Glass Formulation Development for INEEL Sodium-Bearing Waste

Abstract

For about four decades, radioactive wastes have been collected and calcined from nuclear fuels reprocessing at the Idaho Nuclear Technology and Engineering Center (INTEC), formerly Idaho Chemical Processing Plant (ICPP). Over this time span, secondary radioactive wastes have also been collected and stored as liquid from decontamination, laboratory activities, and fuel-storage activities. These liquid wastes are collectively called sodium-bearing wastes (SBW). About 5.7 million liters of these wastes are temporarily stored in stainless steel tanks at the Idaho National Engineering and Environmental Laboratory (INEEL). Vitrification is being considered as an immobilization step for SBW with a number of treatment and disposal options. A systematic study was undertaken to develop a glass composition to demonstrate direct vitrification of INEEL's SBW. The objectives of this study were to show the feasibility of SBW vitrification, not a development of an optimum formulation. The waste composition is relatively high in sodium, aluminum, and sulfur. A specific composition and glass property restrictions, discussed in Section 2, were used as a basis for the development. Calculations based on first-order expansions of selected glass properties in composition and some general tenets of glass chemistry led to an additive (fit) composition (68.69 mass % SiO{sub 2}, 14.26 mass% B{sub 2}O{sub 3}, 11.31 mass% Fe{sub 2}O{sub 3}, 3.08 mass% TiO{sub 2}, and 2.67 mass % Li{sub 2}O) that meets all property restrictions when melted with 35 mass % of SBW on an oxide basis, The glass was prepared using oxides, carbonates, and boric acid and tested to confirm the acceptability of its properties. Glass was then made using waste simulant at three facilities, and limited testing was performed to test and optimize processing-related properties and confirm results of glass property testing. The measured glass properties are given in Section 4. The viscosity at 1150 C, 5 Pa{center_dot}s, is nearly ideal for waste-glass processing in a standard liquid-fed joule-heated melter. The normalized elemental releases by 7-day PCT are all well below 1 g/m{sup 2}, which is a very conservative set point used in this study. The T{sub L}, ignoring sulfate formation, is less than the 1050 C limit. Based on these observations and the reasonable waste loading of 35 mass 0/0, the SBW glass was a prime candidate for further testing. Sulfate salt segregation was observed in all test melts formed from oxidized carbonate precursors. Melts fabricated using SBW simulants suggest that the sulfate-salt segregation seen in oxide and carbonate melts was much less of a problem. The cause for the difference is likely H{sub 2}SO{sub 4} fuming during the boil-down stage of wet-slurry processing. Additionally, some crucible tests with SBW simulant were conducted at higher temperatures (1250 C), which could increase the volatility of sulfate salts. The fate of sulfate during the melting process is still uncertain and should be the topic of future studies. The properties of the simulant glass confirmed those of the oxide and carbonate glass. Corrosion tests on Inconel 690 electrodes and K-3 refractory blocks conducted at INEEL suggest that the glass is not excessively corrosive. Based on the results of this study, the authors recommend that a glass made of 35% SBW simulant (on a mass oxide and halide basis) and 65% of the additive mix (either filled or raw chemical) be used in demonstrating the direct vitrification of INEEL SBW. It is further recommended that a study be conducted to determine the fate of sulfate during glass processing and the tolerance of the chosen melter technology to sulfate salt segregation and corrosivity of the melt.