• Journal of Hydrogen and New Energy
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• v.18 no.2
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• pp.197-206
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• 2007

There are several methods for the hydrogen production such as steam reforming of natural gas, photochemical method, biological method, electrolysis and thermochemical method, etc. Many researches have been widely performed for the hydrogen production method having low production cost and high efficiency. In this paper, the patents concerning the photochemical hydrogen production method were gathered and analyzed. The search range was limited in the open patents of USA(US), European Union(EP), Japan(JP), and Korea(KR) from 1996 to 2005. Patents were gathered by using key-words searching and filtered by filtering criteria. The patent application trend was analyzed by the years, countries, companies, and technologies.

• Transactions of the Korean Society of Automotive Engineers
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• v.14 no.3
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• pp.170-177
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• 2006

Hydrogen can extend the lean misfire limit to a large extent when it is mixed with conventional fuels for a spark ignition engine. In this study, hydrogen-enriched gaseous fuels by reforming process were simulated according to their proportions of $H_2$, CO, $CO_2$ and $N_2$ gases. Pure hydrogen and two different hydrogen-enriched gaseous mixtures(A-, B-composition) were tested for their basic effects on the engine performances and emissions in a single cylinder research engine. A- and B-composition showed different results from 100% $H_2$ addition because air/fuel mixtures were more diluted by their additions. Even though the energy fraction of reformed gases was increased, combustion stabilities and lean misfire limits were not sensitively improved. It means that combustion augmentation by $H_2$ addition was offset by the charge dilution of $N_2$ and $CO_2$. In addition, the low flammability of CO gas deteriorated thermal efficiencies. CO emission was drastically increased with B-composition which included higher CO component. However, $NO_x$ was reduced as energy fraction($X_e$) rised except for the case of 100% $H_2$ addition at $\lambda=1.2$ and was, for A-composition, lowered to a factor of ten when compared with that of $H_2$ addition. HC emissions were largely influenced by $COV_{imep}$ due to misfire and partial burns.

• Journal of the Korean Institute of Gas
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• v.27 no.3
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• pp.77-83
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• 2023

Energy consumption is increased by rapid industrialization. As a result, climate change is accelerating due to the increase in CO₂ concentration in the atmosphere. Therefore, a shift in the energy paradigm is required. Hydrogen is in the spotlight as a part of that. Currently 95% of hydrogen is fossil fuel-based reforming hydrogen which is accompanied by CO₂ emissions. This is called gray hydrogen, if the CO₂ is captured and emission of CO₂ is reduced, it can be converted into blue hydrogen. There are 3 technologies to capture CO₂: absorption, adsorption and membrane technology. In order to select CO₂ capture technology, the analysis of the exhaust gas should be carried out. The concentration of CO₂ in the flue gas from the hydrogen production process is higher than 20%if water is removed as well as the emission scale is classified as small and medium. So, the application of the membrane technology is more advantageous than the absorption. In addition, if LNG cold energy can be used for low temperature CO₂ capture system, the CO₂/N₂ selectivity of the membrane is higher than room temperature CO₂ capture and enabling an efficient CO₂ capture process. In this study, we will analyze the flue gas from hydrogen production process and discuss suitable CO₂ capture technology for it.

• Journal of Hydrogen and New Energy
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• v.23 no.3
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• pp.213-218
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• 2012

Steam reforming of methane (SRM) is the primary method to produce hydrogen. Commercial Ni-based catalysts have been optimized for SRM with excess steam ($H_2O/CH_4$ > 2.5) at high temperatures (> $700^{\circ}C$). However, commercial catalysts are not suitable under severe conditions such as stoichiometric steam over methane ratio ($H_2O/CH_4$ = 1.0) and low temperature ($600^{\circ}C$). In this study, 15wt.% Ni catalysts supported on $Ce_{0.8}Zr_{0.2}O_2$ were prepared at various calcination temperatures for SRM at a very high gas hourly space velocity (GHSV) of $621,704h^{-1}$. The calcination temperature was systematically varied to optimize 15wt.% $Ni-Ce_{0.8}Zr_{0.2}O_2$ catalyst at a $H_2O/CH_4$ ratio of 1.0 and at $600^{\circ}C$. 15wt.% $Ni-Ce_{0.8}Zr_{0.2}O_2$ catalyst calcined at $500^{\circ}C$ exhibited the highest $CH_4$ conversion as well as stability with time on stream. Also, 15wt.% $Ni-Ce_{0.8}Zr_{0.2}O_2$ catalyst calcined at $500^{\circ}C$ showed the highest $H_2$ yield (58%) and CO yield (21%) among the catalysts. This is due to complex NiO species, which have relatively strong metal to support interaction (SMSI).

