In this study, a model to optimize residual chlorine concentrations in a water supply system was developed using a multi-objective genetic algorithm. Moreover, to quantify the effects of optimized residual chlorine concentration management and to consider customer service requirements, this study developed indices to quantify the spatial and temporal distributions of residual chlorine concentration. Based on the results, the most economical operational method to manage booster chlorination was derived, which would supply water that satisfies the service level required by consumers, as well as the cost-effectiveness and operation requirements relevant to the service providers. A simulation model was then created based on an actual water supply system (i.e., the Multi-regional Water Supply W in Korea). Simulated optimizations were successful, evidencing that it is possible to meet the residual chlorine concentration demanded by consumers at a low cost.
Global fitting functions for Fe-selective chlorination in ilmenite(FeTiO2) and successive chlorination of beneficiated TiO2 are proposed and validated based on a comparison with experimental data collected from the literature. The Fe-selective chlorination reaction is expressed by the unreacted shrinking core model, which covers the diffusion-controlling step of chlorinated Fe gas that escapes through porous materials of beneficiated TiO2 formed by Fe-selective chlorination, and the chemical reaction-controlling step of the surface reaction of unreacted solid ilmenite. The fitting function is applied for both chemical controlling steps of the unreacted shrinking core model. The validation shows that our fitting function is quite effective to fit with experimental data by minimum and maximum values of determination coefficients of R2 as low as 0.9698 and 0.9988, respectively, for operating parameters such as temperature, Cl2 pressure, carbon ratio and particle size that change comprehensively. The global fitting functions proposed in this study are expressed simply as exponential functions of chlorination rate(X) vs. time(t), and each of them are validated by a single equation for various reaction conditions. There is therefore a certain practical merit for the optimal process design and performance analysis for field engineers of chlorination reactions of ilmenite and TiO2.
There has been an accelerating increase in water reuse due to growing world population, rapid urbanization, and increasing scarcity of water resources. However, it is well recognized that water reuse practice is associated with many human health and ecological risks due to numerous chemicals and pathogenic microorganisms. Especially, the potential transmission of infectious disease by hundreds of pathogenic viruses in wastewater is one of the most serious human health risks associated with water reuse. In this study, we determined the response of different bacteriophages representing various bacteriophage groups to chlorination in real wastewater in order to identify a more reliable bacteriophage indicator system for chlorination in wastewater. Different bacteriophages were spiked into secondary effluents from wastewater plants from three different geographic areas, and then subjected to various doses of free chlorine and contact time at 5˚C in a bench-scale batch disinfection system. The inactivation of φX174 was relatively rapid and reached ∼4 log10 with a CT value of 5 mg/L*min. On the other hand, the inactivation of bacteriophage PRD1 and MS2 were much slower than the one for φX174 and only ~1 log10 inactivation was achieved by a CT value of 10 mg/L*min. Overall, the results of this study suggest that bacteriophage both MS2 and PRD1 could be a reliable indicator for human pathogenic viruses for chlorination in wastewater treatment processes and water reuse practice.
It has been confirmed that some Trihalomethanes (THMs) suspected as carcinogens, can be formed during chlorination for water supply through the reaction of chlorine and humic substances in water. The electrochemical characteristics on activated carbon fiber filter (ACF) electrode were investigated to remove the THMs in the chlorination process of drinking water. The electrochemical removal efficiency depended on the applied voltage and flow rate. In this study, the best result showed that the removal efficiency of THMs was higher than 99%.
This study was conducted to recover the aluminum from water treatment plant sludge containing alumina. The optimum reaction conditions about chlorination of sludge with NH4Cl are as follows: the weight ratio of sludge to NH4Cl is 4, the reaction time is 60min, and the temperature is 300℃. And the result of leaching time test showed that the highest yield of alumina at 160℃ was 96% but the result of leaching test at 160℃ was little better than that of leaching test at 100℃ while the leaching concentration of HCl was 4N. The optimum reaction conditions of chlorinated sludge with NH4Cl, gave the highest yield of 95.41% based on aluminum.
사염화우라늄 제조를 위해 염소가스와 탄소를 이용한 이산화우라늄의 염소화반응에 대하여 연구하였다. 이론적측면에서 열화학적 자료를 이용한 계산을 통하여 일어날 수 있는 반응들을 확인하였으며, 염소화반응이 진행되는 동안 초래될 현상에 대하여 검토하였다. 실험결과로 부터 반응온도, 반응시간 및 질소가스 주입비율이 사염화우라늄 제조에 미치는 영향을 정량적으로 평가하였다. 순수한 이산화우라늄을 사용한 사염화우라늄 제조공정에서의 적절한 반응시간과 반응온도는 각각 약 2시간과 500˚C-700˚C범위였으며, 질소가스의 적정 주입량은 염소가스의 약 50%로 나타났다.
