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Master of Science / Department of Civil Engineering / Natalie Mladenov / In the United States approximately 37% of the 4 trillion kWh of electricity is generated annually by combusting coal (USEPA, 2013). The abundance of coal, ease of storage, and transportation makes it affordable at a global scale (Ghose, 2009). However, the flue gas produced by combusting coal affects human health and the environment (USEPA, 2013). To comply with federal regulations coal-fired power plants have been implementing sulfur dioxide scrubbing systems such as flue gas desulfurization (FGD) systems (Alvarez-Ayuso et al., 2006). Although FGD systems have proven to reduce atmospheric emissions they create wastewater containing harmful pollutants. Constructed wetlands are increasingly being employed for the removal of these toxic trace elements from FGD wastewater. In this study the effectiveness of using a constructed wetland treatment system was explored as a possible remediation technology to treat FGD wastewater from a coal-fired power plant in Kansas. To simulate constructed wetlands, a continuous flow-through column experiment was conducted with undiluted FGD wastewater and surface sediment from a power plant in Kansas. To optimize the performance of a CWTS the following hypotheses were tested: 1) decreasing the flow rate improves the performance of the treatment wetlands due to an increase in reaction time, 2) the introduction of microbial cultures (inoculum) will increase the retention capacity of the columns since constructed wetlands improve water quality through biological process, 3) the introduction of a labile carbon source will improve the retention capacity of the columns since microorganisms require an electron donor to perform life functions such as cell maintenance and synthesis. Although the FGD wastewater collected possessed a negligible concentration of arsenic, the mobilization of arsenic has been observed in reducing sediments of wetland environments. Therefore, constructed wetlands may also represent an environment where the mobilization of arsenic is possible. This led us to test the following hypothesis: 4) Reducing environments will cause arsenic desorption and dissolution causing the mobilization of arsenic. As far as removal of the constituents of concern (arsenic, selenium, nitrate, and sulfate) in the column experiments, only sulfate removal increased as a result of decreasing the flow rate by half (1/2Q). In addition, sulfate-S exhibited greater removal as a result of adding organic carbon to the FGD solution when compared to the control (at 1/2Q). Moderate selenium removal was observed; over 60% of selenium in the influent was found to accumulate in the soil. By contrast, arsenic concentrations increased in the effluent of the 1/2Q columns, most likely by dissolution and release of sorbed arsenic. When compared to the control (at 1/2Q), arsenic dissolution decreased as a result of adding inoculum to the columns. Dissolved arsenic concentrations in the effluent of columns with FGD solution amended with organic carbon reached 168 mg/L. These results suggest that native Kansas soils placed in a constructed wetland configuration and amended with labile carbon do possess an environment where the mobilization of arsenic is possible.

O carvão mineral apresenta-se como uma importante alternativa para geração termoelétrica no Brasil. Os carvões brasileiros, porém, são caracterizados por elevados teores de enxofre, e na sua combustão libera-se consideráveis de quantidades dióxido de enxofre. O processo de combustão em leito fluidizado apresenta-se particularmente adequado para a queima destes carvões, notadamente devido à possibilidade da utilização de absorventes calcários para remoção in loco do dióxido de enxofre produzido na combustão. Neste trabalho estudou-se a combustão em leito fluidizado atmosférico borbulhante de um carvão mineral beneficiado para uso termoelétrico denominado CE4500, procedente de Criciúma-SC. Para absorção de enxofre utilizou-se um calcário dolomítico procedente de Ipeúna-SP. Utilizou-se a planta piloto para combustão em leito fluidizado do Laboratório de Engenharia Térmica e Fluidos da EESC-USP, com câmara de combustão de 0,5 x 0,5 m de seção transversal e 3 m de altura. Ensaios foram realizados para diferentes velocidades de fluidização e relações (Ca+Mg)/S de alimentação. Concentrações de gases foram medidas ao longo da altura e da seção transversal do reator, permitindo verificar a homogeneidade do processo, além do efeito dos pontos de alimentação de carvão e calcário sobre esta homogeneidade. Determinou-se conversões e coeficientes globais de taxa de reação para a combustão do carvão e para a sulfatação do calcário. Avalia-se que os resultados obtidos representam uma significativa contribuição para auxílio ao projeto de reatores, e para a validação de modelos matemáticos de simulação. / Mineral coal stands as an important alternative for thermoelectric power generation in Brazil. Brazilian coals, however, are characterized by high sulfur contents, and significant amounts of sulfur dioxide are produced in its combustion. The fluidized bed combustion process is particularly suitable for burning those coals, notably due to the possibility of using limestone absorbents to in loco remove the sulfur dioxide produced in the combustion. In this work the atmospheric bubbling fluidized bed combustion of a mineral coal was studied, which is a benefited coal for thermoelectric use named CE4500, from Criciúma-SC. A dolomitic limestone from Ipeúna-SP was used for sulfur absorption. The pilot scale fludized bed combustion plant of the Laboratory of Thermal and Fluids Engineering of EESC-USP was used, which has a combustion chamber of 0.5 x 0.5 m of cross section and is 3 m high. Tests were performed for different fluidization velocities and (Ca+Mg)/S feed ratios. Gas concentrations were measured along the height and the cross section of the reactor, allowing to verify the process homogeneity, besides the effect of the coal and limestone feeding points over this homogeneity. Conversions and global reaction rates were determined for both coal combustion and absorption by limestone. It is evaluated that the results that were obtained represent a significant contribution regarding reactor design as well as modeling validation.

