Abstract Biomass, such as wood, binds CO2 as it grows, and is thus considered an environmentally friendly alternative fuel to replace coal. In Finland, biomass is typically co-combusted with peat, and also municipal waste is becoming more common as a fuel for power plants. Wood, peat and waste-based fuels are typically burned in fluidized bed combustion (FBC) boilers. Ash is the inorganic, incombustible residue resulting from combustion. The annual production of biomass and peat ash in Finland is 600 000 tonnes, and this amount is likely to increase in the future, since the use of coal for energy production will be discontinued during the 2020s. Unfortunately, FBC ash is still largely unutilized at the moment and is mainly dumped in landfills. The general aim of this thesis was to generate information which could potentially improve the utilization of FBC ash by alkali activation. The specific objective was to produce geopolymer aggregates by means of a simultaneous alkali activation-granulation process. It was shown that geopolymer aggregates with physical properties comparable to commercial lightweight expanded clay aggregates (LECAs) can be produced from FBC fly ash containing heavy metals. Although the ashes were largely unreactive and no new crystalline phases were formed by alkali activation, a new amorphous phase was observed in the XRD patterns, possibly representing micron-sized calcium aluminate silicate hydrate-type gels. The heavy metal immobilization efficiency of alkali activation varied with the type of fly ash. Good stabilization was generally obtained for cationic metals such as Ba, Pb and Zn, but in common with the results obtained with alkali activation of coal fly ash, anionic metals became leachable after alkali activation. The efficiency of immobilization depended on the physical and chemical properties of the fly ash and was not related to the total content of the element. All the geopolymer aggregates met the criteria for a lightweight aggregate (LWA) as defined by EN standard 13055-1. Their strength depended on the reactivity and particle size distribution of the fly ash. Mortars and concretes prepared with such geopolymer aggregates had higher mechanical strength, higher dynamic modulus of elasticity and higher density than concrete produced with commercial LECA, while exhibiting similar rheology and workability. / Tiivistelmä Biopolttoaineet, esimerkiksi puu, ovat ympäristöystävällinen vaihtoehto kivihiilelle, koska ne sitovat hiilidioksidia kasvaessaan. Suomessa biopolttoaineita poltetaan tyypillisesti turpeen kanssa, ja nykyään myös jätteen hyödyntäminen polttoaineena on yleistynyt. Puu, turve ja jätepolttoaineet poltetaan tyypillisesti leijupetipoltto-tekniikalla. Tuhka on polton epäorgaaninen, palamaton jäännös. Puun ja turpeen tuhkaa tuotetaan Suomessa 600 000 tonnia vuodessa ja määrän odotetaan kasvavan, sillä kivihiilen poltto lopetetaan 2020-luvulla. Leijupetipolton tuhkaa ei tällä hetkellä juurikaan hyödynnetä ja tuhka päätyykin pääasiassa kaatopaikoille. Tämän tutkielman päämääränä oli tuottaa tietoa, joka parantaisi leijupetipolton tuhkien hyödyntämistä alkali-aktivaatiolla. Erityisesti tavoitteena oli valmistaa geopolymeeriaggregaatteja yhtäaikaisella alkali-aktivaatiolla ja rakeistuksella. Tutkielmassa osoitettiin, että raskasmetalleja sisältävistä tuhkista valmistettujen geopolymeeriaggregaattien fysikaaliset ominaisuudet ovat vertailukelpoiset kaupallisten kevytsora-aggregaattien (LECA) kanssa. Vaikka tuhkien reaktiivisuus oli matala, ja uusia kidefaaseja ei muodostunut alkaliaktivaatiolla, uusi amorfinen faasi havaittiin XRD-mittauksissa. Uusi amorfinen faasi oli mahdollisesti mikrometrikokoluokan kalsium-aluminaatti-silikaatti-hydraatti-tyyppinen rakenne. Raskasmetallien stabiloinnin tehokkuus vaihteli tuhkien välillä. Kationiset metallit, kuten barium, lyijy ja sinkki, stabiloituivat pääasiassa hyvin, mutta anionisten metallin liukoisuus kasvoi alkali-aktivoinnin myötä. Stabiloinnin tehokkuus riippui tuhkien fysikaalisista ja kemiallisista ominaisuuksista, mutta raskasmetallin kokonaispitoisuudella ei ollu vaikutusta. Kaikki geopolymeeriaggregaatit olivat kevytsora-aggregaatteja standardin EN 13055-1 mukaisesti. Aggregaattien lujuus riippui tuhkan reaktiivisuudesta ja partikkelikokojakaumasta. Geopolymeeriaggregaateilla valmistettujen laastien ja betonien mekaaninen lujuus, Youngin moduuli ja tiheys olivat korkeampia kuin kaupallisella kevytsora-aggregaateilla valmistetut, vaikka niiden reologia ja työstettävyys olivat samanlaisia.

