This thesis describes the development and experimental testing of a 100 kW dual fluidized bed biomass gasifier (also called a Fast Internally Circulating Fluidized Bed (FICFB) biomass gasifier). This steam-blown gasifier is being studied for its suitability within combined heat and power plant systems for the New Zealand forest products industry. This advanced design of gasifier has the ability to generate producer gas with a lower heating value (LHV) of 11.5-13.4 MJ/Nm3, which is two to three times higher than yielded by conventional gasification systems. This is accomplished because the gasification and combustion processes occur in two physically separated reactors. Several modifications to the gasifier were required after it was first constructed in order to achieve stable and reliable operation. Producer gas yields were measured through the use of helium as a tracer gas. A new simultaneous producer gas and tar sampling system was developed, allowing accurate samples to be obtained in a matter of minutes. Experimental testing included a cold testing exercise which provided valuable information on the circulation behaviour of the bed material and char within the gasifier. This helped in achieving stable and reliable operation of the plant. Producer gas yields of 14.6 Nm3/h were recorded with a fuel (radiate pine wood pellets) feed rate of 18.9 kgdry/h. The cold gas efficiency ranged from 16-40 % with limited heat recovery in place, but depended noticeably on the plant operating conditions especially gasification temperature. The amount of polycyclic aromatic hydrocarbon (PAH) tars measured in the producer gas ranged between 0.9-4.7 g/Nm3 with naphthalene and acenapthylene being the most abundant compounds. The moisture content of the producer gas was determined to be 0.9-1.2 g/gdry gas. It was found that a steam to biomass ratio of 0.45-0.7 kg/kgdry was most favourable for generating a 12-13.4 MJ/Nm3 producer gas while limiting the amount of steam generation. Gasification temperatures above 750 °C encouraged higher producer gas yields and higher cold gas efficiencies. The catalytic bed material olivine (forsterite olivine) was found to increase the producer gas yield by approximately 20 % compared to the non-catalytic bed material greywacke. The use of olivine meant higher cold gas efficiencies were achieved for a given wood feed rate.

Cette étude est consacrée à l'élaboration de vernis d'enrobage composites constitués d'une fine dispersion de matériau hydrophobe dans une matrice de polymère. Ce type de matériau est appliqué à la surface de particules alimentaires, grâce à un procédé de pulvérisation en lit fluidisé, afin d'assurer la protection de ces particules vis-à-vis d'atmosphères humides. Nous avons développé un protocole de formulation, des vernis d'enrobage et des outils de caractérisation des dispersions liquides mais également des vernis secs sous forme de films minces. Nous avons étudié l'influence des paramètres liés au protocole de formulation et à la composition sur la stabilité de la dispersion, sur les propriétés d'usage des films d'enrobage secs mais également sur les interactions entre les différents constituants. A partir de l'ensemble de ces résultats, deux formulations ont été retenues. Afin d'étudier l'influence des conditions séchage sur les propriétés des films d'enrobage, nous avons conçu une veine de séchage convectif. Les résultats ont montré que la morphologie et les propriétés des films secs sont essentiellement pilotées par la période de séchage à vitesse décroissante, lorsque la cinétique d'évaporation du solvant est limitée par la diffusion de celui-ci à travers le film de vernis. De plus, nous avons observé que l'augmentation de la température de séchage, notamment pour des températures de séchage proche de la température de fusion des composés fusibles des vernis (40°C pour le PEG 1500 et 55°C pour l'acide stéarique), induit des transformations morphologiques importantes des films. L'apparition de cette nouvelle morphologie provoque une amélioration notable des possibilités de déformation des films secs sans modifier leurs propriétés barrières. / This study deals with the elaboration of a composite coating agent made of a fine dispersion of a hydrophobic material in a polymeric solution. Such material is applied on particles surface, thanks to a fluidised bed pulverization, to ensure their protection from wet atmosphere. We have developed a formulation protocol, coating agents and characterization tools of liquid formulation and dry thin coating films. These tools allow us to assess the influence of formulation and composition parameters on dispersion stability, valuable film properties and on interactions between film components. Thanks to these experiments, two formulations have been developed. To study the drying parameters impact on coating agent properties, a convective dryer have been designed. Dry films morphology and properties strongly depend on fallen drying rate period when solvent evaporation is limited by its diffusion through the wet film. Furthermore, we have observed that the drying temperature rise induces film morphology transformation, especially with drying temperature close to melting temperature of film fusible components (40°C with PEG 1500 and 55°C with stearic acid). This new morphology causes a great increasing of film plastic properties without endangered their barrier properties.

