In Hinblick auf den stetig steigenden Bedarf der chemischen Industrie an Grundstoffchemikalien und der teilweise unsicheren Versorgung mit Erdöl und Erdgas ist es notwendig alternative Rohstoffe und Verwertungspfade für die Bereitstellung von Basischemikalien zu finden. Ziel der vorliegenden Arbeit war die Untersuchung der Hydrogenolyse von Lignin in niedermolekulare Produkte unter Verwendung geeigneter Salzschmelzen. Es konnte gezeigt werden, dass Lignin in Zinkchlorid/Kaliumchloridschmelzen in niedermolekulare Produkte abgebaut werden kann. Hierbei erwiesen sich der Einsatz eines entsprechenden Eutektikums und einer Alternativschmelze mit niedrigem Schmelzpunkt als hilfreich. Durch den Einsatz verschiedener Apparaturen wurden Untersuchungen in statischer und dynamischer Atmosphäre durchgeführt. Es ergaben sich während der Untersuchung Abhängigkeiten der Hydrogenolyse von verschiedenen Reaktionsparametern. Optima der Umsetzung hinsichtlich der Reaktionsparameter Temperatur, Zeit und Ligninanteil in der Schmelze wurden herausgearbeitet. Die Ausbeute an gewünschten Flüssigprodukten wurde, im Untersuchungsbereich, an diesen Punkten maximiert. Gleichzeitig war die Rückstands- und Gasbildung eingeschränkt. Es konnten Erkenntnisse eines komplexen Systems der Abhängigkeiten der Ausbeuten an Reaktionsprodukten von den Parametern der Untersuchung gewonnen werden. Die Hydrogenolyse von Lignin führte zur Aromatisierung fester Residuen sowie zur Abreicherung von Sauerstofffunktionalitäten. Komplexe Reaktionsmechanismen bewirkten den Abbau von Methoxyl-, Carboxyl- und Hydroxylgruppen der Ligninstruktur. Carbeniumionmechanismen konnten als wichtige Reaktionen zur Spaltung von Ether Arylbindungen identifiziert werden. Die Freisetzung von Monomeren und die Polymerisation anderer Intermediäre sind durch Sekundärreaktionen denkbar. Die gebildeten Flüssigprodukte bestanden hauptsächlich aus Monoaromaten (v.a. Guajakole und Kresole) und wenigen Polyaromaten. Die Selektivität der Bildung einzelner Verbindungen war gering, d.h. die Flüssigprodukte sind eine heterogene Mischung mit geringen Konzentrationen der Einzelsubstanzen. Die Unterschiede in der Struktur der Ausgangslignine bildeten sich auch in der Zusammensetzung der Flüssigprodukte ab. / In view of the steadily increasing demand of the chemical industry to base chemicals and the partial uncertain supply of crude oil and gas, it is necessary to find alternative raw materials and conversion routes for the provision of basic chemicals. The aim of the present work was to investigate the hydrogenolysis of lignin in low molecular weight products using appropriate molten salt media. It could be demonstrated that lignin can be convert in low molecular weight products using zinc chloride/potassium chloride molten salt media. The use of an appropriate eutectic melt and of an alternative melt with low melting point proved helpful. By the use of different apparatus investigations in static and dynamic atmosphere could be carried out. During the investigation dependencies of the hydrogenolysis of various reaction parameters are submitted. Optima of the hydrogenolysis regarding to reaction temperature, time and lignin content at the melt could be identified. The yields were maximized at these points in the range of investigation. Concurrently formation of gases and residues were suppressed. Some evidence of a complex system of the dependencies of the yields of reaction products are obtained from the parameters of the investigation. Hydrogenolysis of lignin leads to aromatic solid residues and to a loss of oxygen containing structures. Structures containing methoxyl-, carboxyl- and hydroxyl groups are degraded by various complex reaction mechanisms. Mechanisms of the formation of carbonium ions were identified as important reactions of the cleavage of ether aryl bonds. Secondary reactions caused the liberation of monomers and polymerisation of some intermediaries. The resulting liquid products consist mainly of monoaromatics (guaiacols and cresols) and less of polyaromatics. The selectivity of the formation of single compounds was low, i.e. the liquid products constitute a heterogenous mixture with low concentrations of the single compounds. The structural differencies of the feedstock lignins also showed at the composition of the liquid products.

