A mathematical model for entrained flow coal gasification was developed with the objective of predicting the influence of coal properties and gasification conditions on the performance of entrained flow gasifiers operating at pressures up to 21 atmospheres (2.1MPa). The model represents gasifiers as plug flow reactors and therefore neglects any mixing or turbulence effects. Coal properties were predicted through use of correlations from a variety of literature sources and others that were developed from experimental data in the literature. A sensitivity analysis of the model indicated that errors in the calculated values of coal volatile yield, carbon dioxide gasification reactivity and steam gasification may significantly affect the model predictions. Similarly errors in the input values for gasifier wall temperatures and gasifier diameter, when affected by slagging, can cause model prediction errors. Model predictions were compared with experimental gasification results for a range of atmospheric and high pressure gasifiers, the majority of the results being obtained by CSIRO at atmospheric pressure for a range of coals. Predictions were accurate for the majority of atmospheric pressure results over a large range of gas feed mixtures. Due to the limited range of experimental data available for high pressure gasification the capability of the model is somewhat uncertain, although the model provided accurate predictions for the majority of the available results. The model was also used to predict the trends in particle reactions with gasification and the influence of pressure, gasifier diameter and feed coal on gasifier performance. Further research on coal volatile yields, gasification reactivities and gas properties at high temperatures and pressures was recommended to improve the accuracy of model inputs. Additional predictions and model accuracy improvements could be made by extending the model to include fluid dynamics and slag layer modelling. / PhD Doctorate

No description available.

This work has examined the thermochemical conversion of sugar cane processing wastes (bagasse and cane harvesting trash) for use in the design of pressurised entrained flow gasification power cycles (~20 Barg, 600-900oC). The two key parameters of interest were the residual char yield from initial pyrolysis and the heterogeneous reactivity of the char with respect to carbon dioxide. Char yield and gasification rates were measured by a conventional wire mesh reactor and thermogravimetric (TGA) technique, an in-situ sample charring TGA technique and with an entrained flow reactor specifically designed for this work. The new experimental reactor concept is one of the major contributions of the work. Chars from the entrained flow experiments were characterised by optical microscope, SEM/EDS, TEM/EDS and XPS techniques, to help elucidate the processes occurring during pyrolysis and gasification. The key findings and conclusions of the work were as follows: 1. Initial (pyrolysis) char yields were consistent with the data reported in literature for similar materials. Char yields varied with reaction conditions, from 6 to 49 wt% daf for cane trash and 4 to 40 wt% daf for bagasse. Ash content also had a significant effect on char yield. The char yield for both cane trash and bagasse increased in proportion to the logarithm of system pressure. 2. A relatively simple empirical model for char yield under pressurised entrained flow conditions was formulated. This could predict char yields for both the experimental data in this work and those reported in literature for similar biomass materials. While temperature, pressure and ash content were all significant parameters in the model, the primary fitting parameter was a measure of the contribution of secondary char forming reactions and ongoing pyrolysis to char yield. The identification of this parameter is one of the contributions of this work. 3. The measured initial rate of char gasification by carbon dioxide was 0.06 to 1.2 mg per gram of initial char, over the temperature range 750 to 900oC. The rate of gasification was so low as to not contribute significantly to overall fuel conversion in the reaction residence times iv expected of a commercial gasifier. In essence almost all of the experimentally measured fuel conversion could be attributed to pyrolysis, which resulted in 85-95% fuel conversion. 4. Both the raw materials and the residual chars had low surface areas and negligible microporosity. The majority of the measured surface area may have been associated with the ash component rather than the carbonaceous component, which supported the finding of low reactivity. 5. The silica component of the chars exhibited crystalline silicate formation by migration of metal species over time periods of minutes. These silicates displayed signs of sintering, but otherwise remained physically intact; leaving a characteristic skeleton that corresponded to the original structure in the raw materials. 6. The gasification rate showed a time dependent decrease in the entrained flow experiments. This was attributed to coke formation on the char surface, followed by carbon trapping in the ash component at high levels of conversion. Both findings are significant contributions from this work, because they highlight key mechanisms that hinder fuel conversion in the proposed gasification concept. The broad coverage achieved in this work has provided an overall picture of how fuel conversion progresses during the pressurised entrained flow gasification of sugar cane wastes. It is recommended that many of the aspects highlighted in this work be examined further, to confirm the findings and to investigate the means to avoid the factors identified in this work as hindering fuel conversion.

