Supercritical Steam power cycle for Line-Focus Solar Power Plants

The supercritical Rankine power cycle offers a net improvement in plant efficiency compared with a subcritical Rankine cycle. For fossil power plants the minimum supercritical steam turbine size is about 450MW. A recent study between Sandia National Laboratories and Siemens Energy, Inc., published on March 2013, confirmed the feasibility of adapting the Siemens turbine SST-900 for supercritical steam in concentrated solar power plants, with a live steam conditions 230-260 bar and output range between 140-200 MWe. In this context, this analysis is focused on integrating a line-focus solar field with a supercritical Rankine power cycle. For this purpose two heat transfer fluids were assessed: direct steam generation and molten salt Hitec XL. To isolate solar field from high pressure supercritical water power cycle, an intermediate heat exchanger was installed between linear solar collectors and balance of plant. Due to receiver selective coating temperature limitations, turbine inlet temperature was fixed 550ºC. The design-point conditions were 550ºC and 260 bar at turbine inlet, and 165 MWe Gross power output. Plant performance was assessed at design-point in the supercritical power plant (between 43-45% net plant efficiency depending on balance of plantconfiguration), and in the subcritical plant configuration (~40% net plant efficiency). Regarding the balance of plant configuration, direct reheating was adopted as the optimum solution to avoid any intermediate heat exchanger. One direct reheating stage between high pressure turbine and intermediate pressure turbine is the common practice; however, General Electric ultrasupercritical(350 bar) fossil power plants also considered doubled-reheat applications. In this study were analyzed heat balances with single-reheat, double-reheat and even three reheating stages. In all cases were adopted the proper reheating solar field configurations to limit solar collectors pressure drops. As main conclusion, it was confirmed net plant efficiency improvements in supercritical Rankine line-focus (parabolic or linear Fresnel) solar plant configurations are mainly due to the following two reasons: higher number of feed-water preheaters (up to seven)delivering hotter water at solar field inlet, and two or even three direct reheating stages (550ºC reheating temperature) in high or intermediate pressure turbines. However, the turbine manufacturer should confirm the equipment constrains regarding reheating stages and number of steam extractions to feed-water heaters.

Production of biodiesel from animal fat using supercritical ethanol

Biodiesel is currently produced from a catalytic transesterification reaction of various types of edible and non-edible oil with methanol. The use of waste animal tallow instead of edible oils opens a route to recycle this waste. This material has the advantage of lower costs but the problem of high content of free fatty acids, becoming necessary a pre-esterification reaction that increases the cost of the catalytic process. The production of biodiesel using supercritical alcohols is appropriate for materials with high acidity and water content, therefore the use of this process with animal fat is a promising alternative. Ethanol has been used because it can be produced from biomass via fermentation resulting in a complete renewable biodiesel, instead of methanol that derives from fossil feedstocks. Two different processes have been studied: first, the direct transesterification of animal fat using supercritical ethanol and second a two-step process where the first step is a hydrolysis of the animal fat and the second step is the esterification of the resulting fatty acids. The temperature, the molar ratio ethanol:fat and the time have been modified in the different reactions to study the effect in the final conversion and the degradation of the unsaturated fatty acid esters, main inconvenient of these high temperature and pressure processes.

Diffuse Soil Co2 Flux To Assess The Reliability Of Co2 Storage In The Mazarrón-Gañuelas Tertiary Basin (Spain)

Geological storage of CO2 is nowadays internationally considered as the most effective method for greenhouse gas emission mitigation, in order to minimize its effects on the global climatology. One of the main options is to store the CO2 in deep saline aquifers at more than 800 m depth, because it achieves its supercritical state. Among the most important aspects concerning the performance assessment of a deep CO2 geological repository is the evaluation of the CO2 leakage rate from the chosen storage geological formation. Therefore, it is absolutely necessary to increase the knowledge on the interaction among CO2, storage and sealing formations, as well as on the flow paths for CO2 and the physico-mechanical resistance of the sealing formation. Furthermore, the quantification of the CO2 leakage rate is essential to evaluate its effects on the environment. One way to achieve this objective is to study of CO2 leakage on natural analogue systems, because they can provide useful information about the natural performance of the CO2, which can be applied to an artificial CO2 geological storage. This work is focused on the retention capacity of the cap-rock by measuring the diffuse soil CO2 flux in a site selected based on: i) the presence of a natural and deep CO2 accumulation; ii) its structural geological characteristics; and iii) the nature of the cap-rocks. This site is located in the so-called Mazarrón-Gañuelas Tertiary Basin, in the Guadalentin Valley, province of Murcia (Spain) Therefore the main objective of this investigation has been to detect the possible leakages of CO2 from a deep saline aquifer to the surface in order to understand the capability of this area as a natural analogue for Carbon Capture and Sequestration (CCS). The results obtained allow to conclude that the geological sealing formation of the basin seems to be appropriate to avoid CO2 leakages from the storage formation.