The Department of Energy funded a project to determine if the specific heat of thermal energy storage materials could be improved by adding nanoparticles. The standard thermal energy storage materials are molten salts. The chosen molten salt was a sodium nitrate and potassium nitrate eutectic, commercially called Hitec Solar Salt. Two nanoparticle types were chosen, alumina and silica. The nanoparticle composite materials were fabricated by mixing the components in an aqueous solution, mixing that solution for a set amount of time using a sonic mixer, then removing the water from the aqueous solution, leaving the composite molten salt behind as a fine white powder. The thermal properties of the composite and plain material were measured using two techniques: American Society for Testing and Materials (ASTM) 1269E and Modulating Differential Scanning Calorimetry (MDSC). These two techniques measured the specific heat and the heat of fusion of the plain and composite materials. The results of all the ASTM and MDSC measurements suggest that the addition of the nanoparticles using the given manufacturing technique increased the specific heat of the molten salt by approximately 20 percent, with both measurement techniques showing approximately the same level of increase. The silica and the alumina improved the specific heat by nearly the same amount over the base material. The heat of fusion did not seem to be significantly altered compared to the observed heat of fusion value of the unmodified material. It was also observed that the nitrate and silica composite material's specific heat decreased if the material was raised to a temperature above 400C. The specific heat was observed to decrease over time, even when the temperature was well below 400C. It is unknown why this occurred. The nitrate plus alumina composite and the plain nitrate were stable to a temperature of 450C for the test duration.

Main reason for the current losses in electrolytic magnesium production is the reaction between electrode products. Present study was devoted to effective separation of chlorine gas from the electrolysis environment by a new cell design and thus reducing the extent of back reaction between magnesium and chlorine to decrease energy consumption values. The new cell design was tested by changing temperature, cathode surface, current density, anode cathode distance and electrolyte composition. Both the voltages and the current efficiencies were considered to be influenced by the amount and hydrodynamics of chlorine bubbles in inter-electrode region. Cell voltages were also found to be affected from the nucleation of magnesium droplets and changes in electrolyte composition that took place during the electrolysis. A hydrodynamic model was used to calculate net cell voltage by including the resistance of chlorine bubbles on anode surface to theoretical decomposition voltage during electrolysis. Good correlations were obtained between experimental and calculated voltages. The same model was used to calculate current efficiencies by considering chlorine diffusion from bubble surfaces. A general agreement was obtained between calculated and experimental current efficiencies. Desired magnesium deposition morphology and detachment characteristics from cathode were obtained when MgCl2-NaCl-KCl-CaCl2 electrolytes were employed. Current efficiencies higher than 90% could be achieved using the above electrolyte. The cell consumes around 8 kWh&amp / #903 / kg-1 Mg at 0.43 A&amp / #903 / cm-2 as a result of high chlorine removal efficiency and capability of working at low inter-electrode distances. Furthermore, the cell was capable of producing magnesium with less than the lowest energy consumption industrially obtained, at about double the commonly practiced industrial current density levels.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第23999号 / エネ博第435号 / 新制||エネ||82(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 野平 俊之, 教授 萩原 理加, 教授 宇田 哲也 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第15375号 / 工博第3254号 / 新制||工||1490(附属図書館) / 27853 / 京都大学大学院工学研究科原子核工学専攻 / (主査)教授 森山 裕丈, 教授 山名 元, 准教授 佐々木 隆之 / 学位規則第4条第1項該当

