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Energetic materials encompass a wide range of chemical compounds all associated with a significant risk of fire and explosion. They include explosives, fireworks, pyrotechnics, powders, propellants and other unsteady chemicals. These materials store a high level of chemical energy and are able to release it rapidly without external contribution of oxygen or any other oxidizer. The behaviour of these materials in case of explosive detonations is relatively wellknown from empirical and practical points of view. However, fundamental scientific questions remain unanswered related to the mechanisms of heat release. The current understanding of these mechanisms lacks appropriate thermochemical characterisation. The aim of the study is the analysis of thermal and chemical characteristics of energetic materials under conditions that exclude detonations. Detonation is excluded in order to better isolate the thermal and chemical mechanisms involved in the burning process. The experimental work has been conducted using the FM Global Fire Propagation Apparatus (FPA) [ASTM E2058‐03]. One of the benefits of using this experimental apparatus rather than the Cone Calorimeter is that it allows controlling the feed of heat and oxidizer to the reaction zone. The material chosen to conduct experiments on is a ternary smoke powder based on a mixture of starch and lactose as fuel components and potassium nitrate as oxidizer. This product is currently used by fire brigades to assess smoke venting systems efficiency of buildings. The kinetics associated with the combustion of the material was assessed slow enough to allow measuring instruments to capture the thermal and chemical evolution during combustion reaction. Thermal analysis has first been carried out by means of DSC, TGA, DTA, MS and FTIR data in order to understand the decomposition of the material and its energetic evolution when undergoing heating. However, if the latter methods help defining the decomposing path of the material, they do not provide an integral view of its combustion behaviour, in particular, the emissions of toxics which are kinetic path dependent. Subsequently, combustion tests have been carried out using the FPA. Its ability to capture the evolution of gases emissions formed during the reaction has been proved. The influence of two configuration parameters on the combustion behaviour and on the gaseous emissions of the material has been investigated. The proportion fuel/oxidizer has been varied as well as the composition of the reacting atmosphere. Results shows that the quantity of oxidizer in the material affects the kinetics of the reactions taking place in the condense phase. Increasing the concentration of potassium nitrate in the mixture enhanced the reaction rate of the smouldering combustion. Higher quantity of volatiles is released which favoured the initiation of a diffusion flame regime in the gaseous phase, above the sample. While the kinetics of the condense phase is governed by the oxidizer concentration, experiments show that the flaming regime is influenced by the concentration of oxygen (O2) in the reacting atmosphere. A transition from diffusion to premixed flame is found when the concentration of O2 surrounding the sample is reduced below 18%. An analytical model has been used to explain the existence of a transition for a critical O2 concentration. Finally, thermal and combustion analyses have allowed to characterise the behaviour of the material under critical conditions, in terms of decomposition taking place in the condense phase but also potential toxic emissions that can be released. Toxicity, kinetics, temperature evolution do not provide a complete view of the combustion phenomenon. Beside these elements that characterise the behaviour of a material for given conditions as well as also the degree of fire hazard encountered, the energetic issue holds as an essential feature that cannot be neglected. The heat release rate (HRR) is a critical parameter that defines a fire. It does not constitute an intrinsic material property but it describes the energetic response of the couple formed by the material and its environment. Oxygen Consumption calorimetry (OC) and Carbon Dioxide Generation calorimetry (CDG) are widespread methods to calculate the HRR resulting from a combustion reaction. Apparatuses such as the FPA or the cone calorimeter have already proved their potential to qualify the burning behaviour of common fuels in addition to polymers when their data are combined with an adapted calorimetric procedure. The same approach has been applied to energetic materials. However, prior to using these techniques, it is fundamental to have identified their restrictions. These techniques provide approximate estimations of the HRR. Results are affected by the propagation of uncertainties. Several sources of uncertainties can be found. One can cite: 1. Uncertainties associated with the sample material; 2. Uncertainties associated with the test conditions; 3. Uncertainties associated with the measurements; 4. Uncertainties associated with calculation assumptions. If uncertainties cannot always be estimated, the three first sources cited have received attention in the past from the scientific community, alike the last one. The restrictions associated with the assumptions developed for using the OC and CDG principles have to be clarified. The limits of validity of the hypotheses have to be clearly defined. In particular, the present dissertation questions the relevance of the energy constants that have been specified for OC and CDG as well as their related uncertainties. One of the purposes of the research deals with the ability to estimate accurate error bars for the calculation of the HRR. Once uncertainties related to the calorimetric methods are assessed, a method adapted from the basic OC and CDG principles is introduced that allows estimating the HRR of energetic materials. The approach is based on considering the chemical decomposition of the burning compound and defining a fictitious molecule for which energy coefficients can be calculated. Nevertheless, it requires the material to be known. Finally, the question of the advantage brought by these techniques over others, in terms of accuracy, is discussed within the framework of unconventional products, such as energetic materials or compounds whose composition is ignored. The results from this work will contribute to the development of fireanalysis methodologies and validate their use with energetic materials.

