Master of Science / Department of Biological and Agricultural Engineering / Donghai Wang / Biomass torrefaction is an important preprocessing step in improving biomass quality, specifically in terms of physical properties and chemical composition. The objective of this research was to study effects of torrefaction as a pretreatment method on chemical and elemental compositions and thermal properties of Conservation Reserve Program (CRP) biomass. Most CRP grasslands are a mixture of native grasses, and in the state of Kansas, species including indiangrass, big bluestem, little bluestem, sideoats grama, and switchgrass comprise a majority of CRP grounds. Pure forms of big bluestem biomass were analyzed and compared with a mixture of the species that make up CRP lands. Two strategies for torrefaction were tested: one with a pre-dry step and one without. After torrefaction, big bluestem and CRP biomass showed an increase in energy density, making the biomass more attractive as a biofuel source than raw biomass. Big bluestem also showed slightly higher calorific values than that of CRP biomass. The torrefaction process had a significant effect on chemical composition and elemental composition of the biomass. Carbon content increased and oxygen content decreased as torrefaction temperature increased. Glucan and xylose decreased and lignin increased as torrefaction temperature increased. Pre-drying biomass before torrefaction is beneficial to torrefaction of biomass with high moisture content because moisture removal leads to less dry matter loss while maintaining the same calorific value.

No contexto mundial atual, a busca de fontes de energia renováveis e menos poluentes que o petróleo tornou-se inevitável. O uso da biomassa como fonte de energia é extremamente importante, devido principalmente ao seu caráter renovável e a sua abundância. Os resíduos florestais são cada vez mais preconizados como uma importante fonte de biomassa. Isto se deve a sua abundância, facilidade de aprovisionamento e baixo custo. Podemos citar, como exemplo, os resíduos gerados durante a colheita florestal (cascas, folhas, galhos, ponteiros, entre outros) e durante o processamento mecânico da madeira (costaneiras, aparas, pó de serra, entre outros). O uso deste tipo de material para fins energéticos vem crescendo, porém, há um grande espaço para melhorias a serem implementadas nesse campo, envolvendo o melhor conhecimento de suas características e o potencial de aplicação de processos para sua conversão em produtos mais otimizados em relação aos seus valores energéticos. Diante desse quadro, e em se considerando a madeira, surge a oportunidade para adoção de processos de tratamento térmico, para os quais já existem referências que indicam a ocorrência de mudanças nas características desse material, o que conduz à previsão de se poder obter resultados positivos em relação ao que se exige para usos energéticos. Além do tradicional e amplamente usado processo de secagem, constatase, no campo do tratamento térmico, o crescimento do interesse pela aplicação da chamada torrefação e da termorretificação, compreendendo faixas de temperatura entre 150 e 300 °C. Neste contexto, resíduos da colheita florestal de eucalipto e pinus foram submetidos a tratamento térmico conduzido em estufa elétrica laboratorial, numa faixa de temperatura entre 140 e 300 °C. O objetivo foi estudar as alterações que o tratamento pudesse proporcionar às características do material, no sentido de se potencializar ainda mais o seu uso para fins energéticos, mediante a avaliação da densidade a granel do material, tamanho das partículas dos resíduos, poder calorífico superior, índice de combustão, análise imediata, resistência à moagem (redução granulométrica) e avaliação de imagens microscópicas. Os resultados indicaram, para ambas as espécies, que o aquecimento exerceu influência significativa nos rendimentos mássicos e nas características dos ensaios acima citados, com alteração dos valores com a elevação da temperatura, exceto para o teor de cinzas do eucalipto. A influência exercida pelo tratamento térmico foi mais evidente a partir de 220 °C, sendo isto mais fortemente observado à temperatura de 300 °C, com a constatação da maior fragmentação dos materiais tratados em comparação ao material testemunha. Além do aumento da friabilidade dos materiais estudados, constatado pelo ensaio de resistência à moagem, onde houve um relevante aumento da quantidade de material de baixa granulometria (menor que 4 mm), os mesmos apresentaram um maior ganho energético (maior poder calorífico) levando-se em conta a testemunha, principalmente a 300 °C, com índices de combustão elevados para os resíduos de eucalipto e pinus. / In the current worldwide context, the search for renewable energy sources and less polluting fuels than petroleum has become unavoidable. The use of biomass energy as source of energy is extremely important, especially due to its renewable character and abundance. The forest residues have been increasingly recommended as an important source of biomass. This is due to its abundance, facility of provision and low cost. We can cite examples such as the residues generated during the forest harvest (bark, leaves, branches, stem tips, among others) and during the mechanical processing of wood (slabs, chips, sawdust, among others). The use of this kind of material for energetic purposes has been increasing, however, there is room for benefits to be implemented in this field, involving a deeper knowledge on its characteristics and the potential for the application of processes to its conversion into more optimized products in relation to its energy values. In this scenario, and considering the wood, there comes the opportunity to the adoption of thermal treatment processes, to