Hydrodynamic and mass transfer in inertial gas–liquid flow regimes through straight and meandering millimetric square channels

Heat-exchanger reactors are an important part of process intensification technology. For plate geometries, one solution for intensifying transfer and increasing residence times is to construct two-dimensional meandering channels. Supported by this scientific context, the present work aims at characterising gas–liquid mass transfer in the same square millimetric meandering channel, as in Anxionnaz (2009), this constituted the preliminary step required for performing exothermic gas–liquid reactions. Firstly, the gas–liquid hydrodynamics were characterised for a water/air system. When compared to a straight channel of identical compactness and sectional-area (2×2 mm2), the meandering channel induced (i) a delay in the transition from Taylor to annular-slug regimes, (ii) a rise of 10–20% in bubble lengths while conserving almost identical slug lengths, (iii) higher deformations of bubble nose and rear due to centrifugal forces (bends). Secondly, an original method for verifying the relevancy of the plug flow model and accurately determining kla was used (measurements of concentrations in dissolved oxygen along the channel length). For the Taylor flow regime, kla increased coherently when increasing jg, and the meandering geometry had a small influence. On the contrary, this effect was found no more negligible for the slug-annular flow regime. Whatever the channels, the NTUl remained low, thus showing that, even if millimetric channels allowed to intensify kla, a special attention should be paid for generating sufficient residence times. At identical compactness, the meandering channel was found to be the most competitive. Finally, results on gas–liquid interfacial areas and mass transfer coefficients were confronted and discussed with respect to the predictions issued from the model developed by Van Baten and Krishna (2004)

Current methods for characterising mixing and flow in microchannels

This article reviews existing methods for the characterisation of mixing and flow in microchannels, micromixers and microreactors. In particular, it analyses the current experimental techniques and methods available for characterising mixing and the associated phenomena in single and multiphase flow. The review shows that the majority of the experimental techniques used for characterising mixing and two-phase flow in microchannels employ optical methods, which require optical access to the flow, or off-line measurements. Indeed visual measurements are very important for the fundamental understanding of the physics of these flows and the rapid advances in optical measurement techniques, like confocal scanning laser microscopy and high resolution stereo micro particle image velocimetry, are now making full field data retrieval possible. However, integration of microchannel devices in industrial processes will require on-line measurements for process control that do not necessarily rely on optical techniques. Developments are being made in the areas of non-intrusive sensors, magnetic resonance techniques, ultrasonic spectroscopy and on-line flow through measurement cells. The advances made in these areas will certainly be of increasing interest in the future as microchannels are more frequently employed in continuous flow equipment for industrial applications

Liquid-liquid microreactors for phase transfer catalysis

The research carried out within this thesis studied the hydrodynamics, reaction applications and scale-up of liquid-liquid microreactors. The liquid-liquid flow patterns in microchannels were evaluated in terms of stability, surface-to-volume ratio, achieved throughput and extraction efficiency. The research focused on the optimal flow patterns, the slug and bubbly flow. A liquid-liquid slug flow pressure drop model was developed and validated on examples of water-toluene and water/ethylene glycol-toluene slug flow. The fluidic control over the interfaces in a slug flow microreactor was employed to study a complex system of liquid-liquid phase transfer catalyzed alkylation of phenylacetonitrile. Last, a novel microstructured redispersion reactor was developed and tested on the example of phase transfer catalyzed esterification, allowing for significant increases in yield, process safety and waste reduction compared to the conventional process

Optimisation of operating conditions in batch for more sustainable continuous process transposition

Implementation of exothermic and fast reactions requires a perfect temperature control to avoid thermal runaway and in most cases to limit by-products production. In order to fit with the heat removal capacity of common devices, expensive strategies are currently used to slow down this kind of reactions in order to avoid a strong temperature increase such as reactants dilution. Within the concept of process intensification, industries could move towards more sustainable process by reducing technology constraints to the benefit of chemistry. For that purpose, a two-step methodology is implemented. The first step consists in the optimisation of the operating conditions only based on stoichio-chemical scheme and kinetic laws. This is carried out by adjusting temperature profile and feeding rate strategy in a batch operation. Then a design for a continuous process is proposed, trying to approach the optimal batch operating conditions. This methodology is applied to the linear alkylbenzene sulfonation

