Avaliação do potencial pozolânico da cinza de lodo de águas residuárias por meio de técnicas instrumentais

Pós-graduação em Engenharia Civil - FEIS

Avaliação da auto-suficiência energética em reatores anaeróbios aplicados ao tratamento de resíduos da indústria de produção do etanol

Ethanol, the main automotive biofuel, has its production based on the fermentation of sugars found in biological materials and on the distillation of the alcoholic media formed during the fermentative process. Stillage is the main residue from ethanol production, containing a high organic loading in addition to acidic and corrosive characteristics. Considering the available technologies to treat stillage, we highlight anaerobic digestion, which allows the reduction of the impacts associated to pollutants loading of this effluent and the generation of energy from the methane gas produced in the process. Based on the high treatment efficiency usually associated to the anaerobic process, this work aimed to assess whether anaerobic systems applied to the treatment of stillage are energetically self-sufficient. First we evaluated the energy recovery capacity in an anaerobic reactor applied to the treatment of stillage resulting from corn-to-ethanol processing. The results indicated the great influence that a correct selection of electrical equipment and their respective operating periods have on the net energy balance of the anaerobic treatment. The high energy consumption of the heater would not allow the system to achieve a positive net energy balance – the maximum energy recovery would reach only 0.68% of the consumption. However, the replacement of the mixture equipment would result in energy gains ranging from 8.5 to 967.9% of the consumption. In this work we also assessed the efficiency of methane yields for a few studies and the correlation between some parameters of the anaerobic process. With respect to the methane yield, we noted that mesophilic systems tend to be more advantageous than the thermophilic ones (efficiency of 76.45 ± 22.51% vs. 69.40 ± 30.36%). Considering the study... (Complete abstract click electronic access below)

Avaliação da auto-suficiência energética de reatores anaeróbios no tratamento de esgoto sanitário e água cinza

The anaerobic treatment of sewage is widely employed in Brazil and it is an appreciated way for the treatment of effluents, helping to reduce the environmental impact in rivers. The methane gas obtained from the process can be applied to improve the energetic efficiency of the system, reducing the amount of waste and the cost of the treatment process. This work presents the net energy balance of anaerobic reactors applied to the treatment of sewage. The analysis was performed considering full-scale and laboratory-scale treatment systems. In laboratory scale, the results from three kinds of systems were compared regarding the biological treatment of greywater. Two of them (UASB7 and UASB12) were anaerobic and the other one was a combined anaerobic-aerobic system (UASB7/SBR6). Greywater methanization (compared to theoretical maximum) was calculated considering 100% removal (g BOD/day), the literature percentage removal and the anionic surfactant presence in the effluentt. For each of these three cases, the efficiencies were, respectively, 16.9%, 43.6% and 51.3% in UASB7 reactor, 25.6%, 50.3% and 59.2% in UASB12 reactor and 30.6%, 61.2% and 71.9% in UASB7/SBR6 reactor. The energetic potential was found to be 4.66x10-4, 7.77x10-4 and 5.12x10-4 kWh/L for the UASB7, UASB12 and UASB7/SBR6 reactors, respectively. The pumping system, the aeration (in the anaerobic-aerobic system) and the temperature controlled heating system were considered to calculate the energetic consumption. However, the third one was not employed since tropical regions like Brazil do not need heating systems and also because of its high energetic consumption. The calculated net energy balance in the reactors was negative in the case of greywater, respectively -0.16, -0.28 and -0.18 kWh/L for the reactors UASB7, UASB12 and UASB7/SRB6. In full scale (ETE Jardim das Flores - Rio Claro, SP), the average energy... (Complete abstract click electronic access below)

Remoção de hidrocarbonetos do gás natural visando o ajuste do índice de metano

The use of the natural gas is growing year after year in the whole world and also in Brazil. It is verified that in the last five years the profile of natural gas consumption reached a great advance and investments had been carried through in this area. In the oil industry, the use of the natural gas for fuel in the drive of engines is usual for a long date. It is also used to put into motion equipment, or still, to generate electric power. Such engines are based on the motor cycle of combustion Otto, who requires a natural gas with well definite specification, conferring characteristic anti-detonating necessary to the equipment performance for projects based on this cycle. In this work, process routes and thermodynamic conditions had been selected and evaluated. Based on simulation assays carried out in commercial simulators the content of the methane index of the effluent gas were evaluated at various ranges of pressure, temperature, flowrate, molecular weight and chemical nature and composition of the absorbent. As final result, it was established a route based on process efficiency, optimized consumption of energy and absorbent. Thereby, it serves as base for the compact equipment conception to be used in locu into the industry for the removal of hydrocarbon from the natural gas produced

Avaliação da emissão de gás SF6 de cápsulas utilizadas na mensuração de metano entérico em bovinos.

