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Development of New Eutectic Phase Change Materials and Plate-Based Latent Heat Thermal Energy Storage Systems for Domestic Cogeneration Applications

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Development of New Eutectic Phase Change Materials and Plate-Based Latent Heat Thermal Energy Storage Systems for Domestic Cogeneration Applications Development of new eutectic phase change materials and plate-based latent heat thermal energy storage systems for domestic cogeneration applications Gonzalo Diarce Belloso Dissertation presented at the University of the Basque Country (UPV/EHU) in fulfillment of the requirements for the degree of PhD in Thermal Engineering of the PhD program of the Department of Thermal Engineering Under the supervision of: Dr. Ane Miren García-Romero Prof. José Mª Pedro Sala Lizarraga (cc)2017 GONZALO DIARCE BELLOSO (cc by-nc-sa 4.0) Preamble With the aim of assisting the reading and understanding of the present PhD dissertation, a brief explanation about its structure and main contents is herein given. The dissertation starts with a list of the funding sources and collaborations of the thesis. Then, an index is provided, where the starting page number of each chapter is shown, followed by the nomenclature employed along the document. Afterwards, a summary is presented, written in English and in Spanish. It intends to provide the reader with an overall idea of the work carried out. The seven chapters that follow make up the main body of the thesis. Regarding the content, the first chapter consists of a brief introduction on latent thermal energy storage systems that includes the main objectives of the thesis and the methodology followed to achieve them. The second chapter corresponds to the development of new eutectic mixtures of sugar alcohols for their use as phase change materials. In the third chapter, the eutectic mixture formed by sodium nitrate and urea is studied for thermal energy storage purposes. The fourth chapter covers the investigation of the erythritol-urea eutectic mixture with the same objective. These chapters correspond to articles accepted in peer reviewed journals; however, in order to give uniformity and consistency to the dissertation, their content and format have been adapted to agree with the rest of the document. The bibliographic details of the articles are provided on the initial page of each chapter. After these chapters, dealing with the development of new PCMs, the following chapters present the research carried out to develop the plate-based LHTES system for domestic use with a cogeneration installation. Accordingly, the fifth chapter displays the study to develop an overall design methodology for plate-based LHTES systems, while the sixth chapter deals with the design, construction and evaluation of a full-scale prototype. The dissertation finishes with the seventh chapter, where the main conclusions derived from the research are presented and summarized. A brief analysis of the works required in the future is provided as a final point. Preamble 3 Funding sources and collaborations of the thesis This thesis has been developed under the framework of a grant from the Research Personnel Training Program awarded by the Department of Education, Universities and Research of the Basque Government (reference no.: BFI-2012-293). Besides, the work has been performed within the ENEDI (Energy in Buildings) research group from the University of the Basque Country (UPV/EHU), which is recognized as a consolidated group by the Basque Government. The research performed has also been funded by the following projects: MicroTES project (ENE2012–38633, FEDER funding included) of the Spanish's Ministry of Economy and Competitiveness (MINECO) CogTES project (SA-2012/00329) of the Department of Education, Universities and Research of the Basque Government Two research stays have been performed in international institutions during the thesis, one of 3 months at the University of Innsbruck (Austria) under the supervision of Prof. Ulrich J. Griesser and another of 10 months at the University of New South Wales (Australia) under the supervision of Dr. Robert Taylor. The latter stay was funded by the Panther Erasmus Mundus exchange program. In addition, the author of the thesis has actively participated within the SHC/ ECES Task 42/29 research program of the International Energy Agency. Funding sources and collaborations of the thesis 5 Index of contents Preamble ............................................................................................................................................... 3 Funding sources and collaborations of the thesis................................................................................... 5 Index of contents ................................................................................................................................... 7 Index of figures .................................................................................................................................... 13 Index of tables ..................................................................................................................................... 21 Nomenclature and symbols ................................................................................................................. 25 Summary ............................................................................................................................................. 28 Resumen .............................................................................................................................................. 35 CHAPTER 1: Introduction, objectives and structure of the PhD thesis ................. 43 1. Introduction ................................................................................................................................ 47 2. Thermal Energy Storage: Description of the main aspects ........................................................... 49 3. Design features of the previously developed finned plate-based LHTES system .......................... 52 3.1. General aspects of the design proposed .................................................................................. 53 3.2. Materials selected for the LHTES system .................................................................................. 55 3.3. Design considerations of finned plate LHTES systems for CHP ................................................. 56 3.4. Main tasks and conclusions of the previous PhD dissertation ([5]) .......................................... 58 4. Objectives and structure of the PhD dissertation ........................................................................ 59 CHAPTER 2: Eutectic mixtures of sugar alcohols as PCMs for space heating and DHW LHTES systems ............................................................................................... 65 1. Introduction ................................................................................................................................ 69 1.1. General aspects and requirements of PCMs ............................................................................. 69 1.2. PCMs for heating and DHW applications: brief literature survey and objectives of the chapter.. ................................................................................................................................................. 70 2. Experimental methods and theoretical considerations................................................................ 73 2.1. Materials employed and their thermal properties ................................................................... 74 2.2. Preparation of the binary mixtures for the experimental determination of the phase diagrams. ................................................................................................................................................ 74 2.3. Differential Scanning Calorimetry ............................................................................................. 75 General index 7 2.4. Polarized thermomicroscopy .................................................................................................... 75 2.5. X-ray diffraction ........................................................................................................................ 77 2.6. Modeling of the phase diagrams. Theory and calculations ...................................................... 77 3. Results and discussion ................................................................................................................. 78 3.1. Relationship between a DSC thermogram and the experimental liquidus temperature of a phase diagram ........................................................................................................................................ 78 3.2. Experimental determination of phase diagrams of mixtures. Evaluation of thermophysical properties and economical aspects of the eutectic compositions......................................................... 81 3.3. Crystallization behavior of the materials .................................................................................. 88 3.4. Theoretical prediction of phase diagrams by thermodynamic modeling ................................. 93 3.4.1. Comparison between experimental and predicted phase diagrams ........................................ 93 3.4.2. Influence of properties of the pure materials on resultant binary eutectic systems ............... 94 4. Conclusions of the chapter and further work .............................................................................. 95 CHAPTER 3: The sodium nitrate-urea eutectic mixture as a PCM for heating and DHW LHTES systems ............................................................................................... 97 1. Introduction .............................................................................................................................
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