which there are already references that indicate the occurrence of changes in the characteristics of this material, which leads to the prediction of the possibility to obtain positive results in relation to what is demanded for energetic uses. Besides the traditional and widely used process of drying, it is observed, in the field of thermal treatment, the increase in the interest for the application of the so-called torrefaction and thermal rectification, comprising zones of temperature between 150 and 300 °C. In this context, residues of eucalyptus and pine forest harvest were submitted to a thermal treatment conducted in an electric laboratory oven, at temperatures between 140 and 300 °C. The goal was to study the alterations that the treatment might provide to the characteristics of the material, aiming at empowering its use to energetic purposes, through the density evaluation of a sample of the material, the size of residue particles, gross calorific value, combustion index, immediate analysis, resistance to grinding (particle size reduction) and the evaluation of microscopic images. The results indicated, for both species, that the heating caused a significant influence on the gravimetric yields and on the characteristics of the experiments cited above with changes in the values with the increase of the temperature, except for the ash content of eucalyptus. The effect of the thermal treatment was more evident from 220 °C, which is more strongly observed at the temperature of 300 °C, with a larger fragmentation of the treated materials in comparison to the control material. Besides the increase in the friability of the studied materials, found in the experiment of resistance to grinding, in which there was a relevant increase in the amount of low granulometry material (smaller than 4 mm), they presented a higher energetic gain (more calorific value) considering the witness, mainly at 300 °C, with high combustion indexes for the eucalyptus and pine residues.

No contexto mundial atual, a busca de fontes de energia renováveis e menos poluentes que o petróleo tornou-se inevitável. O uso da biomassa como fonte de energia é extremamente importante, devido principalmente ao seu caráter renovável e a sua abundância. Os resíduos florestais são cada vez mais preconizados como uma importante fonte de biomassa. Isto se deve a sua abundância, facilidade de aprovisionamento e baixo custo. Podemos citar, como exemplo, os resíduos gerados durante a colheita florestal (cascas, folhas, galhos, ponteiros, entre outros) e durante o processamento mecânico da madeira (costaneiras, aparas, pó de serra, entre outros). O uso deste tipo de material para fins energéticos vem crescendo, porém, há um grande espaço para melhorias a serem implementadas nesse campo, envolvendo o melhor conhecimento de suas características e o potencial de aplicação de processos para sua conversão em produtos mais otimizados em relação aos seus valores energéticos. Diante desse quadro, e em se considerando a madeira, surge a oportunidade para adoção de processos de tratamento térmico, para os quais já existem referências que indicam a ocorrência de mudanças nas características desse material, o que conduz à previsão de se poder obter resultados positivos em relação ao que se exige para usos energéticos. Além do tradicional e amplamente usado processo de secagem, constatase, no campo do tratamento térmico, o crescimento do interesse pela aplicação da chamada torrefação e da termorretificação, compreendendo faixas de temperatura entre 150 e 300 °C. Neste contexto, resíduos da colheita florestal de eucalipto e pinus foram submetidos a tratamento térmico conduzido em estufa elétrica laboratorial, numa faixa de temperatura entre 140 e 300 °C. O objetivo foi estudar as alterações que o tratamento pudesse proporcionar às características do material, no sentido de se potencializar ainda mais o seu uso para fins energéticos, mediante a avaliação da densidade a granel do material, tamanho das partículas dos resíduos, poder calorífico superior, índice de combustão, análise imediata, resistência à moagem (redução granulométrica) e avaliação de imagens microscópicas. Os resultados indicaram, para ambas as espécies, que o aquecimento exerceu influência significativa nos rendimentos mássicos e nas características dos ensaios acima citados, com alteração dos valores com a elevação da temperatura, exceto para o teor de cinzas do eucalipto. A influência exercida pelo tratamento térmico foi mais evidente a partir de 220 °C, sendo isto mais fortemente observado à temperatura de 300 °C, com a constatação da maior fragmentação dos materiais tratados em comparação ao material testemunha. Além do aumento da friabilidade dos materiais estudados, constatado pelo ensaio de resistência à moagem, onde houve um relevante aumento da quantidade de material de baixa granulometria (menor que 4 mm), os mesmos apresentaram um maior ganho energético (maior poder calorífico) levando-se em conta a testemunha, principalmente a 300 °C, com índices de combustão elevados para os resíduos de eucalipto e pinus. / In the current worldwide context, the search for renewable energy sources and less polluting fuels than petroleum has become unavoidable. The use of biomass energy as source of energy is extremely important, especially due to its renewable character and abundance. The forest residues have been increasingly recommended as an important source of biomass. This is due to its abundance, facility of provision and low cost. We can cite examples such as the residues generated during the forest harvest (bark, leaves, branches, stem tips, among others) and during the mechanical processing of wood (slabs, chips, sawdust, among others). The use of this kind of material for energetic purposes has been