste. Efforts in this direction have been described in some recent flow sheets [37]. 

Recuplex A variant of the Purex process for extracting plutonium, in which the tributyl phosphate is dissolved in carbon tetrachloride in order to make the organic phase denser than the aqueous phase. 

The Purex process, ie, plutonium uranium reduction extraction, employs an organic phase consisting of 30 wt % TBP dissolved in a kerosene-type diluent. Purification and separation of U and Pu is achieved because of the extractability of U02+2 and Pu(IV) nitrates by TBP and the relative inextractability of Pu(III) and most fission product nitrates. Plutonium nitrate and U02(N03)2 are extracted into the organic phase by the formation of compounds, eg, Pu(N03)4 -2TBP. The plutonium is reduced to Pu(III) by treatment with ferrous sulfamate, hydrazine, or hydroxylamine and is transferred to the aqueous phase U remains in the organic phase. Further purification is achieved by oxidation of Pu(III) to Pu(IV) and re-extraction with TBP. The plutonium is transferred to an aqueous product. Plutonium recovery from the Purex process is ca 99.9 wt % (128). Decontamination factors are 106 — 10s (97,126,129). A flow sheet of the Purex process is shown in Figure 7. 

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