L'augmentation croissante de la demande énergétique mondiale entraine une production importante de dioxyde de carbone fossile. Pour limiter ces émissions, les énergies alternatives renouvelables sont prometteuses, et notamment, l'utilisation de la biomasse. C'est dans ce contexte qu'a été mis en place le projet ANR GAMECO par un consortium rassemblant des laboratoires universitaires et des unités de R&D industrielles. Ce projet vise à consolider l'utilisation d'un lit fluidisé bouillonnant de gazéification sous air pour convertir de la biomasse lignocellulosique en gaz de synthèse. Ce travail de doctorat a pour ambition de répondre à l’une des problématiques de ce projet : la répartition des particules de biomasses et de semi-coke ou charbon au sein du lit fluidisé et sa prise en compte dans la modélisation du gazéifieur. L'étude a porté sur des mélanges contenant de l'olivine et des particules de bois de caractéristiques différentes. Les résultats de mélange-ségrégation présentés ont été obtenus grâce à des mesures en maquette froide développée dans le cadre de cette thèse. Les données expérimentales obtenues ont permis de valider et consolider un modèle de mélange-ségrégation de la littérature. La dernière étape de la thèse consiste en la mise en place d'un modèle global du réacteur à lit fluidisé de gazéification de la biomasse pour prédire la productivité et la qualité du gaz produit. Ce modèle intègre les résultats hydrodynamiques précédents auxquels sont couplés des réactions chimiques de conversion de la biomasse (pyrolyse, oxy-gazéification du charbon, craquage des goudrons) provenant de la littérature. Les résultats de ce modèle sont comparés aux résultats obtenus sur une maquette chaude / The increasing population in the world leads to increasing energy demand. In order to limit emissions of fossil carbon dioxide, a solution is to develop renewable energy alternatives. In this context, the use of biomass is one of the solutions to study. It is in this context that implemented the project ANR GAMECO by a consortium of academic and industrial. This project aims to make reliable use of a bubbling fluidized bed of gasification with air to convert lignocellulosic biomass into synthesis gas. This PhD work aims to address one of the problems of this project: the distribution of biomass and char particles in the fluidized bed and the impact of these distributions when modeling of the gasifier. The study focused on mixtures containing olivine and wood particles of different characteristics. Mixing-segregation results were obtained through measurements in a cold model developed during this PhD work. The obtained experimental data were used to validate and consolidate existing hydrodynamic mixing model of the literature. The last step of the thesis consists in establishing a global model of the fluidized bed reactor for gasification of biomass. This model incorporates the previous hydrodynamic results, coupled with chemical reactions models describing biomass conversion (pyrolysis, oxy-coal gasification tar cracking) after the literature. The results of this model are then compared with results obtained on a hot model

