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ACPF 전해환원 실험 및 결과

  • Park, Byeong-Heung;Hong, Sun-Seok;Heo, Jin-Mok;Lee, Han-Su
    • Proceedings of the Korean Radioactive Waste Society Conference
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    • 2009.06a
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    • pp.291-291
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    • 2009
  • 한국원자력연구원의 파이로 실험 시설인 ACPF (ACP Facility)에는 공학규모 전해환원 반응기가 설치되어 공정 대용량화를 위한 연구가 수행되고 있다 본 연구에서는 전해환원 공정의 Scale-up을 위해 기존 반응기를 개선하여 전해환원 실험을 수행한 결과를 담고 있다. 장치의 대형화 빛 원격운전성 향상을 위해 기존의 전해환원 반응기의 상부 플랜지는 보다 간단하게 정리되었으며 염 이송에 의한 고온 조건 노출 시간을 줄임과 동시에 염 재사용을 목적으로 상부 플랜지는 이중으로 설계되었다. 따라서, 반응 종료후 전극이 설치된 상부 플랜지를 들어 올림으로서 반응기를 불활성 분위기로 유지하는 동시에 전해환원 금속전환체를 회수 할 수 있도록 반응기가 제작되었다. 또한, 새로운 반응기는 용융염 내의 강제 유동을 위해 아르곤 버블링이 가능하도록 설계 제작되었다. 새로 제작 설치된 전해환원 반응기를 사용하여 산화물 분말을 혼합하여 준비한 모의 사용후핵연료를 사용하여 전해환원 실험을 수행하였다. 그 결과, 산화물이 충진된 음극의 전영역에서 고루 96% 이상의 높은 금속전환율을 얻었으며 시간에 따라 선택된 FP들의 용융염 내 거동을 측정하였다. 실리더 형태의 음극에서 Cs, Sr 등의 원소들이 용융염으로 시간에 따라 용출되는 것을 확인하였으며 동시에 반응기 재질인 Fe 등도 일부 용융염에서 검출되었다. 아르곤 버블링에 의한 강제 유동은 전압 및 전류 거동에는 큰 영향을 미치지 못하였으나 염의 휘발량을 증가시켜 영조성올 변화시키는 것으로 측정되었다. ACPF의 전해환원 실험결과를 바탕으로 반응기를 상부 기체상과 하부 액체상으로 나누어 전산모사를 수행하였다 상부 기체상은 유입되는 아르곤 기체와 발생되는 산소기체의 흐름을 모사하는 결과를 얻었으며 온도 및 산소의 분압을 계산하였다. 하부 액체상에서는 전기장을 모사하여 전류 밀도 등을 3차원으로 모사하였다.

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An Electrochemical Reduction of TiO2 Pellet in Molten Calcium Chloride (CaCl2 용융염에서 TiO2 펠렛의 전기화학적 환원반응 특성)

  • Ji, Hyun-Sub;Ryu, Hyo-Yeol;Jeong, Ha-Myung;Jeong, Kwang-Ho;Jeong, Sang-Mun
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.10 no.2
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    • pp.97-104
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    • 2012
  • A porous $TiO_2$ pellet was electrochemically converted to the metallic titanium by using a $CaCl_2$ molten salt system at $850^{\circ}C$. Ni-$TiO_2$ and graphite electrodes were used as cathode and anode, respectively. The electrochemical behaviour of $TiO_2$ pellet was determined by a constant voltage control electrolysis. Various reaction intermediates such as $CaTiO_3$, $Ti_2O$ and $Ti_6O$ were observed by XRD analysis during electrolysis of the pellet. Once $TiO_2$ pellet was converted to a porous metallic structure, the porous structure disappeared by sintering and shrinking with increasing the reaction time at high temperature.