Les travaux menés dans cette Thèse ont consisté à développer un pilote expérimental prouvant la faisabilité de la capture de CO2 par boucle chimique calcium en utilisant des chaudières du type Lit Fluidisé Circulant. Ceux-ci ont été conduits en deux phases: une phase expérimentale à l'échelle du laboratoire avec l'interprétation théorique des résultats et une phase expérimentale à l'échelle du pilote dans le but de valider le procédé. Les résultats expérimentaux à 1'échelle du laboratoire ont permis de montrer que le frittage de CaOest la cause de la décroissance du taux de carbonatation au cours des cycles successifs calcination/carbonatation. La vitesse de frittage étant accélérée par la présence de CO2 pendant la phase de calcination. Les analyses menées sur les échantillons calcinés ont révélé l'apparition d'une structure de micrograin à l'intérieur des grains initiaux de carbonate. Les micrograins de CaO non frittés sont le siège de la réaction de carbonatation.Un procédé de capture de CO2 par boucle chimique calcium a été conçu et réalisé. Il se compose de deux lits fluidisés circulants, un réacteur de carbonatation assurant la capture du CO2 et un réacteur de calcination permettant la régénération de la chaux. Ces deux lits fluidisés circulants sont couplés de façon à permettre un fonctionnement continu du procédé de capture de CO2. Malgré le faible rendement de capture obtenu à l'échelle de ce pilote (entre 18 à 23%), ces résultats apparaissent encourageants pour le développement de cette technologie, compte tenu du fait que beaucoup de facteurs limitant le rendement de capture disparaissent avec le changement d'échelle. / The works led in this Thesis consisted in developing an experimental pilot proving CO2 capture feasibility by calcium chemical looping using Circulating Fluidised Bed as boilers. These were undertaken in two step: At the laboratory scale with theoretical interpretation of the experimental results and at the pilot scale in the aim to validate the process.The experimental results on the scale of the laboratory allowed to show that the sintering of CaO bring about the decreasing of the carbonation rate during calcination/carbonation cycles. The sintering velocity are accelerated by CO2 during the calcinations step. The analysis of the calcined samples showed a micrograins structure inside the initial carbonate grains The not sintered CaO micrograins are the location of the carbonation reaction.A process of CO2 capture by calcium chemical looping was designed and built. It was made by two circulating fluidized beds, a carbonator where the CO2 capture were performed and the calcinator allowing the lime regeneration. These two circulating fluidized beds are coupled allowing a continuous CO2 capture.In spite of the low capture efficiency obtained on the scale of this pilot (from 18 to 23 %), these results seem encouraging for the development of this technology, considering the fact that many limiting factors of the capture efficiency disappear with the change of scale.

The present work is concerned with the mathematical modelling of a bed of granular material in a gravitational field vertically fluidised by a vibrating surface. The particles are in rapid motion, and lose energy by inelastic collisions. The steady state is maintained by a balance of the rate of dissipation of energy in inelastic particle collisions and the rate of transfer of energy due to particle collisions with the vibrating surface. The limit where the energy dissipation due to inelastic collisions is small compared to the mean kinetic energy of the particles is considered. This non-equilibrium steady state is similar to a dilute gas at equilibrium with a uniform temperature and an exponentially decaying density, obtained from the ideal gas equation of state. From the analysis of this state, four non-dimensional numbers are derived which uniquely specify the state of the system. A perturbative analysis about the uniform temperature state is carried out and analytical solutions to the macroscopic variables of the system are obtained using two types of approximations. The first is a hydrodynamic model using constitutive relations from the general kinetic theory of granular media, and the second is a kinetic theory formulation derived exclusively for the vibro-fluidised bed. The latter permits an anisotropy between the horizontal and vertical directions due to the anisotropic nature of the source of energy at the bottom wall. The kinetic theory is extended to incorporate the corrections due to the high density effects, which is similar to the Enskog correction to dense gases. An event driven (ED), or hard sphere molecular dynamic (MD), simulation of the vibrated bed is carried out. The quantitative predictions of the theories are validated by the simulation. A systematic probing of the parameter space within the ED simulations revealed two new phenomena in a vibro-fluidised bed which are inhomogeneous in the horizontal direction. These are convection rolls similar to the Rayleigh-Benard instability in fluids, and a clustering instability leading to a phase separation. The instabilities are characterised using a phase diagram. The homogeneous states close to these new states are adequately described by the models developed here. An analysis of the stability of this state could have implications in understanding the instabilities in driven granular materials (such as in sheared media and fluidised beds) in general, and pattern formation in vibrated beds in particular.

