Torrefaction and densification of biomass can provide an important piece in the puzzle of phasing out fossil fuels in favor of renewable alternatives. This new energy carrier shares many of the advantages with fossil coal in terms of energy density, hydrophobicity and burner feeding but is carbon neutral and renewable. It also lacks the challenges of many other renewable alternatives, especially irregular availability. A model was developed in Excel as sales support for BioEndev, one of the leading actors in the process of taking torrefaction to a commercial market, assessing the black pellet supply chain from feedstock to end user and comparing it to white pellets. Data was obtained from literature, industry and BioEndev. The model can be used for different parameters for price of feedstock, capital and operating expenditures, transport and handling costs and analyze 28 different cases. It also includes simplified calculations for energy input and greenhouse gas emissions. A case study for two different supply chains was performed with the model. One assessed a production facility in northern Sweden with distribution to a consumer in Denmark. The other a torrefaction plant in southeastern USA with distribution to a consumer in the Netherlands. The cost for delivering black and white pellets from Sweden to Denmark was found to be 33.0 €/MWh and 35.3 €/MWh respectively. For the case of delivering from USA to the Netherlands, the total supply chain cost was 27.6 €/MWh for white pellets and 24.7 €/MWh for black pellets. Suggestions for further work are to 1) develop the model outside this study’s limitations, for example by adding integration options for the torrefaction facility or by different end user configurations, and 2) expand the scope to also comparing black pellets to coal to see how big the gap is and which political incentives that could shrink this gap.

Nowadays, there is an increasing awareness on the importance of biomass waste as a renewable source of energy, materials and chemicals. In this context, the European project MOBILE FLIP aims at developing and demonstrating mobile conversion processes suitable with variousunderexploited agro- and forest based biomass resources in order to produce energy carriers, materials and chemicals. One of these processes is torrefaction, which consists in a mild thermal treatment, occurring typically between 200 and 300°C during a few tens of minutes in a defaultoxygen atmosphere. The solid product obtained has thermal and processing properties closer to coal, and thus is suitable as fuel for combustion or gasification. During torrefaction, condensable coproducts are released, that may also be source of “green” chemicals. It is therefore crucial to characterize them to optimize the torrefaction process and design industrial units. Up to now, only few works have been focused on characterizing and modelling both solid and condensable species during torrefaction versus operating conditions and feedstock type. Furthermore, these studies typically include a reduced number of biomasses. Cellulose, hemicellulose and lignin,which constitute biomass macromolecular composition, are determining properties to predict biomass behaviour during torrefaction. However, torrefaction tests on these constituents are rare and always based on commercial compounds, which were proved as little representative of the native biomass. The objective of this study is to analyse the influence of biomass characteristics, mainly represented by the macromolecular composition in cellulose, hemicellulose and lignin, on the global behaviour of biomass in torrefaction, both in terms of solid mass loss and of productionprofiles of the volatile species released, in function of the operating conditions.14 biomasses from the main biomass families (deciduouswood, coniferous wood, agricultural byproductsand herbaceous crops) were selected for this study. An optimized extraction procedure was proposed to recover cellulose, hemicellulose and lignin fractions from 5 reference biomasses. Experiments were performed on a thermogravimetric analyzer coupled to a gas chromatography mass spectrometer device through a heated storage loop system (TGA-GC/MS). Solid degradation kinetics and volatile release profiles were followed during torrefaction experiments combining non-isothermal (200 to 300°C at 3°C/min) and isothermal (300°C, 30 min) conditions, ensuring the chemical regime thanks to the appropriate operating conditions. The results obtained with the raw materials demonstrated that biomass macromolecular composition is a main factor influencing biomass behavior in torrefaction. Consequently, the heterogeneity of the resource results in a diverse behavior in torrefaction, particularly in the case of agricultural biomasses. The results with the extracted components evidenced their very different behavior compared to thecommercial compounds, particularly in the case of cellulose. This suggests that a limitation could be induced by the common use in literature of commercial components for torrefaction modelling. The impact on the characterization of macromolecular components was also shown to be prevailing in their behavior in torrefaction, especially in the case of hemicellulose sugar composition and cellulose crystallinity. Furthermore, differences in release kinetics of volatile species during torrefaction were observed, even for volatiles belonging to the same chemical family (acids, furans, ketones). Derived from these results, a torrefaction model based on the additive contribution of extracted cellulose, hemicelluloses and lignin to the global behavior of biomass in torrefaction was proposed, and this for the 5 representative biomasses.

