Development of a novel microreactor-based calorimeter for the study of fast exothermal reactions in liquid phase

Following several tragic chemical accidents that have occurred in recent years, some directives concerning chemical process safety have been issued. The Seveso directive, for example, requires a precise description of the consequences of a possible chemical accident assuming a worst-case scenario. However, to build such scenarios and, hence, make chemical processes safe, profound knowledge of the kinetic and thermal parameters of the reactions in question is necessary. These parameters are usually determined by calorimetric methods. However, in the existing commercial calorimeters the characterization of fast, exothermal reactions raises several problems. Indeed, on the one hand, it is difficult to maintain the isothermal conditions required to determine the kinetics simply and precisely. On the other hand, the calorimeter should be able to measure the heat flow generated as soon as the reactants are brought into contact. It should be able to do this without the need for a period of thermal equilibration that would perturb the measurements, and without any limitations due to the mixing of the reactants. The aim of this work is to develop a calorimetric method that is particularly adapted to studying fast exothermal reactions. The proposed system combines a microreactor with a commercially available microcalorimeter. In the first part of this project a flexible technique for constructing microreactors was chosen. The technique had to be precise, reproducible and inexpensive. The geometry of the microreactor had to fit into the cavity of the commercially available microcalorimeter. The technique chosen was the silk-screen printing of a thick film dielectric. This method makes it possible to build quickly and at low cost numerous microreactors that can be regarded as disposables. The geometry of the reaction channel can be varied and can be adapted to the type of reaction. Once the microreactors were built, the degree of mixing obtained in the microchannels was estimated first by simulation and then by experiment. The flow in the reaction channel was found to be purely laminar and the mixing time corresponded to the time for radial diffusion. Due to the small size of the channels, the mixing time was found to be adequate and not limiting for the characterization of fast reactions. The microreactor was then inserted into the cavity of the commercial calorimeter. The resulting microsystem was calibrated using the neutralization reaction of sulphuric acid with NaOH. This system was further modified to optimize the thermal transfer between the reaction channel and the sensor of the microcalorimeter and to increase its thermal efficiency. Finally, an electrical preheating system of the incoming liquids was put in place and tested. Once the quality of the thermal signal had been optimized, kinetic studies of chemical reactions could be undertaken. First, a model reaction was studied in order to validate the results obtained with the microsystem and to avoid the risk of systematic errors. In the second stage, a previously unknown fast exothermal reaction was characterized. The heat flows measured during the reaction reached 160'000 W·kg-1 but the conditions, however, remained completely isothermal. The global kinetics of this reaction as well as its activation energy were determined.

