Orientador: Prof. Dr. Antonio Garrido Gallego / Dissertação (mestrado) - Universidade Federal do ABC. Programa de Pós-Graduação em Energia, 2017. / A gaseificação é o processo de conversão termoquímica de um combustível sólido em um gasoso, produzindo o chamado gás de síntese a partir da sua combustão incompleta. O caráter energético do gás de síntese provém das parcelas metano (CH4), monóxido de carbono (CO), hidrogênio (H2) presentes, permitindo assim a utilização de resíduos sólidos para produção de um gás combustível, possibilitando sua melhor valoração em energia (waste-to-energy) com a sua utilização em ciclos de potência mais eficientes a partir de ciclos combinados e ganhos ambientais com esta conversão. Também há sua valoração para síntese de outros produtos químicos (waste-to-products) com maior valor agregado. Este trabalho tem como objetivo o estudo do processo de gaseificação, culminando na criação de modelos termodinâmicos para a descrição e predição deste fenômeno. Para isso foi realizada uma revisão bibliográfica, na qual foi feito um levantamento dos principais mecanismos descritivos do processo, principais aspectos relevantes de influência, parâmetros de análise e configurações dos principais gaseificadores utilizados atualmente. Também foram avaliados os modelos utilizados na literatura para descrição do processo, que dentre os quais escolheu-se metodologias baseadas na condição de equilíbrio químico para este trabalho. Estas metodologias utilizaram o chamado modelo estequiométrico e não-estequiométrico que se baseiam na condição supracitada. Foram identificadas deficiências quanto a previsão do gás de síntese resultante dos modelos propostos quando comparadas a dados experimentais levantados na literatura. Estas derivam principalmente da não representação de alguns fatores cinéticos, principalmente no tocante ao fenômeno de decomposição térmica no processo de gaseificação. Para contornar estas limitações, a introdução de correlações externas se mostra uma ferramenta comumente utilizada na bibliografia. Assim, foi analisada a inclusão de correlações para a previsão das parcelas de CO2, H2 e CH4, e uma função para a previsão de carbono não convertido (coque). Esta última se mostrou fundamental para uma melhor acurácia da previsão do poder calorífico do gás de síntese pelos modelos propostos. / Gasification is a thermochemical conversion process of a solid combustible into gaseous phase, producing a so-called syngas from an incomplete combustion. The energetic value of syngas is due to fractions of methane (CH4), carbon monoxide (CO) and hydrogen (H2), which enable the utilization of solid residues to produce a combustible gas (waste-to-energy). Gasification provides a better energetic valuation with its utilization on more efficient power cycles through combined cycles and environmental gains due to the conversion process. In addition, it is possible to usage utilize syngas to produce other chemical compounds (waste-to-products) with a higher commercial value. This thesis main objective is to study the gasification process, where it is proposed mathematical models to describe and predicts this phenomenon. It is conducted a bibliographical review, of which includes the descriptive mechanism and main analysis influential parameters related to this process, where commonly utilized configurations gasifier is also explored. It was also analyzed the main models observed on the literature to describe the gasification process, of which was selected methodologies based on the chemical equilibrium for this work. These methodologies utilized the stoichiometric and non-stoichiometric models that were based on the previously mentioned condition. Deficiencies related to predicted values of the composition fractions of the syngas are observed when compared to experimental data from the literature. These derive mainly from the non-representation of kinetic factors, primarily due to the pyrolysis stage of the gasification process. The usage of external correlations are useful tools to smooth these deficiencies. Therefore, an analysis of the inclusion of correlations to predict gaseous fractions of CO2, H2 and CH4 of the syngas and the fraction of non-converted carbon (char) was made. The latter proposal has shown essential to a better accuracy of the modelled calorific value of syngas.

