• Title/Summary/Keyword: 산소 환원 반응

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Multiscale Modeling and Simulation of Direct Methanol Fuel Cell (직접메탄올 연료전지의 Multiscale 모델링 및 전산모사)

  • Kim, Min-Su;Lee, Young-Hee;Kim, Jung-Hwan;Kim, Hong-Sung;Lim, Tae-Hoon;Moon, Il
    • Membrane Journal
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    • v.20 no.1
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    • pp.29-39
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    • 2010
  • This study focuses on the modeling of DMFC to predict the characteristics and to improve its performance. This modeling requires deep understanding of the design and operating parameters that influence on the cell potential. Furthermore, the knowledge with reference to electrochemistry, transport phenomena and fluid dynamics should be employed for the duration of mathematical description of the given process. Considering the fact that MEA is the nucleus of DMFC, special attention was made to the development of mathematical model of MEA. Multiscale modeling is comprised of process modeling as well as a computational fluid dynamics (CFD) modeling. The CFD packages and process simulation tools are used in simulating the steady-state process. The process simulation tool calculates theelectrochemical kinetics as well as the change of fractions, and at the same time, CFD calculates various balance equations. The integrated simulation with multiscal modeling explains experimental observations of transparent DMFC.

Effects of La Addition and Preparation Methods on Catalytic Activities for Methane Partial Oxidation Catalysts (메탄 부분산화반응 촉매에 La 첨가 및 제조방법에 따른 촉매활성에 미치는 영향)

  • Cheon, Han-Jin;Shin, Ki-Seok;Ahn, Sung-Hwan;Yoon, Cheol-Hun;Hahm, Hyun-Sik
    • Journal of the Korean Institute of Gas
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    • v.14 no.2
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    • pp.7-14
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    • 2010
  • Synthesis gas was produced by the partial oxidation of methane. For the preparation of catalysts, Ni, known to be active in this reaction and cheap, was used as the active component and $CeO_2$, having high oxygen storage capability and high redox ability, was used as the support. The catalysts were prepared by the impregnation and urea methods. The catalyst prepared by the urea method showed about 11 times higher surface area and finer particle size than that prepared by the impregnation method. The catalysts prepared by the urea method showed higher methane conversion and synthesis gas selectivity than that prepared by the impregnation method. In this reaction, carbon deposition is a problem to be solved, so La was added to the catalyst system to reduce the carbon deposition. TGA analysis results showed that there was 2% carbon deposition with La-added catalysts and 16% with La-free catalysts. It was found that the addition of La decreases the amount of carbon deposition and prevents catalyst deactivation.

Hydrodynamic Properties of Interconnected Fluidized Bed Chemical-Looping Combustors (상호 연결된 유동층 매체 순환식 연소로의 수력학적 특성)

  • Son, Sung Real;Go, Kang Seok;Kim, Sang Done
    • Korean Chemical Engineering Research
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    • v.48 no.2
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    • pp.185-192
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    • 2010
  • The chemical-looping combustion(CLC) has advantages of no energy loss for separation of $CO_2$ without $NO_x$ formation. This CLC system consists of oxidation and reduction reactors where metal oxides particles are circulating through these two reactors. In the present study, the reaction kinetic equations of iron oxide oxygen carriers supported on bentonite have been determined by the shrinking core model. Based on the reactivity data, design values of solid circulation rate and solids inventory were determined for the rector. Two types of interconnected fluidized bed systems were designed for CLC application, one system consists of a riser and a bubbling fluidized bed, and the other one has a riser and two bubbling fluidized beds. Solid circulation rates were varied to about $30kg/m^2s$ by aeration into a loop-seal. Solid circulation rate increases with increasing aeration velocity and it increases further with an auxiliary gas flow into the loop-seal. As solid circulation rate is increased, solid hold up in the riser increases. A typical gas leakage from the riser to the fluidized bed is found to be less than 1%.

