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
The understanding of the permeation rate of metal ions through liquid membranes is important for the design of such systems. In this paper, the permeation rates of copper ions through liquid surfactant membranes, including interfacial reaction rates and the diffusion rate of the copper ion, were analyzed using a model based on a mobilized hollow spherical globule configuration. The analysis shows that the extracting reaction is dominant at the external interface of the membrane and the stripping reaction is dominant at the internal interface; this means the reactions at both interfaces are not in equilibrium during the course of extraction. It also shows that the extraction rate, the diffusion rate and the stripping rate are not of equal value, especially at the early stage of the run. 相似文献
Barium copper oxalate was grown in silica hydrogel at ambient temperature. The effect of various parameters like gel pH, gel
density, gel aging and concentrations of reactants on the growth of these crystals was studied. The crystals grown were characterized
by chemical analysis, X-ray powder diffractometry, infrared spectroscopy, thermogravimetric and differential thermal analysis.
The results of these observations are described and discussed. 相似文献
When freshly etched samples of various types of copper were exposed in moderately acid, aerated chloride solutions, two phenomena were observed. First the corrosion potential and the pH of the solution decreased over a shorter time, then the potential increased over a long period (600-1500 min), following an s-shaped pattern. Increase in pH during the second stage was avoided using a pH-stat. The corrosion rate increased little or not at all over the entire period. A tentative interpretation of the short-term behaviour is presented with some reservation. The long-term development of the potential suggests phase formation or transformation following the Avrami pattern. By suitable derivations it was possible to fit the development of potentials to the Avrami equation. Subsequent examinations by Auger spectroscopy proved the presence of thin layers of Cu2O on the copper surfaces, increasing in thickness with exposure time. The dissolution kinetics can be described in terms of two parallel electrochemical reactions and a simultaneous non-electrochemical dissolution reaction. 相似文献