The electrorefiner (ER) is the heart of pyroprocessing technology operating at a high-temperature (723 K – 773 K) to separate uranium from Experimental Breeder Reactor-II (EBR-II) used metallic fuel. One of the most common electroanalytical methods for determining the thermodynamic and electrochemical behavior of elemental species in the eutectic molten salt LiCl-KCl inside ER is cyclic voltammetry (CV). Information from CV can possibly be used to estimate diffusion coefficients, apparent standard potentials, transfer coefficients, and numbers of electron transferred. Therefore, predicting the trace of each species from the CV method in an absence of experimental data is important for safeguarding this technology. This work focused on the development an interactive computational design for the CV method by analyzing available uranium chloride data sets (1 to 10 wt%) in a LiCl-KCl molten salt at 773 K under different scan rates to help elucidating, improving, and providing robustness in detection analysis. A principle method and a computational code have been developed by using electrochemical fundamentals and coupling various variables such as: the diffusion coefficients, formal potentials, and process time duration. Although this developed computational model works moderately well with reported uranium data sets, it experiences difficulty in tracing zirconium data sets due to their complex CV structures. Therefore, an artificial neural intelligent (ANI) data analysis has been proposed to resolve this issue and to provide comparative study to the precursor computational modeling development. For this purpose, ANI has been applied on 0.5 to 5 wt% of zirconium chloride in LiCl-KCl eutectic molten salt at 773 K under different scan rates to mimic the system and provide current and potential simulated data sets for the unseen data. In addition, a Graphical User Interface (GUI) through the commercial software Matlab was created to provide a controllable environment for different users. The computational code shows a limitation in high concentration CV prediction, capturing the adsorption peaks, and provides a dissimilarity. However, the model is able to capture the important anodic and cathodic peaks of uranium chloride CV which is the main focus of this study. Furthermore, the developed code is able to calculate the concentration of each species as a function of time. Due to the complexity of the CV of zirconium chloride, the computational model is used to predict the probability reactions occurring at each peak. The resulting study reveals that the reaction at the highest anodic peak is related to the combination of 70% Zr/Zr+4 and 30% Zr/Zr+2 for the 1.07 wt% and 2.49 wt% zirconium chloride and 30% Zr/Zr+4 and 70% Zr/Zr+2 combination for 4.98 wt% ZrCl4. The proposed alternative ANI method has demonstrated its capability in predicting the trend of species in a new situation with a high accuracy on predictions without any dissimilarity. Two final structures from zirconium chloride study which high accuracy (that is, a low error) are related to [9, 15, 10]-18 and [10, 11, 25]-19. These two final structures have been applied on uranium chloride salt experimental data sets to further validate the ANI’s ability and concept. Three different fixed data combinations were considered. The result indicates that by increasing the number of training data sets it does not necessarily help improving the prediction process. ANI implementation outcome on uranium chloride data set illustrates a good prediction with a specific fixed data combination and [9, 15, 10]-18 structure. Thus, it can be concluded that ANI is a promising method for safeguarding pyroprocessing technology due to its robustness in predicting the CV plots with high accuracy.

In recent years power generation from renewable energy has grown substantially both in South Africa and around the world. This growth is set to continue as there is more pressure to reduce the burning of fossil fuels. However, renewable energy power generation suffers from unpredictability, which causes problems when it comes to managing power grids. Concentrated Solar Power (CSP) plants offer a practical solution to store power in the form of thermal energy storage (TES). Thus, the plant can run when there is no solar energy available, leading to a more stable power supply. Unfortunately, CSP plants cost more than other renewables such as photovoltaic and wind power. Thus, there is a need for research into how to bring down the cost of CSP plants. One of the most proven types of CSP is the parabolic trough plant. The most recent innovation is to try and use molten salt as the heat transfer fluid which would reduce the cost of the plant. However, this new technology has not been implemented on a full scale CSP plant and little testing has been done to prove the technology. The HPS2 is a test facility aimed at testing the use of molten salt as a heat transfer fluid (HTF). This test facility, located in Evora Portugal, is being developed by an international consortium led by the German DLR institute of Solar Research. It is one of the first test facilities of its kind where experiments will be conducted to demonstrate the validity of using molten salt as a HTF and a storage medium in a parabolic trough CSP plant. The HPS2 test facility is not yet operational and there is a need for a dynamic thermofluid process model to better understand and predict both its steady state and transient operational behaviour. This dissertation reports on the development of such a dynamic thermofluid process model and the results obtained from it. The process model developed primarily focuses on the steam cycle with the TES incorporated into the model. The physical geometry of each of the components are employed to construct discretized elements for which the conservation of mass, energy, and momentum are applied in a one-dimensional network approach. The economizer and evaporator combined has a helical coil geometry and uses molten salt as a heat transfer fluid, which is unique. Thus, correlations had to be adjusted for the flow characteristics found in the economizer/evaporator. Results from the steady state simulations of the steam cycle show that the molten salt mass flowrate through the steam generation system will have to be reduced from the initially expected value to meet operational requirements. Results of the dynamic simulations show that the test facility will be able to produce a constant power supply despite transient solar conditions and highlights key dynamic responses for operators to be aware of.

