• Bulletin of the Korean Chemical Society
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• v.31 no.5
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• pp.1295-1300
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• 2010

The $CO_2-CH_4$ reaction catalyzed by Ni/silicon wafers was kinetically studied by using a photoacoustic technique. The catalytic reaction was performed at various partial pressures of $CO_2$ and $CH_4$ (50 Torr total pressure of $CO_2/CH_4/N_2$) in the temperature range of 500 - $650^{\circ}C$ in a static reactor system. The photoacoustic signal that varied with the $CO_2$ concentration during the catalytic reaction was recorded as a function of time. Under the reaction conditions, the $CO_2$ photoacoustic measurements showed the as-prepared Ni thin film sample to be inactive for the reaction, while the $CO_2/CH_4$ reactions carried out in the presence of the sample pre-treated in $H_2$ at $600^{\circ}C$ were associated with significant time-dependent changes in the $CO_2$ photoacoustic signal. The rate of $CO_2$ disappearance was measured from the $CO_2$ photoacoustic signal data in the early reaction period of 50 - 150 sec to obtain precise kinetic data. The apparent activation energy for $CO_2$ consumption was determined to be 6.9 kcal/mol from the $CO_2$ disappearance rates. The partial reaction orders, determined from the $CO_2$ disappearance rates measured at various $PCO{_2}'S$ and $PCH{_4}'S$ at $600^{\circ}C$, were determined to be 0.33 for $CH_4$ and 0.63 for $CO_2$, respectively. Kinetic data obtained in these measurements were compared with previous works and were discussed to construct a catalytic reaction mechanism for the $CO_2-CH_4$ reaction over Ni/silicon wafer at low pressures.

• Korean Journal of Soil Science and Fertilizer
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• v.45 no.5
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• pp.853-860
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• 2012

To estimate potential use of fly ash in reducing $CH_4$ and $CO_2$ emission from soil, $CH_4$ and $CO_2$ fluxes from a paddy soil mixed with fly ash at different rate (w/w; 0, 5, and 10%) in the presence and absence of fertilizer N ($(NH_4)_2SO_4$) addition were investigated in a laboratory incubation for 60 days under changing water regime from wetting to drying via transition. The mean $CH_4$ flux during the entire incubation period ranged from 0.59 to $1.68mg\;CH_4\;m^{-2}day^{-1}$ with a lower rate in the soil treated with N fertilizer due to suppression of $CH_4$ production by $SO_4^{2-}$ that acts as an electron acceptor, leading to decreases in electron availability for methanogen. Fly ash application reduced $CH_4$ flux by 37.5 and 33.0% in soils without and with N addition, respectively, probably due to retardation of $CH_4$ diffusion through soil pores by addition of fine-textured fly ash. In addition, as fly ash has a potential for $CO_2$ removal via carbonation (formation of carbonate precipitates) that decreases $CO_2$ availability that is a substrate for $CO_2$ reduction reaction (one of $CH_4$ generation pathways) is likely to be another mechanisms of $CH_4$ flux reduction by fly ash. Meanwhile, the mean $CO_2$ flux during the entire incubation period was between 0.64 and $0.90g\;CO_2\;m^{-2}day^{-1}$, and that of N treated soil was lower than that without N addition. Because N addition is likely to increase soil respiration, it is not straightforward to explain the results. However, it may be possible that our experiment did not account for the substantial amount of $CO_2$ produced by heterotrophs that were activated by N addition in earlier period than the measurement was initiated. Fly ash application also lowered $CO_2$ flux by up to 20% in the soil mixed with fly ash at 10% through $CO_2$ removal by the carbonation. At the whole picture, fly ash application at 10% decreased global warming potential of emitted $CH_4$ and $CO_2$ by about 20%. Therefore, our results suggest that fly ash application can be a soil management practice to reduce green house gas emission from paddy soils. Further studies under field conditions with rice cultivation are necessary to verify our findings.

• Applied Chemistry for Engineering
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• v.23 no.3
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• pp.253-258
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• 2012

The effects of active sites and valence states were investigated over $Pd/TiO_2$ catalyst on simultaneous oxidation of $CH_4$ and CO. The Pd species (PdO) crystallite size increased with increasing Pd loadings, which results in enhancement of the activity of $CH_4$ oxidation. Different results from the activity of $CH_4$ and CO oxidation were shown to be dependent on the Pd valence state on the surface of the catalyst prepared through a thermal treatment. XRD and $H_2-TPR$ analysis confirmed that $Pd^{2+}$species was predominated in the calcination catalyst, while $Pd^0$species was predominated in the reduction catalyst. Additionally, it could be found that the valence state of Pd was a more important factor on the catalytic activity than that of factors as the surface area and pore volume. The reaction mechanism of $CH_4$ and CO followed by the valence state of Pd could be identified using FT-IR analysis.

