Increase in global energy demand has brought to a massive rise in greenhouse gases emissions. In particular, the continuously increasing atmospheric concentration of carbon dioxide is a major concern among the scientific community. This paved the way for an intense research of CO2 emissions mitigating technologies. Those ones including carbon capture, storage and utilisation are seen as part of the solution for this global problem. In this framework, Zero Emission Fuels (ZEF), a startup company located in Delft (The Netherlands) set the ambitious goal of developing a micro process plant producing methanol from ambient air and sunlight only. Part of the process involves direct capture of carbon dioxide from the atmosphere (direct air capture) with the use of a pure tetraethylenepentamine (TEPA) absorbent. ZEF sets itself aside from the rest of the industry developing an absorber which collects CO2 with no support structure by continuously flowing TEPA inside open channels. Previous research shows how this approach brings limitations connected to slowly diffusing CO2 molecules in the absorbent liquid film in proximity of the gas-liquid interface. In this framework, circulation of TEPA particles from the gas-liquid interface into the bulk of the flowing absorbent is seen as a viable solution to improve the process. This thesis focuses on investigating this hypothesis by inducing mixing on the liquid side. That is done by building two experimental setups investigating both passive and active mixing. Experimental results show that active mixing can be used to improve the rate of CO2 absorption, while passive mixing does not bring significant advantages. Results from the passive mixing experiments are further investigated by modelling the fluid dynamics of the process through a Direct Numerical Simulation of the particular Stokes’ flow in the engineered absorption channel. The process is characterised with the definition of a theoretical framework describing mass transfer in the liquid side. Following an analogy with ice formation on top of a frozen lake, this theory, also known as the ”Ice-Sheet” theory, shines some light on the way this diffusion limitations are happening at a molecular level. In particular, a highly viscous, heavily loaded layer of sorbent on the gas-liquid interface is believed to be the cause for observed CO2 diffusion limitations. This theory is backed-up by defining its mathematical equivalent in the form of a mass transfer model. Comparing the results of the model with experimental results, a very good agreement is observed. That is believed to add credibility to the proposed theory. Moreover, that is also found to be in line with the latest knowledge available in literature about CO2 absorption in TEPA films. Finally, the experimental results and the developed models are used to engineer a new iteration of ZEF’s absorber on a cost reduction basis.

In conventional compressor technology, high pressure ratios are often achieved by multiple, successive compression stages. This is done to avoid high temperatures due to the adiabatic nature of most compression processes which deteriorates the working of oil lubrication. The aim of this work is to reduce a conventional four-stage system to only two stages as this may improve the size and expenses of the system. This goal combined with a long desired lifetime, makes that a compressor is developed that operates based on gas bearing technology. The design is focused on two main subjects. Firstly, the load capacity of the gas bearings is significantly lower than oil lubricated bearings due to the reduced viscosity. To avoid mechanical contact and wear of the components this has been thoroughly analysed using finite element methods. The oscillating nature of the loads in the system enhances the squeeze effect from the Reynolds equation. Secondly, the sealing function of gas bearings opposing internal leakage is evaluated carefully to obtain a desired efficiency. Based on these simulations, the mechanical design of the compressor is optimized to improve the manufacturing of the compressor components.

To answer the need for renewable fuels, Zero Emission Fuels is designing a microplant to create methanol from carbon dioxide and water from the ambient air using only renewable energy from solar panels. For this microplant, gaseous carbon dioxide must be compressed from 1 to 50 [bar] with the low mass flow of 336.7 [g/h]. This thesis examines the compression system which uses rolling piston compressors. This thesis also examines a solution to compress the carbon dioxide optimally. Because of the low mass flows, the compressors are very small and have relatively high friction and leakage losses. Meanwhile, due to the high pressure ratio of the system, the temperature increase due to compression also poses a problem for the lubrication of the system. Therefore, this thesis looks for solutions for these problems while trying to gain a better understanding of what exactly is happening inside the compressors. For the temperature regulation, different options for active cooling were assessed with a dimensionless analysis. Eventually, the concept of cooling through the compressor housing was chosen. Afterwards, a computational model was made to calculate the inner workings of the compressors and assess whether the concept of active cooling would still work. Then the computational model was verified by doing experimentation. After that, the results from the model and the experimentation were compared. The model was able to predict the mass flow and the outside heat transfer coefficient accurately. However, the model was still off from the experimental values by quite a margin. After assessing all the data, the system seemed to perform better as a 2-stage system then as a 3-stage system. However, due to the inaccuracies of the model and experimentation, a definite recommendation on the number of stages of the system cannot be formed.

