• Bulletin of the Korean Chemical Society
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• 제11권2호
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• pp.109-114
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• 1990

The anionic transition metal hydrides $(HW(CO)_4P(OMe)_3\;^-,\;HW(CO)_5\;^-,\;HCr(CO)_5\;^-,\;HFe(CO)_4\;^-)$ react with transition metal alkyl $(CpMo(CO)_3(CH_3)$ to yield $CH_4\;and\;CH_3CHO$ in addition to the inorganic products $(CpMo(Co)_3\;^-$, etc.). The reaction of these anionic metal hydrides with CpMo(CO)3{CH2CH(CH2)2} may lead to an elucidation of the reaction mechanisms involved; the organic product distributions are among $CH_4,\;CH_2\;=\;CHCH_2CH_3$, and $CH_3CH(CH_2)_2$, depending upon the anionic metal hydride used. These anionic metal hydrides also are reported to undergo a hydride-halide exchange reaction with organic halides; therefore, these similar reactions have been compared in terms of leaving group ability $(CpMo(CO)_3\;^-\;vs.\;Br^-)$ and the mechanistic pathways.

• Environmental Engineering Research
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• 제20권2호
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• pp.191-197
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• 2015

The first objective of this study was to discuss the applicability of the $CO_2/CH_4$ ratio method in order to assess $CH_4$ oxidation efficiency. To achieve this objective, a comparison between $CO_2/CH_4$ ratios and the mass balance method was conducted. The second objective of this study was to estimate the $CH_4$ oxidation efficiency in an interim landfill soil cover and assess how a $CH_4$ influx influences the $CH_4$ oxidation efficiency. The results showed that despite the $CO_2$ problems brought by respiration, the $CH_4$ oxidation efficiencies obtained by the $CO_2/CH_4$ ratio method led to similar results compared to the mass balance method. In this respect, the $CO_2/CH_4$ ratio method can be an indicator of the $CH_4$ oxidation efficiencies for landfill cover soils. The $CH_4$ oxidation efficiencies derived in this study through the $CO_2/CH_4$ ratio method ranged between 46% and 64%, and between 41% and 62% through the mass balance method. The results imply that the Intergovernmental Panel on Climate Change's (IPCC) default value of 10% for the $CH_4$ oxidation efficiency is an underestimation for landfill cover soils. $CH_4$ oxidation efficiency tends to be negatively correlated with $CH_4$ influx. Therefore, $CH_4$ influx reaching a landfill cover should be limited in order to increase the $CH_4$ oxidation efficiency.

• 공업화학
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• 제22권6호
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• pp.653-657
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• 2011

대기압 플라즈마 반응기를 이용한 메탄과 이산화탄소의 전환처리로 수소와 일산화탄소로 구성된 합성가스를 제조하는 공정특성을 연구하였다. 유전체 격벽 방전방식의 플라즈마 반응기를 인가전력, 혼합가스의 구성비 및 사용된 반응기의 갯수 등의 공정변수들에 대하여 메탄과 이산화탄소의 전환율에 미치는 영향이 분석되었다. 인가전력의 공급에 따라 플라즈마 반응기 자체의 온도 상승이 일어나지만 반응기 온도 증가가 반응기체의 전환율 향상에 효과가 크지 않았다. 그러나 인가전력이 증가할수록 메탄과 이산화탄소의 전환율이 크게 증가하였다. 반응기체인 $CH_4/CO_2$ 비가 커질수록 $CH_4$의 전환율은 감소하나 $CO_2$의 경우는 증가하였다. 전체적으로 반응에 따른 $CH_4$의 전환율이 $CO_2$의 전환율보다 큰 경향성을 보인다.

