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

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

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

Citral-to-Menthol Transformations in a Continuous Reactor over Ni/Mesoporous Aluminosilicate Extrudates Containing a Sepiolite Clay Binder

One-pot continuous synthesis of menthols from citral was performed over 5 wt % Ni supported on a mesoporous aluminosilicate catalyst with sepiolite as a binder at 70 degrees C with a selectivity of 75% to menthols. Catalyst deactivation with time-onstream resulted in a decrease of the conversion and selectivity to menthols at the expense of higher selectivity to isopulegols. Stereoselectivity to isopulegols and menthols only slightly changed with conversion and TOS. A kinetic model capable of describing experimental data for transformations of citral to menthol in a continuous mode was developed. It was based on a detailed reaction network and also comprised deactivation on both metal and acid sites. Numerical data fitting confirmed a good correspondence between the experimental data and calculations

Interactions between Iron and Nickel in Fe–Ni Nanoparticles on Y Zeolite for Co-Processing of Fossil Feedstock with Lignin-Derived Isoeugenol

A set of low-cost monometallic Fe, Ni, and bimetallic Fe–Ni bifunctional H–Y-5.1 catalysts with different metal ratios were synthesized by sequential incipient wetness impregnation. The catalysts were characterized in detail by N$_2$ physisorption, Fourier transform infrared spectroscopy with pyridine, inductively coupled plasma optical emission spectroscopy, X-ray diffraction (XRD), transmission and scanning electron microscopy (TEM–SEM), magic angle spinning nuclear magnetic resonance, X-ray photoelectron spectroscopy (XPS), Mössbauer spectroscopy, magnetic measurements, temperature-programmed reduction (TPR), and X-ray absorption spectroscopy (XAS). The results revealed that introduction of Fe led to a decrease of strong acid sites and an increase of medium Brønsted acid sites, while introduction of Ni increased the number of Lewis acid sites. The particle size of iron was approx. 5 nm, being ca. fourfold higher for nickel. XPS demonstrated higher iron content on the catalyst surface compared to nickel. Both Mössbauer spectroscopy and magnetic measurement confirmed the ferromagnetic behavior of all catalysts. In addition, the results from XRD, TEM, XPS, XAS, and magnetization suggested strong Fe–Ni nanoparticle interactions, which were supported by modeling of TPR profiles. Catalytic results of the co-processing of fossil feedstock with lignin-derived isoeugenol clearly showed that both product distribution and activity of Fe–Ni catalysts strongly depend on the metals’ ratio and their interactions. Key properties affected by the Fe–Ni metal ratio, which played a positive role in co-processing, were a smaller medial metal nanoparticle size (<6 nm), a lower metal–acid site ratio, as well as presence in the catalyst of fcc FeNi alloy structure and fcc Ni doped with Fe

One-Pot Transformation of Citronellal to Menthol Over H-Beta Zeolite Supported Ni Catalyst: Effect of Catalyst Support Acidity and Ni Loading

Citronellal was converted to menthol in a one-pot approach using H-Beta zeolite-based Ni catalyst in a batch reactor at 80 degrees C, under 20 bar of total pressure. The effects of H-Beta acidity (H-Beta-25 with the molar ratio SiO2/Al2O3 = 25 and H-Beta-300 with SiO2/Al2O3 = 300) and Ni loading (5, 10 and 15 wt %) on the catalytic performance were investigated. Ni was impregnated on H-Beta support using the evaporation-impregnation method. The physico-chemical properties of the catalysts were characterized by XRD, SEM, TEM, ICP-OES, N-2 physisorption, TPR, and pyridine adsorption-desorption FTIR techniques. Activity and selectivity of catalysts were strongly affected by the Bronsted and Lewis acid sites concentration and strength, Ni loading, its particle size and dispersion. A synergetic effect of appropriate acidity and suitable Ni loading in 15 wt.% Ni/H-Beta-25 catalyst led to the best performance giving 36% yield of menthols and 77% stereoselectivity to (+/-)-menthol isomer at 93% citronellal conversion. Moreover, the catalyst was successfully regenerated and reused giving similar activity, selectivity and stereoselectivity to the desired (+/-)-menthol isomer as the fresh one.[GRAPHICS]

The physicochemical and catalytic properties of clay extrudates in cyclization of citronellal

Four clay materials, namely, bentonite, bleaching earth, attapulgite and sepiolite, were shaped into the cylindrical body by extrusion. Clays were characterized in depth by TEM, SEM-EDX, N2 physisorption, pyridine FTIR, pH measurements, contact angle measurements, 27Al MAS NMR, and the crush test. Catalytic properties were investigated in the citronellal cyclization as a model reaction. The reaction was performed in the trickle-bed reactor at 70 °C, 10 bar of Ar with 0.086 M initial citronellal concentration in cyclohexane. The best results were obtained over attapulgite with isopulegols yield of 24% and stereoselectivity to the desired isopulegol isomer of 61%. Attapulgite had the highest meso-to-micropore volume ratio, the highest basicity, a low Brønsted-to-Lewis acid sites ratio, and the lowest amount of Brønsted acid sites compared to other extrudates. In addition, same clay exhibited the highest mechanical strength of extrudates.</p

Kinetics and Rate Law Determination of 2-Methylpropene Hydrogenation in a Packed-Bed Microreactor

This study focuses on hydrogenation of C4 fraction, more specifically on development of the methodology of kinetic data collection and evaluation. The hydrogenation of 2- methylpropene on platinum catalyst was investigated as a model reaction