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Development of electrocatalytic layers and thermo-fluid dynamic evaluation for high temperature membrane reactorsCatalán Martínez, David 20 January 2020 (has links)
[ES] En la presente tesis se han desarrollados estudios sobre reactores de membrana de alta temperatura. Entre estos se puede diferenciar entre un trabajo experimental y un trabajo de simulación.
En el bloque experimental se han desarrollado electrodos basados en cobre para reactores de membrana electroquímicos tubulares de alta temperatura basados en electrolitos protónicos. Para depositar estos electrodos sobre los tubos se han desarrollado diferentes técnicas. Se ha optimizado el método dip-coating para depositar un cermet basado en cobre utilizando la misma cerámica que el electrolito de los soportes tubulares. Las condiciones con las que se llevó a cabo el proceso de dip-coating provocan disminuciones de varios ordenes de magnitud en la resistencia de polarización del electrodo final. Se trata de un método que es muy sensible a posibles defectos en electrolito, como pequeñas grietas o poros, ya que el cobre del electrodo depositado se introduce por estos defectos reaccionando con el níquel del electrodo interno. Asimismo, se ha empleado el método de sputtering para depositar cobre metálico sobre soportes tubulares electroquímicos. Aumentar la temperatura de deposición genera mejores fijaciones electrodo-electrolito. Las celdas con el cobre depositado a alta temperatura mostraron resistencias de polarización inferiores a 0.1 ¿·cm^2.
En el bloque de simulaciones mediante métodos de elementos finitos se han desarrollado diferentes modelos para la caracterización de los fenómenos que tienen lugar en reactores de membrana de alta temperatura. Se ha estudiado: (i) la permeación de oxígeno a través de una membrana de conducción iónica-electrónica mixta; (ii) la electrólisis del agua utilizando celdas basadas en conductores protónicos de alta temperatura; (iii) la integración de una celda protónica para la extracción de hidrógeno en un reformador de metano; (iv) la integración de una celda de conductividad co-iónica en la deshidroaromatización de metano en un reactor de lecho catalítico.
El modelo de permeación de oxígeno a través de una membrana de conductividad mixta se ajustó a datos experimentales. El modelo ajustado ha permitido caracterizar la importancia del efecto dilutivo y de arrastre sobre el transporte de oxígeno a través de la membrana. Se ha observado que, aunque el efecto de arrastre tenga menor importancia que el dilutivo, su efecto es importante ya que previene la formación de concentraciones de polarización.
El estudio de electrolizadores que utilizan conductores protónicos sólidos de alta temperatura ha permitido estudiar el efecto del escalado en este proceso y evaluar la eficiencia en el almacenamiento de energía.
El modelo de un reactor de membrana electroquímico basado en conductores protónicos integrado en un reformador de metano ha permitido comprobar que la demanda térmica del proceso se cubre por el efecto Joule y la electrocompresión del hidrógeno. Se ha comprobado como el coarsening observado en las partículas de níquel no limita la extracción de hidrógeno para la celda estudiada.
Un último modelo fue construido para estudiar un reactor de membrana para el proceso de deshidrogenación de metano utilizando una celda co-iónica. El modelo fue validado utilizando datos experimentales. Se utilizó el modelo validado para realizar estudios para analizar posibles limitaciones del proceso. Finalmente, se ha comprobado que el desplazamiento del equilibrio de reacción mediante la extracción de hidrógeno se frena debido a limitaciones cinéticas. / [CAT] Esta tesi presenta resultats sobre reactors de membrana a alta temperatura. Dos blocs diferenciades poden ser identificats: (i) treball experimental; (ii) treball de modelat.
En el bloc experimental, elèctrodes basats en coure han siguts optimitzats per a tubular cells de conductor protòniques. La deposició de la capa basada en coure es va fer amb diferents tècniques. La tècnica de dip-coating ha sigut usada per a depositar una capa de cermet basada en coure. Aquesta tècnica es molt sensible a les condicions amb les que es desenvolupa la deposició perquè causa canvis de varis ordres de magnitud en la resistència de polarització del elèctrode. A més, la tècnica de sputtering ha sigut triada per a depositar coure. Per a depositar correctament la capa de coure, altes temperatures durant la deposició foren requerides. El elèctrode optimitzat presenta resistències de polarització inferiors a 0.1 ¿·cm2.