Effects on the shallow aquifers by CO2 leakages in a tertiary basin (province of Murcia, Spain)

Geological storage of CO2 is nowadays internationally considered as the most effective method for greenhouse gas emission mitigation, in order to minimize its effects on the global climatology. One of the main options is to store CO2 in deep saline aquifers at more than 800m depth, because it reaches its supercritical state. Study of the CO2 natural accumulations as natural analogues of an artificial CO2 storage is very useful in order to understand the CO2 long term behaviour and thus to predict its possible impact on the surficial environment and life. Therefore the main objective of this work is to detect the affection of the CO2 leakages from a deep saline aquifer on the shallow aquifers, all of them located in the Gañuelas-Mazarrón Tertiary basin (Province of Murcia, Spain). This CO2 storage and leakage natural system can be analogous to an artificial CO2 storage with leakage phenomena. In order to reach these objectives, groundwaters from different aquifers in the site have been sampled and analysed for major elements, free and dissolved gases and stable isotopes, particularly ∂ 13 C and 3 He/ 4 He. The results obtained allow to conclude that this natural system is an interesting example of natural analogue for an artificial CO2 storage affected by leakage processes because the shallow fresh aquifers in the site are polluted by CO2 from the deep saline aquifer as a consequence of an intensive over-exploitation of these freshwater aquifers

Desarrollo de un modelo para la caracterización termoeconómica de ciclos combinados de turbinas de gas y de vapor en condiciones de carga variable

En la actualidad, el interés por las plantas de potencia de ciclo combinado de gas y vapor ha experimentado un notable aumento debido a su alto rendimiento, bajo coste de generación y rápida construcción. El objetivo fundamental de la tesis es profundizar en el conocimiento de esta tecnología, insuficientemente conocida hasta el momento debido al gran número de grados de libertad que existen en el diseño de este tipo de instalaciones. El estudio se realizó en varias fases. La primera consistió en analizar y estudiar las distintas tecnologías que se pueden emplear en este tipo de centrales, algunas muy recientes o en fase de investigación, como las turbinas de gas de geometría variable, las turbinas de gas refrigeradas con agua o vapor del ciclo de vapor o las calderas de paso único que trabajan con agua en condiciones supercríticas. Posteriormente se elaboraron los modelos matemáticos que permiten la simulación termodinámica de cada uno de los componentes que integran las plantas, tanto en el punto de diseño como a cargas parciales. Al mismo tiempo, se desarrolló una metodología novedosa que permite resolver el sistema de ecuaciones que resulta de la simulación de cualquier configuración posible de ciclo combinado. De esa forma se puede conocer el comportamiento de cualquier planta en cualquier punto de funcionamiento. Por último se desarrolló un modelo de atribución de costes para este tipo de centrales. Con dicho modelo, los estudios se pueden realizar no sólo desde un punto de vista termodinámico sino también termoeconómico, con lo que se pueden encontrar soluciones de compromiso entre rendimiento y coste, asignar costes de producción, determinar curvas de oferta, beneficios económicos de la planta y delimitar el rango de potencias donde la planta es rentable. El programa informático, desarrollado en paralelo con los modelos de simulación, se ha empleado para obtener resultados de forma intensiva. El estudio de los resultados permite profundizar ampliamente en el conocimiento de la tecnología y, así, desarrollar una metodología de diseño de este tipo de plantas bajo un criterio termoeconómico. ABSTRACT The growing energy demand and the need of shrinking costs have led to the design of high efficiency and quick installation power plants. The success of combined cycle gas turbine power plants lies on their high efficiency, low cost and short construction lead time. The main objective of the work is to study in detail this technology, which is not thoroughly known owing to the great number of degrees of freedom that exist in the design of this kind of power plants. The study is divided into three parts. Firstly, the different technologies and components that could be used in any configuration of a combined cycle gas turbine power plant are studied. Some of them could be of recent technology, such as the variable inlet guide vane compressors, the H-technology for gas turbine cooling or the once-through heat recovery steam generators, used with water at supercritical conditions. Secondly, a mathematical model has been developed to simulate at full and part load the components of the power plant. At the same time, a new methodology is proposed in order to solve the equation system resulting for any possible power plant configuration. Therefore, any combined cycle gas turbine could be simulated at any part load condition. Finally a themoeconomic model is proposed. This model allows studying the power plant not only from a thermodynamic point of view but also from a thermoeconomic one. Likewise, it allows determining the generating costs or the cash flow, thus achieving a trade off between efficiency and cost. Likewise, the model calculates the part load range where the power plant is profitable. Once the thermodynamic and thermoeconomic models are developed, they are intensively used in order to gain knowledge in the combined cycle gas turbine technology and, in this way, to propose a methodology aimed at the design of this kind of power plants from a thermoeconomic point of view.

