• Korean Chemical Engineering Research
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• v.51 no.6
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• pp.700-708
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• 2013

Pyroprocessing has been developed for the purpose of resolving the current spent nuclear fuel management issue and enhancing the recycle of valuable resources. Pyroprocessing has been developed with the dry technologies which are performed under high temperature conditions excluding any aqueous processes. Pyro-processes which are based on the electrochemical principles require pretreatment processes and a voloxidation process is considered as a pretreatment step for an electrolytic reduction process. Various kinds of gas conditions are applicable to the voloxidation process and the understanding of Cs behavior during the process is of importance for the analyses of waste characteristics and heat load on the overall pyroprocessing. In this study, the changes of chemical compounds with the gas conditions were calculated by analyzing gas-solid reaction behavior based on the chemical equilibria on a Cs-Te-O system. $Cs_2TeO_3$ and $Cs_2TeO_4$ were selected after a Tpp diagram analysis and it was confirmed that they are relatively stable under oxidizing atmospheres while it was shown that Cs and Te would be removed by volatilization under reducing atmosphere at a high temperature. This work provided basic data for predicting Cs behavior during the voloxidation process at which compounds are chemically distributed as the first stage in the pyroprocessing and it is expected that the results would be used for setting up material balances and related purposes.

• Nuclear Engineering and Technology
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• v.47 no.3
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• pp.380-387
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• 2015

A lead slowing-down spectrometer (LSDS) system is a promising nondestructive assay technique that enables a quantitative measurement of the isotopic contents of major fissile isotopes in spent nuclear fuel and its pyroprocessing counterparts, such as $^{235}U$, $^{239}Pu$, $^{241}Pu$, and, potentially, minor actinides. The LSDS system currently under development at the Korea Atomic Energy Research Institute (Daejeon, Korea) is planned to utilize a high-flux ($>10^{12}n/cm^2{\cdot}s$) neutron source comprised of a high-energy (30 MeV)/high-current (~2 A) electron beam and a heavy metal target, which results in a very intense and complex radiation field for the facility, thus demanding structural shielding to guarantee the safety. Optimization of the structural shielding design was conducted using MCNPX for neutron dose rate evaluation of several representative hypothetical designs. In order to satisfy the construction cost and neutron attenuation capability of the facility, while simultaneously achieving the aimed dose rate limit (< $0.06{\mu}Sv/h$), a few shielding materials [high-density polyethylene (HDPE)eBorax, $B_4C$, and $Li_2CO_3$] were considered for the main neutron absorber layer, which is encapsulated within the double-sided concrete wall. The MCNP simulation indicated that HDPE-Borax is the most efficient among the aforementioned candidate materials, and the combined thickness of the shielding layers should exceed 100 cm to satisfy the dose limit on the outside surface of the shielding wall of the facility when limiting the thickness of the HDPE-Borax intermediate layer to below 5 cm. However, the shielding wall must include the instrumentation and installation holes for the LSDS system. The radiation leakage through the holes was substantially mitigated by adopting a zigzag-shape with concrete covers on both sides. The suggested optimized design of the shielding structure satisfies the dose rate limit and can be used for the construction of a facility in the near future.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.12 no.3
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• pp.179-189
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• 2014

Pyroprocessing has been developed for the purpose of resolving the current spent nuclear fuel management issue and enhancing the recycle of valuable resources. An electrolytic reduction of the pyroprocessing is a process to reduce oxides into metals using LiCl as an electrolyte and requires a post-treatment process due to the inclusion of residual salt in porous metal products. A vacuum distillation has been adopted for various molten salt systems and could be applied to the post-treatment process of the electrolytic reduction. The residual salt in the metal products includes LiCl, alkali chlorides, and alkaline earth chlorides. In this paper, vapor pressures of chlorides have been estimated and the composition changes on the residual liquid during the vacuum distillation process have been calculated. A model combining a material balance and vapor-liquid equilibrium relations has been proposed under a constant vapor discharging flow rate and liquid composition changes have been calculated using the vapor pressures with respect to a dimensionless time. The behaviors have been compared with temperature and molten salt composition changes to simulate the process condition variation. The distillation of the residual salt has been dominated by LiCl which is the main component of the salt and CsCl of which vapor pressure is higher than that of LiCl would be readily removed. RbCl exhibits similar vapor pressure with LiCl and maintains its composition. However, $SrCl_2$ and $BaCl_2$ of which vapor pressures are much lower than that of LiCl are concentrated with time and expected to be possibly precipitated during the distillation when the initial compositions are increased.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.7 no.4
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• pp.213-218
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• 2009

Electrowinning process recovers uranium with actinide elements from spent fuels and is a key step in the Pyroprocessing because of proliferation resistance. An analysis of heat transfer of the Electrowinning cell was conducted to develop basic tool for designing engineering-scale Electrowinner. For the calculation of the heat transfer, ANSYS CFX commercial code was adapted. As a result of the calculation, the vertical Heating Zone length had great effect upon temperature of LiCl-KCl eutectic salt. To maintain constant temperature in the salt, the Heating Zone length should be three times longer than the height of the salt. However, the argon and salt temperatures were barely affected by the Cooling Zone length. The temperature under the Cell cover was mainly influenced by the number of the cooling plates. When the cooling plates were installed more than the number of 5, temperature under the cover was maintained below $250^{\circ}C$. These temperature properties had similar tendency toward the temperature of the Cell which was measured from experiments, Simulated heat transfer information from this study could be used to design engineering-scale Electrowinner.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.1
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• pp.49-56
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• 2010

