Cold-cap reactions in vitrification of nuclear waste glass: Experiments and modeling

Cold-cap reactions are multiple overlapping reactions that occur in the waste-glass melter during the vitrification process when the melter feed is being converted to molten glass. In this study, we used simultaneous differential scanning calorimetry–thermogravimetry (DSC–TGA) to investigate cold-cap reactions in a high-alumina high-level waste melter feed. To separate the reaction heat from both the heat associated with the heat capacity of the feed and experimental artifacts, we employed the run/rerun method, which enabled us to define the degree of conversion based on the reaction heat and to estimate the heat capacity of the reacting feed. Assuming that the reactions are nearly independent and can be approximated by an nth order kinetic model, we obtained the kinetic parameters using the Kissinger method combined with least squares analysis. The resulting mathematical simulation of the cold-cap reactions provides a key element for the development of an advanced cold-cap model.

► We measured enthalpy-based conversion degree of overlapping reactions using DSC.
► We employed the run/rerun technique to obtain heat flow associated with reactions.
► Batch-to-glass conversion advances via multiple overlapping reactions.
► The kinetic model is intended for the source term in the energy transfer equation.
► The results are relevant for industrial glass making and nuclear waste vitrification.