放射性三辛胺二甲苯废液的催化氧化处理

    Catalytic Oxidation Treatment of Radioactive Trioctylamine-Xylene Waste Liquids

    • 摘要: 通过催化氧化的方法处理一批放射性三辛胺二甲苯(v/v = 20%/80%)有机废液,废液主要含某超铀核素,总α活度108 Bq。选择经济、合成简单、性质稳定的纳米二氧化锰作为催化剂,冷实验工艺验证连续运行90小时,结果显示三辛胺二甲苯混合有机液体经催化氧化后主要产物为二氧化碳、水及少量小分子有机物,无机化率>95%,催化氧化效果较好。确定工艺参数后在热室内顺利完成了该批放射性有机废液的催化氧化处理,放射性测量衡算结果表明98%以上的超铀核素截留在催化剂残渣和催化装置内,以气载放射性废物形式排放的核素含量小于0.001%,表明该工艺设备能有效防止核素扩散,本研究通过冷试验证和工程应用证明了催化氧化法处理放射性有机废液的技术可行性。

       

      Abstract:   This study investigates the catalytic oxidation treatment of radioactive trioctylamine-xylene (v/v = 20%/80%) organic waste liquid containing a transuranic nuclide using nano manganese dioxide (MnO2) as the catalyst. The waste liquid exhibited an α-activity concentration with a total α-activity of 108 Bq. Nano MnO2 was selected for its cost-effectiveness, simple synthesis, and chemical stability. A cold test was conducted under optimized parameters (reactor temperature: 190 ± 20°C, feed rate: 87 mL/h, stirring speed: 30 rpm) to validate the process, achieving continuous operation for 90 hours. The results demonstrated that the primary products of catalytic oxidation were carbon dioxide, water, and trace small-molecule organics (e.g., benzene, toluene, ethylbenzene), with a mineralization rate exceeding 95%. Trioctylamine exhibited higher catalytic efficiency compared to xylene, likely due to its greater polarity, while the presence of ethylbenzene in exhaust gases indicated chemical reforming of xylene during oxidation.
        Following cold test validation, the radioactive waste was successfully treated in a hot cell. Radiometric analysis revealed that 96.86% of transuranic nuclide was retained in catalyst residues, 1.95% adhered to reactor surfaces, and 1.06% remained in local ventilation systems. Airborne emissions accounted for less than 0.001% of the total activity, confirming the system’s effectiveness in preventing radionuclide dispersion. Exhaust gas analysis via gas chromatography-mass spectrometry (GC-MS) detected volatile organic compounds (VOCs) totaling 925.1 mg/m³, including benzene (25.38 mg/m³), toluene (17.97 mg/m³), and ethylbenzene (116.59 mg/m³), with minimal nitrogen oxides (NO: 0.05 mg/m³; NO2: 0.52 mg/m³). Post-catalysis, the carbon content in the catalyst increased from 0.044% to 2.08%, suggesting residual organic deposition or elemental carbon formation.
        The process achieved the critical objective of converting liquid radioactive waste into solid residues, enhancing storage safety. Post-treatment, the catalyst residues were immobilized using a glass matrix for interim storage. Error analysis attributed minor discrepancies to residual waste adhesion and analytical uncertainties, yet the overall transuranic nuclide retention efficiency reached 99.87%. Compared to conventional methods such as cementation or vitrification—which face challenges in volume expansion, leaching resistance, and compatibility with flammable organics—this catalytic oxidation process offers a viable alternative for managing medium-level radioactive organic wastes. The study underscores the technical feasibility of catalytic oxidation using nano MnO2, aligning with regulatory requirements for radionuclide immobilization and environmental safety.

       

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