En el treball de modelat, la metodologia de elements finits va ser utilitzada per a modelar diferents fenòmens concernits a reactors de membrana de elevada temperatura.
La permeació de oxigen per membranes de conducció mixta ha sigut modelada per a avaluar la importància de la dilució i del arrossegament. Els resultats mostren que, encara que el efecte dilutiu es predominant, el efecte del arrossegament no pot ser depreciat. Un adequat arrossegament del oxigen permeat es necessari per evitar polaritzacions en la concentració del oxigen els quals limitarien la permeació. El efecte del arrossegament es major quan el gas portador es mes pesat.
El model per estudiar un procés de electròlisis basat en conductors protòniques a elevada temperatura ha permès estudiar l'efecte de l'escalat de aquest procés i avaluar l'eficiència en l'emmagatzemament d'energia.
Modelant un reformador de membrana protònica ha permès comprovar la microintegració tèrmica de tots el fenòmens que tenen lloc en aquest procés. Aquest procés compren les reaccions de reformat, extracció electroquímica de hidrogen i electrocompressió del hidrogen generat. La electrocompressió del hidrogen és un procés isoterma que allibera la energia demanda en forma de calor. El model ha permès comprovar que l'engrossiment de les partícules de níquel no limita l'extracció de hidrogen.
Un últim model va ser construït per estudiar l'extracció de hidrogen en un reactor de membrana per al procés de dehidroaromatizatió de metà. El reactor de membrana utilitza materials co-iòniques per l'extracció de hidrogen de la càmera de reacció. Aquest model va ser validat amb resultats experimentals. El model va mostrar que no hi ha limitacions amb la difusió del hidrogen. A més, el desplaçament del equilibri mediant l'extracció de hidrogen està limitat per la baixa activitat cinètica del procés. / [EN] In this thesis several studies were developed about membranes reactor at high temperature. Two differentiated blocks could be identified: (i) experimental works; (ii) modelling works.
In the experimental block, electrodes based on copper was developed for tubular protonic based cells. The deposition of the copper layer on the tubes was developed by different techniques. Dip-coating method was optimized to a copper-based cermet on the tube. Conditions of the dip-coating procedure has a critical impact in the final performance of the electrochemical cell whose supposes several orders of magnitude in the polarization resistance. It is a sensitive process with the defect of the tube as shows the copper spread over these defects. Additionally, sputtering technique was used to deposit copper layer on the tube. High temperature is required to achieve suitable attachments copper-tube. This high temperature deposited layer present polarization resistances lower than 0.1 ¿·cm2.
In the modelling block, finite element methodology was used to build different models to study different phenomena concerning membrane reactors at high temperature. It was studied: (i) the oxygen permeation across a mixed ionic and electronic conducting membrane; (ii) water electrolysis based on high temperature protonic cells; (iii) hydrogen extraction from a steam methane reforming using a protonic cell; (iv) the intensification of the methane dehydromatization reactor using co-ionic membrane.
Oxygen permeation model was built to evaluate the effect of the dilutive and the sweep contribution over the permeation process. The fitted model allowed the importance of the dilutive and sweep effect over the oxygen permeation. Although the sweep effect present lower influence in the oxygen transport across the membrane, its effect prevents concentration polarization limitations.
Modelling the protonic cell based electrolysis allowed to study the effect of the scale up in this process and to evaluate the efficiency in the energy storing in form of hydrogen.
Modelling protonic membrane reformer allowed checking the thermal microintegration of all the heats which take place in the setup. The electrocompression of hydrogen is an isothermal phenomenon which releases the demanded energy as heat. The model allowed to check the coarsening of the Ni particles does not limit the hydrogen extraction for the studied cell.