Numerical Investigation of Cryopreserved Zebrafish Sperm Cell Activation in Microchannels

This aim of this research project is to probe the activation process of zebrafish spermatozoa. Zebrafish are a model species for biological engineering applications, and the cryopreservation of their reproductive cells allows for inexpensive cataloging and maintenance of valuable biological material. Evaluation of cryopreservation protocols for aquatic sperm cells is typically accomplished by motility analysis after subjecting cells to a cryopreservation treatment. In zebrafish sperm cells, motility is initiated when cells come into contact with a hypo-osmotic environment. Subsequent activation analysis is currently done manually and brings with it an inherent difficulty and error. This process is slow and not ideal for high-throughput sample processing and analysis. As such, there is a critical need for an influx of enabling technologies to improve the throughput and optimization of these procedures. Microfluidics offers an intriguing solution to this problem. These devices, the size of a single 1-inch by 3-inch glass slide, offer automated, high-throughput, highly reproducible results. Additionally they utilize small sample volumes, which is important in minimizing valuable sample loss. Cells can be input into a micromixer which can rapidly dilute the extracellular environment, and then sent to an analysis chamber that acn determine the efficacy of a cryopreservation treatment. Despite its popularity in other fields, computational modeling of sperm cell activation has been nearly non-existent in literature. In this work, we model both the macroscopic aspects of particulate flow in a microchannel, and the microscopic mass transport across the cellular membrane. By tracking cells as they move throughout a simulated microdevice, we can find a history for each particle and predict cell outcomes. We are the first to introduce this combinatory model to the problem of cryoprotectant loading, where numerical modeling has well-established presence, and to the problem of zebrafish sperm cell activation. I envision the combination of microfluidics, with their controllable and reproducible flow patterns, and computational methods capturing both macro- and micro-transport, as two examples of the very enabling technologies that cryopreservation needs. While we apply these methods primarily to sperm cell analysis, the framework can be widely applied to a variety of cells and tissues

Simulations and Experimental Analysis of High-Aspect-Ratio Diffusive Micro-Mixers

Passive (diffusional) mixing has been used in designing high-aspect-ratio micro-mixers for the purpose of performing the Liagase Detection Reaction (LDR). A simple model was used to design such mixers optimized for pressure drop or time required to deliver a prescribed volume of mixture. The types of mixers considered are simple, cheap, and durable and can perform over a broad range of volumetric flow rates at reasonably modest pressure drops. The fluids typically have a very low diffusion coefficient of=1.2x10^10m^2/s, and thus diffusional mixing can only be effective in high-aspect-ratio micro-channels. A realizable aspect ratio of 6 has been considered initially because it is easily releasable using the LIGA technique. Numerical simulations were performed on various diffusional-based micromixer configurations. Two variants of a Y-type mixer with contraction and several variants of a mixer employing jets in cross-flow have been simulated. The various mixers have been evaluated in terms of volumetric mixing efficiencies and maximum pressure drops. One of the mixers with jets-in-cross-flow was found to perform best. In addition, the effect of jet width and expansion after the mixing were assessed. Experimental validations for the jets-in-cross-flow mixer were performed. The mixer was manufactured using a micromilled brass mold insert hot embossed into a Polymethyl-methacrylate (PMMA) substrate, which was then covered with 0.125mm PMMA coverslip. A chemiluminescence technique was applied for the first time to make Qqualitative observations of the mixing zones. Quantitative mixing efficiency experiments were performed by using Rhodamine B fluorescent dye solution and de-ionized water. The experimental results show good agreement with numerical simulations

Heat Management for Process Intensification of Fast Exothermic Reactions in Microstructured Reactors

