For 2010 the European Union has a goal to increase the share of renewable energyware to 12%. For 2020 the goal is 20%. One of visions to reach this is to raise the share of solid biofuels. Politicans all over ideologycal spectrum collectively propagate, that farming and waste management sector industry has developed ways to produce solid recovered fuels with reliable qualities, which are used successfully regarding economic and environmental aspects. One of prerequisites to reach this will be to achieve the standardization of solid biofuels. This leads to a need for flexible market, which is attainable only by common understanding concerning terminology, sampling and test methods. European energetically non-intensive industries and settlements are looking for ecologically friendly alternative fuels in order to save fossil fuels. And by doing so, enforce the development of fitting technical norms to facilitate the meeting of offer and demand for the product. Pressed biofuels like pellets are today playing the key role for the small house market as well as for large scale coal substitution in local power plants. The thesis is a part of scientific contemplation MSM 06/2/4a solved by professors S.Kužel and L.Kolář and is trying to answer the question: ``Is combustion of solid biofuels ecologically friendly?{\crqq}

Le traitement thermique est une méthode appropriée pour la valorisation d'essences européennes peu durables. Les modifications chimiques en résultant confèrent au bois une meilleure stabilité dimensionnelle et durabilité aux attaques fongiques, alors que les propriétés mécaniques diminuent plus ou moins. Le verrou actuel de ce procédé reste la grande difficulté à produire à l'échelle industrielle un produit de qualité constante (durabilité, stabilité dimensionnelle, couleur). Ces difficultés sont dues à l'hétérogénéité du matériau et des conditions de traitement réalisé généralement par convexion. La mise au point d'un pilote de traitement thermique par conduction permettant une mesure en dynamique de la perte de masse a été réalisée pour optimiser la conduite du traitement, mieux comprendre les réactions de thermodégradation et développer un outil de contrôle de la qualité du bois traité. Les résultats obtenus, réalisés dans des conditions de traitement proches des conditions industrielles, indiquent un effet important de l'essence de bois traitée sur les cinétiques de perte de masse observées, les feuillus étant généralement plus sensibles à la thermodégradation que les résineux. Il a ensuite été établi une forte corrélation entre le niveau de thermodégradation du bois estimé à partir de sa perte de masse et l'augmentation de sa durabilité aux champignons basidiomycètes. L'analyse fine et la compréhension des mécanismes réactionnels intervenant durant le traitement ont permis de mettre en évidence un lien direct entre la composition élémentaire du bois et la perte de masse due aux réactions de thermodégradation, permettant également de prédire la durabilité aux attaques fongiques. Le taux de carbone, d'oxygène ou encore le rapport O/C peuvent de ce fait être considérés comme des marqueurs pertinents permettant de contrôler la qualité du bois traité thermiquement. / Thermal treatment has been used to improve properties of non durable European species. Chemical modification of some of the wood components provides improved dimensional stability and biological performance against decay fungi while mechanical properties such as modulus of rupture are reduced. Quality control of commercially made thermally treated wood is one of the major road blocks of its industrial development. The variability inherent within a wood species and between wood species, density and chemical compositions variation combined with the heat treatment parameters such as temperature duration and levels contribute to the production of heterogeneous heat treated wood. The development of a heat treatment process by conduction which monitors the weight changes during the process will facilitate and help in controlling, in understanding and predicting the properties of heat treated wood. Data collected from a pilot study of heat treated wood using conditions similar to commercial process show that hardwood species were more susceptible to thermal degradation as compared to softwood. It was also established that wood chemical composition is directly connected to the percent of weight loss due to thermodegradation, allowing the use of chemical composition to predict fungi durability. Carbon and oxygen contents and/or oxygen to carbon ratio of heat treated wood can be therefore used as valuable markers to develop quality control assessment of heat treated wood.