Optimización de la metodología de contratación de carbones térmicos con destino a la generación eléctrica

En los últimos quince años se ha producido una liberalización de los mercados eléctricos en los distintos países de ámbito occidental que ha ido acompañado de un incremento por la preocupación por la incidencia de las distintas tecnologías de generación en el entorno medioambiental. Ello se ha traducido en la aparición de un marco regulatorio más restrictivo sobre las tecnologías de generación fósiles, con mayor incidencia en las derivadas de productos petrolíferos y carbón. A nivel mundial han ido apareciendo cambios normativos relativos a las emisiones de distintos elementos contaminantes (CO2, SO2, NOx…), que hacen que en particular las centrales térmicas de carbón vean muy afectadas su rentabilidad y funcionamiento. Esta situación ha supuesto que la tecnología de generación eléctrica con carbón haya avanzado considerablemente en los últimos años (calderas supercríticas, sistemas de desulfuración, gasificación del carbón…). No obstante, el desarrollo de la generación con energías renovables, la generación con gas mediante centrales de ciclo combinado y la opinión social relativa a la generación con carbón, principalmente en Europa, suponen un serio obstáculo a la generación con carbón. Por consiguiente, se hace necesario buscar vías para optimizar la competitividad de las centrales de carbón y el camino más razonable es mejorar el margen esperado de estas plantas y en particular el coste de adquisición del carbón. Ello se hace aún más importante por el hecho de existir numerosas centrales de carbón y un elevado número de nuevos proyectos constructivos de centrales de carbón en países asiáticos. Por consiguiente, el objeto de la presente tesis doctoral se centra en definir una metodología para optimizar la compra de carbón, desde el punto de vista económico y técnico, con destino a su consumo en una central térmica, con ello reducir el coste del carbón consumido y mejorar su competitividad. También se enfoca a determinar que herramientas pueden ser utilizadas para optimizar la gestión del carbón después de su compra y con ello abrir la posibilidad de obtener márgenes adicionales para dicho carbón. De acuerdo con este objetivo, el autor de la presente Tesis Doctoral realiza tres aportaciones novedosas en el ámbito de la contratación de carbón térmico y su optimización posterior: - Evaluación de carbones para su adquisición considerando el efecto de la calidad del carbón en el coste de generación asociado a cada carbón ofertado. - Creación, desarrollo, implantación y utilización de una potente herramienta de planificación de Combustibles. Esta herramienta, está diseñada con el objeto de determinar la solución económica óptima de aprovisionamientos, consumos y niveles de existencias para un parque de generación con centrales de carbón y fuelóleo. - La extensión de una metodología contractual habitual en el mercado spot de Gas Natural Licuado, a la contratación spot de Carbón de Importación. Esta se basa en el desarrollo de Acuerdos Marcos de Compra/Venta de carbón, que por su flexibilidad permitan obtener resultados económicos adicionales después de la compra de un carbón. Abstract In the last fifteen years, a liberalization of the electrical markets has occurred in the western countries. This process has been accompanied by an increasing concern of the impact of the different generation technologies towards the environment. This has motivated a regulated framework restricting the use of fossil fuels, impacting a great deal in coal and oil based products. Worldwide, new legal changes have been arising related to the emissions of the different pollutants (CO2, SO2, NOx…). These changes have had a deep impact in the feasibility, profit and running of coal fired power plants. This situation has motivated the coal electrical generation technologies to move forward in an important way in the last few years (supercritical furnaces, desulphuration plants, coal gasification…). Nevertheless, the development of the renewable generation, the gas combined cycle generation and the social opinion related to the coal electrical generation, mainly in Europe, have created a serious obstacle to the generation of electricity by coal. Therefore it is necessary to look for new paths in order to optimize the competitiveness of the coal fired power plants and the most reasonable way is to improve the expected margin of these plants and particularly the coal purchase cost. All of the above needs to be taken into context with the large number of existing coal fired power plants and an important number of new projects in Asian countries. Therefore, the goal of the current doctoral dissertation is focused to define a methodology to be considered in order to optimize the coal purchase, from an economical and a technical point of view. This coal, destined for power plant consumption, permits the reduction of consumption coal cost and improves the plant’s competitiveness. This document is also focused to define what tools we can use to optimize the coal management after deal closing and therefore open the possibility to get further margins. According to this goal, the author of this doctoral dissertation provides three important new ideas in the ambit of contracting steam coal and the posterior optimization: - Evaluation of coal purchases, considering the effect of coal quality on the cost of generation associated with each type of coal offered. - The creation, development, deployment and use of a strong planning tool of fuels. This tool is designed for the purpose of determining the optimal economic solution of fuel supply, consumption and stock levels for a power generation portfolio using coal and fuel oil fired power plants. - The application of a common contractual methodology in the spot market of Liquid Natural Gas, for the contracting spot imported coal. This is based on the development of Framework Agreements for the Purchasing / Sale of coal, which because of its flexibility allows for the gain of additional financial results after the purchase of coal.

Geochemical monitoring in the Hontomín (Burgos, Spain) injection site: preliminary results and perspectives

CO2 capture and storage (CCS) projects are presently developed to reduce the emission of anthropogenic CO2 into the atmosphere. CCS technologies are expected to account for the 20% of the CO2 reduction by 2050. One of the main concerns of CCS is whether CO2 may remain confined within the geological formation into which it is injected since post-injection CO2 migration in the time scale of years, decades and centuries is not well understood. Theoretically, CO2 can be retained at depth i) as a supercritical fluid (physical trapping), ii) as a fluid slowly migrating in an aquifer due to long flow path (hydrodynamic trapping), iii) dissolved into ground waters (solubility trapping) and iv) precipitated secondary carbonates. Carbon dioxide will be injected in the near future (2012) at Hontomín (Burgos, Spain) in the frame of the Compostilla EEPR project, led by the Fundación Ciudad de la Energía (CIUDEN). In order to detect leakage in the operational stage, a pre-injection geochemical baseline is presently being developed. In this work a geochemical monitoring design is presented to provide information about the feasibility of CO2 storage at depth.

