随着我国核能事业的高速发展，越来越多的放射性废金属也随之产生，需要通过高效的去污技术将其去污。铈去污技术就是一种高效的放射性污染金属去污技术，但其二次废液量大，且二次废液中含有氨根离子，较难处理，严重制约该技术的发展。本文从解决铈去污技术二次废液问题入手，结合我国国内实际放射性废水接受条件，提出了铈/硝酸去污剂无铵化制备工艺路线。该工艺路线通过电化学氧化的方法，将硝酸亚铈与硝酸的混合溶液氧化为四价铈/硝酸溶液，代替国内目前常用的四价铈产品硝酸铈铵，使得去污剂中不再含有氨根离子，且可实现再生循环利用。该工艺研究确立了电解装置，并在此基础上完成了电解核心部件离子膜和电极的性能研究与工艺参数研究，完成了初步放大研究并推荐了工程应用放大策略，实现了铈/硝酸去污剂的无铵化制备及循环利用，对于提高铈去污工艺技术应用前景有着重要意义。首先，本文设计并建立了铈/硝酸去污剂无铵化制备实验装置。重点对核心部件离子膜和电极进行了性能研究。研究过程中选择了6种不同离子交换膜与10种不同基材或涂层的电极，研究了离子膜与电极的电催化性能与稳定性。同时，设计了硝酸体系下的电极强化寿命实验，得到了不同涂层在硝酸体系下的强化寿命。结果表明，加强型全氟磺酸离子膜最适宜作为该工艺的离子膜，钛镀铱钽或钛钯镀铱钽应选取作为阳极电极，钛镀铱或钛镀铱钽应选择作为阴极电极。其次，在确定的实验装置基础上进一步进行了制备工艺研究，结果表明，初始铈浓度推荐为0.8mol/L；电流密度推荐范围为1000～3000A/m2；循环流速推荐范围为5～7次/min；电解温度范围为40~60℃；阴、阳极酸度为2.0～3.0mol/L；在推荐的工艺参数条件下，铈/硝酸去污剂无铵化制备的四价铈转化率可达到80%以上。最后，在台架实验的基础上，将装置扩大5倍与10倍进行单槽放大实验，验证工艺参数的可行性。结果表明，单槽放大5倍的效果较好，四价铈转化率能满足80%以上。进一步的，通过计算，确立了工业装置的放大策略为单槽放大5倍，多槽并联组成电解槽组并设计了模块儿化工业装置的设计构想图。
With the rapid development of China's nuclear energy industry，more and more radioactive waste metal will be produced, which needs efficient decontamination technologyto decontaminate.Ce decontamination technology is one of it. But because of it has large amout of second waste having ammonia ion, it is difficult to dispose and seriously restricting the development of the technology.Combined with China's actual domestic radioactive wastewater acceptance conditions, this paper provide a technology to dissolve the problem of the second waste, which can be prepared detergents with no ammonia ion. Instead of the commonly used cerium ammonium nitrate, this technology can oxidate the Ce3+ to Ce4+, using electrochemical method, and make the second waste can be recycled. This technology not only designed the electrolysis device，but also studied the performance of ionosphere and electrode , completed the study of theprocess parameters ,the preliminary amplification studyand recommended engineering application amplification strategy.This method not only prepared the detergents with no ammonia ion, but also realized cyclic utilization of second waste，which is of great significance to improve the application prospect of the Ce decontamination technology.At first, this paper designed and established the experimental device, focusing on the core components of the ion film and electrode performance research, which selected six different ion membranes and ten different substrates or coatings electrode and studied the electrocatalytic performance and stability of the ion film and the electrode. Simultaneously，The experiment of electrode strengthening life under nitric acid system was designed，and the enhanced life of different coatings under nitric acid system was obtained. The results showed that the einforced perfluorosulfonic acid ion membrane was the most suitable membrance，titanium plating iridium tantalum or titanium palladium plating iridium tantalum suitable as an anode, titanium plating iridium or titanium plating iridium tantalum suitable as a cathode.Secondly, the process researchfurther carried out. The results showed that the recommended initial Ce concentration was 0.8mol/l, the recommended current density was 1000~3000A/m2, the recommended circulating flow rate was 5~7 times/min, the recommended electrolysis temperature was 40~60 and the recommended cathodic acidity and anodic acidity was 2.0～3.0 mol/L， In the recommended process parameters, Ce conversion rate can up to 80% or more.Finally, on the basis of bench test，the device was expanded five times and ten times to carry out a single slot amplification test, verifying the feasibility of the process parameters. The results showed that the effectof single slot magnification five times is better, Ce conversion rate can up to 80% or more. Further more, by calculation, the amplification strategy of the industrial device is established, which the single tank is magnified five times, the multi-slot is connected with the electrolytic cell group, and the design concept of the modular industrial plant is designed.