Alkaline water electrolysis will become increasingly important for supplying the world with sufficient renewable energy, and with raw material for the chemical and pharmaceutical industry. Zero Emission Fuels B.V. (ZEF), a technology start-up based in the Netherlands, is developing a small scale alkaline electrolysis cell (AEC), which is integrated in a methanol producing micro-plant. The challenge of this project is to look into the use of polymers for the encapsulation of the ZEF AEC. The conditions of the ZEF AEC are not to be neglected. The system will run in a 30wt% KOH solution at a temperature of 90 °C and a pressure of 50 bar. Not many polymers will be able to withstand these conditions for a desired lifetime of 20 years. Using CES EduPack, a selection of 30 potentially suitable polymers has been made, from which high density polyethylene (HDPE), 40% glass-reinforced polyphenylene sulfide (PPS-40%gf) and polysulfone (PSU) are further investigated. Based on a literature review and a simple KOH ageing test, HDPE is found unsuitable for application in the ZEF AEC. PPS-40%gf and PSU have been subjected to durability testing for a range of different conditions involving a variety of KOH concentrations (15, 30 and 45wt%), and two oxygen partial pressures (O2 at 5 bar and air with pO2=20%) at different temperatures (90, 120 and 170 °C). The purpose of the ageing experiments is to give a better understanding of the effect of these parameters on the structure and integrity of the polymer; and to eventually be able to acquire a lifetime prediction. Extensive characterisation of the exposed samples has been carried out using different techniques, including weight measurement, tensile testing, DMA, creep-recovery testing, DSC, FTIR, XRD and SEM. After 12 weeks of ageing, it is found that glass-filled polymers are unsuitable for application in a strong alkaline solution at elevated temperatures, due to the dissolution of the glass fibres, which leads to a reduction in mechanical and barrier properties. However, the PPS matrix and PSU are found to be resistant to thermo-oxidative and chemical degradation in the tested ageing conditions. Only subtle changes in mechanical, visco-elastic and thermal behaviour are observed, which can be assigned to the effects of physical ageing. Due to the undesirable brittle nature of PPS, it can be concluded that PSU is the most promising candidate for the long-term application in alkaline electrolysis.

In recent years, the energy transition has led to increasingly higher installed capacities of intermittent renewable energy sources. This has sparked the interest in power-to-fuel technology to store excess renewable energy in the chemical bonds of synthetic fuels. As a highly reactive, turn-key process, plasma-chemical conversion offers a promising approach to power-to-fuel technology. However, recent studies have shown limitations in either energy efficiency, conversion or flow rate. The novel Spinning Arc Plasma Reactor (SAPR) developed by J. van Kranendonk stabilises the plasma by mechanical rotation with the potential to contain a liquid film for in-situ product removal. The aim of this thesis is to characterise this reactor by studying the effect of rotational confinement on the reactor performance. To this end, the prototype initially built by J. van Kranendonk was further developed. A wealth of recent studies on the plasma-chemical conversion of CO2 as a step in the formation of synthetic fuels serves as a benchmark to compare reactor performance of the SAPR concept against. A series of experiments with argon were performed to establish the relationship between the system variables (pressure, power, flow rate and rotational speed) and the plasma parameters (electron temperature and electron density). Based on this knowledge, a series of experiments with CO2 were performed to establish the relationship between the reactor performance measured by the conversion and energy efficiency and the system variables: pressure, power and flow rate. The maximum conversion of about 30% to 55% was obtained at an energy efficiency of approximately 0.25% and the maximum energy efficiency of about 3% was achieved at a conversion of approximately 8.5% conversion. Similarly to other studies, improvements to either one came at the expense of the other. The performance of the SAPR proved comparable to dielectric barrier and other glow discharges but was outperformed by microwave and gliding arc discharges. Especially energy efficiency was inferior to these configurations. Further analysis of the discharge emission spectra suggested that CO2 dissociation mainly occurred through electron impact excitation. This explains the large difference in energy efficiency as microwave and gliding arc configurations are able to exploit more energy efficient dissociation channels. Nonetheless, this study was able to further develop the concept and has laid the ground work to explore the potential effect of a liquid film and in-situ product removal on the reactor performance.

