Micromixing in a Rotor-Stator Spinning Disc Reactor.

This paper presents the micromixing times in a rotor-stator spinning disc reactor. Segregation indices are obtained at different rotational speeds performing the Villermaux-Dushman parallel-competitive reaction scheme. Consequently, the corresponding micromixing times are calculated using the engulfment model, while considering the self-engulfment effect. It was found that the segregation index decreases with an increasing disc speed. Furthermore, for the investigated operational conditions, the estimated micromixing times are in the range of 1.13 × 10-4 to 8.76 × 10-3 seconds, in agreement with the theoretical dependency on the energy dissipation rate of ε-0.5. In a rotor-stator spinning disc reactor it is thus possible to further continue the theoretical trend of decreasing micromixing times with very high levels of energy dissipation rates that are unattainable in traditional types of process equipment.

Facile Synthesis of Catalytic AuPd Nanoparticles within Capillary Microreactors Using Polyelectrolyte Multilayers for the Direct Synthesis of H2O2.

Microreactors present innovative solutions for problems pertaining to conventional reactors and therefore have seen successful application in several industrial processes. Yet, its application in heterogeneously catalyzed gas-liquid reactions has been challenging, mainly due to the lack of an easy and flexible methodology for catalyst incorporation inside these reactors. Herein, we report a facile technique for obtaining small (<2 nm) and well-distributed catalytic nanoparticles on the walls of silica-coated capillaries, that act as micro(channel) reactors. These particles are formed in situ on the reactor walls using polyelectrolyte multilayers (PEMs), built by layer-by-layer self-assembly. Manipulating the PEMs' synthesis condition gives easy control over metal loading, without compromising on particle size. Both monometallic (Au and Pd) and bimetallic (AuPd) nanoparticles were successfully obtained using this technique. Finally, these catalytic microreactors were found to exhibit exceptional activity for the direct synthesis of hydrogen peroxide from H2 and O2.

Rapid trifluoromethylation and perfluoroalkylation of five-membered heterocycles by photoredox catalysis in continuous flow.

Trifluoromethylated and perfluoroalkylated heterocycles are important building blocks for the synthesis of numerous pharmaceutical products, agrochemicals and are widely applied in material sciences. To date, trifluoromethylated and perfluoroalkylated hetero-aromatic systems can be prepared utilizing visible light photoredox catalysis methodologies in batch. While several limitations are associated with these batch protocols, the application of microflow technology could greatly enhance and intensify these reactions. A simple and straightforward photocatalytic trifluoromethylation and perfluoroalkylation method has been developed in continuous microflow, using commercially available photocatalysts and microflow components. A selection of five-membered hetero-aromatics were successfully trifluoromethylated (12 examples) and perfluoroalkylated (5 examples) within several minutes (8-20 min).

Gas-liquid-liquid three-phase flow pattern and pressure drop in a microfluidic chip: similarities with gas-liquid/liquid-liquid flows.

We report a three-phase slug flow and a parallel-slug flow as two major flow patterns found under the nitrogen-decane-water flow through a glass microfluidic chip which features a long microchannel with a hydraulic diameter of 98 µm connected to a cross-flow mixer. The three-phase slug flow pattern is characterized by a flow of decane droplets containing single elongated nitrogen bubbles, which are separated by water slugs. This flow pattern was observed at a superficial velocity of decane (in the range of about 0.6 to 10 mm s(-1)) typically lower than that of water for a given superficial gas velocity in the range of 30 to 91 mm s(-1). The parallel-slug flow pattern is characterized by a continuous water flow in one part of the channel cross section and a parallel flow of decane with dispersed nitrogen bubbles in the adjacent part of the channel cross section, which was observed at a superficial velocity of decane (in the range of about 2.5 to 40 mm s(-1)) typically higher than that of water for each given superficial gas velocity. The three-phase slug flow can be seen as a superimposition of both decane-water and nitrogen-decane slug flows observed in the chip when the flow of the third phase (viz. nitrogen or water, respectively) was set at zero. The parallel-slug flow can be seen as a superimposition of the decane-water parallel flow and the nitrogen-decane slug flow observed in the chip under the corresponding two-phase flow conditions. In case of small capillary numbers (Ca ≪ 0.1) and Weber numbers (We ≪ 1), the developed two-phase pressure drop model under a slug flow has been extended to obtain a three-phase slug flow model in which the 'nitrogen-in-decane' droplet is assumed as a pseudo-homogeneous droplet with an effective viscosity. The parallel flow and slug flow pressure drop models have been combined to obtain a parallel-slug flow model. The obtained models describe the experimental pressure drop with standard deviations of 8% and 12% for the three-phase slug flow and parallel-slug flow, respectively. An example is given to illustrate the model uses in designing bifurcated microchannels that split the three-phase slug flow for high-throughput processing.

