Alumina-supported vanadium oxide, VOx/Al2O3, and binary vanadium–antimony oxides, VSbOx/Al2O3, have been tested in the ethylbenzene dehydrogenation with carbon dioxide and characterized by SBET, X-ray diffraction, X-ray photoelectron spectroscopy, hydrogen temperature-programmed reduction and CO2 pulse methods. VSbOx/Al2O3 exhibited enhanced catalytic activity and especially on-stream stability compared to VOx/Al2O3 catalyst. Incorporation of antimony into VOx/Al2O3 increased dispersion of active VOx species, enhanced redox properties of the systems and formed a new mixed vanadium–antimony oxide phase in the most catalytically efficient V0.43Sb0.57Ox/Al2O3 system. 相似文献
Low-loaded vanadia-titania catalysts have been prepared by impregnation of titania P-25 (Degussa). The catalysts were characterized by X-ray diffraction, specific surface area and porosity assessment by nitrogen adsorption at 77 K. For very low vanadia contents the absence of surface acid Brønsted sites leads to dimerization on surface acid Lewis sites, whereas the presence of surface acid Bransted sites when the vanadia content is increased leads to oxidation to carbonyl and carboxylate species. 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
Supported vanadium-containing catalysts were prepared by impregnation of Al-pillared clays with NaVO3 precursor aqueous solutions. A montmorillonite and a saponite, both natural as well as previously pillared with Al13-Keggin polycations, were used as supports, being impregnated with solutions of the precursor by means of the incipient wetness technique. The layered structure of the supports is maintained after impregnation, and even after calcination of the impregnated solids at 500 °C, although with a significant worsening of the textural properties of the solids, in particular, a loss of specific surface area. Three crystalline vanadium-containing phases were identified in the impregnated solids, namely, NaV3O8, AlVO4 and V2O5 (shcherbinaite). The reduction of these phases to V3+ species was observed as wide processes in the 450–750 °C range, all of them centred at ca. 600 °C. 相似文献
Silica-supported Ni-Ag catalysts with a loading of 2·1·0.6% (w/w) total metal have been prepared using the precursors nickel dimethylglyoxime and silver nitrate by means of a simple impregnation method. The resulting catalysts were activated by calcination at 260°C in air, followed by hydrogen reduction at 450°C. They were then employed for soyabean oil hydrogenation at 1 bar H2 pressure and 160°C in a stirred batch reactor. Characterisation of the catalysts using temperature-programmed reduction and electron microscopy indicated that alloying of nickel and silver had occurred, but metal particle composition, for a given overall composition, varied with metal particle size and smaller metal particles were nickel rich. The hydrogenation activity and selectivity measurements revealed that the catalysts were more active and selective than a commercial nickel catalyst. Furthermore, the specific activities of the alloy catalysts were a maximum for alloys in the range 70–90 at. % Ni. However, the supported alloy catalysts also gave rise to greater trans isomerisation than the commercial catalyst. This is attributed to hydrogen deficiency caused by large triglyceride molecules blocking hydrogen chemisorption on small nickel particles (10–50 Å in diameter), leading to enhanced cis-trans isomerisation. 相似文献
Pt catalysts supported on a carbon aerogel with different Pt particle sizes were studied in the combustion of o-xylene and m-xylene. Results found show that the activity of the catalysts increased with larger Pt particle size. In addition, the catalysts were activated during consecutive combustion runs and during time on stream. This activation depends on the Pt particle size and type of xylene isomer. Activation was due to the increase in Pt particle size during reaction. The lower activity of catalysts with smaller Pt particle size was due to the stronger PtO bonds formed during xylene combustion by the smaller Pt particles. 相似文献
The oxidative dehydrogenation of ethane is carried out in short contact time reactors over Pt and LaMnO3 based catalysts supported on a large number of different ceramic substrates (45, 60 and 80 ppi foam monoliths and 200, 400, 600, 900 and 1200 cpsi honeycomb monoliths). Experimental results, obtained under the same conditions at varying the C2H6/O2 ratio, showed that the highest performance in terms of ethylene selectivity and yield is always attained on LaMnO3 catalysts. Furthermore, the results are significantly influenced by the morphology and cell density of the support, with 45 and 60 ppi foams and 400 and 600 cpsi honeycombs giving the best performance. The experimental results are explained by means of geometrical and fluid dynamic considerations on the support, and by means of a 2D mathematical model, which clearly indicates an optimal intermediate cell density for maximising ethylene selectivity and yield. 相似文献