Various transition metal oxides are deposited on the surface of materials such as stainless steel, which is used in the coolant systems of nuclear power plants. The task of removing harmful radionuclides can be solved through the dissolution reaction of the deposited corrosion oxide layer. In this study, for the first time, the reaction thermodynamics of the hydrazine-based reductive metal ion decontamination (HyBRID) reaction developed by the Korea Atomic Energy Research Institute were studied considering the formation of a strong ion − ligand chemical bond complex between Cu ions and hydrazine. When considering complex formation, we found that it had a significant impact on the thermodynamic decontamination reactions of magnetite, nickel ferrite, and chromite. The reactions were proven to be much more thermodynamically favorable than the reaction energies reported thus far, which did not consider complex formation. We demonstrated that not only the thermodynamic energy but also the structures of the HyBRID reaction products can be significantly changed, depending on complex formation considerations.

KAERI has been developing a new decontamination process that does not contain any organic chemicals in the decontamination solution and minimizes the use of ion exchange resin in the solution as a purifying step. The process is hydrazine based reductive metal ion decontamination for decommissioning (HyBRID) and consists of N2H4, H2SO4 and Cu+ ions. The primary system of the LWR is composed of materials with high corrosion resistance, such as stainless steel and Inconel, but among the materials, the feeder and header of the primary system of the PHWR are composed of carbon steel (SA106Gr.B) with low corrosion resistance. Therefore, when decontamination of PHWRs, attention should be paid to corrosion of carbon steel. Since Fe3O4, a contaminating oxide film formed on the surface of carbon steel dissolves faster than ferrite or chromite formed on the surface of Inconel or stainless steel, the base material is exposed to the solution and is corroded during decontamination. When a large amount of iron ions is eluted into the decontamination agent due to corrosion of carbon steel, not only the soundness of the base metal is adversely affected, but also the amount of decontamination waste increases. The purpose of this study is to develop inhibitors that can minimize corrosion of carbon steel when decontamination of PHWRs using the HyBRID decontamination process. CG, 570S and PP3 were selected as corrosion inhibitors. In addition, corrosion tests of carbon steel were conducted in the HyBRID solution with corrosion inhibitors. The best corrosion inhibitors and optimal operating conditions were selected, and HyBRID decontamination agents with corrosion inhibitors were much better in corrosion resistance than existing commercial decontamination agents.

In the field of 3H decontamination technology, the number of patent applications worldwide has been steadily increasing since 2012 after the Fukushima nuclear accident. In particular, Japan has a relatively large number of intellectual property rights in the field of 3H processing technology, and it seems to have entered a mature stage in which the growth rate of patent applications is slightly reduced. In Japan, tritium is being decontaminated through the Semi-Pilot-class complex process (ROSATOM, Russia) using vacuum distillation and hydrogen isotope exchange reaction, and the Combined Electrolysis Catalytic Exchange (CECE, Kurion, U.S.) process. However, it is not enough to handle the increasing number of HTOs every year, so the decision to release them to the sea has been made. Another commercial technology in foreign countries is the vapor phase catalyst exchange process (VPCE) in operation at the Darlington Nuclear Power Plant in Canada. This process is a case of applying tritium exchange technology using a catalyst in a high-temperature vapor state. The only commercially available tritium removal technology in Korea is the Wolseong Nuclear Power Plant’s Removal Facility (TRF). However, TRF is a process for removing HTO from D2O of pure water, so it is suitable only for heavy water with high tritium concentration, and is not suitable for seawater caused by Fukushima nuclear power plant’s serious accident, and surface water and groundwater contaminated by environmental outflow of tritium. Until now, such as low-temperature decompression distillation method, water-hydrogen isotope exchange method, gas hydrate method, acid and alkali treatment method, adsorption method using inorganic adsorbent (zeolite, activated carbon), separator method using electrolysis, ion exchange adsorption method using ion exchange resin, etc. have been studied as leading technologies for tritium decontamination. However, any single technology alone has problems such as energy efficiency and processing capacity in processing tritium, and needs to be supplemented. Therefore, in this study, four core technologies with potential for development were selected to select the elemental technology field of pilot facilities for treating tritium, and specialized research teams from four universities are conducting technology development. It was verified that, although each process has different operating conditions, tritium removal performance is up to 60% in the multi-stage zeolite membrane process, 30% in the metal oxide & electrochemical treatment process, 43% in the process using hydrophilic inorganic adsorbent, and 8% in the process using functional ion exchange resin. After that, in order to fuse with the pretreatment process technology for treating various water quality tritium contaminated water conducted in previous studies, the hybrid composite process was designed by reflecting the characteristics of each technology. The first goal is to create a Pilot hybrid tritium removal facility with 70% tritium removal efficiency and a flow rate of 10 L/hr, and eventually develop a 100 L/hr flow tritium removal system with 80% tritium removal efficiency through performance improvement and scale-up. It is also considering technology for the postprocessing process in the future.

원전 일차계통 HyBRID 제염공정에서 발생되는 제염폐액에는 황산이온과 방사성 핵종을 포함한 금속이온 및 발암성 물질의 하이드라진을 포함하고 있어 이를 안전한 수준으로 처리할 수 있는 기술개발이 필요하다. 본 연구에서는 모의 제염폐액 내 황산 및 금속이온의 제거와 하이드라진의 분해시험을 실시하여 황산이온, 금속이온 및 하이드라진을 효과적으로 제거할 수 있는 HyBRID 제염폐액 처리공정을 도출하였으며, 1 L 규모에서의 반복실험과 Pilot 규모(300 L/batch)에서의 평가시험을 통해 도출한 HyBRID 제염폐액 처리공정의 성능 재현성과 적용성을 검증하였다.