Redispersion Microreactor System for Phase Transfer Catalyzed Esterification

An interdigital mixer - redispersion capillary assembly was applied to prevent the liquid-liquid bubbly flow coalescence in microreactors. The redispersion capillary consisted of 1 mm long and 0.25 mm inner-diameter constrictions placed every 0.50 m along the channel length. The system was tested on the phase transfer catalyzed esterification to produce benzyl benzoate. The application of constrictions to prevent coalescence resulted in a better reproducibility compared to a capillary without the constrictions. By controlling the total flow rate and the aqueous-to-organic ratio the bubbly flow surface-volume ratio could be increased up to 230 700 m(2)m(-3). Compared to the conventional phase transfer catalyzed esterification, the continuous operation in the interdigital-redispersion capillary assembly eliminated the use of solvents and bases, removing an energy intensive step of distillation, while increasing process safety.

Liquid-Liquid Flow in a Capillary Microreactor: Hydrodynamic Flow Patterns and Extraction Performance

The capillary micro reactor, with four stable operating flow patterns and a throughput range from grams per hour to kilograms per hour, presents an attractive alternative to chip-based and microstructured reactors for laboratory- and pilot-scale applications. In this article, results for the extraction of 2-butanol from toluene under different flow patterns in a water/toluene flow in long capillary microreactors are presented. The effects of the capillary length (0.4-2.2 m), flow rate (0.1-12 mL/min), and aqueous-to-organic volumetric flow ratio (0.25-9) on the slug, bubbly, parallel, and annular flow hydrodynamics were investigated. Weber-number-dependent flow maps were composed for capillary lengths of 0.4 and 2 m that were used to interpret the flow pattern formation in terms of surface tension and inertia forces. When the capillary length was decreased from 2 to 0.4 m, a transition from annular to parallel flow was observed. The capillary length had little influence on slug and bubbly flows. The flow patterns were evaluated in terms of stability, surface-to-volume ratio, throughput, and extraction efficiency. Slug and bubbly flow operations yielded 100% thermodynamic extraction efficiency, and increasing the aqueous-to-organic volumetric ratio to 9 allowed for 99% 2-butanol extraction. The parallel and annular flow operating windows were limited by the capillary length, thus yielding maximum 2-butanol extractions of 30% and 47% for parallel and annular flows, respectively.

Thin catalytic coatings on microreactor walls A way to make industrial processes more efficient

Current trends in the development of microstructured reactors with thin catalytic films (from 100 nm up to several microns) that have self-assembled nanostructures are discussed. A major technique that is used to prepare such films is sol-gel processing. This involves depositing a complex fluid on a microstructured substrate by dip, spin, or spray coating, followed by surfactant removal to form the porous nanostructures. A novel methodology has been developed by which a uniform coating containing controlled amounts of (poly) metallic nanoparticles can be obtained. This elegant strategy is based on the condensation of metal oxide species by self-assembly in the presence of metallic colloids. The potential microreactor applications brought forth by this innovative protocol are placed in perspective in the light of its versatility.

Method for the in situ preparation of a single layer of zeolite Beta crystals on a molybdenum substrate for microreactor applications

A method for the hydrothermal synthesis of a single layer of zeolite Beta crystals on a molybdenum substrate for microreactor applications has been developed. Before the hydrothermal synthesis, the surface of the substrate was modified by an etching procedure that increases the roughness at the nanoscale level without completely eliminating the surface lay structure. Then, thin films of Al2O3 (170 nm) and TiO2 (50 nm) were successively deposited by atomic layer deposition (ALD) on the substrate. The internal Al2O3 film protects the Mo substrate from oxidation up to 550 degrees C in an oxidative environment. The high wettability of the external TiO2 film after UV irradiation increases zeolite nucleation on its surface. The role of the metal precursor (TiCl4 vs TiI4), deposition temperature (300 vs 500 degrees C), and film thickness (50 vs 100 nm) was investigated to obtain titania films with the slowest decay in the superhydrophilic behavior after UV irradiation. Zeolite Beta coatings with a Si/Al ratio of 23 were grown at 140 degrees C for 48 It. After ion exchange with a 10(-4) M cobalt acetate solution, the activity of the coatings was determined in the ammoxidation of ethylene to acetonitrile in a microstructured reactor. A maximum reaction rate of 220 mu mol C2H3N g(-1) s(-1) was obtained at 500 degrees C, with 42% carbon selectivity to acetonitrile. (C) 2007 Elsevier Inc. All rights reserved.