The placement of an unconformable surface within a stratal succession affects the interpreted thickness of units and sequences in contact with that surface. Unit thickness influences the interpretation of basin subsidence, paleotopography, diagenesis, and depositional style. Accurate placement of an unconformity results in true formational thicknesses for formations associated with that unconformity. True thicknesses aid in producing more precise surface to subsurface correlations, isopach maps, and paleogeographic maps. An unconformity may be difficult to identify in the stratal succession due to similar rocks above and below the unconformity and the presence of multiple candidate surfaces. Using statistical discriminant analysis of XRF data, formations bounding an unconformity can be discriminated by elemental composition which results in delineation of the associated unconformity. This discrimination is possible even for rocks that do not have significant differences in provenance if they have experienced distinct diagenetic histories. Elemental differences can be explained by quantity and type of cement. Three discriminant models were created. These models were tested with samples from three formations of similar facies, appearance, and provenance that are all associated with the same regional unconformity. All data, regardless of location, facies, or tectonic feature were used to create the first model. This model achieved moderate success by correctly classifying 80% of known samples. In a second model, data were grouped by facies trends. Separating the data by facies resulted in 94% of known samples being correctly classified. This model was most useful for delineation of an unconformity and discrimination of formations. A third model based solely on location or local tectonic feature produced the best results statistically. 96% of known samples were classified correctly. This third model does not compare locations to each other, thus making it less robust. This last model contributes by adding detail to interpretations made with the facies trend model.

Made available in DSpace on 2017-07-24T19:38:07Z (GMT). No. of bitstreams: 1 FABIOMALINOSKI.pdf: 1967487 bytes, checksum: a8c89b1d9584a90151895d2cdcb1b6d6 (MD5) Previous issue date: 2012-05-07 / This work presents the compilation and analysis of several analytical data obtained in the characterization of shale fine and lime schist, two abundant residuals in the Petrosix process. In order to ensure better representativeness of results, samples of lime schist extracted from complete vertical cuts of the layer were analyzed, and indirect analysis procedure was adopted for the shale fine residual, which basically consists of the characterization of samples obtained from complete vertical sections of superior and inferior shale layers in the Mine Rio das Pedras pit, within the Irati formation, in São Mateus do Sul PR. Analytical results obtained though Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) revealed that the lime schist layer presents mass predominance of the elements: Calcium, Silicon and Magnesium, and that this predominance, as indicated by the X-Ray Diffraction analysis (XRD), is due to the significant presence of Dolomite (CaMg(CO3)2) and Quartz (SiO2), and that the great reduction of mass after the Fixed Mineral Residue analysis is mainly related to CO2 elimination, in the dolomite thermal decomposition process. In the shale fine characterization, analytical results obtained through ICP-AES demonstrated that superior and inferior shale layers presented mass predominance of the elements silicon and iron, and this predominance, as indicated by the XRD is mainly due to the presence of Quartz (SiO2) and Pyrite (FeS2), and that the mass reduction after Fixed Mineral Residue analysis is related to the elimination of organic matter and the Pyrite thermal decomposition, with the former as the most relevant factor. Shale layers also presented Albite, Microcline and Muscovite, particle density similar values, crude oil with chromatographic profile of relative elevation in mass between the Heptane and Undecane peaks, uniform distribution between Dodecane and Octacosane peaks, decreasing distribution between the Nonacosane and C72 peaks, with normal spare paraffins in an unresolved complex organic mixture. These results indicate that the fine shale residue has a composition that oscillates between the narrow parameters of superior and inferior shale. / Neste trabalho apresentamos