The capture of carbon dioxide before or after it is emitted has been regarded as a crucial mitigation pathway to prevent the rapidly increasing accumulation of CO2 in the atmosphere. The valorisation of the captured CO2 into value added products such as methanol provides an additional economic incentive to continue developing these technologies. The company Zero Emission Fuels B.V. (ZEF) is currently developing a mass-producible miniature methanol plant that houses a Direct Air Capture and CO2-compression unit, an Alkaline Electrolysis Cell, a Methanol Reactor, and a Distillation unit. Potential benefits of this approach are in the economies of scale of production, and autonomous operation in areas of high solar irradiation due to direct integration with PV systems. To validate the microplant-concept from an environmental perspective, a research project was executed with the goal to establish the environmental profile of the microplant, to identify hotspots for impact mitigation, and to assess the position of the microplant’s environmental profile in relation to results of comparable technologies reported in literature. To do so, multiple technological development pathways were considered that project the current microplant’s performance into a range of future states. The impact assessment of the future PV-powered air-to-methanol plant, suggests that it is likely that methanol produced using this approach will exhibit a low (negative cradle-to-gate) climate change impact along its production chain, especially compared to conventional methanol produced via the steam reforming of natural gas. Environmental trade-offs are incurred by the additional material demand compared to conventional methanol, instilled both by the electricity generation from PV panels and the added material demand of the thousands of micro-plants that need to be produced for sufficient methanol production volume. Using polyamine sorbents for the process of capturing CO2 from the atmosphere inevitably leads to sorbent degradation which in turn can cause emissions of various substances. Using rough estimations via a worst/best case approach, it was analysed that emissions from the capture unit are relevant in three impact categories. Overall, the additional material demand and sorbent-related emissions introduce significant trade-offs in between 5-8 impact categories, depending on the followed technological scenarios. Additional technological improvement may reduce the trade-off effect, leading to a reduction of trade-off categories to a number of four. The analysis concluded that it is likely that there are benefits to using the microplant-approach to methanol production, though additional research is critical to iron out the large uncertainties that are paired with future-oriented life cycle assessment.

