A pilot scale fluidized bed biomass gasifier developed at Texas A&M University in College Station, Texas was instrumented with thermocouples, pressure transducers and motor controllers for monitoring gasification temperature and pressure, air flow and biomass feeding rates. A process control program was also developed and employed for easier measurement and control. The gasifier was then evaluated in the gasification of sorghum, cotton gin trash (CGT) and manure and predicting the slagging and fouling tendencies of CGT and manure. The expected start-up time, operating temperature and desired fluidization were achieved without any trouble in the instrumented gasifier. The air flow rate was maintained at 1.99 kg/min and the fuel flow rate at 0.95 kg/min. The process control program considerably facilitated its operation which can now be remotely done. The gasification of sorghum, CGT and manure showed that they contained high amounts of volatile component matter and comparable yields of hydrogen, carbon monoxide and methane. Manure showed higher ash content while sorghum yielded lower amount of hydrogen. Their heating values and gas yields did not vary but were considered low ranging from only 4.09 to 4.19 MJ/m3 and from 1.8 to 2.5 m3/kg, respectively. The production of hydrogen and gas calorific values were significantly affected by biomass type but not by the operating temperature. The high values of the alkali index and base-to acid ratio indicated fouling and slagging tendencies of manure and CGT during gasification. The compressive strength profile of pelleted CGT and manure ash showed that the melting (or eutectic point) of these feedstock were around 800 degrees C for CGT and 600 degrees C for manure. Scanning electron microscopy (SEM) images showed relatively uniform bonding behavior and structure of the manure ash while CGT showed agglomeration in its structure as the temperature increased. The instrumentation of the fluidized bed gasifier and employing a process control program made its operation more convenient and safe. Further evaluation showed its application in quantifying the gasification products and predicting the slagging and fouling tendencies of selected biomass. With further development, a full automation of the operation of the gasifier may soon be realized.

To handle a great demand for biomass, alternative biomasses beyond stem wood are being introduced into the solid fuel combustion market, fuels with generally higher (>0,5 wt-%) ash content and different fuel ash compositions compared to stem wood, such as forest residue, bark, grass and straw. Unfortunately, combustion of these alternative fuels often causes more ash related problems such as fouling, slagging and higher particle emissions compared to combustion of stem wood. Many research studies have been conducted regarding ash melting and ash sintering in biomass combustion. However, literature discussing slagging of biomass ash is rather scarce, especially relating to fixed bed combustion. The majority of the biomass fuels available on the market today are phosphorus-poor and this thesis emanates from those. The overall objective was to obtain knowledge of slag formation in fixed-bed combustion of phosphorus-poor biomass, based on bench- and full-scale experiments, chemical analysis of produced ash fractions, chemical equilibrium calculations, viscosity estimations and statistical evaluations.   This thesis investigates slagging of [phosphorus-poor] biomass in fixed bed combustion. 85 fuels and 10 different burner/boiler technologies were utilized. The results in this thesis highlight the importance of the ash forming elements Si, Ca, K and Alin the slag formation process in fixed bed combustion of phosphorus-poor biomass. Increased Ca/Si ratios in the fuel reduce slag formation due to formation of more temperature stable phases, i.e. Ca/Mg-oxides and/or formation of carbonate melts with lower viscosity (not sticky) that are less prone to forming slag. A high Al/Si ratio increases the possibility of forming solid and thermally stable K−Al silicates that can reduce slag formation.   The fraction of ash melt, along with viscosity, are critical for slag formation and these parameters vary between different fuels. Four classes were defined according to their slagging potential; 1) No slag: fuel composition and the bottom ash contains low Si and K contents and higher Ca content. Fuel examples: non-contaminated stem- and pulpwood/energy wood, 2) Minor slagging tendency: fuel compositions show increased Si compared to non-slagging fuels and the bottom ash contains lower Ca, but increased Si content and approximately unchanged K content compared to the former category. Fuel examples: stem wood, bark and logging residue with increased Si-content due to light contamination. 3) Moderate slagging tendency: fuel composition contains further increased Si content. Increased share of formed silicate melt and higher viscosity (more sticky) compared to minor slagging fuels. Fuel examples: mostly contaminated woody fuels and grass and straws with relatively high amount of Ca. and 4) Major slagging tendency: Fuel composition contains high Si and K content. Sticky K-silicates causes major increase in slagging tendency. Fuel examples: different types of grass and straw fuels.   The burner/boiler technology can affect whether slagging will induce major problems in the burner or not. However, long residence times and high temperatures for the combustion residues in the hot part of the fuel bed are technical prerequisite for increased slag formation.   This thesis developed two qualitative fuel indices for predicting slagging in fixed bed combustion of phosphorus-poor biofuels – one index for fraction of fuel ash that forms slag and one index for sintering category of the formed slag. Both novel indices deliver acceptable results and are more reliable than previous indices found in the literature. Importantly, the fraction of fuel ash that forms slag index outperforms the sintering category for qualitative prediction of the problematic slagging potential of a certain fuel. Additional work is needed to further widen the compositional range as well as to fine tune the indices’ boundaries.

