Identification and time evolution of thionyl chloride (SOCl2) radiolysis products

Abstract

Innovative solutions are needed to reduce the amount of high-level waste generated by used nuclear fuel recycling strategies to support the widespread adoption of sustainable nuclear fission energy technologies. To this end, a new sulfur chloride-based process has been developed to recycle zirconium alloy-based materials, which make up a significant fraction of high-level radioactive waste. To support the continued development of this process, we present new data on the potential reaction pathways over time of the products arising from the gamma and electron beam radiolysis of neat thionyl chloride (SOCl2). Interrogation of the gamma irradiated liquid by Raman spectroscopy provided more conclusive identification of the SOCl2 degradation products, specifically sulfur dichloride (SCl2), molecular chlorine (Cl2), sulfur dioxide (SO2), and sulfuryl chloride (SO2Cl2). In comparison, the high dose rate (∼107 Gy s−1) electron beam irradiations formed significantly more degradation products. For both cobalt-60 gamma and electron beam irradiations, the observed degradation products were found to evolve as a function of time post-irradiation via the same reaction pathways, with indication of a solvent regeneration mechanism. These findings are fortuitous for process development, as such a mechanism would be beneficial for process longevity and cost effectiveness.