To produce an alternative fuel like Methanol from scratch, on a miniature scale- the reactants CO2 and H2O are sourced locally. Zero Emission Fuels B.V. (ZEF) does this by collecting carbon dioxide from the air, via carbon capture techniques and compressing it to high pressure of 55bars. As a consequence of humidity inside the captured CO2, condensation is observed which is detrimental to the life of the compressor. To avoid this, a packed-bed drying system is designed as an auxiliary to the rolling piston compressor. This study aims to understand and model these two systems and subsequently integrate them to examine the effects of their dynamic operation. The purpose of this model is to provide a design tool, with the ability to predict the reaction of the system when sized differently, in various environments. At first, the physics and governing principles of the two subsystems are studied and a layered modelling approach was devised. The systems were modelled individually and then integrated using Simulink- a tool that allows this layering up of the models. To build a dynamic model of such a setup, a characteristic time scale analysis was performed to identify the relevant phenomena inside each subsystem. Significant internal factors to be modelled were variations in relative humidity and temperature caused by the drying system, the changes in thermo-physical properties of the gas due to a change in temperature and the pressure fluctuations caused by the compressor. The external factors to be modelled were the changes in ambient temperature over operation time, caused by a variation in solar irradiation. The main finding was that the compressor's characteristic time scale (300s) was considerably smaller than that of the drying system (4-8hours/day). This meant an almost instantaneous operation of the compressor, rendering it uninteresting in the dynamic model of the integrated system. A mechanistic dynamic model of the drying system, based on literature, was made with inherent controls to flip it between adsorption and desorption modes. It is responsive to the changes in the ambient and allows optimisation by changing the duty cycles of energy inputs. The model was then validated using experimental data from two working prototypes at ZEF. Some heat and mass transfer properties were then fitted to conform to these setups. A methodology to obtain these parameters while sizing a new design is discussed. The key performance indicators, which are cycle time and cycle capacity are given by the model and are crucial in deciding the energy consumption of the system. On the other hand, an empirical model is built to replicate the rolling-piston compressor. The compressor is treated like a grey box and is described by a polytropic coefficient. A novel approach to create a compressor map for a positive displacement compressor, that is not mass-produced, is chosen. This compressor map is then used to predict the mass flow and output temperature of the system. Since the compressor map is empirical, the model was also validated using data from the literature. Finally, the drying system and the compressor were integrated, in the model and experiments, by means of a capillary tube. A model was made for this as well to obtain the `interacting parameters'- which were the mass flow into the compressor, mass flow out of the capillary tube and the temperature and pressure of this re-loop flow. The effects of integration and the consequences to other systems upstream and downstream of this setup were scrutinised. To conclude, a validated model is built to size new iterations of the setup. Multiple cycle models of a packed bed drying system and compressor maps of positive displacement compressors- that are not found commonly in literature are explored in this study and recommendations to further develop them are given towards the end.

Climate change is real. Energy transition plays a crucial role in addressing climate change where solar fuels have emerged as a critical player in reducing the dependence on fossil fuels in industries that cannot transition into renewable electricity as an energy source such as aviation, industrial feedstocks etc. Green methanol is a promising solar fuel if it is sourced via carbon capture technologies. This thesis aims to build and use a model of an integrated methanol synthesis microplant as a tool to predict methanol production and the performance of the microplant under multiple system architectures at Zero Emission Fuels B.V (ZEF) who are developing a solar powered green methanol synthesis plant. The research commenced with data preprocessing which utilised historical weather data from the C3S database. Subsequently, individual subsystem models were developed such as solar photovoltaic (PV) modules, direct air capture (DAC), fluid machinery (FM), alkaline electrolysis cell (AEC), methanol synthesis (MS), distillation (DS), buffer tanks, and battery system. To ensure the microplant's functionality, a sophisticated control algorithm was devised, operating on two distinct levels: battery management and power distribution. Moreover, diverse microplant architectures were designed, to address unique operational scenarios and environmental conditions. The investigation further explored the influence of temporal granularity, and component sizing on microplant behavior. Ultimately, this thesis establishes the feasibility of the ZEF microplant, offering valuable insights for practical implementation across multiple locations. Consequently, it underscores the potential of the ZEF microplant as a promising solution in the transition towards sustainable energy alternatives.