increasing, however, there is room for benefits to be implemented in this field, involving a deeper knowledge on its characteristics and the potential for the application of processes to its conversion into more optimized products in relation to its energy values. In this scenario, and considering the wood, there comes the opportunity to the adoption of thermal treatment processes, to which there are already references that indicate the occurrence of changes in the characteristics of this material, which leads to the prediction of the possibility to obtain positive results in relation to what is demanded for energetic uses. Besides the traditional and widely used process of drying, it is observed, in the field of thermal treatment, the increase in the interest for the application of the so-called torrefaction and thermal rectification, comprising zones of temperature between 150 and 300 °C. In this context, residues of eucalyptus and pine forest harvest were submitted to a thermal treatment conducted in an electric laboratory oven, at temperatures between 140 and 300 °C. The goal was to study the alterations that the treatment might provide to the characteristics of the material, aiming at empowering its use to energetic purposes, through the density evaluation of a sample of the material, the size of residue particles, gross calorific value, combustion index, immediate analysis, resistance to grinding (particle size reduction) and the evaluation of microscopic images. The results indicated, for both species, that the heating caused a significant influence on the gravimetric yields and on the characteristics of the experiments cited above with changes in the values with the increase of the temperature, except for the ash content of eucalyptus. The effect of the thermal treatment was more evident from 220 °C, which is more strongly observed at the temperature of 300 °C, with a larger fragmentation of the treated materials in comparison to the control material. Besides the increase in the friability of the studied materials, found in the experiment of resistance to grinding, in which there was a relevant increase in the amount of low granulometry material (smaller than 4 mm), they presented a higher energetic gain (more calorific value) considering the witness, mainly at 300 °C, with high combustion indexes for the eucalyptus and pine residues.

The greatest political, scientific, and engineering challenge of the 21st century is finding a viable solution to limit anthropogenic greenhouse gas emissions (CO2) to curb the effects of global climate change. All sectors of society need to contribute to alleviate this problem, but industrial operations must play a significant leadership role. Some of these industries include: metallurgy, cement, power, agriculture and forestry. In particular, the iron/steel, cement, and power generation industries use coal on account of its high energy density among solid fuels. Coal combustion yields 720 tonne CO2/GWh, and produces fine particulates, sulphur and nitrous oxides, along with excess CO2 contributing to climate change. In comparison, biomass (such as agricultural and forestry residues) has a solid fuel rating of 25-100 tonne CO2/GWh; therefore, biomass fuels are considered more sustainable since the living biomass consumed CO2 in the early part of its life cycle. However, biomass has significant industrial shortcomings for its use as fuel at large scale, including low energy content, density, and hydrophobicity relative to coal. In short, biomass fuels cannot be substituted without major infrastructure changes which add economic penalties that industry is currently unwilling to absorb. Biomass upgrading routes were considered in this thesis. These include densification, torrefaction, and integrated torrefaction and densification (ITD). The first half of the methodology involved converting woody biomass (willow residue and poplar bark), agricultural residue (switchgrass plants), and pulp mill waste via a single pellet/briquette press at different densification temperatures and pressures. The second half of the methodology involved product characterization of each batch of pellets and briquettes. In this work, pellets and briquettes were tested for physical characteristics (density and durability), chemical differences (energy content and hydrophobicity), and transport phenomena characteristics (drying profiles). First, results showed that extrusion of torrefied biomass at 300°C with an estimated pressure of 10 MPa creates partially formed pellets from agricultural residues. Using the concept of ITD (temperature range 220-325°C and pressure range 40 and 215 MPa), the density was found to be 1000-1250 kg/m3 for pellets and briquettes. The degree of compression from the loose biomass was on the order of 3-10 which corresponds with theoretical expectations. Material density increased with increasing pressure. The solid yield of pellets and briquettes decreased with increasing temperature, and results aligned with micro-scale thermogravimetric analysis. The larger ITD briquettes (produced at T = 325°C, P = 40 MPa) were evaluated for calorific value and found to fall in the lignite classification (O/C < 0.4 and H/C < 1.2) on a van Krevelen diagram. The resulting ITD pellets and briquettes were found to have a durability similar to commercial materials (durability > 97%), and to be more hydrophobic (8 wt% moisture absorption compared to 35 wt%). The drying time of ITD materials was faster than commercial torrefied briquettes, with an effective diffusivity of 1.5×10-6 m2/s compared to 7.3×10-9 m2/s likely because of a smaller pore volume in ITD briquettes. Further pilot scale studies would help improve the ITD methodology and make the process more appealing for the replacement of coal fuels.