Nanofibres de carbone sur filtre métallique comme support catalytique structuré

Pascal Tribolet

The main objectives of this work are 2-fold : The development of a novel type of composite material based on carbon nanofibers supported on sintered metal fibers filters (CNF/SMF) and to explore the use of this material as a catalytic support for a model reaction: selective hydrogenation of acetylene. The advantages of this novel support are: Due to carbon nanofibers, it combines a graphitic structure with a high specific surface area without microporosity. Supported carbon nanofibers can be used in a fixed bed reactor without very high pressure drop. Combination of two materials with high thermal conductivity gives a composite which keeps this property. It is suitable for highly exo/endothermic reactions, diminishing temperature gradients in the catalytic bed. The synthesis of carbon nanofibers on SMF filters was carried out by ethane catalytic decomposition at 655°C directly on metallic filters. An oxidation of SMF followed by a reduction in H2 create surface roughness, leading to a larger area for CNF nucleation. The CNF formation mechanism includes several steps: it starts with carbon deposition on metallic surface followed by its diffusion into the metal leading to carbides formation. When the limit of carbon solubility is attained, a layer of carbon is formed on the surface of metallic fibers. High tension within the bulk metal leads to carbide dissociation and by phase separation to graphite formation, which pushes the metallic particles through the carbon layer. Nickel, stainless steel an Inconel (an alloy of mainly nickel, iron and chromium) filters were used. The latter gave the highest uniformity of the carbon nanofibers layer showing an excellent mechanical stability. In order to control carbon deposition on the filters, a formal kinetic analysis of the decomposition reaction was undertaken. Partial orders of 1 for ethane, -2 for hydrogen and an apparent activation energy of 235 kJ/mol were obtained. The observed kinetics suggests strongly that the C – C bond scission is the rate determining step and not carbon diffusion into the metal which is often reported in the literature. The synthesis procedures like time on stream and reaction temperature were optimized: 1 hour of a mixture C2H6:H2:Ar (3:17:80) decomposition over SMFInconel at 655°C lead to ∼6% of carbon, leading to a CNF layer of 1 µm thickness covering the metallic fibers entirely. This material presents a high specific surface area (22.2 m2/g) and a low pressure drop for the gas flowing through. The carbon nanofibers have a diameter between 20 and 50 nm and a crystalline structure with platelets morphology where the graphene layers are stacked one above the other. Their surface is composed almost exclusively of carbon and hydrogen. Amongst the multiple possible applications of this novel composite material, its use as a catalyst support was assessed. Selective hydrogenation of acetylene was carried out over palladium supported on CNF/SMF and compared with commercial supports (ACF, EGF and AGF). The activated carbon fibers cloth (ACF) led to a Pd activity at least twice as E-type glass fibers tissue (EGF) or EGF covered by an alumina layer (AGF). Reaction kinetics was studied for Pd/ACF, leading to acetylene and hydrogen partial orders of -0.5 and 2.4, respectively and apparent activation energy of 50 kJ/mol. The negative partial order for C2H2 suggests high adsorption strength of this compound compared to other reagents on palladium. This particularity allows Pd to be selective. Hydrogenations are known to be structure sensitive. Therefore the catalyst activity for the model reaction depends on Pd particle size. It increases for large particle sizes. The control of this parameter was a priority. Variations of the palladium precursor, of the support and catalyst treatment were carried out. Micro-wave plasma was used since it is fast and has low energy consumption allowing chemically modifying the carbon support surface and activating catalyst after impregnation. This controls not only palladium sintering, but also decomposes tetraaminopalladate more efficiently, resulting in a catalyst activity of one order of magnitude higher. In order to control the palladium deposition on CNF/SMFInconel composite, it is important to have surface functional groups. The activation of carbon nanofibers was carried out with a 4 hours treatment in a boiling aqueous solution of hydrogen peroxide. This led to an amount on surface oxygen containing groups, per mass of carbon, higher than in ACF. Palladium particle size on the composite was controlled by support activation, the use of several metal precursors or different loadings or by a thermal treatment in argon at 500°C. Optimisation of the procedure allowed to obtain in a controlled way an average palladium particle sizes between 3.6 and 25 nm. The activity and selectivity towards ethylene of Pd/CNF/SMFInconel were observed to be higher compared to palladium supported on activated carbon, alumina or barite. Graphitic nature of carbon nanofibers, leading to strong metal-support interaction, was accounted as responsible for these improvements. The high thermal conductivity of the composite CNF/SMF ensured good heat transfer released due to the exothermicity of the reaction and allowed to work close to isothermal conditions in the catalytic bed. Finally it can be concluded, that for the first time carbon nanofibers synthesis was carried out in one step on sintered metal fibers filters, resulting in a novel structured composite material combining different specific properties and having promising potential applications.

EPFL2006

Intensification of Gas/Liquid Chemical Synthesis Using Microreactors and New Operating Windows

Anne-Laure Dessimoz

Process intensification is a vibrating topic in the field of chemical engineering. Its aim is to develop processes and methods with increased performance for a given chemical transformation at decreased energy consumption and waste production. Among all methods of process intensification, the microreactors are very promising (chapter I). In the case of fast gas-liquid reactions, microreactors allow to speed up the physical processes. Due to high surface to volume ratio, high mass and heat transfer performances can be achieved compared to conventional processes, leading to process intensification. In the present work (chapter III), the flow patterns and the mass transfer were studied in glass microreactors for CO2-water based systems. Volumetric mass transfer coefficients up to 9 s-1 were measured for slug flow regime in microreactors with hydraulic diameters of 400 µm. These values are at least one order of magnitude higher than for conventional contactors. Based on the experimental results, empirical correlations were developed to predict the flow regimes and the mass transfer performance. The obtained results enable a rational design of microreactors for fast gas-liquid transformations. In the case of slow chemical reactions, high pressure and temperature (high P&T) can be used to speed up the intrinsic kinetics. The microreactors offer the opportunity to perform reactions under harsh conditions due to excellent control of process parameters. The potential of unusual operating conditions (high P&T) was investigated to reduce the reaction time and increase the specific productivity of the aqueous Kolbe-Schmitt synthesis of beta-resorcylic acid (chapter IV). Based on a kinetic and thermodynamic model, the optimal operating window for the reaction was defined. The model prediction was successfully validated with a new micro-plant operated under high pressure and temperature. Moreover, a scale-up strategy was proposed using Sulzer milli static mixers. The new process allows to synthesise beta-resorcylic acid with 100% selectivity, to increase the performance by 2 orders of magnitude as compared to conventional batch process and to reduce by a factor of 4.2 the consumption of the costly reagent KHCO3. The same strategy was further applied to intensify the ethoxylation of dodecanol, an important industrial reaction (chapter V). As ethylene oxide processes have inherent safety vulnerability, an extensive calorimetric study was carried out under high P&T. For the first time, solubility and kinetic models were established up to 523K and 50 bar. Simulations were performed to predict the productivity of a new milli-plant based on Sulzer milli static mixers. It was demonstrated that, using a multi-injection reactor, the specific productivity can be increased 6 times as compared to conventional semi-batch reactors.

EPFL2011

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