Numerical characterization and engineering of transport in morphologically complex heterogeneous media

A multi-scale numerical methodology for the assessment of radiation and optical characteristics of complex structured soot-contaminated snow layers was investigated first. The methodology accounted for the exact morphology at the various scales and utilizes volume-averaging approaches with the corresponding effective properties to couple the scales. At the continuum level, the volume-averaged coupled radiative transfer equations were solved utilizing i) effective radiative transport properties obtained by direct Monte Carlo simulations at the pore level, and ii) averaged bulk material properties obtained at particle level by discrete dipole approximation calculations. The contribution of soot additives to the radiative forcing was quantitatively estimated by numerical simulation and qualitatively validated with the published experimental data.Additional coupled heat and mass transfer phenomena were then investigated for a two-step solar thermochemical water/carbon dioxide splitting reactor. It was composed of two distinct scales: porous reacting materials at the mesoscale and a batch reactor at the macro-scale. A transient multi-physics volume-averaged model of the reactive porous media undergoing the reduction and oxidation steps was developed. The effective heat and mass transport properties of reticulated porous foams were incorporated through porosity-dependent empirical correlations. Porosity-dependent reduction, oxidation, and cyclic performance for a uniform and homogenous porous structure were assessed and followed by the investigation of diverse structures with non-uniform porosities along the reactor. Subsequently, the effect of structural anisotropy on the system performance was assessed by extending the previous model into 2-dimensions. The porous medium was assumed to exhibit anisotropic transport behaviors in terms of heat transfer (radiation, conduction, convection) and mass transfer. Additionally, two operational configurations were investigated: a conventional concurrent flow configuration of fluid and irradiation and a scenario where the principal flow axis was perpendicular to the irradiation direction. In terms of radiative properties, a structure with a complete forward scattering phase function and low scattering albedo ensured the largest absorption, increasing the production rate. Anisotropic structures with a higher degree of anisotropy in permeability were more favored when the incoming radiation was perpendicular to the fluid flow direction, where the interphase heat convection was enhanced.Lastly, the engineering of the porous structure was explored by establishing a direct relationship between the local morphological characteristics and the reduction performance. This was implemented by direct-pore simulations on the discrete scale that were directly coupled to the volume-averaged finite volume simulations on the continuum scale. A large number of porous structures were artificially generated and its transport characteristics calculated by the pore-levels simulations. These calculated results were used to train a machine-learning algorithm that predicted the oxygen yield solely from based on the morphology. The learning algorithm identified the most significant morphological descriptors for a specific performance target and provided guidelines for the optimal porous structure design.

Replicated microcellular aluminium structures for thermal management

Alexandros Athanasiou-Ioannou

Open-pore aluminium foams are of interest in thermal management of power electronics due to their large specific surface area, low weight and relatively high thermal conductivity. The replication process is a low-cost and simple foam manufacturing method that offers many opportunities for the investigation of the influence exerted by the microstructure (porosity, pore size) and geometry or their combination in the performance of metal foams in heat-exchange applications. In this study, we explored replicated aluminium foams as a part of an integrated heat sink manufactured in one step that seamlessly combines metal and ceramic phases. Replicated aluminium foams were manufactured and tested first under natural and then under forced convection. A dedicated test apparatus was built to test these samples under both natural and forced convection, using the guarding ring technique. In the case of natural convection, the aluminium foams had different pore sizes (125-180 µm, 400-450 µm and 5 mm), porosities (78 to 86%) and geometry (disk, cylinder and finned structures). In all cases, replicated aluminium foams were found to dissipate the same amount of heat as their bulk aluminium (alloy) equivalents. The thermal heat exchange performance of replicated microcellular aluminium was also measured under forced convection. The test rig was modified to measure the pressure drop and volumetric air flow in a cylindrically symmetric jet impingement configuration. Foams of different pore size (125-180, 400-450 and 900-1300 µm), porosity (between 75 and 85 %), height (1 and 2.8 cm) and infiltrated at various pressures (between 2.7 and 70 bars) were manufactured for thermal testing, all having a hollow central channel, through which air is injected at a range of flow rates. The results show that within the covered parameter range foams of higher porosities, larger pore sizes and lower infiltration pressures dissipate more heat at lower cost in terms of pumping power. Shorter heights also dissipate more heat for a given volumetric flow but do so at the cost of an increased pressure drop and hence greater pumping power expenditure. A numerical model, developed and written by Dr. D. Ingram, using the finite-volumes technique, was employed to elucidate how the various parameters influence the heat transfer. The model solves the Darcy-Forchheimer formulation of fluid flow in porous media, which is then coupled to a convective/conductive heat transfer model of the same structure. These simulations were used to perform parametric studies on the influence of height and pore size with regard to the thermal behaviour of replicated foams. Furthermore, the model was benchmarked against the experimental results; overall, despite some discrepancies with measured temperature profiles, the model captures data trends well, and provides insight on the physical phenomena that underlie the experimental data and observations. In particular, the presence and influence of recirculating air flow along the inner portion of the heat exchanger structures was identified. Finally, we successfully fabricated the proposed integrated multimaterial structure and tested it under forced convection, using the same conditions as the replicated aluminium foams. Results demonstrate that this type of structures can be effectively used to cool power electronics.