The thermochemical process converts almost any kind of biomass to a desired final product, i.e. gaseous or liquid transportation fuels and chemicals. The transportation fuels obtained in this way are renewable biofuels, which are alternatives to fossil fuels. During the last few years, thermochemical plants for the production of bioethanol have been launched and another is under construction. A total of about 290 million liters of ethanol are expected to be processed per year, mostly using municipal solid waste. Considerable efforts have been made in order to find a more selective catalyst for the conversion of biomass-derived syngas to ethanol. The thesis is the summary of five publications. The first two publications (Papers I and II) review the state of the art of ethanol and higher alcohols production from biomass, as well as the current status of synthetic fuels production by other processes such as the Fischer-Tropsch synthesis. Paper III analyses the catalytic performance of a mesoporous Rh/MCM-41 (MCM-41 is a hexagonal mesoporous silica) in the synthesis of ethanol which is compared to a typical Rh/SiO2 catalyst. Exhaustive catalytic testing including the addition of water vapor and modifying the hydrogen partial pressure in the syngas feed-stream which, in addition to the catalyst characterization (XRD, BET, XPS, chemisorption, TEM and TPR) before and after the catalytic testing, have allowed concluding that some water vapor can be concentrated in the pores of the Rh/MCM-41 catalyst. The concentration of water-vapor promotes the occurrence of the water gas shift reaction, which in turn induces some secondary reactions that change the product distribution, as compared to results obtained from the typical Rh/SiO2 catalyst. These results have been verified in a wide range of syngas conversion levels (1-68 %) and for different catalyst activation procedures (catalyst reduction at 200 °C, 500 °C and no-reduction) as shown in Paper IV. Finally, similar insights about the use of mesoporous catalyst have been found over a Cu/MCM-41 catalyst, shown in Paper V. Also in Paper V, the effect of metal promoters (Fe and K) has been studied; a noticeable increase of ethanol reaction rate was found over Cu-Fe-K/MCM-41 catalyst as compared to Cu/MCM-41. / <p>QC 20161125</p>

Doctor of Philosophy / Department of Chemical Engineering / Peter H. Pfromm / Approximately 45% of the global hydrogen production (from fossil fuels such as natural gas or coal totaling 2% of the global energy generation) is absorbed as feedstock in the synthesis of over 130 million metric tons ammonia (NH[subscript]3) annually. To achieve food security for a growing world population and to allow for additional uses of the nitrogen-fertilizer for production of bio-energy feedstock or as combustion fuel or H[subscript]2 carrier - demand for NH[subscript]3 is projected to increase. This work pursues the synthesis of ammonia at atmospheric pressure and without fossil fuel. Conceptually, concentrated solar radiation is utilized to transfer electrons from the lattice oxygen of a transition metal oxide to the metal ion. This yields a metallic reactant that provides the reducing power for the subsequent six-electron reductive cleavage of N[subscript]2 forming a transition metal nitride. In a second reaction, the generated lattice nitrogen is hydrogenated with hydrogen from H[subscript]2O to NH[subscript]3. This furnishes the transition metal oxide for perpetuated NH[subscript]3 synthesis. Theory and experimentation identified manganese nitride as a promising reactant with fast diffusion characteristics (8 ± 4 x 10[superscript]-9 cm[superscript]2 s [superscript]-1 apparent nitrogen diffusion constant at 750 degree C) and efficient liberation of 89 ± 1 mol% nitrogen via hydrolysis at 500 degree C. Opposed to only 2.9 ± 0.2 mol% NH[subscript]3 from manganese nitride, 60 ± 8 mol% of the nitrogen liberated from molybdenum nitride could be recovered as NH[subscript]3. Process simulation of a Mo-based NH[subscript]3 synthesis at 500-1200 degree C estimates economically attractive production under fairly conservative process and market conditions. To aid the prospective design of a Mn or Mo-based reactant, correlating the diffusion constants for the hydrolysis of seven nitrides with the average lattice nitrogen charge (9.96-68.83%, relative to an ideal ionic solid) indicates the utility of first-principle calculations for developing an atomic-scale understanding of the reaction mechanism in the future.