When experimenting with the compression of a gas similar to the output of a CO2 Direct Air Captureunit using an off-the-shelf lubricated compressor, Zero Emission Fuels B.V.(ZEF) encountered severecondensation, damaging the compressor. This explorative study aims to identify the cause of thisproblem, create a concept solution, and test this concept based on model-supported experimentation.Based on a literature study all theoretical concepts are divided into three solution classes. Twoconcepts are then created and theoretically compared. A concept is selected that is based on theadsorption of water into a solid desiccant.As the concept solution is to operate in a closed system, regeneration of the desiccant needs to befaster than its utilization. For this, an experiment is made where a controlled quantity of inert gas ismoisturized, dried, and used to regenerate a second column. From this it can be concluded that thegas can be dried adequately, and that regeneration can be done thoroughly.A model is made to verify the experiment’s workings, based on models from literature. This modelis then validated using literature, and then fitted to experimental data. Combining experiment andliterature data, three key performance indicators are calculated: Cyclic capacity, energy usage, anddesorption rate. The design tools and models developed throughout this thesis are used to size thenext iteration of the concept according to the needs of ZEF.From this, it is concluded that the presented concept is indeed viable to prevent, rather than solve,the problem stated at the start of this thesis. Recommendations are done concerning further develop-ment of the prototype, experiments, model, and overall system

Zero Emission Fuels B.V. (ZEF) is developing a microplant, which ultimately provides a pathway to produce a hydrocarbon in a sustainable manner. This microplant consists of several subsystems. One of which is an alkaline water electrolyser, in which water is split into oxygen and hydrogen under specific operating conditions. As a mixture of the product gasses can be highly explosive, gas crossover in alkaline water electrolysis (AEC) systems is a point of concern in terms of safety. This explorative study aims to identify the main routes for crossover in AEC systems, as well as characterizing the ZEF AEC system. This characterization has been accomplished by studying the effect of process conditions and system geometry on gas crossover. Based on a literature study, gas crossover is found to be the result of diffusion as well as convection. Both of these phenomena occur at the interconnects between the sides of the system, which is over the diaphragms and over the pressure equalization tube (PET) in case of the ZEF AEC system. Gas measurements where conducted during over 194 hours of experiments. From this it was concluded that hydrogen crossover is the main point of concern in terms of safety. Operating pressure and temperature both very clearly affect hydrogen crossover. The effect of current density is also significant but obscured by the fact that temperature is an uncontrollable variable in the ZEF AEC system. From the steady-state data a window for safe operations has been framed. Upon start-up of the system a spike in oxygen-side hydrogen concentration is consistently measured, which is a result of crossover by diffusion during system off-time. This spike in concentration also poses a threat in terms of safety. Three different pressure equalization tubes have been tested to investigate the influence of interconnect geometry on gas crossover. In order to identify the main route for hydrogen crossover a CSTR model of the oxygen side gas phase was developed, in which temperature and pressure effects were taken into account. The model showed that hydrogen crossover by diffusion could be held accountable for ~8% of the total amount of crossed-over hydrogen, which is in line with reports in literature for a mixed electrolyte cycle AEC system. The model also showed that crossover by solely diffusion through the PET is negligible compared to through the diaphragm. From this, it was concluded that the ZEF AEC system behaves more like a system with mixed electrolyte cycles with respect to gas crossover levels. Recommendations are made in order to reduce hydrogen crossover, and enlarge the window for safe operation as a result.

