The influence of metal particle size of monometallic and bimetallic supported catalysts (Au, Pd, Au–Pd)/C was studied using
as a model reaction the liquid phase oxidation of glycerol. By tuning the metal particle size from 2 to 16 nm a progressive
decrease of activity and simultaneously an increase in the selectivity to sodium glycerate was observed. Moreover, the influence
of the temperature was studied and it was found that by increasing the temperature, only with a large particle size the formed
glycerate was retained and not over-oxidized to tartronate. 相似文献
This study deals with the development of a laboratory bench for the practical evaluation of catalysts that are useful for the direct conversion of NOx and soot in the exhaust of diesel engines. The employed model exhaust is generated by using a diffusion burner with additionally dosing some gaseous components to the burner gas to obtain a realistic feed composition. The produced soot is extensively characterized by employing thermogravimetry, transmission electron microscopy, N2 physisorption and temperature programmed techniques. The results of the different characterization methods show that the present soot is suitable for the intended catalytic investigations. The simultaneous conversion of NOx and soot is examined like in practice, i.e. the soot is separated from the tail gas by a diesel particulate filter (DPF) that is coated with the catalyst. The deposited soot is then catalytically converted by NOx and O2 to form N2 and CO2. The conversions of NOx and soot are measured by exclusively applying gas analysers, whereby a special experimental procedure is developed to determine the soot removal. Hence, additional soot related analytics are not required. To show the suitability of the constructed bench a Pt/Fe2O3/β-zeolite sample is taken as test catalyst that is reported to be very active in NOx/soot reaction. The measurements performed with and without catalyst clearly show the effect of the used sample in simultaneous NOx/soot conversion. We therefore consider the constructed laboratory bench to be a useful tool for testing and ranking catalytic materials. 相似文献
The formation of a low Cr-volatility and electrically conductive oxide outer layer atop an inner chromia layer via thermal oxidation is highly desirable for preventing chromium evaporation from solid oxide fuel cell (SOFC) metallic interconnects at the SOFC operation temperatures. In this paper, a number of ferritic Fe–22Cr alloys with different levels of Mn and Ti as well as a Ni-based alloy Haynes 242 were cyclically oxidized in air at 800 °C for twenty 100-h cycles. No oxide scale spallation was observed during thermal cycling for any of these alloys. A mixed Mn2O3/TiO2 surface layer and/or a (Mn, Cr)3O4 spinel outer layer atop a Cr2O3 inner layer was formed for the Fe–22Cr series alloys, while an NiO outer layer with a Cr2O3 inner layer was developed for Haynes 242 after cyclic oxidation. For the Fe–22Cr series alloys, the effects of Mn and Ti contents as well as alloy purity on the oxidation resistance and scale area specific resistance were evaluated. The performance of the ferritic alloys was compared with that of Haynes 242. The mismatch in thermal expansion coefficient between the different layers in the oxide scale was identified as a potential concern for these otherwise promising alloys. 相似文献
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