2016

Avaliação do possível impacto das técnicas de MEOR (Microbial Enhanced Oil Recovery) no fator de recuperação das reservas de petróleo e gás do Brasil

Os métodos tradicionais de estimular a produção de petróleo, envolvendo a injeção de água, vapor, gás ou outros produtos, estabeleceram a base conceitual para novos métodos de extração de óleo, utilizando micro-organismos e processos biológicos. As tecnologias que empregam os processos de bioestimulação e bioaumentação já são amplamente utilizadas em inúmeras aplicações industriais, farmacêuticas e agroindustriais, e mais recentemente, na indústria do petróleo. Dada a enorme dimensão econômica da indústria do petróleo, qualquer tecnologia que possa aumentar a produção ou o fator de recuperação de um campo petrolífero gera a expectativa de grandes benefícios técnicos, econômicos e estratégicos. Buscando avaliar o possível impacto de MEOR (microbial enhanced oil recovery) no fator de recuperação das reservas de óleo e gás no Brasil, e quais técnicas poderiam ser mais indicadas, foi feito um amplo estudo dessas técnicas e de diversos aspectos da geologia no Brasil. Também foram realizados estudos preliminares de uma técnica de MEOR (bioacidificação) com possível aplicabilidade em reservatórios brasileiros. Os resultados demonstram que as técnicas de MEOR podem ser eficazes na produção, solubilização, emulsificação ou transformação de diversos compostos, e que podem promover outros efeitos físicos no óleo ou na matriz da rocha reservatório. Também foram identificadas bacias petrolíferas brasileiras e recursos não convencionais com maior potencial para utilização de determinadas técnicas de MEOR. Finalmente, foram identificadas algumas técnicas de MEOR que merecem maiores estudos, entre as técnicas mais consolidadas (como a produção de biossurfatantes e biopolímeros, e o controle da biocorrosão), e as que ainda não foram completamente viabilizadas (como a gaseificação de carvão, óleo e matéria orgânica; a dissociação microbiana de hidratos de gás; a bioconversão de CO2 em metano; e a bioacidificação). Apesar de seu potencial ainda não ser amplamente reconhecido, as técnicas de MEOR representam o limiar de uma nova era na estimulação da produção de recursos petrolíferos existentes, e até mesmo para os planos de desenvolvimento de novas áreas petrolíferas e recursos energéticos. Este trabalho fornece o embasamento técnico para sugerir novas iniciativas, reconhecer o potencial estratégico de MEOR, e para ajudar a realizar seu pleno potencial e seus benefícios.

Potencial de geração de metano em aterros sanitários através dos modelos IPCC, USEPA e Scholl Canyon estudo de caso do aterro sanitário de Moskogen, Kalmar, Suécia.