The replacement of fossil resources through renewable alternatives is one way to mitigate global climate change. Biomass is the only renewable source of carbon available for replacing oil as a refining feedstock. Therefore, it needs to be utilized not just as a fuel but for both biochemical and thermochemical conversion through biorefining. Optimizing and combining various conversion processes using a system perspective to maximize the valorization, biomass usage, and environmental benefits is of importance. This thesis work has evaluated the integration opportunities for various thermochemical conversion processes within a biorefinery system. The aim for all evaluated concepts were syngas production through gasification or reforming. Two potential residue streams from an existing biorefinery were evaluated as gasification feedstocks, thereby combining biochemical and thermochemical conversion. Torrefaction as a biomass pretreatment for gasification end-use was evaluated based on improved feedstock characteristics, process benefits, and integration aspects. A system concept, “Bio2Fuels”, was suggested and evaluated for low-temperature slow pyrolysis as a way to achieve simultaneous biomass refinement and transport driven CO2 negativity. Syngas was identified as a very suitable intermediate product for residue streams from biochemical conversion. Resulting syngas composition and quality showed hydrolysis residue as suitable gasification feedstock, providing some adjustments in the feedstock preparation. Gasification combined with torrefaction pretreatment demonstrated reduced syngas tar content. The co-gasification of biogas and wood in a FBG was successfully demonstrated with increased syngas H2/CO ratio compared to wood gasification, however high temperatures (≥1000°C) were required for efficient CH4 conversion. The demonstrated improved feedstock characteristics for torrefied biomass may facilitate gasification of biomass residue feedstocks in a biorefinery. Also, integration of a torrefaction unit on-site at the biorefinery or off-site with other industries could make use of excess low-value heat for the drying step with improved overall thermal efficiency. The Bio2Fuels concept provides a new application for slow pyrolysis. The experimental evaluation demonstrated significant hydrogen and carbon separation, and no significant volatilization of ash-forming elements (S and Cl excluded)  in low-temperature (<400°C) pyrolysis. The initial reforming test showed high syngas CH4 content, indicating the need for catalytic reforming. The collective results from the present work indicate that the application of thermochemical conversion processes into a biorefinery system, making use of by-products from biochemical conversion and biomass residues as feedstocks, has significant potential for energy integration, increased product output, and climate change mitigation.

Increased amounts of available biomass residues from agricultural food production are present widely around the globe. These biomass residues can find essential applications as bioenergy feedstock and precursors to produce value-added materials. This study assessed the production of biogenic silica (SiO2) from different biomass residues in Africa, including cornhusk, corncob, yam peelings, cassava peelings and coconut husks. Two processes were performed to synthesize the biogenic silica. First, the biomass fuels were chemically pre-treated with 1 and 5% w/v citric acid solutions. In the second stage, combustion at 600 °C for 2 h in a muffle oven was applied. The characterization of the untreated biomasses was conducted using Inductively coupled plasma—optical emission spectrometry (ICP-OES), thermal analysis (TG-DTA) and Fourier-transform infrared spectroscopy (FTIR). The resulting ashes from the combustion step were subjected to ICP, nitrogen physisorption, Energy dispersive X-ray spectroscopy (EDX) as well as X-ray diffraction (XRD). ICP results revealed that the SiO2 content in the ashes varies between 42.2 to 81.5 wt.% db and 53.4 to 90.8 wt.% db after acidic pre-treatment with 1 and 5 w/v% acid, respectively. The relative reductions of K2O by the citric acid in yam peel was the lowest (79 wt.% db) in comparison to 92, 97, 98 and 97 wt.% db calculated for corncob, cassava peel, coconut husk and cornhusk, respectively. XRD analysis revealed dominant crystalline phases of arcanite (K2SO4), sylvite (KCl) and calcite (CaCO3) in ashes of the biomass fuels pre-treated with 1 w/v% citric acid due to potassium and calcium ions present. In comparison, the 5 w/v% citric acid pre-treatment produced amorphous, biogenic silica with specific surface areas of up to 91 m2/g and pore volumes up to 0.21 cm3/g. The examined biomass residues are common wastes from food production in Africa without competition in usage with focus application. Our studies have highlighted a significant end-value to these wastes by the extraction of high quality, amorphous silica, which can be considered in applications such as catalyst support, construction material, concrete and backing material.

