Methanol and formaldehyde were produced directly by the partial oxidation of methane over mixed oxide catalysts. The catalysts were composed of Mo and Bi with late-transition metals, such as Mn, Fe, and Co. The reaction was carried out at 450℃, 50 bar in a fixed-bed differential reactor. The prepared catalysts were characterized by O2-TPD and BET apparatus. Among the catalysts used, the catalyst composed of 1:1:2.5 molar ratio of Mo:Bi:Mn showed the best methane conversion and methanol selectivity. The change in ratio of methane to oxygen affected at the conversion and selectivity, and the most proper ratio was 10:1.5. Methane conversion, methanol and formaldehyde selectivities increased with the surface areas of the catalysts. From the O2-TPD result, it was found that the oxygen species responsible for this reaction might be the lattice oxygen species desorbed at high temperature around 800℃.

Direct decomposition of methane over three types of carbon black (N330-p, N330-f, and HI-900L) was carried out in a fluidized bed quartz reactor. Properties of carbon black before and after reaction were measured and found to be related with surface structure and weight gain. For N330-p and N330-f, some carbon deposit on the surface was considered to be the reason for the increase of BET surface area and pore volume with weight gain. Carbon deposits on the surface and the conglutination of some aggregates may explain the slight increase of particle size. Properties of HI-900L changed much more significantly with weight gain. It is supposed that the increase of aggregate size of HI-900L were due to some unknown oily components. The corresponding agglomeration might be the reason for the decrease of BET surface area with weight gain, as compared with the increase of that for the case of N330 black.

Methanol and formaldehyde were produced directly by the partial oxidation of methane. The catalysts used were mixed oxides of late-transition metals, such as Mn, Fe, Co, Ni and Cu. The reaction was carried out at 450℃, 50 bar in a fixed-bed differential reactor. The prepared catalysts were characterized by XRD, TPD and BET apparatus. Of the catalysts, A-Mn0.2-6, which contains 0.2 mole of Mn and calcined at 600℃, showed the best catalytic activity: 3.7% methane conversion, and 30 and 28% methanol and formaldehyde selectivities, respectively. The catalytic activity was changed with the content of Mn and the calcination temperature. Catalytic activity increased with the specific surface areas of the catalysts. With XRD, it was found that the structure of the catalysts are changed with calcination temperature. Through O2-TPD experiment, it was found that the catalysts showing good catalytic activity showed O2 desorption peak around 800℃.

Like bamboo-sprouts after rains, numerous subμm-sized pyrocarbon whiskers growth on the Mullite (3Al2O3·2H2O) substrate could be observed through a looking glass during methane pyrolysis at the temperature of 1050℃ in this study. If the surface of substrate would be scrubbed strongly with iron metals, then finely sticked iron particles were more effective catalytic for nm-sized whisker growth. Numerous fine flakes of pyrolytic carbon were hanging by invisible nm-whiskers as like as small spiders hanging by a spiderweb. This is the identification of nm-sized whisker growth. Therefore if the pyrolysis would be stopped at the initial stage of the whisker growth, the primary lengthening growth was nm-sized whisker. So could we vary arbitrarily sizes of whisker from nm- to μm-sizes. But μm- and nm-whiskers grown with the different growth mechanism; the former was straight and the latter has twigs, The lengthening growth of whisker was depended on the flow pattern pyrolysis species on the active sites of substrate and on the growth duration. We could obtained straight whisker length of 10~20 μm/min during the primary growth and laboratory spiral whisker of 30~40 μm-diameter/hr during the secondary growth.

Methanol was synthesized by homogeneous and catalytic reactions of partial oxidation of methane. The effect of pressure, temperature and oxygen concentration on methanol synthesis was investigated. The catalyst used was Bi-Cs-Mg-Cu-Mo mixed oxide. The partial oxidation reaction was carried out in a fixed bed reactor at 20~46 bar and 450~480℃ and oxygen concentration of 5.3~7.7mol%. The results were compared with results of homogeneous reaction performed at the same conditions. Methane conversions of the homogeneous and catalytic reactions increased with temperature. Methanol selectivity of the homogeneous reaction decreased with increasing temperature. However, the methanol selectivity of catalytic reaction increased with temperature. For both homogeneous and catalytic reactions, the methane conversions were around 5%. This may be due to the low oxygen concentration. Methanol selectivity of the catalytic reaction was higher than that of homogeneous one.