Selective Reduction by Microbial Aldehyde Reductase (미생물 알데히드 환원효소에 의한 선택적 환원)

  • Lee Young-Soo;Kim Kyung-Soon
    • Journal of Life Science
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    • v.16 no.3 s.76
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    • pp.375-381
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    • 2006
  • Aldehyde reductase was purified to electrophoretic homogeneity from Saccharomyces cerevisiae, and then enzymatic reduction of substituted carbonyl compounds was carried out by using the purified aldehyde reductase as a biocatalyst. Under preparative scale reaction renditions, the enzymatic reduction proceeded in high chemical yield with excellent chemoselectivity. The enzymatic reduction product was identified by TLC, GC, Mass, NMR and FT-IR. Benzoic acid, an inhibitor of aldehyde reductase, also potently inhibited the reduction of substituded carbonyl compounds. This enzyme exhibited a broad substrate specificity , and can utilize both NADH and NADPH as cofactors. The enzyme was strongly inhibited by benzoic acid and quercetin. The apparent Km for 4-cyanobenzaldehyde and 3-nitrobenzamide were 4.894 mM and 0.305 mM, respectively.

The Reactivity for the SO2 Reduction with CO and H2 over Sn-Zr Based Catalysts (Sn-Zr계 촉매 상에서 CO와 H2를 이용한 SO2 환원 반응특성)

  • Han, Gi Bo;Park, No-Kuk;Ryu, Si Ok;Lee, Tae Jin
    • Korean Chemical Engineering Research
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    • v.44 no.4
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    • pp.356-362
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    • 2006
  • The $SO_2$ reduction using CO and $H_2$ over Sn-Zr based catalysts was performed in this study. Sn-Zr based catalysts with Sn/Zr molar ratio (0/1, 1/4, 1/1, 2/1, 3/1, 1/0) were prepared by the precipitation and co-precipitation method. The effect of the temperature on the reaction characteristics of the $SO_2$ reduction with a reducing agent such as $H_2$ and CO was investigated under the conditions of space velocity of $10,000ml/g_{-cat.}h$, $([CO(or\;H_2)]/[SO_2])$ of 2.0. As a result, the activity of Sn-Zr based catalysts were higher than $SnO_2$ and $ZrO_2$. The reactivity for the $SO_2$ reduction with CO was higher than that with $H_2$, and sulfur yield in the $SO_2$ reduction by $H_2$ was higher than that by CO. The reactivity for the $SO_2$ reduction with $H_2$ was increased with the reaction temperature regardless of Sn-Zr based catalyst with a Sn/Zr molar ratio. $SnO_2-ZrO_2$ (Sn/Zr=1/4) had highest activity at $550^{\circ}C$, in the $SO_2$ reduction with $H_2$ and $SO_2$ conversion of 94.4% and sulfur yield of 66.4% were obtained at $550^{\circ}C$. On the other hand, in the $SO_2$ reduction by CO, the reactivity was decreased with the increase over $325^{\circ}C$. At the optimal temperature of $325^{\circ}C$, $SO_2$ conversion and sulfur yield were about 100% and 99.5%, respectively, in the $SO_2$ reduction over $SnO_2-ZrO_2$ (Sn/Zr=3/1). Also, the $SO_2$ reduction using syngas with $CO/H_2$ ratio over $SnO_2-ZrO_2$ (Sn/Zr=2/1) was performed in order to investigate the application possibility of the simulated coal gas as the reductant in DSRP. As a result, the reactivity of the $SO_2$ reduction using syngas with $CO/H_2$ ratio was increased with increasing the CO content of syngas. Therefore, it could be known that DSRP using the simulated coal gas over Sn-Zr based catalyst is possible to be realized in IGCC system

Oxygen Reduction Mechanism and Electrode Properties of (La,Sr)$MnO_3$-YSZ Composite Cathode for Solid Oxide Fuel Cell (Part I: Oxygen Reduction Mechanism) (고체산화물 연료전지용 (La,Sr)$MnO_3$-YSZ 복합체 양극의 산소환원 반응기구 및 전극 특성 (Part I: 산소환원 반응기구))

