• Applied Chemistry for Engineering
• /
• v.35 no.2
• /
• pp.79-84
• /
• 2024

Methane is an abundant and renewable hydrocarbon, but it causes global warming as a greenhouse gas. Therefore, methods to convert methane into useful chemicals or energy sources are needed. Methanol is a simple and abundant chemical that can be synthesized by the partial oxidation of methane. Methanol can be used as a chemical feedstock or a transportation fuel, as well as a fuel for low-temperature fuel cells. However, the electrochemical oxidation of methanol is a complex and multi-step reaction. To understand and optimize this reaction, new electrocatalysts and reaction mechanisms are required. This review discusses the methanol oxidation reaction mechanism, recent research trends, and future research directions.

• Journal of the Korean Applied Science and Technology
• /
• v.22 no.1
• /
• pp.56-61
• /
• 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.

• Transactions of the Korean hydrogen and new energy society
• /
• v.13 no.2
• /
• pp.119-126
• /
• 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
• /
• v.13 no.3
• /
• pp.354-361
• /
• 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
• /
• v.50 no.1
• /
• pp.41-49
• /
• 2012

This study was aimed at the development of catalysts for the direct methanol synthesis by partial oxidation of methane. Mo-Bi-V-Al mixed oxide catalysts were prepared and characterized and used in the direct methanol synthesis reaction. The catalysts prepared by the sol-gel method had much larger surface areas than those prepared by the co-precipitation method. The larger the surface area was, the less the methanol selectivity was. The catalysts having larger surface area facilitate the complete oxidation of methane, decreasing the selectivity of methanol. The catalysts prepared by the sol-gel method showed higher methanol selectivity of 13% at $20^{\circ}C$ lower temperature than those prepared by the co-precipitation method. Through XRD analysis, it was revealed that the structures of the catalysts prepared by the two methods were different. In the reaction, methanol selectivity increased and carbon dioxide selectivity decreased with pressure due to the suppression of complete oxidation reaction at a high pressure.

• 한국생물공학회:학술대회논문집
• /
• 2003.04a
• /
• pp.116-120
• /
• 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.

• Journal of the Korean Applied Science and Technology
• /
• v.31 no.3
• /
• pp.446-452
• /
• 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.

• Journal of Korean Society for Atmospheric Environment
• /
• v.11 no.1
• /
• pp.77-84
• /
• 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.

• Journal of Korean Society for Atmospheric Environment
• /
• v.20 no.4
• /
• pp.515-521
• /
• 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.

• Journal of the Korean Chemical Society
• /
• v.58 no.1
• /
• pp.76-79
• /
• 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%.