In the radioactive waste management, metal chloride wastes from a pyrochemical process is one of problematic wastes not directly applicable to a conventional solidification process. Different from a use of minerals or a specific phosphate glass for immobilizing radioactive waste salts, our research group applied an inorganic composite, SAP (SiO(2)-Al(2)O(3)-P(2)O(5)), to stabilize them by dechlorination. From this method, a unique wasteform composing of phosphate and silicate could be fabricated. This study described the characteristic of the wasteform on the morphology, chemical durability, and some physical properties. The wasteform has a unique "domain-matrix" structure which would be attributed to the incompatibility between silicate and phosphate glass. At higher amounts of chemical binder, "P-rich phase encapsulated by Si-rich phase" was a dominant morphology, but it was changed to be Si-rich phase encapsulated by P-rich phase at a lower amount of binder. The domain and subdomain size in the wasteform was about 0.5-2 μm and hundreds of nm, respectively. The chemical durability of wasteform was confirmed by various leaching test methods (PCT-A, ISO dynamic leaching test, and MCC-1). From the leaching tests, it was found that the P-rich phase had ten times lower leach-resistance than the Si-rich phase. The leach rates of Cs and Sr in the wasteform were about 10(-3)g/m(2)· day, and the leached fractions of them were about 0.04% and 0.06% at 357 days, respectively. Using this method, we could stabilize and solidify the waste salt to form a monolithic wasteform with good leach-resistance. Also, the decrease of waste volume by the dechlorination approach would be beneficial in the final disposal cost, compared with the present immobilization methods for waste salt.
Pyroporcessing of spent nuclear fuel generates a considerable amount of LiCl-KCl eutectic waste salt containing radioactive rare earth (RE) chlorides. In this study, a series of processes, which consist of a phosphorylation/distillation process and a solidification process, were performed to minimize volume of the LiCl-KCl eutectic waste salt and solidify a residual waste into a stable form at a relatively low temperature. Over 99wt% of RE chlorides in LiCl-KCl eutectic salt was converted and separated into REPO 4 in the phosphorylation/distillation process using a mixture of Li 3 PO 4 -K 3 PO 4 . The separated REPO 4 was solidified into a homogeneous and fine-grained form at 1,050℃ using LIP(Lead Iron Phosphate) as a solidification agent. The final waste volume was reduced below about 10% through the series of the processes. stirring rate: 300 rpm, phosphorylation agent: 1 eq.). Fig. 3. XRD patterns of products obtained from phosphorylation and distillation processes (RE: rare earth).
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