An experimental apparatus was designed and built to study the thermal autoxidative carbon deposition, or coking, in the fuel injection nozzles of small gas turbine engines. The apparatus is a simplified representation of an aircraft fuel system, consisting of a preheating section and a test section, which is a passage that simulates the geometry, temperatures, pressures and flow rates seen by the fuel injection nozzles. Preliminary experiments were performed to verify the functionality of the apparatus. Pressure drop across the test section was measured throughout the experiments to monitor deposit buildup, and an effective reduction in test section diameter due to deposit blockage was calculated. The preliminary experiments showed that the pressure drop increased more significantly for higher test section temperatures, and that pressure drop measurement is an effective method of monitoring and quantifying deposit buildup.

An experimental apparatus was designed and built to study the thermal autoxidative carbon deposition, or coking, in the fuel injection nozzles of small gas turbine engines. The apparatus is a simplified representation of an aircraft fuel system, consisting of a preheating section and a test section, which is a passage that simulates the geometry, temperatures, pressures and flow rates seen by the fuel injection nozzles. Preliminary experiments were performed to verify the functionality of the apparatus. Pressure drop across the test section was measured throughout the experiments to monitor deposit buildup, and an effective reduction in test section diameter due to deposit blockage was calculated. The preliminary experiments showed that the pressure drop increased more significantly for higher test section temperatures, and that pressure drop measurement is an effective method of monitoring and quantifying deposit buildup.

Lors du procédé de cokéfaction, en raison de la faible largeur de la chambre de carbonisation des fours modernes, l’expansion horizontale de la pâte à coke génère une poussée sur les parois de chauffage. L’objectif de cette thèse, qui s’inscrit dans le cadre du projet européen « Swelling Pressure in a Coke Oven, Transmission on Oven walls », est de mieux comprendre le phénomène de poussée des charbons lors de la cokéfaction et de développer un modèle permettant d’anticiper ce phénomène. Pour cela, un modèle phénoménologique prenant en compte les phénomènes physico-chimiques en présence a été développé. Une mise en équation originale est proposée pour la cinétique de condensation des goudrons et le gonflement des grains de charbon lors de la pyrolyse. Le modèle proposé est le premier reproduisant simultanément la poussée sur les piédroits et la pression des gaz produits lors de la cokéfaction. Les résultats de simulation du cas particulier de la cokéfaction du charbon Blue Creek dans le four pilote du Centre de Pyrolyse de Marienau et les mesures de pression, de température et de poussée réalisées lors des essais présentent des écarts mais demeurent en bon accord. Ces écarts sont essentiellement dus à la méconnaissance des propriétés du charbon et de son comportement mécanique. L’hypothèse d’un comportement élastique linéaire entraîne une surestimation de la poussée. L’étude de sensibilité amène, entre autres, à la conclusion que la poussée ne dépend pas directement de la pression des gaz et que le gonflement des grains de charbon joue un rôle déterminant. / During the coking process, due to the small width of the carbonization chamber of modern ovens, horizontal expansion of coal generates a pressure on the oven walls. The objective of this thesis, which is part of European project « Swelling Pressure in a Coke Oven, Transmission on Oven walls », is to better understand the wall pressure phenomenon during coking process and to develop a model which can permit to anticipate this phenomenon. For this, a phenomenological model which takes into account the physical chemistry phenomena in presence is developed. An original implementation is proposed for the kinetic of tars condensation and the coal swelling during pyrolysis. The proposed model is the first which reproducing simultaneously the wall pressure and the gas pressure during coking process. The simulation results of coking process of the specific case of Blue Creek coal in the pilot oven of Centre de Pyrolyse de Marienau and the measurements of gas pressure, of temperature and of wall pressure performed during the tests have discrepancies but remain in good agreement. The discrepancies are mainly due to the ignorance of coal properties and its mechanical behavior. The assumption of linear elastic behavior leads to wall pressure overestimation. The sensitivity study permits to conclude that the wall pressure is not directly dependant to the gas pressure and that coal swelling play a causal role.

