• Analytical Science and Technology
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• v.13 no.3
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• pp.309-314
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• 2000

The quantitative analysis of various trace metals including fission products in lithium molten salts has been performed using a inductively coupled plasma atomic emission spectrometer (ICP-AES). The spectral interferences of lithium content, 500, 1,000 and 2,000 mg/L, in the sample solution were investigated using an optimum wavelength for the respective metal species. As a result, the line intensities for Y, Nd, Sr, and La had no influences from the lithium content up to 2,000 mg/L, while Mo, Ba, Ru, Pd, Rh, Zr and Ce showed spectral interferences of 10% to 50%. The group separation of metals from lithium in the molten salts solution was carried out by adding ammonia water into the solution. The recovery of Ru, Y, Rh, Zr, Nd, Ce, La and Eu was found to be over 90%, while Mo, Ba, Pd, and Sr provided low recovery percentages.

• Korean Journal of Materials Research
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• v.26 no.12
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• pp.681-687
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• 2016

Zirconium(Zr) nuclear fuel cladding tubes are made using a three-time pilgering and annealing process. In order to remove the oxidized layer and impurities on the surface of the tube, a pickling process is required. Zr is dissolved in HF and $HNO_3$ mixed acid during the process and pickling waste acid, including dissolved Zr, is totally discarded after being neutralized. In this study, the waste acid was recycled by adding $BaF_2$, which reacted with the Zr ion involved in the waste acid; $Ba_2ZrF_8$ was subsequently precipitated due to its low solubility in water. It is very difficult to extract zirconium from the as-recovered $Ba_2ZrF_8$ because its melting temperature is $1031^{\circ}C$. Hence, we tried to recover Zr using an electrowinning process with a low temperature molten salt compound that was fabricated by adding $ZrF_4$ to $Ba_2ZrF_8$ to decrease the melting point. Change of the Zr redox potential was observed using cyclic voltammetry; the voltage change of the cell was observed by polarization and chronopotentiometry. The structure of the electrodeposited Zr was analyzed and the electrodeposition characteristics were also evaluated.

• Analytical Science and Technology
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• v.16 no.4
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• pp.261-268
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• 2003

To investigate the matrix effect of sample for hydrogen analysis by inert gas fusion-thermal conductivity detection, calibration factor for the hydrogen analyser of the inert gas fusion-thermal conductivity detection method was measured with hydrogen standard materials in Ti, Zr-2.5Nb and by hydrogen gas dosing method. Also the hydrogen extraction efficiency for the different sample matrix, Ti and Zr-2.5Nb, was evaluated without adding tin flux. The calibration factor of the hydrogen analyser which was calibrated by hydrogen standard material in Zr-2.5Nb and Ti was 2~3% and 14% higher than that by hydrogen gas dosing method, respectively. Based on the results of calibration factor measurement, it could be concluded that the hydrogen extraction efficiency of the Ti matrix sample will be 12% lower than that of the Zr-2.5Nb. And according to the experimental results of hydrogen recovery test by no tin flux, the hydrogen recovery percentage of the Ti and Zr-2.5Nb matrix sample was about 70% but the recovery rate of Ti matrix sample was slightly lower than that of Zr-2.5Nb.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.11 no.1
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• pp.69-75
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• 2013

The recovery of Zr from Zircaloy-4 (Zry-4) cladding hulls was demonstrated to investigate the effect of the oxidation process on the reaction rate of the chlorination reaction. In chlorination reaction experiments performed for 6 h, where reaction products were collected every 2 h, it was observed that a significant decrease in the reaction rate was caused by the oxidation process ($500^{\circ}C$, 10 h under an air atmosphere) within the reaction period of 0 - 2 h. The amount of reaction residue increased from 0.95 to 1.65wt% of initial weights in the fresh and Zry-500-10 (Zry-4 hulls oxidized at $500^{\circ}C$ for 10 h under an air atmosphere) hulls, respectively. The purity of the recovered Zr was identical at 99.61wt% for the fresh Zry-4 and Zry-500-10 hulls. Quantitative analysis of the chlorination reaction rate was performed by varying the reaction time from 0.5 to 1.0, 2.0, and 4.0 h. The fitting results showed that the relationship between weight loss and reaction time can be interpreted by a linear line with a slope of 23.35wt%/h for the fresh Zry-4 case, while two linear lines were necessary to fit the results of Zry-500-10. In addition, the slope values were 17.12 and 27.16wt%/h for (0 - 20) and (20 - 100)wt% loss regions, respectively.

• Resources Recycling
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• v.26 no.6
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• pp.29-37
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• 2017

Nuclear fuel cladding tube is fabricated by pilgering and annealing process. In order to remove impurity and oxygen layer on the surface, pickling process is carried out. When Zirconium(Zr) is dissolved and saturated in acid solution during the pickling process, all the waste acid including Zr is disposed. Therefore, $BaF_2$ is added into the waste acid to extract Zr and $Ba_2ZrF_8$ is subsequently formed. To recycle Zr by electrowinning process, $Ba_2ZrF_8$ is used as electrolyte, but it has high melting point ($1053^{\circ}C$). $ZrF_4$ should be added into $Ba_2ZrF_8$ to decrease the melting point. In this paper, it was investigated that $Ba_2ZrF_8$ was separated to $BaF_2$ and $ZrF_4$ by vacuum distillation. Firstly, $BaF_2$ with different particle size ($1{\mu}m$, $35{\mu}m$, $110{\mu}m$) was added into the waste acid and the respective precipitation property was estimated. $BaF_2$ obtained by vacuum distillation was shattered by ball-milling with different time. The precipitation efficiency was compared with $1{\mu}m$ of ${BaF_2}^{\prime}s$ one, which was not used as precipitation agent.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.10 no.4
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• pp.229-236
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• 2012

