Gold-Catalyzed Aerobic Oxidation of Benzyl Alcohol: Effect of Gold Particle Size on Activity and Selectivity in Different Solvents

The effect of the size of gold particles deposited on CeO₂ and TiO₂ supports on their catalytic behavior in the aerobic oxidation of benzyl alcohol in different solvents (mesitylene, toluene, and supercritical carbon dioxide) has been investigated. The size of supported gold particles deposited via a colloidal route was in the range 1.3–11.3 nm, as determined by means of EXAFS and HAADF-STEM measurements. The catalytic performance of the supported gold catalysts in the different solvents revealed a significant effect of the gold particle size. Optimal activity was observed for catalysts with medium particle size (ca. 6.9 nm) whereas smaller and bigger particles showed inferior activity. Identical trends for the activity–particle size relationship were found using Au/CeO₂ and Au/TiO₂ for the reaction at atmospheric pressure in conventional solvents (mesitylene, toluene) as well as under supercritical conditions (scCO₂). Selectivity to benzaldehyde was only weakly affected by the gold particle size and mainly depended on reaction conditions. In supercritical CO₂ (scCO₂) selectivity was higher than in the conventional solvents under atmospheric pressure. All catalysts tested with particle sizes ranging from 1.3 to 11.3 nm showed excellent selectivity of 99% or higher under supercritical conditions.     

Enantioselective interactions at the solid-liquid interface of an HPLC column under working conditions

A technique is presented which allows studying the enantioselective interactions occurring at the solid-liquid interface of a chiral stationary phase (CSP) and a racemate relevant to high performance liquid chromatography (HPLC). A conventional chiral column (Chiralpak AS) was mounted on an attenuated total reflection-infrared (ATR-IR) cell mimicking an HPLC setup equipped with an ATR-IR detector. Racemic pantolactone (PL) was used as the selectand. This setup in combination with modulation excitation spectroscopy (MES) allows for the identification of inter- and intramolecular hydrogen bonds being crucial for enantioseparation under HPLC operation conditions. The method is based on a two step strategy. In a first step, the enantiomers are separated by the chiral column similar to a standard HPLC experiment and upon adsorption on the identical CSP deposited on the internal reflection element (IRE), they are detected by ATR-IR spectroscopy. This experiment provides a retention time for each enantiomer. From the difference in retention, a suitable frequency is calculated which is used in a second experiment where the racemate concentration is varied alternately (modulation) in a way that the pulses of ( R)-PL and ( S)-PL exhibit a phase lag of 90 degrees after elution through the column. This procedure allows one to gain separate information of the enantioselective selectand-CSP interaction after performing a demodulation similar to a phase sensitive detection (PSD). A further benefit of this method is the strong enhancement of the signal-to-noise ratio. The effectiveness of the method is demonstrated by investigating the observed faster decrease in retention time of the later-eluted ( R)-PL, as compared to ( S)-PL, when separating at higher temperatures (from 12 to 36 degrees C). The origin is attributed to a weakening of a specific hydrogen bond between the C=O of ( R)-PL and the N-H of the CSP.     

Catalytic dehydrogenation of iminodibenzyl to iminostilbene. A comparison of potassium-promoted manganese,iron and cobalt oxide catalysts

The dehydrogenation of iminodibenzyl (10,11-dihydro-5-dibenz[b.f]azepine) to iminostilbene (5H-dibenz[b.f]azepine) was investigated over potassium-promoted oxides of manganese, iron and cobalt. Both unsupported oxides as well as corresponding oxides supported on magnesium oxide were examined. Catalytic tests were carried out in a continuous fixed-bed reactor in the presence of steam in the temperature range of 400–550°C and at atmospheric pressure. Unsupported, potassium-promoted iron oxide proved to be the most suitable catalyst for the dehydrogenation of iminodibenzyl, yielding iminostilbene with 80% selectivity at nearly 100% conversion.     

Investigation of a fixed-bed pilot plant reactor by dynamic experimentation. Part 2. Simulation of reactor behaviour

Data collected with forced uncorrelated sinusoidal changes of the process variables are used to simulate the behaviour of a non-isothermal non-adiabatic pilot plant fixed-bed reactor. The test reaction applied is the hydrogenation of toluene to methylcyclohexane on an industrial nickel catalyst. A pseudo-homogeneous two-dimensional model as well as a one-dimensional model are applied to describe the reactor behaviour. The model parameters are estimated by defining an objective function based upon residuals of the discretized differential equations instead of upon deviation from the observed variables. This procedure leads to a drastic reduction of computer expenditure. Measured and simulated temperature and concentration profiles are compared on the basis of a number of plots and fitting quality criteria. The model parameters estimated from data collected during dynamic runs are comparable to those obtained from a series of stationary experiments (2₃ experimental design). However, with the dynamic experiments the data necessary for modelling can be collected much more efficiently.     

