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

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.8 no.1
• /
• pp.77-84
• /
• 2010

Reduction of oxides has been investigated for the volume reduction and recycling of the spent oxide fuel from commercial nuclear power plants. Various oxide reduction methods were proposed and KAERI (Korea Atomic Energy Research Institute) is currently developing an electrochemical reduction process using a LiCl-$Li_2O$ molten salt as a reaction medium. The electrochemical reduction process, the front end of the pyroprocessing, can connect the PWR (Pressurized Water Reactor) oxide fuel cycle to a metal fuel cycle of the sodium cooled fast reactor. This paper summarizes KAERI efforts on the development, improvement, and scale-up of the oxide reduction process.

• Proceedings of the Korean Institute of Surface Engineering Conference
• /
• 2017.05a
• /
• pp.136-136
• /
• 2017

화학제염 기술은 산화제, 환원제, 금속이온, 무기산등이 혼합되어 있는 화학용액을 사용하여 원전기기 계통 내부에 생성된 고방사능 준위의 산화막과 오염물질을 제거하는 기술이다. 원전의 해체 및 유지보수에 있어 방사능 피복저감을 위한 필수적인 기술이다. 현재 원전 해체 산업은 잠재성이 높은 고부가가치 창출 산업으로 주목을 받고 있다. 원전 보유국의 경우, 기존 상용 제염기술과는 차별성 있는 제염기술을 확보하고자 노력하고 있다. 기존의 공정과 비교하여 공정비용 및 시간을 감소시킬 수 있어야 할 뿐만 아니라, 화학용액에 의한 원전 계통 금속 부품의 부식 및 손상을 최소화해야 한다. 금속 부품이 화학약품에 의한 부식손상을 받는다면 금속 부품의 수명 및 재활용 가치가 감소하기 때문에, 화학제염 기술 적용에 있어 용액에 대한 재료의 건전성 평가가 사전에 필히 이루어져야 한다. 본 연구에서는 원전 냉각재 펌프용 재료로 주로 사용되는 Stainless 304강을 시험편으로 선정하여, 화학제염 시험공정 3가지에 대한 부식손상 특성을 규명하였다. 산화공정은 과망간산($HMnO_4$) 용액을 공통으로 사용하였으며, 산화공정 종료 후 환원공정은 각 시험공정에 따라 시험공정 1은 옥살산($H_2C_2O_4$) 2000ppm, 시험공정 2는 옥살산($H_2C_2O_4$)1500ppm + 시트르산($H_8C_6O_7$)500ppm, 그리고 시험공정 3은 옥살산($H_2C_2O_4$) 3000ppm 용액을 각각 투입하여 수행하였다. 산화, 환원공정을 1Cycle로 하여, 각 시험공정 별로 총 5Cycle을 실시하였다. 각 시험공정 Cycle종료 후 시험편을 취외하여 무게감량측정, SEM(Scanning electron microscope) 분석, 3D현미경분석 그리고 타펠분극 실험을 실시하였다. 각 분석결과를 토대로 하여, Stainless 304강에 대한 화학제염 시 모델별 시험공정에 따른 부식특성을 규명하였다.

• Proceedings of the Korean Radioactive Waste Society Conference
• /
• 2009.11a
• /
• pp.345-345
• /
• 2009

전기화학적 환원 기술을 이용한 고온 용융염 전해환원의 결과 생산되는 금속전환체는 다공성 특성에 의해 전해환원의 매질인 용융염을 함유하게 된다. 전해환원과 후속 전기화학 공정인 전해정련의 전해질은 각각 LiCl과 LiCl-KCl 공융염으로 상이하기 때문에 이렇게 금속전환체에 포함된 LiCl 염이 동반되어 전해정련 공정에 도입될 경우 전해정련 공정의 공융염 조성을 어긋나게 한다. 이에 따라 금속전환체의 잔류염은 효과적으로 제거되어야 하며 공정으로 감압 증류에 의한 잔류염 제거 공정이 고려되고 있다. LiCl은 증기압이 비교적 낮기 때문에 감압의 고온 조건이 공정에 필요하다. 그러나 상평형도 분석 결과 전해환원 공정에서 산화물을 담아 음극으로 사용되어 환원된 금속전환체와 함께 도입되는 SUS 재질의 바스켓과 사용후핵연료 금속전환체의 주된 원소인 우라늄과는 공융할 수 있기 때문에 LiCl 증발 온도는 $720^{\circ}C$ 이하로 유지되어야 한다. 이와 같은 조건에서 LiCl 증발 속도를 높이기 위해서는 감압 조건이 필수적이다. 본 연구에서는 감압조건에서 LiCl 휘발 실험을 위해 폐쇄형 및 개방형 반응기를 제작하여 압력 조건 및 Ar 유량 등에 따른 LiCl 휘발율을 측정하였다. 증발된 LiCl은 일정 감압 조건에서 분말형으로 냉각부위에 회수 될 수 있었으나 완전 진공 조건에서는 결정형으로 냉각 부위에 응축되는 것으로 확인 되었으며 일정 진공 조건에서는 Ar 유량에 따라 증발량이 의존하지 않는 것으로 나타났다. 연구 결과 증발염의 취급 빛 이송을 위해 분말형 회수를 목표로 설정할 수 있었으며 공정조건으로 일정 수준의 감압 조건을 제시하였다. 이 후 후속 연구로 장치의 대형화 및 증발 속도 향상을 위한 추가적인 연구가 계획되어 있으며 연구 결과에 기초하여 공학규모 파이로 공정 시설인 PRIDE에 도입될 장치의 기초 설계 자료를 생산할 예정이다.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.17 no.1
• /
• pp.15-28
• /
• 2019

