• Korean Journal of Metals and Materials
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• v.56 no.12
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• pp.893-899
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• 2018

In the present study, we investigated the sulfur poisoning of the Ni anode in solid oxide fuel cells (SOFCs) as a function of operating conditions. Anode supported cells were fabricated, and sulfur poising tests were conducted as a function of current density, $H_2S$ concentration and humidity in the anode gas. The voltage drop was significant under the higher current density (${\sim}714mA/cm^2$) condition, while it was much reduced under the lower current density (${\sim}389mA/cm^2$) condition, at 100 ppm of $H_2S$. A secondary voltage drop, which occurred only at the high current density, was attributed to Ni oxidation in the anode. Thus, operation at high current density with high $H_2S$ concentration may lead to permanent deterioration in the anode. The effect of water content (10%) on the sulfur poisoning was also investigated through a constant current test (${\sim}500mA/cm^2$) at 10 ppm of $H_2S$. The cell operating with 10% wet anode gas showed a much smaller initial voltage drop, in comparison with a dry anode gas. The present study indicates that operating conditions, such as gas humidity and current density, should be carefully taken into account, especially when fuel cells are operated with $H_2S$ containing fuel.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.135.1-135.1
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• 2010

최근 고온에서 사용 가능한 PEMFC용 고분자전해질 막 개발에 대한 연구가 활발히 진행되고 있다. PEMFC가 고온에서 작동하게 되면 높은 성능과 많은 장점을 갖게 된다. PEMFC를 $100^{\circ}C$ 이상에서 운전하게 될 경우 백금 전극 반응을 향상시켜 고가의 백금 촉매 양을 줄일 수 있게 되고, 수소연료 속에 미량 포함된 CO에 의한 촉매표면 피독현상에 대한 내구성을 높일 수 있어 저 순도 수소연료 사용이 가능해 진다. 또한 가습장치와 수소 연료 개질장치의 부피를 줄일 수 있게 되어 전체적인 PEMFC 시스템이 단순화 된다. 현재 연료전지용 고분자 전해질막으로 DuPont사의 과-불소계 고분자 전해질막인 Nafion$^{(R)}$이 가장 널리 사용되고 있다. Nafion$^{(R)}$은 유연한 분자구조 안에 소수성이 강한 주사슬과 친수성을 나타내는 술폰산이 결합된 곁사슬이 존재하여 술폰화 곁사슬의 클러스터 둘레에는 친수성 영역이 형성이 되기때문에 소수/친수 상 분리가 잘되어 이온 클러스터 형성이 용이하지만 제조비용이 높은 단점을 갖고 있다. 특히, 전해질 막내에서 Bronsted base 역할을 하는 물에 의해 이온전도가 이루어지기 때문에 고온에서는 수분증발로 인해 성능이 급격히 감소된다. 따라서, 본 연구에서는 고온 저가습 조건에서 운전이 가능하고 Nafion이 갖는 문제점을 해결하고자, 내열특성이 뛰어나며 높은 수소이온 전도도 학보가 용이한 Sulfonated Poly(aryl ether)sulfone(SPAES) 고분자 전해질에, 고온에서도 수화성이 유지될 수 있도록 지르코니아를 황산화한 sulfated zirconia(s-$ZrO_2$)를 함침하여 복합 고분자전해질막을 제조하여 고온 저가습 조건에서의 수소이온 전도 특성에 관한 연구를 수행하였다. 개발된 막의 물리/화학적 특성은 water content(Wup%), 이온교환 용량(IEC, meq $g^{-1}$), 수소이온전도도(s $cm^{-1}$) 열 중량 분석(TGA), X선 회절분석(XRD) 등을 통하여 분석 및 관찰하였다. 내화학 및 열적 특성분석 결과, 황산화 반응공정으로 $ZrO_2$에 술폰산기가 안정적으로 결합하고 있음이 관찰되었으며, 본 연구에서 개발된 유 무기 복합막이 $250^{\circ}C$이상 열적안정성을 확보하고 있는 것으로 판단되었다. $100^{\circ}C$ 이하의 저온 영역에서, 일정 비율의 s-$ZrO_2$/SPAES막에서 이온교환용량(IEC)이 순수 SPAES 막보다 낮음에도 불구하고, water uptake가 증가함과 동시에 수소이온 전도도가 향상된 것을 관찰하였다. 또한, 고온에서는 수소이온이 자유롭게 이동할 수 있는 water channel을 형성하는 free water는 증발 하지만 s-$ZrO_2$와 SPAES의 술폰산기 사이에 강력하게 결합하고 있는 bound Water는 $100^{\circ}C$ 이상의 고온 영역에서도 존재하여, 비록 무가습 조건에서도 일정 비율의 s-$ZrO_2$/SPAES50 전해질 막의 경우, 높은 전도도를 나타냄을 관찰할 수 있었다. 따라서 본 연구를 통해 저가습 고온 적용을 목적으로 개발된 s-$ZrO_2$/SPAES50막은 우수한 내열 특성을 나타냄과 동시에 저가습 고온 영역($120^{\circ}C$, $50RH{\downarrow}$)에서 높은 수소이온 전도도를 유지하여, 고온 저가습 연료전지 운전에 적합할 것으로 사료된다.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.224.2-224.2
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• 2010