Neste trabalho, foi estudado a oxidação do ferro com vapor d\'água em forno elétrico, para a produção de gás hidrogênio. Partindo-se da revisão bibliográfica, escolheu-se o ferro devido suas propriedades e por apresentar um bom rendimento, além disso o ferro é um material barato e abundante. Na estudo experimental foi três experimentos diferentes. No primeiro, o ferro foi oxidado em forno elétrico em temperaturas de 600 a 1000ºC, variando a cada 100ºC, e tempo fixado em 3 horas. Na segunda série de experimento, foi fixado a temperatura em 800ºC e variou a duração do processo de oxidação de 1 a 4 horas, com variação de 1 hora. E na terceira série de experimentos foi realizado a análise termogravimétrica para avaliação da cinética química do processo de oxidação. Os resultados dos experimentos indicaram a produção de gás hidrogênio em quantidades maiores em temperatura de 1000ºC. Além disso foi possível observar que a taxa de oxidação do ferro é maior durante a primeira hora de ensaio. A estimativa de hidrogênio produzido é de 0,9549 g/min -m2 em oxidação a 1000ºC. Já nos resultados da termogravimetria foi obtido a energia de ativação de 147 kJ/mol. / In this work was studied the oxidation of iron by steam in the electric furnace to produce hydrogen. The first step was the literature review and iron oxide was chose to be oxidized, due to its characteristics and good yield. Furthermore, the iron is a cheap and abundant in the earth. In the experimental studies was conducted three different experiments. The First one, the iron was oxidized in the electric furnace in the temperature range of 600 - 1000ºC with a variation of 100ºC and the oxidation time was fixed in 3 hours. The second experiment was conducted with fixed temperature of 800ºC and varied the oxidation time, the range of time was from 1 to 4 hours with a variation of 1 hour. The third experiment was the thermogravimetric analysis to study the chemical kinetics, with three different temperature, 600, 800 and 1000ºC. The result of studies showed that a high temperature the hydrogen production increased and decreased with low temperature. Furthermore, the high oxidation rate was observed in the first hour of the experiment. The hydrogen production was estimated in 0.9549 g/min - m2 at 1000ºC. Another result was the activation energy Ea= 147 kJ/mol.

Salt hydrates have the potential to be used in heat storage as both phase-change materials (PCMs) and thermochemical materials (TCMs). These materials offer advantages over traditional heat storage methods due to their high energy densities. However, both domestic and industrial applications require thousands of thermal cycles and there are often many issues that need to be overcome before these materials can be used reliably for heat storage. One of the major issues with using salt hydrates as PCMs is incongruency - the formation of anhydrous phases during melting. In this research, the mechanisms of the action of polymers to prevent incongruency in sodium acetate trihydrate have been investigated. A new polymorph of anhydrous sodium acetate, Form IV, was obtained in the presence of the polymer. This polymorph crystallises as long, blade-shaped crystals, thereby increasing the surface area to volume ratio. Indexing of the crystal faces revealed that every face had Na+ or the oxygen atoms of the acetate ion near or on the surface, as opposed to hydrophobic methyl groups found on the faces of the anhydrous salt grown without polymer. These two factors are believed to significantly increase the dissolution kinetics. This technique has the potential to be used for screening polymers to reformulate other salt hydrates that display incongruent behaviour. Eutectic compositions of NaCl and KCl with strontium hydroxide octahydrate were investigated as a potential means to prevent the incongruency of this PCM. However, degradation was observed with thermal cycling. Variable temperature PXRD studies discovered a new Sr(OH)2 hydrate when heating above 75 °C - Sr(OH)2. ⅓H2O. The recrystallisation of the octahydrate from the new phase was slow with incomplete conversion, explaining the degradation with continuous cycling. The effect of addition of NaCl and KCl to congruent barium hydroxide octahydrate was also investigated. On heating, a phase transition was observed, but the samples remained solid. Variable temperature PXRD investigations discovered that this was due to the formation of the salt hydrate, Ba(OH)Cl.2H2O. This hydrate melted at 110 °C, showing its potential as a high temperature PCM. The dehydration pathways of magnesium sulfate heptahydrate were investigated. In-situ PXRD studies showed that