Hydrogeochemical and Environmental Isotope Study of Groundwaters in the Pungki Area (풍기 지역 지하수의 수리지구화학 및 환경동위원소 특성 연구)

  • 윤성택;채기탁;고용권;김상렬;최병영;이병호;김성용
    • Journal of the Korean Society of Groundwater Environment
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    • v.5 no.4
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    • pp.177-191
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    • 1998
  • For various kinds of waters including surface water, shallow groundwater (<70 m deep) and deep groundwater (500∼810 m deep) from the Pungki area, an integrated study based on hydrochemical, multivariate statistical, thermodynamic, environmental isotopic (tritium, oxygen-hydrogen, carbon and sulfur), and mass-balance approaches was attempted to elucidate the hydrogeochemical and hydrologic characteristics of the groundwater system in the gneiss area. Shallow groundwaters are typified as the 'Ca-HCO$_3$'type with higher concentrations of Ca, Mg, SO$_4$and NO$_3$, whereas deep groundwaters are the 'Na-HCO$_3$'type with elevated concentrations of Na, Ba, Li, H$_2$S, F and Cl and are supersaturated with respect to calcite. The waters in the area are largely classified into two groups: 1) surface waters and most of shallow groundwaters, and 2) deep groundwaters and one sample of shallow groundwater. Seasonal compositional variations are recognized for the former. Multivariate statistical analysis indicates that three factors may explain about 86% of the compositional variations observed in deep groundwaters. These are: 1) plagioclase dissolution and calcite precipitation, 2) sulfate reduction, and 3) acid hydrolysis of hydroxyl-bearing minerals(mainly mica). By combining with results of thermodynamic calculation, four appropriate models of water/ rock interaction, each showing the dissolution of plagioclase, kaolinite and micas and the precipitation of calcite, illite, laumontite, chlorite and smectite, are proposed by mass balance modelling in order to explain the water quality of deep groundwaters. Oxygen-hydrogen isotope data indicate that deep groundwaters were originated from a local meteoric water recharged from distant, topograpically high mountainous region and underwent larger degrees of water/rock interaction during the regional deep circulation, whereas the shallow groundwaters were recharged from nearby, topograpically low region. Tritium data show that the recharge time was the pre-thermonuclear age for deep groundwaters (<0.2 TU) but the post-thermonuclear age for shallow groundwaters (5.66∼7.79 TU). The $\delta$$\^$34/S values of dissolved sulfate indicate that high amounts of dissolved H$_2$S (up to 3.9 mg/1), a characteristic of deep groundwaters in this area, might be derived from the reduction of sulfate. The $\delta$$\^$13/C values of dissolved carbonates are controlled by not only the dissolution of carbonate minerals by dissolved soil CO$_2$(for shallow groundwaters) but also the reprecipitation of calcite (for deep groundwaters). An integrated model of the origin, flow and chemical evolution for the groundwaters in this area is proposed in this study.

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Electrochemical properties of $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3$ cathodes for medium-temperature SOFC (중간온도형 고체산화물 연료전지의 양극재료로서 $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3$의 전기화학특성)

  • Ryu Ji-H.;Jang Jong-H.;Lee Hee-Y.;Oh Seung-M.
    • Journal of the Korean Electrochemical Society
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    • v.1 no.1
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    • pp.1-7
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    • 1998
  • For the purpose of finding new cathode materials for medium-temperature $(700\~800^{\circ}C)$ solid oxide fuel cells, $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3,\;(x=0.0\~0.5)$ are prepared, and their thermal stability and conductivity characteristics are investigated. Also, the cathodic activities are measured after the cathode layer being attached on CGO (cerium-gadolinium oxide) electrolyte disk. The X-ray analyses indicate that the materials prepared by calcining the citrate-gels at $800^{\circ}C$ have the orthorhombic perovskite structure without discernible impurities. The thermal stability of the undoped Co perovskite is so poor that it is decomposed to the individual binary oxide even at $1300^{\circ}C$. But the partially Fe-doped cobaltates exhibit a better thermal stability to retain their structural integrity up to $1400^{\circ}C$. The observation whereby both the undoped and Fe-doped cobaltates melt at ca. $1300^{\circ}C$ leads us to perform the electrode adhesion at <$1300^{\circ}C$. The cathodic activity of $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3,\;(x=0.0\~0.5)$, electrodes is superior to $La_{0.9}Sr_{0.1}MnO_3$, among the samples of $x=0.0\~0.5$, the x=0.2 cathode shows the best activity for the oxygen reduction reaction. It is likely that the Fe-doping provides a better thermal stability to the materials but in turn imparts an inferior cathodic activity, such that the optimum trade-off is made at x=0.2 between the two factors. The total electrical conductivity and ion conductivity of $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3$, are measured to be 51 S/cm and $6.0\times10^{-4}S/cm\;at\;800^{\circ}C$, respectively. The conductivity values illustrate that the materials are a mixed conductor and the reaction sites can be expanded to the overall electrode surface, thereby providing a better cathodic activity than $La_{0.9}Sr_{0.1}MnO_3$.

