Multi-configuration evaluation of a megajoule-scale high-temperature latent thermal test-bed

Thermal energy storage via latent heat provides an energy dense solution and, during discharge, a hot stream at a well-defined temperature. Utilizing metal phase change materials (PCMs) and high-temperature operation might enable fast (dis)charging and application in previously unexplored areas (e.g. high-temperature processing industry). But detailed characterization and design guidelines of high-temperature metal latent heat storage systems with tailored characteristics are missing. Here, we introduce a combined experimental-numerical characterization and design tool for high-temperature heat storage units. We apply it to a megajoule-scale test-bed operated with steel encapsulated Al68.5Cu26.5Si5 (weight%) (melting temperature 791 K) as the PCM and air as heat transfer fluid (HTF) for charging and discharging. Thermocouples positioned at multiple locations throughout the storage unit are used to characterize the performance and heterogeneity. For the inaugural experimental campaign, three encapsulated tubes with a total of 1.83 kg PCM were vertically arranged in one of the modular stacks and several multi-hour charging/discharging cycles were performed with the HTF heated up to 30 - 70 K above and below the PCM melting point at a flow rate of 1500 lmin(-1). Specifically designed open-cell cellular Si-SiC lattices were wrapped around the PCM tubes to enhance the heat transfer. The experimental results showed a near-isothermal (+/- 10 K) exit temperature discharge maintained for 0.39 2.67 h. Temperature variations throughout the test-bed indicated that test-bed design is important to ensure homogeneous usage of the PCM and controlled phase change. A quasi-1D lumped parameter multi-mode heat transfer model was developed to quantify the thermal stratification within the PCM, heat losses, and phase change characteristics in the thermal storage, and provided explanation and quantification for the experimentally observed heterogeneities. The model was used to extrapolate the heat storage characteristics to larger scales: a 16.84 MJ and 50.51 MJ latent heat storage with the modular stacks filled with 25.7 kg (42 encapsulated tubes) and 77 kg (126 encapsulated tubes) of the PCM, respectively. The coupled experimental- numerical approach allowed for model validation, explanation of experimental variation, and to provide general design guidelines for practically relevant latent high-temperature (metal) thermal energy storage.

Multi-Scale Study of High-Temperature Latent Heat Storage With Metallic Phase Change Materials

Nithin Mallya

Energy storage is a central issue in the green economy with half the global end energy usage being heat. Latent heat thermal energy storage (LHTES) provides an energy dense heat storage solution with a well-defined discharge temperature. Utilizing low-cost, high-temperature, high-conducting metal alloys as phase change materials (PCMs) enables high energy and power density LHTES systems. Detailed characterization, reliable design tools and guidelines for modelling and building such systems are missing. This thesis presents design-related and operation-oriented innovations for such systems at different scales: (a) application-scale experimental-numerical demonstration of a LHTES test-bed, (b) non-dimensional numerical study of low and high-conducting PCMs at storage-unit scale, (c) novel power dense macro-porous PCM structures at encapsulation scale, and (d) interface scale experimental melt interface tracking by advanced tomography techniques for high-temperature PCMs.A megajoule scale high-temperature LHTES modular LHTES test-bed was built and tested, for charging-discharging at temperatures up to 950 K with aluminium alloy PCM encapsulated in stainless steel and air as the heat transfer fluid (HTF). Engineered open-cell cellular ceramic lattice were used as porous fins for enhancing the HTF-PCM heat transfer. Successful first operation was demonstrated with near-isothermal discharge for 2.7 hours in a 1.31 MJ storage. A quasi-1D lumped parameter model was developed and validated to quantify its thermal stratification, heat losses, and phase change characteristics. Heat storage characteristics of scaled configurations of the test-bed were predicted using the model.A 2D transient phase change model was used to compare a high-conducting, high melting point aluminium alloy PCM with a commercially available low-conducting, low melting point paraffin wax to quantify the effect of PCM properties, encapsulation shape, load conditions, and buoyancy driven internal convection on the power density. Parametric study and non-dimensional analysis quantified the influence of thermal and geometrical parameters on phase change and contribution of natural convection inside the encapsulations linking the melt fraction and heat transfer rates to combination of Fourier, Stefan, Rayleigh and Nusselt numbers.With high-conducting PCMs, the LHTES power density is limited by HTF-PCM convective heat transfer which can be enhanced by using novel macro-porous encapsulation designs. A comparison of several random and ordered macro-porous cells was performed with a 3D coupled CFD-phase change model. A mesh-based convolutional neural network was trained to emulate the 3D model and predict phase change time and pressure drop characteristics. Finally, a synchrotron source X-ray tomography experimental campaign to create a validation case for phase change models of high-temperature PCMs is detailed. Transient 3D melt interface tracking was conducted for aluminium alloy in cylindrical encapsulations heated using lasers. As the beamline was limited to small samples, a furnace heating setup was also built for radiography experiments of larger cubic samples at a tabletop CT facility.This thesis presents a combination of modelling frameworks and experimental setups to provide general understanding of transient heat transfer in PCMs at different scales, provide novel approaches for heat transfer enhancement, and tools for designing high-temperature LHTES systems.