연료개질기는 연료전지 시스템의 핵심 구성요소 중의 하나로 도시가스로부터 수소를 생산하는 역할을 담당한다. 연료개질기는 주로 탈황, 수증기 개질, 수성가스 전이, 선택적 산화 반응의 4단계로 구성되어 있으며 이 중 상온 탈황부분을 제외한 나머지 부분은 일체화 설계를 통해 제작된다. 탈황의 경우 도시가스에 포함된 부취제인 황화합물를 제거하여 후단에 위치한 촉매층이 황에 의해 피독되는 것을 막는 역할을 하며 주로 상온흡착식 탈황제를 사용한다. 황이 제거된 도시가스는 물과 함께 연료개질기로 도입되어 수증기 개질반응을 통하여 수소, 일산화탄소, 이산화탄소 및 소량의 메탄과 미반응 수증기로 구성된 개질가스로 전환된다. 이후의 수성가스 전이반응에서는 일산화탄소가 물과 반응하여 수소 생산량을 늘리며 동시에 일산화탄소의 농도를 낮추게 된다. 또한 고분자 전해질 연료전지에 공급되는 개질가스는 선택적 산화반응을 통하여 일산화탄소의 농도를 10ppm이하로 유지하게 된다. 이러한 기능의 연료개질기 개발의 주요 이슈로는 컴팩트화 및 고효율화이며 이 두가지 요소를 고려하여 연료개질기를 설계하여야 한다. 연료전지 시스템의 전체부피를 줄이기 위한 노력의 일환으로 연료개질기의 컴팩트화가 요구되는데 가정용 연료전지 기술 선진국인 일본 제품의 경우 $1Nm^3/h$급 연료개질기의 부피는 20L정도로 알려져 있다. 또한 연료전지 시스템의 효율은 연료개질기의 개질효율과 연료전지 스택의 발전효율의 곱으로 계산되기 때문에 연료개질기의 연료개질 효율은 전체 시스템의 효율에 직접적으로 영향을 미치게 된다. 한국에너지기술연구원에서는 수소생산량 기준 $1Nm^3/h$급 연료개질기의 개발을 완료하였으며 크기 및 효율면에서 선진국 제품과 비교하여 동등 또는 우위의 수준을 달성하였다. 연료개질기 내부의 혼합 및 분배 구조를 개선하고 각 촉매층의 최적 배치를 통해 연료개질기의 부피를 최소화 하였으며 연료개질기 내부에서 고온부위와 저온부위 사이의 최적 열교환을 통해 열효율을 극대화 시켰다. 현재 개발된 $1Nm^3/h$급 개질기의 단열 후 부피는 13.5L 그리고 단독운전 시 열효율은 80%(LHV)로 측정되었다. 또한 $1Nm^3/h$급의 연료개질기의 스케일-업 설계를 통하여 수소생산량 3, $5Nm^3/h$ 규모의 연료개질기를 개발하였으며 성능평가가 진행 중이다.

