A promising catalytic system for the low temperature oxidation of methane to a methanol derivative has been investigated under both batch and semi-continuous operation in two different reactor types. The system comprises of a bimetallic palladium and copper(II) chloride catalyst contained in a trifluoroacetic acid (TFA) and an aqueous phase. Methane, oxygen and a co-reductant carbon monoxide constitute the gas phase. Typical operating conditions were a temperature of 85 °C and a pressure of 83 bar.
The yields of the methyl trifluoroacetate product observed in this present work were less than those obtained in other batch autoclave works, which employed only 4 ml of liquid phase, compared with 50 ml in this study. Furthermore, an encouraging initial product formation rate of ca. 40 mol/m3 h, quickly decreased after the first hour, and came to an apparent end after only 2 h. This observation had not been reported previously.
Work performed in a semi-continuous porous tube reactor (300 ml of re-circulating liquid phase) also showed the same reaction characteristics as in the batch reactor. Thus, the deteriorating product formation rate cannot be attributed to gaseous reactant depletion (batch operation). The results suggest problems associated with catalyst instabilities, e.g. with the previously elucidated Wacker chemistry. 相似文献
Manganese oxides having a tunnel structure (OMS-2) have been utilized as selective catalysts for alcohol oxidation. In this study manganese oxide catalysts were synthesized in different media and modified by exchanging the tunnel cation by H+, using acid treatment or exchanging with NH4+ followed by thermolysis. Various alcohol oxidations were performed using these catalysts to ascertain the influence of synthesis method on their activity. A correlation is made between lattice oxygen instability and activity of the catalysts, which indicates involvement of the lattice oxygen in the mechanism. The exchange of the tunnel cation with the smaller H+ ions leads to weakening of the Mn–O bond, as verified by temperature programmed desorption (TPD) results. Only the chemisorbed oxygen on the surface (O−) and the lattice oxygen in the layers close to the surface is involved in the oxygen transfer during the reaction. 相似文献
Liquid-phase oxidation of cyclohexane with Co(III) catalyst and gaseous oxygen was found to be influenced by reaction temperature, catalyst concentration and the duration. Maximum adipic acid product selectivity (77%) with about 85% cyclohexane conversion was attained at 100°C using catalyst: cyclohexane molar ratio 0·08. Under these conditions more than 80% cyclohexane was converted in the first hour, although selectivity to adipic acid continued to increase for the next 5 h. Cyclohexyl acetate and cyclohexyl monoadipate were identified as important intermediates. This study supports the mechanism proposed by Schultz, J. G. D. and Opchenko, A., J. Org. Chem., 38 (21) (1973) 3729. 相似文献
At high temperatures in clean oxidizing environments, SiC forms a very protective SiO2 film, but, in environments containing low levels of gaseous alkali salt contaminants or where condensed salts may deposit on the surface, the resistance of the film is significantly reduced. Oxidation kinetics of SiC were measured by continuous thermogravimetric analysis in a controlled environment containing CO2, H2O, and O2 plus low levels of potassium-containing salts. Potassium was found to be incorporated into the SiO2 scale and to significantly change its transport properties and its morphology. The rate of scale formation was found to increase directly in proportion to K in the scale. A change in mechanism was observed when water vapor was added to the reacting gas stream. 相似文献
We developed a process to obtain sharper silicon tips by employing anisotropic etching in a KOH solution followed by SF6 plasma etch. The tips were further sharpened using the established thermal oxidation technique to decrease the cone angle and, therefore, obtain smaller curvature radii. We have analyzed the impact of such changes in geometry on a figure of merit associated with the field emission characteristics. An increase in the figure of merit by a factor of three was found in relation to the tips before sharpening. 相似文献
The catalyst behaviour of titanium silicalite, which was found the most active and selective catalyst for liquid-phase ammoximation of cyclohexanone to the corresponding oxime with hydrogen peroxide, was investigated in the gas-phase ammoximation with molecular oxygen in and compared with those of pure silicalite and samples of vanadium and chromium silicalites. The results showed that Ti-silicalite is a selective catalyst not only in the reaction with hydrogen peroxide but also in the reaction with molecular oxygen. However, a big limitation was found in the poor activity of the silicalites which do not allow to reach high oxime yields. 相似文献
Low carbon steel was oxidized over the temperature range 1000‐1250°C in O2‐CO2‐H2O‐N2, O2‐H2O‐N2, and O2‐CO2‐N2 gas mixtures. Oxidation times were 12‐120 min. and the scales were 50‐2000 μm thick. The variations of these parameters were chosen to elucidate the phase composition of oxide scales under conditions similar to those of reheating furnaces in hot strip mills, using either thin slab casting or conventional casting and rolling technology. Two types of scales have been observed which are influenced by the furnace atmosphere, oxidation time, and temperature. The first type is a crystalline scale with an irregular outer surface, composed mostly of wustite (FeO), and a negligible amount of magnetite (Fe3O4). The second type is the classical three‐layer scale, composed of wustite (FeO), magnetite (Fe3O4), and hematite (Fe2O3). In general, the experiments showed that an increase in oxidation time decreased the percentage of wustite while the percentages of magnetite and hematite increased. A rise in oxygen concentration in the gas mixture increased the percentages of magnetite and hematite, confirming earlier experimental findings. In water vapour‐free atmospheres O2‐CO2‐N2, the oxide scales had a low percentage of wustite, and high percentage of magnetite and hematite. Carbon dioxide showed a small influence at 1100°C, and a negligible one at 1250°C. 相似文献
The role of gas phase CH3 radicals in the oxidative coupling of CH4 over 1 wt% Sr/La2O3 is supported by the observations that (i) this is a very effective catalyst for the generation of CH3 · radicals and (ii) the concentration of CH3 · radicals increases with temperature over the range of 450 °C–800 °C. 相似文献