In the pyroprocessing of spent nuclear fuels, LiCl-KCl waste salt containing radioactive rare earth chlorides are generated. The radioactive rare earth oxides are recovered by co-oxidative precipitation of rare earth elements. The powder phase of rare eath oxide waste must be immobilized to produce a monolithic wasteform suitable for storage and ultimate disposal. The immobilization of these waste developed in this study involves a solid state sintering of the waste with host borosilicate glass and zinc titanate based ceramic matrix(ZIT). And the rare-earth monazite which synthesised by reaction of ammonium di-hydrogen phosphate with the rare earth oxides waste, were immobilzed with the borosilicate glass. It is shown that the developed ZIT ceramic wasteform is highly resistant the leaching process, high density and thermal conductivity.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.18 no.2
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• pp.207-215
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• 2020

The feasibility of rare earth (RE) removal process via oxidation reactions with UCl₃ was investigated using the HSC Chemistry code to reduce the concentrations of RE in transuranic (TRU) products. The composition and thermodynamic data of TRU and RE elements contained in the reference spent fuel were examined. The reactivity was evaluated by calculating equilibrium data considering oxidation reactions with UCl₃. Both RE removal rate and TRU recovery rate were evaluated for the two cases, wherein TRU products with different RE concentrations were used. When TRU products were reacted with UCl₃, selective oxidation was driven by the difference in the Gibbs free energy of each element. The calculation results imply that the TRU/RE ratio of the final product can be increased by removing RE elements while maintaining the maximum recovery rate of TRU, which is accomplished by controlling the amount of UCl₃ injected. Since the results of this study are based on thermodynamic equilibrium data, there are many limitations to apply to the actual process. However, it is expected to be used as an important data for the process design to supply the TRU product of pyroprocessing to SFR's fuel demanding low RE concentrations.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2005.11b
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• pp.280-289
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• 2005

A pyrochemical process has been introduced and utilized so that the transmutation of spent PWR fuel in PEACER can produce mainly low and intermediate level waste for near surface disposal. Major radioactive nuclides from PEACER pyroprocessing are composed of TRU and LLFP. In this study, the requirement for the final waste from PEACER is evaluated based on the methodology for establishment of waste acceptance criteria. Also, sensitivity analysis for several input parameters is conducted in order to determine acceptable decontamination factor (DF) and LLFP removal efficiency and to find out input parameter that extremely have an effect on DE As a result of the study, LLFP removal efficiency, especially Sr-90 and Tc-99, is proved to be a major nuclide which contributes to annual dose by human intrusion scenario rather than TRU DF. More than $98.5\%$ of LLFP have to be removed to meet below dose constraint within the DF more than 5.0E+03. Besides, because of the relative short half-life of Sr-90, the increasing of the institutional control period is recommended for most important input parameter to determine DF.

• Nuclear Engineering and Technology
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• v.44 no.7
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• pp.767-772
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• 2012

In support of optimizing electrorefining technology for treating spent nuclear fuel, lithium drawdown has been investigated for separating actinides from molten salt electrolyte. Drawdown reaction selectivity is a major issue that requires investigation, since the goal is to remove actinides while leaving the fission products and other components in the salt. A series of lithium drawdown tests with surrogate fission product chlorides was run to obtain selectivity data with non-radioactive salts, develop a predictive model, and draw conclusions about the viability of using this process with actinide-loaded salt. Results of tests with CsCl, $LaCl_3$, $CeCl_3$, and $NdCl_3$ are reported here. Equilibrium was typically achieved in less than 10 hours of contact between lithium metal and molten salt under well-stirred conditions. Maintaining low oxygen and water impurity concentrations (<10 ppm) in the atmosphere was observed to be critical to minimize side reactions and maintain stable salt compositions. An equilibrium model has been formulated and fit to the experimental data. Good fits to the data were achieved. Based on analysis and results obtained to date, it is concluded that clean separation between minor actinides and lanthanides will be difficult to achieve using lithium drawdown.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.11 no.4
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• pp.325-332
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• 2013

Pyroporcessing of spent nuclear fuel generates a considerable amount of LiCl-KCl eutectic waste salt containing radioactive rare earth (RE) chlorides. In this study, a series of processes, which consist of a phosphorylation/distillation process and a solidification process, were performed to minimize volume of the LiCl-KCl eutectic waste salt and solidify a residual waste into a stable form at a relatively low temperature. Over 99wt% of RE chlorides in LiCl-KCl eutectic salt was converted and separated into $REPO_4$ in the phosphorylation/distillation process using a mixture of $Li_3PO_4-K_3PO_4$. The separated $REPO_4$ was solidified into a homogeneous and fine-grained form at $1,050^{\circ}C$ using LIP(Lead Iron Phosphate) as a solidification agent. The final waste volume was reduced below about 10% through the series of the processes.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.1
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• pp.57-63
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• 2010

Layer crystallization process was tested for the separation(or concentration) of cesium and strontium fission products in a LiCl waste salt generated from an electrolytic reduction process of a spent oxide fuel. In a crystallization process, impurities (CsCl and $SrCl_2$) are concentrated in a small fraction of the LiCl salt by the solubility difference between the melt phase and the crystal phase. Based on the phase diagram of LiCl-CsCl-$SrCl_2$ system, the separation possibility by using crystallization was determined and the molten salt temperature profile during layer crystallization operation was predicted by using mathematical calculation. In the layer crystallization process, the crystal growth rate strongly affects the crystal structure and therefore the separation efficiency. In the conditions of about 20-25 l/min cooling air flow rate and less than 0.2g/min/$cm^2$ crystal flux, the separation efficiency of both CsCl and $SrCl_2$ showed about 90% by the layer crystallization process, assuming a LiCl salt reuse rate of 90wt%.