<p> Demand ever increases for clean-burning, high-efficiency, and power-dense jet engines. This demand raises the thermal requirements and stresses on fuel systems for every new generation of gas turbine engine. Fuel is used to cool subsystems such as engine oil, pumps, electronics, valves, etc. resulting in elevated fuel temperatures upstream of combustor nozzles. Carbonaceous deposits or fouling occurs if the wetted wall temperature is elevated sufficiently, especially at fuel nozzle tips where temperatures are maximized. Fouling within fuel nozzles diminish atomization performance producing incomplete combustion, instability, and polluting byproducts. Therefore, the industry seeks strategies to mitigate carbon deposition without reducing the thermal requirements placed on the fuel. Existing carbon mitigation techniques rely on coating the fuel-wetted surfaces in an inert layer via anodic oxidation, chemical vapor deposition, etc. In this proposal, we aim to investigate a novel approach: inducing the lotus effect (heterogenous wetting) along the walls of fuel passageways. The lotus effect minimizes wetting area along a liquid-solid interface using a highly ordered set of micro or nano features with weak interfacial energy resulting in the liquid only wetting the peaks of said features. We hypothesized that the combination of a chemically inert surface with reduced wetting area diminishes the opportunity for deposit to form. The mitigating effect can be enhanced by the thermal insulation provided by the vapor or gas pockets trapped between the liquid-solid interface, passively reducing the thermal loading of the fuel. As a preliminary step, we produced the lotus effect on multiple aerospace alloys such as Inconel 718, stainless steel 304, and pure titanium via electrochemical etching and surface modification. We then exposed treated tubes to fuel under fouling-favorable conditions to compare their relative deposition rates. Our results indicate that the lotus effect loses stability at pressures well below those used in practical applications. However, the electrochemical etch we developed consistently produced negligible deposit where it would typically be maximized. Depending on if the surface is etched, FAS17 (a perfluoroalkyl silane used to generate superphobicity) can act to encourage or discourage carbon deposition. We determined that the electrochemical etch or FAS17 alone may be a method to mitigate carbon deposition regardless of the wetting behavior </p>

In der vorliegenden Arbeit wird die Konzeptionierung und die Realisierung eines teilkontinuierlichen Thermolyseverfahrens zur rohstofflichen Verwertung von Polyethylen- und Polypropylenabfällen beschrieben. Die Ausführung in der zweistufigen Rührkesselkaskade gewährleistete dabei die Trennung der Prozessschritte Schmelzen sowie Cracken der Einsatzmaterialien, woraus ein Thermolyseöl hervorging, welches weitestgehend frei von den Verunreinigungen aus den Abfällen war. Das Thermolyseöl wies eine Zusammensetzung aus Benzin- und Dieselkomponenten auf und erfüllte einige entscheidende Kraftstoffkriterien. Zur Senkung der qualitätsmindernden Olefingehalte wurden in einem weiteren Teil dieser Arbeit Untersuchungen zur heterogen-katalysierten Hydrierung der Siedeschnitte im Schüttgutreaktor und im Rührautoklav durchgeführt. Dabei konnten die Olefingehalte durch den Einsatz eines Palladium-Platin-Trägerkatalysators sowie durch einen Nickel-Gerüstkatalysator maßgeblich gesenkt werden. Als unerwünschtes Nebenprodukt des Thermolyseprozesses resultierte ein geringer Anteil Koks, welcher in der Schmelze akkumulierte und sich teilweise an der Reaktorwand ablagerte. Die entstandenen Mengen wiesen eine Abhängigkeit von der Prozesstemperatur und -dauer auf und mussten aus dem Prozess geschleust werden. Als weitere Nebenprodukte traten ein leichtflüchtiges Spaltgas sowie ein Sumpfrückstand auf. Darüber hinaus wurde gezeigt, dass die aufzuwendende Energie für den Thermolyseprozess durch die Energiegehalte der Nebenprodukte gedeckt werden kann. Neben dem Einsatz als Kraftstoff empfahl sich das Thermolyseöl aufgrund seiner physikalischen und chemischen Eigenschaften gerade im Hinblick auf einen nachhaltigen Umgang mit Ressourcen als beachtenswerter Ersatz für fossiles Rohöl.