Selective production of methane from aqueous biocarbohydrate streams over a mixture of platinum and ruthenium catalysts.

A one-step process for the selective production of methane from low-value aqueous carbohydrate streams is proposed. Sorbitol, used herein as a model compound, is fully converted to methane, CO2 , and a minor amount of H2 by using a physical mixture of Pt and Ru (1:5 in mass basis) at 220 °C and 35 bar. This conversion is the result of hydrogenolysis of part of the sorbitol over Ru and the in situ production of H2 through the aqueous-phase reforming of the remaining carbohydrate over Pt. A synergistic effect of the combination of these two catalysts results in the rapid and highly selective conversion of the carbohydrate to methane. This process offers the possibility of upgrading a low-value carbohydrate stream into a valuable fuel with no addition of H2. Exergy analysis reveals that nearly 80 % of the exergy of the reactant is recovered as methane.

Microreactors with integrated UV/Vis spectroscopic detection for online process analysis under segmented flow.

Combining reaction and detection in multiphase microfluidic flow is becoming increasingly important for accelerating process development in microreactors. We report the coupling of UV/Vis spectroscopy with microreactors for online process analysis under segmented flow conditions. Two integration schemes are presented: one uses a cross-type flow-through cell subsequent to a capillary microreactor for detection in the transmission mode; the other uses embedded waveguides on a microfluidic chip for detection in the evanescent wave field. Model experiments reveal the capabilities of the integrated systems in real-time concentration measurements and segmented flow characterization. The application of such integration for process analysis during gold nanoparticle synthesis is demonstrated, showing its great potential in process monitoring in microreactors operated under segmented flow.

Glucose dehydration to 5-hydroxymethylfurfural in a biphasic system over solid acid foams.

A solid acid foam-structured catalyst based on a binderless zirconium phosphate (ZrPO) coating on aluminum foam was prepared. The catalyst layer was obtained by performing a multiple washcoating procedure of ZrPO slurry on the anodized aluminum foam. The effect of the pretreatment of ZrPO, the concentration of the slurry, and the amount of coating on the properties of the foam was studied. The catalytic properties of the prepared foams have been evaluated in the dehydration of glucose to 5-hydroxymethylfurfural (HMF) in a biphasic reactor. The catalytic behavior of ZrPO foam-based catalysts was studied in a rotating foam reactor and compared with that of bulk ZrPO. The effect of a silylation procedure on the selectivity of the process was shown over bulk and foam catalysts. This treatment resulted in a higher selectivity due to the deactivation of unselective Lewis acid sites. Addition of methylisobutylketone leads to extraction of HMF from the aqueous phase and stabilization of the selectivity to HMF over bulk ZrPO. A more intensive contact of the foam with the aqueous and organic phases leads to an increase in the selectivity and resistance to deactivation of the foam in comparison with a bulk catalyst.

Hydrogen production through aqueous-phase reforming of ethylene glycol in a washcoated microchannel.

