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%.     

Synthesizing Energy-Efficient Embedded Systems with LOPOCOS

In this paper, we introduce the LOPOCOS (Low Power Co-synthesis) system, a prototype CAD tool for system level co-design. LOPOCOS targets the design of energy-efficient embedded systems implemented as heterogeneous distributed architectures. In particular, it is designed to solve the specific problems involved in architectures that include dynamic voltage scalable (DVS) processors. The aim of this paper is to demonstrate how LOPOCOS can support the system designer in identifying energy-efficient hardware/software implementations for the desired embedded systems. Hence, highlighting the necessary optimization steps during design space exploration for DVS enable architectures. The optimization steps carried out in LOPOCOS involve component allocation and task/communication mapping as well as scheduling and dynamic voltage scaling. LOPOCOS has the following key features, which contribute to this energy efficiency. During the voltage scaling valuable power profile information of task execution is taken into account, hence, the accuracy of the energy estimation is improved. A combined optimization for scheduling and communication mapping based on genetic algorithm, optimizes simultaneously execution order and communication mapping towards the utilization of the DVS processors and timing behaviour. Furthermore, a separation of task and communication mapping allows a more effective implementation of both task and communication mapping optimizationsteps. Extensive experiments are conducted to demonstrate the efficiency of LOPOCOS. We report up to 38% higher energy reductions compared to previous co-synthesis techniques for DVS systems. The investigations include a real-life example of an optical flow detection algorithm.     

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     

The effect of support morphology on the reaction of oxidative dehydrogenation of ethane to ethylene at short contact times

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.     

Preparation of monodisperse poly(vinyl alcohol) microspheres by heterogeneous surface saponification and iodine complex formation

Monodisperse poly(vinyl acetate) (PVAc) microspheres with high molecular weight obtained by suspension polymerization of vinyl acetate were saponified in alkaline aqueous solution to keep their spherical structure. The saponification was restricted on the surface of the PVAc microspheres and obtained particles had skin/core structure. Various poly(vinyl alcohol) (PVA) microspheres with different diameters and degrees of saponification (DSs) were obtained. The conversion of PVAc to PVA during the heterogeneous surface saponification time were examined by nuclear magnetic resonance spectroscopy and after 72 h hydrogel type PVA microspheres completely saponified were obtained. The crystal melting temperatures of the microspheres obtained by the saponification were measured a constant value of 238°C irrespective of varying DS, and the peaks became enlarged as reaction time. Iodine complexes were formed in saponified microspheres with DS of 41% and 99% by immersing them in I₂/KI aqueous solution and decomposed by the reduction of I₂ in the complexes to 2I^? using sodium sulfite to confirm whether the skin formed through the saponification was composed of PVA with high VA content. Obviously, characteristic blue color developments owing to I₅^?‐PVA complexes were observed in both saponified regions and a red in the PVAc core. Consequently, it was concluded that the PVA skins formed by heterogeneous surface saponification had high DSs. Such complexes endowed polymeric microspheres a good radiopacity which would be useful in clinical treatment of vascular diseases and were examined by X‐ray irradiation image. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Maghnite‐H+, a solid catalyst for the cationic polymerization of α‐methylstyrene

The polymerization of α‐methylstyrene (AMS) catalyzed by Maghnite‐H⁺ (Mag‐H) was investigated. Mag‐H is a montmorillonite sheet silicate clay, exchanged with protons. It was found that the cationic polymerization of AMS is initiated by Mag‐H at ambient temperature in bulk and in solution. The effect of the amount of Mag‐H, the temperature, and the solvent was studied. The polymerization rate increased with increase in the temperature and the proportion of catalyst, and it was larger in nonpolar solvents. These results indicated the cationic nature of the polymerization. It may be suggested that the polymerization is initiated by proton addition to monomer from Mag‐H. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Characterization of supported Pd-Pt catalysts by chemical probes

The temperature programmed (palladium) hydride decomposition appeared very effective method for diagnosing the extent of alloying in Pd-Pt/SiO₂ catalysts. Introduction of Pt to Pd catalysts moves the TPHD peak gradually towards lower temperatures and the shift in hydride decomposition peak is accompanied by a decrease in the amount of released hydrogen. The catalysts prepared the direct redox method showed much better alloy homogeneity than the samples prepared by coimpregnation. The results of probing with other techniques, i.e. catalytic probing with hydrodechlorination of CCl₂F₂ and XRD, were in line with TPHD data. The catalytic probing showed the presence of synergistic effect, a clear indication of Pd-Pt mixing. XRD data of post-reaction samples showed carbon incorporation into Pd-rich phase, whereas separate Pt-rich phase did not experience any bulk carbiding.     

Influence of water and ammonia on hydrotreating catalysts and activity for tetralin hydrogenation

The effects of H₂O and NH₃ on the kinetics of the liquid phase hydrogenation of tetralin to decalin at 6.9 MPa and 330°C over commercial P---Ni---Mo/alumina catalysts in the presence of H₂S have been investigated. H₂O functioned as a mild kinetic inhibitor to an extent sensitive to the H₂S level. Quasi in situ XPS was used to investigate the catalyst structure after exposure to H₂0/H₂S.