Effect of Pt as a Promoter in Decomposition of CH4 to Hydrogen over Pt(1)-Fe(30)/MCM-41 Catalyst (Pt(1)-Fe(30)/MCM-41 촉매상에서 수소 제조를 위한 메탄의 분해 반응에서 조촉매 Pt의 효과)

  • Ho Joon Seo
    • Applied Chemistry for Engineering
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    • v.34 no.6
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    • pp.674-678
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    • 2023
  • The effect of Pt was investigated to the catalytic methane decomposition of CH4 to H2 over Pt(1)-Fe(30)/MCM-41 and Fe(30)/MCM-41 using a fixed bed flow reactor under atmosphere. The Fe2O3 and Pt crystal phase behavior of fresh Pt(1)-Fe(30)/MCM-41 were obtained via XRD analysis. SEM, EDS analysis, and mapping were performed to show the uniformed distribution of nano particles such as Fe, Pt, Si, O on the catalyst surface. XPS results showed O2-, O- species and metal ions such as Pt0, Pt2+, Pt4+, Ft0, Fe2+, Fe3+ etc. When 1 wt% of Pt was added to Fe(30)/MCM-41, automic percentage of Fe2p increased from 13.39% to 16.14%, and Pt4f was 1.51%. The yield of hydrogen over Pt(1)-Fe(30)/MCM-41 was 3.2 times higher than Fe(30)/MCM-41. The spillover effect of H2 from Pt to Fe increased the reduction of Fe particles and moderate interaction of Fe, Pt and MCM-41 increased the uniform dispersion of fine nanoparticles on the catalyst surface, and improved hydrogen yield.

Pilot-scale Applications of a Well-type Reactive Barrier using Autotrophic Sulfur-oxidizers for Nitrate Removal (독립영양 황탈질 미생물을 이용한 관정형 반응벽체의 현장적용성 연구)

