Solvent-free semihydrogenation of acetylene alcohols in a capillary reactor coated with a Pd-Bi/TiO2 catalyst

© 2016 Elsevier B.V. All rights reserved. A solvent-free semihydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol was performed in a capillary reactor (10 m long, 0.53 mm i.d.) coated with a titania supported Pd-Bi catalyst. Several coatings with different Pd/Bi ratio have been prepared. The catalysts have been characterized with SEM, TEM, EDX, XRD analysis and N 2 adsorption-desorption measurements. The maximum alkene yield of 90% was obtained at a molar Pd/Bi ratio of 11. The yield was increased to 95% in the presence of 10 mol.% pyridine in the reaction mixture. The alkene selectivity decreased with time due to leaching of Bi. The leaching was fully suppressed in the presence of 1 vol.% acetic acid in the reaction mixture. The catalyst remained stable for 100 h of continuous operation. The results demonstrate that capillary reactors provide alkene selectivity the same compared to ideal stirred tank batch reactors

Scale up study of capillary microreactors in solvent-free semihydrogenation of 2‐methyl‐3‐butyn‐2‐ol

A 2.5 wt.% Pd/ZnO catalytic coating has been deposited onto the inner wall of capillary reactors with a diameter of 0.53 and 1.6 mm. The coatings were characterised by XRD, SEM, TEM and elemental analysis. The performance of catalytic reactors was studied in solvent-free hydrogenation of 2-methyl-3-butyn-2-ol. No mass transfer limitations was observed in the reactor with a diameter of 0.53 mm up to a catalyst loading of 1.0 kg (Pd) m −3 . The activity and selectivity of the catalysts has been studied in a batch reactor to develop a kinetic model. The kinetic model was combined with the reactor model to describe the obtained data in a wide range of reaction conditions. The model was applied to calculate the range of reaction conditions to reach a production rate of liquid product of 10–50 kg a day in a single catalytic capillary reactor

Sustainable Plasma-Catalytic Nitrogen Fixation with Pyramid Shaped μ-Electrode DBD and Titanium Dioxide

This research explores the potential of electric field enforcement in dielectric barrier discharge using specially designed pyramid-shaped μ-electrodes for a plasma-assisted nitrogen fixation process. The obtained results are compared under varying conditions, including the presence and absence of titanium dioxide ((Formula presented.)), different oxygen concentrations in the nitrogen-feeding gas, and residence time. The results demonstrate that the μ-electrodes lead to an enhancement of nitrogen oxidation, which is further intensified by (Formula presented.). The introduction of 60–70 % oxygen with nitrogen achieves the highest level of (Formula presented.) production. The synergistic effect of plasma and the catalytic effect of (Formula presented.) increase the rate of (Formula presented.) production by 20 %, resulting in a 23 % increase in energy yield. The introduction of (Formula presented.) leads to a sharp increase in (Formula presented.) production even at lower oxygen concentrations. The crucial role played by ultraviolet light-induced electron-hole pairs in (Formula presented.) is highlighted to promote nitrogen oxidation. Nevertheless, it is crucial to emphasize that prolonged residence times may cause the photocatalytic effect to generate alternative byproducts rather than (Formula presented.), consequence of excessive oxidation that could prove counterproductive. These findings emphasize the potential of plasma-assisted nitrogen fixation technology in reducing energy costs and meeting the growing demand for sustainable nitrogen-based fertilizers.</p

Direct amide synthesis over composite magnetic catalysts in a continuous flow reactor

Composite magnetic catalysts containing different amounts of sulfated titania (33−50 wt %) have been prepared by means of high energy ball-milling between TiO2 and NiFe2O4. The catalysts have been characterized with N2 adsorption/desorption isotherms, XRD, temperature programmed oxidation (TPO) and vibrating sample magnetometer (VSM). The catalytic activity was measured in the reaction of aniline and 4-phenylbutyric acid in the continuous mode under conventional and inductive heating. The effect of catalyst loading in the reactor on reaction and deactivation has been studied, indicating the catalyst containing 50 wt % titania gave the highest reaction rate and least deactivation. The operation in a flow reactor under inductive heating increased the amide yield by 25% as compared to conventional heating. The initial reaction rate decreased by 30% after a period of 15 h on stream. The catalyst activity was fully restored after a treatment with an air flow at 400 °C