Multi-walled carbon nanotubes (CNTs) were prepared by microwave plasma chemical vapor deposition (MPCVD) using various combination of binary catalysts and methane precursor. The maximum yield (10.3 %) of CNTs was obtained using a methane-hydrogen-nitrogen mixture with volume ratio of 1:1:2 at 1000 W of microwave power. As the microwave power increased up to 1000 W, the deposition yield of CNTs raised from 4.1 % to 10. 3 %. However, the prepared CNTs at 800 W showed the more crystalline structure than those prepared at 1000 W. The prepared CNTs over different binary catalysts had various structural conformations such as aligned cylinder, bamboo, and nanofibers. The Id/Ig value of CNTs overFe-Fe/Al2O3, Co-Co/Al2O3, and Co-Cu/Al2O3 were in the range of 0.89~0.93. Among the various binary catalysts used, Fe-Co./Al2O3 showed the highest yield.

본 연구는 전남 무안 관측소에서 1995년 8월부터 1997년 12월까지 측정된 CH4의 농도자료를 이용하여, 비교대상으로 설정된 국내·외 관측점들과의 관계를 설명하기 위해 다양한 분석을 수행하였다. 연구관측 기간동안 무안지역에서는 CH4의 평균농도가 1898 ± 85.3 ppb로 나타나, 여타 모든 관측지점들 중에서 가장 높게 측정되었다. 그리고 국내의 또 다른 관측점인 태안 지역에서도 이에 가까운 고농도를 유지하였다. 또한 기타 국외 지점들에서는 인구가 적고 해양이 많은 남반구에 비해 북반구에서, 그리고 저위도에서 고위도로 갈수록 CH4의 농도가 높게 나타났다. 무안지역의 월주기 농도경향을 분석한 결과, 2, 3월에 CH4의 농도가 서서히 증가하여 8월에 1958 ppb로 정점을 보여주었다. 모든 관측점들에서 월별 변화양상을 동일한 기준으로 비교분석하기 위해서, 월별 진동폭의 변화를 살펴보았다. 그 결과, 국내의 두 지점에서 80 ppb이상의 높은 진동폭을 띠는 것으로 보아서, 국외 관측점들에 비해 CH4의 발생/소멸이 매우 불규칙하게 진행되고 있음을 볼 수 있었다. 이와 더불어 무안지역의 자료를 계절적 주기를 중심으로 분석하면, 농경지나 측사와 같은 인근지역에 위치한 자연적 발생원의 영향이 강한 여름철을 전후하여 고농도를 보였다. 반면 북반구에 위치한 국외 관측지점들에서 동일 계절에 저농도를 보이는 것으로 나타났다. 이러한 현상은 이 기간에 OH radical의 생성이 활발해져, CH4의 소멸이 촉진되었을 가능성이 큰 것으로 나타났다. 전체 CH4의 일평균 농도를 이용한 장주기적 추세에 대한 분석결과에 따르면, 국내의 두 관측지점들(무안, 태안)에서는 수일 주기의 농도 변화가 급격하게 이루어졌지만, 뚜렷한 계절적 주기는 발견하기가 어려웠다. 그런데 국외의 관측지점들에서는, 계절적 주기의 변화가 상대적으로 뚜렷하고 규칙적인 양상을 보여주었다. 지역별 CH4 농도간의 상관분석을 실시한 결과, 국내 두 지점들 간에는 양의 상관관계, 무안지역과 북반구의 관측점들과는 음의 상관관계를 보였다. 반면 남반구에 위치한 관측점들과는 양의 상관관계를 확인 할 수 있었다. CH4 농도의 장주기적 변화경향을 분석하기 위해, 단순회귀분석을 실시한 결과, CH4 농도의 증가율이 무안과 태안 지역에서 각각 연간 16.5, 14.8 ppb로 가장 높게 관측되었다. 관측점 주변에 복잡한 배출원의 작용이 가능하다는 점을 감안하여, 무안지역의 CH4 농도변화와 풍향과의 연계성을 비교해 보았다. 이 결과에 의하면, 동풍계열의 풍계가 나타날 때 고농도의 값이 나타났으며, 청정한 공기가 유입되는 남서풍의 풍계시에는 비교적 낮은 CH4 농도가 유지되었다. 이처럼 CH4의 장주기적 분포특성은 연구대상지역의 복잡한 배출·소별작용과 연계되어 매우 다양하고 독특한 형태를 띠고 있음을 확인할 수 있었다.

