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<p>  </p> <p>Concentrated solar power (CSP) is a technology that utilizes focused sunlight to heat a high-temperature medium (such as a molten salt). Heat from this medium can be transferred to a working fluid (such as supercritical CO2) that is then used to drive a turbine to generate electricity. Alternatively, the hot medium/fluid can be pumped into tanks for thermal energy storage (TES), for heat extraction later to generate dispatchable electricity and/or for electricity production at night or on cloudy days. By increasing the fluid temperature to <u>></u>750oC and utilizing TES, CSP can become more cost competitive with fossil-based electricity production. Current CSP systems utilize molten nitrate salts for heat transfer and TES that are known to thermally degrade at temperatures >600oC. To achieve temperatures <u>></u>750oC, molten chloride salts, such as ternary MgCl2-KCl-NaCl compositions, are being considered as heat transfer and thermal energy fluids for next generation CSP plants due to their higher temperature stability, low cost, and availability. </p> <p>In this work, it was demonstrated that MgCl2-containing molten salts are prone to oxidation in ambient air at 750oC, which can enhance corrosion of the containment materials and alter the thermophysical properties of the fluid. An alternative, low-cost, earth-abundant, MgCl2-free, oxidation-resistant molten salt, a eutectic CaCl2-NaCl composition, was developed, along with a corrosion mitigation strategy, to enable the slow growth of protective oxide layers on metals that are resistant to dissolution by such MgCl2-free molten chloride salts. </p> <p>This strategy was expanded to other low-cost, oxidation resistant compositions, such as eutectic BaCl2-CaCl2-KCl-NaCl with tailored chemical and thermophysical properties for CSP and TES. The melting temperature, heat capacity, oxidation resistance, and crystallization behavior were measured for eutectic a BaCl2-CaCl2-KCl-NaCl(17.5-47.8-3.3-31.4 mol%) (BCKN) salt and a MgCl2-KCl-NaCl (40-40-20 mol%) salt. BCKN salt was shown to have a similar melting temperature while having a higher heat capacity and far better oxidation resistance. </p> <p>The corrosion of the nickel-based superalloy Haynes 214 was studied in molten MgCl2-KCl-NaCl (40-40-20 mol%) salt at 750oC under inert atmosphere conditions using a custom-built rotating-disc corrosion testing apparatus that maintained laminar fluid flow on the sample. Non-protective external Cr-, Al-, and Mg- oxide layers were formed on Haynes 214 that were prone to spallation. Internal oxidation of Al was also observed along with Cr depletion zones within Haynes 214.  Corrosion kinetics were evaluated to quantify the role of fluid flow for application of this alloy for use in containment and transportation of this molten chloride salt. </p>

Nowadays the main challenge for the energy system is the capability of storing the energy forlater use. To deal with this problem, molten salt storage technology is being used in some solarfacilities. By its implementation, the energy can be stored in the form of heat. However, thefeasibility of this technology is in a testing stage. Its implementation could be done in differentenergy fields. In this thesis, a novel implementation is suggested nearby a CHP, with the aim ofutilizing the excess electricity provided by the grid in high energy production days. Differentimplementation methods and a real scenario are presented. A study analysis of the tank’s sizeand the amount of molten salt needed as well as an economic analysis are provided. Numericalapproximations are given and results shown according to the theoretical analysis developed.

The traditional aluminum production process (Hall-Héroult process) involves electrolyzing the alumina dissolved in the molten cryolite salt. This process is energy intensive and emits massive amounts of CO2 and other greenhouse gases. The market demand of aluminum and the environmental impact of the current aluminum production process justify research and development of alternative electrolytic processes for aluminum production that can both reduce the cost and eliminate adverse environment impacts. Solid oxide membrane (SOM) based electrolysis process is an innovative technology that has been demonstrated to successfully produce many energy-intensive metals directly from their oxides in an efficient, economical and environmentally sound way. During the SOM electrolysis process, an oxygen-ion-conducting SOM tube made of ytteria-stabilized zirconia (YSZ) separates the pre-selected molten flux with dissolved metal oxide from the inert anode assembly inside the YSZ tube. When the applied DC potential between the cathode and the anode exceeds the dissociation potential of desired metal oxide, the metal is reduced at the cathode while oxygen ions migrate through the YSZ membrane and are oxidized at the anode. Employing the inert anode allows the oxygen to be collected at the anode as a value added byproduct. In this work, a zero-direct-carbon-emission aluminum production process utilizing SOM electrolysis is presented. The molten flux used in the electrolysis process is optimized through careful measurements of its physio-chemical properties. The liquidus temperature, volatilization rate, alumina solubility, aluminum solubility, YSZ membrane degradation rate and electrical conductivity of various flux compositions were measured, and the flux chosen for SOM electrolysis was a eutectic MgF2-CaF2 system containing optimized amounts of YF3, CaO and Al2O3. Laboratory scale SOM electrolysis employing the inert anode were performed at 1100 ~ 1200oC to demonstrate the feasibility of producing and collecting aluminum while producing pure oxygen as a byproduct. The aluminum product was characterized by scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS). An equivalent circuit model for the electrolysis process was developed in order to identify the polarization losses in the SOM electrolysis cell. / 2016-12-21T00:00:00Z