The global energy transition from a fossil fuel base energy system to a renewable energy source base system is the key mission for a low-carbon future. The target of CO2 emission reduction by 2050, following the Paris Climate Agreement, is 90% compared to the CO2 level of 1990. Haber-Bosch process is the main industrial procedure for the production of ammonia today and about 80% of the global ammonia is consumed by the fertilizer industry. However, the century old Haber-Bosch process is normally energized by fossil fuel and it releases about 3% of the global carbon footprint. In light of this fact, replacing the conventional fossil fueled Haber-Bosch process for manufacturing ammonia with renewable source powered ammonia production is the main goal of this study. Instead of obtaining H2 from steam-reformed CH4, H2 is produced from electrolyzed H2O. This transition enables the conventional ammonia manufacturing process transforming into a green Haber-Bosch production of ammonia. Two Dutch companies, TNO and Zero Emission Fuels, are cooperating and developing a small scale of reactor system that can convert ammonia from air and water by using solar PV panels. In this work, a new design of ammonia reactor system is developed. Ammonia is typically formed at high pressure (150 - 250 bar) and high temperature (400 - 500oC) using a promoted iron base catalyst. High temperature ensures rapid reaction kinetics, and high pressure boosts the product yield. Here a reactor system, that is operated at lower pressure (≤100 bar) and uses condensation to remove ammonia, is kinetically simulated in ASPEN. The effect of different operation conditions - reaction temperature (300oC, 350oC and 400oC) , pressure (50, 75 and 100 bar) and feed gas (N2 : H2) ratio (1 : 3 and 1 : 5) - on the production rate in a small-scale ammonia reactor have been systematically computed. The mass flow rate of the single pass reactor is set to 50 g/h in this work. With a catalyst bed length of 15 cm and inner diameter of 3.6 cm, according to the simulation, reaction temperature of 400oC and operating pressure of 100 bar can lead to the highest conversion (40%) in a single pass reactor. The average heat transfer area of the reactor system is to a great extend less than 50 m2, therefore, the double pipe heat exchanger is a favorable heat exchange system for the proposed reactor system. In the reactor design validation section, the selected optimum operation conditions are tested in the same scale reactor laboratory setup. Experimental results show that the single pass conversion of nitrogen at 400oC and 100 bar in such a small-scale reactor can reach 15.4% which is in the range of the industrial one pass conversion level. For reaction operated at 50 bar, 6% of ammonia yield is obtained. It is clear that ammonia production in small-scale and in milder operation condition is possible and the results are promising. The techno-economic analysis has been performed based on above mentioned outcome. The reactor system is integrated with ZEF AEC, ZEF compressor system and a membrane nitrogen separation system. With current ammonia design production (350 g/day), the cost of ammonia per kilogram can be achieved in the range of €1.8 to €2 depending on the operation condition. This is about 5 times more than fossil ammonia prices, but it is very competitive with biomass ammonia. In accordance with the sensitivity analysis, increasing the capacity of feed gas production or reducing the cost in plant equipment can remarkably reduce the ammonia price to less than 1 €/kg NH3. Furthermore, recommendations in four categories are discussed in the last section of this work, which can lead to a further step towards a green ammonia plant in small-scale.

To anticipate for future demand of sustainable liquid fuels, Zero Emission Fuels B.V. develops a solar powered micro plant which produces methanol from water and carbon dioxide captured from outside air. An intermediate step in this process is the electrolysis of water to create hydrogen which reacts with carbon dioxide to methanol. This study encompasses an integration of the pressurised alkaline electrolysis system, in which problems observed in previous generations of the electrolyser have been solved and functionalities have been added. In addition to that, electrolyte samples are taken after different periods of operation to investigate electrolyte deterioration over time. A new Balance of Plant (BoP) has been designed, realised and tested. Eight new features to the system can be distinguished, two of which are included to add functionality: the degasser to decontaminate the carbon dioxide-rich feed water and the pressure booster to replenish the consumed water at system pressure. The other features are integrated to enlarge the operational envelope, the determination of which was central to the experiments conducted in this research. Experiments are conducted to find and characterise the four limitations to the operational envelope: the relative valve opening duty (RVOD), flow stagnation, temperature control and crossover. The RVOD experiments showed deviations from the modelled valve opening cycles, attributed to additional pressure drops, valve opening interference and smaller discharge volumes. Subsequently a corrected model is presented to improve valve cycle time predictions. Flow stagnation was investigated at various current densities, pressures and temperatures using camera images and a characteristic temperature response to establish flow stagnation. The results showed a minimum volume flow rate decrease in comparison to the previous system, expressed in parameter 𝑋 which decreased from 3.4 to 0.74 A K bar-1 cm-2. The minimum volume flow rate decrease is attributed to the larger number of cells and the increase of the height difference between the stack and buffer tanks. In the temperature control experiments, steady state temperatures were monitored at different current densities, with and without crossflow fan operation. This resulted in a temperature control map, in which the reachable temperatures for different current density are depicted. Furthermore, electrolyte mass flows are determined and pressure dependency of temperature control was investigated at low current densities, concluding that steady state temperatures are independent from pressures in the 10 bar to 50 bar regime.  Hydrogen crossover was tested by taking gas samples at different operating conditions and subsequent gas composition analysis in a gas chromatograph; oxygen crossover was determined by an oxygen sensor implemented downstream the hydrogen exhaust. All steady state crossovers values were found to be below the safety limits, concluding that crossover is not limiting in the acquired system on all possible operating points. Overnight diffusion crossover experiments showed that maintaining the system under pressure overnight, keeps crossover values below the safety limit. In addition to the operational envelope, complementary general characteristics such as power consumption and efficiency are presented and compared to industry and literature. On top of that, unexpected findings, design deficits and other relevant phenomena are described to complete the perspective on system performance and behaviour of the electrolysis system. Due to the electrolyte mist purged into the degasser and pressure booster, the electrolyte deterioration experiments are deemed inconclusive. Moreover, a demister is found to be an essential system feature to include in the next generation electrolyser, because both degasser and pressure booster were damaged by the electrolyte spill.

