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  • Author or Editor: M. Kumagai x
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Summary  

To separate minor actinides from HLLW by extraction chromatography, a few novel silica-based di(2-ethylhexyl)phosphoric acid (HDEHP), 4,4¢,(5¢)-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6), octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO), and N,N,N¢,N¢-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) polymeric adsorption materials (HDEHP/SiO2-P, DtBuCH18C6/SiO2-P, CMPO/SiO2-P, and TODGA/SiO2-P) were synthesized by impregnating HDEHP, DtBuCH18C6, CMPO, and TODGA into the pores of porous SiO2-P particles, which were the new kind of inorganic/organic composites consisted of macroporous SiO2 and copolymer. The bleeding behavior of these composites was investigated by examining the effect of contact time and HNO3 concentration. It was found that in the tested HNO3 concentration range, a noticeable quantity of DtBuCH18C6, at least 600 ppm, leaked out from DtBuCH18C6/SiO2-P because of the protonation of DtBuCH18C6 with hydrogen ion, while the others were lower and basically equivalent to the solubility of HDEHP, CMPO, or TODGA in corresponding acidities solutions. Based on the batch experiment, the bleeding of CMPO/SiO2-P and TODGA/SiO2-P, the main adsorbents used in MAREC process for HLLW partitioning, was evaluated by column operation in 0.01M HNO3 and 3M HNO3. The quantity of CMPO leaked was ~48 ppm in 0.01M HNO3 and ~37 ppm in 3.0M HNO3. The bleeding of TODGA decreased from 23.2 ppm to 7.27 ppm at the initial stage and then basically kept constant. An actual bleeding of TODGA was evaluated by the separation of Sr(II) from a 2.0M HNO3 solution containing 5.0 . 10-3M of 6 typically simulated elements.

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Abstract  

A novel macroporous silica-based 2,6-bis(5,6-diisobutyl-1,2,4-triazine-3-yl)pyridine (iso-Bu-BTP), a neutral chelating agent having several softatom nitrogen, polymeric composite (iso-Bu-BTP/SiO2-P) was synthesized. It was done through impregnation and immobilization of iso-Bu-BTP molecule into the pores of SiO2-P particles with 40–60 μm of bead diameter and 0.6 μm of mean pore size. The effective impregnation resulted from the intermolecular interaction of iso-Bu-BTP and co-polymer inside the SiO2-P particles by a vacuum sucking technique. To understand the possibility of applying iso-Bu-BTP in the MAREC process developed, the adsorption behavior of a few representative rare earths (REs) such as Ce(III), Nd(III), Gd(III), Dy(III), Er(III), Yb(III), and Y(III) towards iso-Bu-BTP/SiO2-P was investigated at 298 K. The influence of the HNO3 concentration in a wide range of pH 5.52–3.0M and a few chelating agents such as formic acid, citric acid, and diethylenetriaminepentaacetic acid (DTPA) on the adsorption of RE(III) was examined. It was found that in the presence of chelating agent, the adsorption ability of the tested RE(III) towards iso-Bu-BTP/SiO2-P decreased due to two competition reactions of RE(III) with iso-Bu-BTP/SiO2-P and chelating agents. In a 0.01M HNO3 solution containing 1M formic acid or 1M citric acid, light RE(III) showed lower adsorption towards iso-Bu-BTP/SiO2-P than that of the heavy one. This makes the separation of light RE(III) from the heavy one possible. Based on the similarity of minor actinides and heavy RE(III) in chemical properties and the results of column separation experiments, chromatographic partitioning of light RE(III) from a simulated high level liquid waste solution composed of the heavy RE(III) and minor actinides in MAREC process is promising.

