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Experimental and Theoretical Study of Solubility of New Absorbents in Natural Refrigerants

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Experimental and Theoretical Study of Solubility of New Absorbents in Natural Refrigerants EXPERIMENTAL AND THEORETICAL STUDY OF SOLUBILITY OF NEW ABSORBENTS IN NATURAL REFRIGERANTS. Javier Mesones Mora Dipòsit Legal: T 1549-2014 ADVERTIMENT. L'accés als continguts d'aquesta tesi doctoral i la seva utilització ha de respectar els drets de la persona autora. Pot ser utilitzada per a consulta o estudi personal, així com en activitats o materials d'investigació i docència en els termes establerts a l'art. 32 del Text Refós de la Llei de Propietat Intel·lectual (RDL 1/1996). Per altres utilitzacions es requereix l'autorització prèvia i expressa de la persona autora. En qualsevol cas, en la utilització dels seus continguts caldrà indicar de forma clara el nom i cognoms de la persona autora i el títol de la tesi doctoral. No s'autoritza la seva reproducció o altres formes d'explotació efectuades amb finalitats de lucre ni la seva comunicació pública des d'un lloc aliè al servei TDX. Tampoc s'autoritza la presentació del seu contingut en una finestra o marc aliè a TDX (framing). Aquesta reserva de drets afecta tant als continguts de la tesi com als seus resums i índexs. ADVERTENCIA. El acceso a los contenidos de esta tesis doctoral y su utilización debe respetar los derechos de la persona autora. Puede ser utilizada para consulta o estudio personal, así como en actividades o materiales de investigación y docencia en los términos establecidos en el art. 32 del Texto Refundido de la Ley de Propiedad Intelectual (RDL 1/1996). Para otros usos se requiere la autorización previa y expresa de la persona autora. En cualquier caso, en la utilización de sus contenidos se deberá indicar de forma clara el nombre y apellidos de la persona autora y el título de la tesis doctoral. No se autoriza su reproducción u otras formas de explotación efectuadas con fines lucrativos ni su comunicación pública desde un sitio ajeno al servicio TDR. Tampoco se autoriza la presentación de su contenido en una ventana o marco ajeno a TDR (framing). Esta reserva de derechos afecta tanto al contenido de la tesis como a sus resúmenes e índices. WARNING. Access to the contents of this doctoral thesis and its use must respect the rights of the author. It can be used for reference or private study, as well as research and learning activities or materials in the terms established by the 32nd article of the Spanish Consolidated Copyright Act (RDL 1/1996). Express and previous authorization of the author is required for any other uses. In any case, when using its content, full name of the author and title of the thesis must be clearly indicated. Reproduction or other forms of for profit use or public communication from outside TDX service is not allowed. Presentation of its content in a window or frame external to TDX (framing) is not authorized either. These rights affect both the content of the thesis and its abstracts and indexes. UNIVERSITAT ROVIRA I VIRGILI EXPERIMENTAL AND THEORETICAL STUDY OF SOLUBILITY OF NEW ABSORBENTS IN NATURAL REFRIGERANTS. Javier Mesones Mora Dipòsit Legal: T 1549-2014 DOCTORAL THESIS EXPERIMENTAL AND THEORETICAL STUDY OF SOLUBILITY OF NEW ABSORBENTS IN NATURAL REFRIGERANTS Javier Mesones Mora Supervised by: Prof. Dr. Alberto Coronas Dr. Daniel Salavera Department of Mechanical Engineering CREVER - Group of Applied Thermal Engineering Tarragona, June 2014 UNIVERSITAT ROVIRA I VIRGILI EXPERIMENTAL AND THEORETICAL STUDY OF SOLUBILITY OF NEW ABSORBENTS IN NATURAL REFRIGERANTS. Javier Mesones Mora Dipòsit Legal: T 1549-2014 UNIVERSITAT ROVIRA I VIRGILI EXPERIMENTAL AND THEORETICAL STUDY OF SOLUBILITY OF NEW ABSORBENTS IN NATURAL REFRIGERANTS. Javier Mesones Mora Dipòsit Legal: T 1549-2014 UNIVERSITAT ROVIRA I VIRGILI DEPARTAMENT D’ENGINYERIA MECÀNICA Escola Tècnica Superior d’Enginyeria Química (ETSEQ). Av. Països Catalans 26. 43007 Tarragona (Spain) Los abajo firmantes Dr. Alberto Coronas, Catedrático de Universidad y Dr. Daniel Salavera, Profesor Lector, ambos del Departamento de Ingeniería Mecánica de la Universidad Rovira i Virgili de Tarragona. HACEN CONSTAR: Que el siguiente estudio titulado: “Experimental and Theoretical Study of Solubility of New Absorbents in Natural Refrigerants” presentado por el Sr. Javier Mesones Mora para optar al grado de Doctor, ha sido desarrollado bajo nuestra supervisión en el Grupo de investigación de Ingeniería Térmica Aplicada – CREVER del Departamento de Ingeniería Mecánica de la Universidad Rovira i Virgili. Que todos los resultados han sido obtenidos de las experiencias y trabajos realizadas por dicho doctorando. Que cumple los requisitos para poder optar al grado de Doctor en Ingeniería Termodinámica de Fluidos con Mención Internacional. Y para que así conste a los efectos oportunos, firmamos este documento, en Tarragona, 11 de Junio de 2014. i UNIVERSITAT ROVIRA I VIRGILI EXPERIMENTAL AND THEORETICAL STUDY OF SOLUBILITY OF NEW ABSORBENTS IN NATURAL REFRIGERANTS. Javier Mesones Mora Dipòsit Legal: T 1549-2014 UNIVERSITAT ROVIRA I VIRGILI EXPERIMENTAL AND THEORETICAL STUDY OF SOLUBILITY OF NEW ABSORBENTS IN NATURAL