La torréfaction est un traitement thermique opéré entre 200 et 300 °C en atmosphère inerte améliorant certaines propriétés de la biomasse, afin d’utiliser celle-ci comme biocombustible. Nos travaux portent spécifiquement sur la caractérisation des espèces condensables produites en torréfaction, aux échelles laboratoire et pilote. En laboratoire, des échantillons de pin, frêne, miscanthus et paille de blé ont été torréfiés à 250, 280 et 300 °C en réacteur à lit fixe. Les espèces condensables ont ensuite été analysées par GC-MS, GC-GC et HPLC-MS. Cette analyse a permis d’identifier une centaine d’espèces, dont une vingtaine, quantifiée, représente 77 % des condensables. À l’échelle pilote, un réacteur continu a été conçu, amélioré et caractérisé pour torréfier quelques kg.h-1 de biomasse. Un système de récupération multi-étagée des condensables a été développé. Des essais de torréfaction ont montré que les fractions condensées présentent des compositions chimiques différentes. / Orrefaction is mild thermal treatment carried out between 200 and 300 °C, in an inert atmosphere, improving properties of biomass, in order to use it as a biocombustible. This study focuses on the characterisation of the condensable species released during torrefaction, at laboratory and pilot scale. In the laboratory, some samples of pine, ash wood, miscanthus and wheat straw were torrefied at 250, 280 and 300 °C in a fixed bed reactor. The condensable species were analysed by GC-MS, GC-GC and HPLC-MS. Around a hundred of species were identified, including around twenty were quantified and represented 77 % of the condensable species. At pilot scale, a continuous reactor was designed, improved and characterised to treat several kg.h-1 of biomass. A multi-step recovery system for the condensable species was developped. Torrefaction experiments showed that the condensed fractions had different chemical compositions

Le calebassier (Crescentia alata) ou jicaro, est un arbre très important dans les systèmes agropastoraux des régions tropicales sèches d'Amérique. Ses fruits contiennent de nombreuses graines consommées traditionnellement, mais malgré son importance, peu d’informations existent sur ses propriétés nutritionnelles et son potentiel industriel.Dans un premier temps les caractéristiques physico-chimiques des graines, des cotylédons ainsi que des coques ont été analysées. Le cotylédon résulte contenir en moyenne 43% de protéines et 38 % de lipide (b.s.), ce qui est comparable à la plupart des graines d’oléagineux. La graine ne contient pas d’inhibiteur de trypsine, peu de phytates et pratiquement aucun sucre non digestible. Une analyse protéomique a révélé que les protéines sont principalement de faible poids moléculaire (~10 kDa), plutôt de type albumine 2S contenant comme le soja jusqu’à 16 % d’acides aminées essentiels. Parmi les lipides, 77.6 % sont des acides gras insaturés, en particulier l'acide oléique.S’agissant d’une graine consommée traditionnellement après torréfaction, cette opération unitaire a été étudié. Pour la première fois a été identifié par chromatographie en phase gazeuse olfactométrie (GC-O) un composé d’arôme caractéristique de la graine, l’éthyl-2-méthyl-butyrate dont la teneur augmente au cours de la torréfaction. Néanmoins, d’autres composés d’arôme tels que les pyrazines et certains aldéhydes contribuent aussi aux notes aromatiques spécifiques et agréables qui se révèlent après torréfaction. Cette opération thermique induit des changements physiques et micro-structurales dont la coalescence des globules gras observés par microscopie à balayage et le gonflement (puffing) qui est à l´origine de l’ouverture de la coque. Ce dernier changement a été exploité pour le décorticage de la graine afin de libérer le cotylédon blanc. Cette opération a été optimisée en fonction de la couleur et le nombre de graines ouvertes avec un modelage cinétique, obtenant un taux d’ouverture de plus de 90% avec une perte de luminance de moins de 10%. Après la torréfaction, un traitement de ré-humidification a été effectué pour durcir le cotylédon et obtenir une meilleure efficacité de décorticage.Les cotylédons ainsi libérés peuvent utilisés pour la fabrication d’un lait végétal qui présente des caractéristiques physico-chimiques, sensorielles et nutritionnelles supérieures à de nombreux laits végétaux présents sur le marché. Une analyse préliminaire a montré que le lait contient plus de 6% de lipides et 4% de protéines et maintient le couleur blanc des cotylédons et l’arôme caractéristique du jicaro. Des études cliniques ont aussi révélé que le lait obtenu a un indice glycémique bas (11). Cela vient confirmer son potentiel comme alternative bon pour la santé, s’agissant d’un lait sans lactose, sans facteurs anti-nutritionnels et avec un indice glycémique bas. / The calabash tree (Crescentia alata) or jicaro is a very important tree in the agro-pastoral systems of the dry tropical regions of America. Its fruits contain many seeds