This master thesis describes the co-firing concept, benefits and opportunities of pretreated biomass in pulverized coal boilers for industrial use. Burning fossil fuels, i.e. coal is under immense political pressure as European Union (EU) and other countries are trying to bring down the CO2 emission. Biomass combustion is already a proven technology and it plays a greater role in reducing CO2 emission. The main objective of this thesis is the brief study of computational fluid dynamics (CFD) modelling to examine the co-firing of greater amount of pretreated biomass and pulverized coal in a 200MWe pulverized coal boiler. Here, we exchange around 50 % of existing fuel in pulverized coal boiler with torrefied biomass. Torrefied biomass aids to increase the efficiency of existing coal boiler and cut down the CO2 emission. In this work, two cases of co-firing of pretreated biomass and coal have been investigated by CFD. Firstly, an experimental work was done in a laboratory scale to have few different types of torrefied biomass with different degrees of torrefaction. The devolatilization kinetics and char oxidation kinetics were also determined by experiments and other parameters have been calculated. One important aspect of this work has been to evaluate the performance of torrefaction based co-firing. Therefore, co-firing case has been compared to the 100 % coal feed case to understand the performance of torrefaction based co-firing. Furthermore, fluid flow, particles trajectories, heat transfer, and different emission behaviors have been studied. In addition, mechanisms of corrosion during co-firing have been studied and a guideline has been provided for corrosion model for analyzing the characteristics of alkali metals and their effects in co-firing coal boiler. The outcome from the CFD simulation indicated that boiler efficiency increases and the net CO2 emission reduced with increasing the biomass percentage in the co-firing system.

The steel industry is aiming to reduce CO2 emissions by different means; in the short-term, by replacing fossil coal with highly reactive carbonaceous material like bio-coal (pretreated biomass) and, in the longer term, by using hydrogen. The use of bio-coal as part of top charged briquettes also containing iron oxide has the potential to lower the thermal reserve zone temperature of the Blast furnace (BF) and, due to improved gas efficiency, thereby give a high replacement ratio to coke. In order to select a suitable bio-coal to be contained in agglomerates with iron oxide, the current study aims at investigating the devolatilization behavior and related kinetics of different types of bio-coals. In addition, the aim is to investigate the self-reduction behavior of bio-coal-containing iron ore composite under inert condition and simulated blast furnace thermal profile. In the BF the temperature of the top-charged material will increase rather quickly during the descent in the upper part. Ideally, all the carbon and hydrogen contained in the top-charged bio-coal should contribute to the reduction. The devolatilization of bio-coal is thus important to understand and to compare between different types of bio-coal. To explore the devolatilization behavior for different materials, a thermogravimetric analyzer equipped with a quadrupole mass spectrometer was used to monitor the weight loss and off-gases during non-isothermal tests for bio-coals having different contents of volatile matter. The samples were heated in an inert atmosphere up to 1200°C at three different heating rates: 5, 10 and 15°C/min. The thermogravimetric data were evaluated by using the Kissinger–Akahira–Sonuse (KAS) iso-conversational model and the activation energy was determined as a function of the conversion degree. Bio-coals with both low and high content of volatile matter can produce reducing gases that can contribute to the reduction of iron oxide in bio-agglomerates. Bio-coals containing a higher content of catalyzing components such as CaO and K2O will enhance the devolatilization and release of volatile matter at a lower temperature.  The self–reduction of composites was investigated by thermogravimetric analyses in argon atmosphere up to 1100°C and evolved gases were monitored by means of quadrupole mass spectroscopy. Composites with and without 10% bio-coal and sufficient coke breeze to keep the C/O molar ratio equal to one were mixed and Portland cement was used as a binder. To explore the effect of added bio-coals, interrupted vertical tube furnace tests were conducted in a nitrogen atmosphere at temperatures selected based on thermogravimetric results, using a similar thermal profile as for the thermogravimetric analyzer. The variation between fixed carbon, volatile matter contents and ash composition for different types of bio-coal influences the reduction of iron oxide. The results showed that the self-reduction proceeds more rapidly in the bio-coal-containing composite and that the volatile matter could have contributed to the reduction. The self-reduction of bio-coal-containing composites started at 500°C, while it started at 740°C with coke as the only carbon source. The hematite was successfully reduced to metallic iron at 850°C with bio-coal present as a reducing agent, but not until 1100°C when using coke. Use of bio-coal with high content of volatile matter but low content of catalyzing elements as potassium, sodium and calcium in bio-agglomerates for the BF can be recommended because it enhances the self-reduction of iron oxide, e.g., wustite was detected by XRD analysis in samples treated up to 680°C. Bio-coal with low content of volatile matter, low alkalis, low phosphorous and high content of fixed carbon will also be suitable to use in the BF.