Experimental validation of the performance of a microreactor for the high-throughput screening of catalytic coatings

In this paper, the results of computational fluid dynamics simulations of flow, temperature, and concentration distributions used in the design of a microreactor for the high-throughput screening of catalytic coatings (Mies et al., Chem. Eng. J. 2004, 101, 225) are compared with experimental data, and good agreement is obtained in all cases. The experimental results on flow distribution were obtained from laser Doppler anemometry measurements in the range of Reynolds numbers from 6 to 113. The measured flow nonuniformity in the separate reactor compartments was below 2%. The temperature distribution was obtained from thermocouple measurements. The temperature nonuniformity between the reactor compartments was below 3 K at a maximum heat production rate of 1.3 W in ethylene oxidation at 425 degrees C over CuO/Al2O3/Al coatings. With respect to concentration gradients, a deviation from the average rate of reaction of only 2.3% was obtained at realistic process conditions in the ethylene ammoxidation process over identical Co-ZSM-5 coatings in all reactor compartments. The cross talking noise between separate compartments does not exceed 0.1% when the reactor parts have a smooth surface finish. This illustrates the importance of ultraprecision machining of surfaces in microtechnology, when interfaces cannot be avoided.

Development of the kinetic model of platinum catalyzed ammonia oxidation in a microreactor

The ammonia oxidation reaction on supported polycrystalline platinum catalyst was investigated in an aluminum-based microreactor. An extensive set of reactions was included in the chemical reactor modeling to facilitate the construction of a kinetic model capable of satisfactory predictions for a wide range of conditions (NH3 partial pressure, 0.01-0.12 atm; O-2 partial pressure, 0.10-0.88 atm; temperature, 523-673 K; contact time, 0.3-0.7 ms). The elementary surface reactions used in developing the mechanism were chosen based on the literature data concerning ammonia oxidation on a Pt catalyst. Parameter estimates for the kinetic model were obtained using multi-response least squares regression analysis using the isothermal plug-flow reactor approximation. To evaluate the model, the behavior of a microstructured reactor was simulated by means of a complete Navier-Stokes model accounting for the reactions on the catalyst surface and the effect of temperature on the physico-chemical properties of the reacting mixture. In this way, the effect of the catalytic wall temperature non-uniformity and the effect of a boundary layer on the ammonia conversion and selectivity were examined. After further optimization of appropriate kinetic parameters, the calculated selectivities and product yields agree very well with the values actually measured in the microreactor. (C) 2002 Elsevier Science B.V. All rights reserved.

Miniaturization of heterogeneous catalytic reactors: Prospects for new developments in catalysis and process engineering

This paper gives an overview of the research done since 1999 at Eindhoven University of Technology in the Netherlands in the field of miniaturization of heterogeneous catalytic reactors. It is described that different incentives exist for the development of these microstructured reaction systems. These include the need for efficient research instruments in catalyst development and screening, the need for small-scale reactor devices for hydrogen production for low-power electricity generation with fuel cells, and the recent quest for intensified processing equipment and novel process architectures (as in the fine chemicals sector). It is demonstrated that also in microreaction engineering, catalytic engineering and reactor design go hand-in-hand. This is illustrated by the design of an integrated microreactor and heat-exchanger for optimum performance of a highly exothermic catalytic reaction, viz. ammonia oxidation. It is argued that future developments in catalytic microreaction technology will depend on the availability of very active catalysts (and catalyst coating techniques) for which microreactors may become the natural housing.

Optimization of heat transfer characteristics, flow distribution, and reaction processing for a microstructured reactor/heat-exchanger for optimal performance in platinum catalyzed ammonia oxidation