• Membrane Journal
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• v.25 no.1
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• pp.27-31
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• 2015

PEBAX[poly(ether-block-amide)]-NaY zeolite composite membrane was studied on the permeability of penetrant $H_2$, $N_2$, $CO_2$ and $CH_4$ and the selectivity. When the NaY zeolite contents of PEBAX-NaY zeolite membranes were increased, the permeability of $H_2$ was increased, but the permeability of $N_2$, $CH_4$ and $CO_2$ was decreased. By the addition of NaY zeolite into PEBAX, the gas selectivity for $H_2$, $N_2$ and $CO_2$ was decreased except the increase of selectivity of $H_2/N_2$. $CO_2/N_2$, $H_2/CO_2$ and Gas/$CH_4$. The highest selectivity among these gases was from $CO_2$. In particular, the gas selectivity for $CO_2$ was the greatest with a value of 12~156.

• Korean Journal of Materials Research
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• v.6 no.3
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• pp.324-332
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• 1996

DLC 박막을 RF 플라즈마 화학증착법(PECVD)을 이용하여 CH4와 CO2기체로부터 합성하였다. 증착압력, CH4와 CO2가스의 조성비, 바이어스 전압(-VB) 등의 증착조건 변화에 따른 증착속도는 증착층의 두께를 알파스텝으로 측정하여 결정하였으며, 박막의 구조 변화에 따른 증착속도는 증착층의 두께를 알파스텝으로 측정하여 결정하였으며, 박막의 구조 변화는 FTIR 분광분석을 이용하여 분석을 행하였다. 이 연구로부터 얻은 실험 결과는 다음과 같다: 1) 증착속도는 증착압력 및 바이어스 전압의 증가에 따라 증가한다. 2)바이어스 전압 300V이상에서, CO2량 증가는 순증착속도를 증가 시킨다. 3) 순수한 CH4가스를 사용할 경우에는 바이어스전압(-VB)이 증가함에 따라 박막내 수소의 함량과 sp3/sp2비는 감소하는 경향을 나타낸다. 4)증착압력이 증가함에 따라 박막내 수소함량은 증가하며, sp3/sp2비는 감소한다. 5)50mTorr의 증착압력에 증착시, CH4-+Co2 혼합가스에서 이산화탄소의 부피분율에 따라서는 박막내 수소함량은 감소하며, sp3/sp2비는 증가한다.

• Bulletin of the Korean Chemical Society
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• v.8 no.3
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• pp.179-183
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• 1987

Reactions of $Rh(ClO_4)(CO)(AsPh_3)_2$ with unsaturated nitriles and aldehyde, L, produce a series of new cationic rhodium (I) complexes, $[RhL(CO)(AsPh_3)_2]ClO_4$ (L = $CH_2$ = CHCN, $CH_2$ = C($CH_3$)CN, trans-$CH_3CH$ = CHCN, $CH_2$ = CH$CH_2$CN, trans-$C_6H_5CH$ = CHCN, and trans-$C_6H_5CH$ = CHCHD) where L are coordinated through the nitrogen and oxygen, respectively but not through the ${\pi}$-system of the olefinic group. Dissociation constants for the reaction, $[RhL(CO)(AsPh_3)_2]ClO_4$ $\rightleftharpoons$ $Rh(ClO_4)(CO)(AsPh_3)_2$ + L, have been measured to be $1.20{\times}10^{-4}$ M (L = $CH_2$ = CHCN), $1.05{\times}10^{-4}$ M (L = $CH_2$ = C($CH_3$)CN, $3.26{\times}10^{-5}$ M (L = trans-$CH_3$CH = CHCN) and $6.45{\times}10^{-5}$ M (L = $CH_2$ = CH$CH_2$CN) in chlorobenzene at $25^{\circ}C, and higher than those of triphenylphosphine complexes, $[RhL(CO)(AsPh_3)_2]ClO_4$ where L are the corresponding nitriles that are coordinated through the nitrogen atom. The differences in dissociation constants seem to be predominantly due to the differences in ${\Delta}H$ (not due to the differences in ${\Delta}S$). The weaker Rh-N (unsaturated nitriles) bonding in $AsPh_3$ complexes than in $PPh_3$ complexes (based on ${\Delta}H$ values) suggests that the unsaturated nitriles in 2∼5 are good ${\sigma}$-donor and poor ${\pi}$-acceptor.

• Journal of the Korean Chemical Society
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• v.28 no.6
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• pp.384-392
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• 1984

Reaction of the Fe(II) complex of a fully saturated tetradentate macrocyclic ligand [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$, where [14]ane$N_4$ represents 1,4,8,11-tetraazacyclotetradecane, with $O_2$ has been investigated in acetonitrile solutions. [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$ reacts with oxygen to yield low spin Fe(III) species, [Fe([14]aneN$_4)(CH_3CN)_2]^{3+}$, which undergoes metal ion assisted oxidative dehydrogenation of the macrocyclic ligand to produce low spin Fe(II) complex, [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$. The macrocyclic ligand in [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$ is highly unsaturated and its double bonds are conjugated. [Fe([14]dieneN$_4)(CH_3CN)_2]^{2+}$ and [Fe([14]dieneN$_4)(CH_3CN)_2]^{3+}$ are isolated as the intermediates of the reaction. The Fe(II) complexes involved in this oxidative dehydrogenation reaction react with carbon monoxide to give respective carbon monoxide derivatives, [FeL$(CH_3CN)(CO)]^{2+}$ (where L = macrocyclic ligand). The values of $v_{CO}$ of [FeL$(CH_3CN)(CO)]^{2+}$, and the electrochemical oxidation potentials of Fe(II) ${\to}$ Fe(III) and the qualitative stability toward air-oxidation for [FeL(CH$_3CN_2)^{2+}$ increase as the degree of unsaturation of the macrocyclic ligands increase.