Degree: PhD Department: Engineering / 1997, South African’s major power utility, recognised the need to improve the understanding of fly ash formation and slag deposition of South African coals. This requirement is due to the predicted quality changes of power station feedstocks and the limited research into the slagging propensity of South African coals. This research seeks to develop an analytical technique and a fly ash formation model for predicting the slagging propensity of coals. The research will establish if the models based on Carboniferous coals can be applied to South African Permian coals. A water-cooled suction pyrometer with a custom designed slag probe was used to obtain samples of fly ash and slag from within a 200 MWe pulverised fuel boiler. Simultaneously, samples of pulverised fuel feedstock were collected. The mineral attributes in the pulverised fuel and the phases in fly ash and slag deposit were quantified by CCSEM. The analytical procedure, CCSEM, has been developed with a novel procedure for identifying minerals and C-bearing phases. The new fly ash formation model assumes that the mineral attributes of the combusting pulverised fuel particle controls the size and elemental signature of the resultant fly ash particle(s). The new model has shown that the inherent mineral attributes controls the physical and chemical characteristics of the initial fly ash phases. Thereafter, conditions (stoichiometric, temperature and turbulence) within the combustion chamber promote the physical and/or chemical interaction of the initial fly ash particles. Slag deposits are enriched in Ca- and Fe-bearing alumino-silicates. The new slagging propensity index is based on either predicting or measuring the proportion of Ca- and Fe-bearing alumino-silicates. iv The numerous fly ash formation models, based on Carboniferous coals are not necessarily valid for South African coals. It is not the integrity of the actual fly ash formation mechanisms that is questioned, but rather the experimental scale on which the models are based. This research has produced an analytical technique and a fly ash formation model to predict the slagging propensity of coals. This forms a platform for further research into the role that organically bound cations, combustion conditions and boiler configuration has on the formation of Ca- and Fe-bearing alumino-silicates.

Coal plays a significant role in meeting the world's need for energy and will continue to do so for many years to come. Economic, environmental, and public opinion are requiring coal derived energy to be cleaner and operate in a more narrow window of operating conditions. Fouling and slagging of heat transfer surfaces continues to be a challenge for maintaining boiler availability and expanding the use of available fuels and operating conditions. The work incorporates existing information in the literature on ash deposition into a User-Defined Function (UDF) for a commercial comprehensive combustion and CFD code. Results from the new submodel and CFD code is are then compared to deposition measurements in on a simulated boiler tube where particle mass deposited and ash size distribution are measured. Several model components governing various aspects of ash deposition have been incorporated into the UDF which has been implemented in a quasi-unsteady Computation Fluid Dynamics (CFD) simulation. The UDF consists of models governing ash particle impaction and sticking, thermal and physical properties of ash deposits, unsteady growth of the ash deposits, and the effects of the insulating ash layers on the combustion processes. The ash layer is allowed to transition from an accumulation of individual particles, to a sintered layer, and finally to a molten or frozen slag layer. The model attempts to predict the deposit thickness, thermal conductivity, and emittance. Measurements showed fly ash particle sizes that were much smaller than predicted under a non-fragmentation assumption. Use of a fragmentation model matched mean particle diameters well but did not match the upper tail of the particle sizes where inertial impaction takes place. Assuming 100% capture efficiency for all particles provided reasonably good agreement with measured deposition rates. The observed trend of lower deposition rates under reducing conditions was captured when the gas viscosity was calculated using the probe temperature.