Améliorer la compréhension des phénomènes pilotant l’agglomération au sein des réacteurs à lit fluidisé lors de la conversion thermochimique de biomasse (700-1000°C) est important pour prédire son occurrence à l’échelle industrielle. L’agglomération est liée à la formation de phases liquides (oxydes liquides et/ou sels fondus) provenant de la fusion des espèces inorganiques contenues dans la ressource (cendres). Leur présence conduit à la défluidisation des matériaux de lit, à l’origine d’une baisse des rendements de production en gaz, voire d’un « blocage » du réacteur. La phénoménologie de l’agglomération est examinée à partir de trois approches expérimentales, en matériaux simulants et réels, à trois échelles différentes et dans des gammes de températures allant de l’ambiante à 1000°C. L’analyse des mécanismes à l’origine de cette agglomération du lit montre que la formation du liquide est le seul paramètre limitant dans la formation d’agglomérats. Ce phénomène provoque une augmentation du diamètre apparent des particules de lit en parallèle d’une diminution de leur masse volumique. Ces modifications peuvent être associées à un déplacement au sein de la classification de Geldart de la catégorie B vers la catégorie D. D’un point de vue hydrodynamique, la défluidisation du lit résulte de la ségrégation des agglomérats au fond du réacteur. Ce phénomène contribue à dégrader l’homogénéité de répartition du gaz de fluidisation dans le réacteur. La défluidisation complète du lit survient pour une fraction de liquide dans le lit très faible (quelques % vol. de lit). Sur la base de ces résultats, une formulation simplifiée a été proposée et permet de prédire, à partir de la ressource utilisée et pour un fonctionnement simplifié, la durée de fonctionnement avant défluidisation. / Improving the knowledge on the driving phenomena of agglomeration during fluidized-bed conversion of biomass (700-1000°C) is essential to predict its occurrence at industrial scale. Agglomeration is due to liquid phase formation (molten salts and/or molten silicates) coming from the melting of inorganic species contained inside the biomass (ash). Their presence leads to bed materials defluidization, reducing the process efficiency and even going up to a “blockage” of the reactor. The phenomenology of agglomeration is investigated with three experimental approaches, using simulant and real materials, at three different scales, and with a temperature ranging from ambient one to 1000°C. The analysis of the mechanisms underlying the bed agglomeration indicates that the liquid formation is the single limiting parameter for agglomerates formation. This phenomenon leads to an increase of the apparent diameter of the bed particles and at the same time to a decrease of their density. These modifications can be seen as a shift among the Geldart’s classification, from the B to the D-class. Concerning the hydrodynamic aspect, the bed defluidization is due to the agglomerates segregation at the bottom of the reactor. This phenomenon contributes to degrade the homogenous fluidization gas distribution across the reactor. The total bed defluidization occurs for a very low liquid fraction in the bed (few % vol. of bed materials). Based on these results, a simplified model has been proposed in order to predict the operating time before defluidization of the reactor, taking into account the biomass composition and simplified operating conditions.

In der vorliegenden Arbeit werden verschiedene Simulationsansätze angewandt um die Hydrodynamik in einem neu entwickelten Wirbelschichtvergaser zu untersuchen. Die Ansätze umfassen a) entdimensionalisierter Ähnlichkeitskennzahlen und empirischer Gleichungen, b) 1D Simulationen mittels ASPEN Plus®, c) 3D CFD Simulationen mittels Ansys Fluent® zur detaillierten Abbildung der zu erwartenden Hydrodynamik. Vor- und Nachteile der jeweiligen Ansätze sowie Klassen von ermittelbaren Simulationsdaten werden diskutiert. Ein Schwerpunkt der Arbeit liegt in der Identifizierung geeigneter Experimente aus der Literatur, auf Basis von Ähnlichkeitskennzahlen, um die Simulationen zu validieren. Die Vergasersimulationen zeigen, dass sich erwartungsgemäß ein aus hydrodynamischer Sicht gestufter Prozess ausbildet. Die entstehenden Zonen lassen sich als Festbett, blasenbildende Wirbelschicht, Jet-Wirbelschicht mit Rezirkulationszelle und strähnenbildende, zirkulierende Wirbelschicht identifizieren und entsprechen demnach dem Verfahrensanspruch.

The thesis is oriented on monitoring of hydration process of portland cement based on fluidized bed ash, firstly on investigation of AFt phases, mainly ettringite and thaumasite. Specific aim of the task is to prepare the scheme of these minerals synthetic preparation and to verify their laboratory preparation by different ways, using methods of RTG-diffraction analysis and scanning electron microscopy.

Subject of the present Ing. thesis is problem of incineration of sewage sludge and influence of lime on production of editions. In work are described kinds of sewage sludge combustion and possibilities of edition cleaning. Work includes design and description of experimental combustion of sewage sludge mixtured with kalcite in fluidized bed reactor. The end of work delal with, evaluation of editions from combustion experiment. Evaluated components of bunt gases are: heavy metals, TZL, SO2, CO, CO2, HCl, HF, O2, NO, PAH, PCB, PCDD/F.

This diploma thesis deals with the control calculation of fluid biomass boilers with circulating fluidized bed. The introduction briefly introduced fluidized bed boilers and explained what biomass is. Furthermore there is a stoichiometric calculation of combustion. The calculation of the losses and the efficiency of the boiler is following. Desulphurization is calculated briefly. The main part is devoted to the design and calculation of individual heat exchanging surfaces: superheater P1, superheaters 2 and 3, the wall superheater, the return chamber, hanging tubes, economizer and air heater. At the end is calculated total tolerance boiler. Work is completed with a diagram of temperature of working media and combustion.

