On the performance of Ag/Al2O3 as a HC-SCR catalyst – influence of silver loading, morphology and nature of the reductant

This study focuses on the performance of Ag/Al2O3 catalysts for hydrocarbon selective catalytic reduction (HC-SCR) of NOx under lean conditions, using complex hydrocarbons as reductants. The aim is to elucidate the correlation towards the silver loading and morphology, with respect to the nature of the reductant. Ag/Al2O3 samples with either 2 or 6 wt% silver loading were prepared, using a sol–gel method including freeze-drying. The catalytic performance of the samples was evaluated by flow reactor experiments, with paraffins, olefins and aromatics of different nature as reductants. The physiochemical properties of the samples were characterized by scanning electron microscopy/energy dispersive X-ray spectroscopy, scanning transmission electron microscopy/high angle annular dark field imaging, X-ray photoelectron spectroscopy and N2-physisorption. The 2 wt% Ag/Al2O3 sample was found to be the most active catalyst in terms of NOx reduction. However, the results from the activity studies revealed that the decisive factor for high activity at low temperatures is not only connected to the silver loading per se. There is also a strong correlation between the silver loading and morphology (i.e. the ratio between low- and high- coordinated silver atoms) and the nature of the hydrocarbon, on the activity for NOx reduction. Calculated reaction rates over the low-coordinated step and high- coordinated terrace sites showed that the morphology of silver has a significant role in the HC-SCR reaction. For applications which include complex hydrocarbons as reductants (e.g. diesel), these issues need to be considered when designing highly active catalysts

Cascade transformations of (±)-citronellal to menthol over extruded Ru-MCM-41 catalysts in a continuous reactor

Cascade transformations of (±)-citronellal in a continuous mode were investigated over a bifunctional shaped ruthenium catalyst bearing metal clusters of the size 7–13 nm. Four types of Ru/H-MCM-41 extrudates (1.5 × 10 mm) containing 30% of Bindzil-50/80 colloidal silica binder were prepared varying in metal location and metal-to-acid ratio, while the concentration of Brønsted and Lewis acid sites and textural properties of the final extrudates were comparable. Catalytic tests were performed in the trickle-bed reactor under 70 °C, 10 bar of H2, and the initial reactant concentration in cyclohexane 0.086 mol L−1 for the liquid residence time of 12.5 min. As a reactant, isopulegol, citronellol or (±)-citronellal was used. Metal location in extrudates has a significant effect on the catalytic activity and selectivity especially in terms of isopulegol isomers which content correlated with the metal-to-acid site ratio. Stereoselectivity to the desired (±)-menthol was 68–70%. The highest amount of the desired menthol, 32% yield, was obtained over extrudates where Ru was deposited on the catalytic support, i.e. with the shortest distance between the acid and metal sites, the lowest Brønsted acidity, the lowest Brønsted–Lewis acid sites ratio, the highest specific surface area and the narrowest range of the Ru particle size distribution.</p

Transformations of citral over bifunctional Ru-H-Y-80 extrudates in a continuous reactor

One-pot transformations of citral were investigated over Ru-catalysts in a batch and a continuous mode over a powder catalyst and extrudates, respectively. Ru/H-Y-80 catalysts were prepared by different impregnation methods to obtain different particle sizes of Ru.The highest yield of isopulegols was 15% and yield of menthols was 3% with stereoselectivity to the desired (±)-menthol isomer of 42% after 5 h over the Ru/H-Y-80 powder catalyst with the smallest metal particles prepared by the incipient wetness impregnation method with six impregnation steps using Ru(NO)(NO3)3 as a precursor. This catalyst was synthesized with the Bindzil binder and shaped by extrusion.For comparison, also a catalyst with Ru deposited on the binder was prepared. Addition of 30 wt% Bindzil binder to Ru/H-Y-80 catalyst caused significant catalyst deactivation. Z/E-citral ratio decreased with increasing Ru particle size. Citral conversion and the yield of acyclic hydrogenation products were higher over the powder catalysts containing a mixture of zeolite and binder with a larger distance between the metal and the acid sites, i.e. with Ru deposited on the Bindzil binder. Long-term experiments in the continuous mode revealed comparable catalytic behaviour of both Ru-extrudates with the controlled metal location due to the presence of diffusion regime. The maximum yield of menthols, 6%, with stereoselectivity to the desired (±)-menthol of 73% was obtained during the transient state, below 2 h of time-on-stream. The reuse of Ru/H-Y-80 extrudates was successfully demonstrated.</p