Cinzas de carvão mineral são resíduos gerados em grandes quantidades nas usinas termelétricas. Este é um dos resíduos de maior geração no Brasil, aproximadamente 1,7 milhões de toneladas por ano. A disposição muitas vezes irregular deste resíduo pode causar problemas de ordem ambiental, como contaminação de águas subterrâneas, do solo e desequilíbrio de sistemas ecológicos. Uma possibilidade de uso para estas cinzas é a síntese de zeólitas, que são minerais aluminossilicatos microporosos com propriedades interessantes para uso na indústria. Neste trabalho, estudou-se a síntese de zeólitas a partir de cinzas volantes visando à sua aplicação em dessulfuração de gases. A síntese foi realizada pelo método hidrotérmico, utilizando solução alcalina de KOH e relação solução/sólido de 2 mL g-1. As variáveis estudadas foram temperatura (100 e 150 °C), concentração da solução alcalina (3 e 5 mol L-1) e tempo de reação (8, 24, 48 e 72 h). Os produtos obtidos e as cinzas precursoras foram caracterizados quanto à composição química (FRX), mineralógica (DRX), morfológica (MEV), área específica (BET) e capacidade de troca catiônica (CTC). A partir da determinação das estruturas cristalinas (DRX) foi possível identificar a formação das zeólitas merlinoíta e perlialita em algumas das condições investigadas. O maior valor de área específica BET foi de 102,42 m2 g-1, nas condições de síntese de 150 °C, 5 mol L-1 e 72 h, representando um aumento de 30 vezes em relação à área das cinzas. Os valores de capacidade de troca catiônica ficaram entre 0,71 e 2,02 meq NH4+ g-1 para as diferentes condições estudadas. Com as amostras que apresentaram os melhores resultados nas caracterizações foram realizados testes de dessulfuração e seu desempenho foi comparado com as cinzas precursoras, carvão ativado e zeólita comercial. Foram construídas curvas de ruptura e isotermas de adsorção para esses sistemas. As zeólitas sintetizadas a partir das cinzas apresentaram maiores valores de adsorção máxima. A zeólita que apresentou melhor resultado de adsorção foi a sintetizada nas condições de 150 °C, 5 mol L-1 e 72 h de tempo de reação, sendo esta também a que apresentou maior valor de área específica. Sendo assim, a síntese de zeólitas a partir de cinzas de carvão, geradas no próprio processo de combustão em usinas térmicas, mostra-se como uma potencial aplicação no sentido de que estas podem ser utilizadas na própria usina para adsorção do SO2 gerado durante a combustão. / Coal ash is a waste generated in large quantities in the power plants. This is one of the wastes generated in larger quantities in Brazil, approximately 1.7 million tons per year. The often irregular disposal of this waste can cause environmental problems, such as contamination of groundwater, soil and imbalance of ecological systems. One possibility for using ashes is the synthesis of zeolites, which are microporous aluminosilicate minerals with interesting properties for use in industry. In this work, the synthesis of zeolites from fly ash was studied, aiming its application for gas desulfurization. The synthesis was performed by the hydrothermal method using an alkaline solution of KOH and a solution/solid ratio of 2 mL g-1. The variables temperature (100 and 150 °C), alkaline solution concentration (3 and 5 mol L-1) and reaction time (8, 24, 48 and 72 hours) were studied. The products obtained and the precursory ashes were characterized by its chemical composition (FRX), mineralogical (XRD), morphological (SEM), specific surface area (BET) and cation exchange capacity (CEC). From the determination of the crystalline structures (XRD) it was possible to identify the formation of the merlinoite and perlialite zeolites for some of the investigated conditions. The highest BET surface area was 102.42 m2 g-1 under the synthesis conditions of 150 °C, 5 mol L-1 and 72 hours. This value represented an increase of 30 times in the surface area comparing to the ash. The cation exchange capacity values varied between 0.71 and 2.02 meq NH4+ g-1 for the different conditions studied. Desulfurization tests were carried out for the samples that showed the best characterization results and its performance was compared with the precursor ash, activated carbon and commercial zeolite. Rupture curves and adsorption isotherms were constructed for these systems. The zeolites synthesized from ash showed higher values of maximum adsorption. The zeolite that showed the best adsorption result was synthesized at the conditions of 150 °C, 5 mol L-1 and 72 hours of reaction time, which also had the highest surface area value. Thus, the synthesis of zeolites from coal ash, generated in the combustion process in thermal plants, is shown as a potential application in the sense that these can be used in the plant to adsorb SO2 generated during combustion.

