Sulfur Hexafluoride Treatment of Used Nuclear Fuel to Enhance Separations

Abstract

SUMMARYReactive Gas Recycling (RGR) technology development has been initiated at Savannah River National Laboratory (SRNL), with a stretch-goal to develop a fully dry recycling technology for Used Nuclear Fuel (UNF). This approach is attractive due to the potential of targeted gas-phase treatment steps to reduce footprint and secondary waste volumes associated with separations relying primarily on traditional technologies, so long as the fluorinators employed in the reaction are recycled for use in the reactors or are optimized for conversion of fluorinator reactant. The developed fluorination via SF 6 , similar to the case for other fluorinators such as NF 3 , can be used to address multiple fuel forms and downstream cycles including continued processing for LWR via fluorination or incorporation into a aqueous process (e.g. modified FLUOREX) or for subsequent pyro treatment to be used in advanced gas reactor designs such metal-or gas-cooled reactors. This report details the most recent experimental results on the reaction of SF 6 with various fission product surrogate materials in the form of oxides and metals, including uranium oxides using a high-temperature DTA apparatus capable of temperatures in excess of 1000 o C . The experimental results indicate that the majority of the fission products form stable solid fluorides and sulfides, while a subset of the fission products form volatile fluorides such as molybdenum fluoride and niobium fluoride, as predicted thermodynamically. Additional kinetic analysis has been performed on additional fission products. A key result is the verification that SF 6 requires high temperatures for direct fluorination and subsequent volatilization of uranium oxides to UF 6 , and thus is well positioned as a head-end treatment for other separations technologies, such as the volatilization of uranium oxide by NF 3 as reported by colleagues at PNNL, advanced pyrochemical separations or traditional full recycle approaches.Based on current results of the research at SRNL on SF 6 fluoride volatility for UNF separations, SF 6 treatment renders all anticipated volatile fluorides studied to be volatile, and all non-volatile fluorides studied to be non-volatile, with the notable exception of uranium oxides. This offers an excellent opportunity to use this as a head-end separations treatment process because:

Non-Aqueous Electrochemical Fluorination of Used Nuclear Fuel as an Advanced Separation Process

“…Two non-aqueous methods that have been developed for nuclear fuel processing are pyroprocessing [9][10][11][12][13][14] and fluoride volatility. [15][16][17][18][19] Pyroprocessing converts UNF into a metallic form and uses electrorefining in a molten chloride electrolyte to deposit uranium on a stainless steel electrode. The fluoride volatility process fluorinates the elements in UNF by reacting it with fluorine gas at high temperature.…”