Aqueous-phase reforming (APR) of biocarbohydrates is conducted in a catalytically stable washcoated microreactor where multiphase hydrogen removal enhances hydrogen efficiency. Single microchannel experiments are conducted following a simplified model based on the microreactor concept. A coating method to deposit a Pt-based catalyst on the microchannel walls is selected and optimized. APR reactivity tests are performed by using ethylene glycol as the model compound. Optimum results are achieved with a static washcoating technique; a highly uniform and well adhered 5 µm layer is deposited on the walls of a 320 µm internal diameter (ID) microchannel in one single step. During APR of ethylene glycol, the catalyst layer exhibits high stability over 10 days after limited initial deactivation. The microchannel presents higher conversion and selectivity to hydrogen than a fixed-bed reactor. The benefits of using a microreactor for APR can be further enhanced by utilizing increased Pt loadings, higher reaction temperatures, and larger carbohydrates (e.g., glucose). The use of microtechnology for aqueous-phase reforming will allow for a great reduction in the reformer size, thus rendering it promising for distributed hydrogen production.

Dissolved gas and ultrasonic cavitation--a review.

The physics and chemistry of nonlinearly oscillating acoustic cavitation bubbles are strongly influenced by the dissolved gas in the surrounding liquid. Changing the gas alters among others the luminescence spectrum, and the radical production of the collapsing bubbles. An overview of experiments with various gas types and concentration described in literature is given and is compared to mechanisms that lead to the observed changes in luminescence spectra and radical production. The dissolved gas type changes the bubble adiabatic ratio, thermal conductivity, and the liquid surface tension, and consequently the hot spot temperature. The gas can also participate in chemical reactions, which can enhance radical production or luminescence of a cavitation bubble. With this knowledge, the gas content in cavitation can be tailored to obtain the desired output.

Micro/milliflow processing with selective catalyst microwave heating in the Cu-catalyzed Ullmann etherification reaction: a µ(2)-process.

A µ(2)-process in the Ullmann-type C-O coupling of potassium phenolate and 4-chloropyridine was successfully performed in a combined microwave (MW) and microflow process. Selective MW absorption in a micro-fixed-bed reactor (µ-FBR) by using a supported Cu nanocatalyst resulted in an increased activity compared to an oil-bath heated process. Yields of up to 80 % were attained by using a multisegmented µ-FBR without significant catalyst deactivation. The µ-FBR was packed with beads coated with Cu/TiO(2) and CuZn/TiO(2) catalysts. Temperature measurements along axial positions of the reactor were performed by using a fiber-optic probe in the catalyst bed. The simultaneous application of MW power and temperature sensors resulted in an isothermal reactor at 20 W. Initially, only solvent was used to adjust the MW field density in the cavity and optimize the power utility. Subsequently, the reaction mixture was added to ensure the maximum MW power transfer by adjusting the waveguide stub tuners to steady-state operations as a result of the changed reaction mixture composition and, therefore, the dielectric properties. Finally, the beneficial influence of the Cu/TiO(2)- and CuZn/TiO(2)-coated glass beads (200 µm) on the MW absorption as a result of the additional absorbing effect of the metallic Cu nanoparticles was optimized in a fine-tuning step. For the catalyst synthesis, various sol-gel, deposition, and impregnation methods provided Cu catalyst loadings of around 1 wt %. The addition of Zn to the Cu nanocatalyst revealed an increased catalyst activity owing to the presence of stable Cu(0). Multilaminar mixing was necessary because of the large difference in fluid viscosities. To the best of our knowledge, this work is the first extended experimental survey of the decisive parameters to combine microprocess and single-mode MW technology following the concepts of "novel process windows" for organic syntheses.

Fructose dehydration to 5-hydroxymethylfurfural over solid acid catalysts in a biphasic system.

Different acidic heterogeneous catalysts like alumina, aluminosilicate, zirconium phosphate, niobic acid, ion-exchange resin Amberlyst-15, and zeolite MOR have been studied in fructose dehydration to 5-hydroxymethylfurfural (HMF). The acidity of these materials was characterized using temperature-programmed desorption of NH3 and IR spectroscopy of adsorbed pyridine. The nature and strength of acid sites was shown to play a crucial role in the selectivity towards HMF. Brønsted acid sites in the case of zeolites and ion-exchange resin led to high selectivities in the dehydration of fructose with an increase in selectivity with the addition of an organic phase. Lewis acidity in the case of phosphate and oxides resulted in the intensive production of humins from fructose at the initial stages of the process, whereas organic phase addition did not affect selectivity.

New Cu-based catalysts supported on TiO2 films for Ullmann S(N)Ar-type C-O coupling reactions.