Devido aos diversos efeitos causados pela presença de \'SO IND.2\' em gases liberados na atmosfera, considerável atenção tem sido dada às técnicas para remoção deste poluente proveniente do processo de combustão. Neste trabalho apresenta-se um estudo relacionado com a determinação das melhores condições de granulometria e temperatura no processo de sorção de \'SO IND.2\' por um calcário dolomítico, denominado DP, e um calcário calcítico, denominado ICB, empregando-se a termogravimetria e porosimetria de adsorção de nitrogênio. Foram estudadas cinco faixas de granulometria média (385, 460, 545, 650 e 775 µm) e temperatura (variando de 745 a 920 ºC) para cada calcário. Com a aplicação do planejamento experimental, obtiveram-se superfícies de resposta com pontos de máximo indicando as melhores condições para cada calcário. Para o calcário DP, as maiores conversões (52%) foram obtidas na temperatura de calcinação de 850ºC e granulometria de 545 µm e as menores conversões foram obtidas para temperaturas acima de 900ºC e abaixo de 780ºC. Para o calcário ICB, as melhores condições foram obtidas em temperatura de 815ºC e 274 µm (conversão de 36,7%). Estabelecendo-se uma correlação entre a superfície de resposta e os parâmetros da estrutura física, os calcários, na condição de máxima conversão, apresentaram maior distribuição de poros na região de 20 a 110 A, indicando que a quantidade de poros menores pode ser um fator importante na reatividade do calcário. Pelos resultados apresentados na porosimetria, ambos os calcários apresentaram a média de diâmetro de poros próxima a 0,01 µm, indicando que o processo de difusão deveria seguir a Lei de Fick. No entanto, para calcário ICB observou-se o maior desenvolvimento de microporos, indicando que o mecanismo de difusão deste calcário possivelmente segue a Lei de Knudsen, justificando as menores conversões pelo rápido bloqueio dos poros, que impedem que as camadas mais internas sejam atingidas. Por meio das imagens obtidas por MEV, observou-se que a superfície do calcário ICB sulfatado apresentou uma camada mais fechada e compactada do que o calcário DP. / Due to various effects caused by the presence of \'SO IND.2\' in gases released into the atmosphere, considerable attention has been given to techniques of removal of this pollutant from the combustion processes. This dissertation reports on studies related to the determination of the optimum conditions of temperature and particle size in \'SO IND.2\' sorption by a dolomite, called DP and a calcite, called ICB. Five ranges of granulometry (385, 460, 545, 650 e 775 µm) and temperature (from 745 to 920ºC) were studie for each limestone. The application of experimental design resulted in a response surface with maximum values of temperature and particle size. For DP, the highest conversions (52%) were obtained at 850ºC and particle size of 545 µm and the lowest conversions were obtained at temperatures over 900ºC and below 780ºC. For ICB, the best conditions were obtained at 815ºC and 274 µm (36.7% conversion). The correlation between response surface and physical structure parameters showed that the amount of small pores is an important factor in the reactivity of the sorbents. For both DP and ICB, the average of pore size is close to 0.01 µm, indicating that the diffusion mechanism should follow the Fick law. However, in limestone ICB a further development of micropores was observed, allowing concluding that the diffusion mechanism possibly follows Knudsen law, which justifies the lowest conversions by quick pore blockage, consequently making the inner layers inaccessible. These assumptions were evidenced by the scanning electron microscopy (SEM), in which a compacted and closed layer was showed on ICB sulfated surface.