A monolithic and flexible fluoropolymer film microreactor for organic synthesis applications

A photocurable and viscous fluoropolymer with chemical stability is a highly desirable material for fabrication of microchemical devices. Lack of a reliable fabrication method, however, limits actual applications for organic reactions. Herein, we report fabrication of a monolithic and flexible fluoropolymer film microreactor and its use as a new microfluidic platform. The fabrication involves facile soft lithography techniques that enable partial curing of thin laminates, which can be readily bonded by conformal contact without any external forces. We demonstrate fabrication of various functional channels (similar to 300 mu m thick) such as those embedded with either a herringbone micromixer pattern or a droplet generator. Organic reactions under strongly acidic and basic conditions can be carried out in this film microreactor even at elevated temperature with excellent reproducibility. In particular, the transparent film microreactor with good deformability could be wrapped around a light-emitting lamp for close contact with the light source for efficient photochemical reactions with visible light, which demonstrates easy integration with optical components for functional miniaturized systems.open1112Ysciescopu

Functional Relationships between Kinetic, Flow, and Geometrical Parameters in a High-Temperature Chemical Microreactor.

Computational fluid dynamics (CFD) simulations and isothermal approximation were applied for the interpretation of experimental measurements of the C10H7Br pyrolysis efficiency in the high-temperature microreactor and of the pressure drop in the flow tube of the reactor. Applying isothermal approximation allows the derivation of analytical relationships between the kinetic, gas flow, and geometrical parameters of the microreactor, which, along with CFD simulations, accurately predict the experimental observations. On the basis of the obtained analytical relationships, a clear strategy for measuring rate coefficients of (pseudo) first-order bimolecular and unimolecular reactions using the microreactor was proposed. The pressure- and temperature-dependent rate coefficients for the C10H7Br pyrolysis calculated using variable reaction coordinate transition state theory were invoked to interpret the experimental data on the pyrolysis efficiency

Optimal design of multi-channel microreactor for uniform residence time distribution

Multi-channel microreactors can be used for various applications that require chemical or electrochemical reactions in either liquid, gaseous or multi phase. For an optimal control of the chemical reactions, one key parameter for the design of such microreactors is the residence time distribution of the fluid, which should be as uniform as possible in the series of microchannels that make up the core of the reactor. Based on simplifying assumptions, an analytical model is proposed for optimizing the design of the collecting and distributing channels which supply the series of rectangular microchannels of the reactor, in the case of liquid flows. The accuracy of this analytical approach is discussed after comparison with CFD simulations and hybrid analytical-CFD calculations that allow an improved refinement of the meshing in the most complex zones of the flow. The analytical model is then extended to the case of microchannels with other cross-sections (trapezoidal or circular segment) and to gaseous flows, in the continuum and slip flow regimes. In the latter case, the model is based on second-order slip flow boundary conditions, and takes into account the compressibility as well as the rarefaction of the gas flow

Online monitoring of vinyl chloride polymerization in a microreactor using raman spectroscopy

A novel capillary-based microfluidic device has been designed to follow the vinyl chloride polymerization reaction. The use of a co-flow generation system enabled obtaining monodisperse vinyl chloride droplets within 200 µm in diameter, each one being considered as a polymerization reactor. During polymerization VCM droplets were visualized with a high speed camera. At the end of the reaction PVC grains were observed with a Scanning Electron Microscopy technique. Real-time non-invasive Raman measurement has been performed on stationary vinyl chloride monomer droplets and has provided values of effective reaction orders n and effective rate constants k. This microdevice allowed the investigation in difficult conditions (pressure, temperature) with a minimal amount of reagents and consequently under safe conditions

Accelerated gas-liquid visible light photoredox catalysis with continuous-flow photochemical microreactors

In this protocol, we describe the construction and use of an operationally simple photochemical microreactor for gas-liquid photoredox catalysis using visible light. The general procedure includes details on how to set up the microreactor appropriately with inlets for gaseous reagents and organic starting materials, and it includes examples of how to use it to achieve continuous-flow preparation of disulfides or trifluoromethylated heterocycles and thiols. The reported photomicroreactors are modular, inexpensive and can be prepared rapidly from commercially available parts within 1 h even by nonspecialists. Interestingly, typical reaction times of gas-liquid visible light photocatalytic reactions performed in microflow are lower (in the minute range) than comparable reactions performed as a batch process (in the hour range). This can be attributed to the improved irradiation efficiency of the reaction mixture and the enhanced gas-liquid mass transfer in the segmented gas-liquid flow regime

