Carbon supports for dispersed platinum (Pt) electrocatalysts in direct methanol fuel cells (DMFCs) are being continuously developed to improve electrochemical performance and catalyst stability. However, carbon supports still require solutions to reduce costs and improve catalyst efficiency. In this study, we prepare well-dispersed Pt electrocatalysts by introducing titanium dioxide (TiO2) into biomass based nitrogen-doped carbon supports. In order to obtain optimized electrochemical performance, different amounts of TiO2 component are controlled by three types (Pt/TNC-2 wt%, Pt/TNC-4 wt%, and Pt/TNC-6 wt%). Especially, the anodic current density of Pt/TNC-4 wt% is 707.0 mA g−1 pt, which is about 1.65 times higher than that of commercial Pt/C (429.1 mA g−1 pt); Pt/TNC-4wt% also exhibits excellent catalytic stability, with a retention rate of 91 %. This novel support provides electrochemical performance improvement including several advantages of improved anodic current density and catalyst stability due to the well-dispersed Pt nanoparticles on the support by the introduction of TiO2 component and nitrogen doping in carbon. Therefore, Pt/TNC-4 wt% may be electrocatalyst a promising catalyst as an anode for high-performance DMFCs.

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 O2-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℃. The optimum reaction condition for methanol production was 420°C, 50 bar, flow rate of 115 mL/min, and CH4/O2 ratio of 10/1.5, providing methane conversion and methanol selectivity of 3.2 and 26.7%, respectively.

페롭스카이트 촉매와 Mo, Bi를 기본으로 하는 복합 산화물 촉매를 이용하여 천연가스의 주성분인 메탄의 부분산화를 통하여 메탄올을 직접 합성하였다. 페롭스카이트(ABO₃) 촉매는 A 및 B site 성분을 변화시키면서 사과산법으로 제조하였으며, Mo, Bi를 기본으로 하는 3성분계 복합 산화물 촉매는 공침법으로 제조하여 반응특성을 살펴보았다. 페롭스카이트 촉매에서 A site에 알칼리 금속인 Sr을, B site에 전이금속인 Cr을 도입한 SrCrO₃ 촉매가 400℃에서 메탄올 선택도 11%로 가장 우수한 결과를 보였다. Mo, Bi를 기본으로 하는 3성분계 복합 산화물 촉매의 경우 모든 촉매에서 메탄 전환율에는 큰 차이를 보이지 않았으며, Cr을 첨가한 Mo-Bi-Cr 복합 산화물 촉매가 400℃에서 메탄올 선택도 15.3% 로 가장 우수한 결과를 나타냈다. 3성분계 복합 산화물 촉매에서 촉매의 활성과 메탄올 선택도는 촉매의 표면적에 정비례하였다.

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℃.

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℃.

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.

Liquid-phase methanol synthesis via methyl formate using coal-derived syngas was carried out in a bench-scale(diameter 173 mm and dispersion height 1200 mm) slurry bubble column reactor(SBCR) Under the condition of 180˚. 61 atm, 30 L/min, H2/CO=2 and a slurry mixture of 2 kg of copper chromite and 0.5 kg of KOCH3 suspended in 14 L of methanol, the per pass conversions of syngas is 6 %, maximum concentration of methyl formate 3.088 mol% and maximum synthesis, rate of methanol 0.8 gmole/kg · hr. It is a significant evidence that copper chromite powder as heterogeneous catalyst didn't active for the hydrogenolysis of methyl formate to methanol, resulting copper chromite powder was not efficiently suspended in a slurry mixture. To enhance the hydrogenolysis of methyl formate in liquid-phase methanol synthesis process, the designed SBCR have need to use the higher specific gravity solvent and/or decrease the catalyst particle size.

본 연구는 SAPO-34 결정골격에 도입된 Fe(III)의 메탄올 전환성능에 미치는 영향에 중점을 두었다. 신속결정화법에 의해 높은 결정화도, 좁은 입자 분포도를 갖는 결정(FeAPSO-34; Si/Fe=40,20,5)들이 얻어졌으며, SRD와 SEM의 결과로부터, 골격에 도입된 Fe양이 증가할수록 결정화도는 감소하고, 그 입자크기도 아울러 감소함이 관찰되었다. 한편, 이들의 산성도는 골격에 도입된 Fe양이 증가할수록 감소하였고, 그 결과 메탄올 전환에 있어서 에틸렌의 선택성이 향상되는 결과를 가져왔다.

Methanol is one of the clean burning fuel with versatile applications. As a combustion fuel, it provides extremely low emissions. Methanol can also be used as a primary transporation fuel or a fuel additive and expecially as a raw metalial for methyl t-butyl ether. Methanol synthesis from synthetic gas was carried out in the Ru-CuO/ZnO/Al2O3 catalytic system. The influence of various factors, such as the reaction temperature, the concentration of ruthenium (Ru) and the reaction pressure was discussed, respectively, and the most preferred condition were obtained. The results showed that metanol synthesis could be prepared from carbon monoxide and hydrogen under reaction conditions. The reaction of Ru-CuO/ZnO/Al2O3 catalyst (E-catalyst) was operated most preferably at 160oC and 40 bar.