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Summary  

The Minor Actinides Recovery from HLW by Extraction Chromatography (MAREC) process was used mainly for the separation of minor actinides (MAs) and some specific fission products (FPs) from highly active liquid waste (HLW) by the composite CMPO/SiO2-P of the macroporous silica based polymeric octyl(phenyl)-N,N-diisobutylcarbamoylmethylphoshine oxide (CMPO) and others. In this study a cascade of chromatographic separation was performed on a 3.0M HNO3 solution containing 5.0 . 10-3M of 13 elements, at 323 K. The cascade consisted of three columns the first and second ones were packed with CMPO/SiO2-P and the third with SiO2-P particles. The first column was employed to prepare various eluents containing saturated CMPO. The second column was used for separation into groups. The CMPO of CMPO/SiO2-P was recovered from the effluent by the third column and a CMPO-free effluent containing minor actinides was obtained. The elements contained in the simulated HLW of 3.0M HNO3 were separated into (1) a non-adsorption group (Sr, Cs, and Ru etc.), (2) a MA-hRE (heavy rare earth)-Mo-Zr group, and (3) a lRE (light rare earth) group by eluting with 3.0M HNO3, 0.05M DTPA (diethylenetriaminepentaacetic acid) (pH 2.0) and HNO3 (pH 3.5), respectively. The resultant MA-hRE-Mo-Zr mixture containing minor actinides was then separated into the groups (1) Pd-Ru, (2) MA-hRE, and (3) Mo-Zr by utilizing 3.0M HNO3, distilled water, and 0.05M DTPA (pH 2.0) as eluents. More than 92% of CMPO in the MA-hRE containing effluent was adsorbed by SiO2-P particles. The effectivity and technical feasibility of MAREC process were demonstrated.

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Abstract  

Electroreduction of Tc(VII) was studied in nitric acid solution using glassy carbon electrode. The electroreduction was conducted at a constant potential –300 mV (vs. Ag/AgCl) with a potentiostat. It was found that the difference of the Tc concentration in the solutions before and after the electrolysis was negligibly small. This means that there were almost no TcO2 or Tc deposited on the carbon fiber electrode during the electroreduction. Absorption spectra and distribution coefficients obtained by ion-exchange analysis indicated that Tc(VII) was reduced to Tc(IV).

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Abstract  

Electrochemical reduction of U(VI) in nitric acid-hydrazine solution is greatly influenced by the concentration of nitric acid. In low acidity nitric acid solution such as 0.1M (M=mol/dm3) HNO3, U(VI) was firstly reduced to U(V) and then partially reduced to U(IV). In high acidity nitric acid solution, e.g., 3-6M HNO3, an electrode process of two-electron transfer was involved in the reduction of U(VI). A higher U(IV) yield could be achieved in nitric acid solution with higher concentration. Hydrazine was very effective in suppressing the reduction of concentrated nitric acid, and the optimal concentration of hydrazine added was 0.075 to 0.15M in 6M HNO3

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Abstract  

New lanthanoid-iron complexes having phenanthlorine as the chelating ligand were synthesized and characterized by151Eu- and57Fe-Mössbauer spectroscopy. The temperature dependence of the area intensity of Mössbauer lines of europium complexes (single crystals) has been correlated to the state of molecular association in the solid state. The crystal structure of europium complex, {[Eu(phen)2(H2O)2][(μ-NC)2 Fe(CN)4]·2phen]}x was determined by X-ray crystal analysis. This complex consists of one-dimensional zig-zag chain structure.

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Abstract  

A new type of silica-based chelating extraction resin, DtBuCH18C6/SiO2-P, was prepared by impregnating a crown ether derivative, 4,4,(5)-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6), into the porous silica/polymer composite particles (SiO2-P). The adsorption of Sr(II) and some other fission product elements was investigated by a batch adsorption experiment in HNO3 medium. It was found that Sr(II) exhibits a strong adsorption onto the extraction resin, while the other fission product elements show almost no or only weak adsorption. The adsorption kinetics of Sr(II) was explained by assuming as the rate-controlling step the complex-formation reaction between Sr(II) and DtBuCH18C6 contained in the extraction resin. The rate equation of Sr(II) adsorption was determined as:-d[Sr(II)]/dt = k[Sr(II)][DtBuCH18C6][NO3 ]0.5.

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