Vanadia/silica model catalyst: AFM and XPS investigation of morphological and chemical changes occurring upon exposure to different gas atmospheres

A model vanadia/silica interface has been prepared by vapour deposition of vanadium-oxy-triisopropoxide onto the native oxide layer of a silicon wafer. The VO _x /SiO₂/Si model system has been used to investigate the morphological and chemical changes occurring with vanadia/silica catalysts when they are exposed to different gas atmospheres. Atomic force microscopy and X-ray photoelectron spectroscopy have been used to follow these changes. The studies show that exposure of the vanadia/silica interface to conditions prevailing during the selective reduction of NO by NH₃ results in temperature dependent morphological changes, while the oxidation states of the vanadia species reflected by the ratio V(III)/V(V) change only little during the surface reconstruction.     

Comparative study of synthesis of methylamines from carbon oxides and ammonia over Cu/A12O3

Methylamines have been synthesized from carbon dioxide, hydrogen and ammonia using Cu/Al₂O₃ catalysts with different copper loading. The reaction was performed in a fixed-bed micro reactor in the temperature range 473–573 K and at 0.6 MPa total pressure. The product amines were mono-, di- and trimethylamine (MMA, DMA, TMA). The distribution of the amines depended mainly on the reaction temperature and the NH₃/CO₂ ratio in the feed gas. At elevated temperatures and higher NH₃ concentrations methanol synthesis is suppressed and MMA is the main amine product, reaching a ratio of MMA:DMA:TMA of 1:0.23:0.07. Conversion and product distribution were compared to that of the corresponding reaction starting from CO or methanol instead of CO₂. With CO conversion was lower but the selectivity to MMA was higher. If CO₂ was replaced by methanol, conversion increased and TMA was the main product. In all experiments a change of space velocity had relatively little influence on both conversion and distribution of amines.     

Investigation of a fixed-bed pilot plant reactor by dynamic experimentation. Part 1. Apparatus and experimental results

A non-isothermal, non-adiabatic fixed-bed pilot reactor specially designed for fast measurement of axial and radial temperature and concentration profiles during dynamic experiments is described. The pilot plant is interfaced to a process computer and facilitates conducting different types of dynamic experiments, such as those with simultaneous un-correlated periodic changes of the process variables. This type of dynamic experiments proved to be most efficient for collecting the data necessary for reactor modelling. Axial and radial temperature and concentration profiles in the fixed bed were measured during catalytic hydrogenation of toluene on an industrial nickel catalyst. Peak shaped perturbations were employed to study the parametric sensitivity of the reactor behaviour and to estimate the reaction kinetics.     

Enantioselective hydrogenation of 2-methyl-2-pentenoic acid over cinchonidine-modified Pd/alumina

A chiral alkanoic acid was prepared with up to 52% excess of the (S) enantiomer by hydrogenating an,-unsaturated carboxylic acid with a cinchonidine-Pd/Al₂O₃ catalyst system. Favourable conditions are: high surface hydrogen concentration ( 60 bar hydrogen pressure, low catalyst concentration and apolar solvents), near ambient temperature and a cinchonidine/reactantmolar ratio of at least 0.4 mol%. It is proposed that high hydrogen solubility and the presence of 2-methyl-2-pentenoic acid reactant as dimers are advantageous for enantiodifferentiation.     

Titania-silica aerogels with superior catalytic performance in olefin epoxidation compared to large pore Ti-molecular sieves

The paper provides a short overview on the various Ti- and Si-containing epoxidation catalysts, with a focus on the development and characterisation of titania-silica mixed oxides prepared by the sol-gel-aerogel method. Titania-silica aerogels, dried by semicontinuous extraction of the solvent with supercritical CO₂ at low temperature, possess high surface area, an amorphous mesoporous structure, and a rather even distribution of Ti in the silica matrix. The catalytic activities of mixed oxides, silica-supported titania and Ti-substituted molecular sieves (TS-1, Ti- and Ti-MCM-41) are compared in the epoxidation of 1-hexene, 1-octene, cyclohexene, cyclododecene and norbornene, based on literature data. The activities (i.e. the amount of converted olefin per unit time and catalyst weight) vary in a broad range of several orders of magnitude. It is shown that the low temperature aerogel containing 20 wt% TiO₂ is superior to any other Ti- and Si-containing catalyst for the epoxidation of cyclic olefins. In the epoxidation of linear alkenes TS-1 has outstanding activity. Ti-substituted large and ultra-large pore molecular sieves require further development concerning their catalytic performance.