Pyrochemical Processing Of Idaho Chemical Processing Plant (ICPP) High Level Waste (HLW) Calcine

The feasibility of several pyrochemical approaches-for separating non-radioactive constituents from ICPP HLW calcine were examined. The removal of aluminum as AICI3 from aluminia calcine was successfully demonstrated. The examination of pyrochemical processes to remove non-radioactive constituents, primarily aluminium, zirconium, calcium and fluorine, from zirconia calcine showed that fluorine removal was required in order to chlorinate the calcine. A molten calcium chloride wash, a calcium reduction, and. a sulfuric acid treatment were examined as possible zirconia calcine pretreatment options for fluorine removal. Fluorine removal from simulated ICPP zirconia calcine was demonstrated by both a CaCl2 wash method and a sulfuric acid treatment method. X-ray fluorescence analysis indicated that greater than 97% of the fluorine can be removed by either method. Fluorine removal by a calcium reduction using an alloying agent, zinc, or a calcium reduction using, a filtration separation were also demonstrated, but the efficiencies of fluorine removal were considerably less ranging from 50 to 90%. Regeneration of CaCl2 from the salt and oxide residues of the CaCl2 wash experiments was also demonstrated 'by an aqueous dissolution method. From the salt residue, 85% or more of the CaCl2 was recovered and contained little if any CaF2 or CaO. From the oxide residue close to 100% of the CaC12 was recovered. Because of the overall success of the CaCI2 wash, it was determined to be the preferred fluorine removal process. The sulfuric acid treatment to remove fluorine is effective, but the proposed overall flowsheet has not' been adequately demonstrated.