Die Arbeit zeigt wichtige Nutzungswege von fester Biomasse in Form von Holzhackschnitzel (HHS). Einleitend wird das Potenzial und der derzeitige Stand dargestellt. Es werden die physikalischen und chemischen Eigenschaften mit dem Schwerpunkt Wassergehalt in bezug auf die energetische Nutzung der HHS behandelt. Kerne der Nutzungswege bilden dabei die Vergasung im Gleichstromvergaser und die Co-Verbrennung in der Zirkulierenden Wirbelschicht. Mit Hilfe eines Versuchsvergasers werden die Auswirkungen von HHS-Eigenschaften auf den Betrieb untersucht. Der Modellvergaser IGEL bietet durch seine Konstruktion die Möglichkeit, innere Vorgänge zu beleuchten und Messungen in verschiedenen Vergaserebenen durchzuführen. Die Auswirkungen von verschiedenen Brennstoffchargen mit unterschiedlichem Wassergehalt führten zu Änderungen in der Gaszusammensetzung. Eigene Untersuchungen ermittelten einen Grenzwassergehalt, mit dem der Vergaser noch betrieben werden kann. Die Experimente an der Pilotanlage mit zirkulierender atmosphärischer Wirbelschicht befass-ten sich mit der wichtigen Frage, ob und welches NOx-Minderungspotenzial beim Einsatz von Biomasse vorliegt. Die mathematische Modellierung verdeutlicht die Nutzbarkeit von Simulationsprogrammen bei der Untersuchung von Einflüssen der Co-Verbrennung auf die NOx-Bildung. Hier wurden die Gesichtspunkte der Luftzahl, der Luftstufung, des Wassergehaltes, das Mischungsverhältnis und die Brennstoffstufung betrachtet. Eine Wirtschaftlichkeitsbetrachtung führt zu dem Ergebnis, dass Anlagen zur reinen Stromerzeugung mit Biomasse nur nahe der gesetzlichen Höchstleistung von 20 MWel zur Einspeisevergütung von wirtschaftlich betrieben werden können. Die ökologisch und ökonomisch günstigste Variante stellt die Co-Verbrennung in vorhandenen Anlagen dar. Die Kalkulationen zu den in Deutschland benötigten 20-MWel-Anlagen verdeutlichen, dass bei den gegenwärtig geplanten Heizkraftwerken das Potenzial an HHS schnell aufgebraucht ist.

Production of high-quality syngas from biomass gasification in a dual fluidised bed gasifier (DFBG) has made a significant progress in R&D and Technology demonstration. An S&M scale bio-automotive fuel plant close to the feedstock resources is preferable as biomass feedstock is widely sparse and has relatively low density, low heating value and high moisture content. This requires simple, reliable and cost-effective production of clean and good syngas. Indirect DFBGs, with steam as the gasification agent, produce a syngas of high content H2 and CO with 12-20 MJ/mn3 heating value. The Mid Sweden University (MIUN) gasifier, built for research on synthetic fuel production, is a dual fluidised bed gasifier. Reforming of tars and CH4 (except for methanation application) in the syngas is a major challenge for commercialization of biomass fluidised-bed gasification technology towards automotive fuel production. A good syngas from DFBGs can be obtained by optimised design and operation of the gasifier, by the use of active catalytic bed material and internal reforming. This thesis presents a series of experimental tests with different operation parameters, reforming of tar and CH4 with catalytic bed material and reforming of tar and CH4 with catalytic internal reformer.   The first test was carried out to evaluate the optimal operation and performance of the MIUN gasifier. The test provides basic information for temperature control in the combustor and the gasifier by the bed material circulation rate.    After proven operation and performance of the MIUN gasifier, an experimental study on in-bed material catalytic reforming of tar/CH4 is performed to evaluate the catalytic effects of the olivine and Fe-impregnated olivine (10%wtFe/olivine Catalyst) bed materials, with reference to non-catalytic silica sand operated in the mode of dual fluidised beds (DFB). A comparative experimental test is then carried out with the same operation condition and bed-materials but when the gasifier was operated in the mode of single bubbling fluidised bed (BFB). The behaviour of catalytic and non-catalytic bed materials differs when they are used in the DFB and the BFB. Fe/olivine and olivine in the BFB mode give lower tar and CH4 content together with higher H2+CO concentration, and higher H2/CO ratio, compared to DFB mode. It is hard to show a clear advantage of Fe/olivine over olivine regarding tar/CH4 catalytic reforming.    In order to significantly reduce the tar/CH4 contents, an internal reformer, referred to as the FreeRef reformer, is developed for in-situ catalytic reforming of tar and CH4 using Ni-catalyst in an environment of good gas-solids contact at high temperature.  