Ion exchange resins are commonly employed in the treatment of liquid radioactive waste generated in nuclear power plants (NPP). The ion exchange resin used in NPP is a mixed-bed ion exchange resin known as IRN-150, which is of nuclear grade. This resin is a mixture of cation exchange resin and anion exchange resin. The cation exchange resin removes cationic radionuclides such as Cs and Co, while anion exchange resin handles anions (e.g., H14CO3 -), effectively purifying the liquid waste. Spent ion exchange resins (spent resin) containing C-14 are classified as low and intermediate level radioactive waste, and their radioactivity needs to be reduced as it exceeds the disposal limit regulated by law. Therefore, the microwave technology for the removal of C-14 from spent resin has been investigated. Previous studies have successfully developed a method for the effective removal of C-14 during the resin treatment process. However, it was observed that, in this process, functional groups in the resin were also removed, resulting in the generation of off-gases containing trimethylamine. These off-gases can dissolve in water from process, increasing its pH, which can subsequently hinder the recovery of C-14. In this study, we investigated the high-purity recovery of C-14 by adjusting the moisture content within the reactor following microwave treatment. Mock spent resins, consisting of 100 g of resin with HCO3 - ion-exchanged and 0, 25, or 50 g of deionized water, were subjected to microwave treatment for 40 or 60 minutes. Subsequently, the C-14 desorption efficiency of the mock spent resins was evaluated using an acid stripping process with H3PO4 solution. The functional group status of the mock spent resins was analyzed using 15N NMR spectroscopy. The results showed that the mock spent resins exhibited efficient C-14 recovery without significant functional group degradation. The highest C-14 desorption efficiency was achieved when 25 g of deionized water was used during microwave treatment.
The intermediate level spent resins waste generated from water purification for the the moderator and primary heat transport system during operaioin of heavy water reactor (HWR). Especially, moderator resins contain high level activity largely because of their C-14 content. So spent resins are considered as a problematirc solid waste and require special treatment to meet the waste acceptance criteria for a disposal site. Various methods have been studied for the treatment of spent resins which include thermal, destructive, and stripping methods. In the case of solidification methods, cement, bitument or organic polymers were suggested. In the 1990s, acid stripping using nitric acid and thermal treatment methods were actively investigated in Canada to remove C-14 nuclide from waste resin. In Japan, thermal distructive method was studied in the 1990s. Since 2005, KAERI developed acid stripping method using phosphate salt. However, acid stripping method are not suitable due to large amounts of 2nd waste containing acid solution with various nuclides. To solve this probelm, KAERI has been suggested the microwave treatment method for C-14 selective removal from waste resin in the 2010s. Pilot scale demonstration tests using radioactive waste resin generated from Wolsung unit 1 and unit 2 were successfully conducted and 95% of C-14 was selectively removed from the radioactive waste resin. In recent years, price of C-14 source is dramatically increased due to market growth of C-14 utilization and exclusive supply chain depending on China and Russia. High purity of C-14 were captured in HWR waste resin. Interest of C-14 recovery research from HWR waste resin is currently increased in Canada. In this study, microwave method is suggested to treat HWR waste resin with C-14 recovery process. Additionally, status of waste resin management and research trends of HWR waste resin treatment are introduced.
Mixed-bed ion exchange resin consist of anion exchange resin and cation exchange resin is used to treat liquid radioactive waste in nuclear power plants. C-14 from heavy water reactors (HWR) is adsorbed on the anion exchange resin and is considered intermediate-level radioactive waste. The total amount of radioactivity of C-14 in spent ion exchange resin exceeds the activity limits for the disposal facility. Therefore, it is necessary to reduce the radioactivity through pre-treatment. There are thermal and non-thermal methods for the treatment of spent ion exchange resin. However, destructive methods have the problem of emitting off-gas containing radionuclides. To solve this challenge, various methods have been developed such as acid stripping, PLO process, activity stripping, thermal treatment and others. In this study, spent ion exchange resin (spent resin) was treated using microwave. The reaction characteristics of the resin to microwave were used to selectively remove the C-14 on the functional groups. Simulated spent anion exchange resin and spent resin from Wolseong NPP were treated with the microwave method, and the desorption rate was over 95%. An integrated process system of 1 kg/batch was built to produce operating data. After the operation of the process, characterization and evaluation of post-treatment for condensate water and adsorbent used in the process were performed. When the process system was applied to treat simulated spent resin and real spent resin, both showed a desorption rated of more than 97%. It means that the C-14 was successfully removed from the radioactive spent resin.
