Uranium hexone process

Redox [Reduction oxidation] A process for separating the components of used nuclear fuel by solvent extraction. It was the first such process to be used and was brought into operation at Hanford, WA, in 1951, but was superseded in 1954 by the Purex process.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 wobutyl ketone), so the process was also known as the Hexone process. The aqueous phase contained a high concentration of aluminum nitrate to salt out the uranium and plutonium nitrates into the organic phase. The presence of this aluminum nitrate in the wastes from the process, which made them bulky, was the main reason for the abandonment of the process. See also Butex. 

A modification of the Redox process, the U-hexone process, was used at the Idaho Chemical Processing Plant of the U.S. AEC, to recover highly enriched uranium from U-A1 alloy fuel elements irradiated in the Materials Testing Reactor. The aluminum nitrate needed as salting agent was provided when the fuel was dissolved in nitric acid. The plutonium content of the fuel was too low to warrant recovery. Plutonium was made trivalent and inextractable before solvent extraction and thus routed to the aqueous high-level waste. 

When an extractable cation, such as Zi, is readily hydrolyzed, reduction of hydrogen ion concentration will reduce the distribution coefficient by increasing the proportion of the element in the form of partially hydrolyzed, nonextractable ions such as ZrO . This principle was used in the Redox process [B2, C7, C8] for the hexone extraction of plutonium from irradiated uranium, wherein the aqueous phase was made sUghtly acid-deficient with ammonium hydroxide, to reduce the extraction of zirconium and rare-earth fission products. 

The solvent used in the Redox process was hexone, methyl isobutyl ketone, an extractant already in use for purifying uranium ore concentrates (Chap. 5)., Hexone is immiscible with water and will extract uranyl nitrate and plutonyl nitrate selectively from fission-product nitrates if the aqueous solution has a sufficiently high nitrate ion concentration. In the Redox process, aluminum nitrate was used as salting agent because high concentrations of nitric acid would decompose the hexone solvent. 

Figure 10.1 is a material flow sheet for the first cycle of one form of the Redox process [F3]. Rutonium in the feed was converted to hexavalent plutonyl nitrate Pu 02(N0s)j, by oxidation with dichromate ion Cr2 07 ", as this is the plutonium valence with highest distribution coefficient into hexone. In the decontamination contactor, hexavalent uranium and plutonium nitrates were extracted into hexone solvent, and fission-product nitrates were removed from the solvent by a scrub solution containing aluminum nitrate, sodium nitrate, and sodium dichromate. 

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