• Journal of Digital Convergence
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• v.10 no.8
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• pp.201-210
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• 2012

Because sensing odor varies depending on each person, even if the odor is released in line with the legal emission permission concentration levels, it can still become a social issue if a civil complaint is made. The purpose of this research is to study the possibility of putting Mn-Cu metallic oxide catalysts into practical use to economically eliminate acetaldehyde which produces a odor in the industrial process. An optimal operating parameter to eliminate acetaldehyde was deduced through a performance evaluation in the research laboratory and the performance was verified by applying the parameter into an actual facility as an on-the-site experiment through a Scale-up of pilot size. The operating temperature of the metallic oxide catalysts researched so far was at the minimum close to $220^{\circ}C$, and the $220^{\circ}C$ elimination efficiency was 50% or below. However, having experimented by using a Mn-Cu metallic oxide catalyst in this research, optimum elimination efficiency showed when space velocity (GHSV) was equal to or below 6,000 $hr^{-1}$. The average elimination efficiency was 61.2% when the catalyst controlling temperature was $120^{\circ}C$, 93.3% when the catalyst controlling temperature was $160^{\circ}C$, and 94.9% when catalyst controlling temperature was $180^{\circ}C$, thereby reflecting high elimination efficiency. The specific surface area of the catalyst was $200m^2/g$ before use, however, was reduced to $47.162m^2/g$ after 24 months and therefore showed that despite the decrease in specific surface area as time passed, there was no significant influence on the performance. Having operated Mn-Cu metallic oxide catalyst systems for at least two years on a site where there was no inflow of toxins like sulfur compounds and acidic gases, we were able to confirm that elimination efficiency of at least 90% was maintained.

• Applied Chemistry for Engineering
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• v.10 no.7
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• pp.963-968
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• 1999

The global environmental problems have been caused by the release of CFCs. Therefore, methods for safe destruction of recoverd CFCs will be eventually needed. The objective of this study was to develop and test a catalyst operating at a mild condition for the decomposition of CFC-113. In this work, catalytic oxidative decomposition of CFC-113 was carried out over aerosol $TiO_2/SiO_2(ATS)$ catalysts prepared by the sol-gel method. All ATS catalysts(Ti/Si mol ratio=1, 2, 2.33, 4) showed high initial activity. However, the deactivation of ATS catalysts was found that more remarkable due to an attack of fluorine and the destruction of ATS structure(Si-F reaction) from analyses of SEM-EDX, XRD than $TiO_2/SiO_2(ATS)$ catalyst prepared by the precipitation method. ATS catalysts prepared by more acidic prehydrolysis condition were found to have still more activity and longer life-time by increasing of acidity. The activity of ATS catalyst also depend on the content of $TiO_2$. There was reason that the acidity of the ATS catalyst was increased with the increased content of $TiO_2$ from 50 to 80 mol %. Solid superacid catalyst ($ATX/SO_4{^{2-}}$) modified with $H_2SO_4$ solution was prepared for high activity and lower deactivation. The reaction of $ATS/SO_4{^{2-}}$ catalyst also exhibited even higher activity and lower deactivation than the original ATS catalyst. It is suggested that the addition of the sulphate species clearly inhibit the deactivation.

• Journal of the Korea Organic Resources Recycling Association
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• v.17 no.2
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• pp.59-72
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• 2009

In order to utilize sewage sludge as a heat source of energy, it goes without saying that the fuel should be clean and pose no threat to the environment. As a consequent, it should not contain even minute quantities of heavy metals / impurities. The SOCA (Sludge-Oil-Coal- Agglomerates) fuel can meet all these requirements. SOCA being a solid fuel can be gasified for the production of clean energy. Wet catalytic gasification is the most appropriate process for SOCA containing nearly 60% water. It is important to note that the SOCA thus obtained inherits ca. 40~50% of sulfur from the coal used. It can poison the catalyst during catalytic gasification process. Consequently, it becomes important to choose a proper catalyst for the gasification. Calcium was found to be ideal choice as a catalyst for the gasification of SOCA. The optimal gasification was performed at $850^{\circ}C$ with water vapor. The role of fuel-N is of utmost importance in the gasification of SOCA. The gasification should be controlled to reduce the production of HCN to a minimum and enhance its conversion to $N_2$ and/or $NH_3$.

• Journal of Korean Society of Environmental Engineers
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• v.30 no.1
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• pp.54-60
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• 2008

Deactivation of SCR catalyst applied in Orimusion fuel power plant was investigated to develope the technique for the regeneration of deactivated SCR catalyst and optimize the operation of SCR facility. The characterization study of the catalysts was carried out using XRD, ICP-AES, SEM and EDS. The NO$_X$ removal activity and SO$_2$ oxidation activity of the catalysts were measured. The NO$_X$ conversion of the deactivated catalyst was 5$\sim$10% lower than that of the fresh catalyst and the value of SO$_2$conversion to SO$_3$ over the deactivated catalyst was about 0.59% higher than that of the fresh catalyst. Vanadium(V), Magnesium(Mg) and Sulfur(S) were largely accumulated in the deactivated catalyst. The accumulation of Vanadium(V) and Sulfur(S) is due to the components of the Orimulsion fuel and the accumulation of Magnesium(Mg) is due to MgO that is injected in the boiler to prevent the oxidation of SO$_2$ to SO$_3$. The diffraction line of the TiO$_2$ of the deactivated catalyst was identified as the crystalline peaks of anatase as the fresh catalyst.