A utilização do metano (CH4) presente no biogás gerado através da degradação anaeróbica de resíduos orgânicos depositados em aterros sanitários como fonte de energia é uma tecnologia em expansão, principalmente nos países em desenvolvimento. Para assegurar um melhor aproveitamento do CH4 e a viabilidade econômica do projeto de exploração energética é necessário que estes empreendimentos avaliem sua capacidade de produzir este gás com o passar dos anos, mesmo após o encerramento da deposição de resíduos. O potencial de geração é comumente estimado a partir de modelos cinéticos de primeira ordem propostos por conceituadas instituições, entretanto, estudos recentes apontam alto grau de incerteza e diferenças relevantes entre os resultados obtidos com cada metodologia. Este trabalho tem por objetivo analisar a variação dos resultados das estimativas de emissão de metano dos modelos recomendados pela USEPA, Banco Mundial (Scholl Canyon) e IPCC utilizando tanto dados e informações disponibilizadas do aterro sanitário Moskogen, localizado em Kalmar, Suécia, que foi operado entre 1977 e 2008. Além de estimar a capacidade de geração de CH4, objetiva-se identificar qual o modelo cujas estimativas mais se aproximam dos dados de biogás efetivamente medidos e quanto gás ainda pode ser extraído do aterro. O estudo ainda avaliou como valores diferentes para os parâmetros principais dos modelos afetam a estimativa de geração final. O modelo IPCC mostrou-se o mais confiável dentre os analisados, estimando que o aterro Moskogen produza mais de 102 milhões de m de CH4 entre 1977 e 2100, sendo 39,384 milhões passíveis de extração de 2012 a 2100. Os demais modelos apresentaram premissas inadequadas com a realidade do aterro sanitário estudado. Contudo, mesmo com a superioridade do modelo proposto pelo IPCC, maiores estudos são necessários no local, que levantem outras informações de campo como a vazão passiva de gás pela camada de cobertura do aterro e uma melhor estimativa do percentual de material orgânico biodegradável presente em cada fração de resíduos depositada em Moskogen.

Sistema sensor em fibra ótica para deteção de gás

O presente trabalho descreve duas técnicas de deteção de gás baseadas em fibra ótica e apresenta dois sistemas sensores testados em ambiente laboratorial, usando técnicas de processamento de sinal usualmente associadas à espetroscopia de absorção. O estudo inicial do estado da arte dos sensores baseados em fibra ótica para a deteção de gases apresenta soluções com elevada seletividade, sensibilidade e resolução que permitem tempos de resposta curtos e esquemas de multiplexagem versáteis. A técnica de espetroscopia de absorção direta (DAS) permite a deteção de gases de forma simples e com alguma eficácia, mas com uma baixa relação-sinal-ruido. A espetroscopia por modulação de comprimento de onda (WMS) é uma técnica muito eficaz e de elevada sensibilidade para a deteção de gases, dado que a deteção é deslocada para frequências afastadas do ruído base, melhorando significativamente a relação-sinal-ruído. Estas técnicas foram escolhidas para a implementação de dois sistemas optoeletrónicos, totalmente controlados pelas respetivas aplicações em LabVIEW para a deteção e monitorização de amónia (NH3), dióxido de carbono (CO2) e metano (CH4). O trabalho é finalizado com a caraterização laboratorial dos sistemas e avaliação do desempenho, permitindo a otimização dos sistemas e técnicas implementados. De referir que o trabalho realizado nas instalações da Unidade de Optoeletrónica e Sistemas Eletrónicos (UOSE) do Instituto de Engenharia de Sistemas e Computadores (INESC), Tecnologia e Ciência (TEC), laboratório associado coordenado pelo INESC Porto, permitiu, excelentes condições de trabalho, essenciais para implementar de forma prática os diversos conceitos estudados, bem como testar e caraterizar todos os sistemas desenvolvidos em ambiente laboratorial. O trabalho desenvolvido enquadra-se no âmbito do projeto europeu ECOAL-MGT (Gestão ecológica de pilhas de resíduos de carvão), que será implementado para monitorização remota de parâmetros fundamentais de uma escombreira de carvão em auto-combustão em S.ºPedro da Cova, Portugal.

Avaliação da dolomita funcionalizada para remoção de H2S em gás natural

The natural gas is an alternative source of energy which is found underground in porous and permeable rocks and being associated or not to the oil. Its basic composition includes methane, other hydrocarbon and compounds such as carbon dioxide, nitrogen, sulphidric gas, mercaptans, water and solid particles. In this work, the dolomite mineral, a double carbonate of calcium and magnesium whose the chemical formula is CaMg(CO3)2, was evaluated as adsorbent material. The material was characterized by granulometric analysis, X-ray fluorescence, X-ray diffraction, thermogravimetric analysis, differential thermal analysis, specific surface area, porosity, scanning electronic microscopy and infrared spectroscopy. Then the material was functionalized with diethanolamine (dolomite+diethanolamine) and diisopropylamine (dolomite+diisopropylamine). The results indicated that the adsorbents presented appropriate physiochemical characteristics for H2S adsorption. The adsorption tests were accomplished in a system coupled to a gas chromatograph and the H2S monitoring in the output of the system was accomplished by a pulsed flame photometric detector (PFPD). The adsorbents presented a significant adsorption capacity. Among the analyzed adsorbents, the dolomite+diethanolamine presented the best capacity of adsorption. The breakthrough curves obtained proved the efficiency of this process

