• Applied Chemistry for Engineering
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• v.8 no.4
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• pp.685-693
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• 1997

We have studied the reforming of carbon dioxide with methane over various supported nickel catalysts. The nickel supported on natural zeolite showed the highest activity and the nickel on acidic support showed higher activity and slow deactivation compared to nickel on basic support. The activity of nickel on natural zeolite increased with increasing loading ratio and showed almost constant activity above 10wt.% loading of nickel. The conversion and yield of products were affected by the mole ratio of reactants and the highest yields of CO and $H_2$ were obtained at $CH_4/CO_2=1$. The deactivation of catalyst was caused by deposition of coke which was formed by the decomposition of methane. The shape of coke was shown to be whisker tripe carbon, and it brought out the slow deactivation of catalyst.

• Transactions of the Korean hydrogen and new energy society
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• v.14 no.1
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• pp.69-80
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• 2003

Nickel catalyst has been used for natural gas reforming with carbon dioxide, In this study, catalyst support used was HY zeolite. The optimum loading of Ni in the catalysts was 13 wt%. The effect of promoters, such as Mg, Mn, and K, was also studied. The addition of promoters to Ni catalyst improved the stability of catalysts and carbon deposition on Ni catalyst was suppressed. The reforming reactivity of promoter-added Ni catalyst was higher than that of Ni catalyst without any promoters. SEM, XRD, BET, TGA and FTIR tests were tried to characterize the catalyst structure before and after reaction.

• 한국태양에너지학회:학술대회논문집
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• 2012.03a
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• pp.267-273
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• 2012

Solar reforming of methane with CO2 was successfully tested with a direct irradiated absorber on a parabolic dish capable of 5kWth solar power. And the new type of double-layer absorber-the front layer, porous metal foam which absorbs the radiation and transfers the heat from material to gas, and the back layer, catalytically-activated metal foam-was prepared, and its activity was tested by using electric furnace. Ni was applied as the active metal on the gamma-Al2O3 coated Ni metal foam for the preparation of the catalytically-activated metal foam layer. Compared to conventional direct irradiation of the catalytically activated metal foam absorber, this new type of double layer absorber is found to exhibit a superior reaction and thermal storage performance at the fluctuating incident solar radiation. In addition, unlike direct irradiation of the foam absorber, double layer absorber has better thermal resistance, which prevents the emergence of cracks caused by mechanical or thermal shock. The total solar power absorbed reached up to 3.25kW and the maximum CH4 conversion was almost 59%.

• 한국태양에너지학회:학술대회논문집
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• 2011.11a
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• pp.80-86
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• 2011

Solar reforming of methane with CO2 was successfully tested with a direct irradiated absorber on a parabolic dish capable of 5kWth solar power. And the new type of double-layer absorber - the front layer, porous metal foam which absorbs the radiation and transfers the heat from material to gas, and the back layer, catalytically-activated metal foam - was prepared, and its activity was tested by using electric furnace. Ni was applied as the active metal on the gamma-Al2O3 coated Ni metal foam for the preparation of the catalytically-activated metal foam layer. Compared to conventional direct irradiation of the catalytically activated metal foam absorber, this new type of double layer absorber is found to exhibit a superior reaction and thermal storage performance at the fluctuating incident solar radiation. In addition, unlike direct irradiation of the foam absorber, double layer absorber has better thermal resistance, which prevents the emergence of cracks caused by mechanical or thermal shock. The total solar power absorbed reached up to 3.25kW and the maximum CH4 conversion was almost 59%.

• Journal of the Korean Society of Marine Environment & Safety
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• v.27 no.1
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• pp.135-144
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• 2021

In this study, we investigated the characteristics of the process of hydrogen production using boil-of gas (BOG) generated from an LNG-fueled ship and the application of hydrogen fuel cell systems as auxiliary engines. In this study, the BOG steam reformer process was designed using the UniSim R410 program, and the reformer outlet temperature, pressure, and the fraction and consumption of the product according to the steam/carbon ratio (SCR) were calculated. According to the study, the conversion rate of methane was 100 % when the temperature of the reformer was 890 ℃, and maximum hydrogen production was observed. In addition, the lower the pressure, the higher is the reaction activity. However, higher temperatures have led to a decrease in hydrogen production owing to the preponderance of adverse reactions and increased amounts of water and carbon dioxide. As SCR increased, hydrogen production increased, but the required energy consumption also increased proportionally. Although the hydrogen fraction was the highest when the SCR was 1.8, it was confirmed that the optimal operation range was for SCR to operate at 3 to prevent cocking. In addition, the lower the pressure, the higher is the amount of carbon dioxide generated. Furthermore, 42.5 % of the LNG cold energy based on carbon dioxide generation was required for cooling and liquefaction.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.322-322
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• 2013