EPFL2022

Production d'hydrogène dans un réacteur microstructuré

Pierre Reuse

The aim of this work was to operate the steam reforming of methanol and the total oxidation of methanol in a microstructured two-passage reactor. The steam reforming enables the production of hydrogen at relatively low temperatures (250 °C) with only a small amount of carbon monoxide (~ 1%). After a cleaning step (CO preferential oxidation, for example), this hydrogen would be a good feed for a fuel cell to produce electricity for mobile applications. Steam reforming is an endothermic reaction. The energy needed to run this reaction is produced by the total oxidation, a strongly exothermic reaction. To allow an efficient heat transfer between these two reactions, a microstructured reactor was used. These structures, with dimensions in the micron range, are widely known to have far better heat transfer capacity than traditional heat exchangers. Furthermore, these structures have some unique features with respect to classical reactors. A narrow residence time distribution, close to that of a plug flow reactor, can be obtained, keeping selectivity high for complex reactions. Microstructured reactors also have small residence time, allowing very quick variations in the feed and experimental conditions. In chapter 4, the concepts relating to the channel coatings will be presented. A Cu/Zn/Al catalyst provided by Süd-Chemie was transformed into a suspension of nanoparticles in isopropanol by using an attrition grinding apparatus. A thin layer (~5 µm) of catalyst was formed on the microchannel walls. Several tests were performed to characterize the adhesion of this layer. The influence of the layer on the residence time distribution was also investigated; it was possible to maintain Bodenstein numbers as high as 50. Chapter 5 is focused on the steam reforming of methanol, the reaction that generates hydrogen. A kinetic analysis in differential and integral modes established that the rate of the reaction is inhibited by hydrogen, the main product of the reaction; the partial order is - 0.2. The influence of water on the rate of reaction is negligible (partial order of 0.1), and methanol has a positive partial order of 0.7. A kinetic constant of 5.57 · 10-6 mol0.4 · (m3)0.6 · gcat-1 · s-1 at 200 °C and an activation energy of 73.9 kJ · mol-1 complete the description of the kinetics of the steam reforming. Throughout the comparisons, we showed that the catalyst coated in the microchannels has an initial rate for the steam reforming 30% higher than the original catalyst in fixed bed. We can therefore conclude that the catalyst modification procedure does not diminish the catalyst activity. This was also shown by comparing our results with results available in the scientific literature for similar catalysts. CO2 selectivity remains high and constant then decreases as 90% conversion is approached. Working with an excess of water with respect to methanol contributes to keeping the selectivity high. A molar ratio of 1.2 is a good compromise between selectivity and increased energy costs due to the vaporization of the additional water. It's also beneficial to work at conversions below 90% to be in the high selectivity domain and to diminish the inhibiting influence of hydrogen. Finally, we showed that this catalyst deactivates over 100 hours at a temperature of 300 °C. A kinetic model for the deactivation at temperatures between 300 °C and 330 °C was established. In chapter 6 the total oxidation of methanol was studied. A cobalt based catalyst was developed to allow the synchronization of the two reactions temperatures. The minimum temperature for complete conversion for the total oxidation reaction must clearly not exceed an acceptable working temperature for the steam reforming catalyst (i.e. a temperature that results in an acceptable catalyst lifetime). A kinetic analysis determined partial orders for methanol and oxygen as 0.67, the kinetic constant at 230 °C as 5.45 · 10-3 mmol-0.33 · m4 · (gcat · s)-1 and the activation energy as 130 kJ · mol-1. The copper based catalyst used for the steam reforming of methanol was also active for the total oxidation of methanol. Unfortunately the minimal temperature to ensure a total conversion was not compatible with the working temperature of the steam reforming. In chapter 7, the results concerning the coupling of the two previously studied reactions are presented. The numerous fittings and cables necessary for the operation of the reactor didn't allow the reactor to be run in an autothermal mode. Therefore constant, not regulated, heating was used to compensate the thermal losses. By coupling the two reactions and by studying the dynamic response time of the reactor (temperature and conversion of the steam reforming reaction) at the time of stopping and starting the oxidation reaction, we've seen that the temperature increase was around +10 °C within 60 seconds and that the conversion for the steam reforming of the methanol fitted well with the temperature increase. This reactor also has good dynamics and responds quickly to feed variations. When the coupling mode was changed from co-current to counter-current we noticed a significant increase in conversion. Furthermore, selectivity in counter-current mode remained high, even for conversion approaching 100%.

EPFL2003

Phase Change Material Systems for High Temperature Heat Storage

Selmar Rudolf Binder, Sophia Haussener, Alberto Ortona, David Yann Samuel Perraudin, Ehsan Rezaei

Efficient, cost effective, and stable high-temperature heat storage material systems are important in applications such as high-temperature industrial processes (metal processing, cement and glass manufacturing, etc.), or electricity storage using advanced adiabatic compressed air. Incorporating phase change media into heat storage systems provides an advantage of storing and releasing heat at nearly constant temperature, allowing steady and optimized operation of the downstream processes. The choice of, and compatibility of materials and encapsulation for the phase change section is crucial, as these must guarantee good and stable performance and long lifetime at low cost. Detailed knowledge of the material properties and stability, and the coupled heat transfer, phase change, and fluid flow are required to allow for performance and lifetime predictions. We present coupled experimental-numerical techniques allowing prediction of the long-term performance of a phase change material-based high-temperature heat storage system. The experimental investigations focus on determination of material properties (melting temperature, heat of fusion, etc.) and phase change material and encapsulation interaction (stability, interface reactions, etc.). The computational investigations focus on an understanding of the multi-mode heat transfer, fluid flow, and phase change processes in order to design the material system for enhanced performance. The importance of both the experimental and numerical approaches is highlighted and we give an example of how both approaches can be complementarily used for the investigation of long-term performance.