A study on the internal reformer filled with and without Ni-catalytic pellets was carried out by evaluation of the syngas composition and tar/CH4 content. It can be concluded that the reformer with Ni-catalytic pellets clearly gives a higher H2 content together with lower CH4 and tar contents in the syngas than the reformer without Ni-catalytic pellets. The gravimetric tar content decreases from 25 g/m3 down to 5 g/m3 and the CH4 content from 11% down below 6% in the syngas.   The MIUN gasifier has a unique design suitable for in-bed tar/CH4 catalytic reforming and continuously internal regeneration of the reactive bed material. The novel design in the MIUN gasifier increases the gasification efficiency, suppresses the tar generation and upgrades the syngas composition. / Gasification-based Biorefinery for Mechanical Pulp Mills

A mathematical model for the drying of particulate solids in a continuous vibrated fluidised bed dryer was developed and applied to the drying of grain wetted with a single liquid and porous particles containing multicomponent liquid mixtures. Simple equipment and material models were applied to describe the process. In the plug-flow equipment model, a thin layer of particles moving forward and well mixed in the direction of the gas flow was regarded; thus, only the longitudinal changes of particle moisture content and composition as well as temperature along the dryer were considered. Concerning the material model, mass and heat transfer in a single isolated particle was studied. For grain wetted with a single liquid, mass and heat transfer within the particles was described by effective transfer coefficients. Assuming a constant effective mass transport coefficient and effective thermal conductivity of the wet particles, analytical solutions of the mass and energy balances were obtained. The variation of both transport coefficients along the dryer was taken into account by a stepwise application of the analytical solution in space intervals with non-uniform inlet conditions and averaged coefficients from previous locations in the dryer. Calculation results were verified by comparison with experimental data from the literature. There was fairly good agreement between experimental data and simulation but the results depend strongly on the correlation used to calculate heat and mass transfer coefficients.   For the case of particles containing a multicomponent liquid mixture dried in the vibrated fluidised bed dryer, interactive diffusion and heat conduction were considered the main mechanisms for mass and heat transfer within the particles. Assuming a constant matrix of effective multicomponent diffusion coefficients and thermal conductivity of the wet particles, analytical solutions of the diffusion and conduction equations were obtained. The equations for mass transfer were decoupled by a similarity transformation and solved simultaneously with conduction equation by the variable separation method. Simulations gave a good insight into the selectivity of the drying process and can be used to find conditions to improve aroma retention during drying.   Also, analytical solutions of the diffusion and conduction equations applied to liquid-side-controlled convective drying of a multicomponent liquid film were developed. Assuming constant physical properties of the liquid, the equations describing interactive mass transfer are decoupled by a similarity transformation and solved simultaneously with conduction equation and the ordinary differential equation that describes the changes in the liquid film thickness. Variations of physical properties along the process trajectory were taken into account as in the previous cases. Simulation results were compared with experimental data from the literature and a fairly good agreement was obtained. Simulations performed with ternary liquid mixtures containing only volatile components and ternary mixtures containing components of negligible volatility showed that it is difficult to obtain an evaporation process that is completely controlled by the liquid-side mass transfer. This occurs irrespective of the initial drying conditions.   Despite simplifications, the analytical solution of the material model gives a good insight into the selectivity of the drying process and is computationally fast. The solution can be a useful tool for process exploration and optimisation. It can also be used to accelerate convergence and reduce tedious and time-consuming calculations when more rigorous models are solved numerically. / QC 20110614

