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Ru-Mg-Al-oxide 촉매 상에서 크라프트 리그닌의 저분자화 연구 (Depolymerization of Kraft Lignin over a Ru-Mg-Al-oxide Catalyst)

  • 김한웅;수잔 올리비아;제정호
    • 청정기술
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    • 제27권2호
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    • pp.190-197
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    • 2021
  • 펄프 및 제지산업에서 목재의 셀룰로오스 성분 활용 후 남는 부산물인 크라프트 리그닌(kraft lignin)은 촉매적 저분자화 공정을 통해 바이오연료나 고부가가치 페놀 단량체로 전환될 수 있다. 본 연구에서는 크라프트 리그닌의 효율적인 저분자화를 위한 촉매로 수소화 금속 및 산-염기점을 동시에 지니는 Ru-Mg-Al-oxide 복합 촉매를 제조하고, 리그닌 분해 성능을 평가하고자 하였다. 촉매 내 다양한 활성점들(산점, 염기점, 수소화 금속)이 리그닌 분해 반응에 미치는 영향을 파악하기 위해 MgO, Mg-Al-oxide, Ru-Mg-Al-oxide의 세 가지 촉매를 제조하여 초임계 에탄올 용매 상에서 리그닌 분해 반응을 수행하였고, 리그닌 분해 성능은 바이오오일(bio-oil) 수율 및 분자량, 그리고 페놀계 단량체 수율을 통해 평가하였다. 그 결과, Ru-Mg-Al-oxide 촉매가 다양한 활성점들의 시너지 효과로 인해 가장 높은 수율의 바이오오일 및 페놀 단량체들을 생산한다는 것을 확인하였다. Ru-Mg-Al-oxide 촉매 상에서 분해 효율을 최적화하기 위해 다양한 반응 조건(온도, 시간, 촉매양)에 따른 분해 효율을 평가하였고, 최종적으로 반응온도 350 ℃, 리그닌 대비 촉매 비율 10%, 4 h 반응을 통해 72%의 높은 바이오오일 수율과 무촉매 대비 3.5배 이상 증가한 페놀 단량체를 생산할 수 있었다.

소성/환원 조건이 Ru/TiO2의 NH3-SCO 반응활성에 미치는 영향 (The Effect of Calcination/reduction Condition Over Ru/TiO2 on the NH3-SCO Reaction Activity)

  • 신중훈;홍성창
    • 공업화학
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    • 제31권1호
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    • pp.108-114
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    • 2020
  • 본 연구에서는, Ru[1]/TiO2 촉매 제조 시 소성/환원 조건에 따른 NH3-SCO (selective catalytic oxidation) 효율을 비교하였다. Ru[1]/TiO2 red는 Ru[1]/TiO2 cal에 비하여 NH3 전환율 및 NH3의 N2 전환율이 우수하였다. Ru[1]/TiO2 촉매의 물리·화학적 특성은 BET, XRD, TEM, XPS, H2-TPR 분석에 의해 확인되었으며, 활성금속의 분산도와 표면 흡착 산소종(Oβ)의 비율에 영향을 미치는 것으로 나타났다.

Optical sensitivity of DNA-dispersed single-walled carbon nanotubes within cement composites under mechanical load

  • Kim, Jin Hee;Rhee, Inkyu;Jung, Yong Chae;Ha, Sumin;Kim, Yoong Ahm
    • Carbon letters
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    • 제24권
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    • pp.90-96
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    • 2017
  • We demonstrated the sensitivity of optically active single-walled carbon nanotubes (SWCNTs) with a diameter below 1 nm that were homogeneously dispersed in cement composites under a mechanical load. Deoxyribonucleic acid (DNA) was selected as the dispersing agent to achieve a homogeneous dispersion of SWCNTs in an aqueous solution, and the dispersion state of the SWCNTs were characterized using various optical tools. It was found that the addition of a large amount of DNA prohibited the structural evolution of calcium hydroxide and calcium silicate hydrate. Based on the in-situ Raman and X-ray diffraction studies, it was evident that hydrophilic functional groups within the DNA strongly retarded the hydration reaction. The optimum amount of DNA with respect to the cement was found to be 0.05 wt%. The strong Raman signals coming from the SWCNTs entrapped in the cement composites enabled us to understand their dispersion state within the cement as well as their interfacial interaction. The G and G' bands of the SWCNTs sensitively varied under mechanical compression. Our results indicate that an extremely small amount of SWCNTs can be used as an optical strain sensor if they are homogeneously dispersed within cement composites.