REFRIGERANTS. Javier Mesones Mora Dipòsit Legal: T 1549-2014 Dedicated to my mother iii UNIVERSITAT ROVIRA I VIRGILI EXPERIMENTAL AND THEORETICAL STUDY OF SOLUBILITY OF NEW ABSORBENTS IN NATURAL REFRIGERANTS. Javier Mesones Mora Dipòsit Legal: T 1549-2014 UNIVERSITAT ROVIRA I VIRGILI EXPERIMENTAL AND THEORETICAL STUDY OF SOLUBILITY OF NEW ABSORBENTS IN NATURAL REFRIGERANTS. Javier Mesones Mora Dipòsit Legal: T 1549-2014 “There is a driving force more powerful than steam, electricity and atomic energy: the will” Albert Einstein (1879-1955) v UNIVERSITAT ROVIRA I VIRGILI EXPERIMENTAL AND THEORETICAL STUDY OF SOLUBILITY OF NEW ABSORBENTS IN NATURAL REFRIGERANTS. Javier Mesones Mora Dipòsit Legal: T 1549-2014 UNIVERSITAT ROVIRA I VIRGILI EXPERIMENTAL AND THEORETICAL STUDY OF SOLUBILITY OF NEW ABSORBENTS IN NATURAL REFRIGERANTS. Javier Mesones Mora Dipòsit Legal: T 1549-2014 I would like to thank Dr. Alberto Coronas for letting me do this doctoral thesis as well as its support along all these years in CREVER group. I also would like to thank Dr. Daniel Salavera for all the unconditional help and valuable advices given in all the work carried out in this thesis, especially in laboratory tasks. Furthermore, I want to express my acknowledgment to Dr. María Soledad Larrechi for the help and advices provided in some tasks of this work. Acknowledgments to Ministry of Science and Innovation (project ref. ENE2009- 14177) and Ministry of Economy and Competitiveness (project ref. DPI2012-38841-C02-01) for providing the financial support of this research, as well as to Universitat Rovira Virgili for funding my doctoral thesis and the stay in France through a scholarship. Thanks to Dr. Jean-Yves Coxam for providing me the opportunity to do a stage in the Institute of Chemistry of Clermont-Ferrand (France) and also to Dr. Karine Ballerat-Busserolles for the help provided along the stay. Finally I would like to thank to the rest of professors and colleagues from CREVER group as well as the secretary of Mechanical Engineering Department for their support and help received along all these years, creating a nice working environment and making the work easier and peaceful. vii UNIVERSITAT ROVIRA I VIRGILI EXPERIMENTAL AND THEORETICAL STUDY OF SOLUBILITY OF NEW ABSORBENTS IN NATURAL REFRIGERANTS. Javier Mesones Mora Dipòsit Legal: T 1549-2014 UNIVERSITAT ROVIRA I VIRGILI EXPERIMENTAL AND THEORETICAL STUDY OF SOLUBILITY OF NEW ABSORBENTS IN NATURAL REFRIGERANTS. Javier Mesones Mora Dipòsit Legal: T 1549-2014 In this doctoral thesis it has been carried out an experimental and theoretical study of solubility of new absorbents in natural refrigerants for absorption refrigeration cycles. Commercial absorption refrigeration systems use H2O/LiBr and NH3/H2O (refrigerant/absorbent) as working fluids with good performance in air conditioning and refrigeration applications. However these systems have some drawbacks that have driven research in improving their efficiency, enlarging the working ranges and extending to new applications. These limitations are caused by the physicochemical properties of such mixtures: crystallization, corrosion and operating vacuum pressure for H2O/LiBr mixture or the need of rectification of the stream generated in the generator and the high level of the activation thermal energy required for NH3/H2O mixture. The use of absorbents such as LiNO3 or NaSCN in NH3 allow the operation of the refrigeration system at lower temperatures than in the case of NH3/H2O mixture, facilitating the use of solar thermal energy at low temperature or waste heat as activation energy as well as avoiding the need of rectification in the cycle. On the other hand, the use of additives like NaOH to the conventional NH3/H2O mixture allows better separation of the ammonia in the generator. In the case of absorption systems with H2O/LiBr as working fluid, the addition of LiNO3 and LiI involve a significant solubility improvement of the mixture, allowing the equipment to operate at higher temperatures in the absorber and the use of air-coolers for the heat dissipation to the environment. The use of CO2 as refrigerant and amines as absorbents have been currently proposed as alternatives to conventional ammonia/water systems, avoiding toxicity and flammability problems that ammonia presents. Regarding the available information of physicochemical properties of the new working fluids, in the case of NH3/LiNO3 and NH3/NaSCN the solubility data available in literature is scarce, old and incomplete. Also, for NH3/(H2O+NaOH) system, no solubility data were found in literature. Thus, in order to complete the solubility data of these mixtures it has been designed and built a new experimental device based on the visual-polythermal method with the capacity to work at moderate-high pressures to keep the ammonia in liquid state. Validation of the experimental device and methodology performed at atmospheric pressure with H2O/LiNO3 system and at a pressure conditions up to 20 bar with the system NH3/LiNO3. Additionally, to avoid the subjective criterion in the solubility temperature measurements, it has been developed a new image processing method based on the analysis of images taken and recorded during the experiment.
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