Defect chaos and bursts: Hexagonal rotating convection and the complex Ginzburg-Landau equation

We employ numerical computations of the full Navier-Stokes equations to investigate non-Boussinesq convection in a rotating system using water as the working fluid. We identify two regimes. For weak non- Boussinesq effects the Hopf bifurcation from steady to oscillating (whirling) hexagons is supercritical and typical states exhibit defect chaos that is systematically described by the cubic complex Ginzburg-Landau equation. For stronger non-Boussinesq effects the Hopf bifurcation becomes subcritical and the oscil- lations exhibit localized chaotic bursting, which is modeled by a quintic complex Ginzburg-Landau equation.

Caracterización geoquímica orgánica de los materiales de la zona de Hontomín para almacenamiento de Co2

Ante la perspectiva del Cambio Global propiciado por la acción antrópica debido al vertido de CO2 a la atmósfera desde el inicio de la Era Industrial, el Protocolo de Kyoto (firmado en 1997), seguido de las tímidas propuestas derivadas de la Reunión de Copenhague, más acciones derivadas de la reunión de los ministros de medio ambiente en Sevilla, la acción de captura y secuestro del CO2inevitablemente generado por la industria pesada y la generación de energía ha ido adquiriendo un progresivo interés al estar la Península Ibérica constituida en más del 50% de su superficie por rocas sedimentarias susceptibles de constituir almacenamientos subterráneos. El objetivo fundamental de este proyecto fin de carrara, es determinar los cambios que se producen en los compuestos orgánicos de las posibles rocas almacén y sello de la zona de Páramos de la Lora en Burgos, (donde se pretende realizar el secuestro de CO2) después de la inyección de CO2 supercrítico en experimentos. Fundamentalmente, el estudio se centra en la familia de alcanos, cetonas y ácidos. Para ello se realizará una caracterización geoquímica orgánica de los materiales antes y después de haber inyectado CO2 a altas presiones (100 bar – 120 bar) y en las condiciones térmicas existentes a la profundidad del almacén (40º C - 50º C) durante períodos de tiempo variables, para lo que se empleará cámara hiperbárica del Grupo de Estudios Ambientales. Abstract In view Global Change led by the anthropic action due to the discharge of CO2 into the atmosphere since the start of the Indistrual Era, the Protocolo de Kyoto (signed in 1997), followed by the timid proposals arising from the Copenhague Meeting, more action arising of the meeting of the environment minister in Sevilla, the action of captura and sequestration of CO2 inevitably generated by heavy industry and the energy generation has acquired a progressive interest because de Península Ibérica is formed in more than fifty percent of the surface by sedimentary rock susceptible of provide underground storage. The objetive of this Project is determining the changes produced in organics compounds of potential reservoir rocks and seal rocks in Páramos de la Lora in Burgos, after injection supercritical CO2 in experiment. Fundamentally, the study focuses in the alcanos, cetonas and ácidos family. For this, a geochemical characterizacion will be performed in the materials before and after injection of high pressure CO2 (100bar-120bar) and in the existing termal conditions in the depth of the warehouse (40º C-50º C) for varying period of time, for what is used hyperbaric chamber environmental studies group.

Modelización de una central térmica supercrítica de 700 MW con captura de CO₂

El objetivo de este proyecto es realizar la simulación de una central térmica supercrítica de 700 MW con captura de CO₂ para producir electricidad y verterla a la red. El proyecto describe los equipos e instalaciones de la central y define los balances técnicos de la misma, probando que es viable técnicamente la incorporación de una planta de captura de CO₂ a una central térmica, a pesar del bajo rendimiento de la central. Además incluye el estudio económico que indica la viabilidad económica del proyecto, aunque con una rentabilidad baja. Este proyecto mira hacia el futuro debido a la necesidad de reducir las emisiones contaminantes, ya de casi la misma importancia que generar electricidad, y demuestra que es posible generar una energía limpia en centrales de carbón. ABSTRACT The purpose of this project is to carry out the simulation of a 700 MW supercritical coal thermal power plant with CO₂ capture to produce electricity and send it to the grid. The project describes the equipment, the installations and defines technical balances of the power plant. It shows that a CO₂ capture plant in a coal power plant is technically possible, in spite of the low power plant efficiency. In addition, it includes the economic analysis that shows the economic viability of the project, with a low profitability. This project looks into the future due to the need of reducing the pollutant emissions, which are almost as important as the generation of electricity, and demonstrates that a green energy in coal power plants is possible.

