• Journal of the Korean Wood Science and Technology
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• 제47권3호
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• pp.344-359
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• 2019

Effects of various types of zeolite on the catalytic performance of hydrodeoxygenation (HDO) of bio-oil obtained from waste larch wood pyrolysis were investigated herein. Bifunctional catalysts were prepared via wet impregnation. The catalysts were characterized through XRD, BET, and SEM. Experimental results demonstrated that HDO enhanced the fuel properties of waste wood bio-oil, such as higher heating values (HHV) (20.4-28.3 MJ/kg) than bio-oil (13.7 MJ/kg). Water content (from 19.3 in bio-oil to 3.1-16.6 wt% in heavy oils), the total acid number (from 150 in bio-oil to 28-77 mg KOH/g oil in heavy oils), and viscosity (from 103 in bio-oil to $40-69mm^2/s$ in heavy oils) also improved post HDO. In our experiments, depending on the zeolite support, NiFe/HBeta exhibited a high Si/Al ratio of 38 with a high specific surface area ($545.1m^2/g$), and, based on the yield of heavy oil (18.3-18.9 wt%) and HHV (22.4-25.2 MJ/kg), its performance was not significantly affected by temperature and solvent concentration variations. In contrast, NiFe/zeolite Y, which had a low Si/Al ratio of 5.2, exhibited the highest improved quality for heavy oil at high temperature, with an HHV of 28.3 MJ/kg at $350^{\circ}C$ with 25 wt% of solvent.

• 한국결정성장학회지
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• 제28권1호
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• pp.44-50
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• 2018

The improved high-performance Fe-based perovskite-type oxides ($La_{0.7}Sr_{0.3}M_xFe_{1-x}O_3$, M = Cu, Cr, Ni) were synthesized by a citrate method and characterized by SEM, EDS, XRD and NMR spectroscopy analyses. The characterization analyses revealed that the stoichiometric amounts of lattice oxygen were existed in all of perovskite samples except for a nickel-doped perovskite. Fe-based perovskites exhibited a surprising result for ortho-para $H_2$ spin conversion reaction, indicating two orders of magnitude higher conversions and conversion rates than commercial $Fe_2O_3$. It was considered that this conversion difference might be attributed to the presence of oxygen vacancies in Fe-based perovskites prepared in this study.

• 청정기술
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• 제25권1호
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• pp.81-90
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• 2019

프로페인($C_3H_8$)의 건식 개질($CO_2$ 개질)을 통한 합성 가스($H_2$와 CO 혼합물) 제조를 위해 $Ni-CeO_2/{\gamma}-Al_2O_3$ 촉매가 충진된 유전체 장벽 방전 플라즈마 반응기를 사용하였다. 열 또는 플라즈마에 의해 환원된 $Ni-CeO_2/{\gamma}-Al_2O_3$ 촉매를 사용하여 $C_3H_8/CO_2$ 비율 1/3, 총 유량 $300mL\;min^{-1}$에서 플라즈마-촉매 건식 개질을 수행하였다. 건식 개질에 대한 촉매 활성은 온도범위 $500{\sim}600^{\circ}C$에서 평가되었다. $Ni-CeO_2/{\gamma}-Al_2O_3$ 촉매 제조를 위해 전구물질 수용액(질산니켈, 질산세륨)으로 함침된 ${\gamma}-Al_2O_3$를 공기 분위기에서 소성시킨 후, $H_2/Ar$ 분위기에서 환원시켰다. 촉매 특성 조사에는 X-선 회절분석기(XRD), 투과전자현미경(TEM), 전계 방출 주사전자현미경(FE-SEM), 승온 탈착($H_2-TPD$, $CO_2-TPD$) 및 라만 분광기가 이용되었다. 열로 환원된 촉매와 비교하면 플라즈마 방전하에서 환원된 $Ni-CeO_2/{\gamma}-Al_2O_3$ 촉매가 개질 반응을 통한 합성 가스 생산에서 보다 우수한 촉매 활성을 나타내었다. 또한, 플라즈마로 환원된 $Ni-CeO_2/{\gamma}-Al_2O_3$가 개질 반응의 문제점인 탄소퇴적 관점에서 장기 촉매 안정성을 보여주었다.

