• 공업화학
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• 제35권2호
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• pp.79-84
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• 2024

메탄은 풍부하고 재생 가능한 탄화수소이지만, 온실가스로서 지구 온난화를 발생시킨다. 따라서 메탄을 유용한 화학물질이나 에너지원으로의 변환이 필요하다. 메탄올은 메탄의 부분 산화 반응을 통해 합성할 수 있는 간단하고 풍부한화학물질이다. 메탄올은 화학 공급 원료나 수송 연료로 사용될 뿐만 아니라, 저온 연료 전지의 연료로도 적합하다. 그러나 메탄올의 전기화학 산화는 복잡하고 다단계의 반응이므로, 이 반응을 이해하고 최적화하기 위해서는 새로운 전기화학촉매와 반응 메커니즘의 연구가 필요하다. 본 총설에서는 메탄올 산화 반응 메커니즘 및 최근 연구 동향과 향후 연구 방향을 고찰하였다.

• 한국응용과학기술학회지
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• 제22권1호
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• pp.56-61
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• 2005

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${\sim}$46 bar and $450{\sim}480^{\circ}C$ and oxygen concentration of 5.3${\sim}$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.

• 한국수소및신에너지학회논문집
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• 제13권2호
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• pp.119-126
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• 2002

The methanol partial oxidation using commercial $CuO/ZnO/Al_2O_3$ catalysts in a plug flow reactor was studied in the temperature range of $200{\sim}250^{\circ}C$ at atmospheric pressure, It was achieved the high activities by Cu-based catalysts and the selectivity of $CO_2$/$H_2$ was 100% when $O_2$ was fully convened. The reactivity changes and their hysteresis with increasing/decreasing temperatures were observed due to the chemical state differences between the oxidation and the reduction on the Cu surface, It was suggested as the two-step reaction: the complete oxidation and the following steam reforming for methanol, which was indicated by the distributions of final products vs. the residence time. In addition, the complete oxidation step was shown to be extremely fast and the total reaction rate can be controlled by the steam reforming reaction.

• Journal of Electrochemical Science and Technology
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• 제13권3호
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• pp.354-361
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• 2022

In a direct methanol fuel cell system (DMFC), one of the drawbacks is methanol crossover. Methanol from the anode passes through the membrane and enters the cathode, causing mixed potential in the cell. Only Pt-based catalysts are capable of operating as cathode for oxygen reduction reaction (ORR) in a harsh acidic condition of DMFC. However, it causes mixed potential due to high activity toward methanol oxidation reaction of Pt. To overcome this situation, developing Pt-based catalyst that has methanol tolerance is significant, by controlling reactant adsorption or reaction kinetics. Pt/C decorated with phosphate ion was prepared by modified polyol method as cathode catalyst in DMFC. Phosphate ions, bonded to the carbon of Pt/C, surround free Pt surface and block only methanol adsorption on Pt, not oxygen. It leads to the suppression of methanol oxidation in an oxygen atmosphere, resulting in high DMFC performance compared to pristine Pt/C.

• Korean Chemical Engineering Research
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• 제50권1호
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• pp.41-49
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• 2012

본 연구는 메탄 부분산화에 의한 메탄올 직접 합성을 위한 촉매 개발을 목표로 수행되었다. 이를 위하여 Mo-Bi-V-Al 복합 산화물 촉매를 제조하였으며, 제조 방법에 따른 촉매 물성을 비교하고, 제조한 촉매를 이용하여 메탄올 합성반응을 수행하여 그 결과를 검토하여 보았다. 졸-겔법으로 제조한 촉매가 공침법으로 제조한 촉매보다 비표면적이 훨씬 컸다. 입자가 작고 표면적이 클수록 부분산화반응보다는 완전산화반응이나 메탄올 산화반응이 더 잘 진행되어 메탄올의 선택도는 낮아지고 이산화탄소의 선택도는 증가하였다. 졸-겔법으로 제조한 촉매가 공침법으로 제조한 촉매보다 약 $20^{\circ}C$ 정도 더 낮은 온도에서 더 높은 메탄올 선택도(13%)를 보였다. 두 방법으로 제조한 촉매의 XRD 분석 결과 두 촉매의 결정 구조가 서로 달랐다. 본 반응에서 압력이 증가할수록 완전산화 반응이 억제되고 부분산화 반응이 일어나서 메탄올의 선택도는 증가하였고 이산화탄소의 선택도는 감소하였다.