A final model was built to study a catalytic membrane reactor for the methane dehydroaromatization using co-ionic conducting cells. The model was validated using experimental data. Additionally, different studies were performed to analyze possible limitation in the process. Results show that there are no hydrogen diffusion limitations in this process. Additionally, the shift of the equilibrium by extracting hydrogen has to be stopped because kinetic limitations. / Catalán Martínez, D. (2019). Development of electrocatalytic layers and thermo-fluid dynamic evaluation for high temperature membrane reactors [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/135278 / TESIS
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A COMPARISON OF THE OBSERVED WAKE EFFECT WITH SEVERAL WAKE MODELS USING BOTH ANALYTIC AND CFD SIMULATION METHODS - FOR THE CASE OF BLOCK ISLAND OFFSHORE WIND FARMPratt, Robbie January 2019 (has links)
This paper sets out to analyze the observed wake effect at Block Island Wind Farm. A comparison is made between several wake simulation methods and the observed data at Block Island using analytic and CFD (Computational Fluid Dynamics) modelling methods. The observed wake results at Block Island show a similar trend evident in earlier papers- a large power deficit found between the first two Wind Turbine Generators (WTGs) in the row followed by a slight variation in power along the row for the remainder of the WTGs. A noticeable difference is seen between the last two WTGs in the row where an increase in power is found. This increase in power is thought to be due to the alignment of the wind farm. Nevertheless, when the observed data is compared with the modeled results, the observed data seem to underestimate the wake effect due to misalignment issue with the nacelle wind direction measurement. A sensitivity analysis is conducted on the Wake Decay Constant (WDC) and Turbulence Intensity (TI) values. The results show a maximum power variation of ≈30% between a WDC value of 0.07 and 0.04 and ≈18% for TI values between 8% and 14%. The findings show that a value in the higher range of the examined WDC (0.06 and 0.07) and TI (12% and 14%) values represent a better comparison to the observed data. Nevertheless, it is not recommended to alter these parameters to fit the observed data. Furthermore, due to high uncertainty in the data measurements, and hence observed results, a clear conclusion indicating which wake model best represents the wake effect at Block Island cannot be stated.
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CFD Modelling and Mathematical Optimisation of a Continuous Caster Submerged Entry NozzleDe Wet, Gideon Jacobus 31 January 2006 (has links)
In the continuous casting of steel, the Submerged Entry Nozzle (SEN), in particular the SEN geometry, has a primary influence on the flow pattern: the SEN controls the speed, direction and other characteristics of the jet entering the mould. The SEN is however relatively inexpensive to change (in comparison with other continuous casting equipment). Thus; there is a feasible incentive to exactly understand and predict the flow of molten steel through the SEN and into the mould, in order to maximise the quality of the steel by altering the design of the SEN. By changing the SEN geometry and SEN design, the flow pattern in the mould will also change: it is thus possible to obtain an optimum SEN design if (or when) the desired flow patterns and/or certain predetermined temperature distributions are achieved. Expensive and risky plant trials were traditionally utilised to “perfect” continuous casting processes. As opposed to the plant trials, this dissertation is concerned with the Computational Fluid Dynamics (CFD) modelling of the SEN and mould, which, when used in conjunction with the Mathematical Optimiser LS-OPT, will enable the optimisation of the SEN design to achieve desired results. The CFD models are experimentally verified and validated using 40%-scaled (designed and built in-house) and full-scale water model tests. This dissertation proves that the CFD modelling of the SEN and mould can be quite useful for optimisation and parametric studies, especially when automated model generation (geometry, mesh and solution procedures) is utilised. The importance of obtaining reliable and physically correct CFD results is also emphasised; hence the need for CFD model verification using water modelling. / Dissertation (MEng (Mechanical Engineering))--University of Pretoria, 2007. / Mechanical and Aeronautical Engineering / unrestricted
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Modelování procesu spalování při využití vzduchu s obsahem kyslíku vyšším než 21 % / Modelling of oxygen-enhanced combustion processNaď, Martin January 2014 (has links)
The main purpose of the master´s thesis is the experimental study and the mathematical modelling of the combustion process in which the combustion air is enriched with the high-purity oxygen, i.e. the oxygen content is more than 21 %. This combustion technology is called as the oxygen-enhanced combustion (OEC). Since the experimental work required the manipulation with the pure oxygen, a part of the thesis is focused on risks and necessary safety associated therewith. The detailed description of the combustion chamber as well as of the components necessary for the operation of OEC is included. The main part of the thesis is the computational model of the combustion chamber and the simulation of OEC using CFD methods. The numerical results were then compared with the experimental data acquired during the combustion tests, namely the heat flux distribution along the combustion chamber and the distribution of in-flame temperatures in the horizontal symmetry plane of the chamber.