Flash calculations are used for the dynamic simulation of vapor-liquid phase equilibria (VLE) in many chemical processes. When used to predict the composition of mixtures in VLE, the repeated applicatino of these flash calculations, particularly in dynamic cases can cause small inaccuracies to cascade. One way to prevent this, is to have strong predictions and initial guesses for what a mixture in equilibrium will look like. For this, stability tests can be employed. Stability tests require the minimisation of the tangent plane distance, which is derived from the excess Gibbs Energy. The VLE problem and stability tests have been approached from a viewpoint based in mathematical optimisation, not one based in thermodynamics. As such, this work provides a slightly different description of flash calculations and stability tests, and can serve as both an introduction to the problems, as well as an approach to the problem in a different way than is traditionally done. In this report, the tangent plane distance function has been studied and applied to an example to gain intuition on the problem, and different optimisation methods were considered for minimising this function. A stochastic- and a deterministic method were applied to the stability problem to gain a better understanding of which type of method will work better for minimising the tangent plane distance. Both methods seem sufficient, but the scalability to higher dimensions is lacking, especially in the deterministic case.

Power-to-gas (PtG) technology represents a promising route in providing long-term energy security and involves pairing volatile sources of renewable energy (solar and wind energy) with alkaline water electrolysis (AWE) to create a wide range of products based on intermediate hydrogen gas for end-users across various industries such as in fuels, chemicals and power sectors. However, PtG currently lacks the technical adaptability to match the intermittency of these sources caused by daily and seasonal weather patterns, and suffers from a low turndown ratio (TDR) as a consequence. Zero Emission Fuels (ZEF) B.V. aim to adapt this process to create an autonomous, dynamically operated solar panel add-on known as a micro-plant that will produce methanol from CO2 and H2O in the atmosphere. In doing so, the company looks to extend the TDR, but requires the micro-plant and by extension, its AWE unit to operate in wider partial load ranges, in which lower current densities dominate. These cause a rise in gas crossover within the electrolyser, creating impure and potentially flammable H2-O2 mixtures in the outlet that hinder the functionality of the micro-plant. Specifically within the AWE unit, the risk of oxygen crossover has been qualitatively identified as a likely safety hazard. Therefore, the focus of this thesis was set on studying the feasible development of a prototype (gas scavenger) that can remove trace O2 within the techno-economic scope of ZEF’s micro-plant and electrolyser. To determine a viable method that meets ZEF’s constraints on cost, size, weight and efficiency, industry techniques were studied that either purify hydrogen gas streams or destructively remove flammable H2-O2 mixtures. Based on a subsequent numerical estimation on each method’s limiting factors, a local combustion process in the form of a micro-combustor was identified to be the most suitable method. To quantitatively estimate the safety risk crossover poses, two models were developed: a non-dimensional model to analyse how 50 bar pressure influences crossover during operation, and a two-dimensional, transient diffusion model to analyse the extent of trace O2 contamination overnight. Results indicate that to mitigate dangerous impurity levels, a gas scavenger needs to be implemented: (a) above a 0.1% difference in pressure between electrolyser half cells during operation, and (b) upon start-up to remove overnight gas accumulation that may not pose an immediate severe risk at 0.079 mol% contamination relative to amount of stored hydrogen, but has the potential to build-up on a monthly timescale. Finally, the feasibility of the micro-combustor was preliminarily characterised at 50 bar and 80 ⁰C through flame simulations. The variability in low amounts of trace oxygen content show that the mixture is normally non-flammable. Further studies on geometry design and control strategies of the micro-combustor must consider how to achieve optimal ignition conditions, determined to be at richer fuel mixtures between 휙 = 1.03−1.40, and how to contain the flame within a well-defined region. Initial suggestions include using a small volume to induce ignition and relying on wall effects to promote flame quenching.