In this work the differences between and characteristics of water and high solids, heated black liquor sprays from air-assist atomizers are examined. Sprays were imaged with a high speed camera and the images analyzed with computer code to produce droplet size data and macroscopic spray characteristics such as mass distribution. Fluid flow rates were measured to allow relevant dimensionless groups for the spray to be calculated. A 1000 degree C tubular furnace was placed around the spray to determine the effect of industrially relevant temperatures on the droplet formation process, relative to room-temperature conditions. It was found that high solids black liquor forms long, thin ligaments rather than droplets. In high-temperature surroundings the size of these ligaments increases, which from a comparison with theory in the literature was attributed to enhanced skin-formation driven by heat transfer. The data suggest that this skin formation may prevent secondary breakup. All sprays for both fluids produced droplet size mass distributions that were well described by the square-root normal distribution. The normalized width (s*) of these distributions was similar for all sprays and consistent with literature data for other nozzle designs (0.24 < s* < 0.38). The image analysis method assumed droplets were spheres with the same projected area. When this assumption was changed for black liquor sprays to a cylindrical droplet assumption, the shape and normalized width of the resulting mass distributions remained the same, but the representative diameter (calculated from surface area to volume ratios) decreased. Based on the agreement between the normalized distribution width in this work and that in the black liquor spraying literature it was concluded that the addition of atomizing air cannot be considered a means to narrow a droplet size distribution independent of droplet size. The results also indicate the importance of including the effects of skin formation and temperature- and time-dependent fluid properties in spray modeling. It is intended that these results contribute to increased understanding of the black liquor atomization process and lead to improved computational modeling of the same.

Increasing the share of biomass, preferably by replacing fossil fuels, is one way to mitigate the present climate change. Fossil coal can be directly replaced by co-combustion of coal and biomass and fossil engine fuels (gasoline and diesel) could potentially partly be replaced by synthetic renewable fuels produced via entrained flow gasification of biomass. The use of biomass in these processes is so far limited, partly because of the fibrous and hygroscopic nature of biomass which leads to problem in storing, transportation, handling and feeding. This thesis demonstrates how the challenging characteristics of raw biomass are mitigated by the pretreatment method torrefaction. Torrefaction is a process where biomass is heated in an oxygen deficient atmosphere to typically between 240 and 350°C for a time period of 2 minutes to 1 hour. Most of the torrefaction R&amp;D in the literature have so far been performed with bench-scale batch reactors. For the purpose of carefully studying continuous torrefaction, a 20 kg/h torrefaction pilot plant was therefore designed, constructed and evaluated. The overall conclusion from this thesis is that the many benefits of torrefied biomass are valid also when produced with a continuous pilot plant and for typically Swedish forest biomasses. Some of the documented improved biomass properties are increased heating value, increased energy density, higher friability (lower milling energy) and less hydrophilic biomass (less moisture uptake). Most of the improvements can be attributed to the decomposition of hemicellulose and cellulose during torrefaction. The most common variables for describing the torrefaction degree are mass yield or anhydrous weight loss but both are challenging to determine for continuous processes. We therefore evaluated three different methods (one existing and two new suggestions) to determine degree of torrefaction that not require measurement of mass loss. The degree of torrefaction based on analyzed higher heating value of the raw and torrefied biomass (DTFHHV) predicted mass yield most accurate and had lowest combined uncertainty. Pelletizing biomass enhance transportation and handling but results from pelletization of torrefied biomass is still very limited in the literature and mainly reported from single pellet presses. A pelletization study of torrefied spruce with a ring die in pilot scale was therefore performed. The bulk energy density was found to be 14.6 GJ/m3 for pelletized torrefied spruce (mass yield 75%), a 40% increase compared to regular white pellets and therefore are torrefied pellets more favorable for long distance transports. More optimization of the torrefied biomass and the pelletization process is though needed for acquiring industrial quality pellets with lower amount of fines and higher pellet durability than attained in the present study. Powders from milled raw biomass are generally problematic for feeding and handling and torrefied biomass has been proposed to mitigate these issues. The influence of torrefaction and pelletization on powder and particle properties after milling was therefore studied. The results show that powder from torrefied biomass were enhanced with higher bulk densities, lower angle of repose as well as smaller less elongated particles with less surface roughness. Even higher powder qualities were achieved by pelletizing the torrefied biomass before milling, i.e. another reason for commercial torrefied biomass to be pelletized. Entrained flow gasification (EFG) is a promising option for conversion of biomass to other more convenient renewable energy carriers such as electricity, liquid biofuels and green petrochemicals. Also for EFGs are torrefied fuels very limited studied. Raw and torrefied logging residues were successfully gasified in a pilot scale pressurized entrained flow biomass gasifier at 2 bar(a) with a fuel feed corresponding to 270 kWth. Significantly lower methane content (50% decrease) in the syngas was also demonstrated for the torrefied fuel with mass yield 49%. The low milling energy consumption for the torrefied fuels compared to the raw fuel was beneficial for the gasification plant efficiency.