$CO_2$를 $CH_4$와 열 및 전기화학적인 반응을 통해 고농도의 CO 및 $H_2$로 구성된 합성가스로 효율적으로 전환시키기 위해, 반응가스 주입용 간극형 노즐을 가진 비이송식 직류 열플라즈마 토치 시스템을 설계, 제작하고 다양한 조건에서 이 두 가스의 개질 실험을 수행하였다. 설계 제작된 간극형 노즐과 리액터 내 고온 반응 영역을 활용한 $CO_2$ 및 $CH_4$ 반응가스의 효율적인 처리를 통하여, 최고 70% 이상의 $CO_2$ 및 $CH_4$의 전환율과 최고 80% 이상의 CO 및 $H_2$선택도를 달성할 수 있음을 확인하였다. 또한, 상기 조건의 경우, 플라즈마 입력 전력 10.6 kW 대비 49 lpm 의 반응가스 처리량을 통하여 얻은 것으로 최고 2.5 mmol/kJ 이상의 Specific Energy Requirement (SER) 조건도 만족할 수 있음을 보였다. 특히, 제안된 막대 음극-반응 가스 주입구를 가진 양극 노즐 플라즈마 토치의 경우, $CH_4$ 반응가스를 음극에 직접 닿지 않도록 간극을 통해 주입하게 함으로써, 반응 가스 분해에 의한 음극 등 전극 부식을 최소화하면서도 고에너지 전자가 풍부한 아크 컬럼에 의해 $CO_2$ 및 $CH_4$의 전환 반응을 효율적으로 일으킬 수 있어 효율적인 $CO_2$ 및 $CH_4$ 개질을 위한 열플라즈마 토치 시스템의 개발이 기대된다.

• Journal of Korean Society of Environmental Engineers
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• v.30 no.12
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• pp.1268-1272
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• 2008

Low temperature plasma applied with partial oxidation is a technique to produce synthesis gas from methane. Low temperature plasma reformer has superior miniaturization and start-up characteristics to reformers using steam reforming or CO$_2$ reforming. In this research, a low temperature plasma reformer using GlidArc discharge was proposed. Reforming characteristics for each of the following variables were studied: gas components ratio (O$_2$/CH$_4$), the amount of steam, comparison of reaction on nickle and iron catalysts and the amount of CO$_2$. The optimum conditions for hydrogen production from methane was found. The maximum Hydrogen concentration of 41.1% was obtained under the following in this condition: O$_2$/C ratio of 0.64, total gas flow of 14.2 L/min, catalyst reactor temperature of 672$^{\circ}C$, the amount of steam was 0.8, reformer energy density of 1.1 kJ/L with Ni catalyst in the catalyst reactor. At this point, the methane conversion rate, hydrogen selectivity and reformer thermal efficiency were 66%, 93% and 35.2%, respectively.

• Korean Chemical Engineering Research
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• v.52 no.6
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• pp.727-735
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• 2014

For improved sustainability of the biorefinery industry, biorefinery-byproduct glycerol is being investigated as an alternate source for hydrogen production. This research designs and optimizes a hydrogen-production process for small hydrogen stations using steam reforming of purified glycerol as the main reaction, replacing existing processes relying on steam methane reforming. Modeling, simulation and optimization using a commercial process simulator are performed for the proposed hydrogen production process from glycerol. The mixture of glycerol and steam are used for making syngas in the reforming process. Then hydrogen are produced from carbon monoxide and steam through the water-gas shift reaction. Finally, hydrogen is separated from carbon dioxide using PSA. This study shows higher yield than former U.S. DOE and Linde studies. Economic evaluations are performed for optimal planning of constructing domestic hydrogen energy infrastructure based on the proposed glycerol-based hydrogen station.

• Applied Chemistry for Engineering
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• v.23 no.2
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• pp.176-182
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• 2012

The methane dry reforming has received the considerable attention in recent years, mainly as an attractive route to produce synthesis gas (CO, $H_2$) from green-house gases ($CH_4$, $CO_2$) for resources. However, this process has not been commercialized due to the high temperature and catalyst deactivation. In this study, Co-Ru-Zr catalysts supported on $SiO_2$ were studied for the characterization of methane dry reforming reaction and the preliminary data for process development were achieved. The crystal structure of catalysts was measured by XRD, the surface area and pore size were analyzed by BET, and the element composition of catalyst were analyzed by EDS. Conversions of methane and carbon dioxide were analyzed by GC. In addition, reaction rate constants were obtained from the reaction kinetic study and the optimum catalyst size that does not affect mass transfer from reactants was also determined. The selected pellet-type catalyst maintained activation for 720 h at $850^{\circ}C$.

• 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.