The need for effective disposal of huge volumes of industrial waste is becoming more challenging due to expected imposition of stringent pollution control regulations in the near future. Thermochemical conversion, particularly gasification of organics in the waste is considered the best route from the perspective of volume reduction and prevalent eco-friendly concept of waste-to-energy transformation. It is considered imperative to have adequate understanding of basic combustion features as a part of the thermochemical conversion process, leading to gasification. The aim of this thesis is to understand the fundamental combustion processes associated with one of the top listed hazardous wastes from distilleries (Biochemical Oxygen Demand (BOD) ~ 40,000 - 50,000 mg/L), commonly known as vinasse, stillage or spent wash, through experiments and modeling efforts. Specially designed experiments on distillery effluent combustion and gasification are conducted in laboratory scale reactors. As an essential starting point of the studies on ignition and combustion of distillery effluent containing solids consisting of 62 ± 2 % organics and 38 ± 2 % inorganics (primarily sugarcane derivatives), the roles of solids concentration, drop size and ambient temperature were investigated through experiments on (1) liquid droplets of 65 % and 77 % solids (remaining water) and (2) spheres of dried effluent (100 % solids) of size 0.5 mm to 20 mm diameter combusted at ambient temperatures of 773 to 1273 K. The investigation reveals that the droplets burn with two distinct regimes of combustion, flaming and char glowing. The ignition delay ‘t1’ of the droplets increased with size as is in the case of non-volatile droplets, while that of bone-dry spheres was found to be independent of size. The ‘t1’ decreased with increase in solids concentration. The ignition delay has showed an Arrhenius dependence on temperature. The initial ignition of the droplets and the dry spheres led to either homogeneous (flaming) or heterogeneous (flameless) combustion, depending on the ambient temperature in the case of sphere and on solid concentration and the ambient temperature, in the case of liquid droplets. The weight loss during the flaming combustion was found to be 50 - 80 % while during the char glowing it was 10-20 % depending on the ambient temperature. The flaming time tc is observed as tc~ d2c , as in the case of liquid fuel droplets and wood spheres. The char glowing time tc' is observed as tc ~ d2c as in the case of wood char, though the inert content of effluent char is as large as 50 % compared to 2 - 3 % in wood char. In the case of initial flameless combustion, the char combustion rate is observed to be lower. The heterogeneous char combustion in quiescent air in controlled temperature conditions has been studied and modeled using one-dimensional, spherico-symmetric conservation equations and the model predicts most of the features of char combustion satisfactorily. The measured surface and core temperatures during char glowing typically are in the range of 200 to 400 K and are higher than the controlled temperature of the furnace. Based on the results of single droplet combustion studies, combustion experiments were conducted in a laboratory scale vertical reactor (throughput ranging from 4 to 10 g/s) with the primary aim of obtaining sustained combustion. Spray of effluents with 50 % and 60 % solids (calorific value 6.8 - 8.2 MJ/kg), achieved by an air blast atomizer, was injected into a hot oxidizing environment to determine the parameters (ambient temperature and air-fuel ratio) at which auto-ignition could occur and subsequently studies were continued to investigate pre-ignition, ignition and combustion processes. Effluent with lower solids concentration was considered first from the point of view of the less expensive evaporator required in the field conditions for concentration and a spin-off in terms of better atomization consequently. Three classes of experiments were conducted: 1) Effluent injection from the wall with no auxiliary heat input, 2) Effluent injection with auxiliary heat input and 3) effluent injection within kerosene enveloping flame. Though individual particles in the spray periphery were found to combust, sustained spray combustion was not achieved in any of the three sets of experiments even with fine atomization. While conducting the third class of experiments in an inclined metallic reactor, sustained combustion of the pool resulting of accumulated spray seemed to result in large conversion of carbon. This led to the adoption of a new concept for effluent combustion in which the residence time is controlled by varying reactor inclination and the regenerative heat transfer from the product gases supplies heat for endothermic pre-ignition process occurring on the bed. Combustion and gasification experiments were conducted in an inclined plate reactor with rectangular cross section (80 mm x 160 mm) and 3000 mm long. A support flame was found necessary in the injection zone in addition to the regenerative heat transfer. Effluent with 60% solids was injected as film on the reactor bed. This film disintegrated into fine particles due to induced aerodynamic stretching and shear stripping. Combustion of individual particles provided exothermic heat profile and resulted into high carbon conversion. However, effluent clogging in the cold injection zone hindered system from attaining steady state. Effluent injected directly on the hot zone caused it to remain mobile due to the spheroidal evaporation and thus assuaging this problem. Improved mass distribution was achieved by