El análogo natural de almacenamiento y escape de Co2 de la cuenca de Gañuelas-Mazarrón : implicaciones para el comportamiento y la seguridad de un almacenamiento de Co2 en estaso supercrítico

El aumento de la temperatura media de la Tierra durante el pasado siglo en casi 1 ºC; la subida del nivel medio del mar; la disminución del volumen de hielo y nieve terrestres; la fuerte variabilidad del clima y los episodios climáticos extremos que se vienen sucediendo durante las ultimas décadas; y el aumento de las epidemias y enfermedades infecciosas son solo algunas de las evidencias del cambio climático actual, causado, principalmente, por la acumulación de gases de efecto invernadero en la atmósfera por actividades antropogénicas. La problemática y preocupación creciente surgida a raíz de estos fenómenos, motivo que, en 1997, se adoptara el denominado “Protocolo de Kyoto” (Japón), por el que los países firmantes adoptaron diferentes medidas destinadas a controlar y reducir las emisiones de los citados gases. Entre estas medidas cabe destacar las tecnologías CAC, enfocadas a la captura, transporte y almacenamiento de CO2. En este contexto se aprobó, en octubre de 2008, el Proyecto Singular Estratégico “Tecnologías avanzadas de generación, captura y almacenamiento de CO2” (PSE-120000-2008-6), cofinanciado por el Ministerio de Ciencia e Innovación y el FEDER, el cual abordaba, en su Subproyecto “Almacenamiento Geológico de CO2” (PSS-120000-2008-31), el estudio detallado, entre otros, del Análogo Natural de Almacenamiento y Escape de CO2 de la cuenca de Ganuelas-Mazarrón (Murcia). Es precisamente en el marco de dicho Proyecto en el que se ha realizado este trabajo, cuyo objetivo final ha sido el de predecir el comportamiento y evaluar la seguridad, a corto, medio y largo plazo, de un Almacenamiento Geológico Profundo de CO2 (AGP-CO2), mediante el estudio integral del citado análogo natural. Este estudio ha comprendido: i) la contextualización geológica e hidrogeológica de la cuenca, así como la investigación geofísica de la misma; ii) la toma de muestras de aguas de algunos acuíferos seleccionados con el fin de realizar su estudio hidrogeoquímico e isotópico; iii) la caracterización mineralógica, petrográfica, geoquímica e isotópica de los travertinos precipitados a partir de las aguas de algunos de los sondeos de la cuenca; y iv) la medida y caracterización química e isotópica de los gases libres y disueltos detectados en la cuenca, con especial atención al CO2 y 222Rn. Esta información, desarrollada en capítulos independientes, ha permitido realizar un modelo conceptual de funcionamiento del sistema natural que constituye la cuenca de Ganuelas-Mazarrón, así como establecer las analogías entre este y un AGP-CO2, con posibles escapes naturales y/o antropogénicos. La aplicación de toda esta información ha servido, por un lado, para predecir el comportamiento y evaluar la seguridad, a corto, medio y largo plazo, de un AGP-CO2 y, por otro, proponer una metodología general aplicable al estudio de posibles emplazamientos de AGP-CO2 desde la perspectiva de los reservorios naturales de CO2. Los resultados más importantes indican que la cuenca de Ganuelas-Mazarrón se trata de una cubeta o fosa tectónica delimitada por fallas normales, con importantes saltos verticales, que hunden al substrato rocoso (Complejo Nevado-Filabride), y rellenas, generalmente, por materiales volcánicos-subvolcánicos ácidos. Además, esta cuenca se encuentra rellena por formaciones menos resistivas que son, de muro a techo, las margas miocenas, predominantes y casi exclusivas de la cuenca, y los conglomerados y gravas pliocuaternarias. El acuífero salino profundo y enriquecido en CO2, puesto de manifiesto por la xx exploración geotérmica realizada en dicha cuenca durante la década de los 80 y objeto principal de este estudio, se encuentra a techo de los materiales del Complejo Nevado-Filabride, a una profundidad que podría superar los 800 m, según los datos de la investigación mediante sondeos y geofísica. Por ello, no se descarta la posibilidad de que el CO2 se encuentre en estado supe critico, por lo que la citada cuenca reuniría las características principales de un almacenamiento geológico natural y profundo de CO2, o análogo natural de un AGP-CO2 en un acuífero salino profundo. La sobreexplotación de los acuíferos mas someros de la cuenca, con fines agrícolas, origino, por el descenso de sus niveles piezométricos y de la presión hidrostática, el ascenso de las aguas profundas, salinas y enriquecidas en CO2, las cuales son las responsables de la contaminación de dichos acuíferos. El estudio hidrogeoquímico de las aguas de los acuíferos investigados muestra una gran variedad de hidrofacies, incluso en aquellos de litología similar. La alta salinidad de estas aguas las hace inservibles tanto para el consumo humano como para fines agrícolas. Además, el carácter ligeramente ácido de la mayoría de estas aguas determina que tengan gran capacidad para disolver y transportar, hacia la superficie, elementos pesados y/o tóxicos, entre los que destaca el U, elemento abundante en las rocas volcánicas ácidas de la cuenca, con contenidos de hasta 14 ppm, y en forma de uraninita submicroscópica. El estudio isotópico ha permitido discernir el origen, entre otros, del C del DIC de las aguas (δ13C-DIC), explicándose como una mezcla de dos componentes principales: uno, procedente de la descomposición térmica de las calizas y mármoles del substrato y, otro, de origen edáfico, sin descartar una aportación menor de C de origen mantélico. El estudio de los travertinos que se están formando a la salida de las aguas de algunos sondeos, por la desgasificación rápida de CO2 y el consiguiente aumento de pH, ha permitido destacar este fenómeno, por analogía, como alerta de escapes de CO2 desde un AGP-CO2. El análisis de los gases disueltos y libres, con especial atención al CO2 y al 222Rn asociado, indican que el C del CO2, tanto disuelto como en fase libre, tiene un origen similar al del DIC, confirmándose la menor contribución de CO2 de origen mantélico, dada la relación R/Ra del He existente en estos gases. El 222Rn sería el generado por el decaimiento radiactivo del U, particularmente abundante en las rocas volcánicas de la cuenca, y/o por el 226Ra procedente del U o del existente en los yesos mesinienses de la cuenca. Además, el CO2 actúa como carrier del 222Rn, hecho evidenciado en las anomalías positivas de ambos gases a ~ 1 m de profundidad y relacionadas principalmente con perturbaciones naturales (fallas y contactos) y antropogénicas (sondeos). La signatura isotópica del C a partir del