• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.71.2-71.2
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• 2013

천연가스를 화학적 전환에 의해 부가가치를 높이기 위해서는 리포밍에 의해 합성가스(CO/H2)를 경유하는 간접전환경로가 현재로서는 가장 현실적인 방법이라 할 수 있다. 천연가스를 이용한 합성가스 제조기술은 수증기개질법(SRM), 이산화탄소 개질법(CDR, dry reforming), 부분산화법, 촉매 부분 산화법, 자열개질법 등으로 구분되며, 최근에는 각각의 제조방법의 장점을 고려하여 혼합개질법 또는 일련의 리포머 조합 방법이 개발되고 있다. CDR은 촉매 하에서 메탄과 이산화탄소의 직접접촉에 의해 반응이 일어나며, 수소와 일산화탄소의 비가 같은 합성가스가 제조된다. SRM에 비하여 고온에서 반응이 일어나고 전환율이 더 낮으므로 에너지 소비가 상대적으로 높다. 하지만, SRM과 함께 사용하면 합성가스 비율을 F-T합성이나 메탄올 합성에 적절한 비율로 조절이 가능한 장점이 있으며, 온실가스를 저감시킬 수 있는 전환기술로도 각광받고 있다. 본 발표에서는 최근의 CDR을 이용한 가스로부터 합성석유(GTL)와 메탄올을 고효율로 생산하는 기술 개발 동향에 대해서 소개하고자 한다.

• 한국연소학회:학술대회논문집
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• 2005.10a
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• pp.64-68
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• 2005

Methane reforming processes to obtain hydrogen were investigated experimentally by using atmospheric plasma source. Among possible reforming processes, such as a $CO_2$ reforming(dry reforming), a partial oxidation (POx), a steam reforming(SR), and a steam reforming with oxygen(SRO or auto-thermal reforming), partial oxidation and the steam reforming with oxygen were considered. We choose a rotating arc plasma as an atmospheric plasma source, since it shows the best performances in our preliminary tests in terms of a methane conversion, a hydrogen production, and a power consumption. Then, the effects of a feeding flow-rate, an electrical power input to a plasma reaction, an $O_2/C$ ratio and a steam to carbon ratio in the case of SRO on the reforming characteristics were observed systematically. As results, at a certain condition almost 100% of methane conversion was obtained and we could achieve the same hydrogen production rate by consuming a half of electrical power which was used by the best results for other researchers.

• Transactions of the Korean hydrogen and new energy society
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• v.17 no.2
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• pp.166-173
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• 2006

Catalytic reforming of $CO_2$ by $CH_4$ over Ni-YSZ based catalysts was investigated to produce syngas as raw material of high valued chemicals and develop high performance catalyst electrode for an internal reforming of $CO_2$ in SOFC system. Ni-YSZ based catalysts were prepared using physical mixing and maleic acid methods to improve catalytic activity and inhibition of carbon deposition. The catalysts before and after the reaction were characterized by $N_2$ physisorption, TPR(temperature programed reduction), XRD and impedance analyzer. The conversions for $CO_2$ and $CH_4$ over Ni-MgO catalyst showed 90% but much amount of carbon deposition was detected on catalyst surface. On the other hand, the conversions for $CO_2$ and $CH_4$ over NiO-YSZ-$CeO_2$ catalyst showed 100% and 85% respectively, and carbon deposition on catalyst surface was inhibited under the tested condition. It was concluded that NiO-YSZ-$CeO_2$ catalyst is a promising candidate for the catalytic reforming of $CO_2$ and the internal reforming in SOFC system.

• Transactions of the Korean hydrogen and new energy society
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• v.27 no.5
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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.

• International Journal of Advanced Culture Technology
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• v.3 no.2
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• pp.110-117
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• 2015

10 wt% (Ni-Co) catalysts with different Ni and Co content : 10%Ni, 9%Ni1%Co, 7%Ni3%Co, 5%Ni5%Co, 3%Ni7%Co, and 10%Co; were prepared using sol-gel method followed by incipient wetness impregnation method. To investigate the catalytic activity including the stability, dry methane reforming were demonstrated over the pelletized catalysts at $620^{\circ}C$ under atmospheric pressure in a $CH_4:CO_2:N_2$ feedstock for 360 min. The results showed that bimetallic catalysts with the Co content equal to or greater than 3% were more stable than monometallic catalysts (10%Ni and 10%Co). The temperature programmed hydrogenation interpreted that the additional of Co into Ni catalyst improved the carbon resistance from methane cracking. Promoted this type of bimetallic catalyst using 1wt% K (trimetallic catalyst) prevented the carbon formation on the catalyst. The temperature programmed desorption of $CO_2$ indicated that this trimetallic catalyst has a greater number of strong basic sites. Moreover, the appearance of K lowered the number of weak basic sites and decreased the conversion of methane by 12 %.