A molten salt technology using $Li_2O$-LiCl has been extensively investigated to recover uranium metal from spent fuels in the field of nuclear energy. In the reduction process, it is an important point to maintain the concentration of $Li_2O$. $ZrO_2$ is inevitably contained in the spent fuels because Zr is one of the main components of fuel rod hulls. Therefore, the fate of $ZrO_2$ in $Li_2O$-LiCl molten salt has been investigated. It was found that $Li_2ZrO_3$ and $Li_4ZrO_4$ were formed chemically and electrochemically and they were not reduced to Zr. The recycling of $Li_2O$ is the key mechanism ruling the total reaction in the electrolytic reduction process. However, $ZrO_2$ will have a role as a $Li_2O$ sink.

• Proceedings of the Korean Nuclear Society Conference
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• 1998.05b
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• pp.521-526
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• 1998

군분리공정의 관심대상 핵종인 잔존 U, MA인 Am, Np 및 백금족원소의 장수명핵종인 Tc을 방사성모의용액으로부터 효과적으로 분리할 수 있었다. 각 단위공정에 주입되는 용액의 농도를 기준으로 하여 볼 때 잔존 U 제거 공정에서 U, Np, 및 Tc의 회수율은 각각 99.1%. 31.9%, 및 99.5%였다. 개미산 탈질 공정에서는 탈질 용액의 총 산도를 0.4M 이하까지 감소시켰으며, 부수적으로 후속용매추출 공정 전반에 걸쳐 문제 핵종으로 작용하는 Zr, Mo, Fe 등을 각각 99.8%, 94.2%, 22.4% 침전 제거시킬 수 있었다. 마지막으로 DEHPA에 의한 AM/RE 상호분리 공정에서는 연속적인 선택적역추출에 의해 Am 및 Np 의 회수율은 각각 99.8% 및 98.2％ 정도였고, Am의 경우 7.6%읜 Fe및 81.6% 의 Mo가, Np의 경우 5.8%의 Fe이 불순물로서 여전히 존재하고 있다. 한편 RE 생성물에서는 97～99.9%의 RE가 회수 제거되었다.

• Clean Technology
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• v.20 no.3
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• pp.212-217
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• 2014

In order to regenerate the sulfidated desulfurization sorbent, oxygen is used as the oxidant agent on the regeneration process. The small amount of oxygen un-reacted in regeneration process is flowed into direct sulfur recovery process. However, the reactivity for $SO_2$ reduction can be deteriorated with the un-reacted oxygen by various reasons. In this study, the deactivation effects of un-reacted oxygen contained in the off-gas of regeneration process flowed into direct sulfur recovery process of hot gas desulfurization system were investigated. Sn-Zr based catalysts were used as the catalyst for $SO_2$ reduction. The contents of $SO_2$ and $O_2$ contained in the regenerator off-gas used as the reactants were fixed to 5.0 vol% and 4.0 vol%, respectively. The catalytic activity tests with a Sn-Zr based catalyst were for $SO_2$ reduction performed at $300-450^{\circ}C$ and 1-20 atm. The un-reacted oxygen oxidized the elemental sulfur produced by $SO_2$ catalytic reduction and the conversion of $SO_2$ was reduced due to the production of $SO_2$. However, the temperature for the oxidation of elemental sulfur increased with increasing pressure in the catalytic reactor. Therefore, it was concluded that the decrease of reactivity at high pressure is occurred by catalytic deactivation, which is the re-oxidation of lattice oxygen vacancy in Sn-Zr based catalyst with the un-reacted oxygen on the catalysis by redox mechanism. Meanwhile the un-reacted oxygen oxidized CO supplied as the reducing agent and the temperature in the catalyst packed bed also increased due to the combustion of CO. It was concluded that the rapidly increasing temperature in the packed bed can induce the catalytic deactivation such as the sintering of active components.

• Analytical Science and Technology
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• v.6 no.3
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• pp.275-282
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• 1993

A direct and simultaneous method to determine the $SiO_2$ and $ZrO_2$ in zircon sand of raw mineral and its treated one were studied by optical emission spectrometer using DC arc source. The synthetic standard was prepared by mixing with pure metal oxide, and it was diluted with buffer(graphite) and flux($Li_2B_4O_7$). The mixing ratio of buffer and flux and its dilution ratio to sample was investigated in order to choose the best excitation conditions. The optimum mixing and dilution ratios were 0.22:1 and 40, and the standard deviations of analytical results were 1.9% for $SiO_2$ and 4.7% for $ZrO_2$.

• Resources Recycling
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• v.26 no.5
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• pp.97-104
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• 2017

Nuclear fuel cladding tubes are manufactured through pilgering and the annealing process. In order to remove the oxidized layer and impurities on the surface of the tube, a pickling process is required. Zirconium (Zr) is dissolved in a HF and $HNO_3$ acid mixture during the process and the pickling waste acid, including the dissolved Zr, is completely discarded after neutralization. This study observes the effects of the residual impurities (Ba) in the pickling solution regenerated from the $BaF_2$ precipitation process on the waste pickling solution. In addition, the concentration of Ba and Zr for the actual nuclear fuel cladding tube process was optimized. The regenerated pickling solution was tested through a pilot plant pickling process device that simulates the commercial pickling process of nuclear fuel cladding tubes, and the pickling efficiency was analyzed through AFM analysis of the roughness of the cladding tube surface.