a compilação e a análise de diversos dados analíticos obtidos na caracterização do Finos de Xisto e do Calcário de Xisto, dois resíduos abundantes do processo Petrosix. Para garantir maior representatividade de resultados, analisam s amostras de Calcário de Xisto extraídas de cortes verticais completos da camada, e adotamos um procedimento de análise indireta para o resíduo denominado Finos de Xisto, que consiste basicamente na caracterização de amostras obtidas de secções verticais completas das camadas de Xisto Superior e Xisto Inferior das cavas da Mina Rio das Pedras, dentro da Formação Irati, na cidade de São Mateus do Sul – PR. Os resultados analíticos obtidos por Espectrometria de Emissão Atômica por Plasma Indutivamente Acoplado (EEA-PIA) demonstraram que a camada denominada Calcário de Xisto apresenta predomínio mássico dos elementos: Cálcio, Silício e Magnésio, que este predomínio, conforme indicado na análise de Difração de Raios X (DRX), deve-se a presença expressiva de Dolomita (CaMg(CO3)2) e Quartzo (SiO2), e que a grande redução de massa após a análise de Resíduos Minerais Fixos está relacionada principalmente a eliminação de CO2, no processo de decomposição térmica da Dolomita. Na caracterização do Finos de Xisto, os resultados analíticos obtidos por EEA-PIA demonstraram que as camadas de Xisto Superior e Xisto Inferior apresentam predomínio mássico dos elementos Silício e Ferro, que este predomínio, conforme indicado na análise de DRX, deve-se em grande parte a presença de Quartzo (SiO2) e Pirita (FeS2), que a redução de massa após a análise de Resíduos Minerais Fixos está relacionada a eliminação da matéria orgânica e a decomposição térmica da Pirita, sendo o primeiro fator muito mais relevante. As camadas de Xisto também apresentaram Albita, Microclínio e Muscovita, valores semelhantes de massa específica de partículas, óleo bruto com perfil cromatográfico de relativa elevação em massa entre os picos de Heptano e Undecano, distribuição uniforme entre os picos de Dodecano e Octacosano, distribuição decrescente entre os picos de Nonacosano e C72, com normais parafinas sobressalentes numa mistura orgânica complexa não resolvida. Estes resultados indicam que o resíduo Finos de Xisto tem composição oscilante entre os estreitos parâmetros do Xisto Superior e do Xisto Inferior.

The global energy demand supplies mainly from fossil fuels, which is neither sustainable nor environmentally friendly and aims to global warming. Therefore, both more investments in renewable energy sources such as bioenergy are required, as well as new technologies such as carbon capture and storage (CCS) to handle the emissions from existing combined heat and power (CHP) plants. In this degree project, the focus is to determine the moisture content, ash content, heating value, and elemental compositions of solid biofuel mixtures in real-time by utilizing the optical technique of near-infrared (NIR) spectroscopy. A total number of 150 samples of solid biofuel mixtures were prepared and illuminated by NIR light. All spectra of the samples were recorded in a wavenumber range of 12000 cm-1 – 400 cm-1 in a dish on a turn table which was in a moving mode with a speed of 0.5 m/s. Each sample was scanned three times to avoid, or at least minimize the deviation of the spectra and the samples were mixed between each scan to get more reliable representative spectra data. Partial least square regression models were created to analyze the spectra data. A data split was done randomly, 100 for calibration and 50 for validation. Then the data was pre-processed with different methods including multiplicative scatter correction (MSC), standard normal variate (SNV), Savitzky-Golay 1st derivative (SG 1st), Savitzky-Golay 2nd derivative (SG 2nd), and orthogonal signal correction (OSC) to reduce noise and scatter effect. The results of NIR spectra treated by OSC method obtained  , RMSE and SE of 0.900, 2.241 and 2.204, respectively for prediction of moisture content, 0.424, 0.913 and 0.922 for prediction of ash content, 0.640, 0.370 and 0.368 for prediction of heating value, respectively. The obtained prediction of  , RMSE and SE were 0.687, 0.066 and 0.058 for nitrogen, 0.636, 0.361 and 0.364 for carbon, 0.483, 0.269 and 0.270 for hydrogen, respectively. As the results shows, these models to predict the ash content and hydrogen content has a lower accuracy than what is expected in process modeling while the prediction of moisture content has the highest accuracy.

