Irradiated fuel processing

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. 

Actinides occurrence and preparation. With the exception of U and Th, the availability of the actinides of the first half of the series ranges from the g to kg scale that of the elements of the second half of the series from the mg scale for Cf to the sub-mg scale for Es. Isotopes of Np, Pu, Am, Cm can be available as byproducts of nuclear fuel processing other elements such as Ac, Cf, Bk, Es can be obtained by irradiation of selected isotopes in high flux reactors, or by reprocessing large quantities of ore (Pa). 

Fig. 12.9 Two-stage acid Thorex process for highly irradiated fuels. Numbers in the frames indicate stage number, whereas numbers on the lines indicate flow volumes relative to the feed volume (DOD and FP are dodecane and hssion products). 

An overall schematic view of the Purex process is shown in Figure 16.10. Detailed descriptions of the process can be found in Benedict and co-workers (1981) and Wymer and Vondra (1981). We shall briefly summarize the important steps. The first step is to prepare the irradiated fuel for dissolution by mechanically chopping it into small pieces ( 1—5 cm). This opening of the cladding causes the... 

Viewed in the context of the actinide lifespan, the nuclear fuel cycle involves the diversion of actinides from their natural decay sequence into an accelerated fission decay sequence. The radioactive by-products of this energy producing process will themselves ultimately decay but along quite different pathways. Coordination chemistry plays a role at various stages in this diversionary process, the most prominent being in the extraction of actinides from ore concentrate and the reprocessing of irradiated fuel. However, before considering these topics in detail it is appropriate to consider briefly the vital role played by coordination chemistry in the formation of uranium ore deposits. 

The uranium and thorium ore concentrates received by fuel fabrication plants still contain a variety of impurities, some of which may be quite effective neutron absorbers. Such impurities must be almost completely removed if they are not seriously to impair reactor performance. The thermal neutron capture cross sections of the more important contaminants, along with some typical maximum concentrations acceptable for fuel fabrication, are given in Table 9. The removal of these unwanted elements may be effected either by precipitation and fractional crystallization methods, or by solvent extraction. The former methods have been historically important but have now been superseded by solvent extraction with TBP. The thorium or uranium salts so produced are then of sufficient purity to be accepted for fuel preparation or uranium enrichment. Solvent extraction by TBP also forms the basis of the Purex process for separating uranium and plutonium, and the Thorex process for separating uranium and thorium, in irradiated fuels. These processes and the principles of solvent extraction are described in more detail in Section 65.2.4, but the chemistry of U022+ and Th4+ extraction by TBP is considered here. 

Figure 29 An outline process for irradiated fuel reprocessing by solvent extraction...

Based on available information, we believe that transfer of the uranate to a molten chloride system with electrolytic reduction is the most feasible method. Electrolytic deposition from molten alkali metal chlorides was an integral step in the pyro-chemical process known as the Hanford Salt Cycle. Documentation of this phase of the process was extensive and also represents one of the very few pyrochemical processes that has been carried through pilot-plant scale on irradiated fuel. Unknowns exist, such as the rate and conditions of uranate dissolution, but considerable use could be made of previously documented results. 

For the purpose of improving the decontamination factor (DF) of FPs from U or Pu in the reprocessing of highly irradiated fuels such as those from FBR, a modified method adding inactive zirconium or hafnium ion is proposed. The feasibility of this concept has been experimentally demonstrated by both batchwise extraction and process studies with miniature mixer-settlers. 

Based on estimates similar to those above, it can be predicted that large amounts of fluoride would be required to obtain PUO2 dissolution rates in irradiated fuel dissolver solutions that are comparable to those in pure HNO3-HF solutions. Because of the effect of the large excess of uranium, it is probably not feasible to add sufficient fluoride (since it is undesirable in later processing and waste storage steps) to reach a dissolution rate more than several-fold lower than in pure HNO3-HF. 

---