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Computational fluid dynamics (CFD) modelling of critical velocity for sand transport flow regimes in multiphase pipe bendsTebowei, Roland January 2016 (has links)
The production and transportation of hydrocarbon fluids in multiphase pipelines could be severely hindered by particulate solids deposit such as produced sand particles which accompany hydrocarbon production. Knowledge of the flow characteristics of solid particles in fluids transported in pipelines is important in order to accurately predict solid particles deposition in pipelines. This research thesis presents the development of a three-dimensional (3D) Computational Fluids Dynamics (CFD) modelling technique for the prediction of liquid-solids multiphase flow in pipes, with special emphasis on the flow in V-inclined pipe bends. The Euler-Euler (two-fluid) multiphase modelling methodology has been adopted and the multiphase model equations and closure models describing the liquid-solids flow have been implemented and calculated using the finite volume method in a CFD code software. The liquid phase turbulence has been modelled using a two-equation k−ε turbulence model which contains additional terms to account for the effects of the solid-particles phase on the multiphase turbulence structure. The developed CFD numerical framework has been verified for the relevant forces and all the possible interaction mechanisms of the liquid-solids multiphase flow by investigating four different numerical frameworks, in order to determine the optimum numerical framework that captures the underlying physics and covers the interaction mechanisms that lead to sand deposition and the range of sand transport flow regimes in pipes. The flow of liquid-sand in pipe has been studied extensively and the numerical results of sand concentration distribution across pipe and other flow properties are in good agreement with published experimental data on validation. The numerical framework has been employed to investigate the multiphase flow in V-inclined pipe bends of ±4o−6o, seemingly small inclined bend angles. The predicted results which include the sand segregation, deposition velocity and flow turbulence modulation in the pipe bend show that the seemingly small pipe bends have significant effect on the flow differently from that of horizontal pipes. The pipe bend causes abrupt local change in the multiphase flow characteristic and formation of stationary sand deposit in the pipe at a relatively high flow velocity. The threshold velocity to keep sand entrained in liquid in pipe bends is significantly higher than that required for flow horizontal pipes. A critical implication of this is that the correlations for predicting sand deposition in pipelines must account for the effect of pipe bend on flow characteristics in order to provide accurate predictions of the critical sand transport velocity (MTV) in subsea petroleum flowlines, which V-inclined pipe bends are inevitable due to seabed topology.
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Méta-modèles réduits et séparés du comportement de balayage d'un moteur Diesel 2-temps pour l'exploration évolutionnaire des espaces de solutions / Reduced and separated meta-models of the scavenging by ports in 2-stroke Diesel engines to use evolutionary algorithms in search spaceCagin, Stéphanie 09 December 2015 (has links)
L’utilisation de techniques numériques lors de la conception d’un produit s’est largement généralisée au cours des 30 dernières années. Pourtant, la lenteur des calculs et la spécialisation des modèles numériques restent problématiques.Nous avons donc choisi de développer des modèles réduits du comportement de balayage sur un moteur Diesel 2-temps à lumières. Ces modèles sont analytiques, génériques, rapides d’utilisation et permettent d’éliminer les problématiques de traitement numérique. Ils sont aussi des instruments performants dans la recherche de solutions de conception. Une modélisation CFD 2D a tout d’abord été développée pour servir de bases de données, avec la définition des paramètres primordiaux à suivre pour quantifier un balayage optimal.Le travail de recherche a dévoilé une méthodologie nouvelle fondée sur un méta-modèle du comportement dit « neuro-séparé » comprenant un modèle neuronal d’état, un modèle neuronal pseudo-dynamique et un modèle à variables séparées. Ensuite, un processus d'aide à la décision exploitant les modèles précédents a été mis en place au travers d’un processus d’optimisation évolutionnaire (fondé sur les algorithmes génétiques) puis de la simulation comportementale rapide des solutions optimales de conception par un krigeage.La démarche de conception multipoints de vue, multi-critères et multi-physiques appliquée au moteur intègre aussi une dimension cognitive : l’exploration évolutionnaire