• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.2
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• pp.115-122
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• 2010

In this study, the removal of Cs and Tc from a simulated fission products (FP) solution which were co-dissolved with U during the oxidative-dissolution of spent fuel in a mixed carbonate solution of $(Na_2CO_3-NaHCO_3)-H_2O_2$ was investigated by using a selective precipitation method. As Cs and Tc might cause an unstable behavior due to the high decay heat emission of Cs as well as the fast migration of Tc when disposed of underground, it is one of the important issues to removal them in views of the increase of disposal safety. The precipitation of Cs and Re (as a surrogate for Tc) was examined by introducing sodium tetraphenylborate (NaTPB) and tetraphenylphosponium chloride (TPPCl), respectively. Precipitation of Cs by NaTPB and that of Re by TPPCl were completed within 5 minutes. Their precipitation rates were not influenced so much by the temperature and stirring speed even if they were increased by up to $50^{\circ}C$ and 1,000 rpm. However, the pH of the solution was found to have a great influence on the precipitation with NaTPB and TPPCl. Since Mo tends to co-precipitate with Re at a lower pH, especially, it was effective that a selective precipitation of Re by TPPCl was carried out at pH of above 9 without co-precipitation of Mo and Re. Over 99% of Cs was precipitated when the ratio of [NaTPB]/[Cs]>1 and more than 99% of Re, likewise, was precipitated when the ratio of [TPPCl]/[Re]>1.

• Bulletin of the Korean Chemical Society
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• v.25 no.2
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• pp.298-300
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• 2004

An alternative molecular porphyrin-phthalocyanine aggregate was prepared and characterized with UV-visible and X-ray absorption spectroscopies. UV-visible experiments evidence 1-dimensional porphyrin-phthalo-cyanine array formed by mixing $SnTPPCl_2 ({\lambda}_{max}=429,\;{\varepsilon}=2.4{\times10^ 5 /M{\cdot}cm)\;and\;NiPc(OBu)_8({\lambda}_{max}=744 nm,\;{\varepsilon}= 2.0{\times}10^ 5 /M{\cdot}cm)$ in solution. In the UV-visible spectrum of the porphyrin-phthalocyanine array, $(SnPNiPc)_n$, a new Q-band appeared at 844 nm with decrease of the Q-band peak of $NiPc(OBu)_8$ at 744 nm. The red-shift of Q-band evidences an alternative porphyrin-phthalocyanine array formed in solution through metal-halide interaction rather than ${\pi}-{\pi}$ facial interaction, in which nickel of $NiPc(OBu)_8$ coordinates with chloride of $SnTPPCl_2$ through self assembly. Ni K-edge XANES (X-ray absorption near edge structure) spectra also support the axial ligation of nickel to chloride. The square planar structure of $NiPc(OBu)_8$ turns to an octahedral structure in (SnPNiPcSnP) by axial ligation. A higher energy-shift (0.2 eV) of the preedge peak of (SnPNiPcSnP) indicaties partial oxidation of nickel by charge transfer from NiPc$(OBu)_8$ to SnTPPCl$_2$.

• Bulletin of the Korean Chemical Society
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• v.26 no.10
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• pp.1600-1602
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• 2005

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2008.11a
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• pp.326-327
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• 2008

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2009.06a
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• pp.333-334
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• 2009

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.9 no.3
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• pp.131-139
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• 2011

This study was carried out to examine the stability of $Na_2CO_3-H_2O_2$ carbonate solution with aging time in the dissolving solution after oxidative dissolution of U by a carbonate solution, the Cs/Re filtrate after selective precipitation of Cs and Re (as a surrogate for Tc), and the acidification filtrate after precipitation of U by acidification, respectively. The compositions of dissolving solution were not changed with ageing time, and the selective precipitation of Re and Cs was also not affected without regard to the aging time of dissolving solution. The successive removal of Cs and Re from a carbonate dissolving solution was possible. However, the recovery yield of U by acidification was decreased with increasing the aging time of the dissolving solution and the Cs/Re-filtrate, respectively, because U was converted from the uranyl peroxocarbonato complex to the uranyltricarbonate in the solution aged for a long time. Accordingly, it is effective that a dissolving solution and a Cs/Re filtrate are treated within the aging of 7 days, respectively, in order to recover U more than 99%. On the other hand, the recovery of U was carried out in order of the oxidative dissolution of U selective precipitation of Re and Cs precipitation of U by acidification. Almost all of U and a part of FP were co-dissolved in oxidative dissolution step. Over 99% of Re and Cs from the FP co-dissolved with U could be removed by a TPPCl (tetraphenylphosphonium chloride) and a NaTPB (sodium tetraphenylborate), respectively. U was precipitated nearly 100% by acidification to pH 4. Therefore, it was confirmed that the validity of recovery of U by precipitation methods from a SF (spent fuel) in the $Na_2CO_3-H_2O_2$ solution.