• 한국연소학회지
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• 제13권4호
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• pp.47-53
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• 2008

The reaction mechanism of methane dry reforming has been investigated using an arc-jet reactor. The effects of input power, $CO_2/CH_4$ and added $O_2$ were investigated by product analysis, including CO, $H_2$, $C_{2}H_{Y}$ and $C_{3}H_{Y}$ as well as $CH_4$ and $CO_2$. In the process, input electrical power activated the reactions between $CH_4$ and $CO_2$ significantly. The increased feed ratio of the $CO_2$ to $CH_4$ in the dry reforming does not affect to the $CH_4$ conversion. but we could observe increase in CO selectivity together with decreasing $H_2$ generation. Added oxygen can also increase not only CO selectivity but also $CH_4$ conversion. However, hydrogen selectivity was decreased significantly due to a increased $H_{2}O$ formation.

• 한국수소및신에너지학회논문집
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• 제27권5호
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• pp.554-561
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• 2016

Depending on the Bio-gas sources, main component gases of $CH_4$ and $CO_2$ are shown to be variously present in amounts. For the anaerobic digester, The concentration of $CH_4$ and $CO_2$ in the gases are 60~70 and 30~35 vol%. For the landfill gas, $CH_4$ and $CO_2$ are 40~60 and 40~60 vol%. For the food wastes, $CH_4$ and $CO_2$ are 60~80 and 20~40 vol%, respectively. In this study, maximum conversion rates of $CO_2$ were obtained from the variety of concentrations of $CH_4$ and $CO_2$ by the catalysts of reforming reactions. Moreover, in order to get maximum producing amount of synthetic gas, experimental studies were performed to optimize the reaction variables. On the basis of $CH_4$, 243 ml, R [$CH_4/(O2+CO_2)$] value were varied from 0.8 to 1.35, in the study of $CH_4$ and $CO_2$ reforming reactions. It was shown that the optimal results were obtained for 1.35 of R value. And also, at $850^{\circ}C$ and 1 atm, the production rate of synthetic gas was 90% and the conversion rates of $CH_4$ and $CO_2$ were higher than 99% and 90%, respectively.

• Korean Chemical Engineering Research
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• 제46권5호
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• pp.1002-1007
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• 2008

이 논문의 목적은 PEMFC 작동을 위한 플라즈마 개질 시스템의 최적 조건을 연구한 것이다. 플라즈마 개질 반응기는 니켈 촉매 반응기와 동시에 사용하여 수소 생성을 증대하였다. 또한 수성가스 전환 반응기 및 선택적 산화 반응기는 연료전지의 촉매 피독에 영향을 주는 일산화탄소의 농도를 10 ppm 이하로 줄이기 위하여 제작되었다. 플라즈마 개질기에서 최대 수소생산 조건은 S/C 비 3.2, 메탄 2.0 L/min, 촉매반응기 온도는 $700{\pm}5^{\circ}C$ 그리고 입력전력 900 W이다. 이때의 합성가스의 농도는 $H_2$ 70.2%, CO 7.5%, $CO_2$ 16.2%, $CH_4$ 1.8% 이다. 수소 수율, 수소 선택도 그리고 메탄 전환율는 각각 56.8%, 38.1%, 92.2%이다. 에너지 효율과 에너지 요구량은 37.0%, 183.6 kJ/mol 이다. 추가적으로 $CO_2/CH_4$ 비 실험을 진행하였다. 또한 수성가스 전환 반응기는 플라즈마 개질 반응기의 최적조건으로 실험을 진행하였으며, 출구 농도는 $H_2$ 68.0%, CO 337 ppm, $CO_2$ 24.0%, $CH_4$ 2.2%, $C_2H_4$ 0.4%, $C_2H_6$ 4.1% 이다. 이때의 선택적 산화 반응기의 실험결과는 $H_2$ 51.9%, CO 0%, $CO_2$ 17.3%를 나타냈다.