  • 김재동;김구대;이기태
    • Journal of the Korean Ceramic Society
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    • v.38 no.1
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    • pp.84-92
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    • 2001
  • (La,Sr)MnO$_3$(LSM)-YSZ 복합체 양극의 산소환원 반응기구에 대해 고찰하였다. YSZ를 첨가함에 따라 복합체 양극의 ohmic 저항이 증가하고, 분극 저항은 YSZ를 40 wt%~50 wt% 혼합하였을 때 최소값을 나타내었다. 또한 LSM-YSZ 복합체 양극의 산소환원 반응기구는 1가 산소이온의 표면확산과 산소이온전달반응에 의해서 지배됨을 알 수 있었다. 임피던스 분석 결과에 따르면 고주파수 영역에서 나타나는 반원은 산소이온전달반응으로 산소분압 의존성이 거의 없고, YSZ가 40 wt% 첨가되었을 때 최소값을 나타내었다. 중간주파수 영역에서 나타나는 반원은 1가 산소이온의 표면확산반응으로 산소분압 의존성은 약 1/4이고, YSZ가 40~50 wt% 첨가되었을 때 최소값을 나타냈다. 한편, 저주파수 영역에 나타나는 반원은 가스확산반응으로 산소분압 의존성이 1이고, 온도에 따른 의존성이 거의 없었다.

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Modification of Indophenol Reaction for Quantification of Reduction Activity of Nanoscale Zero Valent Iron (나노 영가철 환원 반응성의 정량 분석을 위한 수정된 인도페놀법 적용)

  • Hwang, Yuhoon;Lee, Wontae;Andersen, Henrik R.
    • Journal of Korean Society of Environmental Engineers
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    • v.38 no.12
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    • pp.667-675
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    • 2016
  • Nanoscale zero-valent iron (nZVI) has been effectively applied for environmental remediation due to its ability to reduce various toxic compounds. However, quantification of nZVI reactivity has not yet been standardized. Here, we adapted colorimetric assays for determining reductive activity of nZVIs. A modified indophenol method was suggested to determine reducing activity of nZVI. The method was originally developed to determine aqueous ammonia concentration, but it was further modified to quantify phenol and aniline. The assay focused on analysis of reduction products rather than its mother compounds, which gave more accurate quantification of reductive activity. The suggested color assay showed superior selectivity toward reduction products, phenol or aniline, in the presence of mother compounds, 4-chlorophenol or nitrobenzene. Reaction conditions, such as reagent concentration and reaction time, were optimized to maximize sensitivity. Additionally, pretreatment step using $Na_2CO_3$ was suggested to eliminate the interference of residual iron ions. Monometallic nZVI and bimetallic Ni/Fe were investigated with the reaction. The substrates showed graduated reactivity, and thus, reduction potency and kinetics of different materials and reaction mechanism was distinguished. The colorimetric assay based on modified indophenol reaction can be promises to be a useful and simple tool in various nZVI related research topics.

Effect of Sulfate Reduction on the Hydrogen Competition among Dechlorination, Methane Production, and Sulfate Reduction (황산염 환원반응이 탈염소화, 메탄생성 및 황산염 환원 간 수소경쟁에 미치는 영향)

  • Lee, Il-Su;Bae, Jae-Ho
    • Journal of Korean Society of Environmental Engineers
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    • v.27 no.6
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    • pp.635-641
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    • 2005
  • Batch experiments were performed to evaluate the effect of sulfate reduction on methane production and reductive dechlorination, both compete for hydrogen with sulfate reduction. Dechlorination was inhibited by sulfate reduction at lower hydrogen concentration because their threshold values for hydrogen are similar (2 nM). Unlike methane production mainly inhibited transformation of cDCE to ethene, sulfate reduction inhibited the initial dechlorination step, PCE reduction into cDCE as well as cDCE dechlorination. The presence of sulfate eliminated methanogens as hydrogen competitor because of its high threshold value of 10 nM. When sulfate coexisted with PCE, dechlorination efficiency was not affected by the increase of seed concentration as both dechlorination and sulfate reduction were stimulated simultaneously by the increased seeding culture.

