Plutonium processing liquid fuels

AR477 3.10 Liquid waste treatment system design guide for plutonium processing and fuel fabrication... 

Nuclear Waste Reprocessing. Liquid waste remaining from processing of spent reactor fuel for military plutonium production is typically acidic and contains substantial transuranic residues. The cleanup of such waste in 1996 is a higher priority than military plutonium processing. Cleanup requires removal of long-Hved actinides from nitric or hydrochloric acid solutions. The transuranium extraction (Tmex) process has been developed for... 

Reprocessing is based on liquid-liquid extraction for the recovery of uranium and plutonium from used nuclear fuel (PUREX process). The spent fuel is first dissolved in nitric acid. After the dissolution step and the removal of fine insoluble solids, an organic solvent composed of 30% TriButyl Phosphate (TBP) in TetraPropylene Hydrogenated (TPH) or Isopar L is used to recover both uranium and plutonium the great majority of fission products remain in the aqueous nitric acid phase. Once separated from the fission products, back-extraction combined with a reduction of Pu(I V) to Pu(III) allows plutonium to be separated from uranium these two compounds can be recycled.2... 

Utilization of plutonium in early research and commercial orders to fabricate thermal recycle and fast breeder fuels did not coincide in timing with Pu availability from different sources. The plutonium comes mainly from high-exposure light-water reactor fuel reprocessing extended storage of this Pu as a nitrate solution leads to 241 contents up to 3%. For hands-on operation with this material it is necessary to reduce the Am content to about 0.5%. It was also necessary to minimize the liquid waste streams from the plant. In designing a technical-scale process, it was... 

U adioactive wastes have accumulated at Hanford since 1944 when the first reactor fuel was processed for plutonium recovery. High-level liquid wastes generated by the Purex, Redox, and BiP04 processes have been stored as neutralized slurries in 151 underground storage tanks. 

Salt Transport Processing (8, 9, 10, 11) The selective transfer of spent fuel constitutents between liquid metals and/or molten salts is being studied for both thorium-uranium and uranium-plutonium oxide and metal fuels. The chemical basis for the separation is the selective partitioning of actinide and fission-product elements between molten salt and liquid alloy phases as determined by the values of the standard free energy of formation of the chlorides of actinide elements and the fission products. Elements to be partitioned are dissolved in one alloy (the donor... 

An advantage of the Purex process is the low salt content of the aqueous waste stream so the liquid volume can be reduced by evaporation. The HNO3 values are recycled to the process. The Purex process produces nearly pure plutonium and recovers uranium and it is the process that has been adapted to treat domestic spent nuclear fuel. 

Preliminary studies have shown that ionic liquids have potential as solvents and electrolytes for metal recovery, and the feasibility of these solvents has been demonstrated for the extraction of gold and silver from a mineral matrix [7], the recovery of uranium and plutonium from spent nuclear fuel [8], and the electrodeposition and electrowinning of metals (especially, for active metals such as Li, Na, Al, Mg, and Ti) from ionic liquids [9-11], Ionic liquids as green solvents and electrolytes have shown important and potential application in extraction and separation of metals. In this chapter, the new applications and the important fundamental and appUed studies on the extraction and separation of metal in ionic liquids including metal oxides and minerals or ores processing, electrodeposition of metals (mainly for active metals), and extraction and separation of metal ions are described. 

A solvent extraction process similar to Purex using TBP was developed by the Commissariat a I Energie Atomique [Gl] for use in the French plutonium separation plant at Marcoule. Since then, the Purex process has replaced the Butex process at Windscale [W3], has been used in the Soviet Union [Sll], India [S7], and Germany [S3], and by now is the universal choice for separation of uranium and plutonium from fission products in irradiated sUghtly enriched uranium. Fuel from the liquid-metal fast-breeder reactor (LMFBR) is also reprocessed by the Purex process, with modifications to accommodate the higher concentrations of plutonium and fission products. 

Fractional crystallization. Volatile metals with much lower boiling points than uranium, such as magnesium (1103°C), zinc (906°C), and cadmium (767°C), have been extensively studied as solvents for separating constituents of irradiated metal fuel by fractional crystallization, followed by evaporation of the solvent metal from the separated fractions. For example, in liquid magnesium, the solubility of plutonium or thorium is high, but uranium is very low. A process of this type was developed at Argonne National Laboratory [P6] for concentrating plutonium in the uranium metal blanket of a breeder reactor from 1 percent to 40 percent. 

Anywhere spent nuclear liiel is handled, there is a chance that iodine-129 and iodine-131 will escape into the environment. Nuclear fuel reprocessing plants dissolve the spent fuel rods in strong acids to recover plutonium and other valuable materials. In the process, they also release iodine-129 and -131 into the airborne, liquid, and solid waste processing systems. In the U.S., spent nuclear fuel is no longer reprocessed, becau.se of concerns about nuclear weapons proliferation. 

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