• 한국신재생에너지학회:학술대회논문집
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• 2007.06a
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• pp.53-56
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• 2007

미량의 Ru을 증진제로 첨가하여 니켈 촉매의 반응 활성을 증진시킴으로써, 저온 환원성과 장시간 반응에 대한 안정성을 확보하고자 하였다. Ni의 담지량은 12 wt%로 고정하였으며 이에 Ru을 각각 0.1, 0.3, 0.5 wt%로 변화시켜 2차 담지하였다. 메탄의 수증기/이산화탄소 복합 개질 반응에 있어 니켈 촉매에 Ru을 2차 담지 한 촉매는 800 $^{\circ}C$, GHSV(gas hourly space velocity) 265,000 $h^{-1}$ 하에서 100 %에 가까운 $CH_{4}$ 전환율을 보였으며, GHSV 1,060,000 $h^{-1}$ 일 때에도 10시간 동안 90 %의 $CH_{4}$ 전환율을 기록하였다. 또한 이 중 0.3 wt%의 Ru를 담지한 경우가 1,060,000 $h^{-1}$의 조건하에서도 95 %이상으로 가장 높은 $CH_{4}$ 전환율로 유지되었다. $H_{2}-TPR$ 분석 결과, Ni(12)/$MgAl_{2}O_{4}$ 와 비교해 볼 때 Ru(0.5)/Ni(12)/$MgAl_{2}O_{4}$와 Ru(0.3)/Ni(12)/$MgAl_{2}O_{4}$ 촉매의 경우 150 $^{\circ}C$에서 저온 환원이 가능한 $RuO_{2}$의 존재를 확인할 수 있었다.

• Journal of the Korean Applied Science and Technology
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• v.24 no.4
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• pp.427-435
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• 2007

에너지원으로서 수소를 생산하기 위하여 하니컴 구조를 갖는 모노리스에 10 wt% $Ni/CeO_2-ZrO_2$ 촉매를 담지한 후 메탄의 수증기 개질 실험을 수행하였다. 다른 $CeO_2/ZrO_2$ 몰비를 갖는 촉매들 중에서, $Ni/CeO_2-ZrO_2(CeO_2/ZrO_2=4/1)$촉매가 $700-800^{\circ}C$에서 높은 메탄의 전환율을 보여 주었다. 10wt% $Ni/CeO_2-ZrO_2$ 촉매가 담지된 금속 모노리스 촉매체는 높은 열전도도와 비표면적들로 인하여 좋은 촉매 특성을 보여줌을 확인할 수 있었다. 또한, 금속모노리스 촉매체는 반응물에서 과다의 수증기에 의한 수소 수율에서 크게 영향을 받지 않음을 알 수 있었다. $GHSV=30,000h^{-1}$, 반응물 비$(H_2O/CH_4=3.0)$ 반응온도 $800^{\circ}C$에서 금속모노리스 촉매체는 98%이상의 메탄의 전환율을 보여주었다. 생성물 가스에서 $CO_2/CO$의 비는 수증기/메탄의 반응물비가 증가할수록 수성가스화 반응에 의하여 증가됨을 알 수 있었다.