displacing nozzle laterally in a cycle, actuated by a mechanism. Consistent injection led to sustained effluent combustion with resulting carbon conversion in excess of 98 %. The typical gas fractions obtained during gasification condition (air ratio = 0.3) were CO2 = 14.0 %, CO = 7.0 %, H2 = 12.9 %, CH4 - 1 % H2S = 0.6 - 0.8 % and about 2 % of saturated moisture. This composition varied due to variation in temperature (± 30 K) and is attributed to combined effect of local flow variations, shifting zones of endothermic processes due to flowing of evaporating effluent over a large area. In order to minimize this problem, experiments were conducted by injecting effluent at higher solids (73 % solids is found injectable). The effluent was found to combust close to the injection location-due to the reduced ignition delay and lower endothermic evaporation load helped raising the local temperature. This caused the pyrolysis to occur in this hottest zone of the reactor with higher heating rates resulting in larger yield of devolatilized products and improved char conversion. Effluent combustion was found to sustain temperature in the reactor under sub-stoichiometric conditions without support of auxiliary heat input and achieved high carbon conversion. These results inspired the use of higher concentration effluent, which is also known in the case of wood to have improved gasification efficiency due to reduction in moisture fraction. In addition, the recent studies on the sulfur emission in the case of black liquor combustion in recovery boilers have revealed that with increase in solids concentration, release of sulfur in gas phase is reduces. The required concentration can be carried out using low-grade waste heat from the reactor itself. It was found through experiments that, even though spray ignition occurred at this concentration, the confined reactor space prevented the spray from attaining sustained combustion. This led to the conduct of experiments in a new vertical reactor with adequate thermal inertia, essential to prevent variations in local temperature to reach a steady state gasification and required space to accommodate the spray. The results of the experiments conducted in the vertical reactor in which effluents with 73 % solids, heated close to the boiling point and injected as fine spray in a top-down firing mode are consolidated and reported in the thesis in detail. Single particle combustion with enveloping faint flame was seen unlike stable flame found in coal water slurry spray combustion. Sustained gasification of gas-entrained particles occurred at reactor temperature in the range of 950 K - 1000 K and sub-stoichiometric air ratio 03 - 0.35 without the support of auxiliary fuel. The typical gas fractions obtained during gasification condition (air ratio = 0.3) were CO2 = 10.0 -11.5 %, CO - 10.0 - 12.0 %, H2 - 6.7 - 8.0 %, CH4 = 1.75 % H2S = 0.2 - 0.4 % and about 2 % of saturated moisture. The carbon conversion obtained was in the range of 95 - 96 %. These experiments have provided the conditions for gasification. The extraction of potassium salts (mostly sulfates, carbonate and chloride) from the ash, using a simple water leaching process, was found to recover these chemicals to as high an extent as 70 - 75 % of total ash. In summary it is concluded that increasing the solid concentrations to as high levels as acceptable to the system (~ 75 %) and introducing as a fine spray of heated material (~ 363 K) into furnace with air at sub-stoichiometric conditions in a counter current combustion reactor will provide the frame work for the design of a gasification system for vinasse and similar effluent material. The thesis consists of seven chapters. Chapter 1 introduces the problem and motivation of the work presented in the thesis. Literature review is presented in Chapter 2. The Chapter 3 deals with the single particle combustion studies. The results of effluent spray combustion experiments conducted in a laboratory scale vertical reactor are presented in Chapter 4. The results of combustion and gasification experiments conducted in another variant of a reactor, namely, inclined flat plate rectangular reactor is consolidated in Chapter 5. The results of gas-entrained spray gasification experiment of higher concentration effluent injected as spray in the vertical reactor are presented in Chapter 6. The general conclusions and scope for the future work are presented in the concluding chapter 7.

Cette thèse décrit le développement de procédés utilisables pour valoriser des extraits de bois afin de préparer : (1) des combustibles (hydrocarbures) liquides ; (2) des matériaux poreux avec des applications potentielles dans les domaines de l’énergie et l’environnement, notamment isolation thermique, catalyse, piégeage et séparation de micropolluants. Les extraits de bois en question sont des lignines, associées ou non à des tannins. Les deux types de matériaux sont actuellement peu valorisés, et l’on montre qu’ils peuvent être source de valeur ajoutée au travers des procédés rapportés dans ce mémoire / The present thesis describes the development of processes which can be used for valorizing wood extracts in the aim of preparing: (1) liquid (hydrocarbon) fuels; (2) porous materials with potential energy and environmental applications, namely thermal insulation, catalysis, abatement or separation of micropollutants. The wood extracts in question are lignins, associated or not with tannins. Both kinds of materials are presently poorly valorized, and it is shown here that they can lead to high added-value products through the processes reported in this PhD dissertation