Future nuclear fission reactors (GEN IV) are designed to include fast breeder reactor technologies, which can accept transuranics (elements heavier than uranium) as fuel. This has the potential of being more fuel efficient but requires the closing of the nuclear fuel cycle: full recycling of existing and newly generated nuclear waste to extract uranium and transuranic elements which can be reused as fuel. In the UK a system being investigated is electrochemical pyroprocessing which uses molten LiCl-KCl eutectic (LKE), which aims to recover uranium by electrodeposition on an inert (steel) electrode and the transuranics by electrodeposition as alloys with an active metal electrode (bismuth, cadmium or aluminium). Of the three active metal candidates, aluminium has the best separation efficiency of actinides and lanthanides, which is important as lanthanides are neutron poisons and so are not to be extracted. The development of pyroprocessing requires fundamental understandings of electrochemical alloy formation, as well as on-line monitoring tools to ensure the reprocessing occurs safely and efficiently. To that end, this thesis investigates cerium-aluminium alloying (a non-radioactive model system for plutonium-aluminium) on macro- and microelectrodes to understand the limiting factors during the alloying reaction at each electrode scale and also the circumstances under which the Ce3+ concentration can be reliably determined for on-line monitoring. On a bulk aluminium macroelectrode one cerium-aluminium alloying reaction was observed. This reaction was kinetically limited by the phase change from cerium insertion into the aluminium, and resulted in lattice expansion and progressive roughening of the electrode surface. These factors made it difficult to reliably calculate the Ce3+ concentration. Li+ from the solution was also able to reduce and form alloys with aluminium, approximately 0.3 V more negative than the first cerium-aluminium alloying peak. Since lithium atoms are smaller than cerium, and there is an abundance of Li+ in the salt, lithium-aluminium alloy was found to form preferentially to cerium-aluminium alloy at these more negative potentials. By co-depositing Al3+ and Ce3+ together on a tungsten electrode which is inert under these conditions (it does not alloy), the kinetic barrier to alloy formation by cerium insertion was decreased, which is beneficial to studying the thermodynamics of alloying. Studies of pure aluminium plating and pure cerium plating showed each individual reaction was diffusion limited, with an increased contribution of convection to the mass transport at slow scan rates. Co-deposition on macroelectrodes with a low ratio of [CeCl3]:[AlCl3] showed only one cerium-aluminium alloying peak. The co-deposition currents, and ratio of oxidation peaks charges, showed that co-deposition was occurring with both species under diffusion control, resulting in an amorphous alloy with a Ce:Al ratio that smoothly varied with the [CeCl3]:[AlCl3] ratio. This was in contrast to the alloying behaviour of cerium with liquid bismuth, in which co-deposition occurred at specific ratios determined by the crystal phases that could be formed at the applied potentials, with higher co-deposition ratios being achieved at more negative potentials. Co-deposition on macroelectrodes with a high ratio of [CeCl 3]:[AlCl3] could result in up to five cerium-aluminium alloy peaks, corresponding to all five CexAly crystalline phases predicted by the phase diagram. This phase change from amorphous to crystalline was promoted by the high Ce:Al ratio in the amorphous alloy resulting from the high [CeCl3]:[AlCl3] ratio and by plating pure cerium on the surface, which could then insert into the alloy. Charge analysis of these peaks confirmed the expected stoichiometries of the crystal phase from these in-situ measurements which is important for rapid analysis, whereas all previous literature has relied on ex-situ techniques which cooled the alloy, possibly changing its composition and structure. In all circumstances of alloy formation on macroelectrodes, the rate of reduction of Ce3+ was time dependent and sensitive to convection. This significantly complicated analysis of the electrochemical signal, making it very difficult to reliably calculate the concentration of Ce3+, which is required for on-line monitoring. Co-deposition on in-house microfabricated tungsten microelectrodes resulted in steady state currents for both pure aluminium deposition and cerium-aluminium co-deposition (up to the beginning of lithium-aluminium alloying). Thus, unlike on macroelectrodes, the deposition rate occurred at the flux ratio of each species from solution and only one oxidation peak was observed corresponding to the amorphous cerium-aluminium phase, even at high [CeCl3]:[AlCl3] ratios. The steady state alloying current meant that calculating the Ce3+ concentration was relatively simple from co-deposition on microelectrodes. Co-deposition was highly beneficial for studying alloying, however to avoid the addition of Al3+ to the molten salt, in-house microfabricated thin film aluminium microelectrodes were also used to study alloying. Alloying on microfabricated thin film aluminium microelectrodes was hampered by the formation of a native aluminium oxide layer, which prevented cerium insertion into the aluminium. The oxide layer could be disrupted by reduction of lithium, which showed steady state currents (albeit with significant capacitance) could be achieved for alloying by cerium insertion. However, the full surface area of the microelectrode could not be attained and all microelectrodes lost their aluminium layer after multiple lithiation/de-lithiation cycles. These devices need further development to overcome the oxide layer, or prevent its formation, in order to study alloying in greater detail with aluminium microelectrodes to fully realise their advantages for sensing and monitoring in pyroprocessing.

