In this study, a chlorination technique for recycling Li2ZrO3, a reaction product of ZrO2-assisted rinsing process, was investigated to minimize the generation of secondary radioactive pyroprocessing waste. It was found that the reaction temperature was a key parameter that determined the reaction rate and maximum conversion ratio. In the temperature range of 400−600℃, an increase in the reaction temperature resulted in a profound increase in the reaction rate. Hence, according to the experimental results, a reaction temperature of at least 450℃ was proposed to ensure a Li2ZrO3 conversion ratio that exceeded 80% within 8 h of the reaction time. The activation energy was found to be 102 ± 2 kJ·mol−1·K−1 between 450 and 500℃. The formation of LiCl and ZrO2 as reaction products was confirmed by X-ray diffraction analysis. The experimental results obtained at various total flow rates revealed that the overall reaction rate depends on the Cl2 mass transfer rate in the experimental condition. The results of this study prove that the chlorination technique provides a solution to minimize the amount of radioactive waste generated during the ZrO2-assisted rinsing process.

The reaction between Li2CO3 and Cl2 was investigated to verify its occurrence during a carbon-anode-based oxide reduction (OR) process. The reaction temperature was identified as a key factor that determines the reaction rate and maximum conversion ratio. It was found that the reaction should be conducted at or above 500℃ to convert more than 90% of the Li2CO3 to LiCl. Experiments conducted at various total flow rate (Q) / initial sample weight (W i) ratios revealed that the reaction rate was controlled by the Cl2 mass transfer under the experimental conditions adopted in this work. A linear increase in the progress of reaction with an increase in Cl2 partial pressure (pCl2) was observed in the pCl2 region of 2.03–10.1 kPa for a constant Q of 100 mL∙min−1 and W i of 1.00 g. The results of this study indicate that the reaction between Li2CO3 and Cl2 is fast at 650℃ and the reaction is feasible during the OR process.

Strontium is known as a salt-soluble element during the electrolytic oxide reduction (EOR) process. The chemical behavior of SrO during EOR was investigated via thermodynamic calculations to provide quantitative data on the chemical status of Sr. To achieve this, thermodynamic calculations were conducted using HSC chemistry software for various EOR conditions. It was revealed that SrO reacts with LiCl salt to produce SrCl2, even in the presence of Li2O, and that the ratio of SrCl2 depends on the initial concentration of Li2O dissolved in LiCl. It was found that SrO reacts with Li to produce Sr during EOR and that the reduced Sr reacts with LiCl salt to produce SrCl2. As a result, the proportions of metallic forms were lower in Sr than in La and Nd under various EOR conditions. The thermodynamic calculations indicated that the three chemical forms of SrO, SrCl2, and Sr co-exist in the EOR system under an equilibrium with Li, Li2O, and LiCl.

The corrosion behavior of Hastelloy C-276 was investigated to identify its applicability for carbon-anode-based oxide reduction (OR), in which Cl2 and O2 are simultaneously evolved at the anode. Under a 30 mL·min-1 Cl2 + 170 mL·min-1 Ar flow, the corrosion rate was less than 1 g·m-2·h-1 up to 500℃, whereas the rate increased exponentially from 500 to 700℃. The effects of the Cl2-O2 composition on the corrosion rate at flow rates of 30 mL·min-1 Cl2, 20 mL·min-1 Cl2 + 10 mL·min-1 O2, and 10 mL·min-1 Cl2 + 20 mL·min-1 O2 with a constant 170 mL·min-1 Ar flow rate at 600℃ was analyzed. Based on the data from an 8 h reaction, the fastest corrosion rate was observed for the 20 mL·min-1 Cl2 + 10 mL·min-1 O2 case, followed by 30 mL·min-1 Cl2 and 10 mL·min-1 Cl2 + 20 mL·min-1 O2. The effects of the chlorine flow rate on the corrosion rate were negligible within the 5–30 mL·min-1 range. A surface morphology analysis revealed the formation of vertical scratches in specimens that reacted under the Cl2-O2 mixed gas condition.