Geothermal district heating networks: modelling novel operational strategies incorporating heat storage

The value of integrating a heat storage into a geothermal district heating system has been investigated. The behaviour of the system under a novel operational strategy has been simulated focusing on the energetic, economic and environmental effects of the new strategy of incorporation of the heat storage within the system. A typical geothermal district heating system consists of several production wells, a system of pipelines for the transportation of the hot water to end-users, one or more re-injection wells and peak-up devices (usually fossil-fuel boilers). Traditionally in these systems, the production wells change their production rate throughout the day according to heat demand, and if their maximum capacity is exceeded the peak-up devices are used to meet the balance of the heat demand. In this study, it is proposed to maintain a constant geothermal production and add heat storage into the network. Subsequently, hot water will be stored when heat demand is lower than the production and the stored hot water will be released into the system to cover the peak demands (or part of these). It is not intended to totally phase-out the peak-up devices, but to decrease their use, as these will often be installed anyway for back-up purposes. Both the integration of a heat storage in such a system as well as the novel operational strategy are the main novelties of this thesis. A robust algorithm for the sizing of these systems has been developed. The main inputs are the geothermal production data, the heat demand data throughout one year or more and the topology of the installation. The outputs are the sizing of the whole system, including the necessary number of production wells, the size of the heat storage and the dimensions of the pipelines amongst others. The results provide several useful insights into the initial design considerations for these systems, emphasizing particularly the importance of heat losses. Simulations are carried out for three different cases of sizing of the installation (small, medium and large) to examine the influence of system scale. In the second phase of work, two algorithms are developed which study in detail the operation of the installation throughout a random day and a whole year, respectively. The first algorithm can be a potentially powerful tool for the operators of the installation, who can know a priori how to operate the installation on a random day given the heat demand. The second algorithm is used to obtain the amount of electricity used by the pumps as well as the amount of fuel used by the peak-up boilers over a whole year. These comprise the main operational costs of the installation and are among the main inputs of the third part of the study. In the third part of the study, an integrated energetic, economic and environmental analysis of the studied installation is carried out together with a comparison with the traditional case. The results show that by implementing heat storage under the novel operational strategy, heat is generated more cheaply as all the financial indices improve, more geothermal energy is utilised and less fuel is used in the peak-up boilers, with subsequent environmental benefits, when compared to the traditional case. Furthermore, it is shown that the most attractive case of sizing is the large one, although the addition of the heat storage most greatly impacts the medium case of sizing. In other words, the geothermal component of the installation should be sized as large as possible. This analysis indicates that the proposed solution is beneficial from energetic, economic, and environmental perspectives. Therefore, it can be stated that the aim of this study is achieved in its full potential. Furthermore, the new models for the sizing, operation and economic/energetic/environmental analyses of these kind of systems can be used with few adaptations for real cases, making the practical applicability of this study evident. Having this study as a starting point, further work could include the integration of these systems with end-user demands, further analysis of component parts of the installation (such as the heat exchangers) and the integration of a heat pump to maximise utilisation of geothermal energy.

Exploring redox-driven self-assembly of mixed metal polyoxometalates

How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.