Obtenção de óxidos a base de níquel e cobalto para reação de oxidação parcial do metano

Nickel-based catalysts supported on alumina have been widely used in various reactions to obtain synthesis gas or hydrogen. Usually, higher conversion levels are obtained by these catalysts, however, the deactivation by coke formation and sintering of metal particles are still problems to be solved. Several approaches have been employed in order to minimize these problems, among which stands out in recent years the use of additives such as oxides of alkali metals and rare earths. Similarly, the use of methodologies for the synthesis faster, easier, applicable on an industrial scale and to allow control of the microstructural characteristics of these catalysts, can together provide the solution to this problem. In this work, oxides with spinel type structure AB2O4, where A represents divalent cation and B represents trivalent cations are an important class of ceramic materials investigated worldwide in different fields of applications. The nickel cobaltite (NiCo2O4) was oxides of spinel type which has attracted considerable interest due to its applicability in several areas, such as chemical sensors, flat panel displays, optical limiters, electrode materials, pigments, electrocatalysis, electronic ceramics, among others. The catalyst precursor NiCo2O4 was prepared by a new chemical synthesis route using gelatine as directing agent. The polymer resin obtained was calcined at 350°C. The samples were calcined at different temperatures (550, 750 and 950°C) and characterized by X ray diffraction, measurements of specific surface area, temperature programmed reduction and scanning electron microscopy. The materials heat treated at 550 and 750°C were tested in the partial oxidation of methane. The set of techniques revealed, for solid preparations, the presence of the phase of spinel-type structure with the NiCo2O4 NixCo1-xO solid solution. This solid solution was identified by Rietveld refinement at all temperatures of heat treatment. The catalyst precursors calcined at 550 and 750°C showed conversion levels around 25 and 75%, respectively. The reason H2/CO was around 2 to the precursor treated at 750°C, proposed reason for the reaction of partial oxidation of methane, one can conclude that this material can be shown to produce synthesis gas suitable for use in the synthesis Fischer-Tropsch process

Síntese e caracterização de cerâmicas nanométricas para produção de gás de síntese

In this work, ceramic powders belonging to the system Nd2-xSrxNiO4 (x = 0, 0.4, 0.8, 1.2 and 1.6) were synthesized for their use as catalysts to syngas production partial. It was used a synthesis route, relatively new, which makes use of gelatin as organic precursor. The powders were analyzed at several temperatures in order to obtain the perovskite phase and characterized by several techniques such as thermal analysis, X-rays diffraction, Rietveld refinement method, specific surface area, scanning electron microscopy, energy dispersive spectroscopy of X-rays and temperature programmed reduction. The results obtained using these techniques confirmed the feasibility of the synthesis method employed to obtain nanosized particles. The powders were tested in differential catalytic conditions for dry reforming of methane (DRM) and partial oxidation of methane (POM), then, some systems were chosen for catalytic integrals test for (POM) indicating that the system Nd2-xSrxNiO4 for x = 0, 0.4 and 1.2 calcined at 900 °C exhibit catalytic activity on the investigated experimental conditions in this work without showing signs of deactivation

Síntese de catalisadores do tipo LaNixFe1-xO3 como precursores catalíticos para reação oxidação parcial do metano

