Uranium solvent extraction process

Fig. 21.14. Uranium solvent extraction process for purification of ore concentrate and scrap slurry feed eliminates clarification cost and losses. (Courtesy USDOE.)...

An improved solvent extraction process, PUREX, utilizes an organic mixture of tributyl phosphate solvent dissolved in a hydrocarbon diluent, typically dodecane. This was used at Savannah River, Georgia, ca 1955 and Hanford, Washington, ca 1956. Waste volumes were reduced by using recoverable nitric acid as the salting agent. A hybrid REDOX/PUREX process was developed in Idaho Falls, Idaho, ca 1956 to reprocess high bum-up, fuUy enriched (97% u) uranium fuel from naval reactors. Other separations processes have been developed. The desirable features are compared in Table 1. 

In 1942, the Mallinckrodt Chemical Company adapted a diethylether extraction process to purify tons of uranium for the U.S. Manhattan Project [2] later, after an explosion, the process was switched to less volatile extractants. For simultaneous large-scale recovery of the plutonium in the spent fuel elements from the production reactors at Hanford, United States, methyl isobutyl ketone (MIBK) was originally chosen as extractant/solvent in the so-called Redox solvent extraction process. In the British Windscale plant, now Sellafield, another extractant/solvent, dibutylcarbitol (DBC or Butex), was preferred for reprocessing spent nuclear reactor fuels. These early extractants have now been replaced by tributylphosphate [TBP], diluted in an aliphatic hydrocarbon or mixture of such hydrocarbons, following the discovery of Warf [9] in 1945 that TBP separates tetravalent cerium from... 

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. 

Fujii, T., Yamana, H., Watanabe, M., Moriyama, H. 2002. Extraction study for TRUEX process using short-lived radionuclides produced by neutron irradiation of uranium. Solvent Extraction and Ion Exchange 20(2) 151-175. 

The uranium and plutonium are recovered for further use by first dissolving the spent fuel in nitric acid and subjecting the resulting solution to a solvent extraction process. Several different processes exist, the best known being the Purex process (Fig. 18), in which tributyl phosphate (TBP) (30% solution in kerosene) is the extractant. Extraction is carried out in compact mixer-settlers or air-pulsed columns fabricated of stainless steel, with about 99.9% removal of uranium and plutonium in the extract. 

TABLE IV Some Solvent Extraction Processes for Metals Other Than Uranium, Copper, Nickel, and Cobalt... 

Fig. 21.12. Uranium ore mill processes (A) carbonate leach, caustic precipitation process (B) acid leach, ion exchange and acid leach, solvent extraction processes (C) acid leach, resin-in-pulp process.

The control of the actinide metal ion valence state plays a pivotal role in the separation and purification of uranium and plutonium during the processing of spent nuclear fuel. Most commercial plants use the plutonium-uranium reduction extraction process (PUREX) [58], wherein spent fuel rods are initially dissolved in nitric acid. The dissolved U and Pu are subsequently extracted from the nitric solution into a non-aqueous phase of tributyl phosphate (TBP) dissolved in an inert hydrocarbon diluent such as dodecane or odourless kerosene (OK). The organic phase is then subjected to solvent extraction techniques to partition the U from the Pu, the extractability of the ions into the TBP/OK phase being strongly dependent upon the valence state of the actinide in question. 

UREX [URanium Extraction] A solvent extraction process for extracting uranium and technetium from used nuclear fuel, while rejecting all the transuranic elements. Based on the Purex process, which uses tributyl phosphate in a hydrocarbon mixture, but incorporating acetohydroxamic acid, which complexes the Pu and Np and thereby prevents them from being extracted. Developed by the Westinghouse Savannah River Company in 2003. Associated processes are NPEX, TRUEX, and Cyanex 301. 

Liquid extraction is utilized by a wide variety of industries. Applications include the recovery of aromatics, decaffeination of coffee, recovery of homogeneous catalysts, manufacture of penicillin, recovery of uranium and plutonium, lubricating oil extraction, phenol removal from aqueous wastewater, and extraction of acids from aqueous streams. New applications or refinements of solvent extraction processes continue to be developed. 

When more them one solute is involved in the consideration of the process design, the situation becomes much more complex since the extraction behaviours of the different solutes will usually be interdependent. In the case of irradiated thermal reactor fuels the solvent extraction process will be dealing with uranium containing up to ca. 4% of fission products and other actinides. These will have only a minor effect on uranium distribution so that a single-solute model may be adequate for process design. However, in some cases nitric acid extraction may compete with U02 extraction and a two-solute model may be needed. In the case of breeder reactor fuels the uranium may contain perhaps 20% of plutonium or thorium. Neptunium or protactinium levels in such fuels may also not be negligible and, under these circumstances, the single-solute... 

Many variants of the Purex (Plutonium Uranium Reduction Extraction) process based on TBP extraction have been developed but a basic outline flowsheet is illustrated in Figure 38. This shows the so-called early split flowsheet most commonly used in existing plants. It involves the separation of the uranium and plutonium using two different back-extractant streams during the first solvent extraction cycle. Additional solvent extraction cycles are then carried out independently on the uranium and plutonium streams to effect further purification. An alternative arrangement is the late split flowsheet used at the Cap La Hague plant in France, and the... 

High quality requirements particularly as regards uranium concentration and the maximum quantities of undesirable ions such as Mo, V and P are stipulated by the processors for the end product, so-called yellow cake produced by the uranium ore mines. Uranium is generally precipitated as diuranates from the aqueous solutions produced by the ion exchange and solvent extraction processes under precise conditions. 

At the tail end of a solvent extraction process, the solvents are separated from the solutes for recycle. In this application of solvent extraction, vacuum distillation is used to separate volatile zinc and magnesium from coprocessed uranium and plutonium and from the uranium product. Feed to vacuum distillation is solid alloy. Overhead and bottom products are likwise cast into a solid alloy. These vacuum distillation operations are conducted in separate cells. The actinide products are converted to oxide for fuel fabrication. 

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