• KEPCO Journal on Electric Power and Energy
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• 제2권3호
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• pp.447-452
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• 2016

It is imperative to develop an effective pathway to depolymerize lignin into liquid fuel that can be used as a bioheavy oil. Lignin can be converted into liquid products either by a solvent-free thermal cracking in the absence air, or thermo-chemical degradation in the presence of suitable solvents and chemicals. Here we show that the solvent-assisted liquefaction has produced promising results in the presence of metal-based catalysts. The supercritical ethanol is an efficient liquefaction solvent, which not only provides better solubility to lignin, but also scavenges the intermediate species. The concentrated sulfuric acid hydrolysis lignin (CSAHL) was completely liquefied in the presence of solid catalysts (Ni, Pd and Ru) with no char formation. The effective deoxy-liquefaction nature associated with scEtOH with aid hydrodeoxygenation catalysts, resulted in significant reduction in oxygen-to-carbon (O/C) molar ratio up to 61%. The decrease in oxygen content and increase in carbon and hydrogen contents increased the calorific value bio-oil, with higher heating value (HHV) of $34.6MJ{\cdot}Kg^{-1}$. The overall process is energetically efficient with 129.8% energy recovery (ER) and 70.8% energy efficiency (EE). The GC-TOF/MS analysis of bio-oil shows that the bio-oil mainly consists of monomeric species such as phenols, esters, furans, alcohols, and traces of aliphatic hydrocarbons. The bio-oil produced has better flow properties, low molecular weight, and high aromaticity.

• 대한화학회지
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• 제38권9호
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• pp.695-700
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• 1994

여러가지 불균일 촉매$(Rh/Al_2O_3,\;Pd/C,\;Ni,\;Al_2O_3,\;Active\;carbon)$를 이용하여 CFC-113a의 가수소 분해반응을 액상과 기상에서 각각 조사하였다. 액상반응에서는 각 촉매에 따라 반응성은 차이가 났지만, 95% 이상의 높은 선택성으로 $HCFC-123(CF_3CHCl_2)$을 주었다. 특히 $Al_2O-3$가 액상반응에서 상당히 높은 반응성과 선택성을 보인 것은 주목할 만하다. 기상반응의 경우, 전이금속이 포함된 촉매(Pd/C, Pt/C)를 사용하였을 때에는 과수소화물인 $HCFC-133a(CF_3CH_2Cl)$와 HFC-143a(CF_3CH_3)$가 생성되었다. 한편, 액상반응에서 활성을 보이던 $Al_2O_3$는 기상반응에서는 거의 반응성을 보이지 않았다. $Al_2O_3$의 경우 용매로 THF를 사용하였을 경우에는 비교적 부반응 없이 깨끗하게 반응이 진행되었지만, MeOH를 사용하였을 때는 용매로 부터 $CH_3OCH_3$과 $CH_3CH_2OCH_3$ 등이 생성되면서 가수소 분해반응이 진행되었다. 따라서 액상반응에서는 용매의 역할이 중요한 것으로 해석하였다.

• 한국재료학회지
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• 제22권7호
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• pp.358-361
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• 2012

Co and Ni as catalysts in $SnO_2$ sensors to improve the sensitivity for $CH_4$ gas and $CH_3CH_2CH_3$ gas were coated by a solution reduction method. $SnO_2$ thick films were prepared by a screen-printing method onto $Al_2O_3$ substrates with an electrode. The sensing characteristics were investigated by measuring the electrical resistance of each sensor in a chamber. The structural properties of $SnO_2$ with a rutile structure investigated by XRD showed a (110) dominant $SnO_2$ peak. The particle size of the $SnO_2$:Ni powders with Ni at 6 wt% was about 0.1 ${\mu}m$. The $SnO_2$ particles were found to contain many pores according to a SEM analysis. The sensitivity of $SnO_2$-based sensors was measured for 5 ppm of $CH_4$ gas and $CH_3CH_2CH_3$ gas at room temperature by comparing the resistance in air to that in the target gases. The results showed that the best sensitivity of $SnO_2$:Ni and $SnO_2$:Co sensors for $CH_4$ gas and $CH_3CH_2CH_3$ gas at room temperature was observed in $SnO_2$:Ni sensors coated with 6 wt% Ni. The $SnO_2$:Ni gas sensors showed good selectivity to $CH_4$ gas. The response time and recovery time of the $SnO_2$:Ni gas sensors for the $CH_4$ and $CH_3CH_2CH_3$ gases were 20 seconds and 9 seconds, respectively.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2005년도 춘계학술대회
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• pp.256-259
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• 2005