that have traditionally been consumed. However, despite its importance, little information exists on its nutritional properties and its industrial potential.In the first part of this work, the physicochemical characteristics of seeds, cotyledons and coats were analyzed. The cotyledon contains in average 43% protein and 38% lipid (d.b.), which is comparable to most oleaginous seeds. The seed contains no trypsin inhibitors, few phytates and almost no indigestible sugar. A proteomic analysis revealed that proteins are predominantly of low molecular weight (~ 10 kDa) mainly of albumin type 2S, comprising as soybeans up to 16% of essential amino acids. Among lipids, 77.6% are unsaturated fatty acids, mainly oleic acid.As it is a seed traditionally consumed after roasting, this unit operation was studied. For the first time, a volatile compound characteristic of its aroma, and whose content increases as a result of roasting, the ethyl-2-methylbutyrate, has been identified by gas chromatography-olfactometry (GC-O). Yet, other aroma compounds such as pyrazines and certain aldehydes also contribute to the specific and pleasant aromatic notes which are found after roasting. This thermal operation induces physical and microstructural changes, including the coalescence of fat globules, which was observed by scanning microscopy, and puffing which is at the origin of the opening of the seed coat.This last change has been exploited for the dehulling of the seed in order to isolate the white cotyledon. This operation was optimized regarding the color and the number of opened seeds with a kinetic modeling, obtaining an opening rate of more than 90% with a loss of luminance of less than 10%. After roasting, a tempering treatment was carried out to harden the cotyledon and obtain better dehulling efficiency.The isolated cotyledons can be used for the manufacture of a vegetable milk which has physicochemical, sensory and nutritional characteristics superior to many vegetable milks present on the market. A preliminary analysis showed that the milk contains more than 6% lipids and 4% protein and maintains the white color of the cotyledons and the characteristic aroma of jicaro. Clinical studies have also revealed that the obtained milk has a low glycemic index (11). This confirms its potential as a healthy alternative for a lactose-free milk with no anti-nutritional factors and a low glycemic index.

La torréfaction est un procédé thermochimique qui, appliqué à la biomasse, permet d'améliorer les propriétés de ce matériau en tant que vecteur énergétique. Il s'opère entre 250 et 300°C sous atmosphère inerte. Dans le contexte énergétique actuel, l'augmentation des volumes de matières torréfiées produites, transportées et stockées est annoncée pour la décennie à venir. Ce développement à l'échelle industrielle soulève la problématique de l'auto-échauffement et des risques qui lui sont associés. Dans ce travail, une approche multi-échelles a été mise en oeuvre pour étudier le comportement du bois torréfié en présence d'oxygène. Des expériences ont été réalisées à l'échelle du milligramme, à celle d'une sphère de bois torréfié et à celle d'un lit de plaquettes de bois torréfié. Les réactions et l'auto-échauffement généré à l'échelle de la sphère ont été modélisés. Les résultats du modèle présentent une bonne adéquation avec les résultats expérimentaux. Quelle que soit l'échelle considérée, il a été montré que le bois sévèrement torréfié était plus sensible à l'auto-échauffement et à l'auto-combustion que le bois doucement torréfié. Il a également été confirmé que le suivi des gaz émis pourrait être un bon indicateur de la présence d'un auto-échauffement dans un lit de biomasse torréfiée. / Torrefaction is a thermochemical process which, applied to biomass, increases the fuel properties of this material. It operates between 250 and 300°C in an atmosphere depleted of oxygen. Considering the actual energetic context, the large scale development of the torrefied market is expected to the decade to come. This scale-up rises self-heating issue and its associated risks. In this work, a multiscale approach has been used to study the torrefied wood behavior when it gets into contact with oxygen The reactions have been studied at the milligram scale, self-heating has been generated for a unique torrefied wood sphere and self-heating at the reactor scale has been studied to better represent industrial conditions. Experiences have been done at all of these scales. Moreover, a modeled has been proposed to describe the reactions and the self-heating generated at the particle scale. Numerical results show good agreement with experiments. Furthermore, whatever the scale considered, it has been shown that the severely torrefied wood is more prone to self-heating than the mildly torrefied wood. It was also confirmed that continuous emitted gases monitoring could be a good indicator to detect and thus prevent a self-heating of a torrefied biomass bed.

