An Improved CFD Tool to Simulate Adiabatic and Diabatic Two-Phase Flows

With increasing computer capabilities, numerical modeling of two-phase flows has developed significantly over the last few years. Although there are two main categories, namely 'one' fluid and 'two' fluid methods, the 'one' fluid methods are more commonly used for tracking or capturing the interface between two fluids. Level set (LS), volume-of-fluid (VOF), front tracking, marker-and-cell (MAC) and lattice Boltzmann (LB) methods are all 'one' fluid methods. It is clear that there is no perfect method; each method has advantages and disadvantages which make it more appropriate for one kind of problem than for others. For instance, a LS method will accurately compute the curvature and the normal to the interface, but tends to loss mass which is physically incorrect. On the other hand, a VOF method will conserve mass up to machine precision, but the computation of the curvature and normal to the interface is not as accurate. In order to minimize the disadvantages of these methods, several authors have used two or more methods together to model two-phase flows. This is the case for the CLSVOF (Couple Level Set Volume Of Fluid) method, where LS and VOF are coupled together in order to better capture the interface. In CLSVOF, the level set function is used to compute the interface curvature and normal to the interface, while the volume of fluid function is used to capture the interface. For two-phase flows in microchannels, surface tension forces play an important role in determining the dynamics of bubbles whereas gravitational forces are generally negligible. Also it is very important to consider the interaction between the boundaries and the fluids by prescribing or computing the correct contact angle between them. The commercial CFD code FLUENT allows the use of static constant angles, or the use of User Defined Functions (UDF) to compute the dynamic contact angles. It is inappropriate to use a static contact angle to model cases involving moving contact lines. For such cases a dynamic contact angle scheme should be implemented. In this study, FLUENT was used to model adiabatic and diabatic, time dependent two-phase flows. Since FLUENT already contains a VOF method, a LS method was implemented and coupled with VOF into FLUENT via UDFs. Furthermore, since the LS function, used to compute the surface tension force, ceases to be a signed distance to the interface even after one time step, a re-initialization equation was solved after each time step. This involved using a fifth order WENO (Weighted Essentially Non Oscillatory) scheme to discretize the space derivatives (otherwise oscillations of the interface occurred), and a first order Euler method for the time integration. In another part of the study, a 3D dynamic contact angle model based on volume fraction, interface reconstruction, and experimentally available advancing and receding static contact angles was also developed and implemented into FLUENT via UDFs. Several validations for the developed CLSVOF method and dynamic contact angle model are presented in this thesis, these includes a static bubble, a bubble rising in a stagnant liquid for Morton numbers ranging from 102 to 10-11, droplet deformation due to a vortex flow field, droplets spreading over a wall under the gravity effect and droplets sliding over a wall due to gravity. These validations demonstrated the high accuracy and the stability of our methods for modeling these phenomena. A heat and mass transfer model was also implemented into the commercial CFD code FLUENT for simulating of boiling (and condensation) heat transfer. Several simulations were presented with water and R134a as working fluids. The influence of the contact angle and the wall superheat was also studied.

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

Ammonia two-phase flow in a horizontal smooth tube: Flow pattern observations, diabatic and adiabatic frictional pressure drops and assessment of prediction methods

Ricardo Lima, Jesus Moreno Quiben, John Richard Thome

The present study illustrates new experimental two-phase flow pattern observations together with diabatic boiling and adiabatic two-phase frictional pressure drop results for ammonia (R7117) flowing inside a 14-mm internal diameter, smooth horizontal stainless steel tube. The flow pattern observations were made for mass velocities of 50, 100 and 160 kg s(-1) m(-2) and saturation temperatures of -14, -2 and 12 degrees C for vapor qualities ranging from 0.05 to 0.6. The flow patterns observed during the study included: stratified-wavy, slug-stratified-wavy, slug, intermittent and annular. For all the experimental conditions, the flow structure observations were compared against the predictions of the flow pattern map model of Wojtan et al. [L. Wojtan, T. Ursenbacher, J.R. Thome, Investigation of flow boiling in horizontal tubes: part I - a new diabatic two-phase How pattern map, Int. J. Heat Mass Transfer 48 (2005) 2955-2969] and showed very good correspondence. The frictional pressure drop measurements were obtained for vapor qualities from 0.05 to 0.6, saturation temperatures from -14 to 14 degrees C, mass velocities from 50 to 160 kg s(-1) m(-2) and heat fluxes from 12 to 25 kW m(-2). The experimental results show the traditional pressure drop trends: the frictional pressure drop increases with vapor quality and mass velocity. Moreover, the results also show that both diabatic and adiabatic frictional pressure drop values are similar, that is, the boiling process in itself does not affect the frictional pressure drop. The correlations of Friedel [L. Friedel, Improved friction drop correlations for horizontal and vertical two-phase pipe flow, in: European Two-Phase Flow Group Meeting, paper E2, Ispra, Italy, 1979], Lockhart and Martinelli [R.W. Lockhart, R.C. Martinelli, Proposed correlation of data for isothermal two-phase two-component in pipes, Chem. Eng. Process 45 (1949) 39-48] and Muller-Steinhagen and Heck [H. Muller-Steinhagen, K. Heck, A simple friction pressure correlation for two-phase flow in pipes, Chem. Eng. Process 20 (1986) 297-308] predicted only 54%, 52% and 60% of the experimental data within +/- 30%, respectively. The correlation of Gronnerud [R. Gronnerud, Investigation of liquid hold-up, flow-resistance and heat transfer in circulation type of evaporators, part iv: two-phase flow resistance in boiling refrigerans, in: Annexe 1972-1, Bull. de I'Inst. Froid, 1979] predicted 93% of the data and the flow pattern based method of Moreno Quiben and Thome [J. Moreno Quiben, J.R. Thome, Flow pattern based two-phase frictional pressure drop model for horizontal tubes. Part II: new phenomenological model, Int.J. Heat Fluid Flow 28 (2007) 1060-1072] predicted more than 97% of the experimental data within the same error band, while the latter method captures almost 89% of the data within +/- 20%. (C) 2008 Elsevier Ltd. All rights reserved.

2009