Over the past few decades, a growing interest in the thermal conversion of alternative fuels such as biomass and waste-derived fuels has been observed among the energy-producing companies. Apart from meeting the increasing demand for sustainable heat and power production, other advantages such as reducing global warming and ameliorating landfilling issues have been identified. Among the available thermal conversion technologies, combustion in grate-fired furnaces is by far the most common mode of fuel conversion. In recent years, Fluidized-Bed (FB) technologies have grown to become one of the most suitable technologies for combustion and gasification of biomass and waste-derived fuels.In spite of the benefits, however, some difficulties are attributed to the thermal conversion of the alternative fuels. Ash-related issues could be a potential problem, as low-grade fuels may include considerable concentrations of ash-forming elements such as K, Na, S, Ca, Mg, P, Si and Cl. These elements undergo many undesirable chemical and physical transformations during the thermal conversion, and often cause operational problems such as deposition-related issues, slag formation in furnaces, corrosion of the heat transfer surfaces, and bed agglomeration of the fluidized-beds. Ash-related problems in the utility boilers are a major concern that may result in decreased efficiency, unscheduled outages, equipment failures, increased cleaning and high maintenance costs.This thesis investigated the ash behavior and ash-related problems in two different FB conversion systems: a Bubbling Fluidized-Bed (BFB) boiler combusting solid waste, and a Dual Fluidized-Bed (DFB) gasifier using biomass as feedstock. Full-scale measurements, chemical analysis of fuel and ash, as well as thermodynamic equilibrium modeling have been carried out for the BFB boiler (Papers I-IV), to investigate the impact of reduced-bed temperature (RBT) and also co-combustion of animal waste (AW) on the ash transformation behavior and the extent of ash-related issues in the boiler. For the DFB gasifier (Paper V), a thermodynamic equilibrium model was developed to assess the risk of bed agglomeration when forest residues are used as feedstock.The experimental results showed that the RBT and AW co-combustion could decrease or even resolve the ash-related issues in the BFB boiler, resulting in a lower deposit-growth rate in the superheater region, eliminating agglomerates, and a less corrosive deposit (in RBT case). Thermodynamic equilibrium modeling of the BFB boiler gave a better understanding of the ash transformation behavior, and also proved to be a reliable tool for predicting the risk of bed agglomeration and fouling. The modeling of the DFB gasifier indicated a low risk of bed agglomeration using the forest residues as feedstock and olivine as bed material, which was in good agreement following the observations in a full-scale DFB gasifier.

Kernthema der Dissertation ist die Weiterentwicklung von Kohle-Online-Messtechniken zur kontinuierlichen Bestimmung, das Brennstoffverhalten in Kraftwerkskesseln beeinflussender anorganischer Kohleinhaltsstoffe im Rheinischen Braunkohlerevier, die geologisch bedingt, natürlichen Schwankungen unterliegen. Im Rahmen dieses Vorhabens wurden die Gammastrahlenabsorptionsverfahren zur Aschegehaltsbestimmung und die Prompte-Gamma-Neutronen-Aktivierungs-Analyse (PGNAA) zur Multielement-Analyse als innovative Messmethoden zur Analyse des gesamten Kohlestroms auf Förderbandanlagen identifiziert, deren Eignung im Rahmen von Voruntersuchungen bestätigt, betrieblich eingeführt und unter Praxisbedingungen optimiert. Dabei wurde die Wechselwirkung zwischen Gamma- und Neutronenstrahlung unterschiedlicher Energien mit Braunkohlen und Fördergurten unterschiedlicher Eigenschaften sowie Einflüsse variierender homogener und inhomogener Elementzusammensetzungen bei verschiedenen Messsystemanordnungen und Förderleistungen auf die Messergebnisse systematisch erfasst und für die Versuchsanlagen in der betrieblichen Praxis umgesetzt. Die Gamma-Absorptionsmethode ist im betrieblichen Einsatz, die Erprobung der PGNAA-Prototypanlage steht bevor.

