Plutonium processing conversion

The complete chemistry of plutonium 1 iquid-to-solid conversion processes, especially peroxide and oxalate precipitation, should be further studied. Research and development of direct thermal denitration methods should also be pursued. 

The following pages will describe several examples of pyrochemical processing as applied to the recycle of plutonium, and will briefly review the fundamental chemistry of these processes. We shall review the conversion of plutonium oxide to plutonium metal by the direct oxide reduction process (DOR),the removal of americium from metallic plutonium by molten salt extraction (MSE), and the purification of metallic... 

A. Process Schematic. A schematic of the main process sequence for the conversion of plutonia scrap to high-purity metal is shown in Figure 2. Plutonia scrap is fed to both the direct oxide reduction (DOR) process and the plutonium tetrafluoride production/ reduction process. 

Plutonium is subsequently stripped to an aqueous phase containing NH20H HN03 in the CC Column. In order to increase the plutonium concentration of the CC Column product, a portion of this stream (CAIS) is recycled to the CA Column after adjustment with HNO3. The remainder of the stream (CCP) is routed to the product concentrator. The resulting concentrated and purified plutonium nitrate solution is suitable feed to other processes for conversion to the desired product form (e.g., metal or plutonium dioxide). The remainder of the PRF solvent extraction system consists of a series of columns to wash the TBP-CCI4 solvent and prepare it for reuse. 

Plutonium-239. Plutonium-239 represents a fortuitous phenomenon. Whereas U-235 is the only significant fissile nuclide in nature, its major isotope, U-238, captures a neutron to produce another fissile nuclide, plutonium-239. A substantial amount of the energy produced during the life of uranium fuel is produced by the conversion of U-238 to Pu-239 which subsequently fissions. This process provides the basis for the nuclear breeding cycle. 

Plutonium-239 and tritium for use as military explosives are the two major transmutation products. The nuclear process for Pu-239 production is the same as for energy generation, but there are some differences (a) metallic natural uranium clad with aluminum facilitates later dissolution for plutonium recovery, and the reactor operates at a relatively low temperature because of the aluminum clad and better heat transfer (due to the metallic natural uranium) (b) the irradiation cycle is limited to a few months to minimize the Pu-239 conversion to Pu-240 and Pu-241 and (c) a carbon or a heavy water moderator is used to increase the neutron efficiency. 

A prime responsibility of the Rocky Flats Plant since it was built by the Atomic Energy Commission some 25 years ago has been the recovery and purification of plutonium. This recovery and purification has been done using an aqueous process. One of the major steps in that process is the precipitation of plutonium peroxide. This step converts the plutonium from an aqueous to a solid form for further processing and conversion to metal. 

The only other binary oxide of plutonium of practical importance is the peroxide, which is the basis of a process for the purification of plutonium and its conversion to the metal. Addition of H2O2 to an aqueous plutonium solution first converts plutonium ions to the tetravalent state. 

PuOj from direct calcination of Pu(N03 )4. The precipitation steps of the above processes can be avoided by the direct calcination of the plutonium nitrate solution to PuOa. Calcination has been carried out at 350 C in a liquid-phase screw calciner. Half a mole of ammonium sulfate per mole of plutonium is added to the feed solution to increase the production of reactive PuOi. The calcination time and temperature must be low enough to minimize sintering, which would otherwise reduce the chemical reactivity of the oxide particles for subsequent conversion to a halide. 

In the Aquafluor process [G4] developed by the General Electric Company, most of the plutonium and fission products in irradiated light-water reactor (LWR) fuel are separated from uranium by aqueous solvent extraction and anion exchange. Final uranium separation and purification is by conversion of impure uranyl nitrate to UFg, followed by removal of small amounts of PuF , NpFg, and other volatile fluorides by adsorption on beds of NaF and Mgp2 and a final fractional distillation. A plant to process 1 MT/day of irradiated low-enriched uranium fuel was built at Morris, Illinois, but was never used for irradiated fuel because of inability to maintain on-stream, continuous operation even in runs on unirradiated fuel. The difficulties at the Morris plant are considered more the fault of design details than inherent in the process. They are attributed to the attempt to carry out aqueous primary decontamination, denitration, fluorination, and distillation of intensely radioactive materials in a close-coupled, continuous process, without adequate surge capacity between the different steps and without sufficient spare, readily maintainable equipment [G5, R8]. 

Many reprocessing plants are required to convert purified nitrates containing plutonium to oxides before shipment. Conversion processes are described in Chap. 9, Sec. 4.7. 

The plutonium purification may be achieved by additional TBP extraction cycles. U(IV) cannot be used as reductant in this part of the process. The final uranium and plutonium products are nitrate solutions whose conversion to oxides, fluorides, etc., have been described earlier ( 5.5.3). 

At any stage of nuclear material management (closure of plutonium facilities, vitrification processes, fabrication of MOX fuel, metallic plutonium conversion into oxide, etc.), the long-lived radionuclides appearing in case of any deviation from the standard process can be reliably isolated from the environment only by their final disposal in geologic formations. 

PNC developed a co-conversion technology utilizing the microwave heating direct denitration process (MH method) which converts plutonium nitrate and uranyl nitrate solution to MOX powder. Compared with the conventional method, it is a simple process and generates less liquid waste. 

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