This work deals with the determination of the operational efficiency of solid fules boilers for their inclusion in the relevant emission class according to ČSN EN 303-5. Two steel boilers of the same manufacturer, type and performance but of different ages, were measured. The experimental measurments in the real operation of the boilers were carrien out during the combustion of two types of fuels, namely brown coal and spruce wood.The operational efficiency of the monitored sources was calculated from the measured data using both direct and undirect methods. The found efficiency of the boilers corresponds to the expected values, due to their construction, age and the way of using individual components and regulations. In the project part of this work there is a proposal of heating of the family house for the condition of the building before and after the insulation. The calculation was made for the solid fuel boiler and heat pump. The building is heated by radiators and floor heating. The design of the whole system, technical report and project documentation were prepared for each variant.

Cette thèse porte sur l’analyse isotopique de poussières interplanétaires riches en carbone (des micrométéorites ultracarbonées), pour mieux comprendre les processus de fractionnement isotopique des éléments légers (hydrogène et azote) observés dans les phases organiques de la matière extraterrestre primitive. Il est possible, au sein d’une collection de micrométéorites provenant des régions centrales du continent Antarctique, d’identifier des micrométéorites ultracarbonées (UCAMMs – pour UltraCarbonaceous Antarctic MicroMeteorites) qui contiennent environ dix fois plus de carbone que les météorites primitives. Ces particules rares (environ 1% des particules collectées) ouvrent la possibilité d’étudier en laboratoire des particules cométaires de grandes tailles (100-200 microns). Des analyses minéralogiques, chimiques et structurales sur deux fragments de micrométéorites ultracarbonées ont été réalisées dans le cadre de collaborations à l’aide de techniques de microscopie électronique à balayage, microsonde électronique, microspectroscopie infrarouge (synchrotron SOLEIL). Le travail principal de cette thèse concerne l’analyse isotopique de deux UCAMMs par spectrométrie de masse à émission ionique secondaire (SIMS) à l’aide de la microsonde ionique NanoSIMS. Les développements instrumentaux effectués en collaboration entre les équipes du CSNSM et de l’Institut Curie permettent de résoudre les interférences moléculaires avec un pouvoir de séparation en masse supérieur à 20 000 en conservant une sensibilité compatible avec les mesures envisagées. Ainsi, il a été possible de mesurer pour la première fois la composition isotopique de l’hydrogène avec les ions poly-atomiques 12C2D- et 12C2H- et de comparer sa distribution spatiale avec celle de l’azote (12C15N-/12C14N-) obtenue sur la même surface avec le même champ magnétique. Un protocole de fabrication d’une série d’échantillons standards a été développé à partir de polymères isotopiquement marqués en deutérium afin de déterminer le fractionnement instrumental du NanoSIMS démontrant la possibilité d’effectuer des mesures précises de la composition isotopique de l’hydrogène dans la matière organique avec des ions polyatomiques (rapports CD-/CH- et C2D-/C2H-). Les cartographies isotopiques à haute résolution spatiale (200 nm) en C2D-/C2H- et C15N-/C14N- montrent une distribution très hétérogène du deutérium avec des valeurs extrêmes allant jusqu’à 20 fois la valeur des océans terrestres, alors que les rapports 15N/14N restent globalement proches (à 20% près) de la valeur de l’atmosphère terrestre. Les mesures des rapports N/C en imagerie ionique effectuées au NanoSIMS confirment les valeurs mesurées par microsonde électronique et montrent que la matière organique des UCAMMs est riche en azote. Les comparaisons des images isotopiques entre elles et avec les images obtenues par les autres techniques montrent la matière organique des micrométéorites ultracarbonées est constituée de différents composants. Le composant principal ne montre pas de corrélation entre les excès en D et ceux en 15N. Une fraction mineure de la surface analysée montre des excès corrélés en D et en 15N, sans que la composition élémentaire ni la structure de cette composante ne diffèrent significativement