Tianchi Li

The PUREX process is a key technology for spent fuel reprocessing, designed to selectively recover uranium and plutonium mainly through multiple chemical separation stages, minimizing high-level waste. Acetohydroxamic acid (AHA) enhances selectivity in this process but decomposes into acetic acid (HAc), which disrupts chemical equilibrium and reduces extraction efficiency. This study examines the extraction and separation of nitric acid (HNO₃) and HAc using 30% tributyl phosphate in organic kerosene (TBP-OK) under various conditions. Results show that 30%TBP-OK preferentially extracts HAc over HNO₃, especially in the low acid concentration range (HNO₃ < 1 mol/L, HAc < 0.2 mol/L). The selectivity coefficient drops from 3.05 in a 0.5 mol/L HNO₃-0.1 mol/L HAc system to 2.18 in a 1 mol/L HNO₃-0.2 mol/L HAc system. TBP forms stable 1:1 complexes with both acids, with equilibrium constants around 0.85 under typical conditions. Increasing TBP concentration enhances HNO₃ extraction, while phase ratio adjustments improve HAc separation. A 16-stage countercurrent extraction simulation confirms that optimizing these factors effectively separates HNO₃ and HAc, offering theoretical and technical support for refining the PUREX process.

Hydroxylamine nitrate (HAN) and hydrazine nitrate (HN) are commonly found in radioactive waste solutions in nuclear fuel reprocessing, and their efficient removal is essential for waste treatment processes. In this study, six activated carbon carriers were selected to prepare Ru/AC catalysts for the simultaneous catalytic decomposition of HAN and HN, with the aim of exploring the effect of carrier properties on catalytic performance. The catalyst’s activity was evaluated in a batch reaction unit, and its structural properties were characterized using N₂ physical adsorption, XRD, SEM, and TEM techniques. The results revealed that the catalyst’s activity was primarily determined by the carrier’s particle size and specific surface area. Additionally, corrosion-induced damage to the pore structure and Ru loss were identified as the main factors responsible for catalyst deactivation. This study highlights the importance of optimizing carrier structure to enhance the activity and stability of Ru/AC catalysts.

Recent advancements in tritium separation technologies have significantly improved efficiency, particularly through the integration of vapor phase catalytic exchange (VPCE), liquid phase catalytic exchange (LPCE), and combined electrolysis catalytic exchange (CECE) methods. Combining these techniques overcomes individual limitations, enhancing separation efficiency and reducing energy consumption. The CECE process, which integrates electrolysis with catalytic exchange, offers high separation factors, making it effective for high-concentration tritiated water treatment. Solid polymer electrolyte (SPE) technology has also gained prominence for its higher efficiency, smaller equipment size, and longer lifespan compared to traditional alkaline electrolysis. While electrolysis offers high separation factors, its high energy demand limits its cost-effectiveness for large-scale operations. As a result, electrolysis is often combined with other methods like CECE to optimize both energy consumption and separation efficiency. Future research will focus on improving the energy efficiency of electrolysis for large-scale, low-cost tritiated water treatment.

Iodine is one of the key elements that must be removed from the off-gas systems of nuclear fuel reprocessing. This study systematically investigates the iodine vapor adsorption performance of the metal–organic framework (MOF) material HKUST-1(1-(2-methyl-4-(2-oxopyrrolidin-1-yl)phenyl)-3-morpholino-5,6-dihydropyridin-2(1H)-one), with particle sizes of 100 nm and 20 μm. HKUST-1 samples with varying particle sizes were synthesized via a hydrothermal method. The experimental results show that the 20 μm HKUST-1 exhibits superior crystallinity, a more intact pore structure, and a higher iodine adsorption capacity, reaching 700 mg/g, which is significantly greater than the 300 mg/g capacity of the 100 nm HKUST-1. Kinetic analysis reveals that the adsorption process follows the pseudo-second-order model, with physical adsorption as the predominant mechanism, where iodine molecules are accommodated within the pores. FTIR and XRD further confirm the structural stability of the HKUST-1 framework after iodine adsorption. However, desorption experiments show that iodine molecules are easily volatilized into the air, with a 20% weight loss observed within 10 h and a color change from black to green. The results provide experimental evidence for optimizing the application of HKUST-1 materials in iodine capture and suggest that material modification could enhance the long-term stability of iodine fixation.