Considérée comme une forme douce de la pyrolyse, la torréfaction apparaît comme une alternative au traitement thermique de la biomasse où elle est chauffée à des températures de 200-300°C en absence partielle ou totale d'oxygène pour produire un combustible solide plus hydrophobe, homogène et de meilleure qualité par rapport à la matière première. Plusieurs technologies de torréfaction ont déjà été développées et mises en œuvre dans l'industrie. Le présent travail a pour objectif principal d'approfondir les connaissances dans le processus de thermo-dégradation de la biomasse pendant la torréfaction. Pour cela, un appareil expérimental innovant a été développé visant à améliorer le traitement thermique du bois en couplant un champ acoustique au facteur température. L'hypothèse est qu'un champ acoustique dans un réacteur modifie le champ de pression et par conséquent la vitesse des particules autour de l'échantillon en modifiant l'interaction entre l'environnement gazeux et les volatiles à la surface du bois, accélérant son processus de dégradation. Avec cet objectif, un système acoustique a été mis en place dans un réacteur. Une caractérisation et une cartographie du comportement acoustique envisageant la mesure du débit acoustique et de son intensité ont été réalisées. Les expériences physiques et chimiques de la torréfaction ont été effectuées pour deux températures de traitement avec et sans influence de l'acoustique, fournissant le rendement massique, les courbes de température et les propriétés chimiques du matériau torrifié. Concomitamment, un modèle numérique de la cinétique et de la composition élémentaire a été établi pour la prédiction du rendement en masse et de la composition en termes de carbone, d'hydrogène et d'oxygène au cours de la dégradation. Les résultats expérimentaux de la torréfaction, ainsi que l'analyse chimique et la pyrolyse du produit final ont fourni des preuves telles que: réduction du temps de séjour, augmentation de la température interne de l'échantillon et pouvoir calorifique supérieur pour les échantillons traités sous l'influence de l'acoustique. Une dernière comparaison entre les résultats expérimentaux et numériques a permis d'évaluer la précision du modèle pour le traitement de torréfaction et l'influence de l'acoustique sur la cinétique de dégradation / Considered a mild form of pyrolysis, torrefaction appears as an alternative thermal treatment where the biomass is heated at temperatures between 200-300°C in partial or total absence of oxygen to produce a more hydrophobic, homogeneous and higher calorific solid fuel when compared to the raw material. Several torrefaction technologies have already been developed and implemented in the industry. The present work has as main objective to deepen the knowledge in the biomass thermo-degradation process during torrefaction. For this, an innovative experimental apparatus was developed aiming to improve the wood heat treatment by coupling an acoustic field to the temperature parameter. The assumption is that an acoustic field within a reactor modifies the pressure field and consequently the velocity of the particles around the sample by altering the interaction between the gaseous environment and the released volatile around the wood surface, accelerating its degradation process. With this objective, an acoustic system was implemented in a reactor. A characterization and mapping of the acoustic behavior contemplating the measurement of acoustic flux rate and its intensity was performed. The physical and chemical torrefaction experiments were performed for two treatment temperatures with and without influence of the acoustic, providing the mass yield evolution, the temperature curves and the chemical properties of the torrefied material. Concomitantly, a numerical model of kinetics and elemental composition was established for the mass yield and the composition prediction in terms of carbon hydrogen and oxygen during the degradation. The torrefaction experimental results, as well as the chemical analysis and pyrolysis of the final product, provided evidence such as: reduction of residence time, increase of the samples internal temperature during treatment and a greater calorific power for the samples treated under acoustic influence. A final comparison between experimental and simulation results allowed the evaluation of the torrefaction numerical model and the influence of the acoustics on the degradation kinetics / Considerada uma forma suave de pirólise, a torrefação aparece como alternativa de tratamento térmico da biomassa, onde essa é aquecida a temperaturas de 200 - 300 ° C em ausência parcial ou total de oxigênio visando produzir um combustível sólido mais hidrofóbico, homogêneo e com maior teor de carbono quando comparado à matéria-prima. Várias tecnologias de torrefação já foram desenvolvidas e implementadas na indústria. O presente trabalho tem como objetivo principal aprofundar o conhecimento no processo de termo-degradação da biomassa durante a torrefação. Para isso um inovador aparato experimental foi desenvolvido visando aprimorar o tratamento térmico da madeira acoplando um campo acústico ao fator temperatura. O pressuposto é que um campo acústico dentro de um reator modifica o campo de pressão e, consequentemente, a velocidade das partículas ao redor da amostra alterando a interação entre o ambiente gasoso e os voláteis na superfície da madeira, acelerando o seu processo de degradação. Com este objetivo, um sistema acústico foi implementado em um reator. Uma caracterização e mapeamento do comportamento acústico contemplando a aferição da taxa de fluxo acústica e da sua intensidade foi executada. Os experimentos físicos e químicos da torrefação foram realizados para duas temperaturas de tratamento com e sem influência da acústica, fornecendo o rendimento mássico, as curvas de temperaturas e as propriedades químicas do material torrificado. Concomitantemente, foi estabelecido um modelo numérico da cinética e da composição elementar para a predição do rendimento mássico e da composição em termos de carbono hidrogênio e oxigênio durante a degradação. Os resultados experimentais da torrefação, bem como a análise química e pirólise do produto final, forneceram evidências como: redução do tempo de residência, aumento da temperatura interna da amostra e um maior poder calorífico para as amostras tratadas sobre influência da acústica. Uma comparação final entre resultados experimentais e numéricos permitiram a avaliação da precisão do modelo para o tratamento de torrefação e a influência da acústica na cinética de degradação