DIC, de los carbonatos (travertinos), y del CO2 disuelto y libre, sugiere que esta señal puede usarse como un excelente trazador de los escapes de CO2 desde un AGPCO2, en el cual se inyectara un CO2 procedente, generalmente, de la combustión de combustibles fósiles, con un δ13C(V-PDB) de ~ -30 ‰. Estos resultados han permitido construir un modelo conceptual de funcionamiento del sistema natural de la cuenca de Ganuelas-Mazarrón como análogo natural de un AGP-CO2, y establecer las relaciones entre ambos. Así, las analogías mas importantes, en cuanto a los elementos del sistema, serian la existencia de: i) un acuífero salino profundo enriquecido en CO2, que seria análoga a la formación almacén de un AGPxxi CO2; ii) una formación sedimentaria margosa que, con una potencia superior a 500 m, se correspondería con la formación sello de un AGP-CO2; y iii) acuíferos mas someros con aguas dulces y aptas para el consumo humano, rocas volcánicas ricas en U y fallas que se encuentran selladas por yesos y/o margas; elementos que también podrían concurrir en un emplazamiento de un AGP-CO2. Por otro lado, los procesos análogos mas importantes identificados serian: i) la inyección ascendente del CO2, que seria análoga a la inyección de CO2 de origen antropogénico, pero este con una signatura isotópica δ13C(V-PDB) de ~ -30 ‰; ii) la disolución de CO2 y 222Rn en las aguas del acuífero profundo, lo que seria análogo a la disolución de dichos gases en la formación almacén de un AGP-CO2; iii) la contaminación de los acuíferos mas someros por el ascenso de las aguas sobresaturadas en CO2, proceso que seria análogo a la contaminación que se produciría en los acuíferos existentes por encima de un AGP-CO2, siempre que este se perturbara natural (reactivación de fallas) o artificialmente (sondeos); iv) la desgasificación (CO2 y gases asociados, entre los que destaca el 222Rn) del acuífero salino profundo a través de sondeos, proceso análogo al que pudiera ocurrir en un AGP-CO2 perturbado; y v) la formación rápida de travertinos, proceso análogo indicativo de que el AGP-CO2 ha perdido su estanqueidad. La identificación de las analogías más importantes ha permitido, además, analizar y evaluar, de manera aproximada, el comportamiento y la seguridad, a corto, medio y largo plazo, de un AGP-CO2 emplazado en un contexto geológico similar al sistema natural estudiado. Para ello se ha seguido la metodología basada en el análisis e identificación de los FEPs (Features, Events and Processes), los cuales se han combinado entre sí para generar y analizar diferentes escenarios de evolución del sistema (scenario analysis). Estos escenarios de evolución identificados en el sistema natural perturbado, relacionados con la perforación de sondeos, sobreexplotación de acuíferos, precipitación rápida de travertinos, etc., serian análogos a los que podrían ocurrir en un AGP-CO2 que también fuera perturbado antropogénicamente, por lo que resulta totalmente necesario evitar la perturbación artificial de la formación sello del AGPCO2. Por último, con toda la información obtenida se ha propuesto una metodología de estudio que pueda aplicarse al estudio de posibles emplazamientos de un AGP-CO2 desde la perspectiva de los reservorios naturales de CO2, sean estancos o no. Esta metodología comprende varias fases de estudio, que comprendería la caracterización geológico-estructural del sitio y de sus componentes (agua, roca y gases), la identificación de las analogías entre un sistema natural de almacenamiento de CO2 y un modelo conceptual de un AGP-CO2, y el establecimiento de las implicaciones para el comportamiento y la seguridad de un AGP-CO2. ABSTRACT The accumulation of the anthropogenic greenhouse gases in the atmosphere is the main responsible for: i) the increase in the average temperature of the Earth over the past century by almost 1 °C; ii) the rise in the mean sea level; iii) the drop of the ice volume and terrestrial snow; iv) the strong climate variability and extreme weather events that have been happening over the last decades; and v) the spread of epidemics and infectious diseases. All of these events are just some of the evidence of current climate change. The problems and growing concern related to these phenomena, prompted the adoption of the so-called "Kyoto Protocol" (Japan) in 1997, in which the signatory countries established different measurements to control and reduce the emissions of the greenhouse gases. These measurements include the CCS technologies, focused on the capture, transport and storage of CO2. Within this context, it was approved, in October 2008, the Strategic Singular Project "Tecnologías avanzadas de generación, captura y almacenamiento de CO2" (PSE-120000-2008-6), supported by the Ministry of Science and Innovation and the FEDER funds. This Project, by means of the Subproject "Geological Storage of CO2" (PSS- 120000-2008-31), was focused on the detailed study of the Natural Analogue of CO2 Storage and Leakage located in the Ganuelas-Mazarron Tertiary basin (Murcia), among other Spanish Natural Analogues. This research work has been performed in the framework of this Subproject, being its final objective to predict the behaviour and evaluate the safety, at short, medium and long-term, of a CO2 Deep Geological Storage (CO2-DGS) by means of a comprehensive study of the abovementioned Natural Analogue. This study comprises: i) the geological and hydrogeological context of the basin and its geophysical research; ii) the water sampling of the selected aquifers to establish their hydrogeochemical and isotopic features; iii) the mineralogical, petrographic, geochemical and isotopic characterisation of the travertines formed from upwelling groundwater of several hydrogeological and geothermal wells; and iv) the measurement of the free and dissolved gases detected in the basin, as well as their chemical and isotopic characterisation, mainly regarding CO2 and 222Rn. This information, summarised in separate chapters in the text, has enabled to build a conceptual model of the studied natural system and to establish the analogies between both the studied natural system and a CO2-DGS, with possible natural and/or anthropogenic escapes. All this information has served, firstly, to predict the behaviour and to evaluate the safety, at short, medium and long-term, of a CO2-DGS and, secondly, to propose a general methodology to study suitable sites for a CO2-DGS, taking into account the lessons learned from this CO2 natural reservoir. The main results indicate that the Ganuelas-Mazarron basin is a graben bounded by normal faults with significant vertical