Numerical simulations of coal gasification process inside a generic 2-stage entrainedflow gasifier are carried out using the commercial CFD solver ANSYS/FLUENT. The 3-D Navier-Stokes equations and eight species transport equations are solved with three heterogeneous global reactions, three homogeneous reactions, and one thermal cracking equation of volatiles. Finite rates are used for the heterogeneous solid-gas reactions. Both finite rate and eddy-breakup combustion models are calculated for each homogeneous gas-gas reaction, and the smaller of the two rates is used. Lagrangian-Eulerian method is employed. The Eulerian method calculates the continuous phase while the Lagrangian method tracks each coal particle. Fundamental study is carried out to investigate effects of five turbulence models (standard k-ε, k-ω, RSM, k-ω SST, and k-ε RNG) and four devolatilization models (Kobayashi, single rate, constant rate, and CPD) on gasification simulation. A study is also conducted to investigate the effects of different operation parameters on gasification process including coal mixture (dry vs. slurry), oxidant (oxygen-blown vs. air-blown), and different coal distributions between two stages. Finite-rate model and instantaneous gasification model are compared. It is revealed that the instantaneous gasification approach can provide an overall evaluation of relative changes of gasifier performance in terms of temperature, heating value, and gasification efficiency corresponding to parametric variations, but not adequately capture the local gasification process predicted by the finite rate model in most part of the gasifier. Simulations are performed to help with design modifications of a small industrial demonstration entrained-flow gasifier. It is discovered that the benefit of opening the slag tap on the quench-type gasifier wider by allowing slag to move successfully without clogging is compromised by increased heat losses, reduced gasification performance, downgraded syngas heating value, and increased unburned volatiles. The investigation of heat transfer on fuel injectors shows that blunt tip fuel injector is less likely to fail compared to conical tip fuel injector because the maximum high temperature on the injector is scattered. Two concentric fuel/oxidant injections provide better fuel-oxidant mixing and higher syngas heating value than four separate fuel and oxidant injections.

No description available.

La gazéification de la biomasse a été étudiée dans les conditions d'un réacteur à flux entraîné, à savoir à vitesse de chauffage et à température élevées. Des expériences ont été réalisées dans un four à chute entre 800°C et 1400°C, à partir de particules de bois de taille 0,35 mm et 0,80 mm, dans une atmosphère inerte (100% molaire de N2), ou contenant de la vapeur d’eau (25% molaire). Les expériences ont également été simulées grâce à un modèle 1D avec des résultats positifs, ce qui a permis de mieux comprendre les phénomènes mis en jeu. Les solides obtenus (suies et char) ont été analysés et caractérisés. Des rendements élevés en gaz et goudrons, et un faible rendement en char ont été mesurés. Par conséquent, l'évolution de la phase volatile est déterminante pour les rendements des produits finaux. Au-dessus de 1000°C, la formation de suies devient importante. Les suies sont formées à partir de C2H2 et de HAP. En présence de vapeur d’eau, le rendement en suies est nettement moins élevé, ce qui s’explique essentiellement par le vaporeformage des précurseurs de suie, mais aussi par leur gazéification. La réaction de water-gas shift joue un rôle important dans la distribution des gaz majoritaires. La gazéification du char a été mise en évidence à 1200°C et 1400°C sous atmosphère humide. L'ensemble de ces réactions conduit à un gaz riche en H2, CO et CO2. L'équilibre thermodynamique est presque atteint à 1400°C avec une concentration de 25% molaire de H2O dans l’atmosphère. La graphitisation et la désactivation du char porté à haute température ont été mises en évidence expérimentalement. Néanmoins, ces phénomènes ont une influence négligeable sur l’évolution du rendement en char lors des expériences en four à chute. Enfin, la taille des particules n’a presque aucune influence sur les résultats expérimentaux. / Biomass gasification was studied in the conditions of an entrained flow reactor, namely at high heating rate and temperature. Experiments in a drop tube reactor were performed between 800°C and 1400°C, with wood particles of 0.35 mm and 0.80 mm size, under inert and steam containing - 25 mol% of H2O - atmospheres. These experiments were also simulated with a 1D model which gave good predictions. The collected solids, soot and char, were analyzed and characterized. This study highlights the importance of gas phase reactions on the yields of the final products, mainly gaseous compounds, in these conditions. These reactions are hydrocarbons cracking, reforming and polymerization, leading to soot formation, and water-gas shift. Char graphitization and deactivation were experimentally demonstrated. However, these phenomena have a negligible influence on char evolution in the drop tube reactor. Finally, the particle size was shown to have almost no influence on experimental results.

