Modelagem e simulação da formação de hidrocarbonetos na combustão do gás natural

A exaustão de um veículo de motor a diesel é uma importante fonte de poluentes atmosféricos, pois forma uma matriz complexa composta de poluentes regulados e não regulados pelos órgãos governamentais. Dentre os poluentes regulados podemos citar óxidos de nitrogênio (NOx) e material particulado. Os poluentes não regulados são pouco estudados até hoje e dentre estes encontra-se a classe dos hidrocarbonetos policíclicos aromáticos e seus derivados nitrados (nitro-HPA). Estes são encontrados na exaustão do diesel na forma gasosa ou agregados ao material particulado. Hoje, o interesse em estudos destes compostos vem aumentando, devido às suas atividades carcinogênicas e mutagênicas às quais estão sujeitas as populações dos centros urbanos. O impacto causado pelos nitro-HPA emitidos por motores a ciclo diesel ao ambiente não está ainda completamente estabelecido. Este estudo consiste na modelagem e simulação do processo de combustão de hidrocarbonetos na faixa de C1 a C4 com o objetivo de descrever a formação de compostos aromáticos, principalmente HPA, e óxidos de nitrogênio a partir de modelos cinéticos de combustão propostos na literatura como referência e fazendo uso do software de simulação Kintecus. Este projeto tem como objetivo em longo prazo propor um modelo cinético para combustão do óleo Diesel. Foi iniciada a construção de um modelo cinético de combustão a partir de modelos de hidrocarbonetos simples de C1 a C4, com formação de aromáticos, HPA e óxidos de nitrogênio. Os modelos originais foram avaliados e modificados a fim de estudar como parâmetros do modelo afetam a concentração das espécies de interesse. Foi observado a tendência de formação de benzeno e fulveno em baixas temperaturas e a tendência de formação de antraceno, pireno, fenantreno a temperaturas mais altas. Foi avaliado que a conversão NO-NO2 ocorre em maiores proporções em reações iniciadas a baixas temperaturas, 600 K. Os resultados indicam que propano é o maior responsável por esta conversão. O modelo final obtido resultou da união dos modelos de combustão Hori e Marinov mais inclusão do GRI-Mech 3.0 e reações adicionais de NOx retiradas da base de dados NIST

Estudo do Controle das Emissões de poluentes em Caldeira Aquatubular de alta pressão com Queimadores Convencionais, Abordagem da Eficiência Versus Custo do Dano.

As emissões atmosféricas têm sido consideradas por especialistas, poder público, iniciativa privada e organizações ambientalistas, um dos maiores impactos ambientais que o planeta vem enfrentando. Neste contexto estão tanto as fontes estacionárias quanto as fontes móveis. Ao mesmo tempo em que se lançam na atmosfera milhões de toneladas de poluentes a cada ano através da indústria, o homem procura soluções alternativas através de fontes de energia limpa. Adicionalmente, procura-se ao diminuir as emissões das fontes fixas exercer melhor controle e tratamento. Apresenta-se nesse trabalho, a possibilidade da implementação de ações que visem minimizar o impacto causado pelas caldeiras geradoras de energia, em especial as que operam com queimadores convencionais. Experimentou-se um procedimento capaz de ser utilizado de imediato pelas indústrias, antes mesmo de se implementar inovações tecnológicas, que demandam tempo e recursos. Desta forma, pode-se reduzir, de maneira imediata, o volume de poluentes lançados diariamente na atmosfera, em especial o monóxido de carbono, CO, os óxidos de nitrogênio, NOx, e o material particulado, MP. Objetivou-se atingir um nível de emissões capaz de minimizar o custo do dano, sem perder a eficiência da combustão. Apresenta-se ainda a base metodológica de um modelo, utilizando-se a lógica difusa, como forma de se obter um controle e confiabilidade na gestão das emissões.

Estudo de níveis de ozônio troposférico usando métodos de estatística univariada e multivariada para duas localidades da cidade do Rio de Janeiro