• Journal of Electrochemical Science and Technology
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• v.11 no.4
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• pp.336-345
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• 2020

Nickel-doped lanthanum cobalt oxide (LaCo_1-xNi_xO_3-δ, LCN) was investigated as an alternative anode material for solid oxide fuel cells. To improve its catalytic activity for steam methane reforming (SMR) reaction, Ni²⁺ was substituted into Co³⁺ lattice in LaCoO₃. LCN anode, synthesized using the Pechini method, reacts with yttria-stabilized zirconia (YSZ) electrolyte at high temperatures to form an electrochemically inactive phase such as La₂Zr₂O₇. To minimize the interlayer by-products, the LCN was coated via a double-tape casting method on the Ni/YSZ anode as a catalytic functional layer. By increasing the Ni doping amount, oxygen vacancies in the LCN increased and the cell performance improved. CH₄ fuel decomposed to H₂ and CO via SMR reaction in the LCN functional layer. Hence, the LCN-coated Ni/YSZ anode exhibited better cell performance than the Ni/YSZ anode under H₂ and CH₄ fuels. LCN with 12 mol% of Ni (LCN12)-modified Ni/YSZ anode showed excellent long-term stability under H₂ and CH₄ conditions.

• Korean Chemical Engineering Research
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• v.46 no.4
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• pp.813-818
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• 2008

Various additives were added in small amounts on Ni/YSZ anode of SOFC (solid oxide fuel cell) in order to improve reactivity and to inhibit deactivation due to coke deposition during methane reforming using a low mole ratio steam ($H_2O/CH_4=1.5$) at $800^{\circ}C$. Ni/YSZ catalysts added with various perovskites did not show any improvement but exhibited a gradual decrease in the methane conversion. K-doped Ni/YSZ showed a steady increase and maintenance of the conversion up to 42 hours, after which there was an abrupt deactivation of catalyst owing to potassium loss by volatilization. Addition of 5% of $K_2Ti_2O_5$ on Ni/YSZ showed a stable maintenance of the conversion without K loss, and was able to prevent coke formation during a long time operation. Deactivation of catalyst during the reaction was mainly caused by the accumulation of graphidic carbon on the catalyst surface.

• Korean Chemical Engineering Research
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• v.45 no.6
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• pp.656-662
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• 2007

Fuel reformer using plasma and shift reactor for CO oxidation were designed and manufactured as $H_2$ supply device to operate a polymer electrolyte membrane fuel cell (PEMFC). $H_2$ selectivity was increased by non-thermal plasma reformer using GlidArc discharge with Ni catalyst simultaneously. Shift reactor was consisted of steam generator, low temperature shifter, high temperature shifter and preferential oxidation reactor. Parametric screening studies of fuel reformer were conducted, in which there were the variations of the catalyst temperature, gas component ratio, total gas ratio and input power. and parametric screening studies of shift reactor were conducted, in which there were the variations of the air flow rate, stema flow rate and temperature. When the $O_2/C$ ratio was 0.64, total gas flow rate was 14.2 l/min, catalytic reactor temperature was $672^{\circ}C$ and input power 1.1 kJ/L, the production of $H_2$ was maximized 41.1%. And $CH_4$ conversion rate, $H_2$ yield and reformer energy density were 88.7%, 54% and 35.2% respectively. When the $O_2/C$ ratio was 0.3 in the PrOx reactor, steam flow ratio was 2.8 in the HTS, and temperature were 475, 314, 260, $235^{\circ}C$ in the HTS, LTS, PrOx, the conversion of CO was optimized conditions of shift reactor using simulated reformate gas. Preheat time of the reactor using plasma was 30 min, component of reformed gas from shift reactor were $H_2$ 38%, CO<10 ppm, $N_2$ 36%, $CO_2$ 21% and $CH_4$ 4%.

• Journal of Hydrogen and New Energy
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• v.32 no.6
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• pp.534-541
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• 2021

In this study, a novel microwave-matrix reformer was proposed to convert CH₄, which is a major component, to a high quality hydrogen energy. And to identify this performance, it was investigated for O₂/C ratio, steam feed amount and reformed gas recirculation which are affected for methane conversion and product gas yield. Through the parametric screening studies, optimal operating conditions were that O₂/C ratio, steam feed amount and recirculation rate were 1.1, 10 mL/min and 30 L/min. In this conditions, CH₄ conversion was 68.1%, H₂ selectivity 77.2 and H₂/CO ratio 2.62 which are possible applying SOFC stack for RPG (residential power generator).