O controle de processo de uma planta de fabricação de coque depende de muitas variáveis particulares de cada planta. A busca de modelos de controle próprios torna-se necessário. O presente trabalho apresenta um projeto de experimentos, em forno piloto, para investigar a influência dos principais parâmetros de controle de fabricação do coque quanto à produção e consumo de calor e utilizá-los futuramente num modelo de automação do controle do processo dessa planta. O resultado do experimento apresentou significância estatística para os fatores temperatura e umidade da mistura enfornada e para as interações entre umidade e temperatura e entre umidade e granulometria com relação ao consumo de calor e também o fator temperatura com relação ao tempo líquido de coqueificação. Além do projeto de experimentos em forno piloto foi feito também um experimento em um forno industrial cuja metodologia mostrou-se adequada para um projeto em escala industrial. Com os dados dos experimentos obtiveram-se também equações matemáticas de previsão do consumo de calor e do tempo líquido de coqueificação. / The process control of a coke plant depends on a lot of particular parameters. This work describes an experimental design in a pilot oven aiming at getting the influence of the main control factors of a coke oven battery, relating these parameters with production and heat consumption for future process control automation. The result of the experiment showed statistic significance for the factors temperature and coal blend moisture and for the interactions between temperature and coal blend moisture and between moisture and coal size on the heat consumption and also for the factor temperature on the net coking time. Theses relations can be used to develop coking control at an industrial plant. In addition to the design of experiments in a pilot oven, it was also made an experiment in an industrial battery oven whose methodology showed to be appropriated to an industrial design of experiment. With the experimental data it was possible to write mathematical equations for estimation of heating and net coking time.

O controle de processo de uma planta de fabricação de coque depende de muitas variáveis particulares de cada planta. A busca de modelos de controle próprios torna-se necessário. O presente trabalho apresenta um projeto de experimentos, em forno piloto, para investigar a influência dos principais parâmetros de controle de fabricação do coque quanto à produção e consumo de calor e utilizá-los futuramente num modelo de automação do controle do processo dessa planta. O resultado do experimento apresentou significância estatística para os fatores temperatura e umidade da mistura enfornada e para as interações entre umidade e temperatura e entre umidade e granulometria com relação ao consumo de calor e também o fator temperatura com relação ao tempo líquido de coqueificação. Além do projeto de experimentos em forno piloto foi feito também um experimento em um forno industrial cuja metodologia mostrou-se adequada para um projeto em escala industrial. Com os dados dos experimentos obtiveram-se também equações matemáticas de previsão do consumo de calor e do tempo líquido de coqueificação. / The process control of a coke plant depends on a lot of particular parameters. This work describes an experimental design in a pilot oven aiming at getting the influence of the main control factors of a coke oven battery, relating these parameters with production and heat consumption for future process control automation. The result of the experiment showed statistic significance for the factors temperature and coal blend moisture and for the interactions between temperature and coal blend moisture and between moisture and coal size on the heat consumption and also for the factor temperature on the net coking time. Theses relations can be used to develop coking control at an industrial plant. In addition to the design of experiments in a pilot oven, it was also made an experiment in an industrial battery oven whose methodology showed to be appropriated to an industrial design of experiment. With the experimental data it was possible to write mathematical equations for estimation of heating and net coking time.