• Korean Chemical Engineering Research
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• v.46 no.5
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• pp.1002-1007
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• 2008

The purpose of this paper studied the optimal hydrogen production condition of plasma reforming system to operate the PEMFC. Plasma reforming reactor used with Ni catalyst reactor at the same time, So $H_2$ concentration increased. Also the WGS and PrOx reactor were designed to remove CO concentration under 10 ppm, because CO has effect on catalyst poisoning of PEMFC. The maximum $H_2$ production condition in plasma reforming system was S/C ratio 3.2, $CH_4$ flow rate 2.0 L/min, catalytic reactor temperature $700{\pm}5^{\circ}C$ and input power 900 W. At this time, the concentration of produced syngas was $H_2$ 70.2%, CO 7.5%, $CO_2$ 16.2%,$CH_4$ 1.8%. The hydrogen yield, hydrogen selectivity and $CH_4$ conversion rate were 56.8%, 38.1% and 92.2% respectively. The energy efficiency and specific energy requirement were 37.0%, 183.6 kJ/mol. In additional, The experiment of $CO_2/CH_4$ ratio proceeded. Also WGS reactor experiment was proceeding on optimum condition of plasma reactor and the exit concentration were $H_2$ 68%, CO 337 ppm, $CO_2$ 24.0%, $CH_4$ 2.2%, $C_2H_4$ 0.4%, $C_2H_6$ 4.1%. At this time, experiment result of PrOx reactor were $H_2$ 51.9%, CO 0%, $CO_2$ 17.3%.

• Transactions of the Korean hydrogen and new energy society
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• v.25 no.6
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• pp.570-576
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• 2014

LFG (Land-Fill Gas) includes components of $CH_4$, $CO_2$, $O_2$, $N_2$, and water. The preparation of synthesis gas from LFG as a DME (Dimethyl Ether) feedstock was studied by methane reforming of $CO_2$, $O_2$ and steam over NiO-MgO-$CeO_2$/$Al_2O_3$ catalyst. Our experiments were performed to investigate the effects of methane conversion and syngas ratio on the amount of LFG components over NiO-MgO-$CeO_2$/$Al_2O_3$ catalyst. Results were obtained through the activity reaction experiments at the temperature of $900^{\circ}C$ and GHSV of 4,000. The results were as following; it has generally shown that methane conversion rate increased with the increase of oxygen and carbon dioxide amounts. Highly methane conversion of 92~93% and syngas ratio of approximately 1.0 were obtained in the feed of gas composition flow-rate of 243ml/min of $CH_4$, 241ml/min of $CO_2$, 195ml/min of $O_2$, 48ml/min of $N_2$, and 360ml/min of water, respectively, under reactor pressure of 15 bar for 50 hrs of reaction time. Also, it was shown that catalyst deactivation by coke formation was reduced by excessively adding oxygen and steam as an oxidizer of the methane reforming.

• Transactions of the Korean hydrogen and new energy society
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• v.13 no.3
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• pp.214-223
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• 2002

Kinetic and effectiveness factors for methanol steam reforming using commercial copper-containing catalysts in a plug flow reactor were investigated over the temperature ranges of $180-250^{\circ}C$ at atmospheric pressure. The selectivity of $CO_2$/$H_2$ was almost 100%, and CO products were not observed under reaction conditions employed in this work. It was indicated that $CO_2$ was directly produced and CO was formed via the reverse water gas shift reaction after methanol steam reforming. The intrinsic kinetics for such reactions were well described by the Langmuir-Hinshelwood model based on the dual-site mechanism. The six parameters in this model, including the activation energy of 103kJ/mol, were estimated from diffusion-free data. The significant effect of internal diffusion was observed for temperature higher than $230^{\circ}C$ or particle sizes larger than 0.36mm. In the diflusion-limited case, this model combined with internal effectiveness factors was also found to be good agreement with experimental data.

• Transactions of the Korean hydrogen and new energy society
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• v.29 no.1
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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.

• Clean Technology
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• v.23 no.3
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• pp.314-324
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• 2017

To verify the viability of Co, Ru and Zr-based catalyst for $CO_2$ (dry) reforming reaction, catalysts were fabricated using cordierite, silicon carbide and rota monolithic substrates, and they were compared with the conventional $Co-Ru-Zr/SiO_2$ catalyst in terms of performance and durability. Cordierite monolith was showed high activity with the least amount of active component. In addition, when Cordierite monolith was coated with Co-Ru-Zr in various ways, most excellent performance was showed at a precursor solution coating method. In particular, when 0.9 wt% Co-Ru-Zr/Cordierite was used for reaction, it was observed that 95% $CO_2$ conversion was maintained for 300 h at $900^{\circ}C$.