• 한국수소및신에너지학회논문집
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• 제29권1호
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• pp.1-10
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• 2018

The amount of biogas increases as the amount of organic waste increases. Recently, biogas from organic waste have been made much efforts to utilize as a energy. In particular, the concentration of $CH_4$ and $CO_2$ generated from sewage sludge and livestock manure treatment are 60-70% and 30-35%, and $CH_4$ and $CO_2$ generated from food wastes are 60-80% and 20-40%. In case of landfill gas, $CH_4$ and $CO_2$ have a concentration of 40-60% and 40-60% respectively. Therefore, in order to use the biogas more widely, it is necessary to convert the biogas to methanol, LNG or DME. In this study, experiments were conducted to produce hydrogen and carbon monoxide through various biogas reforming reactions on $Ni/Ce-ZrO_2/Al2O3$ catalysts. The experiment of synthetic gas synthesis was carried out on a wide concentrations of methane and carbon dioxide, which were the major constituents of biogas from various organic wastes. The effect of $(O_2+CO_2)/CH_4$ (=R') on the yields of hydrogen and carbon monoxide, the conversion rate of methane and carbon dioxide was investigated. Also simulation for syngas synthesis on the $CO_2$ reforming of $CH_4$ was computed by employing total Gibbs free energy minimization method using PRO/II simulator, and compared with the experimental results on wet and dry reforming reaction of biogas.

• Korean Chemical Engineering Research
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• 제47권6호
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• pp.700-704
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• 2009

GTL(gas-to-liquid) 합성유 제조용 SCR(steam carbon dioxide reforming) 공정의 시뮬레이션 연구를 수행하였다. 온도 및 $CH_4/steam/CO_2$ 반응물 비와 같은 변수를 바꾸어 가면서 SCR 공정을 위한 최적 운전조건을 살펴보았다. 공정 시뮬레이션을 위해 Aspen Plus를 사용하였다. 또한 정상상태 가정하의 열역학적 물성치 계산을 위해 Aspen Plus의 RSK (Redlich-Kwong-Soave) 상태방정식을 사용하였다. FT 공정을 위한$H_2/CO$ 비, $CH_4$ 전환율, $CO_2$ 전환율을 살펴봄으로써 최적의 온도와 최적의 반응물 비를 결정하였다. 시뮬레이션 결과, SCR reformer 촉매층 출구 최적온도는 상압에서 $850^{\circ}C$ 였으며, 이 온도에서 $CH_4$ 전환율은 99%, $CO_2$ 전환율은 49%로 계산되었고, $CH_4/steam/CO_2$ 최적 반응물 비율은 1.0/1.6/0.7로 나타났다.

• Bulletin of the Korean Chemical Society
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• 제23권8호
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• pp.1149-1153
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• 2002

CH4/CO2 dry reforming was carried out to make syn gas on the Ni/Al2O3 catalysts calcined at different temperatures. The Ni/Al2O3 (850 $^{\circ}C)$ catalyst gave good activity and stability w hereas the Ni/Al2O3 $(450^{\circ}C)$ catalyst showed lower activity and stability. The NiO/Al2O3 catalyst calcined at $850^{\circ}C$ for 16 h (Ni/Al2O3 $(850^{\circ}C))$ formed the spinel structure of nickel aluminate, which was confirmed by TPR. The carbon formation rate on the Ni/Al2O3 $(850^{\circ}C)$ catalyst was very low till 20 h, and then steeply increased with reaction time without decreasing the activity for CH4 reforming. The Ni/Al2O3 $(450^{\circ}C)$ catalyst showed high carbon formation rate at the initial reaction time and then, the rate nearly stopped with continuous decreasing the activity for CH4 reforming. Even though the amount of carbon deposition on the Ni/Al2O3 $(850^{\circ}C)$ catalyst was higher than that on the Ni/Al2O3 $(450^{\circ}C)$ catalyst, the activity for CH4ing was also high, which could be attributed to the different type of the carbon formed on the catalyst surface.