Kinetics of dissociative chemisorption of methane and ethane on Pt(110)-(1X2)

The initial probability of dissociative chemisorption Pr of methane and ethane on the highly corrugated, reconstructed Pt(110)‐(1×2) surface has been measured in a microreactor by counting the number of carbon atoms on the surface following the reaction of methane and ethane on the surface which was held at various constant temperatures between 450 and 900 K during the reaction. Methane dissociatively chemisorbs on the Pt(110)‐(1×2) surface with an apparent activation energy of 14.4 kcal/mol and an apparent preexponential factor of 0.6. Ethane chemisorbs dissociatively with an apparent activation energy of 2.8 kcal/mol and an apparent preexponential factor of 4.7×10^(−3). Kinetic isotope effects were observed for both reactions. The fact that P_r is a strong function of surface temperature implies that the dissociation reactions proceed via a trapping‐mediated mechanism. A model based on a trapping‐mediated mechanism is used to explain the observed kinetic behavior. Kinetic parameters for C–H bond dissociation of the thermally accommodated methane and ethane are extracted from the model

Non-equilibrium thermodynamic analysis of double diffusive, nanofluid forced convection in microreactors with radiation effects

This paper presents a theoretical investigation of the second law performance of double diffusive forced convection in microreactors with the inclusion of nanofluid and radiation effects. The investigated microreactors consist of a single microchannel, fully filled by a porous medium. The transport of heat and mass are analysed by including the thick walls and a first order, catalytic chemical reaction on the internal surfaces of the microchannel. Two sets of thermal boundary conditions are considered on the external surfaces of the microchannel; (1) constant temperature and (2) constant heat flux boundary condition on the lower wall and convective boundary condition on the upper wall. The local thermal non-equilibrium approach is taken to thermally analyse the porous section of the system. The mass dispersion equation is coupled with the transport of heat in the nanofluid flow through consideration of Soret effect. The problem is analytically solved and illustrations of the temperature fields, Nusselt number, total entropy generation rate and performance evaluation criterion (PEC) are provided. It is shown that the radiation effect tends to modify the thermal behaviour within the porous section of the system. The radiation parameter also reduces the overall temperature of the system. It is further demonstrated that, expectedly, the nanoparticles reduce the temperature of the system and increase the Nusselt number. The total entropy generation rate and consequently PEC shows a strong relation with radiation parameter and volumetric concentration of nanoparticles

Residence time distribution of gas flows in microreactors: Measurement and model comparison

This paper was presented at the 3rd Micro and Nano Flows Conference (MNF2011), which was held at the Makedonia Palace Hotel, Thessaloniki in Greece. The conference was organised by Brunel University and supported by the Italian Union of Thermofluiddynamics, Aristotle University of Thessaloniki, University of Thessaly, IPEM, the Process Intensification Network, the Institution of Mechanical Engineers, the Heat Transfer Society, HEXAG - the Heat Exchange Action Group, and the Energy Institute.The optimization of microreactor designs for applications in chemical process engineering usually requires knowledge of the residence time distribution (RTD). The applicability of established models to microstructured reactors is currently under debate (Bošković et al. 2008, Günther et al. 2004, Stief et al. 2008). This work provides new experimental data on the residence time distributions of gas flows through different types of microstructured reactors and analyses the data with established RTD models. By this, the dispersion model was found to describe the RTD behavior of gas flow for a majority of the microstructured devices tested. The model could therefore be used to predict the RTD of those reactors.German Federal Ministry of Economics and Technology (IGF Project 15495

Nano-photocatalysts in microfluidics, energy conversion and environmental applications

Extensive studies have been carried out on photocatalytic materials in recent years as photocatalytic reactions offer a promising solution for solar energy conversion and environmental remediation. Currently available commercial photocatalysts still lack efficiency and thus are economically not viable for replacing traditional sources of energy. This article focuses on recent developments in novel nano-photocatalyst materials to enhance photocatalytic activity. Recent reports on optofluidic systems, new synthesis of photocatalytic composite materials and motile photocatalysts are discussed in this article.Postprint (published version