In recent years, the consequences of global warming have increased the discussion about the climate impact caused by humans and the fossil emissions. Sweden has decided to reduce the negative climate impact with a zero vision for the fossil carbon dioxide emissions in year 2045. In order to achieve this, great efforts and changes are needed both in the inhabitants' way of living but primarily in the base industry. The major cause is the use of fossil coal, which generates fossil carbon dioxide in the steel industry in particular. The fossil coal is added to the blast furnace in the steel process in forms of coke and coal, which reduces the iron and emits heat. The quality of the coke is important as it functions reducing agent, provides a mechanical support to the bed and enables the gas flow up through the blast furnace and enables dissolution of carbon in hot metal. Also, coke supplies energy from exothermic reactions between carbon and carbon dioxide that takes part in the blast furnace and the energy are further used for the heating and melting of the cold iron pellets. Due to these factors, the blast furnace process is dependent on coke for its function, which means that the entire process must be replaced if the steel production should work without fossil coal. However, there are many studies that have been done on how to replace some of the fossil coal with bio-coal, which is produced from biomass. If some of the fossil coal could be replaced by some bio-coal, this would mean that fossil carbon dioxide emissions would decrease and lead to a reduced climate impact. The process would still generate carbon dioxide, but on the other hand, a cycle would be formed because when biomass is grown, carbon dioxide is taken up, e.g. by the trees grown for this purpose. However, bio-coal does not have the same properties as fossil coal, which in turn affects the quality of the coke. Bio-coke is more reactive and more porous than fossil coke. In order to be able to replace fossil coke with bio-coke, it is likely necessary to pre-treat the biocoal before it replaces part of the fossil coal in the coke production. Bio-coal contains ash that acts as an internal catalyst. One theory is that if it is possible to produce a bio-coal with ash-free carbon structure, it can be used in the production of coke without having such a great effect on the coke quality. In this project, the ash's impact on the properties of bio-coal in coke was studied. Previous studies have shown that leaching is an effective method for removing ash from bio-coal. It can be leached in three different ways, either with water, weak acid or acid. However, it has been found that acid leaching has a certain impact on the carbon structure itself. For this reason, two types of bio-coal, torrefied Grot (forest residue) and torrefied sawdust were selected, which were leached both with water but also with weak acid in order to achieve an ash-reduced carbon structure. The acid selected was acetic acid, as it has been tested for similar purposes in previous studies. The leaching efficiency was evaluated by analysing the leachate with ICP-OES after leaching. According to the result, a significant part of the ash had been leached out, but the leaching with weak acid was much more effective than water leaching. To ensure that the carbon structure was not altered, light-optical microscopy was made which showed that the structure was intact. However, it was not possible to determine whether the pore sizes were changed after leaching and it is therefore relevant to investigate this further. Moreover, the leached II bio-coal replaced 5% of the fossil coal in the coal mixture for coke making. In addition to this, coke was also made with only the ash from the two bio-coals to see what effect the ash has on the coke quality. The result that was obtained from the TGA showed that the ash had a low impact on the reactivity of the coke. However, the coal structure of the coke had a great impact on the reactivity behaviour. Keywords: Bio-coke, bio-coal, leaching, ash, coke quality, carbon structures, torrefied sawdust

Il existe aujourd’hui une prise de conscience croissante visant à considérer les résidus de biomasse comme source potentielle d’énergie, de matériaux et de produits chimiques. Dans ce contexte, le projet européen Mobile Flip vise à développer des unités mobiles de conversion de biomasse pour la valorisation de ressources agricoles et forestières non exploitées. L’une des technologies proposées est la torréfaction, traitement thermique doux entre 200 et 300°C pendantquelques minutes et en défaut d’oxygène. Le solide torréfié présente des propriétés proches de celles du charbon et convient à la combustion ou à la gazéification. En même temps, des matières volatiles sont relâchées, dont des espèces condensables potentiellement à haute valeur ajoutée en chimie. Il est donc crucial de caractériser le solide torréfié et les espèces volatiles afin d’optimiser le procédé jusqu’à l’échelle industrielle. Jusqu’à présent, peu de travaux ont simultanément cherché à caractériser et à modéliser le comportement du solide et des espèces volatiles produites en torréfaction en fonction des conditions opératoires et du type de biomasse. De plus, ces travaux portaient sur un nombre réduit de biomasses. La composition macromoléculaire de la biomasse en cellulose, hémicelluloses et lignine impacte de manière déterminante les produits de torréfaction. Cependant, les essais de torréfaction avec ces constituants sont peu nombreux et généralement réalisés avec des composants commerciaux peu représentatifs de la biomasse brute. L’objectif de ces travaux de thèse est d’étudier l’influence des caractéristiques de la biomasse, principalement représentée par sa composition en cellulose, hémicellulose et lignine, sur le comportement global de la biomasse en torréfaction, tant en termes de perte de masse du solide que de production d’espèces volatiles, en fonction des conditions opératoires. 