The present work is focused on the demonstration of the advantages of miniaturized reactor systems which are essential for processes where potential for considerable heat transfer intensification exists as well as for kinetic studies of highly exothermic reactions at near-isothermal conditions. The heat transfer characteristics of four different cross-flow designs of a microstructured reactor/heat-exchanger (MRHE) were studied by CFD simulation using ammonia oxidation on a platinum catalyst as a model reaction. An appropriate distribution of the nitrogen flow used as a coolant can decrease drastically the axial temperature gradient in the reaction channels. In case of a microreactor made of a highly conductive material, the temperature non-uniformity in the reactor is strongly dependent on the distance between the reaction and cooling channels. Appropriate design of a single periodic reactor/heat-exchanger unit, combined with a non-uniform inlet coolant distribution, reduces the temperature gradients in the complete reactor to less than 4degreesC, even at conditions corresponding to an adiabatic temperature rise of about 1400degreesC, which are generally not accessible in conventional reactors because of the danger of runaway reactions. To obtain the required coolant flow distribution, an optimization study was performed to acquire the particular geometry of the inlet and outlet chambers in the microreactor/heat-exchanger. The predicted temperature profiles are in good agreement with experimental data from temperature sensors located along the reactant and coolant flows. The results demonstrate the clear potential of microstructured devices as reliable instruments for kinetic research as well as for proper heat management in the case of highly exothermic reactions. (C) 2002 Elsevier Science B.V. All rights reserved.

The preparation of highly ordered single layer ZSM-5 coating on prefabricated stainless steel microchannels

An elegant way to prepare catalytically active microreactors is by applying a coating of zeolite crystals onto a metal microchannel structure. In this study the hydrothermal formation of ZSM-5 zeolitic coatings on AISI 316 stainless steel plates with a microchannel structure has been investigated at different synthesis mixture compositions. The procedures of coating and thermal treatment have also been optimized. Obtaining a uniform thickness of the coating within 0.5 mm wide microchannels requires a careful control of various synthesis variables. The role of these factors and the problems in the synthesis of these zeolitic coatings are discussed. In general, the synthesis is most sensitive to the H2O/Si ratio as well as to the orientation of the plates with respect to the gravity vector. Ratios of H2O/Si=130 and Si/template=13 were found to be optimal for the formation of a zeolitic film with a thickness of one crystal at a temperature of 130 degreesC and a synthesis time of about 35 h. At such conditions, ZSM-5 crystals were formed with a typical size of 1.5 mu mx1.5 mu mx1.0 mum and a very narrow (within 0.2 mum) crystal size distribution. The prepared samples proved to be active in the selective catalytic reduction (SCR) of NO with ammonia. The activity tests have been carried out in a plate-type microreactor. The microreactor shows no mass transfer limitations and a larger SCR reaction rate is observed in comparison with pelletized Ce-ZSM-5 catalysts; (C) 2001 Elsevier Science B.V. All rights reserved.

Numbered-up gas-liquid micro/milli channels reactor with modular flow distributor

Gas-liquid processing in microreactors remains mostly restricted to the laboratory scale due to the complexity and expenditure needed for an adequate numbering-up with a uniform flow distribution. Here, the numbering-up is presented for multi-phase (gas-liquid) flow in microreactor suitable for a production capacity of kg/h. Based on the barrier channels concept, the barrier-based micro/milli reactor (BMMR) is designed and fabricated to deliver flow non-uniformity of less than 10%. The BMMR consists of eight parallel channels all operated in the Taylor flow regime and with a liquid flow rate up to 150. mL/min. The quality of the flow distribution is reported by studying two aspects. The first aspect is the influence of different viscosities, surface tensions and flow rates. The second aspect is the influence of modularity by testing three different reaction channels type: (1) square channels fabricated in a stainless steel plate, (2) square channels fabricated in a glass plate, and (3) circular channels (capillaries) made of stainless steel. Additionally, the BMMR is compared to that of a single channel regard the slug and bubble lengths and bubble generation frequency. The results pave the ground for bringing multi-phase flow in microreactor one step closer for large scale production via numbering-up. © 2012 Elsevier B.V.

Low-temperature oxidation reactions of ethane over a Pt/Al2O3 catalyst

Oxidative dehydrogenation of ethane was performed under conventional microreactor and TAP reactor conditions over a Pt/Al2O3 catalyst between 100 and 600 degreesC. During TAP studies, no ethene was produced whereas under flow conditions small but significant ethene formation was observed. This is consistent with a mechanism involving the gas-phase production of ethene rather than via a surface reaction. In comparison, both hydrogen and methane formation were found under TAP conditions and the trends with temperature and surface oxide composition are interpreted in terms of successive dehydrogenation steps on the catalyst surface. It is further observed that periodic introduction of the reactants can minimize deactivation processes. (C) 2003 Elsevier Inc. All rights reserved.