  • Lee, Byung-Sun;Um, Jae-Yeon;Lee, Kyu-Yeon;Moon, Hee-Sun;Kim, Yang-Bin;Woo, Nam-C.;Lee, Jong-Min;Nam, Kyoung-Phile
    • Journal of Soil and Groundwater Environment
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    • v.14 no.3
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    • pp.40-46
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    • 2009
  • The applicability of a well-type autotrophic sulfur-oxidizing reactive barrier (L $\times$ W $\times$ D = $3m\;{\times}\;4\;m\;{\times}\;2\;m$) as a long-term treatment option for nitrate removal in groundwater was evaluated. Pilot-scale (L $\times$ W $\times$ D = $8m\;{\times}\;4\;m\;{\times}\;2\;m$) flow-tank experiments were conducted to examine remedial efficacy of the well-type reactive barrier. A total of 80 kg sulfur granules as an electron donor and Thiobacillus denitrificans as an active bacterial species were prepared. Thiobacillus denitrificans was successfully colonized on the surface of the sulfur granules and the microflora transformed nitrate with removal efficiency of ~12% (0.07 mM) for 11 days, ~24% (1.3 mM) for 18 days, ~45% (2.4 mM) for 32 days, and ~52% (2.8 mM) for 60 days. Sulfur granules attached to Thiobacillus denitrificans were used to construct the well-type reactive barrier comprising three discrete barriers installed at 1-m interval downstream. Average initial nitrate concentrations were 181 mg/L for the first 28 days and 281 mg/L for the next 14 days. For the 181 mg/L (2.9 mM) plume, nitrate concentrations decreased by ~2% (0.06 mM), ~9% (0.27 mM), and ~15% (0.44 mM) after $1^{st}$, $2^{nd}$, and $3^{rd}$ barriers, respectively. For the 281 mg/L (4.5 mM) plume, nitrate concentrations decreased by ~1% (0.02 mM), ~6% (0.27 mM), and ~8% (0.37 mM) after $1^{st}$, $2^{nd}$, and $3^{rd}$ barriers, respectively. Nitrate plume was flowed through the flow-tank for 49 days by supplying $1.24\;m^3/d$ of nitrate solution. During nitrate treatment, flow velocity (0.44 m/d), pH (6.7 to 8.3), and DO (0.9~2.8 mg/L) showed little variations. Incomplete destruction of nitrate plume was attributed to the lack of retention time, rarely transverse dispersion, and inhibiting the activity of denitrification enzymes caused by relatively high DO concentrations. For field applications, it should be considered increments of retention time, modification of well placements, and intrinsic DO concentration.

Development of cathode catalyst layer using non-Pt catalyst for SAFC (비백금 촉매를 이용한 알칼리 연료전지 캐소드 전극 개발)

  • Park, SeokHee;Choi, YoungWoo;Yim, SungDae;Kim, ChangSoo;Park, Seung Bin
    • 한국신재생에너지학회:학술대회논문집
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    • 2011.05a
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    • pp.97.1-97.1
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    • 2011
  • 저온에서 양이온 고분자막을 사용하는 고분자 연료전지의 경우 뛰어난 성능과 다양한 응용분야로 인해 많은 연구와 실증이 이루어지고 있지만 공기극에서의 느린 산소 환원반응으로 인해 백금과 같은 귀금속의 사용이 불가피하고 백금의 제한된 매장량과 높은 가격으로 인해 상용화가 늦어지고 있다. 그래서 많은 연구자들이 합금 촉매 또는 비귀금속 촉매를 이용한 전극 개발에 집중하고 있다. 알칼리 분위기에서 저가의 전이 금속들이 백금과 비슷한 활성을 보이고 고체 음이온 교환막이 개발됨에 따라 최근 알칼리 연료전지가 다시금 큰 주목을 받고 있다. 그러나 고분자 연료전지와는 달리 아직 촉매나 전해질막, 이오노머의 특성 및 메커니즘에 관해 별로 알려진 것이 없다. 본 연구에서는 직접 개발한 세공충진막 형태의 탄화수소계의 음이온 교환막과 비귀금속 공기극 촉매를 이용하여 막전극접합체(MEA)를 개발하였고 촉매 및 이오노머 함량과 같은 전극 조성, 막전극접합체의 제조 및 체결, 가습이나 가스조성 등의 단위전지 운전조건과 같은 다양한 변수에 대해에 최적 조건을 도출하고자 하였다. 공기극 촉매는 Cu-Fe/C를 이용한 상용 촉매를 이용하였고 이오노머의 경우는 탄화수소계의 상용 제품을 사용하였으며 음이온 교환막에 전극층을 형성하기 위해서는 스프레이 공정을 이용하였다. 단위전지를 통해 성능을 확인하였고 임피던스 및 CV를 통해 전기화학적인 특성을 규명하였다. 조건의 최적화를 통해 상당한 성능 향상을 이루었으나 추가적인 성능 향상 및 내구성 확보 등에 대해 계속적인 실험을 진행할 예정이다.