Com cada vez mais intenso desenvolvimento urbano e industrial, atualmente um desafio fundamental é eliminar ou reduzir o impacto causado pelas emissões de poluentes para a atmosfera. No ano de 2012, o Rio de Janeiro sediou a Rio +20, a Conferência das Nações Unidas sobre Desenvolvimento Sustentável, onde representantes de todo o mundo participaram. Na época, entre outros assuntos foram discutidos a economia verde e o desenvolvimento sustentável. O O3 troposférico apresenta-se como uma variável extremamente importante devido ao seu forte impacto ambiental, e conhecer o comportamento dos parâmetros que afetam a qualidade do ar de uma região, é útil para prever cenários. A química das ciências atmosféricas e meteorologia são altamente não lineares e, assim, as previsões de parâmetros de qualidade do ar são difíceis de serem determinadas. A qualidade do ar depende de emissões, de meteorologia e topografia. Os dados observados foram o dióxido de nitrogênio (NO2), monóxido de nitrogênio (NO), óxidos de nitrogênio (NOx), monóxido de carbono (CO), ozônio (O3), velocidade escalar vento (VEV), radiação solar global (RSG), temperatura (TEM), umidade relativa (UR) e foram coletados através da estação móvel de monitoramento da Secretaria do Meio Ambiente (SMAC) do Rio de Janeiro em dois locais na área metropolitana, na Pontifícia Universidade Católica (PUC-Rio) e na Universidade do Estado do Rio de Janeiro (UERJ) no ano de 2011 e 2012. Este estudo teve três objetivos: (1) analisar o comportamento das variáveis, utilizando o método de análise de componentes principais (PCA) de análise exploratória, (2) propor previsões de níveis de O3 a partir de poluentes primários e de fatores meteorológicos, comparando a eficácia dos métodos não lineares, como as redes neurais artificiais (ANN) e regressão por máquina de vetor de suporte (SVM-R), a partir de poluentes primários e de fatores meteorológicos e, finalmente, (3) realizar método de classificação de dados usando a classificação por máquina de vetor suporte (SVM-C). A técnica PCA mostrou que, para conjunto de dados da PUC as variáveis NO, NOx e VEV obtiveram um impacto maior sobre a concentração de O3 e o conjunto de dados da UERJ teve a TEM e a RSG como as variáveis mais importantes. Os resultados das técnicas de regressão não linear ANN e SVM obtidos foram muito próximos e aceitáveis para o conjunto de dados da UERJ apresentando coeficiente de determinação (R2) para a validação, 0,9122 e 0,9152 e Raiz Quadrada do Erro Médio Quadrático (RMECV) 7,66 e 7,85, respectivamente. Quanto aos conjuntos de dados PUC e PUC+UERJ, ambas as técnicas, obtiveram resultados menos satisfatórios. Para estes conjuntos de dados, a SVM mostrou resultados ligeiramente superiores, e PCA, SVM e ANN demonstraram sua robustez apresentando-se como ferramentas úteis para a compreensão, classificação e previsão de cenários da qualidade do ar

Embodied Energy and Gas Emissions of Retaining Wall Structures

The embodied energy (EE) and gas emissions of four design alternatives for an embankment retaining wall system are analyzed for a hypothetical highway construction project. The airborne emissions considered are carbon dioxide (CO 2), methane (CH 4), nitrous oxide (N 2O), sulphur oxides (SO X), and nitrogen oxides (NO X). The process stages considered in this study are the initial materials production, transportation of construction machineries and materials, machinery operation during installation, and machinery depreciations. The objectives are (1) to determine whether there are statistically significant differences among the structural alternatives; (2) to understand the relative proportions of impacts for the process stages within each design; (3) to contextualize the impacts to other aspects in life by comparing the computed EE values to household energy consumption and car emission values; and (4) to examine the validity of the adopted EE as an environmental impact indicator through comparison with the amount of gas emissions. For the project considered in this study, the calculated results indicate that propped steel sheet pile wall and minipile wall systems have less embodied energy and gas emissions than cantilever steel tubular wall and secant concrete pile wall systems. The difference in CO 2 emission for the retaining wall of 100 m length between the most and least environmentally preferable wall design is equivalent to an average 2.0 L family car being driven for 6.2 million miles (or 62 cars with a mileage of 10,000 miles/year for 10 years). The impacts in construction are generally notable and careful consideration and optimization of designs will reduce such impacts. The use of recycled steel or steel pile as reinforcement bar is effective in reducing the environmental impact. The embodied energy value of a given design is correlated to the amount of gas emissions. © 2011 American Society of Civil Engineers.

On the correlation between microstructural changes of Ag-H-ZSM-5 catalysts and their catalytic performances in the selective catalytic reduction of NOx by methane

The silver catalyzed, selective catalytic reduction (SCR) of nitrogen oxides (NOx) by CH4, is shown to be a structure-sensitive reaction. Pretreatment has a great affect on the catalytic performances. Upon thermal treatment in inert gas stream, thermal induced changes in silver morphology lead to the formation of reduced silver species of clusters and particles. Catalysis over this catalyst indicates an initially higher activity but lower selectivity for the CH4-SCR of NOx Reaction induced restructuring of silver results in the formation of ill-defined silver oxides. This, in turn, impacts the adsorption properties and diffusivity of oxygen over silver catalyst, results in the decrease in activity but increase in selectivity of Ag-H-ZSM-5 catalyst for the CH4-SCR of NO.. (c) 2004 Elsevier B.V. All rights reserved.

Simulation chamber studies of the atmospheric degradation of naphthalene, 1-nitronaphthalene and phthaldialdehyde