In biosphere assessment modeling for the safety assessment of the Wolsong LILW disposal facility, the multi-compartment modeling in which all radionuclides transport is described quantitatively in terms of transfer factors between various environmental compartments has been implemented. In order to reflect the actual transfer mechanisms of 14C in the environment the specific activity (SA) modeling approach can be applied as an alternative to the previous transfer factors (TF) approach. The assumption of full SA equilibrium throughout the terrestrial environment is completely satisfactory for 14C release to the atmosphere if the 12C is emitted as 14CO2. This is the only form that is readily taken up by plants, so that active carbon is incorporated into the plant via photosynthesis at the same rate as stable carbon. Accordingly, the 14C concentration in Bq/g stable carbon is the same in the plant as it is in the air. And animals take up carbon almost entirely through ingestion and the SA ratio in the plant is maintained in the animal. In this study, a specific activity model for 14C was implemented in a GoldSim biosphere assessment model. From the literature survey for existing specific activity models developed, the IAEA model was selected. The farming scenario utilizing well water was simulated and the resulting ingestion dose conversion factors (DCFs) from the IAEA SA model were compared with those of the TF approach. The parameter value for the concentration of stable carbon in the air (gC/m3) is used as 0.20 gC/m3 considering the Suess effect. The dose coefficient for food ingestion used for dose calculations was taken from ICRP-72 as 5.8E-10 Sv/Bq. It was found that the ingestion DCFs of the SA model showed about 3 times lower than those of the TF model in the farming scenario through irrigation of well water, so it is expected that the SA approach could be applied for a more realistic assessment. Though the comparisons were made on the results from the terrestrial ecosystem only in this study, it would be necessary to investigate the applicability of the SA modeling approach for 14C through extensive comparisons and analysis including an aquatic ecosystem, and through parameters survey suitable to the domestic condition.
This study presents a rapid and quantitative sequential separation method for H-3 and C-14 isotopes with distillation apparatus in environmental samples released from nuclear facilities. After adding 200 mg of granulated potassium permanganate and 500 mg of sodium hydroxide in 100 mL of sample solution, the sample solution was heated until approximately 10 mL of distillate, and the distillate fraction was removed. The sample solution was heated again until a minimum 10 mL of additional distillate was collected. 10 mL of distillate was transferred to the LSC vail and the measurement sample for H-3 was made by adding 10 mL of Ultima Gold LLT to the LSC vial. After adding 2.5 g of potassium persulfate, 2 mL of 1M silver nitrate and 15 mL of concentrated nitric acid to the remained sample solution, the sample solution was heated for 90 minutes and C-14 isotopes were adsorbed into 10 mL of Carbo-Sorb solution in glass vial. The measurement sample for C-14 was made by adding 10 mL of Permafluor to the C-14 fraction in glass vial. The purified H-3 and C-14 samples were measured by the liquid scintillation counter after quenching correction. The average recoveries of H-3 and C-14 with CRM were measured to be 96% and 85%, respectively. The sequential separation method for H-3 and C-14 investigated in this study was applied to activated charcoal filter produced from nuclear power plants after validating the reliability by result of proficiency test (KOLAS-KRISS, PT-2021-51).
Radioactive carbon, C-14, can be generated by the neutron capture reaction of O-17 during the nuclear power plant operation. Since C-14 is classified as an intermediate level waste radionuclide, it is required that an effective separation process for C-14. C-14 is mainly absorbed on activated carbon in the air cleanup system. Therefore, the main generation source of C-14 during the nuclear power plant decommissioning is spent activated carbon. KAERI has been developing the treatment of spent activated carbon. In this process, C-14 can be desorbed as a gaseous oxide form from the spent activated carbon at high-temperature vacuum conditions. This radioactive carbon dioxide can be captured into alkaline earth metal incorporated glass and can be transformed into carbonate form. However, the carbonate (e.g. CaCO3 and SrCO3) is dispersive. When the radioactive carbonates are disposed into a geological repository, they should be immobilized to remove future uncertainty. This study examined the stabilization/immobilization of the radioactive carbonates by the cement hydration process. Cement wasteform incorporated with calcium carbonate and strontium carbonate was produced under various waste loading (e.g. 20wt%, 40wt%, and 60wt% of CaCO3 and SrCO3, respectively). Then we evaluated mechanical and chemical durability by measuring compressive strength and leachability according to standard test methods specified in the waste acceptance criteria of the Gyeongju low and intermediate level waste repository (WAC-SIL-2022-1). Also, microstructure and thermal characteristics were investigated by SEM-EDS and TGA analysis.