사염화우라늄을 제조하기 위한 가장 효율적인 반응계는 이산화우라늄, 염소가스와 탄소분말이다. 여러 가지 실험변수 가운데 이산화우라늄의 염소화반응에 사용된 염소가스 주입량과 탄소의 양이 사염화우라늄 제조에 미치는 영향에 관하여 연구하였다. 각각의 실험변수들에 대한 전화율과 휘발률 계산을 통해 효율적인 반응을 위한 적정 염소가스 주입량과 탄소의 양을 구하였고, 이산화우라늄의 증가함에 따라 직접접촉에 의한 기체-고체반응에서는 전화율과 휘발률은 증가했으나 이후 과량을 첨가함에 따라 감소하였고, 용융염내의 기체-액체반응에서는 전화율의 미미한 증가와 휘발률의 감소를 확인하였가. 염소주입량이 증가함에 따라 전화율과 휘발률이 증가했으며, 과량의 염소가수 주입시 고이온가 염화물의 생성량이 증가하였다.
This study investigated the effectiveness of various chlorinating agents in partitioning light water reactor spent fuel, with the aim of optimizing the chlorination process. Through thermodynamic equilibrium calculations, the effects of using MgCl2, NH4Cl, and Cl2 as a single chlorinating agent or applying MgCl2, NH4Cl, and Cl2 sequentially for spent fuel chlorination were evaluated Furthermore, in this study, assuming the actual process operation situation, where only a part of the semi-volatile nuclides is removed during the heat treatment process, and including the process of precipitating the molten salt from the chlorination process with K3PO4 and K2CO3 precipitants, the percentage distribution of 50 nuclides in the light water reactor spent fuel into each process stream was quantitatively calculated using the simulation function of the HSC program and tabulated for intuitive viewing. Compared to a single chlorinator, sequential chlorination more effectively separated the heat and radioactivity of the spent fuel from the uranium-dominated product solids. Specifically, the sequential application of the chlorinating agents following heat treatment led to a final solid separation characterized by 93.1% mass retention, 5.1% radioactivity, and 15.4% decay heat, relative to the original spent fuel. The findings underscore that sequential chlorination can be an effective method for spent fuel partitioning, either as a standalone approach or in combination with other partitioning processes such as pyroprocessing.
This study examined the efficacy of various chlorinating agents in partitioning light water reactor spent fuel, with the aim of optimizing the chlorination process. Through thermodynamic equilibrium calculations, we assessed the outcomes of employing MgCl2, NH4Cl, and Cl2 as chlorinating agents. A comparison was drawn between using a single agent and a sequential approach involving all three agents (MgCl2, NH4Cl, and Cl2). Following heat treatment, the utilization of MgCl2 as the sole chlorinating agent resulted in a moderate separation. Specifically, this method yielded a solid separation with 96.9% mass retention, 31.7% radioactivity, and 44.2% decay heat, relative to the initial spent fuel. In contrast, the sequential application of the chlorinating agents following heat treatment led to a final solid separation characterized by 93.1% mass retention, 5.1% radioactivity, and 15.4% decay heat, relative to the original spent fuel. The findings underscore the potential effectiveness of a sequential chlorination strategy for partitioning spent fuel. This approach holds promise as a standalone technique or as a complementary process alongside other partitioning processes such as pyroprocessing. Overall, our findings contribute to the advancement of spent fuel management strategies.
As temporary storage facilities for spent nuclear fuel (SNF) are becoming saturated, there is a growing interest in finding solutions for treating SNF, which is recognized as an urgent task. Although direct disposal is a common method for handling SNF, it results in the entire fuel assembly being classified as high-level waste, which increases the burden of disposal. Therefore, it is necessary to develop SNF treatment technologies that can minimize the disposal burden while improving long-term storage safety, and this requires continuous efforts from a national policy perspective. In this context, this study focused on reducing the volume of high-level waste from light water reactor fuel by separating uranium, which represents the majority of SNF. We confirmed the chlorination characteristics of uranium (U), rare earth (RE), and strontium (Sr) oxides with ammonium chloride (NH4Cl) in previous study. Therefore, we prepared U-RE-SrOx simulated fuel by pelletizing each elements which was sintered at high temperature. The sintered fuel was again powdered by heating under air environment. The powdered fuel was reacted with NH4Cl to selectively chlorinate the RE and Sr elements for the separation. We will share and discuss the detailed results of our study.