Ce travail de thèse porte sur les conditions économiques nécessaires à l’émergence d’une filière bioénergie par l’intermédiaire de la biomasse torréfiée. Cette recherche a été menée suivant deux approches complémentaires, l’une normative, portant sur l’étude du comportement des acteurs de cette filière, et l’autre positive, portant sur les conditions d’existence du marché de la biomasse torréfiée. Nous étudions les valeurs que l’offreur et le demandeur associent à la décision économique d’investissement dans de nouvelles technologies énergétiques et d’achat de la biomasse. Nous avons mesuré la demande des secteurs énergétiques afin de la confronter à l’offre et en déduire un prix d’échange en fonction de la flexibilité des industriels dans leur procédé de production et des contraintes environnementales auxquelles ils sont soumis. La thèse est composée de trois articles (chapitres 2, 3 et 4 en anglais) et de deux études confidentielles (chapitres 1 et 5 en français). Le chapitre 1 présente une enquête de terrain qualitative menée au niveau national, identifiant les demandeurs potentiels et déterminant les facteurs technico-économiques qui peuvent l’influencer. Le chapitre 2 étudie la décision d’investissement et de production d’un agent averse à l’ambiguïté faisant face à des incertitudes de marché telles que le nombre d’acteurs et l’effet de la concurrence des autres énergies fossiles sur le prix de vente de sa biomasse. Nous observons des effets asymétriques des deux incertitudes sur les montants optimaux de production et nous montrons théoriquement puis numériquement que l’aversion à l’ambiguïté tend à diminuer les niveaux optimaux d’investissement et de production. Le chapitre 3 présente le modèle que nous avons développé pour estimer la pénétration de la biomasse prétraitée dans le marché de la production d’électricité en fonction des politiques climatique et énergétiques modélisées. Nous en déduisons la fonction de demande en biomasse torréfiée. Dans le chapitre 4, nous développons un modèle en équilibre partiel d’offre provenant du secteur torréfaction et de demande en biomasse issue des secteurs électrique et raffinage pour estimer un prix d’équilibre d’échange de la biomasse torréfiée en fonction du prix du CO2 `a long terme. Enfin, cette approche positive est complétée par une étude logistique présentée dans le chapitre 5 afin de déterminer la stratégie d’approvisionnement et la taille optimale des unités de prétraitement implantées dans un bassin de production de biomasse. Le travail de recherche réalisé permet d’élaborer des recommandations destinées aux investisseurs et aux institutions en charge du développement des bioénergies. / This thesis focuses on the economic conditions required for the emergence of a bioenergy supply chain based on torrefied biomass. This research was conducted by using two complementary approaches: the normative one deals with the actors’ behavior in this sector and the positive one deals with the conditions necessary to trigger the torrefied biomass market in France. We study the supplier and demander behaviors regarding the investment in new energy technologies and the purchase of biomass. Then, the biomass demand per sector is modeled in order to compare it to the offer. We deduce an equilibrium selling price which depends on the flexibility of the industry in their production process and the environmental constraints under which they operate. This Ph.D. dissertation is composed of 3 articles (chapters 2, 3 and 4 in English) and 2 confidential studies (chapters 1 and 5 in French). Chapter 1 presents a survey driven at national level, to measure the potential demand and to determine the technical and economic factors influencing it. Chapter 2 analyzes the production and investment decisions of an ambiguity averse agent facing market uncertainties such as demand uncertainty (in terms of number of buyers) and competitive effect uncertainty (in terms of other energy resource). We apply our model on the bioenergy industries. We show that the investment decision of an agent depends on the effects of both the capital investment and the level of production on the cost and the uncertainty the agent is confronted with. Moreover, we find that ambiguity aversion tends to decrease the agent’s optimal levels of production and investment. Chapter 3 studies the penetration of green electricity production from biomass and its impacts on the future electricity generation mix for France incorporating different scenarios of emission allowance prices. The model is applied to the French power market under consideration of the neighboring countries and we determine the torrefied biomass demand function from our model. In chapter 4, we develop a partial equilibrium model of torrefied biomass supply and demand coming from the power sector and the refinery sector on the long term under CO2 price constraints. Our main results are the equilibrium selling prices of torrefied biomass and the break-even CO2 price which triggers the demand. A last chapter aims at studying the strategy of supply and the optimal size of pre-treatment units located in a pool of biomass production. The research carried out allows to propose recommendations for investors and institutions in charge of the development of bioenergies.