나노 흡착제가 Li/S 이차전지용 유황양극의 전기화학적 특성에 미치는 영향 (The Effects of the Nano-sized Adsorbing Material on the Electrochemical Properties of Sulfur Cathode for Lithium/Sulfur Secondary Battery)

  • 송민상;한상철;김현석;안효준;이재영
    • 한국수소및신에너지학회논문집
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    • 제13권4호
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    • pp.259-269
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    • 2002
  • A battery based on the lithium/elemental sulfur redox couple has the advantage of high theoretical specific capacity of 1,675 mAh/g-sulfur. However, Li/S battery has bad cyclic durability at room temperature due to sulfur active material loss resulting from lithium polysulfide dissolution. To improve the cycle life of Li/S battery, PEGDME (Poly(ethylene glycol) dimethyl ether) 500 containing 1M LiTFSI salt which has high viscosity was used as electrolyte to retard the polysulfide dissolution and nano-sized $Mg_{0.6}Ni_{0.4}O$ was added to sulfur cathode as additive to adsorb soluble polysulfide within sulfur cathode. From experimental results, the improvement of the capacity and cycle life of Li/S battery was observed( maximum discharge capacity : 1,185 mAh/g-sulfur, C50/C1 = 85 % ). Through the charge-discharge test, we knew that PEGDME 500 played a role of preventing incomplete charge-discharge $behavior^{1,2)$. And then, in sulfur dissolution analysis and rate capability test, we first confirmed that nano-sized $Mg_{0.6}Ni_{0.4}O$ had polysulfide adsorbing effect and catalytic effect of promoting the Li/S redox reaction. In addition, from BET surface area analysis, we also verified that it played the part of increasing the porosity of sulfur cathode.

고온형 고분자전해질형 연료전지에서의 사형 유로와 평행 유로 성능비교에 대한 수치해석적 연구 (Numerical Study on Comparison of Serpentine and Parallel Flow Channel in High-temperature Proton Exchange Membrane Fuel Cells)

  • 안성하;오경민;주현철
    • 한국수소및신에너지학회논문집
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    • 제29권1호
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    • pp.41-55
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    • 2018
  • General polymer electrolyte fuel cell (PEMFC) operates at less than $80^{\circ}C$. Therefore liquid phase water resulting from electrochemical reaction accumulates and floods the cell which in turn increases the mass transfer loss. To prevent the flooding, it is common to employ serpentine flow channel, which can efficiently export liquid phase water to the outlet. The major drawback of utilizing serpentine flow channel is the large pressure drop that happens between the inlet and outlet. On the other hand, in the high temperature polymer electrolyte fuel cell (HT-PEMFC), since the operating temperature is 130 to $180^{\circ}C$, the generated water is in the state of gas, so the flooding phenomenon is not taken into consideration. In HT-PEMFCs parallel flow channel with lower pressure drop between the inlet and outlet is employed therefore, in order to circulate hydrogen and air in the cell less pumping power is required. In this study we analyzed HT-PEMFC's different flow channels by parallel computation using previously developed 3-D isothermal model. All the flow channels had an active area of $25cm^2$. Also, we numerically compared the performance of HT-PEMFC parallel flow channel with different manifold area and Rib interval against the original serpentine flow channel. Results of the analysis are shown in the form of three-dimensional contour polarization curves, flow characteristics in the channel, current density distribution in the Membrane, overpotential distribution in the catalyst layer, and hydrogen and oxygen concentration distribution. As a result, the performance of a real area fuel cell was predicted.