Direct amide synthesis over core-shell TiO2@NiFe2O4 catalysts in a continuous flow radio frequency-heated reactor

Core-shell composite magnetic catalysts TiO2@NiFe2O4 with a titania loading of 9–32 wt. % have been synthesised by sol-gel method for direct amide synthesis in a radiofrequency (RF)-heated continuous flow reactor. The catalyst calcination temperature was optimised in the range of 350-500 ºC and the highest activity was observed for the catalyst calcined at 500 ºC due to conversion of titania into catalytically active anatase phase. No reaction between the magnetic core and the titania shell was observed up to the calcination temperature of 1000 ºC and no sintering of titania shell was observed after calcination at 500 ºC. The comparison of direct amide synthesis in a continuous flow fixed bed reactor under conventional and RF heating demonstrated that the RF heating mode increased the apparent reaction rate by 60 % and decreased the deactivation rate due to a better temperature uniformity. The titania weight normalised reaction rate in the RF-heated reactor was constant for titania loadings above 17 wt. %, while it decreased by a factor of 3 at lower titania loadings because of interactions between the ferrite core on the thin layer of the catalyst. The catalyst deactivation study showed that the deactivation rate could be accurately described by a first order kinetics and that the main reason of deactivation was coking. The catalyst regeneration via calcination at 400 ºC resulted in the catalyst sintering, while a treatment with a hydrogen peroxide solution at 90 ºC fully recovered catalytic activity

Gas-liquid hydrogenation in continuous flow – The effect of mass transfer and residence time in powder packed-bed and catalyst-coated reactors

Catalyst-coated tube reactors have been compared with the reactors packed with catalyst powder in alkyne semi-hydrogenation over a 5 wt% Pd/ZnO catalyst and cinnamic ester full hydrogenation over a 2.4 wt% Pd/C catalyst. The “powder packed-bed” reactors (packing with catalyst powder below 30 μm) showed irreproducible performance in time due to mobility of the catalyst layer in the bed which altered the fluidic path and therefore affected the mean liquid residence time and the dispersion. The catalyst-coated tube reactors demonstrated an ideal plug-flow behaviour (Péclet number > 120), while the powder packed-bed showed a considerable back-mixing (Péclet ~ 25). Under all conditions studied, the reaction rate in the powder packed-bed was limited by external mass transfer, while in the coated tube – by the intrinsic kinetics. The coated tubes demonstrated a much lower pressure drop, an improved alkene selectivity, and a 5 times higher throughput compared to the powder packed-bed. The dilution of the catalyst bed with glass beads improved the throughput 4-fold at the expense of 4-fold increase in the pressure drop. In full hydrogenation reaction, the catalyst-coated tube showed a 14 times higher throughput than in the powder packed-bed at the full alkyne conversion. A reactor model for the catalyst-coated tube has been proposed that takes into account the change in the fluid velocity during the reaction. The model described the reaction kinetics demonstrating that the catalyst-coated tubes can be used as a tool to obtain kinetic data in gas-liquid reactions in flow

Energy Intensified Nitrogen Fixation Through Fast Modulated Gas Discharge from Pyramid-shaped Micro-electrode

