• Proceedings of the Korean Radioactive Waste Society Conference
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• 2009.11a
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• pp.346-346
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• 2009

산화물 형태 사용후핵연료의 효율적 처분 혹은 재활용을 위한 연구 가운데, 고온의 LiCl 용융염 중에서 전해환원하여 금속으로 환원시킨 후, 환원된 금속을 고온의 LiCl-KCl 용융염에서 전해정련하는 연구가 국내외적으로 활발하게 진행되고 있다. 전해환원을 위해 일정 농도 $Li_2O$가 LiCl 용융염에 첨가되며 $Li_2O$ 농도가 높으면 반응 재질의 부식성이 크게 증가하므로 일반적으로 우라늄 산화물은 1wt% 이하의 $Li_2O$ 농도에서 전해환원 된다. 우라늄 산화물의 전해환원 전위는 $Li_2O$의 전해환원 전위 보다 표준 상태를 기준으로 공정온도인 650 $^{\circ}C$ 에서 약 70 mV 정도 낮기 때문에 전해환원 과정에서 $Li_2O$ 의 환원으로 Li 금속이 생성될 가능성이 있으며 우라늄 산화물은 대부분 직접 전해환원 되지만 일부 Li에 의해 화학적으로 환원되기도 한다. 전해환원 공정에서 환원되지 않은 희토류 산화물은 전해정련 공정에서 $UCl_3$와 반응하여 $UO_2$를 생성시켜 공정 효율을 떨어뜨린다. 따라서 전해환원 공정에서 가능하연 최대한 희토류 산화물을 금속으로 환원시키는 조건을 찾아내는 것이 바람직하고 이를 위해서 우선 전해환원 공정에서 희토류 산화물의 화학적 거동의 이해가 요구된다. 본 연구에서 열역학적 검토를 통하여 희토류 산화물의 환원 조건을 조사한 결과 희토류 산화물은 매운 낮은 $Li_2O$ 농도에서 Li에 의해 환원되고, 1wt% 이하의 $Li_2O$ 농도에서는 Sc와 Lu의 산화물이 $Li_2O$와 복합산화물을 형성하고 이들 복합산화물은 Li에 의해 환원되지 않는 것으로 나타났다. 또한 희토류 원소 별로 희토류 원소 산화물의 Li에 의한 환원 조건으로서 평형상태에서의 $Li_2O$ 농도 즉 환원 임계 $Li_2O$ 농도를 실험적으로 측정하였으며 1wt% $Li_2O$ 농도 이하에서 열역학적 해석과 동일하게 Sc와 Lu만이 복합산화물을 형성하여 Li에 의해 직접환원 되지 않는 것으로 관찰되었다.

• Proceedings of the Materials Research Society of Korea Conference
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• 2007.11a
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• pp.115.2-115.2
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• 2007

• Journal of the Korean Ceramic Society
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• v.38 no.6
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• pp.545-550
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• 2001

본 연구에서는 분사연소합성(SCS)을 위한 기초단계로서 용액연소합성에 대한 거동을 살펴보고자 알루미나 합성을 모델로 하였으며 이를 위해 전구체에 대한 열분해거동, 그리고 각 온도에서의 평형종 분압 계산 및 합성과정을 조사하였다. 각각의 열중량 분석(TGA) 결과 산화제와 환원제(연료)의 열분해 이력이 서로 다르게 나타났으며, 열역학 응용 프로그램인 ChemSag에 의한 평형종 분압의 계산에서 연소속도를 저하시킬 수 있는 $CO_2$와 수증기 가스 분압이 상당부분 존재하였다. 산화제/환원제 혼합물의 열분석(DTA/TG) 결과 산화제와 환원제의 열분해 거동의 차이, 그리고 매우 작은 시료의 양으로 인해 263$^{\circ}C$에서 발열피크가 매우 작게 나타났다. 열분석 시료에 비해 발열 에너지를 높이기 위해 산화제와 환원제 혼합 전구체를 비이커에서 증기압을 조절하며 가열시켜 본 결과 27$0^{\circ}C$에서 $\alpha$-Al$_2$O$_3$생성물을 얻을 수 있었다. 따라서 분사연소합성 반응을 통해 세라믹 원료를 합성하기 위해서는 연소과정 중 열분해 거동과 평형종의 분압을 고려하여야 한다.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2004.06a
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• pp.268-277
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• 2004

process (ACP), electrochemical properties of high heat-generating alkali and alkali earth oxides in molten salt were measured and the behavior of those elements were analyzed. The reduction potentials of Cs, Sr, and Ba in a molten LiCl-$Li_2O$ system were more cathodic than that of Li and closely located one another. Thus, it is expected that the alkali and alkali earth would not hinder the reaction mechanism which is via lithium reduction. Alkali and alkali earth metals are likely to recycle into molten salt when the process is operated beyond metal reduction potentials and the effect of electric current on the mass transport is also determined by measuring the metal concentrations in the molten salt phase at different current conditions.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.1
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• pp.19-32
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• 2010