Nowadays, the production in fine chemical and pharmaceutical industry is mostly carried out in large scale batch reactors having typically dimensions of a few meters to satisfy the demand of the market. Even though this technology has been widely used and developed for centuries, it is by far not optimal for every type of reaction. For example, when working with exothermic reactions, the produced heat can’t be always fully evacuated. To avoid run-aways, high amounts of solvents are used to increase the heat capacity of the mixture, or semi-batch mode with a slow addition of one of the reactants. In both cases, the space-time yield, i.e. mass of product produced per unit of time and per unit of volume, drastically diminishes. One of the main enabling technologies allowing process intensification are the microstructured devices, characterized by high heat and mass transport rates due to the small characteristic dimensions (< 1mm). Using this type of equipment, almost isothermal conditions can be achieved while carrying out fast exothermic reactions (with characteristic reaction times down to tr ≈ 10 s). Thereby, the target throughput is reached by numbering-up, i.e. parallel connection of several identical microreactors. For very fast exothermic reactions, especially for quasi-instantaneous reactions, dimensions smaller than 100 μm are needed to prevent the formation of unwanted hot spots. As such small dimensions are not suitable for industrial scale due to possible clogging and high pressure drops, other solutions are warranted. The aim of this thesis is to develop alternative microstructured reactors enabling quasi-instantaneous reactions to be carried out under intensified conditions while suppressing the large hot spots. The work is divided into two main parts: determination of suitable strategies for the microstructured reactor design via numerical simulations (Chapter 3) and the experimental validation of the best microstructured reactor concept (Chapter 4-6). Three strategies for enhanced temperature control within microstructured reactors for quasi-instantaneous reactions are taken for analysis using numerical simulation: 1) reduction of hot spot temperature by increased axial heat transfer in the reactor wall, 2) by injection of one reactant in multiple points along the reactor length and 3) by continuous injection of one reactant through a porous wall in a concentric reactor geometry. The multi-injection reactor (option 2) is the most effective design since with an optimized dosing with only 4 injection points the temperature rise is 5-fold smaller as compared to the adiabatic temperature rise. Furthermore, the key design requirements for an efficient multi-injection reactor are identified: 1) complete mixing after each injection and 2) evacuation of the produced heat before reaching the next injection point. To experimentally validate the simulation results, in the subsequent chapter, an experimental method to monitor temperature in microstructured reactors is developed (Chapter 4). To track axial temperature profiles quantitatively, a method based on non-intrusive infrared thermography is developed yielding a resolution of 100 points/mm2 and a precision of 1 °C. In the first validation experiments, the heat transfer coefficient determined in a micro heat exchanger (574 W/m2K) is in good agreement with prior estimations. While carrying out the hydrolysis of tetraethoxysilane as a fast model reaction, incomplete mixing of the reactants is detected via the temperature profile, and is ascribed to the high difference in density of the inlet flows. Applying the method of quantitative IR-thermography to a T-micromixer with circular cross section gives insight into the mixing phenomenon (Chapter 5). The latter is studied via the temperature profile of the reactions strongly controlled by mixing, i.e. dilution of sulfuric acid with water and cyclization of pseudoionone. The mass transfer coefficients determined are in the order of 0.1-9 1/s. It is shown that at high Fourier numbers Fo = tdiff/τ (mixing by shearing), the Damköhler number DaI= τ/tmix remains constant with respect to flow rate at the reactor outlet, as both, mixing time and residence time decrease proportionally with the latter parameter. To enhance the mixing performance, two approaches are applied: 1) the introduction of a carrier phase leading to travelling micro-batches with up to 4-fold faster mixing and 2) the structuring of the channel walls leading to the formation of vortices, and thus, to a substantially improved mixing efficiency. For efficient mixing in the multi-injection reactor (Chapter 6), two types of mixing structures, i.e. the tangential mixer and the herringbone mixer, are developed using low temperature co-fired ceramics, and compared using quantitative infrared thermography. The best mixing performance is obtained by the herringbone structure, providing efficient mixing in a large range of flow rates corresponding to Reynolds numbers Re = 20-130. Finally, a multi-injection reactor comprising three injection points and the herringbone microstructure is developed. Using the quasi-instantaneous and exothermic cyclisation of pseudoionone to α-ionone and β-ionone as model reaction, it is demonstrated that the temperature rise can be reduced 8-fold compared to the adiabatic temperature rise due to 1) the high volumetric heat transfer coefficient in the order of 4·106 W/(m3K), 2) the reduced overall transformation rate due to gradual mixing within the herringbone structure and 3) the injection of pseudoionone at three injection points. Yields of α-ionone and β-ionone above 98 % are achieved at a residence time of 3.7 s while efficiently avoiding the unwanted consecutive polymerization in a temperature range of 30-60 °C. Compared to the conventional semi-batch process, where such high yields can only be attained at temperatures below 10 °C, a 500-fold increased space-time- yield is achieved. In addition to the intensification of the process, the required mass of solvent is halved while maintaining good temperature control, rendering the overall process safe