O processo de injeção pelas ventaneiras dos altos-fornos (Pulverized Coal Injection - PCI) é uma das tecnologias mais promissoras para a incorporação de biomassas termicamente tratadas na siderurgia e um dos meios de alcançar uma redução consistente nas emissões de CO2 no setor. O objetivo deste trabalho foi avaliar a combustibilidade e reatividade ao CO2 de biomassas de madeira e caroço de azeitona tratadas em laboratório desde temperaturas de torrefação (250°C) até de carbonização (450°C) e comparar com carvões típicos utilizados em PCI, correlacionando com as características ocorridas devido aos tratamentos térmicos. Além da caracterização química, as transformações devido aos tratamentos térmicos das biomassas foram avaliadas via testes de combustão em termobalança, técnicas de microscopia ótica e eletrônica, espectroscopia de infravermelho por transformada de Fourier (FTIR) e técnicas de adsorção para análise da porosidade. Testes de combustibilidade foram conduzidos em um forno de queda livre (Drop Tube Furnace - DTF) em atmosferas convencional (O2/N2) e de oxi-combustão (O2/CO2) e os chars resultantes destes testes foram caracterizados quanto à estrutura e à reatividade ao CO2 em termobalança. Além disso, foram feitos testes de reatividade ao CO2 de misturas de eucalipto termicamente tratado e carvões em termobalança. A torrefação manteve o alto teor de voláteis das biomassas, enquanto que as biomassas carbonizadas apresentaram teores de carbono e poder calorífico semelhantes aos dos carvões de mais alto rank, com as vantagens típicas de biomassas de manterem um baixo teor de cinzas e enxofre. No entanto, o elevado teor de álcalis e fósforo nas cinzas pode ser um fator limitante na composição de misturas para PCI. O tratamento térmico das biomassas levou a gradual decomposição dos componentes da madeira com uma progressiva homogeneização da estrutura celular, associada a um aumento de aromaticidade e porosidade. De uma maneira geral, quanto menor foi a temperatura de tratamento térmico das biomassas, maior foi o burnout obtido no DTF. Comparada à atmosfera convencional (O2/N2), a atmosfera de oxicombustão (O2/CO2) levou a maiores burnouts para os chars de todas as biomassas e carvões. As biomassas carbonizadas apresentaram burnouts mais elevados que o carvão de mais baixo rank e o caroço de azeitona carbonizado apresentou baixa conversão, equivalente a um carvão de alto rank. Os chars das biomassas torrefeitas apresentaram estruturas cenosféricas isotrópicas de elevada porosidade nas paredes enquanto que os chars das carbonizadas preservaram a morfologia apresentada nas amostras originais. Os chars das biomassas foram altamente porosos, com áreas superficiais de meso e microporos em média 15 e 5 vezes maior que os chars dos carvões, respectivamente. Com relação aos testes de reatividade ao CO2 em termobalança, em geral, a reatividade dos chars das biomassas torrefeitas foi maior do que a reatividade dos chars das biomassas carbonizadas e estes foram pelo menos 10 vezes mais reativos ao CO2 do que o chars do carvão de mais baixo rank. Além das maiores áreas superficiais, principalmente o ordenamento da estrutura carbonosa e a morfologia foram fundamentais nas diferenças de reatividade ao CO2 entre os chars das biomassas e dos carvões. As misturas do carvão de mais baixo rank com a biomassa carbonizada apresentaram os melhores resultados em termos de aditividade na reatividade ao CO2. / Pulverized Coal Injection (PCI) in the blast furnace tuyeres is a promising technology for incorporation of thermally-treated biomasses and it is a way to reduce CO2 emissions in ironmaking processes. The aim of this work was to evaluate combustibility and CO2 reactivity of laboratory torrefied (250°C) and carbonized (450°) olive stone and woody biomasses, comparing with typical PCI coals. The transformations produced in biomasses due to torrefaction and carbonization were evaluated by chemical analyses, combustion tests in thermobalance, Fourier Transform Infrared Spectroscopy (FTIR) and optical and electron microscopy and adsorption techniques. Combustion experiments were carried out in a Drop Tube Furnace (DTF) under conventional (O2/N2) and oxy-fuel (O2/CO2) atmospheres and the chars collected were characterized by its structure and CO2 reactivity in thermobalance. Reactivity tests were also conducted in thermobalance with blends of thermally-treated eucalyptus and coals. Torrefied samples maintained high contents of volatile matter, typical of raw biomasses, while carbonized biomasses showed carbon contents and high heating values similar to that of high rank coals, retaining low ash and sulfur contents. However, its high alkali and phosphorus contents could be a limiting factor to the use in blends for PCI. The thermal treatments of biomasses lead to a gradual decomposition of wood components and to a progressive homogenization of cell structure, associated to an increase in aromaticity and porosity. In general, the lower the thermal treatment temperature, the higher was the burnout in the DTF. Compared to conventional atmosphere, oxy-fuel combustion led to the highest burnouts for all biomass chars. The carbonized biomasses showed higher burnouts than the high-volatile coal and olive stone showed burnouts similar to a low-volatile coal. The chars from the torrefied biomasses showed isotropic cenospheric structures with high porosity within the walls and the chars from the carbonized biomasses preserved the morphology seen in original carbonized samples. The biomass chars presented highly porosity, with micro and mesoporosity in average, 5 and 15 times greater than the coal chars, respectively. In relation to the CO2 reactivity tests, in general, the torrefied biomass chars were more reactive than the carbonized biomass chars. However, due to its higher surface areas, structure arrangement and morphology, the carbonized biomass chars were at least 10 times more reactive than the high-volatile coal chars. The blends of high-volatile coal and carbonized eucalyptus showed good additivity in the CO2 reactivity tests in thermobalance.