Thermodynamically, TRUOx, REOx, and SrOx can be chlorinated using ammonium chloride (NH4Cl) as a chlorinating agent, whereas uranium oxides (U3O8 and UO2) remain in the oxide form. In the preliminary experiments of this study, U3O8 and CeO2 are reacted separately with NH4Cl at 623 K in a sealed reactor. CeO2 is highly reactive with NH4Cl and becomes chlorinated into CeCl3. The chlorination yield ranges from 96% to 100%. By contrast, U3O8 remains as UO2 even after chlorination. We produced U/REOx- and U/SrOx-simulated fuels to understand the chlorination characteristics of the oxide compounds. Each simulated fuel is chlorinated with NH4Cl, and the products are dissolved in LiCl-KCl salt to separate the oxide compounds from the chloride salt. The oxide compounds precipitate at the bottom. The precipitate and salt phases are sampled and analyzed via X-ray diffraction, scanning electron microscope-energy dispersive spectroscopy, and inductively coupled plasma-optical emission spectroscopy. The analysis results indicate that REOx and SrOx can be easily chlorinated from the simulated fuels; however, only a few of U oxide phases is chlorinated, particularly from the U/SrOx-simulated fuels.
Facing the problem of saturation of spent nuclear fuel (SNF) stored in temporary storage facilities on sites, interest in the treatment of SNF is increasing, and it is recognized as a task that needs to be solved promptly. Although direct disposal is a general method for dealing with SNF, the entire fuel assembly is classified as high-level waste; thus, the burden of disposal is high. In order to minimize the disposal burden with enhancing safety for long term storage, it is necessary to develop SNF treatment technologies and continuous efforts are required from a national policy perspective. The present study focused on minimizing the volume of high level waste from light water reactor fuel by separation of uranium, which accounts for most of SNF. The chlorination characteristics of uranium (U), rare earth (RE) oxides were confirmed through lab-scale experiments, and the possibility of uranium separation from U-RE simulated fuel was evaluated using NH4Cl chlorinating agent. The detailed results will be posted and discussed.
To estimate the removal efficiency of TRU and rare earth elements in an oxide spent fuel, basic dissolution experiments were performed for the reaction of rare earth elements from the prepared simfuel with chlorination reagents in LiCl-KCl molten salt. Based on the literature survey, NH4Cl, UCl3, and ZrCl4 were selected as chlorination reagent. CeO2 and Gd2O3 powders were mixed with uranium oxide as a representative material of rare earth elements. Simfuel pellets were prepared through molding and sintering processes, and mechanically pulverized to a powder form. The experiments for the reaction of the simfuel powder and chlorination reagents were carried out in a LiCl-KCl molten salt at 500°C. To observe the dissolution behavior of rare earth elements, molten salt samples were collected before and after the reactions, and concentration analysis was performed using ICP. After the reaction completed, the remaining oxide was washed with water and separated from the molten salt, and XRD was used for structural analysis. As a result of salt concentration analysis, the dissolution performance of rare earth elements was confirmed in the reaction experiments of all chlorination reagents. In an experiment using NH4Cl and ZrCl4, the uranium concentration in the molten salt was also measured. In other words, it seemed that not only rare elements but also uranium oxide, which is a main component of simfuel, was dissolved. Therefore, it is thought that the dissolution of rare earth elements is also possible due to the collapse of the uranium oxide structure of the solid powder and the reaction with the oxide of rare earth elements exposed to molten salt. As a result of analyzing the concentration changes of Simfuel before and after each reaction, there was little loss of uranium and rare earth elements (Ce/Gd) in the NH4Cl experiment, but a significant amount of rare earth elements were found to be reduced in the UCl3 experiment, and a large amount of rare earth elements were reduced in the ZrCl4 reaction.
Strontium-90 is a high heat-generating nuclide in spent nuclear fuel. The removal of the nuclide separation is indispensable to reduce the burden of storage and disposal of high-level radioactive waste. Korea Atomic Energy Research Institute has developed the molten salt immersion technique to separate the strontium by the chlorination of the strontium oxide in molten salt. It is needed to separate the salt for the recovery of strontium from the salt solution after the chlorination reaction. In this study, it was investigated on the recovery of the strontium from the salt. Vacuum distillation was used for the separation of strontium from the molten salt. The vapor pressures of the candidate salts were calculated by HSC chemistry and the apparent evaporation rates (AER) were measured at 830°C to evaluate the salts for strontium recovery. The candidate salts were LiCl, KCl, MgCl2, NaCl and CaCl2. The AERs of MgCl2 and NaCl were 1.9 and 1.3 g/cm2-h, respectively. Those two salts can be separated from the strontium compound even though the AER values are much lower than those of LiCl-KCl (~ 8 g/cm2-h). CaCl2 salt was rarely evaporated (AER < 0.03 g/cm2-h) and it is not suitable to use as a strontium recovery salt. Therefore, MgCl2, NaCl, LiCl and KCl can be regarded as candidates for a strontium recovery salt.