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-07-17T19:26:25Z No. of bitstreams: 1 WelkisonCarvalho.pdf: 2082259 bytes, checksum: a734b522c86b6f9dc34abd2ba1fb6152 (MD5) / Made available in DSpace on 2017-07-17T19:26:25Z (GMT). No. of bitstreams: 1 WelkisonCarvalho.pdf: 2082259 bytes, checksum: a734b522c86b6f9dc34abd2ba1fb6152 (MD5) Previous issue date: 2017-04-25 / The fly ash is a by-product from the combustion of coal which when it is an adequate control of some non-desulphurization process variables, can result in minor impacts and reuse of ash. The objective of this work is to promote the treatment of the fly ash generated by the burning of coal from a thermoelectric plant and to study a proposal to manage this residue in a sustainable way, based on the economic, environmental and social aspects. Thus, the optimization of the desulphurization process was carried out, and afterwards the qualitative and quantitative analysis of the losses of the fire (unbaked), sulfite, mineralogical analysis and classification of the residue generated by the combustion and desulphurization of Mineral coals of different sulfur contents and studies of economic and environmental gain were also carried out. The results showed that after the optimization of some variables in the process of flue gas desulphurization, such as: concentration of calcium hydroxide solution in 10%, flow rate of calcium hydroxide solution in 3.0 m3/h, of virgin lime in the desulfurization system at 0.3 ton/h and the temperature of the exhaust gases in the absorber tower in the range of 80°C to 110 °C, fly ash formation showed acceptable parameters for sulfite content (<5 %) and loss in ignition (<6%); in addition, mineralogical analysis confirmed that light ash presents compositions mainly of silicon, aluminum and iron oxides, which characterizes them as pozzolanic materials qualified for use in the cement industry. The results of the economic gain studies showed reductions in disposal costs of this residue in the range of 18.5 higher than the revenue from the sale of this same residue, the results of environmental gain also showed a reduction of 24,740.30 tons of CO2 and a reduction in the consumption of raw water in the range of 59,376.72 m3, due to the reuse of the light ashes in the incorporation of the cement in the year of 2016. In addition to converging to the guidelines for compliance with the National Policy on Solid Waste. / A cinza leve é um subproduto proveniente da combustão do carvão mineral que quando se tem um controle adequado de algumas variáveis no processo de dessulfurização, pode resultar em menores impactos e o reaproveitamento das cinzas. Este trabalho tem como objetivo promover o beneficiamento das cinzas leves geradas da queima de carvão mineral de uma termoelétrica de São Luís do Maranhão e estudar uma proposta de gerenciar, de forma sustentável esse resíduo, sustentada no tripé dos aspectos econômicos, ambientais e sociais. Assim, fez-se a otimização do processo de dessulfurização e posteriormente analisou-se qualitativa e quantitativamente os teores de perda ao fogo (incombustos), sulfito. Realizou-se também a análise mineralógica e classificação do resíduo gerados a partir da combustão e dessulfurização de carvões minerais de diferentes teores de enxofre e realizou-se ainda os estudos de cunho econômico e ambiental. Os resultados evidenciaram que após a otimização de algumas variáveis no processo de dessulfurização dos gases de combustão, tais como: concentração da solução de hidróxido de cálcio em 10%, vazão de dosagem de solução de hidróxido de cálcio em 3,0 m3/h, dosagem de cal virgem no sistema de dessulfurização em 0,3 ton/h e temperatura dos gases de exaustão na torre absorvedora na faixa entre 80°C a 110°C, a formação de cinzas leves apresentaram parâmetros aceitáveis quanto aos teores de sulfito (<5%) e perda ao fogo (<6%), além disso a análise mineralógica confirmou que as cinzas leves apresentam composições majoritariamente de óxidos de silício, alumínio e ferro, o que as caracteriza como materiais pozolânicos qualificados para utilização na indústria cimenteira. Os resultados dos estudos de ganho econômico mostraram reduções de custos de disposição desse resíduo na faixa de 18,5 maior que a própria receita proveniente da venda desse mesmo resíduo Os resultados de ganho ambiental mostraram também uma redução anual de 24.740,30 ton de CO2 e uma redução anual do consumo de água bruta na faixa de 59.376,72 m3, em virtude do reaproveitamento das cinzas leves na incorporação do cimento no ano de 2016. Além de convergir para às diretrizes de atendimento à Política Nacional de Resíduos Sólidos.