산촉매하의 옥세탄 공중합에 관한 분자 궤도론적 연구 (Theoretical Studies on The Cationic Polymerization Mechanism of Oxetanes)

  • 전용구;김준태;박성규
    • 대한화학회지
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    • 제35권6호
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    • pp.636-644
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    • 1991
  • 에너지기인 methoxy기$(-CH_2OCH_3)$, azido기$(-CH_2N_3)$ 그리고 nitrato기$(-CH_2ONO_2)$로 치환된 옥세탄(oxetane)의 단량체를 산촉매하의 중합반응에 관해서 반경험적인 MINDO/3, MNDO, AMI 방법 등을 사용하여 이론적으로 고찰하였다. 치환체 옥세탄의 친핵성 및 염기성은 옥세탄 산소원자의 음전하 크기로 설명할 수 있으며, 공중합하의 성장단계에서 옥세탄의 반응성은 옥세탄의 반응 중심 탄소의 양전하 크기와 친전자체의 낮은 LUMO 에너지에 좌우됨이 예측된다. 에너지화기 고리형 oxenium 이온형이 열린 carbenium 이온형으로 전환되는 과정은 oxonium 이온과 carbenium 이온 사이의 계산된 안정화에너지(약 10~20 kcal/mole)에 의하면 carbenium 이온이 더 유리함을 예측할 수 있다. 평형상태의 고리형 oxonium 이온과 열린 carbenium 이온의 농도크기가 반응메카니즘의 결정단계이며, 산촉매하의 형태와 계산을 기초로 하여 빠른 평형을 예상하여 볼 때 선폴리머 성장단계에서 SN1 메카니즘이 SN2 메카니즘보다 빠르게 반응할 것으로 예측된다.

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임플랜트 표면 처리 방법에 따른 골조직 반응에 대한 연구 (ON THE BONE TISSUE REACTION TO IMPLANTS WITH DIFFERENT SURFACE TREATMENT METHODS)

  • 김용재;조인호
    • 대한치과보철학회지
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    • 제45권1호
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    • pp.71-84
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    • 2007
  • Statement of problem: Implant surface characteristics plays an important role in clinical success and many studies have been made for improvement of success by changing surface roughness. Purpose: Appropriate increase of surface roughness increases the activity of osteoblast and enhance contact and retention between bone and implant. Material and method- Machined, SLA and RBM surface implants, which are the most commonly used implants were implanted into the tibia of rabbits and after 1 week, 4 weeks, 8 weeks and 12 weeks there were histologic and histomorphometric analysis and study for bone gradient and change of Ca/P ratio using EDS(Energy Dispersive X-ray Spectroscope). Results: Comparison of bone-implant contact showed no significant difference among each implant. In comparison of bone area rates, SLA showed higher value with significant difference at 1 week and 4 weeks, and SLA and RBM at 8 weeks than Machined implant (p<0.05). In analysis of bone constituents with EDS, titanium was specifically detected in new bones and the rates were constant by surface treatment method or period. In case of Ca/P ratio, according to surface treatment method, each group showed significant difference. Lots of old bone fragments produced during implantation remained on the rough surface of RBM implant surface and each group showed histological finding with active synthesis of collagen fibers until 12 weeks. In transmission electronic microscopic examination of sample slice after elapse of twelve weeks, tens nm of borderline (lamina limitans like dense line)was seen to contact the bone, on the interface between bone and implant. Conclusion: SLA and RBM implant with rough surface shows better histomorphometrical result and the trend of prolonged bone formation and maturation in comparison with Machined implant. In addition, implant with rough surface seems to be helpful in early stage bone formation due to remaining of old bone fragments produced in implantation. From the results above, it is considered to be better to use implant with rough surface in implantation.

Oxolane 고폭 화약류의 중합반응에 관한 분자 궤도론적 연구 (A Study Based on Molecular Orbital Theory of Polymerization of Oxolane High Explosives)

  • 김준태
    • 공업화학
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    • 제21권3호
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    • pp.278-283
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    • 2010
  • 폭발성기를 가진 azido기($-CH_2N_3$), nitrato기($-CH_2ONO_2$) 그리고 hydrazino기(-$CH_2N_2H_3$)로 치환된 옥소란 고폭 화약류의 산 촉매 하에서 중합반응을 반경험적인 MINDO/3, MNDO, AM1 방법 등을 사용하여 이론적으로 고찰하였다. 옥소란 고폭 화약류의 친핵성 및 염기성은 옥소란 산소원자의 음전하크기로 설명할 수 있고, 중합하의 성장단계에서 옥소란의 반응성은 옥소란의 반응중심 탄소원자의 양전하크기와 친전자체의 낮은 LUMO 에너지에 좌우됨을 알 수 있다. 옥소란 고폭 화약류의 고리형 oxonium 이온형이 열린 carbenium 이온형으로 전환되는 과정은 oxonium 이온과 carbenium 이온 사이의 계산된 안정화 에너지(17.950~30.197 kcal/mol)에 의하면 carbenium 이온이 더 유리함을 예측 할 수 있다. 평형상태의 고리형 oxonium 이온과 열린 carbenium 이온의 농도 크기가 반응 메카니즘의 결정단계이며, 산 촉매 하의 형태와 계산을 기초로 하여 빠른 평형을 예상하여 볼 때 선폴리머(prepolymer) 성장단계에서 $S_N1$ 메카니즘이 $S_N2$ 메카니즘보다 빠르게 반응 할 것으로 예측된다.

