• Nuclear Engineering and Technology
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• v.45 no.5
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• pp.675-682
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• 2013

The sequential separation process, composed of an oxygen sparging process for separating lanthanides and a zone freezing process for separating Group I and II fission products, was evaluated and tested with a surrogate eutectic waste salt generated from pyroprocessing of used metal nuclear fuel. During the oxygen sparging process, the used lanthanide chlorides (Y, Ce, Pr and Nd) were converted into their sat-insoluble precipitates, over 99.5% at $800^{\circ}C$; however, Group I (Cs) and II (Sr) chlorides were not converted but remained within the eutectic salt bed. In the next process, zone freezing, both precipitation of lanthanide precipitates and concentration of Group I/II elements were preformed. The separation efficiency of Cs and Sr increased with a decrease in the crucible moving speed, and there was little effect of crucible moving speed on the separation efficiency of Cs and Sr in the range of a 3.7 - 4.8 mm/hr. When assuming a 60% eutectic salt reuse rate, over 90% separation efficiency of Cs and Sr is possible, but when increasing the eutectic salt reuse rate to 80%, a separation efficiency of about 82 - 86 % for Cs and Sr was estimated.

• Korean Chemical Engineering Research
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• v.47 no.4
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• pp.465-469
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• 2009

Characteristics of oxidation reaction of four lanthanide chlorides(Ce, Nd, Pr and $EuCl_3$) in a oxygen-eutectic(LiCl-KCl) salt bubble column was investigated. From the results obtained from the thermochemical calculations by HSC chemistry software, the most stable lanthanide compounds in the oxygen-used rare earth chlorides system were oxychlorides(EuOCl, NdOCl, PrOCl) and oxides($CeO_2$, $PrO_2$), which coincide well with results of the Gibbs free energy of the reaction. In this study, similar to the thermochemical results, regardless of the sparging time and molten salt temperature, oxychlorides for Eu, Nd and Pr and oxides for Ce and Pr were formed as a precipitant by a reaction with oxygen. The structure of the rare earth precipitates was divided into two shapes : small cubic(oxide) and large tetragonal (oxychloride) structures. The conversion efficiencies of the lanthanide elements to their molten salt-insoluble precipitates(or compound) were increased with the sparging time and temperature, and Ce showed the best reactivity. In the conditions of $650^{\circ}C$ of the molten salt temperature and 420 min of the sparging time, the conversion efficiencies were over 99% for all the investigated lanthanide chlorides.

• Applied Chemistry for Engineering
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• v.18 no.4
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• pp.361-365
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• 2007

The precipitation reaction of some rare earth chlorides ($Ce/Nd/GdCl_3$) in a LiCl-KCl molten salt has been carried out by reaction with oxygen. Identification of rare earth precipitates by reaction with oxygen and effects of oxygen sparging time (max. 420 min) and molten salt temperature ($450{\sim}750^{\circ}C$) on conversion were investigated. In this study, regardless of the oxygen sparging time and the molten salt temperature, oxychlorides (REOCl) for $NdCl_3$ and $GdCl_3$, and an oxide ($REO_2$) for $CeCl_3$ are formed as a precipitate, which are identical with the estimation results of Gibbs free energy of reaction (${\Delta}G_r$). The conversion of rare-earth chlorides into insoluble precipitates was described by using a conversion ratio. The conversion ratio increased exponentially with the oxygen sparging time and finally showed asymptotic value, over 0.999 at $750^{\circ}C$ of the molten salt temperature and over 300 min of sparging time conditions. The conversion ratios were increased with the molten salt temperature. In case of $CeCl_3$, when the sparging time exceed 60 min, the values of the conversion ratio were nearly constant over 0.999 in all experimental temperature conditions.