movements, which move down the metamorphic substrate (Nevado-Filabride Complex), and filled with acid volcanic-subvolcanic rocks. Furthermore, this basin is filled with two sedimentary formations: i) the Miocene marls, which are predominant and almost exclusive in the basin; xxiv and ii) the Plio-Quaternary conglomerates and gravels. A deep saline CO2-rich aquifer was evidenced in this basin as a result of the geothermal exploration wells performed during the 80s, located just at the top of the Nevado-Filabride Complex and at a depth that could exceed 800 m, according to the geophysical exploration performed. This saline CO2-rich aquifer is precisely the main object of this study. Therefore, it is not discarded the possibility that the CO2 in this aquifer be in supercritical state. Consequently, the aforementioned basin gathers the main characteristics of a natural and deep CO2 geological storage, or natural analogue of a CO2-DGS in a deep saline aquifer. The overexploitation of the shallow aquifers in this basin for agriculture purposes caused the drop of the groundwater levels and hydrostatic pressures, and, as a result, the ascent of the deep saline and CO2-rich groundwater, which is the responsible for the contamination of the shallow and fresh aquifers. The hydrogeochemical features of groundwater from the investigated aquifers show the presence of very different hydrofacies, even in those with similar lithology. The high salinity of this groundwater prevents the human and agricultural uses. In addition, the slightly acidic character of most of these waters determines their capacity to dissolve and transport towards the surface heavy and/or toxic elements, among which U is highlighted. This element is abundant in the acidic volcanic rocks of the basin, with concentrations up to 14 ppm, mainly as sub-microscopic uraninite crystals. The isotopic study of this groundwater, particularly the isotopic signature of C from DIC (δ13C-DIC), suggests that dissolved C can be explained considering a mixture of C from two main different sources: i) from the thermal decomposition of limestones and marbles forming the substrate; and ii) from edaphic origin. However, a minor contribution of C from mantle degassing cannot be discarded. The study of travertines being formed from upwelling groundwater of several hydrogeological and geothermal wells, as a result of the fast CO2 degassing and the pH increase, has allowed highlighting this phenomenon, by analogy, as an alert for the CO2 leakages from a CO2-DGS. The analysis of the dissolved and free gases, with special attention to CO2 and 222Rn, indicates that the C from the dissolved and free CO2 has a similar origin to that of the DIC. The R/Ra ratio of He corroborates the minor contribution of CO2 from the mantle degassing. Furthermore, 222Rn is generated by the radioactive decay of U, particularly abundant in the volcanic rocks of the basin, and/or by 226Ra from the U or from the Messinian gypsum in the basin. Moreover, CO2 acts as a carrier of the 222Rn, a fact evidenced by the positive anomalies of both gases at ~ 1 m depth and mainly related to natural (faults and contacts) and anthropogenic (wells) perturbations. The isotopic signature of C from DIC, carbonates (travertines), and dissolved and free CO2, suggests that this parameter can be used as an excellent tracer of CO2 escapes from a CO2-DGS, in which CO2 usually from the combustion of fossil fuels, with δ13C(V-PDB) of ~ -30 ‰, will be injected. All of these results have allowed to build a conceptual model of the behaviour of the natural system studied as a natural analogue of a CO2-DGS, as well as to establish the relationships between both natural xxv and artificial systems. Thus, the most important analogies, regarding the elements of the system, would be the presence of: i) a deep saline CO2-rich aquifer, which would be analogous to the storage formation of a CO2-DGS; ii) a marly sedimentary formation with a thickness greater than 500 m, which would correspond to the sealing formation of a CO2-DGS; and iii) shallow aquifers with fresh waters suitable for human consumption, U-rich volcanic rocks, and faults that are sealed by gypsums and/or marls; geological elements that could also be present in a CO2-DGS. On the other hand, the most important analogous processes identified are: i) the upward injection of CO2, which would be analogous to the downward injection of the anthropogenic CO2, this last with a δ13C(V-PDB) of ~ -30 ‰; ii) the dissolution of CO2 and 222Rn in groundwater of the deep aquifer, which would be analogous to the dissolution of these gases in the storage formation of a CO2-DGS; iii) the contamination of the shallow aquifers by the uprising of CO2-oversaturated groundwater, an analogous process to the contamination that would occur in shallow aquifers located above a CO2-DGS, whenever it was naturally (reactivation of faults) or artificially (wells) perturbed; iv) the degassing (CO2 and associated gases, among which 222Rn is remarkable) of the deep saline aquifer through wells, process which could be similar in a perturbed CO2- DGS; v) the rapid formation of travertines, indicating that the CO2-DGS has lost its seal capacity. The identification of the most important analogies has also allowed analysing and evaluating, approximately, the behaviour and safety in the short, medium and long term, of a CO2-DGS hosted in a similar geological context of the natural system studied. For that, it has been followed the methodology based on the analysis and identification of FEPs (Features, Events and Processes) that have been combined together in order to generate and analyse different scenarios of the system evolution (scenario analysis). These identified scenarios in the perturbed natural system, related to boreholes, overexploitation of aquifers, rapid precipitation of travertines, etc., would be similar to those that might occur in a CO2-DGS anthropogenically perturbed, so that it is absolutely necessary to avoid the artificial perturbation of the seal formation of a CO2-DGS. Finally, a useful methodology for the study of possible sites for a CO2-DGS is suggested based on the information obtained from this investigation, taking into account the lessons learned from this CO2 natural reservoir. This methodology comprises several phases of study, including the geological and structural characterisation of the site and its components (water, rock and gases), the identification of the analogies between a CO2 storage natural system and a conceptual model of a CO2-DGS, and the implications regarding the behaviour and safety of a CO2-DGS.