changing the heating rate changed the intermediates present during the dehydration. The fast dehydration rate saw both the known phases of trihydrate and 2.5 hydrate form as the dehydration product of the tetrahydrate. These both then dehydrated to the known dihydrate. This differed when the slower heating rate was used, as the trihydrate was the only product of dehydration from the tetrahydrate. The trihydrate then proceeded to dehydrate to a new phase. This was found to be a new polymorph of the dihydrate, β-MgSO4.2H2O. Dehydration of MgSO4.7H2O with 50 mol% NaCl was also performed. Loeweite, Na12Mg7(SO4)13.15H2O, a dication sulfate hydrate, was formed as the major intermediate. This mixture showed advantages over the pure MgSO4.7H2O as dehydration to the monohydrate took less time and occurred at a lower temperature. There were also three fewer intermediate phases before dehydration to the monohydrate. Suspension and encapsulation materials were used in order to overcome the major issue of agglomeration with magnesium sulfate. Liquid water was ruled out as a viable hydration medium. Apparatus was developed to test humidity cycling, which allowed the effects of dehydration time and temperature to be investigated, as well testing a range of different formulations.

Diferentes resíduos são gerados pelas indústrias siderúrgicas, dentre eles o resíduo dos trituradores de sucata (RTS). O destino mais utilizado para o RTS pelas indústrias siderúrgicas brasileiras é o aterro de resíduos industriais. A pirólise se apresenta como uma alternativa para o reaproveitamento do RTS. O objetivo deste trabalho foi avaliar o efeito de diferentes parâmetros operacionais sobre as propriedades e o rendimento dos produtos do processo de pirólise do RTS para fins de um posterior aproveitamento. Um reator de pirólise de leito fixo foi utilizado e as seguintes variáveis foram testadas fazendo-se uso de um planejamento experimental 2k: temperatura (500, 600 e 700 ºC), taxa de aquecimento (5, 20, 35 ºC/min), vazão de gás inerte (N2) (0,03, 0,44 e 0,76 L/min) e razão CaO/RTS (0, 1 e 2). A utilização de uma taxa de aquecimento menor, associada a presença de CaO, resultou nos maiores rendimentos de gás não-condensável (> 50%). O poder calorífico deste gás, aumentou com o incremento da razão CaO/RTS. Este aumento foi atribuído a captura in situ do CO2. A utilização de uma vazão maior de gás inerte, também favoreceu o aumento do poder calorífico do gás não-condensável. Os maiores valores obtidos (25 MJ/Nm3) são apreciáveis, considerando o poder calorífico de outros combustíveis. Os maiores rendimentos de char (> 24%) foram obtidos nos experimentos com a utilização de uma temperatura menor, associada a ausência de CaO. A utilização de uma taxa de aquecimento mais elevada resultou em maiores rendimentos de voláteis condensáveis. Os menores rendimentos de voláteis condensáveis foram obtidos quando a vazão de inerte foi menor. Também foi possível verificar que, houve um aumento do rendimento de voláteis condensáveis com a presença de CaO para a temperatura de 700 ºC. Este comportamento foi atribuído ao maior rendimento global de estireno nas referidas condições operacionais. O rendimento global de 2,4-dimetil-1-heptano também apresentou comportamento semelhante ao observado para o rendimento de voláteis condensáveis, indicando que o AlCl3 pode ter atuado como catalisador da pirólise do PP presente no RTS. Com o aumento da razão CaO/RTS, houve uma redução da concentração de CO2. A redução da concentração de CO2 na presença de CaO está associada a formação de CaCO3. A retenção de cloro no char foi mais elevada nos ensaios conduzidos na presença de CaO. Verificou-se uma redução da retenção de cloro no char com o aumento da temperatura para os ensaios conduzidos na presença de CaO. Uma diminuição da retenção de metais no char foi verificada nos experimentos conduzidos com CaO para os seguintes metais: Co, Cu, Cr, Fe, Ni e Zn. A remoção do cloro permitiria conduzir o processo de pirólise a temperaturas mais elevadas, aumentando a Eficiência Energética mínima (EE) do processo. Desta forma, fica clara a necessidade da remoção do cloro do RTS antes do processo de pirólise, pois a partir disto o uso do CaO contribuiria para o aumento da EE e da retenção de metais no char, e consequentemente da desejabilidade global. / Different wastes are generated by steel industries, among them the shredder residue (SR). The most commonly used destination for SR by Brazilian steel industry is the landfill of industrial waste. The pyrolysis can be considered a solution to this problem. The aim of this work was to evaluate the effects of different operating