본 연구에서는 전남 무안지역을 중심으로 관측한 농도자료와 세계의 주요 배경관측지점인 Point Barrow(Alaska), Mauna Loa(Hawaii)를 중심으로 관측한 농도자료를 이용하여, 메탄의 농도분포특성을 지역 또는 시간의 함수로 비교분석하였다. 이들 관측점들은 주요 위도대를 대표하기 때문에, 위도별 베탄의 분포특성을 파악하는데도 중요한 단서를 제공하였다. 또한 본 연구결과에 기초하여 메탄의 농도변화양상을 여러 가지 시간적 주기로 비교하고, 그러한 결과의 의미를 다양한 통계적 기법에 기초하여 분석하였다. 전체 관측기간동안 확보된 일평균 농도자료로부터 계산된 무안지역의 농도는 1898±85.3ppb(N=812)로 나타났다. 동일한 기관동안 두 개의 비교관측지점인 Point Barrow와 Mauna Loa 지역에서는 1832±29.6ppb(N=823), 1745±14.8ppb(N=818)의 평균농도가 각각 관측되었다. 각 지점에서 관측된 자료를 이용하여 빈도분포를 비교한 결과에 따르면, 무안지역에서 1900ppb의 최빈값을 나타낸 반면, Point Barrow, Mauna Loa 지역에서는 각각 1850, 1750ppb로 (상대적으로) 낮은 최빈값을 보여주었다. 이 논문에서는 국내의 관측점에서 발견되는 고농도의 메탄분포특성을 여러 관점에서 비교하고 해석하고자 하였다. 국외지역에서 주로 발견되는 미미한 수준의 농도변화 경향과 달리, 무안지역에서는 여타 지역들에 비해 절대적으로 높은 농도값이 유지되고 그 농도변화가 주야간대별로 뚜렷하게 구분될 정도로 주기적인 변화의 폭이 큰 것으로 확인되었다. 특히 무안지역에서는 낮시간대(6:00 AM 이후)에 농도가 낮아지고, 저녁시간대에 농도치가 상승하는 경향이 두드러졌다. 풍향과 CH4농도관계를 비교한 결과, 연구대상지역이 서해안에 위치한 지리적인 요건으로 인해 상대적으로 청정한 해풍이 주를 이루는 서풍계열의 풍계가 나타날 때, CH4의 농도는 낮은 수준을 유지하는 것으로 나타났다. 본 연구에 의하면, 국내 지점의 메탄농도는 국외여타 지점에 비해 뚜렷하게 구분이 될 정도로 높은 수준을 유지하고 있다. 이러한 현상을 초래하는 원인으로 여타 비교대상지역들에 비해, 무안지역이 보다 다양한 배출원의 영향에 직접적으로 노출된데 따른 영향을 직간접적으로 반영하는 결과로 사료된다. 연구지점에서 발견된 CH4의 고농도 현상과 일주기를 중심으로 반복되는 농도의 큰 진동폭이 나타나는 현상도 역시 주목할 만하다.

There appeared enhancements of the conversion of methane by adding a small amount of CO in the aromatization reaction of methane using the Mo-zeolite catalyst. In case of adding CO2, CO2 changed to CO first, and then the conversion reaction occurred. It was observed by using isotopes as reactants that CO is related to the aromatization reaction of methane.

The oxidation of methane was carried out in six different configurations of plasma reactors in order to study the radical reactions inside and outside of the plasma zone and to explore the method to control them. Various radicals and reactive molecules, such as CH, CH2, CH3, H, and O(from O2) were generated in the plasma. A variety of products were produced through many competing reaction pathways. Among them. partial oxidation products were usually not favored, because the intermediates leading to the partial oxidation products could be oxidized further to carbon dioxides easily. It is important to control the free radical reactions in the plasma reactor by controlling the experimental conditions so that the reactions leading to the desired products are the major pathways

This study was conducted to find a catalyst system which has high conversion and selectivity for the oxidative coupling of methane to produce ethane and ethylene. Various catalysts were tested in a fixed bed reactor ar 750℃, 1 atm, and the feed ratio(CH4/O2) of 2/1. Under the reaction condition, 10wt%PbSO4/MgO catalyst showed the highest catalytic activity : methane conversion, C2 selectivity and yield were 50, 40 and 20%, respectively. Catalysts containing sulfate compounds, 10wt%PbSO4/MgO, 10wt%MgSO4/MgO and Na2SO4/MgO revealed a moderate methane conversions such as 38, 50 and 50%, respectively and low C2 selectivities such as 18, 5 and 9%, respectively. Catalysts containing carbonate compounds, 10wt%PbCO3/MgO, 10wt%Li2CO3/MgO and NaCO3/MgO, also showed a moderate methane conversions such as 64, 44 and 51%, respectively and low C2 selectivities such as 5, 6 and 2%, respectively. With the existence of chlorine and mercury, C2 selectivity was decreased.

Poly(n-butyl methacrylate)(PnBMA)에 의한 메탄가스의 용해도를 35atm의 압력까지 측정하였다. 용해도의 측정은 -10℃ 에서 30℃ 까지의 온도범위에서 용적법에 의하여 실시하였다. PnBMA에 의한 메탄가스의 용해도는 유리 전이온도 이하에서 측정압력에 대하여 비선형으로 나타났으며, dual-mode sorption model로 만족스럽게 해석할 수 있었다. Langmuri capacity constant는 온도가 증가할수록 감소하였으며 유리전이온도 근처에서 영이 되며, 용해도 등온선은 유리 전이온도 이상에서는 직선으로 나타났다. Dual-mode sorption parameter의 온도 의존성도 고찰하였다.