The last couple of decades have seen entrained-flow gasification of black liquor (BL) undergo an incremental process of technical development as an alternative to combustion in a recovery boiler. The ability of the technology to combine chemical recovery with the production of clean syngas renders it a promising candidate for the transformation of chemical pulp mills into integrated forest biorefineries. However, techno-economic assessments have shown that blending BL with the more easily transportable pyrolysis oil (PO) can not only increase the system efficiency for methanol production but remove a significant roadblock to development by partially decoupling production capacity from limitations on black liquor availability. The verification and study of catalytic co-gasification in an industrially-relative scale can yield both scientifically interesting and practically useful results, yet it is a costly and time-consuming enterprise. The expense and time involved can be significantly reduced by performing thermodynamic equilibrium calculations using a model that has been validated with relevant experimental data. The main objective of this thesis was to study, understand, quantify and compare the gasification behaviour and process performance of black liquor and pyrolysis oil blends in pilot-scale. A secondary objective of this work was to demonstrate and assess the usefulness and accuracy of unconstrained thermodynamic equilibrium modelling as a tool for studying and predicting the characteristics of alkali-impregnated biomass entrained-flow gasification. The co-gasification of BL/PO blends was studied at the 3 MWth LTU Green Fuels pilot plant in a series of experimental studies between June 2015 and April 2016. The results of the studies showed that the blending of black liquor with the more energy rich pyrolysis oil increased the energetic efficiency of the BLG process without adversely affecting carbon conversion. The effect of blend ratio and reactor temperature on the gasification performance of PO and BL blends with up to 20 wt% PO was studied in order to assess the impact of alkali-dilution in fuel on the conversion characteristics. In addition to unblended BL, three blends with PO/BL ratios of 10/90, 15/85 and 20/80 wt% were gasified at a constant load of 2.75 MWth. The decrease in fuel inorganic content with increasing PO fraction resulted in more dilute green liquor (GL) and a greater portion of the feedstock carbon ended up in syngas as CO. As a consequence, the cold gas efficiency increased by about 5%-units. Carbon conversion was in the range 98.8-99.5% and did not vary systematically with either fuel composition or temperature. The validation of thermodynamic equilibrium simulation of black liquor and pyrolysis co-gasifications with experimental data revealed the need to be mindful of errors and uncertainities in fuel composition that can influence predictions of equilibrium temperature. However, provided due care is to taken to ensure the use of accurate fuel composition data, unconstrained TEMs can serve as a robust and useful tool for simulating catalytic entrained-flow gasification of biomass-based feedstocks. / LTU Biosyngas (Catalytic Gasification)

Gasification of black liquor is an alternative to the combustion of black liquor, which is currently the dominant form of chemical recovery in the paper industry. Gasification of black liquor offers the possibility of higher thermal efficiencies than combustion, reducing manufacturing costs and creating new revenue streams through a forest biorefinery. Pressurizing the gasification reactor further enhances the efficiency advantage of gasification over combustion. This study uses a pressurized entrained flow reactor (PEFR) to study black liquor gasification behavior under pressures, temperatures, and heating rates similar to those of next-generation high-temperature black liquor gasifiers. The effects of pressure on black liquor char morphology, gasification rates, pyrolysis carbon yields, and sulfur phase distribution were studied. These characteristics were investigated in three main groups of experiments at 900oC: pyrolysis (100% N2), gasification with constant partial pressure (0.25 bar H2O and 0.50 bar CO2), and gasification with constant mole fraction (10% CO2, 2% H2O, 1.7% CO, 0.3% H2), under five, ten, and fifteen bar total pressure. It was found that pressure had an impact on the char physical characteristics immediately after the char entered the reactor. Increasing pressure had the effect of decreasing the porosity of the chars. Pressure also affected particle destruction and reagglomeration mechanisms. Surface areas of gasification chars decreased with increasing pressures, but only at low carbon conversions. The rate of carbon conversion in gasification was shown to be a function of the gas composition near the particle, with higher levels of inhibiting gases slowing carbon conversion. The same phenomenon of product gas inhibition observed in gasification was used to explain carbon conversions in pyrolysis reactions. Sulfur distribution between condensed and gas phases was unaffected by increasing total pressure in the residence times investigated. Significant amounts of sulfur are lost during initial devolatilization. With water present this gas phase sulfur forms H2S and did not return to the condensed phase.