Reaction of Representative Organic Compounds with Sodium Borohydride in the Presence of Aluminum Chloride (염화알루미늄 존재하에서의 수소화붕소나트륨과 대표적 유기화합물과의 반응)

  • Yoon Nung Min;Ho Jun Leeq;Jin Soon Chung
    • Journal of the Korean Chemical Society
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    • v.17 no.4
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    • pp.275-285
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    • 1973
  • The addition of one mole of aluminum chloride to three moles of sodium borohydride in tetrahydrofuran gives a turbid solution with enormously more powerful reducing properties than those of sodium borohydride itself. The reducing properties of this reagent were tested with 49 organic compounds which have representative functional groups. Alcohols liberated hydrogen immediately but showed no sign of hydrogenolysis of alkoxy group. Aldehydes and ketones were reduced rapidly within one hr. Acyl derivatives were reduced moderately, however, carboxylic acids were reduced much more slowly. Esters, lactones and epoxides were reduced readily than sodium borohydride or borane. Tertiary amide was reduced slowly, however, primary amide consumed one hydride for hydrogen evolution but reduction was sluggish. Aromatic nitrile was reduced much more readily than aliphatic nitrile. Nitro compounds were inert to this reagent but azo and azoxy groups were slowly attacked. Oxime was reduced slowly but isocyanate was only partially reduced. Disulfide and sulfoxide were attacked slowly but sulfide and sulfone were inert. Olefin was hydroborated rapidly.

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Method for Improvement of Reduction Reactivity at High Temperature in a Chemical-Looping Combustor (매체순환식 가스연소기에서 고온 환원반응성 증대 방법)

  • Ryu, Ho-Jung;Park, Sang-Soo;Lee, Dong-Ho;Choi, Won-Kil;Rhee, Young-Woo
    • Korean Chemical Engineering Research
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    • v.50 no.5
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    • pp.843-849
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    • 2012
  • When we use NiO based particle as an oxygen carrier in a chemical looping combustion system, the fuel conversion and the $CO_2$ selectivity decreased with increasing reaction temperature within high temperature range (> $900^{\circ}C$) due to the increment of exhaust CO concentration from reduction reactor. To improve reduction reactivity at high temperature, the applicable metal oxide component was selected by calculation of the equilibrium CO concentration of metal oxide components. After that, feasibility of reduction reactivity improvement at high temperature was checked by using solid mixture of the selected metal oxide particle and NiO based oxygen carrier. The reactivity was measured and investigated using batch type fluidized bed. The solid mixture of $Co_3O_4/CoAl_2O_4$(10%) and OCN706-1100(90%) showed higher fuel conversion, higher $CO_2$ selectivity and lower CO concentration than OCN706-1100(100%) cases. Consequently, we could conclude that improvement of reduction reactivity at high temperature range by adding some $Co_3O_4$ based oxygen carrier was feasible.

Reduction Characteristics of Hexavalent Chromium in Cement/Fe(II) Systems

  • 강희석;서진권;황인성;박주양
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2002.04a
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    • pp.233-236
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    • 2002
  • 다양한 산업활동에 의하여 발생하는 6가 크롬 (Cr(Ⅵ))은 대표적인 토양 및 지하수 오염물질이다. Cr(Ⅵ)은 3가크롬(Cr(III))로의 환원에 의한 침전반응으로 이동성이 저하된다고 알려져 있다. 본 연구에서는 기존의 고형화/안정화 공정에 환원.분해 반응을 추가한 2가철 기반 분해성 고형화/안정화(Degradative Solidification/Stabilization)공정에 의한 Cr(Ⅵ) 처리 특성을 고찰하였다. 회분식 실험결과 cemen/Fe(II) system내에 Cr(Ⅵ)은 환원반응 뿐만 아니라 cement에 의한 침전에 의해서도 제거됨이 밝혀졌다. Cr(Ⅵ)의 제거속도는 Fe(II)의 반응당량에 비례하는 것으로 보여진 반면, cement/solution ratio에 따른 Cr(Ⅵ) 제거동역학의 차이는 그다지 크지 않았다

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