EPFL2017

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

Julien Haber

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.

EPFL2013

Compact reactor for continuous multi-phase reactions

Martin Grasemann

The objective of this thesis is the development of a compact reactor for continuous three-phase reactions in single-pass configurations. The design is based on a bubble column reactor staged with layers of catalytic material. To make the reactor suitable for reactions with high adiabatic temperature rise such as highly exothermic hydrogenation reactions under solvent free conditions, work focuses on two different aspects of integrated reactor and catalyst design: Preparation and characterization of structured catalyst stages optimized for high intrinsic activity as well as for intense gas-liquid redistribution and mass transfer on each reactor stage Development of heat transfer equipment integrated in the staged bubble column for efficient, quasi continuous in-line removal of process heat. Chapter 3 is dedicated to the preparation and characterization of a structured catalyst for the use in a staged bubble column reactor. Sintered Metal Filters (SMF), a material consisting of metal fibers with a diameter of ~ 20 µm forming thin and highly porous sheets is chosen as support material. The fibers are coated with a 5wt% layer of ZnO grains, leaving the open structure of the SMF material intact. Monodispersed Pd nanoparticles as active phase are deposited on the ZnO surface layer with a total metal loading of 0.2wt%. The resulting Pd/ZnO/SMF catalyst shows high activity in the model hydrogenation reaction of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-butene-2-ol (MBE). Semi-batch autoclave hydrogenations show rates of up to 30 mol/molPds with target product (MBE) yields of up to 96.5%. Activity and selectivity of the Pd/ZnO/SMF catalyst are strongly influenced by Strong Metal Support Interaction (SMSI) between the ZnO support and the deposited Pd nanoparticles. XPS and XRD analysis show the formation of a PdZn alloy already under ambient conditions, decreasing the catalyst activity but, on the other hand, preventing strong catalyst deactivation. The formation of this alloy phase was observed under ambient conditions as well as low temperature reaction conditions, but can also be achieved by high temperature treatment of the catalyst in hydrogen atmosphere. The intrinsic kinetics of the MBY hydrogenation was studied in semi-batch experiments. First order towards hydrogen was found and a Langmuir-Hinshelwood kinetic model was developed, describing the experimental data reasonably well. Chapter 4 describes a compact heat exchange (HEX) element integrated in the SBCR. The cross flow heat exchanger design is based on vertical micro-slits of 0.3mm width, a breadth between 12mm and 40mm and 6mm length as reaction side channel geometry, ensuring a minimum of added reaction volume and small heat transfer distances. The single and two-phase heat transfer performance of the HEX element is studied considering the influence of gas and liquid superficial velocities as well as liquid properties. With one SMF layer placed at the HEX element entrance redispersing gas and liquid phase, heat transfer performance was observed to increase linearly with gas and liquid throughput. The maximum heat transfer performance per reaction volume was determined as ~ 0.5 MW/m3K, obtained for moderate gas and liquid superficial velocities. The hydrodynamics of a bubble column staged only with ZnO/SMF sheets show an narrow residence time distribution (RTD) and negligible backmixing through the catalyst layers. The RTD can be described accurately by a "tanks-in-series" model. The gas-liquid pressure drop through the SMF material is mainly governed by capillary effects and the gas velocity. A semi-empirical model is developed, combining both friction and surface tension effects and predicting the pressure drop through the SMF material with an accuracy of ±10%. In Chapter 5, the novel SBCR based on Pd/ZnO/SMF catalytic stages and the integrated micro-HEX elements are tested in the hydrogenation model reaction of MBY to MBE. The reaction in a loop setup comprising 5 HEX/catalyst stages is shown to be strongly influenced by external mass transfer, resulting in an observed catalyst effectiveness below 65%. Intense gas-liquid mass transfer in the SMF structure leads to high volumetric mass transfer coefficient in the staged bubble column of 1s-1 - 4s-1 and an observed reactor productivity of up to ~ 12000 kg/m3h. This signifies an increase of around two orders of magnitude compared to standard industrial semi-batch equipment. High catalyst densities in the reactor lead to high reactor productivity, but have a detrimental effect on product selectivity. The drop in product yield amounts up to 6% for high catalyst density, but can be decreased to only 0.5% if a 5mm distance ring is inserted between HEX stages to decrease the catalyst loading in the reactor.

EPFL2009