New routes for the preparation of highly active TiO(2)-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, (63)Cu nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO(2) catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO(2) at 120 °C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO(2) at 140 °C, corresponding to an initial reaction rate of 104 mmol g(cat) (-1) s(-1). The activation energy on the Cu/mesoporous TiO(2) catalyst was found to be (144±5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123±3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO(2) support (75±2 kJ mol(-1)).

Effect of the load size on the efficiency of microwave heating under stop flow and continuous flow conditions.

A novel heating efficiency analysis of the microwave heated stop-flow (i.e. stagnant liquid) and continuous-flow reactors has been presented. The thermal losses to the surrounding air by natural convection have been taken into account for heating efficiency calculation of the microwave heating process. The effect of the load diameter in the range of 4-29 mm on the heating efficiency of ethylene glycol was studied in a single mode microwave cavity under continuous flow and stop-flow conditions. The variation of the microwave absorbing properties of the load with temperature was estimated. Under stop-flow conditions, the heating efficiency depends on the load diameter. The highest heating efficiency has been observed at the load diameter close to the half wavelength of the electromagnetic field in the corresponding medium. Under continuous-flow conditions, the heating efficiency increased linearly. However, microwave leakage above the propagation diameter restricted further experimentation at higher load diameters. Contrary to the stop-flow conditions, the load temperature did not raise monotonously from the inlet to outlet under continuous-flow conditions. This was due to the combined effect of lagging convective heat fluxes in comparison to volumetric heating. This severely disturbs the uniformity of the electromagnetic field in the axial direction and creates areas of high and low field intensity along the load Length decreasing the heating efficiency as compared to stop-flow conditions.

Mechanism of ultrasound scission of a silver-carbene coordination polymer.

Scission of a supramolecular polymer-metal complex can be carried out using collapsing cavitation bubbles created by ultrasound. Although the most plausible scission mechanism of the coordinative bonds is through mechanical force, the influence of radicals and high hot-spot temperatures on scission has to be considered. A silver(I)-N-heterocyclic carbene complex was exposed to 20 kHz ultrasound in argon, nitrogen, methane, and isobutane saturated toluene. Scission percentages were almost equal under argon, nitrogen, and methane. Radical production differs by a factor of 10 under these gases, indicating that radical production is not a significant contributor to the scission process. A model to describe the displacement of the bubble wall, strain rates, and temperature in the gas shows that critical strain rates for coil-to-stretch transition, needed for scission, are achieved at reactor temperatures of 298 K, an acoustic pressure of 1.2 × 10(5) Pa, and an acoustic frequency of 20 kHz. Lower scission percentages were measured under isobutane, which also shows lower strain rates in model simulations. The activation of the polymer-metal complexes in toluene under the influence of ultrasound occurs through mechanical force.

Continuous synthesis of tert-butyl peroxypivalate using a single-channel microreactor equipped with orifices as emulsification units.

The two-step synthesis of tert-butyl peroxypivalate is performed in a single-channel microreactor. The first step, the deprotonation of tert-butyl hydroperoxide, is done in a simple mixer tube setup. The residence time section for the second reaction step is equipped with orifices for interfacial area renewal, needed for ensuring mass transfer between the two immiscible phases. The strong dependence of the reaction performance on the size of the interfacial area is demonstrated by using a setup with 4 orifices (distance of 52 cm), giving a HPLC yield of 71% at a residence time of 8 s and a reaction temperature of 23 °C. A further shortening of orifice distances helped to shorten the residence time down to 1.5 s and 0.5 s (using 9 orifices and 3 orifices with a distance of 5 cm). When using these setups, the produced heat could not be removed from the system sufficiently quickly (ΔT=38 K). The achieved yields (ca. 70% by HPLC) are close to the state of the art (cascaded batch processing) and provide an indication that the tert-butyl peroxypivalate synthesis can be performed at higher temperatures or at least, a more flexible process control can be allowed compared to high-volume batch reactors. Processing at higher reaction temperatures up to 70 °C shows a slight optimum at reaction temperatures between 40 °C to 50 °C, depending on the setup used. Knowing this novel process window as well as the optimum orifice geometry and distance will allow for tailored design of the microreactor. For the processing in the single-channel microreactor setup using 9 orifices (distance of 5 cm) and a reaction temperature of 40 °C a space-time-yield of 420,000 g L(-1) h(-1) was reached which is higher than the space-time-yield for the industrial 3 cascaded batch reactor process (190 g L(-1) h(-1)).