Though economically favorable when compared to other renewable energy storage technologies, thermal energy storage systems for concentrating solar thermal power (CSP) plants require additional cost reduction measures to help transition CSP plants to the point of grid-parity. Thermocline packed bed storage is regarded as one potential low cost solution due to the single tank requirement and low cost storage media. Thus sensible heat storage (SHS) and latent heat storage (LHS) packed bed systems, which are two thermocline varieties, are frequently investigated. LHS systems can be further classified as single phase change material (PCM) systems or cascaded systems wherein multiple PCMs are employed. This study compared the performance of SHS, single PCM, and cascaded PCM direct storage systems under the conditions that may be encountered in utility-scale molten salt CSP plants operating between 565°C and 288°C. A small-scale prototype SHS packed bed system was constructed and operated for use in validating a numerical model. The drawbacks of the latent heat storage process were discussed, and cascaded systems were investigated for their potential in mitigating the issues associated with adopting a single PCM. Several cascaded PCM configurations were evaluated. The study finds that the volume fraction of each PCM and the arrangement of latent heat in a 2-PCM and a 3-PCM system influences the output of the system, both in terms of quality and quantity of energy. In addition to studying systems of hypothetical PCMs, real salt PCM systems were examined and their selection process was discussed. A preliminary economic assessment was conducted to compare the cost of SHS, single-PCM LHS, cascaded LHS, and state-of-the-art 2-tank systems. To the author's knowledge, this is the first study that compares the cost of all three thermocline packed bed systems with the 2-tank design. The SHS system is significantly lower in cost than the remaining systems, however the LHS system does show some economic benefit over the 2-tank design. If LHS systems are to be viable in the future, low cost storage media and encapsulation techniques are necessary.

A high temperature molten salt test loop that utilizes FLiNaK (LiF-NaF-KF) at 700ºC has been proposed by Oak Ridge National Laboratory (ORNL) to study molten salt flow characteristics through a pebble bed for applications in high temperature thermal systems, in particular the Pebble Bed – Advanced High Temperature Reactor (PB-AHTR). The University of Tennessee Nuclear Engineering Department has been tasked with developing and testing pressure instrumentation for direct measurements inside the high temperature environment. A nickel diaphragm based direct contact pressure sensor is developed for use in the salt. Capacitive and interferometric methods are used to infer the displacement of the diaphragm. Two sets of performance data were collected at high temperatures. The fiber optic, Fabry-Perot interferometric sensor was tested in a molten salt bath. The capacitive pressure sensor was tested at high temperatures in a furnace under argon cover gas.