Influence of the support of copper catalysts on activity and 1,2-dichloroethane selectivity in ethylene oxychlorination

Five different support materials were modified with 5 wt.% Cu, using an evaporation impregnation method. The synthesized CuCl2/γ-Al2O3, CuCl2/TiO2 (Hombikat), CuCl2/TiO2 (Alfa Aesar), CuCl2/SiO2 and CuCl2/H-Beta-25 materials were characterized by nitrogen physisorption, X-ray powder diffraction, scanning electron microscopy, energy dispersive Xray microanalysis, transmission electron microscopy, Fourier transform infrared spectroscopy and CO2-temperature programmed desorption. The physical-chemical characterization was correlated with catalytic activity, stability and selectivity in the ethylene oxychlorination. It was found that γ-Al2O3 and TiO2 support materials demonstrate very good activity and 1,2dichloroethane selectivity compare to other catalysts. Zeolite H-Beta-25 and SiO2 support materials proved to be unusable for this reaction.</p

Microreactor technology in experimental and modelling study of alcohol oxidation on nanogold

Selective oxidation of methanol, ethanol, 1-propanol and 1-butanol to corresponding aldehydes was performed in a microreactor in the presence of a Au/γ-Al2O3 coated catalyst. Nanoparticle size distribution, acidity, specific surface area and the average pore size as well as uniformity and thickness of the coating layer were evaluated with relevant characterization techniques. The experiments were designed to reveal the effect of temperature, residence time and oxygen-to-alcohol ratio on both alcohol conversion and product distribution. Stability and repeatability of the coating procedure was successfully demonstrated. To describe the reaction kinetics, plausible kinetic equations were implemented in a pseudo-homogeneous plug flow model, which turned out to be an adequate approximation to describe the flow pattern in the microreactor. Non-linear regression analysis enabled the determination of the rate and adsorption parameters included in the kinetic model. An advanced kinetic and mass transfer model was developed to reveal the impact of the diffusion inside the catalytic washcoat layer, confirming that molecular diffusion is not a limiting factor for alcohol oxidation in the microreactor.</p

Ultrasound irradiation as an effective tool in synthesis of the slag-based catalysts for carboxymethylation

Waste minimization strategy was applied in the current work for synthesis of the catalysts from industrial solid waste, namely desulfurization slag. The starting slag material comprising CaCO3, Ca(OH)2, SiO2, Al2O3, Fe2O3, and TiO2 was processed by various treating agents systematically varying the synthesis parameters. A novel efficient technique – ultrasound irradiation, was applied as an additional synthesis step for intensification of the slag dissolution and crystallization of the new phases. Physico-chemical properties of the starting materials and synthesized catalysts were evaluated by several analytical techniques. Treatment of the industrial slag possessing initially poor crystal morphology and a low surface area (6 m2/g) resulted in formation of highly-crystalline catalysts with well-developed structural properties. Surface area was increased up to 49 m2/g. High basicity of the neat slag as well as materials synthesized on its basis makes possible application of these materials in the reactions requiring basic active sites. Catalytic performance of the synthesized catalysts was elucidated in the synthesis of carbonate esters by carboxymethylation of cinnamyl alcohol with dimethyl carbonate carried out at 150 ◦C in a batch mode. Ultrasonication of the slag had a positive effect on the catalytic activity. Synthesized catalysts while exhibiting similar selectivity to the desired product (ca. 84%), demonstrated a trend of activity increase for materials prepared using ultrasonication pretreatment. The choice of the treating agent also played an important role in the catalytic performance. The highest selectivity to the desired cinnamyl methyl carbonate (88%) together with the highest activity (TOF35 =3.89*10</p

Pyrolysis of Softwood Carbohydrates in a Fluidized Bed Reactor

In the present work pyrolysis of pure pine wood and softwood carbohydrates, namely cellulose and galactoglucomannan (the major hemicellulose in coniferous wood), was conducted in a batch mode operated fluidized bed reactor. Temperature ramping (5 °C/min) was applied to the heating until a reactor temperature of 460 °C was reached. Thereafter the temperature was kept until the release of non-condensable gases stopped. The different raw materials gave significantly different bio-oils. Levoglucosan was the dominant product in the cellulose pyrolysis oil. Acetic acid was found in the highest concentrations in both the galactoglucomannan and in the pine wood pyrolysis oils. Acetic acid is most likely formed by removal of O-acetyl groups from mannose units present in GGM structure