Synthesis of higher alcohols with cobalt and copper based model catalysts: effect of the alkaline metals

The synthesis of higher alcohols, obtained from CO hydrogenation over transition metals, is an alternative for the production of chemical commodities and less pollutant renewable fuels nowadays. In this work, the influence of different alkali metals (Li, Na, K, Cs) over the formation of active phases of supported catalysts, based on cobalt and copper, as well as the performance of these solids in the reaction of CO hydrogenation under a 50 bar pressure were studied. The solids were prepared by continuous coprecipitation of sodium carbonate with metal nitrate solutions (Al–Co, Al–Cu or Al–Co–Cu) promoted with the alkali metals with dry impregnation. Characterization studies by atomic absorption spectrophotometry, BET, XPS and also the results of catalytic tests show that physico-chemical properties of the obtained catalyst are similar to those of the industrial catalyst used as reference (I).     

Dynamic methods and new reactors for liquid phase molecular catalysis

Kinetic data acquisition and screening of transition metal complexes for homogeneous liquid phase catalysis calls for numerous testing in multiphase G/L, L/L and G/L/L systems. It is shown first, with an example in asymmetric hydrogenation, why detailed kinetics must be performed. Then, new reactors leading to fast experimental techniques are proposed. A liquid–liquid centrifugal partition chromatography is evaluated for determining rate constants and partition isotherms by combining frontal analysis and elution chromatography, the catalyst being maintained in a stationary aqueous phase. Two microreactors offering short residence time have also been tested and compared with a fast test reaction (t_R ca. 5–20 s). The combination of reacting pulses, carrier liquids and micromixer is proposed as a general high throughput tool for the investigation of G/L, L/L and G/L/L catalytic systems in a fast sequential way.     

Effect of the support in Pt and PtSn catalysts used for selective hydrogenation of carvone

In this paper, a study on the hydrogenation of carvone by using Pt/Al₂O₃, PtSn/Al₂O₃, PtGe/Al₂O₃, Pt/C and PtSn/C is reported. TPR, H₂ chemisorption, XPS and test reaction results show that the addition of a second metal to Pt leads to important modifications of the structure of the metallic phase, though these modifications are different according to the nature of the support (Al₂O₃ or C). The activity and selectivity of these catalysts in carvone hydrogenation depend not only on the composition of the metallic phase, but also on the nature of the support. Thus, adding Sn or Ge to Pt/Al₂O₃ enhances the selectivity to unsaturated ketones (at a fixed carvone conversion, X_carv=1). When Pt is supported on activated carbon, small amounts of unsaturated alcohols are observed. The Sn addition to Pt/C sharply enhances the selectivity to carveol formation (the doubly unsaturated alcohol) reaching values close to 100% at the initial stages of the reaction.     

Organo-zincate molten salts as immobilising agents for organometallic catalysis

The combination of 1-n-butyl-3-methylimidazolium chloride with ZnCl₂ affords ionic mixtures with different melting point temperatures depending on the zinc molar fraction. RuCl₂(PPh₃)₃ immobilised in the low melting mixture (60°C) promotes the 1-hexene hydrogenation (turnover frequencies up to 44 min^–1) and the recovered solid catalyst phase can be reused several times.     

Long-Chain-Amine Metal Complexes as Hydrogenation Catalysts. Heterogenisation on Activated Carbon

The catalytic activity of [PdCl₂(NH₂(CH₂)₁₂CH₃)₂] (named [Pd(TDA)]) and [RhCl(NH₂(CH₂)₁₂CH₃)₃] (named [Rh(TDA)]) complexes for the hydrogenation of cyclohexene has been analysed both in homogeneous phase and heterogenised on activated carbon. The [Rh(TDA)] complex has been found to be more active than the [Pd(TDA)], both homogeneous and heterogenised. Experimental and modelled results indicate that these complexes follow a similar reaction mechanism, but with different rates. A clear positive effect of the carbon support has been found in the case of the complex [Rh(TDA)], which has been related to the anchorage of the aliphatic chains of the amine ligands on the activated carbon pores. Experiments in consecutive catalytic runs show that the heterogenised complexes can be used several times giving an acceptable conversion level.     

Oxygen Storage Behavior of Ceria–Zirconia-Based Catalysts in the Presence of SO2

This paper investigates the effect of the presence of SO₂ in the dynamics of oxygen storage on ceria and ceria–zirconia. The introduction of SO₂ under reaction conditions at T<873 K negatively affects CO conversion under oscillating conditions on all the supports studied, owing to the formation of sulfate species. Deactivation is observed on all supports and activity is recovered only after desorption of SO₂, which occurs at 950<T<1000 K, depending on catalyst composition (Ce/Zr ratio) and treatment atmosphere. The amount of sulfur adsorbed is higher over solid solutions, reaching a maximum with Ce _x Zr_1–x O₂ (0.5<x<0.68). However this does not adversely affect activity compared to ceria. In the presence of Rh and Pd, reactivation is favored under reaction conditions. More generally, it appears that the removal of sulfates is facilitated in reductive atmospheres (both hydrogen and CO) over mixed oxides. No differences are observed following regeneration under oxidizing conditions.     

浅析液化石油气钢瓶发生爆炸的原因及火灾扑救技术

介绍了钢瓶的结构及性能指标 ,论述了钢瓶发生爆炸的条件和原因 ,总结出扑救战术     

Computer Simulation of Dissociative Adsorption of Water on the Surfaces of Spinel MgAl2O4

Atomistic simulation techniques have been used to model the dissociative adsorption of water onto the low-index {100}, {110}, and {111} surfaces of spinel MgAl₂O₄. The Born model of solids and the shell model for oxygen polarization have been used. The resulting structures and chemical bonding on the clean and hydrated surfaces are described. The calculations show that the dissociative adsorption of water on the low-index surfaces is generally energetically favorable. For the {110} and {111} orientations, the surfaces cleaved between oxygen layers show high absorption and stability. The calculations also show that, for the {111} orientation, the surfaces may absorb chemically water molecules up to ∼90% coverage and have the highest stability. It is suggested that, during fracture, only partial hydration occurs, leading to cleavage preferentially along the {100} orientation.     

Grain-Size Effect on Compressive Creep of Silicon-Carbide-Whisker-Reinforced Aluminum Oxide

The steady-state compressive creep of Al₂O₃ with 10 vol% SiC whiskers having grain sizes of 1.2, 2.3, and 4.0 μm has been measured at 1400°C in argon. The creep rate is related to the free volume within the whisker network, not the nominal grain size. The results are consistent with diffusional-controlled creep with different contributions from grain-boundary sliding. Under low stresses, only Liftshitz sliding is possible and the diffusional process controls deformation, while at stresses over a threshold, Rachinger sliding is the mechanism controlling deformation. The evolution between Liftshitz and Rachinger sliding is marked by a significant increase in the value of the stress exponent.