Catalytic dehydrogenation of ethylbenzene with carbon dioxide: promotional effect of antimony in supported vanadium–antimony oxide catalyst

Alumina-supported vanadium oxide, VO_x/Al₂O₃, and binary vanadium–antimony oxides, VSbO_x/Al₂O₃, have been tested in the ethylbenzene dehydrogenation with carbon dioxide and characterized by S_BET, X-ray diffraction, X-ray photoelectron spectroscopy, hydrogen temperature-programmed reduction and CO₂ pulse methods. VSbO_x/Al₂O₃ exhibited enhanced catalytic activity and especially on-stream stability compared to VO_x/Al₂O₃ catalyst. Incorporation of antimony into VO_x/Al₂O₃ increased dispersion of active VO_x species, enhanced redox properties of the systems and formed a new mixed vanadium–antimony oxide phase in the most catalytically efficient V_0.43Sb_0.57O_x/Al₂O₃ system.     

以杂多酸为催化剂合成乙二醇-乙醚的研究

研究了杂多酸催化无水乙醇和环氧乙烷(EO)制备乙醇乙醚的醚化反应,考察了不同种类的杂多酸以及醚化反应工艺条件对反应活性和选择性的影响.结果表明,PW_(12)催化剂的反应活性高、反应温度低、选择性好,当用PW_(12)作催化剂,乙醇与环氧化乙烷之比为3.0(mol),反应温度45℃,反应时间1h时,转化率和选择性均超过97%.     

Analysis of XANES for identification of highly dispersed transition metal oxides on supports

XANES of vanadium and niobium oxide on silica or alumina have been analyzed quantitatively by a deconvolution technique. Based on the results for reference compounds, local structures of supported vanadium and niobium species were identified. The composition was estimated from difference spectra for the samples which consisted of two kinds of species.     

A FT-IR assessment of iso-C4H8 reactivity with V2O5/TiO2 catalysts

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.     

铜基催化剂孔隙率对气体有效扩散系数的影响

研究了18种具有不同孔结构参数的粒状铜基甲醇合成催化剂孔隙率对有效扩散系数的影响。结果发现，催化剂微孔孔隙率增大，曲节因子亦增大，扩散阻力增加。将孔隙率与催化剂曲节因子关联，得到了半经验方程，用它可估算催化剂的曲节因子。     

Catalyst instabilities during the liquid phase partial oxidation of methane

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.     

Catalytic wet air oxidation of butyric acid solutions using carbon-supported iridium catalysts

Aqueous solutions of butyric acid were treated by catalytic wet air oxidation using carbon-supported iridium catalysts in a stirred reactor. Under the operating conditions of 6.9 bar of oxygen partial pressure and 200 °C of temperature, conversions up to 52.9% after 2 h were obtained depending on the type of catalyst used. The effects of butyric acid initial concentration, loading of catalyst, oxygen partial pressure and temperature were investigated and the empirical rate law for acid conversion is presented. Oxidation intermediates such as propionic and acetic acid were identified. The heterogeneous catalyzed free-radical oxidation of butyric acid is discussed.     

Preparation and characterisation of vanadium catalysts supported over alumina-pillared clays

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.     

The hydrogenation of triglycerides using supported alloy catalysts. I. Silica-supported Ni—Ag catalysts

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.     

Synthesis of p‐aminophenol from the hydrogenation of nitrobenzene over metal–solid acid bifunctional catalyst

BACKGROUND: A single‐step conversion of nitrobenzene (NB) to p‐aminophenol (PAP) through catalytic hydrogenation is a widely used synthesis route for PAP. The main shortcoming of this route is the use of sulfuric acid for rearrangement of the phenylhydroxylamine (PHA) intermediate. In this paper, S₂O₈^2?/ZrO₂ (PSZ) solid acid and Pt‐S₂O₈^2?/ZrO₂ (Pt‐PSZ) bifunctional catalysts were prepared for the synthesis of PAP in non‐acid medium. RESULTS: Calcination temperature has a substantial effect on the acidity, structure and activity for PHA rearrangement of PSZ. The highest PAP yield was 33.8% over PSZ calcined at 823 K when the reaction was carried out in water at 423 K. A high PAP yield of 23.9% was achieved by a single‐step reaction of nitrobenzene over Pt‐PSZ bifunctional catalysts. CONCLUSION: PSZ solid acid exhibits high activity for PHA rearrangement. Perfect tetragonal ZrO₂ and much stronger acid sites play important roles in catalytic activity. Inhibiting the hydrogenation activity by reducing the amount of Pt loading on Pt‐PSZ can improve the competition of PHA rearrangement on acid sites with hydrogenation of PHA on metal active sites, resulting in better selectivity to PAP. Copyright © 2008 Society of Chemical Industry