Coals, from mines in the Highveld coalfield, as well as gasification ash samples were characterised, in order to understand the mineralogical and chemical properties of the individual components in the gasification feedstocks. X-ray diffraction of low temperature oxygen-plasma ash indicates that the coals contain significant proportions of kaolinite, quartz and a fluxing elements-bearing mineral (dolomite), plus minor concentrations of illite and other fluxing elements-bearing minerals namely calcite, pyrite and siderite. Of the feed coal, the -75+53 mm size fraction has a high pyrite, and to a lesser extent a high calcite and dolomite content. However, the small proportion of iron-bearing phases (from the reaction between kaolinite and pyrite) in samples taken from the gasifier implies that pyrite contributes minimally to sintering or slagging in this case. Calcite is mainly present in the >1.8 g/cm3 density fraction of the feed coal, whereas dolomite is mainly present in the 1.5-1.8 g/cm3 density fraction, as inclusions or fine cleats in the coal matrix. Electron microprobe analyses of coals from the six different South African mines confirmed that some Ca, Mg, Al, Si, Na, K, Ti and Fe are present in the organic matrix in the coal samples tested in this study, but the amounts of these are small compared with the fluxing elements in minerals. XRD and microprobe analyses indicate that the ash clinker samples taken from the gasifiers contain a number of crystalline high temperature phases, including anorthite, mullite, cristobalite, quartz and diopside. FactSage confirmed that anorthite and mullite are equilibrium phases at elevated temperatures in the ash clinkers and heated rock fragments. Limited reaction takes place between the included coal minerals and the extraneous rock fragments. / Thesis (PhD)--University of Pretoria, 2008. / Materials Science and Metallurgical Engineering / unrestricted

Kernthema der Dissertation ist die Weiterentwicklung von Kohle-Online-Messtechniken zur kontinuierlichen Bestimmung, das Brennstoffverhalten in Kraftwerkskesseln beeinflussender anorganischer Kohleinhaltsstoffe im Rheinischen Braunkohlerevier, die geologisch bedingt, natürlichen Schwankungen unterliegen. Im Rahmen dieses Vorhabens wurden die Gammastrahlenabsorptionsverfahren zur Aschegehaltsbestimmung und die Prompte-Gamma-Neutronen-Aktivierungs-Analyse (PGNAA) zur Multielement-Analyse als innovative Messmethoden zur Analyse des gesamten Kohlestroms auf Förderbandanlagen identifiziert, deren Eignung im Rahmen von Voruntersuchungen bestätigt, betrieblich eingeführt und unter Praxisbedingungen optimiert. Dabei wurde die Wechselwirkung zwischen Gamma- und Neutronenstrahlung unterschiedlicher Energien mit Braunkohlen und Fördergurten unterschiedlicher Eigenschaften sowie Einflüsse variierender homogener und inhomogener Elementzusammensetzungen bei verschiedenen Messsystemanordnungen und Förderleistungen auf die Messergebnisse systematisch erfasst und für die Versuchsanlagen in der betrieblichen Praxis umgesetzt. Die Gamma-Absorptionsmethode ist im