• Bulletin of the Korean Chemical Society
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• 제31권5호
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• pp.1295-1300
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• 2010

The $CO_2-CH_4$ reaction catalyzed by Ni/silicon wafers was kinetically studied by using a photoacoustic technique. The catalytic reaction was performed at various partial pressures of $CO_2$ and $CH_4$ (50 Torr total pressure of $CO_2/CH_4/N_2$) in the temperature range of 500 - $650^{\circ}C$ in a static reactor system. The photoacoustic signal that varied with the $CO_2$ concentration during the catalytic reaction was recorded as a function of time. Under the reaction conditions, the $CO_2$ photoacoustic measurements showed the as-prepared Ni thin film sample to be inactive for the reaction, while the $CO_2/CH_4$ reactions carried out in the presence of the sample pre-treated in $H_2$ at $600^{\circ}C$ were associated with significant time-dependent changes in the $CO_2$ photoacoustic signal. The rate of $CO_2$ disappearance was measured from the $CO_2$ photoacoustic signal data in the early reaction period of 50 - 150 sec to obtain precise kinetic data. The apparent activation energy for $CO_2$ consumption was determined to be 6.9 kcal/mol from the $CO_2$ disappearance rates. The partial reaction orders, determined from the $CO_2$ disappearance rates measured at various $PCO{_2}'S$ and $PCH{_4}'S$ at $600^{\circ}C$, were determined to be 0.33 for $CH_4$ and 0.63 for $CO_2$, respectively. Kinetic data obtained in these measurements were compared with previous works and were discussed to construct a catalytic reaction mechanism for the $CO_2-CH_4$ reaction over Ni/silicon wafer at low pressures.

• Korean Chemical Engineering Research
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• 제50권5호
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• pp.802-807
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• 2012

본 연구에서는 메탄으로부터 합성가스를 만드는 자열 개질(Autothermal reforming)반응 특성을 Ni (15 wt%)-Ru (1 wt%)/$Al_2O_3$-MgO 금속모노리스 촉매체와 전기 발열식 촉매를 사용하여 조사하였다. 자체 가동 형 반응기는 자열 개질 반응기에 $700^{\circ}C$ 반응물을 공급하는데 걸리는 start-up 시간이 2분 이내였다. 반응물의 $O_2/CH_4$와 $H_2O/CH_4$ 비가 메탄의 전환율과 반응기의 온도 분포에 미치는 영향은 매우 크다. 반응기의 온도는 $H_2O/CH_4$ 비가 감소할수록 흡열반응에서 발열반응으로 전환되어 증가한다. 또한 $H_2O/CH_4$ 비가 증가함에 따라 수성가스화 전이반응에 의하여 생성물 중에 $CO_2$양이 증가한다. $GHSV=10,000\;h^{-1}$, 반응물 조성($H_2O/CH_4=0.6$과 $O_2/CH_4=0.5$)의 자열 개질반응에서, 97%의 메탄의 전환율을 얻었으며, 반응기의 온도는 $600^{\circ}C$로 유지되었다. 이 반응조건에서 170 cc 금속모노리스 촉매체를 충진한 반응기에서 자열개질 반응으로 생성된 최대 합성가스의 유량은 $0.94\;Nm^3/h$ 이었다.

• Bulletin of the Korean Chemical Society
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• 제23권5호
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• pp.669-673
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• 2002

Ni catalyst (Ni: 15 wt%) supported on precalcined SiO2 has been investigated in reforming reactions of methane to synthesis gas. The catalyst exhibited fairly good activity and stability in partial oxidation of methane (POM), whereas it deactivated in steam reforming of methane (SRM). Pulse reaction results of CH4, O2, and CH4/O2 revealed that Ni/SiO2 has high capability to dissociate methane. The results also revealed that both CH4 and O2 are activated on the surface of metallic Ni, and then surface carbon species react with adsorbed oxygen to produce CO and CO2 depending on the bond strength of the oxygen species on the catalyst surface.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2008년도 춘계학술대회 논문집
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• pp.511-512
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• 2008

For the $CO_2$ reforming of $CH_4$, Ni catalyst was supported on La-hexaaluminate or on $\gamma$-$Al_2O_3$. The catalytic activities of Ni/La-hexaaluminate catalysts were measured at $700^{\circ}C$ using gas chromatography (GC) for 72 h, and the reaction was maintained up to 72 hfor the investigation of catalyst deactivation. The surface of each catalyst after 72 h reaction was investigated using SEM and TEM, and the composition of the carbon deposits was investigated by using EA, TPO and TGA. Ni/La-hexaaluminate shows higher resistance to coke deposition than conventional Ni/$Al_2O_3$ which seems to be due to strong interaction between Ni and the support material. As a result of the reforming reaction, various types of carbon deposits were created on catalyst surface and the amounts of them were much smaller in the case of La-hexaaluminate than on $Al_2O_3$.