des espaces de solutions a été menée de façon libre et forcée. Afin de valider notre approche, nous avons mis en place des critères de qualification appliqués à chacun de nos modèles, permettant de quantifier les écarts visà-vis de la base initiale CFD qui a fondé nos modèles réduits.Notre démarche a mené à la création d’un outil d’aide à la modélisation et à la décision exploitant les modules Python et Matlab développés. / The use of numerical methods to design a product became more and more commonover the past 30 years. However, numerical models are still specialized and they do not run fastwhich make their use problematic. So some reduced models of scavenging have been developed. These models are analytical andgeneric; they run quickly and avoid the numerical treatment problems. They are also some efficienttools in the search of design solutions.The work carried out has led to a new methodology based on a behavioral meta-model called“neuro-separated” including a neuronal model of state, a pseudo-dynamic neuronal model and amodel with separated variables. Then, a process of decision aids exploiting the models previouslydeveloped in evolutionary algorithms (genetic algorithms) and the fast behavioral simulation of theoptimal design solutions thanks to the kriging approach.This design approach is multi-viewpoints, multi-criteria and multi-physics. It also includes acognitive dimension: both free and controlled evolutionary explorations of solution spaces have beendone. To validate the method, some qualification criteria have been evaluated for each model. Theyallow to understand and to assume the gap between the reduced models and the initial CFD base(where the model are coming from). Our approach has led to the development of a tool of model and decision aids using Python and Matlab software programs.
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Contribution à l'étude des échanges convectifs à l'interface fluide paroi en présence de matériaux à changement de phase : Application au bâtiment / Contribution to the study of convective heat transfer at the wall-fluid interface in the presence of phase change materials : Application at the building scaleBykalyuk, Anna 12 December 2014 (has links)
De récentes études expérimentales ont montré que les valeurs usuelles du coefficient d’échange convectif sont différentes en présence de matériaux à changement de phase. Cette thèse de doctorat porte sur l'étude numérique des échanges convectifs fluide/paroi dans une cavité ouverte en régime dynamique. Plus précisément, les parois étudiées sont une paroi avec une capacité thermique et une paroi qui contient des matériaux à changement de phase. Trois modèles distincts ont été développés. Dans un premier temps un modèle (modèle 1) qui concerne l’interaction fluide-paroi à la surface d’une paroi résistive (temperature imposée) en régime laminaire stationnaire a été développé et validé. Les résultats ont été confrontés avec la littérature. Ensuite, les échanges convectifs à la surface d’une plaque capacitive (modèle 2) soumise à une rampe de température d’air ont été étudiés. Finalement, un troisième modèle (modèle 3) a été développé, à la suite du modèle 2. Ce dernier modèle concerne l’interaction fluide-paroi à la surface d’une paroi contenant des matériaux à changement de phase en régime dynamique. Les résultats obtenus révèlent des pics locaux du flux de chaleur au cours du temps. Ce fait témoigne du changement d’état à l’intérieur de la paroi qui contient le materiau à changement de phase. De plus, les courbes des coefficients d’échanges convectifs moyens révèlent la dépendance du coefficient d’echange convectif à la capacité thermique du materiau. Par conséquent, la présence des matériaux à changement de phase à l’intérieur d'une paroi influence l’évolution et la forme de la couche limite thermique. / Recent experimental studies have shown that the usual values of the convective heat transfer coefficient h are no longer valid in the presence of phase change materials. Three separate models were developed. Initially a model 1 which treats the fluid-wall (constant temperature) interaction in steady laminar flow has been developed and validated. Then, the wall with heat capacity (model 2) subjected to an air temperature ramp were studied. Finally, a third model (3) has been developed which treats the interaction fluid-wall which contains a phase change material. The results show local peaks of heat flow over time. This fact reflects the phase change inside the wall. Moreover, the curves of the convective heat transfer coefficient indicate the dependence of the coefficient h to the wall’s energy storage capacity. Therefore, the presence of the phase change materials within a wall effect and changes the shape of the thermal boundary layer.
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