• Membrane Journal
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• v.30 no.4
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• pp.269-275
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• 2020

In this study, CO₂ separation experiment was performed on a CH₄/CO₂ mixed gas using a ceramic hollow fiber membrane contactor (HFMC). In order to fabricate high-performance HFMC, experiments were conducted to manufacture high-permeability hollow fiber membranes, and the prepared hollow fiber membranes were evaluated through N₂ gas permeation experiments. HFMC for CH₄/CO₂ mixed gas separation was manufactured using the manufactured high-permeability hollow fiber membrane. In the experiment, mixed gas of CH₄/CO₂ (34.5% CO₂, CH₄ balance) and monoetanolamine (MEA) was used, and the effect of CO₂ removal efficiency on the flow rate of the absorbent was evaluated. The CO₂ removal efficiency increased as the liquid flow rate increased, and the CO₂ absorption flux also increased with the liquid flow rate.

• Korean Journal of Environmental Agriculture
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• v.31 no.2
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• pp.104-112
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• 2012

BACKGROUND: Agricultural inputs (fertilizer and organic inputs) and water conditions can influence $CH_4$ and $CO_2$ emission from agricultural soils. This study was conducted to investigate the effects of agricultural inputs (fertilizer and organic inputs) under changing water regime on $CH_4$ and $CO_2$ emission from a soil in a laboratory incubation experiment. METHODS AND RESULTS: Four treatments were laid out: control without input and three type of agricultural inputs ($(NH_4)_2SO_4$, AS; pig manure compost, PMC; hairy vetch, HV). Fertilizer and organic inputs were mixed with 25 g of soil at 2.75 mg N/25 g soil (equivalent to 110 kg N/ha) in a bottle with septum, and incubated for 60 days. During the first 30-days incubation, the soil was waterlogged (1 cm of water depth) by adding distilled water weekly, and on 30 days of incubation, excess water was discarded then incubated up to 60 days without addition of water. Based on the redox potential, water regime could be classified into wetting (1 to 30 days), transition (31 to 40 days), and drying periods (41 to 60 days). Across the entire period, $CH_4$ and $CO_2$ flux ranged from 0 to 13.8 mg $CH_4$/m/day and from 0.4~1.9 g $CO_2$/m/day, and both were relatively higher in the early wetting period and the boundary between transition and drying periods. During the entire period, % loss of C relative to the initial was highest in HV (16.4%) followed by AS (8.1%), PMC (7.5%), and control (5.4%), indicating readily decomposability of HV. Accordingly, both $CH_4$ and $CO_2$ fluxes were greatest in HV treatment. Meanwhile, the lower $CH_4$ flux in AS and PMC treatments than the control was ascribed to reduction in $CH_4$ generation due to the presence of oxidized compounds such as ${SO_4}^{2-}$, $Fe^{3+}$, $Mn^{4+}$, and ${NO_3}^-$ that compete with precursors of $CH_4$ for electrons. CONCLUSION: Green manure such as HV can replace synthetic fertilizer in terms of N input, however, it may increase $CH_4$ emission from soils. Therefore, co-application of green manure and livestock manure compost needs to be considered in order to achieve satisfactory N supply and to mitigate $CH_4$ and $CO_2$ emission.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.26 no.5
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• pp.742-749
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• 2002

Numerical Study with detailed chemistry has been conducted to investigate the flame structure and NOx formation characteristics in oxygen -enhanced(CH$_4$/O$_2$-$N_2$) and oxygen-enhanced-EGR(CH$_4$/O$_2$-$CO_2$) counter diffusion flame with various strain rates. A small amount of $N_2$is included in oxygen-enhanced-EGR combustion, in order to consider the inevitable $N_2$contamination by $O_2$production process or air infiltration. The results are as follows : In CH$_4$/O$_2$-$CO_2$flame it is very important to adopt a radiation effect precisely because the effect of radiation changes flame structure significantly. In CH$_4$/O$_2$-$N_2$flame special strategy to minimize NO emission is needed because it is very sensitive to a small amount of $N_2$. Special attention is needed on CO emission by flame quenching, because of increased CO concentration. Spatial NO production rate of oxygen-enhanced combustion is different from that of air and oxygen-enhanced-EGR combustion in that thermal mechanism plays a role of destruction as well as production. In case CH$_4$/O$_2$-$CO_2$flame contains more than 40% $CO_2$it is possible to maintain the same EINO as that of CH$_4$/Air flame with accomplishing higher temperature than that of CH$_4$/Air flame. EINO decreases with increasing strain rate, and those effects are augmented in CH$_4$/O$_2$flame.