The experiment was carried out to determine the optimum application rate of liquid waste from methane fermentation (LW) and its effect on botanical composition, dry matter yields and nutrient quality of pasture mixtures. Experimental fields was designed a

The present study investigated the effect of forage sources and their inclusion levels in diet on the rumen fermentation of Korea traditional goat. Timothy and alfalfa were used as forage sources. Forages were mixed with concentrate diet in different ratios. The ratios of forage to concentrate diets were varied to 1:9, 5:5 and 9:1. The rumen fluid of goat was gathered from slaughter house. Dry matter digestibility was decreased and methane production was increased as forage levels in diet was increased. When forage sources, timothy and alfalfa, were compared, groups with timothy showed greater methane production than the groups of alfalfa. Molar ratio of produced acetate and valerate were increased when forage level in diet was increased. In the case of propionate and butyrate, they were decreased as elevated forage levels in diet. The result of this study provided a basic information for rumen fermentation of Korean traditional goat and these information could be applied in the development of nutritional and feeding strategy.

Organic wastewater generated from polyester manufacturing processes was selected from H company to investigate the feasibility of anaerobic digestion that produces gases including methane. Bio Methane Potential (BMP) tests were conducted to measure the gas production and methane concentration for 7 process wastewater and 2 kinds of sludges from the H company. Also, along with monitoring pH and alkalinity during the anaerobic digestion process, the concentrations of COD and 1,4-dioxane were measured with 4 different operating conditions for N Emulsion (NE) and Ethylene Glycol (EG) wastewater. The BMP tests showed that 65% of methane was produced from NE and EG wastewater. This suggests that the organic wastewater from H company can be effectively treated by an anaerobic digester by which more than 90% of COD was removed.

This study was conducted to investigate for the natural methane emission inhibitor as a feed additive no adversely effect on rumen fermentation. Five different Control (Wheat barn (0.05 g), MRA(Methane Reduction Additive)-1 (Allium fistulosum L. (0.05 g)), MRA-2 (Sodium Lauryl Sulfate (0.025 g) +Wheat barn (0.025 g) mixed), MRA-3 (Sodium Dodecyl Sulfate (0.025 g) + Wheat barn (0.025 g) mixed), and MRA-4 (Allium fistulosum L. (0.02 g) + Tannic acid (0.02 g) + Wheat barn (0.01 g) mixed) contents were used to perform 3, 6, 9, 12, 24 and 48 h incubation for in vitro fermentation. Ruminal pH values were ranged within normal ruminal microbial fermentation. Dry matter digestibility was not significantly different across the treatments during the whole fermentation time. Also, the result of microbial growth had no adversely effect on during the whole fermentation time. At 24 h, methane emission was significantly lower (P<0.05) than all treatments except to MRA-1. Especially, MRA-4 carbon dioxide emission was significantly lower (P<0.05) than control at 9, 24 and 48 h incubation. In addition MRA-4 propionate concentration was significantly higher (P<0.05) than control at 24 h incubation. The result of RT-PCR Ciliate-associated methanogens were significantly lower (P<0.05) at MRA-1, MRA-3 and MRA-4 than control at 24 h incubation. Based on the present results, MRA-4 could be suggestible methane emission inhibitor as a natural feed additive.

Livestock manure treatments have become a more serious problem because massive environmental pollutions such as green and red tides caused by non-point pollution sources from livestock manures have emerged as a serious social issue. In addition, more food wastes are being produced due to population growth and increased income level. Since the London Convention has banned the ocean dumping of wastes, some other waste treatment methods for land disposal had to be developed and applied. At the same time, researches have been conducted to develop alternative energy sources from various types of wastes. As a result, anaerobic digestion as a waste treatment method has become an attractive solution. In this study has three objectives: first, to identify the physical properties of the mixture of livestock wastewater and food waste when combining food waste treatment with the conventional livestock manure treatment based on anaerobic mesophilic digestion; second, to find the ideal ratio of waste mixture that could maximize the collection efficiency of methane (CH4) from the anaerobic digestion process; and third, to promote CH4 production by comparing the biodegradability. As a result of comparing the reactors R1, R2, and R3, each containing a mixture of food waste and livestock manure at the ratio of 5:5, 7:3, and 3:7, respectively, R2 showed the optimum treatment efficiencies for the removal of Total Solids (TS) and Volatile Solids (VS), CH4 production, and biodegradability.