du reste de la particule. Enfin, une seconde composante mineure présentant des enrichissements modérés en D et des rapports 15N/14N inférieurs à la valeur de l’atmosphère terrestre. L’ensemble des données peut être expliqué en supposant que les micrométéorites ultracarbonées proviennent de la surface d’objets glacés transneptuniens. Les caractéristiques élémentaires et isotopiques observées dans la matière organique des UCAMMs pourraient résulter du mélange de différentes strates du corps parent ayant subi une irradiation par le rayonnement cosmique galactique à grandes distances héliocentriques. / This thesis covers the isotopic analysis of carbon-rich interplanetary dust (ultracarbonaceous micrometeorites), in order to better understand the isotopic fractionation process of light elements (hydrogen and nitrogen) observed in the organic phases of primitive extraterrestrial matter. It is possible, within a collection of micrometeorites coming from the central regions of the Antarctic continent, to identify ultra-carbonaceous micrometeorites (UCAMMs – for Ultra-Carbonaceous Antarctic MicroMeteorites) which contain about ten times more carbon than the primitive meteorites. These particles are extremely rare and open the possibility to study in laboratory cometary particles of large sizes (100-200 microns). This thesis focuses on the isotopic analyses of UCAMMs, in order to understand the isotopic fractionation processes of light elements (hydrogen and nitrogen) observed in the organic matter of the primitive solar system. Mineralogical, chemical and structural analyses on two fragments of ultra-carbonaceous micrometeorites were performed in the framework of collaborations using techniques of scanning electron microscopy, electron microprobe, infrared microspectroscopy (SOLEIL synchrotron). The main work of this thesis concerns the isotopic analysis of two UCAMMs by Secondary Ion Mass Spectrometry (SIMS) using the NanoSIMS ion microprobe. The instrumental developments performed in collaboration between the CSNSM and the Curie Institute teams allow to resolve molecular interferences with a mass resolving power higher than 20 000 retaining a sensibility compatible with the measurements considered here. So, it has been possible to measure for the first time the hydrogen isotopic composition with the polyatomic ions 12C2D- and 12C2H- and to compare its spatial distribution with that of the nitrogen (12C15N-/12C14N-) obtained on the same surface with the same magnetic field. A protocol for producing a series of standard samples was developed from polymers isotopically enriched in deuterium in order to determine the instrumental fractionation of the NanoSIMS showing the possibility to perform precise measurements of the hydrogen isotopic composition in the organic matter with polyatomic ions (CD-/CH- and C2D-/C2H- ratios). The isotopic maps at high spatial resolution (200 nm) in C2D/C2H and C15N/C14N show a very heterogeneous distribution in deuterium with extreme values going up to 20 times the terrestrial ocean value, whereas the 15N/14N ratios remain globally close (within 20%) to the terrestrial atmosphere value. Measurements of N/C ratios in ion imaging performed at the NanoSIMS confirm the values measured by electron microprobe and show that the organic matter of UCAMMs is rich in nitrogen. Comparisons between isotopic images with each other and with the images obtained by the other techniques show that the organic matter of ultracarbonaceous micrometeorites is constituted of different components. The main component doesn’t exhibit a correlation between the D and 15N excesses. A minor component of the analyzed surface exhibits correlated excesses in D and in 15N, without neither the elemental or structural composition of this component significantly differs from the rest of the grain. Finally, a minor component showing moderate enrichments in D and 15N/14N ratios lower than the terrestrial atmosphere value could have been identified.All the data can be explained assuming that the ultracarbonaceous micrometeorites come from the surface of transneptunian icy objects. The elemental and isotopic characteristics observed in the organic matter of UCAMMs might result from the mixing of different strata of the parent body having undergone irradiation by the galactic cosmic radiation at large heliocentric distances.