parameters upon the properties and yield of the SR pyrolysis process products for later use. A fixed bed pyrolysis reactor was used and the following variables were tested using a 2k experimental design: temperature (500, 600 and 700 ºC), heating rate (5, 20, 35 ºC/min), flow rate of inert gas (N2) (0.03, 0.44 and 0.76 L/min) and CaO/SR ratio (0, 1 and 2). The use of a lower heating rate, associated with the CaO presence, resulted in higher yields of non-condensable gas (> 50%). The calorific value of this gas increased with the growth of the CaO/SR ratio. This increase was attributed to an in situ CO2 capture. The use of a higher flow rate of inert gas also favored the increase in the calorific power of the non-condensable gas. The highest values (25 MJ/Nm3) are appreciable considering the calorific value of other fuels. The highest char yields (> 24%) were obtained in the experiments using a lower temperature associated with the absence of CaO. The use of a higher heating rate resulted in higher yields of condensable volatiles. The lower yields of condensable volatiles were obtained when the inert flow rate was lower. It was also possible to verify that there was an increase in the condensable volatiles yield with the CaO presence at a temperature of 700 ºC.This behavior was attributed to the higher styrene overall yield under these operating conditions. The 2,4-dimethyl-1-heptane overall yield also presented a similar behavior to that observed for the condensable volatiles yield, indicating that the AlCl3 may have acted as a catalyst for the PP pyrolysis present in the SR. With the increase in the CaO/RTS ratio, there was a reduction in the CO2 concentration. The CO2 concentration reduction in the CaO presence is associated with the CaCO3 formation. The chlorine retention in the char was higher in the experiments conducted with CaO presence. A reduction in the chlorine retention in char was observed with increasing temperature for the experiments conducted with CaO presence. A decrease in metal retention in the char was verified in the experiments conducted with CaO for the following metals: Co, Cu, Cr, Fe, Ni and Zn. Chlorine removal would allow the pyrolysis process to be conducted at higher temperatures, increasing the minimum energy efficiency (EE) of the process. Therefore, it is clear the need to remove chlorine from the SR before the pyrolysis process, since, the CaO use would contribute to the EE increase and the retention of metals in the char, and consequently the global desirability.

Afin de répondre aux problématiques écologique et économique du traitement des Matériaux Contenant de l’Amiante (MCA), un procédé complet permettant de traiter de manière optimale ces déchets a été proposé. Pour cela, trois types de déchets ont d’abord été analysés par plusieurs techniques de caractérisation complémentaires (diffraction des rayons X, microscopie électronique à balayage, infrarouge et RMN du solide). Ces analyses ont permis l’identification des différentes phases présentes au sein des déchets. Cette identification est nécessaire, car elle permet d’adapter de manière optimale le procédé de destruction au déchet. La première étape de ce procédé est le traitement en température des MCA dans une solution d’acide nitrique. Elle permet la dissolution de la matrice du déchet et la dénaturation des fibres de chrysotile qui sont présentes dans 95 % des déchets amiantés. Deux phases sont alors récupérées à l’issue de ce traitement : une phase solide composée de silice pure et une phase liquide contenant, notamment, du calcium, du magnésium et du fer. Si les déchets contiennent des fibres de type amphibole (5 % des MCA) ils sont ensuite traités par voie hydrothermale dans un autoclave contenant une solution de soude. Cette étape mène à la dissolution complète du déchet. Une solution basique contenant du silicium est ainsi récupérée. Différentes voies de valorisations ont été développées. Les ions présents dans la solution acide sont récupérés par précipitation sélective des hydroxydes. Une autre voie consiste à synthétiser une zéolithe à partir de la silice pure et de la solution basique. Les isothermes d’adsorption de cette dernière ont été tracés afin de déterminer sa capacité d’adsorption de certains cations métalliques polluants. Pour terminer, une étude fondamentale a été menée sur les nanotubes de silice obtenus avec le traitement de fibres d’amiante pures et différentes applications de ces nanotubes de silice ont été évoquées. / To answer the ecological and economic problems of the treatment of Materials Containing Asbestos (MCA), a complete process allowing to handle in an optimal way