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 coordination-driven self-assembly with autonomous chemical robots

The work presented herein focused on the automation of coordination-driven self assembly, exploring methods that allow syntheses to be followed more closely while forming new ligands, as part of the fundamental study of the digitization of chemical synthesis and discovery. Whilst the control and understanding of the principle of pre-organization and self-sorting under non-equilibrium conditions remains a key goal, a clear gap has been identified in the absence of approaches that can permit fast screening and real-time observation of the reaction process under different conditions. A firm emphasis was thus placed on the realization of an autonomous chemical robot, which can not only monitor and manipulate coordination chemistry in real-time, but can also allow the exploration of a large chemical parameter space defined by the ligand building blocks and the metal to coordinate. The self-assembly of imine ligands with copper and nickel cations has been studied in a multi-step approach using a self-built flow system capable of automatically controlling the liquid-handling and collecting data in real-time using a benchtop MS and NMR spectrometer. This study led to the identification of a transient Cu(I) species in situ which allows for the formation of dimeric and trimeric carbonato bridged Cu(II) assemblies. Furthermore, new Ni(II) complexes and more remarkably also a new binuclear Cu(I) complex, which usually requires long and laborious inert conditions, could be isolated. The study was then expanded to the autonomous optimization of the ligand synthesis by enabling feedback control on the chemical system via benchtop NMR. The synthesis of new polydentate ligands has emerged as a result of the study aiming to enhance the complexity of the chemical system to accelerate the discovery of new complexes. This type of ligand consists of 1-pyridinyl-4-imino-1,2,3-triazole units, which can coordinate with different metal salts. The studies to test for the CuAAC synthesis via microwave lead to the discovery of four new Cu complexes, one of them being a coordination polymer obtained from a solvent dependent crystallization technique. With the goal of easier integration into an automated system, copper tubing has been exploited as the chemical reactor for the synthesis of this ligand, as it efficiently enhances the rate of the triazole formation and consequently promotes the formation of the full ligand in high yields within two hours. Lastly, the digitization of coordination-driven self-assembly has been realized for the first time using an in-house autonomous chemical robot, herein named the ‘Finder’. The chemical parameter space to explore was defined by the selection of six variables, which consist of the ligand precursors necessary to form complex ligands (aldehydes, alkineamines and azides), of the metal salt solutions and of other reaction parameters – duration, temperature and reagent volumes. The platform was assembled using rounded bottom flasks, flow syringe pumps, copper tubing, as an active reactor, and in-line analytics – a pH meter probe, a UV-vis flow cell and a benchtop MS. The control over the system was then obtained with an algorithm capable of autonomously focusing the experiments on the most reactive region (by avoiding areas of low interest) of the chemical parameter space to explore. This study led to interesting observations, such as metal exchange phenomena, and also to the autonomous discovery of self assembled structures in solution and solid state – such as 1-pyridinyl-4-imino-1,2,3-triazole based Fe complexes and two helicates based on the same ligand coordination motif.