• 멤브레인
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• 제4권4호
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• pp.197-204
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• 1994

본 연구에서는 hollow fiber 막모듈을 통한 순수 $CH_4,\;CO_2$기체와 $CH_4/CO_2$ 혼합기체의 투과 특성을 살펴 보고, 이를 모사값과 비교하여 보았다. 순수 기체의 투고율은 온도에 따라 Arrhenius type으로 증가하였으며, 활성화에너지는 $CO_2$는 6.61kJ/mol, $CH_4$는 25.26kJ/mol로 나타났다. 혼합기체의 투과에 있어서 투과부의 유량과 $CO_2$ 조성, 그리고 배제부의 $CH_4$조성은 cut의 증가에 따라 증가하였다. 분리인자는 5~20atm의 압력과 cut이 20으로 고정된 상태에서 20~40의 범위에 있었으며, 압력이 증가하고 온도가 감소할수록 증가하는 경향을 나타내었다. 실험결과와 모사결과는 투과부 유량과 $CO_2$조성의 경우 8% 이내에서, 배제부의 $CH_4$조성의 경우 15% 이내에서 일치하였다.

• Bulletin of the Korean Chemical Society
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• 제7권6호
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• pp.468-471
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• 1986

The isolated products from the reactions of $Rh(ClO_4)(CO)(PPh_3)_2$ (1) with CH_2$ = $CHCO_2C_2H_5$ (2) and trans-$CH_3CH$ = $CHCO_2C_2H_5$ (3) contain 80∼ 90% of $[Rh(CH_2 = CHCO_2C_2H_5)(CO)(PPh_3)_2]ClO_4$ (4) and [Rh(trans-$CH_3CH = CHCO_2C_2H_5(CO)(PPh_3)_2]ClO_4$ (5), respectively where 2 and 3 seem to be coordinated through the carbonyl oxygen. It has been found that complex 1 catalyzes the isomerization of $CH_2 = CH(CH_2)_8CO_2C_2H_5$ (6) to $CH_3(CH_2)_nCH = CH(CH_2)_{7-n}CO_2C_2H_5$ (n = 0∼7) under nitrogen at 25$^{\circ}C$. The isomerization of 6 is slower than that of $CH_2 = CH(CH_2)_9CH_3$ to $CH_3(CH_2)_nCH$ = $CH(CH_2)_{8-n}CH_3$ (n = 0∼8), which is understood in terms of the interactions between the carbonyl oxygen of 6 and the catalyst. It has been also observed that complex 1 catalyzes the hydrogenation of 2, 3, 6, trans-$C_6H_5CH = CHCO_2C_2H_5$ (7), $CH_3(CH_2)_7CH = CH(CH_2)_7CO_2C_2H_5$ (8) and $CH_2 = CH(CH_2)_9CH_3$ (9), and the isomerization (double bond migration) of 6 and 9 under hydrogen at 25$^{\circ}C$. The interactions between the carbonyl oxygen of the unsaturated esters and the catalyst affect the hydrogenation in such a way that the hydrogenation of the unsaturated esters becomes slower than that of simple olefins.

• 한국수소및신에너지학회논문집
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• 제27권5호
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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.

• 한국에너지공학회:학술대회논문집
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• 한국에너지공학회 2004년도 추계 학술발표회 논문집
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• pp.195-200
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• 2004

Carbon dioxide ($CO_2$) and methane (CH$_4$) are two major greenhouse Bases. $CO_2$is a stack gas of many industrial processes and the main product of the hydrocarbon combustion. There is recent research interest on the synthesis gas (syngas) formation from $CO_2$ and CH$_4$, via the following reaction: CH$_4$+$CO_2$longrightarrow 2H$_2$+$CO_2$, in order to reduce the greenhouse effects and to synthesize various chemicals, Preliminary experiments were conducted on the conversion of $CO_2$ and CH$_4$ to syngas by making use of a microwave plasma torch at atmospheric pressure. Conversion rates of $CO_2$and CH$_4$ to hydrogen (H$_2$), carbon monoxide (CO) and higher hydrocarbons were investigated using Gas Chromatography (GC) and Fourier Transform Infrared (FTIR). The experimental data indicate that the main products were H$_2$, CO and small amount of higher hydrocarbons, such as ethylene (C$_2$H$_4$).