Plasma-assisted nitrogen fixation has emerged as a promising alternative to conventional nitrogen fixation methods. In this study, we investigate the feasibility of plasma-assisted nitrogen fixation using an AC-driven dielectric barrier discharge generated from the micro-tips of a specially designed fast-modulated pyramid-shaped electrode. The obtained result is compared with the conventional flat electrode. Our results demonstrate that pyramid-shaped micro-tip electrodes can excite more nitrogen molecules than flat electrodes. Thus, pyramid electrodes have 58% more nitrogen oxides yield efficiency at 32% less energy cost. The highest nitrogen fixation is attained at 60% to 70% of oxygen concentration in nitrogen-feeding gas. These findings suggest that discharge through microtip is a promising and viable technology that could play a significant role in reducing the energy cost of the plasma-assisted nitrogen fixation method to meet the growing demand for sustainable nitrogen-based fertilizers.</p

Counting bubbles : precision process control of gas-liquid reactions in flow with an optical inline sensor

Quality by Design encouraged by the US Food and Drug Administration (FDA) in the continuous flow synthesis requires tight monitoring of all the reaction input and output parameters to improve reproducibility and eliminate the process rejects. The reaction monitoring, however, relies on costly (above 10,000$) process analytical technology (PAT) – one of the factors that prevents a wider utilisation of continuous processes. In the work, we show that gas-liquid reactions can be monitored using low-cost (10$) hardware – optical liquid inline sensors – that allows instantaneous analysis of gas fraction in the moving stream. We discuss the application of the sensor for various gas-liquid reactions. The gas-consuming reactions such as hydrogenation are the easiest to implement because the sensor without calibration provides accurate readings close to complete consumption of the gas. The gas-evolving reactions can be monitored but require sensor calibration to determine the gas fraction accurately. Operation of the sensor was demonstrated for various hydrogenation reactions self-optimised using a proportional-integral (PID) algorithm which adjusted the substrate concentration to provide high (but not full) pre-defined hydrogen consumption. The optimised hydrogen consumption agreed with the product analysis for a range of the substrates hydrogenated under various pressures and with different selectivities. The optical sensor was also proven to be an efficient tool in adapting the reaction condition to the catalyst deactivation in the reaction of 2-methyl-3-butyn-2-ol semi-hydrogenation – the autonomous reactor allowed reaching a turn-over number (TON) of 2.7·106 with the value of 1.5·107 expected till a twofold decrease in the catalyst activity. The TON values demonstrated are significantly higher than those observed in batch reactors (~103) even in case of catalyst re-use (105) demonstrating a substantial improvement of process sustainability operating with the process control

Enhanced droplet size control in liquid-liquid emulsions obtained in a wire-guided X-mixer

The droplet size in a liquid‐liquid emulsion can be controlled by placing a metal wire along the centerline of an X‐mixer. Droplets gradually form when flowing along the wire, with droplet separation occurring at the tip of the wire rather than at the channel intersection in the X‐mixer. The droplet size is now defined by the Plateau‐Rayleigh instability developing in the axisymmetric annular flow region rather than by a sophisticated and hardly predictable three‐dimensional flow at the channel intersection. The wire‐guided droplet formation allows for fine control of the droplet size by changing the wire diameter, the position of the wire tip, and the flow rates. Further control of the droplet size can be achieved by adjusting the surface tension by adding a surfactant

The effects of pulse shape on the selectivity and production rate in non-oxidative coupling of methane by a micro-DBD reactor

The conversion of methane to ethylene has been investigated in a micro-DBD reactor with electrodes containing charge injector parts and excited with a negatively nano-second pulse voltage superimposed on a positive dc voltage. The effect of changing the characteristics of pulsed voltage such as pulse rise time (5–7 ns), total pulse width (12–14 ns), and pulse fall time (5–7 ns) on generation rate and products selectivity of the methane plasma has been studied. The kinetic model includes twenty species (electron, ions, radicals, and neutrals). The results showed that change in input pulse shape changes the generation rate and selectivity of neutral products. The rate of voltage change during pulse on-time significantly changed the instant C2H4 selectivity. With increasing the pulse rise and fall times the ethylene selectivity decreases, while the hydrogen selectivity increases. Results also showed that the electron reactions are dominant conversion channels during pulse on-time, while they had lower contributions in conversion progress during pulse off-time and the conversion process during this period is mainly governed by the radical reactions