Plutonium-uranium separation in the Purex process using mixtures of hydroxylamine nitrate and ferrous sulfamate Page: 7 of 29
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PLUTONIUM-URANIUM SEPARATION IN THE PUREX PROCESS USING MIXTURES OF
HYDROXYLAMINE NITRATE AND FERROUS SULFAMATE
INTRODUCTION
In all Purex processes the plutonium is reduced to Pu(III) at the
point in the process where plutonium is separated from uranium. The
reductant used at the Savannah River Plant from 1954 to 1978 was
ferrous sulfamate (FS). The principal advantage of FS is that it
gives very rapid reduction of Pu(IV) to Pu(III) even in moderately
strong nitric acid. ‘ However, FS has a major disadvantage; it is
consumed in the large mixer-settler of the Purex first cycle greatly
in excess of its stoichiometric requirement and adds considerably to
the volume of waste.
'In the Purex second plutonium cycle, laboratory and plant testing
completed in 1970 led to the use of hydroxylamine nitrate (HAN) as a
replacement for hydroxylamine sulfate for plutonium reduction. This
work indicated that HAN might also have application in the first
solvent extraction cycle where the plutonium-uranium separation takes
place^^. HAN is a desirable reductant because wlien fed to the
evaporator in normal waste processing, it oxidizes to gases and
contributes no salts to waste. Since little information was available
on its properties, laboratory and plant studies were made to determine
if HAN could be used in the first cycle to reduce the required amount
of ferrous sulfamate.
DISCUSSION
Flowsheet
The overall SRP Purex flowsheet is shown in a simplified schematic
in Figure 1. A solution of dissolved irradiated targets of depleted
uranium is clarified and then processed through solvent extraction.
The first solvent extractioh cycle cleanl/ separates uranium from
plutonium and provides the initial decontamination from fission
products. The partially purified aqueous streams of plutonium and
uranium coming out of the first cycle are each processed through one
additional solvent extraction- cycle for further fission product
decontamination.
Two types of solvent extraction equipment are used. The first
"bank" (1A) consists of eighteen centrifugal contactors; all others
are mixer-settlers that' use gravity for the phase separation. The
centrifugal contactors were designed at SRL^^ and were installed in
the plant in 1966^The principal advantage of centrifugal
contactors is that they give much less solvent radiation exposure than
other types of solvent extraction equipment. Figure 2 shows in more
detail the single-scrub flowsheet used in the Purex first cycle from
1954-1981.
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McKibben, J. M.; Chostner, D. F. & Orebaugh, E. G. Plutonium-uranium separation in the Purex process using mixtures of hydroxylamine nitrate and ferrous sulfamate, report, November 1, 1983; Aiken, South Carolina. (https://digital.library.unt.edu/ark:/67531/metadc1093160/m1/7/: accessed April 19, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.