Aim of this thesis is to design a technology of a flue gas desulphurization of fluidized bed boiler. Currently, the state of technology is not able to provide flue gas desulphurisation to required level. For this reason it is necessary to build additional device for the desulphurisation. Theoretical part of the thesis deals with the emission limits of sulphur dioxide, available methods of desulphurization and sorbents suitable for the desulfurization. In practical part conditioned dry sorption method is chosen for the specified source, technological and structural design for suggested desulphurization technology including design of all device is proposed. The thesis also includes a technology design and a 3D model.

Due to the continuous growth of energy consumption it is required that development in the energy sector is focused on renewable energy sources. Another possibility how to reduce the consumption of primary energy resources is also searching for new and non-traditional fuels. The biomass is the best and potentially expandable renewable energy source in geographic conditions in the Czech Republic. The energy usage of biomass has experienced a significant increase in recent years, however, even in the big energy power plant. This increase in consumption made mainly from wood biomass a shortage fuel, and it began to raise its price. The consumers of biomass fuel are starting to look for a different type of fuel at this time. Stalk and slightly contaminated biomass are representatives of these non-traditional fuels. Stalks are mostly annual plants grown primarily for subsistence. Waste parts of these plants can be utilized for production of energy. The characteristic temperatures of stalk ash have relatively low values. Sintering of ash in a device is one of the obstacles for energy usage of stalk. Sintering of ash brings a number of operational problems at power facilities. Therefore, the part of a research is dedicated to the melting of ash. The thermal gasification is one of the possibilities how to use biomass efficiently. Gasification can be understood as the thermo-chemical conversion of solid fuel into a different state, in this case the gaseous state. The combustion process is generally more manageable for gaseous fuels. Due to this process ower emissions of undesirable compounds at the output of the combustion device can be achieved. Thermal gasification process takes place under stochiometric access of oxidant. The gas with low heating value is on the outlet from gasification process. The main components of produced gas are hydrogen, carbon monoxide and methane. The final gas contains also a lot of undesirable constituents, which make this gas disadvantaged in energy. These constituents are neutral components that dilute gas only, and pollutants as dust, tar and compounds of sulfur and chlorine. These pollutants complicate further use of the generated gas. The tar compounds together with dust causing build-up on the conveyor pipe and also on the combustion equipment, which are using this generated gas. The quality of produced gas is increases by another reprocessing and cleaning. The purified gas can be used for cogeneration of energy and burn it in internal combustion engines or gas turbines. Other possibility is typical usage for heating according to the needs of technology. The atmospheric fluidized bed gasification reactor Biofluid 100th was built for experimental purposes in the laboratories of the Energy Institute. The thesis is focused on thermal gasification of stalk and other non-traditional fuels in Biofluid device. The aim is to achieve a stable gasification process of stalk and thereby verify the possibility of stalk use as fuel for technology Biofluid. Subsequent aim is design of methods for cleaning the raw gas from the tar compounds. The research is focused on the secondary gas cleaning methods due to the requirements of high purity of the resulting gas.

The multi zone fluidized bed reactor instantaneously creates several chemical/physical environments in a single reactor vessel. Effective solid circulation across zones can be achieved by tuning the reactor geometries, solid properties, and operating conditions. However, there is limited research for this innovative reactor concept beyond the laboratory scale, among which a better understanding of the complex fluid dynamics, dominating the solid circulation in different zones, is a basis. This work aims to propose a new method to capture the fluid dynamics of a pilot MZFBR by laboratory measurements with validation from theoretical analysis and simulation. Toward this goal, we first performed particle characterizations, and fluidization testing experiments in a laboratory scale fluidized bed reactor and a pilot scale multi zone fluidized bed reactor at ambient conditions to study the development of fluidization regimes. Then we compared the minimum fluidization velocity with argon and air between the experimental measurements and theoretical calculation results and proposed a modified Ergun equation, which better fits our system. Finally, we conducted computational particle fluid dynamics simulations for the pilot multi zone fluidized bed reactor with the Ergun equation and our modified equation and compared the results against previous experimental observations. Simulations display that the prediction of pressure drop in the pilot scale multi zone fluidized bed reactor with the proposed Ergun equation is similar to that of the original equation, with a relative deviation of around 3%. However, the modified equation captured the bubbling fluidization behavior as the experiment, while the Ergun equation predicted a smooth fluidization without any bubbles. The better agreements validated both our workflow of estimating the fluidization behavior in a pilot multi zone fluidized bed reactor from laboratory measurements and the simulation strategy.