• Journal of the Korean Electrochemical Society
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• v.11 no.1
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• pp.42-46
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• 2008

Even though fuel cell have high efficiency when pure hydrogen from gas tank is used as a fuel source, it is more beneficial to generate hydrogen from city gas (mainly methane) in residential application such as domestic or office environments. Thus hydrogen is generated by reforming process using hydrocarbon. Unfortunately, the reforming process for hydrogen production is accompanied with unavoidable impurities. Impurities such as CO, $CO_2$, $H_2S$, $NH_3$, $CH_4$, and $CH_4$ in hydrogen could cause negative effects on fuel cell performance. Those effects are kinetic losses due to poisoning of the electrode catalysts, ohmic losses due to proton conductivity reduction including membrane and catalyst ionomer layers, and mass transport losses due to degrading catalyst layer structure and hydrophobic property. Hydrogen produced from reformer eventually contains around 73% of $H_2$, 20% or less of $CO_2$, 5.8% of less of $N_2$, or 2% less of $CH_4$, and 10ppm or less of CO. This study is aimed at investigating the effect of carbon dioxide on fuel cell performance. The performance of PEM fuel cell was investigated using current vs. potential experiment, long run(10 hr) test, and electrochemical impedance measurement when the concentrations of carbon dioxide were 10%, 20% and 30%. Also, the concentration of impurity supplied to the fuel cell was verified by gas chromatography(GC).

• Journal of Korean Society of Environmental Engineers
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• v.34 no.6
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• pp.397-405
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• 2012

In this study, performance evaluation of newly developed technology for the economical and safe removal of volatile organic compounds (VOCs) coming out from electronic devices washing operation and offensive odor induction materials was made. Metal oxidization catalyst has shown 50% of removal efficiency at the temperature of $220^{\circ}C$. Composite metal oxidization catalyst applied in this study has shown that the actual catalysis has started at the temperature of $100^{\circ}C$. Comprehensive analysis on the catalyst property using Mn-Cu metal oxidization catalyst in the pilot-scale unit was made and the removal efficiency was variable with temperature and space velocity. Full-scale unit developed based on the pilot-scale unit operation has shown 95% of removal efficiency at the temperature of $160^{\circ}C$. Optimum elimination effective rates for the space velocity was found to be $6,000hr^{-1}$. The most appropriate processing treatment range for the inflow concentration of VOCs was between 200 ppm to 4,000 ppm. Catalyst control temperature showed high destruction efficiency at $150{\sim}200^{\circ}C$ degrees Celsius in 90~99%. External heat source was not necessary due to the self-heat reaction incase of VOCs inflow concentration is more than 1,000 ppm. Equipment and fuel costs compared to the conventional RTO/RCO method can be reduced by 50% and 75% respectively. And it was checked when there was poisoning for sulfide and acid gas.

• Journal of the Korean Electrochemical Society
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• v.10 no.4
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• pp.301-305
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• 2007

The performance of polymer electrolyte membrane fuel cell could be decreased due to coolant leaked from connection part. Micro pump was used to put small amount of coolant and investigate the effect on fuel cell. The stoichiometric ratio of hydrogen/air was 1.5/2.0, both side of gas was fully humidified, and current density of $400mA/cm^2$ was used as standard condition in this experiment. Constant current method was used to check performance recovery from coolant effect in 3 cell stack. The performance was recovered when coolant was injected in cathode side. On the other hand, the performance was not recovered when coolant was injected in anode side. Ethylene glycol could be converted to CO in oxidation process and cause poisoning effect on platinum catalyst or be adhered on GDL and cause gas diffusion block effect resulting performance decrease. Water with nitrogen gas was supplied in anode side to check performance recovery. Polarization curve, cyclic voltammetry, electrochemical impedance spectroscopy was used to check performance, and gas chromatography was used to check coolant concentration. Constant current method was not enough in full recovery of performance. However, water injection method was proved good method in full recovery of performance.