14 représentants des principales familles de biomasse (bois feuillus, bois résineux, sous-produits agricoles et plantes herbacées) ont été sélectionnés pour cette étude. Une procédure d’extraction optimisée a été proposée pour obtenir des fractions de cellulose, hémicellulose et lignine de 5 biomasses de référence. Les données expérimentales ont été obtenues en utilisant une thermobalance couplée à une chromatographie gazeuse et une spectrométrie de masse via un système de boucles de stockage chauffées (ATG-GC/MS). La cinétique de dégradation du solide et les profils de formation des espèces volatiles ont été étudiés au cours des expériences de torréfaction incluant une partie non-isotherme (200 à 300°C, 3°C/min) suivie d’une partie isotherme (300°C, 30 min), dans des conditions expérimentales assurant le régime chimique. Les résultats obtenus avec les biomasses brutes montrent que la composition macromoléculaire de la biomasse est un facteur clé influant sur son comportement en torréfaction. Par conséquent, l’hétérogénéité de la ressource se traduit par une diversité de comportements en torréfaction, en particulier pour les biomasses agricoles. Il a été observé un comportement très différent pour les composants extraits comparés aux composants commerciaux, particulièrement dans le cas de la cellulose. Ceci montre que l’usage commun de composants commerciaux pour bâtir les modèles de torréfaction n’est pas pertinent. L'impact des caractéristiques des composants macromoléculaires sur le comportement en torréfaction a été aussi mis en évidence, particulièrement en ce qui concerne la composition en sucres des hémicelluloses et la cristallinité de la cellulose. En outre, des différences de profils de production des espèces volatiles ont été observées, même pour des composés de même nature chimique. A partir de ces résultats, un modèle de torréfaction basé sur la contribution additive de la cellulose, des hémicelluloses et de la lignine extraites est proposé pour décrire le comportement global de la biomasse en torréfaction, et ceci pour les 5 biomasses de référence. / Nowadays, there is an increasing awareness on the importance of biomass waste as a renewable source of energy, materials and chemicals. In this context, the European project MOBILE FLIP aims at developing and demonstrating mobile conversion processes suitable with variousunderexploited agro- and forest based biomass resources in order to produce energy carriers, materials and chemicals. One of these processes is torrefaction, which consists in a mild thermal treatment, occurring typically between 200 and 300°C during a few tens of minutes in a defaultoxygen atmosphere. The solid product obtained has thermal and processing properties closer to coal, and thus is suitable as fuel for combustion or gasification. During torrefaction, condensable coproducts are released, that may also be source of “green” chemicals. It is therefore crucial to characterize them to optimize the torrefaction process and design industrial units. Up to now, only few works have been focused on characterizing and modelling both solid and condensable species during torrefaction versus operating conditions and feedstock type. Furthermore, these studies typically include a reduced number of biomasses. Cellulose, hemicellulose and lignin,which constitute biomass macromolecular composition, are determining properties to predict biomass behaviour during torrefaction. However, torrefaction tests on these constituents are rare and always based on commercial compounds, which were proved as little representative of the native biomass. The objective of this study is to analyse the influence of biomass characteristics, mainly represented by the macromolecular composition in cellulose, hemicellulose and lignin, on the global behaviour of biomass in torrefaction, both in terms of solid mass loss and of productionprofiles of the volatile species released, in function of the operating conditions.14 biomasses from the main biomass families (deciduouswood, coniferous wood, agricultural byproductsand herbaceous crops) were selected for this study. An optimized extraction procedure was proposed to recover cellulose, hemicellulose and lignin fractions from 5 reference biomasses. Experiments were performed on a thermogravimetric analyzer coupled to a gas chromatography mass spectrometer device through a heated storage loop system (TGA-GC/MS). Solid degradation kinetics and volatile release profiles were followed during torrefaction experiments combining non-isothermal (200 to 300°C at 3°C/min) and isothermal (300°C, 30 min) conditions, ensuring the chemical regime thanks to the appropriate operating conditions. The results obtained with the raw materials demonstrated that biomass macromolecular composition is a main factor influencing biomass behavior in torrefaction. Consequently, the heterogeneity of the resource results in a diverse behavior in torrefaction, particularly in the case of agricultural biomasses. The results with the extracted components evidenced their very different behavior compared to thecommercial compounds, particularly in the case of cellulose. This suggests that a limitation could be induced by the common use in literature of commercial components for torrefaction modelling. The impact on the characterization of macromolecular components was also shown to be prevailing in their behavior in torrefaction, especially in the case of hemicellulose sugar composition and cellulose crystallinity. Furthermore, differences in release kinetics of volatile species during torrefaction were observed, even for volatiles belonging to the same chemical family (acids, furans, ketones). Derived from these results, a torrefaction model based on the additive contribution of extracted cellulose, hemicelluloses and lignin to the global behavior of biomass in torrefaction was proposed, and this for the 5 representative biomasses.

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