betrieblichen Einsatz, die Erprobung der PGNAA-Prototypanlage steht bevor.:1 Hintergrund und Motivation 5 1.1 Belagsbildungen bei der Verbrennung von Braunkohlen in Dampferzeugern 5 1.2 Bildungsbedingungen von Schmelzphasen in Mehrstoffsystemen 6 1.3 Methoden zur Bewertung des Ansatzbildungspotenzials 9 1.4 Geologie des Rheinischen Braunkohlenreviers 9 1.4.1 Tektonische Vorgeschichte der Niederrheinischen Bucht 9 1.4.2 Stratigrafischer und lithologischer Überblick des Rheinischen Braunkohlenreviers 11 1.5 Lagerstätten des Rheinischen Braunkohlenreviers 14 1.5.1 Tagebau Garzweiler 14 1.5.2 Tagebau Hambach 15 1.5.3 Tagebau Inden 16 1.6 Kohlesortenkonzept des Rheinischen Braunkohlenreviers 17 2 Ziel der Arbeit 21 3 Stand von Wissenschaft und Kohle-Online-Messtechnik 22 3.1 Röntgenfluoreszenzanalyse (RFA) 22 3.2 Laser-induzierte-Plasma-Spektroskopie (LIPS) 23 3.3 Gammastrahlenabsorption 24 3.4 Prompte-Gamma-Neutronen-Aktivierungsanalyse 28 3.5 Eingesetzte Messtechniken im Rheinischen Revier 30 4 Anforderungen an Kohle-Online-Messtechniken 31 4.1 Revierweite Anforderungen an Kohle-Online-Messtechniken 31 4.2 Anforderungen an Kohle-Online-Messtechniken zur Aschegehaltsbestimmung 31 4.3 Standortspezifische Anforderungen an Kohle-Online-Messtechniken 32 5 Arbeits- und Versuchsprogramm 33 5.1 Radiometrische Aschegehaltsbestimmung mittels Gammastrahlenabsorption 33 5.2 Prompte Gamma-Neutronen-Aktivierungsanalyse (PGNAA) 36 6 Versuchsergebnisse und Diskussion 41 6.1 Radiometrische Aschegehaltsbestimmung mittels Gammastrahlenabsorption 41 6.1.1 Vorversuche mit einer Americiumquelle (Am-241) am Teilstrom (Firma Berthold) 41 6.1.2 Gammastrahlenabsorption eines stahlarmierten Fördergurts 46 6.1.3 Anlagengeometrie der betrieblichen Versuchsanlagen 57 6.1.4 Vollständige Erfassung der Bandbelegung (Detektorgeometrie) 59 6.1.5 Auswirkungen der Elementverteilungen auf die Gammastrahlenabsorption 60 6.1.6 Fehlerbetrachtungen der Gammastrahlenabsorption und Optimierungsansätze 66 6.1.7 Probennahme-Techniken für Referenzwerte der Kalibrierung 68 6.1.8 Anlagen-Kalibrierung für unterschiedliche Aschegehalte 75 6.1.9 Anlagen-Kalibrierung bei unterschiedlichen Förderleistungen 76 6.1.10 Langzeitversuche zu Lagerstättendaten und weiteren Analysetechniken 77 6.1.11 Zusammenfassung der Ergebnisse 81 6.2 Prompte Gamma-Neutronen-Aktivierungsanalyse (PGNAA) 83 6.2.1 Testmessungen mittels MEDINA-Anlage am Forschungszentrum Jülich (FZJ) 83 6.2.2 Simulationsrechnungen für heterogen verteilte Sandfrachten am FZJ 95 6.2.3 Testmessungen mittels Coalscan-Anlage bei der Firma Scantech (Australien) 99 6.2.4 Zusammenfassung der Ergebnisse 105 7 Schlussfolgerungen und Fazit 106 7.1 Radiometrische Aschegehaltsbestimmung mittels Gammastrahlenabsorption 106 7.2 Prompte Gamma-Neutronen-Aktivierungsanalyse (PGNAA) 107 8 Ausblick 108 8.1 Radiometrische Aschegehaltsbestimmung mittels Gammastrahlenabsorption 108 8.2 Prompte Gamma-Neutronen-Aktivierungsanalyse (PGNAA) 109 9 Abbildungsverzeichnis 111 10 Tabellenverzeichnis 118 11 Abkürzungsverzeichnis 120 12 Literaturverzeichnis 123 13 Anhang 126