Vapor-liquid phase equilibrium (flash) calculations largely contribute to the total computation time of many process simulation models. As a result, process simulations, especially dynamic cases, are limited in the amount of detail that can be included due to time restrictions. In addition, under certain conditions flash calculations can fail to provide acceptable results. In this work, artificial neural networks were investigated as a potentially faster and more robust alternative to conventional flash calculation methods. Classification neural networks were used to determine the phase stability of a given mixture of fluids, while regression networks were used to make predictions of thermodynamic property values. In addition to conventional flash types such as the constant pressure, constant temperature (PT), and constant pressure, constant entropy (PS) flash, neural networks are used to develop two concept flash types: a constant entropy, constant volume (SV), and a constant enthalpy, constant volume (HV) flash. All neural networks were trained on, and compared to, data generated using the PT-flash algorithm from the Thermodynamics for Engineering Applications (TEA) property calculator. Data was generated for mixtures of water and methanol over a wide range of pressures and temperatures. The artificial neural networks showed speed improvements over TEA of up to 35 times for phase classification and 15 times for property predictions. Overall phase classification accuracy scores of around 97% were achieved. Average property value prediction errors range between 0.5% and 7% when compared to the spread in magnitude of the test data, and R2 scores were in the general order of 0.95 and higher, although classification and property prediction in the two-phase region showed markedly higher errors than properties in the pure liquid or vapor regions. Moreover, thermodynamic consistency and the stability of a system consisting of multiple neural network flash types both still require considerable improvement. Finally, this work shows that artificial neural networks can be used to create unconventional flash types such a the SV- and HV-flash.

Zero Emission Fuels B.V. develops a standalone System that produces renewable methanol from air and sunlight. In this thesis the steady-state model of this System is replaced with a Simulation Tool that can predict its behaviour for every minute of a year. The goal is to verify how technical design parameters influence methanol production and to determine if the business case target of 6.7 mole methanol per day is achievable. This thesis will contribute to the understanding of the System, speeds-up the design process and makes it possible to see the impact of fluctuating weather conditions throughout the year at different locations on earth. The System as it was at January 1, 2018 is implemented in the Simulation Tool and its production determined for Tucson, Arizona in the year 2005. The result is an average daily production of 3.0 mole methanol with fluctuations from 1.0 mole during a cloudy winter day to 4.2 mole during a sunny summer day. The minute by minute production is found to be influenced by all System design parameters. They must thus be designed together to make sure the System performs optimally. The Alkaline Electrolysis uses the most energy of all subsystems. Four options to improve the System are identified. These are 1) improving the power the Solar Panel produces, 2) improving the efficiency of each subsystem, 3) improving how the System is controlled and 4) integrating heat. A selection of these improvements shows that it is possible to produce 4.8 mole methanol per day. The observed seasonal and daily fluctuating methanol production demonstrates the importance of the dynamic model developed in this thesis. Compared to the steady-state model it gives a more realistic view of methanol production and can be used to improve System design. However, to reach the business case target more technical improvements are needed. It should be realised that the design decisions will be based on technical, economical and political arguments.