Fast-neutron reactors are an important representative of Generation IV nuclear reactors, and due to the unique structure and material properties of fast reactor fuel, traditional mechanical cutting methods are not applicable. In contrast, laser cutting has emerged as an ideal alternative. However, ensuring the stability of optical fibers and laser cutting heads under high radiation doses, as well as maintaining cutting quality after irradiation, remains a significant technical challenge. Here, we study the performance changes in optical fibers exposed to a total radiation dose of 10⁵ Gy, focusing on power transmission and thermal characteristics. By integrating irradiated optical fibers with irradiated laser cutting heads, simulated cutting experiments on the hexagonal tubes of spent fuel from fast reactors (fast reactor simulation assembly) were conducted. Critical cutting quality parameters, including kerf width, surface roughness, and slagging length, were analyzed. The results indicate that, while the power transmission performance of irradiated optical fibers shows slight degradation, its impact on cutting quality is minimal. High-quality cutting can still be achieved under optimized parameters. This study confirms the feasibility of laser cutting technology in high-radiation environments and provides essential technical support for its application in nuclear fuel reprocessing.

In the PUREX (the plutonium uranium reduction extraction) process, a plutonium barrier unit (1BXX) is used to achieve deep plutonium stripping. According to the operating experience of the French reprocessing plant, after the separation of uranium and plutonium in the first cycle (1B + 1BXX), the plutonium barrier unit has excellent stripping effect, such that the removal of plutonium from uranium can already be achieved in the first cycle, and the second cycle only needs to focus on the removal of neptunium from uranium in order to obtain a qualified uranium product. In recent decades, China has also been actively conducting research on the plutonium barrier unit process to reduce the plutonium concentration in the primary uranium product in the first cycle to avoid the need to remove neptunium and plutonium at the same time in the second cycle, and to improve the efficiency and feasibility of reprocessing. Due to the lack of design basis for plutonium barriers to achieve deep plutonium stripping at present, this study conducts a basic study on the plutonium barrier unit, aiming to provide data for the optimization of plutonium barriers in the actual reprocessing process at a later date. In this work, a kinetic study on the reduction and stripping of trace plutonium from dibutyl phosphate-containing organic phases was carried out first, and the kinetic equations for the reduction and stripping of Pu(IV) by U(IV) under flow process conditions were obtained. The effects of U(IV) addition on the extraction loss of U(IV) and the concentration distribution of U(IV) at various stages were investigated by process simulation. Additionally, the oxidation of U(IV) under process conditions was investigated to clarify the process chemistry of U(IV) oxidation and to provide a reference for the oxidation consumption of U(IV). Finally, the process parameters of the plutonium barrier unit were preliminarily designed based on the above research.

Employing catalytic decomposition to break down reducing agents in intermediate-level radioactive waste during nuclear fuel reprocessing offers significant advantages. This study focuses on investigating the deactivation behavior of 5% Ru/C catalysts by two different synthesis processes used for reducing agent destruction. Deactivation experiments were conducted by subjecting the 5% Ru/C catalysts to 100 and 150 reaction cycles. Changes in the concentration of free radicals on the carbon-based carrier were measured to analyze the loading position and loss of Ru ions. Additionally, sorption–desorption curves and pore size distributions of the four catalysts were obtained. Analysis results reveal that Ru ions on the catalyst adsorb onto active free radical sites on the carbon-based carrier. Under ultrasonic conditions, some Ru ions partially desorb from the free radical sites on the carbon-based carrier, and desorbed Ru ions may adsorb onto weak free radical sites, while undesorbed Ru ions may adsorb onto strong free radical sites. After hundreds of hours of reaction, SM1 and SM2 exhibited approximately a 30% decrease in specific surface area and pore volume compared to SM0. However, the catalyst activity remained unchanged, and the catalyst pore size remained essentially unchanged, which primarily means that the micropores on the catalyst’s surface have undergone corrosion and damage.