• Bulletin of the Korean Chemical Society
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• v.11 no.2
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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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• v.20 no.2
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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.

• Applied Chemistry for Engineering
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• v.22 no.6
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• pp.653-657
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• 2011

Conversion characteristics of $CH_4$ and $CO_2$ was studied using an atmospheric pressure plasma for the preparation of synthesis gas composed of $H_2$ and CO. The effects of delivered power, total gas flow rate, and gas residence time in the reactor on the conversion of $CH_4$ and $CO_2$ were evaluated in a plasma reactor with the type of dielectric barrier discharge. The increase of reactor temperature did not affect on the increase of conversion if the temperature does not reach to the appropriate level. The conversion of $CH_4$ and $CO_2$ largely increased with increasing the delivered power. As the $CH_4/CO_2$ ratio increased, the $CH_4$ conversion decreased, whereas the $CO_2$ conversion increased. Generally, the $CH_4$ convesion was higher than the $CO_2$ conversion through the variation of the process parameters.

• Membrane Journal
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• v.4 no.4
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• pp.197-204
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• 1994

In this study, permeation characteristics of pure $CH_4,\;CO_2$ and $CH_4/CO_2$ gas mixture were examined by permeation experiments through hollow fiber membrane module and experimental results were compared with simulation results. Permeation rate of pure gas increased with increaseing temperature in Arrhenius type. Activation energy was 6.61 kJ/mol for $CO_2$ and 25.26 kJ/mol for $CH_4$. In the permeation experiment of gas mixture, permeate flow rate and $CO_2$ concentration in permeate decreased and $CH_4$ concentration in reject increased with the increase of cut. Separation factor was in the range of 20~40 at 5~20 atm and 20% cut and it increased with pressure and against temperature Experimental values corresponded to numerical values with the deviation of 8% in permeate flow rate and $CO_2$ concentration in permeate and 15% in $CO_2$ concentration in reject.

• Bulletin of the Korean Chemical Society
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• v.7 no.6
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.27 no.5
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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.

• Proceedings of the Korea Society for Energy Engineering kosee Conference
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• 2004.11a
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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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• v.7 no.6
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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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• v.8 no.3
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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 $100^{\circ}C$.

• Membrane Journal
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• v.24 no.1
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• pp.1-9
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• 2014

In this study, four soluble homo- and co-polyimides using 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (DOCDA) and 4,4'-diaminodiphenyl ether (ODA) monomers were synthesized to develop the gas separation membrane with good $CO_2/CH_4$ separation properties. To prepare the copolyimides, 20 mol% of three dianhydrides - (4,4'-(hexafluoroisoproplidene)diphthalic anhydride (6FDA), 4,4'-biphthalic anhydride (BPDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA) - were added in DOCDA-ODA monomer mixture, respectively. All the synthesized homo- and co-polyimides were characterized by FT-IR. Their thermal properties were analyzed with differential scanning calorimeter (DSC). Dense membranes were prepared from these copolyimides to check their gas permeation properties for $CO_2$ and $CH_4$ gases using a time-lag method. The permeation testing results are as follows; DOCDA/ODA homopolymer showed 1.71 barrer of $CO_2$ permeability and 74.35 of $CO_2/CH_4$ selectivity. The three polyimide copolymers (DOCDA/6FDA-ODA, DOCDA/BPDA-ODA, DOCDA/BTDA-ODA) showed lower $CO_2/CH_4$ selectivities and higher $CO_2$ permeabilities than the homopolymer (DOCDA-ODA). DOCDA/6FDA-ODA showed twice times higher $CO_2$ permeabilities without severe $CO_2/CH_4$ selectivity loss than the DOCDA-ODA.