In this study, an aerosol process was introduced to produce CaCO3. The possibility of producing CaCO3 by the aerosol process was evaluated. The characteristics of CaCO3 prepared by the aerosol process were also evaluated. In the CaCO3 prepared in this study, as the heat treatment proceeded, the calcite phase disappeared. The portlandite phase and the lime phase were formed by the heat treatment. Even if the CO2 component is removed from the calcite phase, there is a possibility that the converted CO2 component could be adsorbed into the Ca component to form a calcite phase again. Therefore, in order to remove the calcite phase, carbon components should be removed first. The lime phase was formed when CO2 was removed from the calcite phase, while the portlandite phase was formed by the introducing of H2O to the lime phase. Therefore, the order in which each phase formed could be in the order of calcite, lime, and portlandite. The reason for the simultaneous presence of the portlandite phase and the lime phase is that the hydroxyl group (OH−) introduced by H2O was not removed completely due to low temperature and/or insufficient heating time. When the sufficient temperature (900°C) and heating time (60 min) were applied, the hydroxyl group (OH−) was removed to transform into lime phase. Since the precursor contained the hydrogen component, it could be possible that the moisture (H2O) and/or the hydroxyl group (OH−) were introduced during the heat treatment process.
The permanent shutdown of Wolseong 1, PHWR (Pressurized Heavy Water Reactor) was decided. Accordingly, there is need for C-14 treatment technology to spent resin generated by PHWR in classified Medium Level Radioactive Waste by C-14 specific activity. However, spent resin by PHWR is mixed and stored with activated carbon and zeolite (mixture), not a single storage, and separation from the mixture must be carried out in advance for C-14 treatment in the spent resin. This study developed a C-14 treatment facility that combined with the technology of separating spent resin from spent resin mixture by PHWR NPP and the technology of C-14 treatment for disposal. The C-14 treatment facility consists of spent resin separation (Part 1) and treatment of separated spent resin. (Part 2) Part 1 is applied with a process of separating the mixed and stored spent resin from the spent resin mixture by applying a drum screen method. In the case of Part 2, spent resin treatment process for desorbing and collecting C-14 nuclides in the separated spent resin using microwave reactor was applied. Except for the adsorbent used to collect C-14 detached in the process of separating and treating spent resin, no additional material is introduced into the facility, and thus secondary waste is significantly reduced. In addition, pollution prevention banks at the bottom of the facility and a sealed automated circulation system were applied to prevent unexpected leakage and diffusion of radioactive materials and ensure stability of workers. Currently, the C-14 treatment facility has been verified for spent resin separation and spent resin treatment using simulated spent resin mixture, and the facility will be demonstrated and verified for field applicability. According to derived results, it is believed that it will be possible to apply the C-14 treatment facility when decommissioning of PHWR.
Inorganic and organic ion exchange materials were generally applied to liquid processes in nuclear reactor. In the case of heavy-water reactor (HWR), zeolite, active carbon, anion resin, and cation resin were used to treat liquid processes such as reactor primary coolant cleanup and liquid radioactive waste management system. Then, used ion exchangers were stored at storage tanks. Various kinds of nuclides were adsorbed in ion exchange materials. Especially, C-14, long half-life nuclide, was highly concentrated in anion resin, and waste resin was treated as intermediated level radioactive waste (ILW). Thermal and non-thermal methods such as pyrolysis, incineration, catalytic extraction, acid digestion, and wet oxidation have been studied for treating spent resin. However, destructive methods are not suitable due to massive off gas waste containing radioactive species. To solve this problem, various kinds of processes were developed such as acid stripping, PLO process, activity stripping, thermal treatment, and etc. In this study, microwave method is suggested to treat HWR waste resin. C-14 nuclide was selectively removed from waste resin without decomposition of main structure in waste resin. Radioactive waste resin generated from Wolsung HWR unit 1 and unit 2 was treated using microwave method and 95% of C-14 was successfully removed from the radioactive waste resin.