Die Arbeit zeigt wichtige Nutzungswege von fester Biomasse in Form von Holzhackschnitzel (HHS). Einleitend wird das Potenzial und der derzeitige Stand dargestellt. Es werden die physikalischen und chemischen Eigenschaften mit dem Schwerpunkt Wassergehalt in bezug auf die energetische Nutzung der HHS behandelt. Kerne der Nutzungswege bilden dabei die Vergasung im Gleichstromvergaser und die Co-Verbrennung in der Zirkulierenden Wirbelschicht. Mit Hilfe eines Versuchsvergasers werden die Auswirkungen von HHS-Eigenschaften auf den Betrieb untersucht. Der Modellvergaser IGEL bietet durch seine Konstruktion die Möglichkeit, innere Vorgänge zu beleuchten und Messungen in verschiedenen Vergaserebenen durchzuführen. Die Auswirkungen von verschiedenen Brennstoffchargen mit unterschiedlichem Wassergehalt führten zu Änderungen in der Gaszusammensetzung. Eigene Untersuchungen ermittelten einen Grenzwassergehalt, mit dem der Vergaser noch betrieben werden kann. Die Experimente an der Pilotanlage mit zirkulierender atmosphärischer Wirbelschicht befass-ten sich mit der wichtigen Frage, ob und welches NOx-Minderungspotenzial beim Einsatz von Biomasse vorliegt. Die mathematische Modellierung verdeutlicht die Nutzbarkeit von Simulationsprogrammen bei der Untersuchung von Einflüssen der Co-Verbrennung auf die NOx-Bildung. Hier wurden die Gesichtspunkte der Luftzahl, der Luftstufung, des Wassergehaltes, das Mischungsverhältnis und die Brennstoffstufung betrachtet. Eine Wirtschaftlichkeitsbetrachtung führt zu dem Ergebnis, dass Anlagen zur reinen Stromerzeugung mit Biomasse nur nahe der gesetzlichen Höchstleistung von 20 MWel zur Einspeisevergütung von wirtschaftlich betrieben werden können. Die ökologisch und ökonomisch günstigste Variante stellt die Co-Verbrennung in vorhandenen Anlagen dar. Die Kalkulationen zu den in Deutschland benötigten 20-MWel-Anlagen verdeutlichen, dass bei den gegenwärtig geplanten Heizkraftwerken das Potenzial an HHS schnell aufgebraucht ist.

The topic of this thesis is carbon dioxide (CO2) capture and storage (CCS), which is a technology that is currently being promoted by industries, scientists and governments, among others, in order to mitigate climate change despite a continued use of fossil fuels. Because of the complex nature of CCS and the risks it entails, it is controversial. The aim of this thesis is to analyse how the technology may be further developed in a responsible manner. In the first part of the thesis different methods for capturing CO2 from industrial processes as well as power plants are analysed. The aim is to identify early opportunities for CO2 capture, which is considered important because of the urgency of the climate change problem. Three potential early opportunities are studied: i) capturing CO2 from calcining processes such as cement industries by using the oxyfuel process, ii) capturing CO2 from pressurised flue gas, and iii) capturing CO2 from hybrid combined cycles. Each opportunity has properties that may make them competitive in comparison to the more common alternatives if CCS is realised. However, there are also drawbacks. For example, while capturing CO2 from pressurised flue gas enables the use of more compact capture plant designs as well as less expensive and less toxic absorbents, the concept is neither suitable for retrofitting nor has it been promoted by the large and influential corporations. The second part of the thesis has a broader scope than the first and is multidisciplinary in its nature with inspiration from the research field of Science and Technology Studies (STS). The approach is to critically analyse stakeholder percep-tions regarding CCS, with a specific focus on the CCS experts. The thesis sheds new light on the complexity and scientific uncertainty of CCS as well as on the optimism among many of its proponents. Because of the uncertain development when it comes to climate change, fossil fuel use and greenhouse gas emissions, the conclusion is that CCS has to be further developed and demonstrated. A responsible strategy for a future development of CCS would benefit from: i) a search for win-win strategies, ii) increasing use of appropriate analytical tools such as life-cycle analysis, iii) a consideration of fossil fuel scarcity and increasing price volatility, iv) funding of unbiased research and v) increasing simultaneous investments in long-term solutions such as renewable energy alternatives and efficiency improvements. / QC 20100727