Arsenic and selenium distributions in coal-fired plant samples are studied. This research includes arsenic and selenium concentrations in samples of coal, fly ash, bottom ash, economizer ash, Flue Gas Desulfurization (FGD) slurry and flue gas taken from four power plants with the goal being to examine the distribution of these metals in these materials and calculate a materials balance for the system. All samples were analyzed using ICP-ES. This research shows that 60-80% of the arsenic in coal-fired plant samples will be associated with the fly ash. Approximately 35-55% of the selenium will be associated with the fly ash and approximately 30-40% will be associated with the FGD slurry materials. The amount of arsenic and selenium present in the flue gases escaping the stack is very little, 6-7% or less. Hopefully, research in this area will be helpful when setting emissions limits, identifying and disposing of hazardous wastes and improving air pollution control devices for maximum metal removal.

Furnace slag is the by-product from steel making process. Desulfurization slag (DS) was produced from the desulphurization process of molten irons in high temperature furnaces processes. DS is heterogeneous oxide materials which are compounded by some main oxides such as SiO2, FeO, CaO, SiO2, MnO, Al2O3, and MgO due to their mass percentage. Because DS has high pH characteristics (12.5), this limits its recycle and reuse. The objective of this study was to evaluate the potential of applying DS as the construction materials or amendments in the aquacultural industry to improve the aqualcultural water quality in the fish farm. The basic characteristic analyses show that the major chemical compositions of powder DS were CaO, SiO2, Fe2O3 and Al2O3. The major crystalline phase composed of SiO2, Ca(OH)2 and CaCO3. Results of DS release test show that when DS could increase pH and alkalinity value in water. Results of micro-structure analysis of powder DS surface showed there were many non-porous materials and heavy metals on DS. Results from the nutrient removal tests show that the ammonia nitrogen adsorption capacity were 0.036 mg/L and 0.069 mg/L when the initial concentration were 10 mg/L and 30 mg/L, respectively. Results form the adsorption model validation test indicate that the adsorption phenomena could fit in Langmuir model. The adsorption capacities of phosphate were 26.4 mg/L and 76.6 mg/L when the initial phosphate concentrations were 10 mg/L and 30 mg/L, respectively. The calculated values of thermodynamic parameters show that the adsorption reaction for ammonia nitrogen was endothermic non-spontaneous process, and the adsorption reaction for phosphate was exothermic spontaneous process. However, the enthalpy change (£GH) showed that adsorption reaction of DS for ammonia nitrogen was physical adsorption, and the adsorption reaction for phosphate was chemical sorption. In the algae culture experiment, results show that when 25 mg/L of DS was supplied, the growth rate of Chlorella sp. could be enhanced. Thus, the powder DS could enhance the growth of Chlorella sp. A field study using a fish farm as the study site was conducted to evaluate the impact of DS on fish farm water quality when DS was applied as the filling and construction materials of the fish farm. Results show that addition of DS had no significant effect on groundwater and pond water quality. Results from the organic matter analysis of the pond water using EEFM show that humus-like and soluble microbial product (SMP) materials were detected. The dominant algae in the pond water included Scenedesmus sp. and Chlorella sp. indicating the pond water quality was in good conditions. Addition of DS would increase of water alkalinity preventing the acidification of pond water due to the fish feed and fish excreta. Results of heavy metal analysis of soil, groundwater, and pond water complied with the relevant environmental standards. Results of this study will aid in understanding the characteristics of DS and the results will be useful in designing a DS reuse system to achieve the zero waste and resource reuse goal.

Pipeline natural gas is the primary fuel of choice for distributed fuel cell-based applications. The concentration of sulfur in odorized natural gas is about 30 ppm, with acceptable levels being <1 ppm for catalyst stability in such applications. Packed bed technology for desulfurization suffers from several disadvantages including high pressure drop and slow regeneration rates that require large unit sizes. We describe a novel Rapid Temperature Swing Adsorption (RTSA) system utilizing hollow fibers with polymer 'binder', impregnated with high loadings of sulfur selective sorbent 'fillers'. Steam and cooling water can be utilized to thermally swing the sorbent during the regeneration cycles. An impermeable, thin polymer barrier layer on the outside of fiber sorbents allows only thermal interactions with the regeneration media, thereby promoting consistent sorption capacity over repeated cycles. A simplified flow pattern minimizes pressure drop, porous core morphology maximizes sorption efficiencies, while small fiber dimensions allows for rapid thermal cycles.

No description available.