• Bulletin of the Korean Chemical Society
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• 제7권6호
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• pp.466-468
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• 1986

Reaction of $Ir(ClO_4)(CO)(PPh_3)_2$ with trans-$C_6H_5CH$ = $CHCO_2C_2H_5$ produces a new cationic iridium(I) complex, [Ir (trans-$C_6H_5CH$ = $CHCO_2C_2H_5)(CO)(PPh_3)_2]ClO_4$ where trans-$C_6H_5CH$ = $CHCO_2C_2H_5$ seems to be coordinated through the carbonyl oxygen rather than through the $\pi$-system of the olefinic group according to the spectral data. It has been found that Ir$(ClO_4)(CO)(PPh_3)_2$ catalyzes the hydrogenation of $CH_2$ = $CHCO_2C_2H_5$, trans-$CH_3CH$ = $CHCO_2C_2H_5$ and trans-$C_6H_5CH$ = $CHCO_2C_2H_5$ to $CH_3CH_2CO_2C_2H_5$, $CH_3CH_2CH_2CO_2C_2H_5$ and $C_6H_5CH_2CH_2CO_2C_2H_5$, respectively at room temperature under the atmospheric pressure of hydrogen. The relative rates of the hydrogenation of the unsaturated esters are mostly understood in terms of steric reasons.

• Bulletin of the Korean Chemical Society
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• 제8권3호
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• pp.185-189
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• 1987

Reactions of $Ir(ClO)_4(CO)(PPh_3)_2$ with dicyano olefins, cis-NCCH = CH$CH_2$$CH_2$CN (cDC1B), trans-NCCH = CH$CH_2$$CH_2$CN (tDC1B), trans-NC$CH_2$CH = CH$CH_2$CN (tDC2B), and NC$CH_2$$CH_2$$CH_2$$CH_2$CN (DCB) produce binuclear dicationic iridium (I) complexes, $[(CO)(PPh_3)_2Ir-NC-A-CN-Ir(PPh_3)_2(CO)](ClO_4)_2$ (NC-A-CN = cDC1B (1a), tDC1B (1b), tDC2B (1c), DCB (1d)). Complexes 1a-1d react with hydrogen to give binuclear dicationic tetrahydrido iridium (Ⅲ ) complexes, $[(CO)(PPh_3)_2(H)_2Ir-NC-A-CN-Ir(H)_2(PPh_3)_2(CO)](ClO_4)_2$ (NC-A-CN = cDC1B (2a), tDC1B (2b), tDC2B (2c), DCB (2d)). Complexes 2a and 2b catalyze the hydrogenation of cDC1B and tDC1B, respectively to give DCB, while the complex 2c is catalytically active for the isomerization of tDC2B to give cDC1B and tDC1B and the hydrogenation of tDC2B to give DCB at $100^{\circ}C$.

• 멤브레인
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• 제24권1호
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• pp.1-9
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• 2014

지환족 다이안하이드라이드인 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (DOCDA)와 4,4'-diaminodiphenyl ether (ODA)에서 합성된 폴리이미드는 유기용매에 잘 용해되는 폴리이미드로 알려져 있다. 이러한 DOCDA-ODA 폴리이미드의 기체 투과특성을 평가하고 투과선택도를 개선시키기 위해서 DOCDA-ODA 반응물에 세 가지 dianhydride 단량체((4,4'-(hexafluoroisoproplidene)diphthalic anhydride (6FDA), 4,4'-biphthalic anhydride (BPDA), 3,3', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA))를 각각 20 mol% 첨가하여 순수중합체 및 공중합체를 합성하였다. 폴리이미드 합성이 성공적으로 이루어졌음을 FT-IR을 통해 확인하였고, 그들의 열적특성은 DSC를 통해 알아보았다. 제조된 폴리이미드들의 $CO_2/CH_4$에 대한 기체투과도와 선택도는 time-lag법을 이용하여 측정하였다. 그 결과 순수고분자인 DOCDA-ODA의 경우 $CO_2$ 투과도는 1.71 barrer, $CO_2/CH_4$ 선택도는 74.35의 우수한 투과특성을 보였다. 세 가지 공중합체의 경우 DOCDA-ODA에 비해 $CO_2$ 투과도는 높게 나타난 반면에 $CO_2/CH_4$ 선택도는 감소하였다. 특히, 6FDA를 첨가한 경우 $CO_2/CH_4$ 선택도는 DOCDA-ODA보다 다소 낮은 결과를 나타내었지만 $CO_2$ 투과도가 크게 증가하였음을 확인할 수 있었다.