In accordance with the decommissioning plan for the Kori Unit 1 NPP, the reactor coolant system will be chemically decontaminated as soon as possible after permanent shutdown. This study developed the chemical decontamination process though the development project of decontamination technology of reactor coolant system and dismantled equipment for NPP decommissioning, which has been carried out since 2014. In this study, Oxidation/reduction process was conducted using system decontamination process development equipment of lab scale and was divided into unit and continuous processes. The optimal process time was derived from the unit process, and decontamination agent and the number of process were derived through the continuous processes. Through the unit process, the oxidation process took 5 hours and the reduction process took 4 hours. As optimum decontamination agent, the oxidizing agent was $200mg{\cdot}L^{-1}$ Permanganic acid + $200mg{\cdot}L^{-1}$ Nitric acid and the reducing agent was $2000mg{\cdot}L^{-1}$ Oxalic acid. In the case of the number of processes, all oxide films were removed during the two-cycle chemical decontamination process of STS304 and SA508. In the case of Alloy600, all oxide films were removed when chemical decontamination was performed for three cycles or more.

• Korean Chemical Engineering Research
• /
• v.50 no.4
• /
• pp.696-701
• /
• 2012

Non-aqueous processes have been developed for stable management and reuse of spent fuels. Nowadays, a plan for the management of spent fuel is being sought focusing on a non-aqueous process in Korea. Named as pyroprocessing, it includes an electrolytic reduction process using molten salt at high temperature for the spent fuels, which provides metallic product for a following electro-refining process. The electrolytic reduction process utilizes electrochemical reaction producing Li to convert oxides into metals in high temperature LiCl medium. Various kinds of elements in the spent fuels would be distributed in the system according to their respective reactivity with the reductant, Li, and the medium, LiCl. This study elucidates the reactions of the elements to understand the behavior of composite elements on the spent fuels by thermodynamic calculations. Uranium and transuranic are reduced into their metallic forms while rare-earth oxides, except for Eu, are stable against the reaction at a process temperature. This study also covers the tendency of reactions with respect to the temperature and, finally, estimates radioactivity and heat load on the distributed phases based on the reference spent fuel characteristics.

• Resources Recycling
• /
• v.23 no.3
• /
• pp.30-36
• /
• 2014

A large amount of waste copper slag containing about 35 ~ 45% iron has been generated and discarded every year from pyrometallurgical processes for producing copper from copper concentrate. Thus, recovery of iron from the waste copper slag is of great interest for comprehensive use of mineral resource and reduction of environment problems. In this study, a physico-chemical separation process for upgrading iron from the waste copper slag discharged as an industrial waste has been developed. The process first crushes the waste copper slag below 1 mm (first crushing step), followed by carbon reduction at $1225^{\circ}C$ for 90 min (carbon reduction step). And then, resulting material is again crushed to $-104{\mu}m$ (second crushing step), followed by wet magnetic separation (wet magnetic separation step). Using the developed process, a magnetic product containing more than 66 wt.% iron was obtained from the magnetic separation under a magnetic field strength of 0.2 T for the waste copper slag treated by the reduction reaction. At the same conditions, the percentage recovery of iron was over 72%. The iron rich magnetic product obtained should be used as a iron resource for making pig iron.

• Resources Recycling
• /
• v.31 no.6
• /
• pp.18-24
• /
• 2022

Dry reduction using natural gas was proposed to recover tin from waste tin oxide generated in a tin bath that was used for controlling the smoothness of architectural glass during production, and the reduction behavior was investigated. The utilized vertical natural gas dry reduction system is capable to process 4 L or 20 kg depending on input raw materials. The system was established by applying the upper intake and lower discharge method. The recovery rate was 97.2% at 800 ℃ and 4 sccm flow rate and increased with the amount of input gas. Hydrogen accounted for 23% of the discharge gas, showing a 16.6% hydrogen conversion rate. The reaction behavior of tin recovered via natural gas reduction provides basic data on the new waste resource reduction/recovery technology.

• Proceedings of the Korea Association of Crystal Growth Conference
• /
• 1997.10a
• /
• pp.63-67
• /
• 1997

환원확산법은 저렴한 Nd 산화물을 환원제를 이용하여 환원시키고 환원된 Nd가 Fe, FeB와 확산하여 주상인 Nd$_2$Fe14B가 만들어지는 공정으로 환원제로 사용된 CaO나 미반응 Ca 및 잔존 산소함량을 조절하는데 어려움이 있어 아직까지는 상업되지 못하고 있는 실정이다. 본 연구에서는 환원확산법을 이용하여 Nd-Fe-B계 영구자석에 사용될 미세분말을 제조하고 그 자기적 특성을 관찰하였다.

• Resources Recycling
• /
• v.25 no.4
• /
• pp.54-59
• /
• 2016

EAF processed slag which contains about 20 ~ 35 weight percent FetO is poured to slag pot and cooled. If we recover Fe from molten slag by the reduction, we will improve steel yield rate and reduce slag quantity poured from the furnace. Usually, carbon is used as a reductant and slag foaming agent in the EAF process. In this experiment, after melt the metal in induction furnace and then add slag with carbon and Al dross powder as a reductant, we investigated the reduction of FetO from slag and change of Phophorus content. As the result, when we use Al dross as a reductant, recovery rate is two times more than carbon. Phosphorus pick up is less than 50ppm with reduction of EAF slag.