In KAERI’s previous phosphate precipitation tests, the dispersed powder of lithium phosphate (Li3PO4) as a precipitation agent reacted with various metal chlorides in a simulated LiCl-KCl molten salt. The reaction of metal chlorides composed of actinides such as uranium and three rare earths (Nd, Ce and La) with lithium phosphate is a solid-liquid reaction. A phosphorylation reaction rate is very fast and the metal phosphates as a reaction product precipitated on the bottom of the molten salt crucible. One of the recovery methods of the metal phosphate precipitates is segregation the lower part (precipitates) of the salt ingot using the various cutting tools. Recently, a new phosphorylation experiment using lithium phosphate ingots carried out in order to collect the metal phosphate precipitates into a small recovering vessel, and the test result of this new method was feasible. However, the reaction rate of test using lithium phosphate ingot is extremely slower than that of test using lithium phosphate powder. In this study, the precipitation reactor design (a tapered crucible with polished inner surface) used for phosphorylation reaction showed that the salt ingot with metal phosphate precipitates could be detached from a tapered stainless steel crucible. We propose that the recovery of precipitates from a salt ingot is possible by introducing a dividing plate structure into a molten salt and by positioning it at the interface between salt and precipitated metal phosphate.

Tin bis(monohydrogen orthophosphate) monohydrate 물질의 흡착 성질에 관하여 KCl 수용액을 통하여 조사하였다. 금속이온 농도와 pH를 변화시키면서 어떻게 달라지는지 화학평형에 바탕을 두고 data를 분석하였다. 금속이온들의 흡착 data는 Langmuir 흡착식에 넣어 Langmuir 수치들을 얻는데 사용되었다. Tin phosphate는 산성에서 이온교환 화합물로 작용하였으며, 2가의 전이금속이온에 대해 Cu+2 > Co+2 > Ni+2의 순서로 선택적 흡착성질을 나타내었다. 약한 산성 이온 교환체에서와 같이 금속이온의 교환은 tin phosphate의 선택성을 결정하는데 결정적 역할을 하였다. 모든 경우에서 흡착의 정도는 온도와 농도의 증가와 함께 증가하였다. Lnngmuir 수치들은 흡착과정 동안의 엔트로피, 엔탈피, 자유에너지 변화량같은 열역학적 함수들을 계산하는데 이용되었다.

The objective of this study was to evaluate the immobilization of heavy metals (Cu, Pb, Zn and Cd) in an abandoned mine soil by applying both soluble phosphates and steel slag as stabilizers. The application rate of stabilizers to soils was determinated based on PO4/Pb molar ratio of 2.0 for phosphates and on weight/weight ratio of 2, 5, 10% for steel slag, respectively. Immobilization efficiency of heavy metals in the contaminated soils was evaluated by toxicity characteristics leaching procedure (TCLP). After adding both phosphate and slag, the immobilization efficiencies of Cu, Zn and Cd increased significantly (about 14% - 40%) compared to those of treatment with soluble phosphate alone. The increae in immobilization efficiencies of Cu was the greatest. Whereas, immobilization efficiency of Pb was not significantly different from those with soluble phosphate alone. Among the tested three phosphates (Na2HPO4 ·12H2O, Ca(H2PO4)2 ·H2O, (NH4)2HPO4), the immobilization efficiencies with Na2HPO4 ·12H2O increased more than those of other phosphates. Results of sequential extraction analysis indicated that fraction of reducible form (F3) and residual form (F5) increased, while mobile forms (F1, and F2) decreased after immobilization treatment with both stabilizers resulting in decrease in leachability of heavy meyals in the treated soils. Residual fraction of Cu after treatnment was the highest as 68.5%, it was followed by Cu > Pb > Zn > Cd.

The objective of this study was to evaluate the immobilization efficiency and sequential extraction of soluble phosphates (Na2HPO4 ·12H2O, Ca(H2PO4)2 ·H2O, (NH4)2HPO4) for the stabilization of heavy metals (Cu, Pb, Zn and Cd) in abandoned mine soil. The application rate of stabilizers to soils was determinated PO4/Pbtotal molar ratio of 0.5, 1.0, 2.0, 4.0. The immobilization efficiency was evaluate of TCLP (EPA method 1311) used in a landfill for heavy metals. After processing stabilization, the immobilization efficiency of Pb is more than 95% at molar ratio of 2.0 regardless kind of phosphate. For Cu Zn and Cd, on the other hand, the efficiency has the range of from 30% to 50%, even though molar ratio increase up to 4.0. It is relatively low in comparison with Pb. Leachability of heavy metals was reduced with increasing amounts of added phosphate. Phosphates, Na2HPO4 ·12H2O was more immobilization than Ca(H2PO4)2 ·H2O, (NH4)2HPO4. After sequential extraction, form of heavy metals in soil tends to increase strongly bond like forms of organic matter-bound(F4) and residual (F5). Especially the stable residual form increases in all metals. The growth rate of residual fraction was a little different heavy metals. The growth rate of Zn is greatest increased from 17% to 22% than other metals, it was followed by Zn > Cd > Pb > Cu. Phosphates, Ca(H2PO4)2 ·H2O was the greatest increased for residual fraction.