these waste was proposed. For that purpose, three types of waste were analyzed by several complementary techniques of characterization (X-rays diffraction, Scanning Electron Microscopy, infrared and NMR spectroscopy). These analyses allowed the identification of the present various phases within waste. This identification is necessary, because it allows to adapt in the optimal way for the destruction of the waste. The first stage of the process is a treatment in temperature of the MCA in a solution of nitric acid leading to the dissolution of the matrix of the waste and the denaturation of the fibers of chrysotile which are present in 95 % of MCA. Two phases are then got back at the end of this treatment: a solid phase of pure silica and a liquid phase containing, in particular, calcium, magnesium and iron ions. If previous waste contains fibers of amphibole type (5 % of the MCA) they are then treated through a hydrothermal process in an autoclave containing a solution of soda. This stage leads to the complete dissolution of the waste. The basic solution containing some silicon is so got back. Various ways of valuations were then developed. The present ions in the acid solution are chemically sorted out by a selective precipitation of hydroxides. Another way consists in synthesizing a zeolite from the pure silica coming from the acid treatment and from the basic solution after hydrothermal treatment. The isotherms of adsorption of this synthesized zeolite were established to determine its capacity of adsorption of certain polluting metallic cations. To finish, a fundamental study was led on the nanotubes of silica obtained after the acid treatment of pure asbestos fibers and diverse applications of these nanotubes of silica were evoked.

Aerothermodynamics is an integral component in the design and implementation of hypersonic transport systems. Accurate estimates of the aerodynamic forces and heat transfer rates are critical in trajectory analysis and for payload weight considerations. The present work seeks to investigate the ability of an unstructured Cartesian grid framework in modeling hypersonic viscous flows. The effectiveness of modeling viscous phenomena in hypersonic flows using the immersed boundary ghost cell methodology of this solver is analyzed. The capacity of this framework to predict the surface physics in a hypersonic non-reacting environment is investigated. High velocity argon gas flows past a 2-D cylinder are simulated for a set of freestream conditions (Reynolds numbers), and impact of the grid cell sizes on the quality of the solution is evaluated. Additionally, the formulation is verified over a series of hypersonic Mach numbers for the flow past a hemisphere, and compared to experimental results and empirical estimates. Next, a test case that involves flow separation and the interaction between a hypersonic shock wave and a boundary layer, and a separation bubble is investigated using various adaptive mesh refinement strategies. The immersed boundary ghost cell approach is tested with two temperature clipping strategies, and their impact on the overall solution accuracy and smoothness of the surface property predictions are compared. Finally, species diffusion terms in the conservation equations, and collision cross-section based transport coefficients are installed, and hypersonic flows in thermochemical nonequilibrium environments are studied, and comparisons of the off-surface flow properties and the surface physics predictions are evaluated. First, a 2-D cylinder in a hypersonic reacting air flow is tested with an adiabatic wall boundary condition. Next, the same geometry is tested to evaluate the viscous chemistry prediction capability of the solver with an isothermal wall boundary condition, and to identify the strengths and weaknesses of the immersed boundary ghost cell methodology in computing convective heating rates in such an environment.

This thesis develops analytical and numerical solutions that predict behavior of Cupric-Chloride droplets undergoing spraying and drying processes. Cupric-Chloride (CuCl2) is present as molten salt and slurry within the Copper-Chlorine thermo-chemical cycle for generation of hydrogen. Utilizing low-grade heat from nuclear or industrial sources to assist drying of Cupric-Chloride can increase efficiency of the overall process. Analytical correlations for heat and mass transfer are developed and applied to the analysis of a solution of Cupric-Chloride, subject to various drying conditions. The study provides new information on effects of different concentrations of water in CuCl2 slurry drying at low air temperatures. / UOIT