• 한국생물공학회:학술대회논문집
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• 한국생물공학회 2003년도 생물공학의 동향(XII)
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• pp.116-120
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• 2003

Type strain, Methylosinus trichosporium OB3b, was used to convert methane to methanol. To prevent further oxidation of methanol, NaCl and EDTA were used as inhibitors of methanol dehydrogenase. The reaction temperature was $25^{\circ}C$, and the concentrations of cell and sodium formate added to the reaction mixture were 0.6 mg dry cell wt/ml and 20 mM, respectively. During 12hr reaction, 8 mM methanol was accumulated in the reaction mixture. In this reaction $K_m$ and $V_{max}$ values were found to be 532.6 mM and 1.749 mmol/hr, respectively, and the conversion rate was approximately 37%. To increase the concentration of methanol in the medium, a repeated batch reaction was carried out. In this process, methane was injected every eight hours, and the produced methanol concentration was 18 mM.

• 한국응용과학기술학회지
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• 제31권3호
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• pp.446-452
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• 2014

Methanol was directly produced by the partial oxidation of methane with four-component mixed oxide catalysts. Four-component(Mo-Bi-Cr-Si) mixed oxide catalysts were prepared by the co-precipitation and sol-gel methods. The catalyst prepared by the sol-gel method showed about eleven times higher surface area than that prepared by the co-precipitation method. From the $O_2$-TPD experiment of the prepared catalysts, it was proven that there exists two types of oxygen species, and the oxygen species that participates in the partial oxidation reaction is the lattice oxygen desorbing around $750^{\circ}C$. The optimum reaction condition for methanol production was $420^{\circ}C$, 50 bar, flow rate of 115 mL/min, and $CH_4/O_2$ ratio of 10/1.5, providing methane conversion and methanol selectivity of 3.2 and 26.7%, respectively.

• 한국대기환경학회지
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• 제11권1호
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• pp.77-84
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• 1995

To prevent or reduce air pollutant from methanol fueled vehicles, methanol oxidation reaction was carried out using a heteropoly acid catalysts. Catalytic activities of catalysts have been experimented at atmospheric pressure in a fixed bed flow reactor. Catalysts were characterized by XRD, IR, thermal analysis, N $H_{3}$-TPD and GC pulse technique. Acidities of catalysts were highly affected by poly-atoms. Methanol conversion was much higher on catalyst with W than on catalyst with Mo as a poly-atoms. With the increase of copper content(X) in C $u_{x}$ $H_{{3-2x}}$PMo catalyst, acidity was decreased and oxidation ability was increased. Methanol conversion and product distribution were affected by the acidity and oxidation ability of catalyst. Especially, supported PdSiW(1wt%) catalyst has a very good methanol conversion and C $O_{2}$ selectivity as high as a commertial 3-way catalyst.t.

• 한국대기환경학회지
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• 제20권4호
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• pp.515-521
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• 2004

The catalytic oxidation of volatile organic compounds (methanol. acetaldehyde) has been characterized using the copper phthalocyanine catalyst in a fixed bed flow reactor under atmospheric pressure. The catalytic activity for pretreatment conditions was examined by this reaction system. The catalytic activity was ordered as follows: metal free-PC＜Cu ($\alpha$)-PC＜Cu ($\beta$)-PC The formaldehyde, carbon monoxide as a partial oxidation product of methanol and acetaldehyde over Cu ($\alpha$)-PC catalyst were detected and the conversions of methanol and acetaldehyde were accomplished above 95% over Cu ($\alpha$) -PC, Cu ($\beta$) - PC catalyst at 35$0^{\circ}C$. The pretreated metal free -PC, Cu($\alpha$)-PC, Cu($\beta$)-PC catalysts have been characterised by TGA, EA and XRD analysis. The catalytic activity pretreated with air and $CH_3$OH mixture (P-4) or air only (P-5) was very excellent. XRD and EA results showed that Cu($\alpha$)-PC, Cu($\beta$)-PC were destroyed an(1 new metal oxide such as CuO were formed.

• 대한화학회지
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• 제58권1호
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• pp.76-79
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• 2014

Petroleum refinery effluents are waste originating from industries primarily engaged in refining crude oil. It is a very complex compound of various oily wastes, water, heavy metals and so on. Conventional processes are unable to effectively remove the chemical oxygen demand (COD) of petroleum refinery effluents. Supercritical water oxidation (SCWO) was proposed to treat petroleum refinery effluents. In this paper, methanol was used to investigate co-oxidative effect of methanol on petroleum refinery effluents treatment. The results indicated that supercritical water oxidation is an effective process for petroleum refinery effluents treatment. Adding methanol caused an increase in COD removal. When reaction temperature is $440^{\circ}C$, residence time is 20 min, OE is 0.5 and initial COD is 40000 mg/L, and COD removal increases 8.5%.