본 연구에서는 기존 니켈 활성성분만의 알루미나담지 촉매에 비해 고온에서의 수소를 사용한 환원 전처리 과정을 거치지 않고도 높은 반응활성을 나타내며, 반응 중 탄소침적에 대한 촉매 저항성에서도 우수한 결과를 나타낸 루테늄-니켈 촉매에 대해보고 하고자 한다. 메탄 수증기 개질 반응을 통해, 루테늄을 최종적으로 담지한 알루미나 담지니켈계 촉매는 별도의 전처리과정 없이 $650^{\circ}C$에서부터 높은 반응성을 보였으며, 루테늄과 니켈을 동시에 담지한 경우보다 더 우수한 활성을 나타내었다. Ru의 담지량을 달리한 실험에서는$RU(0.5)/Ni(20)/Al_2O_3$ 촉매가 가장 높은 활성을 보였다. $H_2-TPR$ 분석 결과, $Ru(0.5)/Ni(20)/A1_2O_3$촉매의 경우 세 가지 환원 피크가 나타났으며, $Ni(20)/A1_2O_3$촉매와 비교해 볼 때, 저온(<$130^{\circ}C)$에서 환원가능한 $RUO_2$의 존재를 확인할 수 있었다. 담지된 RU은 분산도가 높아, XRD분석 결과에서 Ru이나 $RuO_2$의 특성 피크가 존재하지 않았다. 또한 $650^{\circ}C$에서 10시간 개질반응 후 얻어진 촉매에 대해 $O_2-TGA$를 분석한 결과, $Ni(20)/Al_2O_3$촉매는 $-7.2wt\%$ 정도의 큰 무게 감소를 보였으며, 이는 촉매 표면에 생성된 carbon tube에 의한 것임을 SEM 분석을 통해 알 수 있었다 이에 반해, $Ru(0.5)/Ni(20)/Al_2O_$ 촉매는 $O_2-TGA$시 $0.3wt\%$ 정도 무게 증가에 그쳤으며, SEM 분석상 carbon tube의 생성이 크게 억제되었음을 알 수 있었다.

• 한국환경과학회지
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• 제28권1호
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• pp.65-73
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• 2019

The catalytic activity of Ni-0.2%YSZ (Yttria-Stabilized Zirconia) with different promoters was evaluated for $CO_2$ methanation. The catalysts were weighed for mixing and they were dried at $110^{\circ}C$ for molding into disks. The concentration of $CO_2$ and $CH_4$ for conducting of $CO_2$ methanation were analyzed by gas chromatography and the physical characteristics of the disk-type catalyst formed were analyzed by X-ray diffraction, scanning electron microscope and energy dispersive x-ray spectrometer. The addition of $CeO_2$ as a promoter for Ni-0.2%YSZ (denoted as Ni-5%Ce-0.2%YSZ) resulted in the highest $CO_2$ methanation. It also showed catalytic activity at a low temperature($200^{\circ}C$). Following this, $ZrO_2$, $SiO_2$, $Al_2O_3$ and $TiO_2$ were added to Ni-5%Ce-0.2%YSZ to compare the $CO_2$ methanation, and the highest efficiency was found for. Ni-1%Ti-5%Ce-0.2%YSZ Then, the concentration of Ti was increased to 10% and the catalytic activity was estimated using seven different types of commercial $TiO_2$. In conclusion, ST-01 $TiO_2$ showed the highest efficiency for $CO_2$ methanation.

• 한국수소및신에너지학회논문집
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• 제30권6호
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• pp.601-607
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• 2019

Ammonia would be formed in natural gas containing small amount of nitrogen reforming process in the process natural gas, which might damage the Pt catalyst and Prox catalyst. In the article, the effect of nitrogen contents on the formation of ammonia in the reforming process has been studied. In the experiments, Ru based and Ni based catalysts were used and the concentration of ammonia in the reformate gas at various gas hourly space velocity was measured. Experimental result shows that relatively higher ammonia concentration was measured with Ru based catalyst than with Ni based catalyst. It also shows that the concentration of ammonia increased rapidly after most of the methane converted into hydrogen. Based on the experimental results to reduce ammonia concentration it might be better to finish methane conversion at the exit position of the reforming reactor to minimize the contact time of catalyst and nitrogen with high concentration of hydrogen.

• 한국수소및신에너지학회논문집
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• 제26권1호
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• pp.21-27
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• 2015

Hydrogen production from commercial diesel fuels is an attactive option for energy generation purpose due to the low cost and good availability of diesel fuels. However, in order to utilize commercial diesel fuels, the sulfur contents must be removed down to approximately 0.1 ppm level to protect the fuel cell catalysts from poisoning. Commercial catalysts $CoMo/Al_2O_3$ and $NiMo/Al_2O_3$ were tested for HDS (Hydrodesulfurization) of model diesel and commercial diesel. The experimental conditions were $250-400^{\circ}C$ and LHSV (Liquid Hourly Space Velocity) $0.27-2.12hr^{-1}$. $NiMo/Al_2O_3$ was found to be more effective than $CoMo/Al_2O_3$ in removing sulfur from model diesel. Based on the experimental results of model diesel, commercial diesel fuel purchased from a local petrol station was tested for HDS using $NiMo/Al_2O_3$. The GC-SCD (Gas Chromatography Sulfur Chemiluminescence Detector) results showed that the DMDBT (Dimethyldibenzothiophene) derivatives were fully removed from the commercial diesel fuel proving that HDS with $NiMo/Al_2O_3$ is technically feasible for industrial applications.