Nickel-bases catalysts have been used in several reform reactions, such as in the partial oxidation of methane to obtain H2 or syngas (H2 + CO). High levels of conversion are usually obtained using this family of catalysts, however, their deactivation resulting from carbon deposition still remains a challenge. Different approaches have been tested aiming at minimizing this difficulty, including the production of perovskites and related structures using modern synthesis methods capable of producing low cost materials with controlled microstructural characteristics at industrial scale. To establish grounds for comparison, in the present study LaNixFe1-xO3 (x=0, 0.3 or 0.7) perovskites were prepared following the Pechini method and by microwave assisted self-combustion. All samples were sub sequently calcined at 900 °C to obtain the target phase. The resulting ceramic powders were characterized by thermogravimetric analysis, infrared spectroscopy, X ray diffraction, specific area and temperature programmed reduction tests. Calcined samples were also used in the partial oxidation reaction of methane to evaluate the level of conversion, selectivity and carbon deposition. The results showed that the calcined samples were crystalline and the target phase was formed regardless of the synthesis method. According to results obtained by Rietveld refinement, we observed the formation of 70.0% of LaNi0.3Fe0.7O3 and 30.0% of La2O3 for samples LN3F7-900- P, LN3F7-900-M and 41,6% of LaNi0.7Fe0.3O3, 30.7% of La2NiO4 and 27.7% of La2O3 for samples LN7F3-900-P and LN7F3-900-M.Temperature-programmed profiles of the LaNiO3 sample revealed the presence of a peak around 510 °C, whereas the LaFeO3 sample depicted a peak above 1000°C. The highest l evel of methane conversion was obtained for LaNiO3 synthesized by the Pechini method. Overall, catalysts prepared by the Pechini method depicted better conversion levels compared to those produced by microwave assisted self-combustion

Síntese e caracterização de catalisadores de LaNiO3 não suportados e suportados em Al2O3 e ZrO2 para a reforma a vapor do metano

Ionic oxides with ABO3 structure, where A represents a rare earth element or an alkaline metal and B is a transition metal from group VIII of the periodic table are potential catalysts for oxidation and good candidates for steam reforming reaction. Different methods have been considered for the synthesis of the oxide materials with perovskite structure to produce a high homogeneous material with low amount of impurities and low calcination temperatures. In the current work, oxides with the LaNiO3 formula had been synthesized using the method of the polymeric precursors. The thermal treatment of the materials took place at 300 ºC for 2h. The material supported in alumina and/or zirconia was calcined at 800 ºC temperature for 4h. The samples had been characterized by the following techniques: thermogravimetry; infrared spectroscopy; X-ray diffraction; specific surface area; distribution of particle size; scanning electron microscopy and thermo-programmed reduction. The steam reforming reaction was carried out in a pilot plant using reducing atmosphere in the reactor with a mixture of 10% H2-Argon, a mass about 5g of catalyst, flowing at 50 mL.min-1. The temperature range used was 50 - 1000 oC with a heating rate of 10 oC.min-1. A thermal conductivity detector was used to analyze the gas after the water trapping, in order to permit to quantify the consumption of hydrogen for the lanthanum nickelates (LaNiO3). The results showed that lanthanum nickelate were more efficient when supported in alumina than when supported in zirconia. It was observed that the methane conversion was approximately 100% and the selectivity to hydrogen was about 70%. In all cases were verified low selectivity to CO and CO2

Reforma a seco de metano com catalisadores Ni/MCM-41 sintetizados a partir de fontes alternativas de sílica

The production of synthesis gas has received renewed attention due to demand for renewable energies to reduce the emissions of gases responsible for enhanced greenhouse effect. This work was carried out in order to synthesize, characterize and evaluate the implementation of nickel catalysts on MCM-41 in dry reforming reactions of methane. The mesoporous molecular sieves were synthesized using as silica sources the tetraethyl orthosilicate (TEOS) and residual glass powder (PV). The sieves were impregnated with 10% nickel to obtain the metallic catalysts (Ni/MCM-41). These materials were calcined and characterized by Thermogravimetric Analysis (TG), Infrared spectroscopy (FTIR), X-ray Diffraction (XRD), Temperature-Programmed Reduction (TPR) and N2 Adsorption/Desorption isotherms (BET/BJH). The catalytic properties of the samples were evaluated in methane dry reforming with CO2 in order to produce synthesis gas to be used in the petrochemical industry. The materials characterized showed hexagonal structure characteristic of mesoporous material MCM-41 type, being maintained after impregnation with nickel. The samples presented variations in the specific surface area, average volume and diameter of pores based on the type of interaction between the nickel and the mesoporous support. The result of the the catalytic tests showed conversions about 91% CO2, 86% CH4, yelds about 85% CO and 81% H2 to Ni/MCM-41_TEOS_C, and conversions about 87% CO2, 82% CH4, yelds about 70% CO and 59% H2 to Ni/MCM-41_PV_C. The similar performance confirms that the TEOS can be replaced by a less noble materials