Master’s thesis focuses on the history and current progress in research of molten salt reactors around the world, with an emphasis placed on the properties of molten salts and the problems associated with their use. In relation to the practical part, one chapter is devoted to the creation of input file in the MCNP software. The practical part deals with neutron activation analysis of graphite prism experiment, which is filled with powder NaCl salt. This experiment is focused on the effect of salt on neutron flux with different energy levels. The whole problem was also simulated in the MCNP environment along with the experiment. At the end of the thesis, the individual methods are compared and evaluated.

>Magister Scientiae - MSc / Phase change material (PCM) through latent heat of molten salt, is a convincing way for thermal energy storage in CSP applications due to its high volume density. Molten salt, with (60% NaNO3 and 40% KNO3) has been used extensively for energy storage however; the low thermal conductivity and specific heat have limited its large implementation in solar applications. For that, molten salt with the additive of silver nanowires (AgNWs) was synthesized and characterized. This research project aims to investigate the thermophysical properties enhancement of nanosalt (Mixture of molten salt and silver nanowires). The results obtained showed that by simply adjusting the temperature, Silver nanowires with high aspect ratio have been synthesized through the enhanced PVP polyol process method. SEM results revealed a network of silver nanowires and TEM results confirmed the presence of silver nanowires with an average diameter of 129 nm and 16 μm in length.

The Solid oxide membrane (SOM) electrolysis is an innovative green technology that produces technologically important metals directly from their respective oxides. A yttria-stabilized zirconia (YSZ) tube, closed at one end is employed to separate the molten salt containing dissolved metal oxides from the anode inside the YSZ tube. When the applied electric potential between the cathode in the molten salt and the anode exceeds the dissociation potential of the desired metal oxides, oxygen ions in the molten salt migrate through the YSZ membrane and are oxidized at the anode while the dissolved metal cations in the flux are reduced to the desired metal at the cathode. Compared with existing metal production processes, the SOM process has many advantages such as one unit operation, less energy consumption, lower capital costs and zero carbon emission. Successful implementation of the SOM electrolysis process would provide a way to mitigate the negative environmental impact of the metal industry. Successful demonstration of producing ytterbium (Yb) and silicon (Si) directly from their respective oxides utilizing the SOM electrolysis process is presented in this dissertation. During the SOM electrolysis process, Yb2O3 was reduced to Yb metal on an inert cathode. The melting point of the supporting electrolyte (LiF-YbF3-Yb2O3) was determined by differential thermal analysis (DTA). Static stability testing confirmed that the YSZ tube was stable with the flux at operating temperature. Yb metal deposit on the cathode was confirmed by scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS). During the SOM electrolysis process for silicon production, a fluoride based flux based on BaF2, MgF2, and YF3 was engineered to serve as the liquid electrolyte for dissolving silicon dioxide. YSZ tube was used to separate the molten salt from an anode current collector in the liquid silver. Liquid tin was chosen as cathode to dissolve the reduced silicon during SOM electrolysis. After electrolysis, upon cooling, silicon crystals precipitated out from the Si-Sn liquid alloy. The presence of high-purity silicon crystals in the liquid tin cathode was confirmed by SEM/EDS. The fluoride based flux was also optimized to improve YSZ membrane stability for long-term use.