Morphologies of Brazed NiO-YSZ/316 Stainless Steel Using B-Ni2 Brazing Filler Alloy in a Solid Oxide Fuel Cell System

  • Lee, Sung-Kyu;Kang, Kyoung-Hoon;Hong, Hyun-Seon;Woo, Sang-Kook
    • 한국분말재료학회지
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    • 제18권5호
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    • pp.430-436
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    • 2011
  • Joining of NiO-YSZ to 316 stainless steel was carried out with B-Ni2 brazing alloy (3 wt% Fe, 4.5 wt% Si, 3.2 wt% B, 7 wt% Cr, Ni-balance, m.p. 971-$999^{\circ}C$) to seal the NiO-YSZ anode/316 stainless steel interconnect structure in a SOFC. In the present research, interfacial (chemical) reactions during brazing at the NiO-YSZ/316 stainless steel interconnect were enhanced by the two processing methods, a) addition of an electroless nickel plate to NiO-YSZ as a coating or b) deposition of titanium layer onto NiO-YSZ by magnetron plasma sputtering method, with process variables and procedures optimized during the pre-processing. Brazing was performed in a cold-wall vacuum furnace at $1080^{\circ}C$. Post-brazing interfacial morphologies between NiO-YSZ and 316 stainless steel were examined by SEM and EDS methods. The results indicate that B-Ni2 brazing filler alloy was fused fully during brazing and continuous interfacial layer formation depended on the method of pre-coating NiO-YSZ. The inter-diffusion of elements was promoted by titanium-deposition: the diffusion reaction thickness of the interfacial area was reduced to less than 5 ${\mu}m$ compared to 100 ${\mu}m$ for electroless nickel-deposited NiO-YSZ cermet.

알루미나에 담지된 Cu-Ce 촉매상에서의 개질수소가스에 포함된 CO의 선택적 산화 반응에 관한 연구 (The Selective Oxidation of CO in Hydrogen Rich Stream over Alumina Supported Cu-Ce Catalyst)

  • 박종원;정진혁;윤왕래;이영우
    • 한국수소및신에너지학회논문집
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    • 제14권2호
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    • pp.155-170
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    • 2003
  • $Cu-Ce/{\gamma}-Al_2O_3$ based catalysts were prepared and tested for selective oxidation of CO in a $H_2$-rich stream(1% CO, 1% $O_2$, 60% $H_2$, $N_2$ as balance). The effects of Cu loading and weight ratio(=Cu/(Cu+Ce)) upon both activity and selectivity were investigated upon the change in temperatures, It was also examined how the activity and selectivity of catalysts were varied with the presence of $CO_2$ and $H_2O$ in the reactant feed. Among the various Cu-Ce catalysts with different catalytic metal composition, Cu-Ce(4 : 16 wf%) /${\gamma}-Al_2O_3$ catalyst showed the highest activity(>$T_{99}$) and selectivities(50-80%) under wide range of temperatures($175-220^{\circ}C$). However, in the Cu-Ce(4 : 16 wt%)/ ${\gamma}-Al_2O_3$, the presence of $CO_2$ and $H_2O$ in the reactant feed decreased the activity and the maximum activity(>$T_{99}$) in terms of reaction temperature moved by about $25^{\circ}C$ toward higher temperature, the $T_{>99}$ window was seen between $210-230^{\circ}C$ (selectivity 50-75%). From $CO_2-/H_2O-TPD$, it can be concluded that the main cause for the decrease in catalytic activity may be attributed to the blockage of the active sites by competitive adsorption of water vapor and $CO_2$ with the reactant at low temperatures.