Taihong Yan

The efficient separation of Zr(IV) ions from strong acidic and radioactive solutions is a significant challenge, especially in the context of the aqueous reprocessing of nuclear fuels. The complexity of such solutions, which are often characterized by high acidity and the presence of radioactive elements, poses formidable challenges for separation processes. Herein, several mesoporous silicas (HMS, MCM-41, KIT-6, and SiO₂-70 Å) with excellent acid and radiation resistance properties were employed as sorbents to remove Zr(IV) ions from simulated high-level liquid waste. The batch experiments were designed to investigate the influence of adsorption time, HNO₃ concentration, initial Zr(IV) concentration, adsorbent dosage, and temperature on the adsorption behavior of Zr(IV). The results indicate that the adsorption equilibrium time of mesoporous silica materials was approximately 8 h, and all the adsorption processes followed the pseudo-second-order kinetics equation. The isotherms of Zr(IV) adsorption by KIT-6 exhibited good agreement with the Langmuir model, while the Freundlich model could be utilized to fit the adsorption on HMS, MCM-41, and SiO₂-70 Å. The adsorption capacity of MCM-41 for Zr(IV) in 3 mol/L HNO₃ was 54.91 mg/g, which is three times the adsorption capacity reported for commercial silica gel (17.91 mg/g). The thermodynamic parameters indicate that the adsorption processes for zirconium are endothermic reactions. Furthermore, the mesoporous silicas exhibited a pronounced selectivity in the adsorption of Zr(IV) within a simulated high-level liquid waste containing 10 co-existing cations (3 mol/L HNO₃). This suggests that mesoporous silicas have great potential for Zr(IV) removal in actual radioactive liquids with high acidity during spent fuel reprocessing.

Continuous dissolution of spent fuel is indeed one of the key technologies that can significantly improve the efficiency and stability of spent fuel reprocessing. The China Institute of Atomic Energy designed a prototype rotary drum dissolver, and the dissolution behavior of UO₂ pellets in the dissolver was calculated using the Discrete Element Method. A kinetic equation was established to model the dissolution behavior, considering variables such as temperature, nitric acid concentration, and stirring intensity. The calculations showed that complete pellet dissolution took about 10 h in the continuous reaction, compared to 6 h in the batch dissolution experiment due to the gradual decrease in nitric acid concentration. A 16 h continuous dissolution experiment confirmed the calculated results, with a deviation of 10.8% between the simulation and experiment in terms of the mass of dissolved pellets. It was also found that it takes approximately 30 h to reach equilibrium in the continuous rotary dissolver, with a nitric acid concentration of 2.8 mol/L and a uranium concentration of 243 g/L at equilibrium.

The use of tetra-alkylcarbamides as novel ligands: N,N-butyl-N’,N’-hexylurea (L1: ABHU), and N,N-butyl-N’,N’-pentylurea (L2: ABPU), for the solvent extraction and complexation behaviors of uranium(VI) was synthesized and investigated in this study. The effects of HNO₃ and NO₃⁻ concentrations in the aqueous phase on the distribution ratio of U(VI) were examined. Under 5 mol/L HNO₃ concentration, D_U reached 5.02 and 4.94 respectively without third-phase formation. During the extraction, slope measurements and IR spectral analysis revealed that the U(VI) complexes are a form of UO₂(NO₃)₂·2L for both ligands. In addition, thermodynamic studies showed that the uranium extraction reaction was a spontaneous exothermic reaction. The deep structural analysis of the complexes was realized with DFT calculation. The bond length, bond properties, and topology of the complexes were discussed in detail to analyze the extraction behavior. This study enriches the coordination chemistry of U(VI) by tetra-alkylcarbamides, which may offer new clues for the design and synthesis of novel ligands for the separation, enrichment, and recovery of uranium in the nuclear fuel cycle.

The reduction of Np(VI) and Np(V) by Dihydroxyurea (DHU) was studied by spectrophotometry. The results show that the reduction of Np(VI) to Np(V) by DHU is particularly fast. The apparent rate constant is 1.86 s -1 at 4 °C as [HNO 3 ]=0.44 M and [DHU]=7.5×10 -2 M. While further reduction of Np(V) to Np(IV) is so slow that no Np(IV) is observed in 2 h. The reduction back-extraction behavior of Np(VI) in 30% tri-butyl phosphate/kerosene was firstly investigated under conditions of different temperature, different concentrations of DHU and HNO 3 and various phase contact time, respectively. The results show that 98% of Np(VI) in the organic phase can be stripped rapidly to the aqueous phase by DHU under the given experimental conditions. As the concentration of HNO 3 in the aqueous phase increases, the stripping efficiency decreases. While the stripping efficiency increases with the increase of the concentration of DHU. Simulating the 1B contactor of the PUREX process using DHU as the stripping agent, the SF U /Np equals to 183 under the given experimental conditions. It indicates that Np will follow with Pu in the U/Pu separation stage in the reprocessing of spent fuels.