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Effect of Mn doping on the dielectric properties of $(Pb_{0.62}Ca_{0.38})ZrO_{3}$ at microwave frequency (고주파 유전체 $(Pb_{0.62}Ca_{0.38})ZrO_{3}$의 Mn 첨가에 따른 유전특성 변화)

  • Gwon, Bu-Yeon;Kim, U-Gyeong;Yeo, Cheol-Hyeon;Choe, Seung-Cheol
    • Korean Journal of Materials Research
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    • v.5 no.1
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    • pp.36-41
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    • 1995
  • Dielectric properties were investigated at Mn doped $(Pb_{1-x}Ca_{x})ZrO_{3}$ with x=0.38 in microwavefrequencies. Both the density and Q values of sintered ceramics increased with increasing calciningtemperature. In the sample sintered at $1300^{\circ}C$ for 2 hrs, the deped Mn ions completely solubled in $(Pb,Ca)ZrO_{3}$ phase until 0.5wt% and the grain size was independent of doping amount. It was observed thathigh dielectric constant of 90 - 100 and high quality factor of 1300 at 4 GHz for O.l5wt% Mn doped$(Pb_{0.62}Ca_{0.38})ZrO_{3}$. The Mn" and Mn" worked as acceptors in $(Pb,Ca)ZrO_{3}$ which created the oxygen vacancies and affected the increment of the Q values. However, the excess Mn doping more than 0.5wt% resulted in decreasing Q values.decreasing Q values.

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Fabrication of $Sr_2FeMoO_6$ thin films by RF Sputtering (RF 스퍼터법에 의한 $Sr_2FeMoO_6$ 박막 제조)

  • Ryu, Hee-Uk;Sun, Ho-Jun
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2010.06a
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    • pp.24-24
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    • 2010
  • 대형구조물의 구조안정성 진단, 로봇과 같은 지능기계의 제어, 환경오염을 감지하기 위한 센서의 중요성은 날로 증대되고 있다. 이러한 센서의 감도와 성능을 높이기 위해서 소형화, 다기능화, 집적화가 요구되고 있는데, 고성능 센서소자들의 집적화를 위해서 기존에 적용된 벌크형태의 재료들을 박막화하여 다층적층 및 소형화할 필요가 있다. 집적화 센서의 구현에 있어서 전극박막은 센서의 특성을 좌우하는 중요한 역할을 한다. 일반적으로 금속박막이 전극으로 사용되고 있으나 열적 불안정성 및 박리현상의 문제점을 지니고 있다. 따라서 이를 해결하기 위해 전도성산화막을 전극으로 적용하고자하는 연구가 요구되고 있다. 전도성산화막을 전극으로 적용하면 센서소자의 성능이 개선되는 경향이 있다. $Sr_2FeMoO_6$(SFMO) 산화물은 자기장을 인가했을 때 저항이 감소하는 CMR(colossal magnetoresistance) 물질이며 상온비저항이 낮은 것으로 알려져 있다. 이중 페롭스카이트 (double perovskite) 구조를 갖는 $Sr_2FeMoO_6$ 박막은 센서소자의 전극으로 적용 가능할 것으로 생각되어 박막을 제조하고자 하였으며 미세구조와 전기전도 특성을 조사하였다. 박막제조를 위해서는 RF 스퍼터법을 사용하였다. 스퍼터를 위한 타겟은 고상반응법으로 분말타겟을 제조하였다. Ar/$O_2$ 가스 유랑변화, 압력변화, 기판 온도변화가 박막의 상형성 등 박막특성에 미치는 영향을 조사하였다. 기판으로는 $SiO_2$(100nm)/Si 기판을 사용하였다. 증착직후에는 비정질막이 얻어졌으며 SFMO 상을 만들기 위해서는 후열처리가 필요하였는데, 환원성 가스 분위기 [$H_2$(5%)/Ar] 에서 열처리 조건을 최적화하여 이중 페롭스카이트 구조의 단일상 박막을 제조할 수 있었다. SFMO 단일상 박막은 증착시에나 후열처리 시 산소의 억제가 중요함을 알 수 있었다.

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