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.

Made available in DSpace on 2016-06-02T19:55:42Z (GMT). No. of bitstreams: 1 6569.pdf: 7813080 bytes, checksum: 5bddbc1ed667ee4456bc01f930d2c15a (MD5) Previous issue date: 2014-11-25 / Financiadora de Estudos e Projetos / study evaluated the production of hydrogen and methane from sugarcane vinasse in anaerobic fluidized bed reactor. Two fluidized bed reactors filled with expanded clay were operated under two different concentrations: R5 (5 gCOD.L-1) and R10 (10 g.CODL-1). During the first stage, glucose was used as the primary carbon source. Along the first step vinasse was added from 0% to 100% of the organic source under HRT of 6 h. In a second step with 100% of sugarcane vinasse, HRT was reduced to 4, 2 and 1 h. In another reactor R15 (15 gCOD.L-1) it was varied the substrate (100% glucose; 50 % glucose/ 50 % vinasse; 100 % vinasse) under HRT of 8 h. All reactors were operated in room temperature and a sludge from the treatment of swine wastewater was used. It was not observed methane production in R15. Hydrogen production rate and hydrogen yield reached, respectively: 0,01 L.h-1.L-1 e 0,10 mmolH2.g-1COD added. In reactors R5 and R10, biogas was formed by H2 and CO2 when glucose was present in the feed. Methane was formed when vinasse became the main substrate. The best operating condition occurred under HRT of 1 h, vinasse 100% at a concentration of 5 gCOD. L-1 with a hydrogen production rate of 0.57 L.h.-1L-1. As regards the yield, the best condition was under HRT of 6 h when the affluent comprised vinasse and glucose (3:1) reaching an yield of 3.07 mmolH2.g-1CODadded. Methane production in acidic conditions showed that the methanogens have adapted to a slightly acidic pH of 4.5. The principal metabolites were ethanol, butyric acid, propionic acid and methanol. Microbial characterization revealed the presence of Prevotella and Megasphaera belonging to the domain Bacteria and Methanobacterium and Methanosphaera belonging to the Archaea domain. / O presente estudo avaliou a produção de hidrogênio e metano a partir de vinhaça de cana-de-açúcar em reator anaeróbio de leito fluidizado. Dois reatores de leito fluidizado preenchidos com argila expandida foram operados sob duas diferentes concentrações de substratos: R5 (5 gDQO.L-1) e R10 (10 gDQO.L-1). Durante a primeira etapa, a glicose foi utilizada como fonte de carbono principal. Em seguida, a vinhaça foi adicionada passando de 0% a 100% da fonte orgânica sob o tempo de detenção hidráulica de 6 h. Numa segunda etapa com 100 % de vinhaça, foi feita a redução do TDH para 4, 2 e 1 h. Um terceiro reator foi empregado com uma concentração maior R15 (15 gDQO.L-1) na qual foi variado o substrato (100% glicose, 50% glicose/50 % vinhaça, 100 % vinhaça) sob o tempo de detenção hidráulica de 8 h. Todos os reatores foram operados em temperatura ambiente e foi utilizado lodo proveniente do tratamento de resíduos da suinocultura. Não foi observada produção de metano no reator R15, apenas H2 e CO2. A produção volumétrica e rendimento de hidrogênio atingiu um máximo de 0,01 L.h-1.L-1 e 0,10 mmolH2.g- 1DQOadicionada na fase de alimentação com vinhaça. Nos reatores R5 e R10 o biogás foi formado por H2 e CO2 quando ainda havia glicose como substrato. Metano foi formado quando a vinhaça se tornou o substrato principal. A melhor condição de operação se deu sob o TDH de 1 h, vinhaça 100 % a uma concentração de 5 gDQO.L-1 quando foi obtida uma produção volumétrica de hidrogênio de 0,57 L.h-1.L-1. No que se refere ao rendimento, a melhor condição se deu sob o TDH de 6 h quando o afluente era constituído por vinhaça e glicose (3:1) e um rendimento de 3,07 mmolH2.g-1DQOadicionada. A produção de metano em condições ácidas mostrou que as metanogênicas consumidoras de hidrogênio se adaptaram ao pH levemente ácido de 4,5. Os principais metabólitos produzidos foram etanol, ácido butírico, ácido propiônico e metanol. A caracterização microbiana revelou a presença de Prevotella e Megasphaera pertencentes ao domínio Bacteria e Methanobacterium e Methanosphaera pertencentes ao domínio Archaea.