Unlike polymer electrolyte fuel cells, solid-oxide fuel cells (SOFCs) have the potential to use a wide variety of fuels, including hydrocarbons and gasified coal or different types of ample carbonaceous solids. However, the conventional anode for an SOFC, a composite consisting of nickel and yttria-stabilized-zirconia (YSZ), is highly susceptible to carbon buildup (coking) and deactivation (poisoning) by contaminants commonly encountered in readily available fuels. Further, the low ionic conductivity of the electrolyte and the poor performance of the cathode at lower temperatures require SOFCs to operate at high temperatures (>800°C), thereby increasing costs and reduce system operation life. Thus, in order to make SOFCs fully fuel-flexible, cost-effective power systems, the issues of anode tolerance to coking and sulfur poisoning as well as the slow ionic conduction in the electrolyte and the sluggish kinetics at the cathode need to be addressed. In this thesis, a novel electrolyte was shown to have the highest ionic conductivity below 750°C of all known electrolyte materials for SOFCs applications, which allowed for fabrication of a thin-electrolyte cell with high power output at lower temperatures. The detailed electrochemical analyses of BZCYYb conductor revealed that the conductivities were sensitive to doping and partial pressure of oxygen, hydrogen, and water. When used in combination with Ni as a composite anode (Ni-BZCYYb), it was shown to provide excellent tolerance to coking and sulfur poisoning. Extensive investigations on surfaces of BZCYYb and Ni by Raman Spectroscopy and Scanning Auger Nanoprobe disclosed that its unique ability appears linked to the mixed conductor's enhanced catalytic activity for sulfur oxidation and hydrocarbon cracking/reforming, as well as enhanced multilayer water adsorption capability. In addition, the nanostructured oxide layers on Ni from dispersion of BZCYYb traces during high-temperature calcinations may effectively suppress the formation of carbon from dehydrogenation. Based on the fundamental understanding on surface properties, a new and simple modification strategy was developed to hinder the carbon-induced deactivation of the state-of-the-art Ni-YSZ anode. Compared to the complex Ni-BZCYYb anode, this modified Ni-YSZ anode could be readily adopted in the latest fuel cell systems based on YSZ electrolyte. The much-improved power output and tolerance to coking of the modified Ni-YSZ anode were attributed to the nanostructured BaO/Ni interfaces observed by synchrotron-based X-ray and advanced electron microscopy, which readily adsorbed water and facilitated water-mediated carbon removal reactions. Density functional theory (DFT) calculations predicted that the dissociated OH from H₂O on BaO reacted with C on Ni near the BaO/Ni interface to produce CO and H species, which were then electrochemically oxidized at the triple-phase boundaries of the anode. Also, some new insights into the sulfur poisoning behavior of the Ni-YSZ anode have been revealed. The so-called "second-stage poisoning" commonly reported in the literatures can be avoided by using a new sealant, indicating that this poisoning is unlikely the inherent electrochemical behavior of a Ni-YSZ anode but associated with other complications. Furthermore, a new composite cathode with simultaneous transport of proton, oxygen vacancies and electronic defects was developed for low-temperature SOFCs based on oxide proton conductors. Compared to the conventional oxygen ion-electron conducting cathode, this cathode is very active for oxygen reduction, extending the electrochemically active sites and significantly reducing the cathodic polarization resistance. Towards the end, these findings have great potential to dramatically improve the economical competitiveness and commercial viability of SOFCs that are driven by cost-effective and renewable fuels.

There is a growing interest in alternative transport fuels. There are two underlying reasons for this interest; the desire to decrease the environmental impact of transports and the need to compensate for the declining availability of petroleum. In the light of both these factors the Diesel Dual Fuel, DDF, engine is an attractive concept. The primary fuel of the DDF engine is methane, which can be derived both from renewables and from fossil sources. Methane from organic waste; commonly referred to as biomethane, can provide a reduction in greenhouse gases unmatched by any other fuel. The DDF engine is from a combustion point of view a hybrid between the diesel and the otto engine and it shares characteristics with both. This work identifies the main challenges of DDF operation and suggests methods to overcome them. Injector tip temperature and pre-ignitions have been found to limit performance in addition to the restrictions known from literature such as knock and emissions of NOx and HC. HC emissions are especially challenging at light load where throttling is required to promote flame propagation. For this reason it is desired to increase the lean limit in the light load range in order to reduce pumping losses and increase efficiency. It is shown that the best results in this area are achieved by using early diesel injection to achieve HCCI/RCCI combustion where combustion phasing is controlled by the ratio between diesel and methane. However, even without committing to HCCI/RCCI combustion and the difficult control issues associated with it, substantial gains are accomplished by splitting the diesel injection into two and allocating most of the diesel fuel to the early injection. HCCI/RCCI and PPCI combustion can be used with great effect to reduce the emissions of unburned hydrocarbons at light load. At high load, the challenges that need to be overcome are mostly related to heat. Injector tip temperatures need to be observed since the cooling effect of diesel flow through the nozzle is largely removed. Through investigation and modeling it is shown that the cooling effect of the diesel fuel occurs as the fuel resides injector between injections and not during the actual injection event. For this reason; fuel residing close to the tip absorbs more heat and as a result the dependence of tip temperature on diesel substitution rate is highly non-linear. The problem can be reduced greatly by improved cooling around the diesel injector. Knock and preignitions are limiting the performance of the engine and the behavior of each and how they are affected by gas quality needs to be determined. Based on experiences from this project where pure methane has been used as fuel; preignitions impose a stricter limit on engine operation than knock. / QC 20120626 / Diesel Dual Fuel

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