The objective of this study is to synthesize nanomaterials by mixing molten salt (alkali nitrate salt eutectics) with inorganic nanoparticles. The thermo-physical properties of the synthesized nanomaterials were characterized experimentally. Experimental results allude to the existence of a distinct compressed phase even for the solid phase (i.e., in the nanocomposite samples). For example, the specific heat capacity of the nanocomposites was observed to be enhanced after melting and re-solidification - immediately after their synthesis; than those of the nanocomposites that were not subjected to melting and re-solidification. This shows that melting and re-solidification induced molecular reordering (i.e., formation of a compressed phase on the nanoparticle surface) even in the solid phase - leading to enhancement in the specific heat capacity. Numerical models (using analytical and computational approaches) were developed to simulate the fundamental transport mechanisms and the energy storage mechanisms responsible for the observed enhancements in the thermo-physical properties. In this study, a simple analytical model was proposed for predicting the specific heat capacity of nanoparticle suspensions in a solvent. The model explores the effect of the compressed phase – that is induced from the solvent molecules - at the interface with individual nanoparticles in the mixture. The results from the numerical simulations indicate that depending on the properties and morphology of the compressed phase – it can cause significant enhancement in the specific heat capacity of nanofluids and nanocomposites. The interfacial thermal resistance (also known as Kapitza resistance, or “Rk”) between a nanoparticle and the surrounding solvent molecules (for these molten salt based nanomaterials) is estimated using Molecular Dynamics (MD) simulations. This exercise is relevant for the design optimization of nanomaterials (nanoparticle size, shape, material, concentration, etc.). The design trade-off is between maximizing the thermal conductivity of the nanomaterial (which typically occurs for nanoparticle size varying between ~ 20-30nm) and maximizing the specific heat capacity (which typically occurs for nanoparticle size less than 5nm), while simultaneously minimizing the viscosity of the nanofluid. The specific heat capacity of nitrate salt-based nanomaterials was measured both for the nanocomposites (solid phase) and nanofluids (liquid phase). The neat salt sample was composed of a mixture of KNO3: NaNO3 (60:40 molar ratio). The enhancement of specific heat capacity of the nanomaterials obtained from the salt samples was found to be very sensitive to minor variations in the synthesis protocol. The measurements for the variation of the specific heat capacity with the mass concentration of nanoparticles were compared to the predictions from the analytical model. Materials characterization was performed using electron microscopy techniques (SEM and TEM). The rheological behavior of nanofluids can be non-Newtonian (e.g., shear thinning) even at very low mass concentrations of nanoparticles, while (in contrast) the pure undoped (neat) molten salt may be a Newtonian fluid. Such viscosity enhancements and change in rheological properties of nanofluids can be detrimental to the operational efficiencies for thermal management as well as energy storage applications (which can effectively lead to higher costs for energy conversion). Hence, the rheological behavior of the nanofluid samples was measured experimentally and compared to that of the neat solvent (pure molten salt eutectic). The viscosity measurements were performed for the nitrate based molten salt samples as a function of temperature, shear rate and the mass concentration of the nanoparticles. The experimental measurements for the rheological behavior were compared with analytical models proposed in the literature. The results from the analytical and computational investigations as well as the experimental measurements performed in this proposed study – were used to formulate the design rules for maximizing the enhancement in the thermo-physical properties (particularly the specific heat capacity) of various molten salt based inorganic nanomaterials. The results from these studies are summarized and the future directions are identified as a conclusion from this study.

A molten carbonate fuel cell (MCFC) is an electro-chemical energy conversion technology that runs on natural gas and employs a molten salt electrolyte. In order to keep the electrolyte in this state, the cell must be kept at a temperature above 500 C, eliminating the need for precious metals as the catalyst. There has been only a limited amount of research on modelling the transport processes inside this device, mainly due to its limited ability for mobile applications. In this thesis, three one-dimensional models of a MCFC are presented based on different types of diffusion and convection. Comparisons between models are performed so as to assess their validity. Regarding ion transport, it is shown that there exists a limiting case for ion migration across the cathode that depends on the conductivity for the liquid potential. Finally, an optimization of the diffusivity across the cathode is carried out in an attempt to increase the cell performance and its longevity. / UOIT

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.