Electrolytic reduction technology is essential for the purpose of adopting pyroprocessing into spent oxide fuel as an alternative option in a back-end fuel cycle. Spent fuel consists of various metal oxides, and each metal oxide releases an oxygen element depending on its chemical characteristic during the electrolytic reduction process. In the present work, an electrolytic reduction behavior was estimated for voloxidized spent fuel based on the assumption that each metal-oxygen system is independent and behaves as an ideal solid solution. The electrolytic reduction was considered as a combination of a Li recovery and chemical reactions between the metal oxides such as uranium oxide and the produced Li metal. The calculated result revealed that most of the metal oxides were reduced by the process. It was evaluated that a reduced fraction of lanthanide oxides increased with a decreasing $Li_2O$ concentration. However, most of the lanthanides were expected to be stable in their oxide forms. In addition, a semi-empirical model for describing $U_3O_8$ electrolytic reduction behavior was proposed by considering Li diffusion and a chemical reaction between $U_3O_8$ and Li. Experimental data was used to determine model parameters and, then, the model was applied to calculate the reduction yield with time and to estimate the required time for a 99.9% reduction.

• Korean Chemical Engineering Research
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• v.55 no.3
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• pp.379-384
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• 2017

An electrochemical reduction of a mixture of NiO and rare earth oxides has been conducted to increase the reduction degree of rare earth oxides. Cyclic voltammetry (CV) measurement was carried out to determine the electrochemical reduction behavior of the mixed oxide in molten LiCl medium. Constant voltage electrolysis was performed with various supplied charges to understand the mechanism of electrochemical reduction of the mixed oxide as a working electrode. After completion of the electrochemical reduction, crystal structure of the reaction intermediates was characterized by using an X-ray diffraction method. The results clearly demonstrate that the rare earth oxide was converted to RE-Ni intermetallics via co-reduction with NiO.

• Journal of the Korean Electrochemical Society
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• v.6 no.3
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• pp.178-182
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• 2003

The oxygen reduction and NiO dissolution behaviors in Li-Na-K three component carbonate melts have been investigated with various compositions through electrochemical and chemical ways. The oxygen reduction currents and NiO solubilities were measured at $650^{\circ}C$ and atmospheric condition in Li-Na-K =47.4-32.6-20, 60-20-20, 50-40-10, $40-40-20 mol\%$ carbonate melts. The oxygen reduction currents showed dependence on the composition, indicating oxygen solubility is a function of carbonate composition. At the composition of $ Li-Na-K=50-40-10 mol%$, a broader peak was observed, suggesting different oxygen reduction mechanism probably prevails in this composition. In contrast, insignificant differences of NiO solubility were obtained among the compositions.

• Resources Recycling
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• v.31 no.1
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• pp.29-36
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• 2022

The hydrogen reduction behavior of molybdenum oxides was studied using a horizontal-tube reactor. Reduction was carried out in two stages: MoO₃ → MoO₂ and MoO₂ → Mo. In the first stage, a mixed gas composed of 30 vol% H₂ and 70 vol% Ar was selected for the MoO₃ reduction because of its highly exothermic reaction. The temperature ranged from 550 to 600 ℃, and the residence time ranged from 30 to 150 min. In the second step, pure H₂ gas was used for the MoO₂ reduction, and the temperature and residence time ranges were 700-750 ℃ and 30-150 min, respectively. The hydrogen reduction behavior of molybdenum oxides was found to be somewhat different between the two stages. For the first stage, a temperature dependence of the reaction rate was observed, and the best curve fittings were obtained with a surface reaction control mechanism, despite the presence of intermediate oxides under the conditions of this study. Based on this mechanism, the activation energy and pre-exponential were calculated as 85.0 kJ/mol and 9.18 × 10⁷, respectively. In addition, the pore size within a particle increases with the temperature and residence time. In the second stage, a temperature dependence of the reaction rate was also observed; however, the surface reaction control mechanism fit only the early part, which can be ascribed to the degradation of the oxide crystals by a volume change as the MoO₂ → Mo phase transformation proceeded in the later part.

• Proceedings of the Korean Powder Metallurgy Institute Conference
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• 2001.04a
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• pp.33-33
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• 2001

• Applied Chemistry for Engineering
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• v.3 no.4
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• pp.663-669
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• 1992

Chromium oxide/zirconia catalysts were prepared by dry impregnation of $Zr(OH)_4$ powder with aqueous solution of $(NH_4)_2CrO_4$ followed by calcining in air. The redox behavior of prepared catalysts were investigated by reacting cumene as test material over catalysts. As a result it was found that $Cr^{6+}$ species(as chromate) on the surface of catalyst was responsible for the formation of strong acid site and the catalytic activity for the dealkylation of cumene. However, much of the $Cr^{6+}$ species was reduced to $Cr^{3+}$ species by $H_2$ formed during the catalytic reaction of cumene and the reduced $Cr^{3+}$ species was an active site for dehydrogenation of cumene to form ${\alpha}$-methyl styrene. The reduced $Cr^{3+}$ species was also reoxidized to a $Cr^{6+}$ species after treatment with $O_2$ and consequently the deoxidized catalyst exhibited catalytic activity for the dealkylation reaction of cumene.