Effect of resonance frequency, power input, and saturation gas type on the oxidation efficiency of an ultrasound horn.

The sonochemical oxidation efficiency (η(ox)) of a commercial titanium alloy ultrasound horn has been measured using potassium iodide as a dosimeter at its main resonance frequency (20 kHz) and two higher resonance frequencies (41 and 62 kHz). Narrow power and frequency ranges have been chosen to minimise secondary effects such as changing bubble stability, and time available for radical diffusion from the bubble to the liquid. The oxidation efficiency, η(ox), is proportional to the frequency and to the power transmitted to the liquid (275 mL) in the applied power range (1-6 W) under argon. Luminol radical visualisation measurements show that the radical generation rate increases and a redistribution of radical producing zones is achieved at increasing frequency. Argon, helium, air, nitrogen, oxygen, and carbon dioxide have been used as saturation gases in potassium iodide oxidation experiments. The highest η(ox) has been observed at 5 W under air at 62 kHz. The presence of carbon dioxide in air gives enhanced nucleation at 41 and 62 kHz and has a strong influence on η(ox). This is supported by the luminol images, the measured dependence of η(ox) on input power, and bubble images recorded under carbon dioxide. The results give insight into the interplay between saturation gas and frequency, nucleation, and their effect on η(ox).

Kinetic study of propylene epoxidation with H2 and O2 over Au/Ti-SiO2 in the explosive regime.

A kinetic study of propene epoxidation with hydrogen and oxygen over a Au/Ti-SiO2 catalyst has been performed in a wide range of reactant concentrations including the explosive region in a micro reactor. The observed rate dependency on the reactants for the epoxidation and the competing direct water formation is discussed in relation to the current mechanistic insights in the literature. The formation rate of propene oxide is most dependent on the hydrogen concentration, in which the formation of an active peroxo species on the gold nanoparticles is the rate determining step. Deactivation is mainly caused by consecutive oxidation of propene oxide. Oxygen favours the regeneration of the deactivated catalytic sites. Water formation and propene epoxidation are strongly correlated. Water is formed via two routes: through the active peroxo intermediate responsible for epoxidation and from direct formation without involving this active intermediate. Improving the hydrogen efficiency should distinguish between these two routes of water formation. The active peroxo intermediate in epoxidation is competitively consumed by hydrogenation and epoxidation. The active gold site is blocked during deactivation.

Capillary microreactors wall-coated with mesoporous titania thin film catalyst supports.

A new method for catalyst deposition on the inner walls of capillary microreactors is proposed which allows exact control of the coating thickness, pore size of the support, metal particle size, and metal loading. The wall-coated microreactors have been tested in a selective hydrogenation reaction. Activity and selectivity reach values close to those obtained with a homogeneous Pd catalyst. The catalyst activity was stable for a period of 1000 h time-on-stream.

Confined palladium colloids in mesoporous frameworks for carbon nanotube growth.

Palladium colloidal nanoparticles with an average size of approximately 2.4 nm have been incorporated into mesoporous inorganic thin films following a multistep approach. This involves the deposition of mesoporous titania thin films with a thickness of 200 nm by spin-coating on titanium plates with a superhydrophilic titania outer layer and activation by calcination in a vacuum furnace at 573 K. Nanoparticles have been confined within the porous titania network by dip-coating noble metal suspensions onto these mesoporous thin films. Finally, the resulting nanoconfined systems were used as substrates for the growth of oriented carbon nanotubes (CNTs) using plasma-enhanced chemical vapour deposition at 923 K in order to enhance their surface area. These CNTs were tested in the hydrogenation of phenylacetylene by hydrogen in a batch reactor. The initial reaction rate observed on a CNT/TiO2 structured catalyst was considerably higher than that on 1 wt% Pd/TiO2 thin films.