Global instability analysis and control of three-dimensional long open cavity flow

The three-dimensional wall-bounded open cavity may be considered as a simplified geometry found in industrial applications such as leading gear or slotted flats on the airplane. Understanding the three-dimensional complex flow structure that surrounds this particular geometry is therefore of major industrial interest. At the light of the remarkable former investigations in this kind of flows, enough evidences suggest that the lateral walls have a great influence on the flow features and hence on their instability modes. Nevertheless, even though there is a large body of literature on cavity flows, most of them are based on the assumption that the flow is two-dimensional and spanwise-periodic. The flow over realistic open cavity should be considered. This thesis presents an investigation of three-dimensional wall-bounded open cavity with geometric ratio 6:2:1. To this aim, three-dimensional Direct Numerical Simulation (DNS) and global linear instability have been performed. Linear instability analysis reveals that the onset of the first instability in this open cavity is around Recr 1080. The three-dimensional shear layer mode with a complex structure is shown to be the most unstable mode. I t is noteworthy that the flow pattern of this high-frequency shear layer mode is similar to the observed unstable oscillations in supercritical unstable case. DNS of the cavity flow carried out at different Reynolds number from steady state until a nonlinear saturated state is obtained. The comparison of time histories of kinetic energy presents a clearly dominant energetic mode which shifts between low-frequency and highfrequency oscillation. A complete flow patterns from subcritical cases to supercritical case has been put in evidence. The flow structure at the supercritical case Re=1100 resembles typical wake-shedding instability oscillations with a lateral motion existed in the subcritical cases. Also, This flow pattern is similar to the observations in experiments. In order to validate the linear instability analysis results, the topology of the composite flow fields reconstructed by linear superposition of a three-dimensional base flow and its leading three-dimensional global eigenmodes has been studied. The instantaneous wall streamlines of those composited flows display distinguish influence region of each eigenmode. Attention has been focused on the leading high-frequency shear layer mode; the composite flow fields have been fully recognized with respect to the downstream wave shedding. The three-dimensional shear layer mode is shown to give rise to a typical wake-shedding instability with a lateral motions occurring downstream which is in good agreement with the experiment results. Moreover, the spanwise-periodic, open cavity with the same length to depth ratio has been also studied. The most unstable linear mode is different from the real three-dimensional cavity flow, because of the existence of the side walls. Structure sensitivity of the unstable global mode is analyzed in the flow control context. The adjoint-based sensitivity analysis has been employed to localized the receptivity region, where the flow is more sensible to momentum forcing and mass injection. Because of the non-normality of the linearized Navier-Stokes equations, the direct and adjoint field has a large spatial separation. The strongest sensitivity region is locate in the upstream lip of the three-dimensional cavity. This numerical finding is in agreement with experimental observations. Finally, a prototype of passive flow control strategy is applied.