A detailed series of simulation chamber experiments has been performed on the atmospheric degradation pathways of the primary air pollutant naphthalene and two of its photooxidation products, phthaldialdehyde and 1-nitronaphthalene. The measured yields of secondary organic aerosol (SOA) arising from the photooxidation of naphthalene varied from 6-20%, depending on the concentrations of naphthalene and nitrogen oxides as well as relative humidity. A range of carbonyls, nitro-compounds, phenols and carboxylic acids were identified among the gas- and particle-phase products. On-line analysis of the chemical composition of naphthalene SOA was performed using aerosol time-of-flight mass spectrometry (ATOFMS) for the first time. The results indicate that enhanced formation of carboxylic acids may contribute to the observed increase in SOA yields at higher relative humidity. The photolysis of phthaldialdehyde and 1-nitronaphthalene was investigated using natural light at the European Photoreactor (EUPHORE) in Valencia, Spain. The photolysis rate coefficients were measured directly and used to confirm that photolysis is the major atmospheric loss process for these compounds. For phthaldialdehyde, the main gas-phase products were phthalide and phthalic anhydride. SOA yields in the range 2-11% were observed, with phthalic acid and dihydroxyphthalic acid identified among the particle phase products. The photolysis of 1-nitronaphthalene yielded nitric oxide and a naphthoxy radical which reacted to form several products. SOA yields in the range 57-71% were observed, with 1,4-naphthoquinone, 1-naphthol and 1,4-naphthalenediol identified in the particle phase. On-line analysis of the SOA generated in an indoor chamber using ATOFMS provided evidence for the formation of high-molecular-weight products. Further investigations revealed that these products are oxygenated polycyclic compounds most likely produced from the dimerization of naphthoxy radicals. These results of this work indicate that naphthalene is a potentially large source of SOA in urban areas and should be included in atmospheric models. The kinetic and mechanistic information could be combined with existing literature data to produce an overall degradation mechanism for naphthalene suitable for inclusion in photochemical models that are used to predict the effect of emissions on air quality.

EPR spectroscopy of nitrite complexes of methemoglobin.

The chemical interplay of nitrogen oxides (NO's) with hemoglobin (Hb) has attracted considerable recent attention because of its potential significance in the mechanism of NO-related vasoactivity regulated by Hb. An important theme of this interplay-redox coupling in adducts of heme iron and NO's-has sparked renewed interest in fundamental studies of FeNO(x) coordination complexes. In this Article, we report combined UV-vis and comprehensive electron paramagnetic resonance (EPR) spectroscopic studies that address intriguing questions raised in recent studies of the structure and affinity of the nitrite ligand in complexes with Fe(III) in methemoglobin (metHb). EPR spectra of metHb/NO(2)(-) are found to exhibit a characteristic doubling in their sharper spectral features. Comparative EPR measurements at X- and S-band frequencies, and in D(2)O versus H(2)O, argue against the assignment of this splitting as hyperfine structure. Correlated changes in the EPR spectra with pH enable complete assignment of the spectrum as deriving from the overlap of two low-spin species with g values of 3.018, 2.122, 1.45 and 2.870, 2.304, 1.45 (values for samples at 20 K and pH 7.4 in phosphate-buffered saline). These g values are typical of g values found for other heme proteins with N-coordinated ligands in the binding pocket and are thus suggestive of N-nitro versus O-nitrito coordination. The positions and shapes of the spectral lines vary only slightly with temperature until motional averaging ensues at approximately 150 K. The pattern of motional averaging in the variable-temperature EPR spectra and EPR studies of Fe(III)NO(2)(-)/Fe(II)NO hybrids suggest that one of two species is present in both of the alpha and beta subunits, while the other is exclusive to the beta subunit. Our results also reconfirm that the affinity of nitrite for metHb is of millimolar magnitude, thereby making a direct role for nitrite in physiological hypoxic vasodilation difficult to justify.

Pittsburgh air quality study overview

Ambient sampling for the Pittsburgh Air Quality Study (PAQS) was conducted from July 2001 to September 2002. The study was designed (1) to characterize particulate matter (PM) by examination of size, surface area, and volume distribution, chemical composition as a function of size and on a single particle basis, morphology, and temporal and spatial variability in the Pittsburgh region; (2) to quantify the impact of the various sources (transportation, power plants, biogenic sources, etc.) on the aerosol concentrations in the area; and (3) to develop and evaluate the next generation of atmospheric aerosol monitoring and modeling techniques. The PAQS objectives, study design, site descriptions and routine and intensive measurements are presented. Special study days are highlighted, including those associated with elevated concentrations of daily average PM2.5 mass. Monthly average and diurnal patterns in aerosol number concentration, and aerosol nitrate, sulfate, elemental carbon, and organic carbon concentrations, light scattering as well as gas-phase ozone, nitrogen oxides, and carbon monoxide are discussed with emphasis on the processes affecting them. Preliminary findings reveal day-to-day variability in aerosol mass and composition, but consistencies in seasonal average diurnal profiles and concentrations. For example, the seasonal average variations in the diurnal PM2.5 mass were predominately driven by the sulfate component. © 2004 Elsevier Ltd. All rights reserved.

Cost Heterogeneity and the Potential Savings from Market-Based Policies

Policy makers and analysts are often faced with situations where it is unclear whether market-based instruments hold real promise of reducing costs, relative to conventional uniform standards. We develop analytic expressions that can be employed with modest amounts of information to estimate the potential cost savings associated with market-based policies, with an application to the environmental policy realm. These simple formulae can identify instruments that merit more detailed investigation. We illustrate the use of these results with an application to nitrogen oxides control by electric utilities in the United States.

The investigation of mechanisms in environmental catalysis using time-resolved methods

The formation of nitrogen oxides (NOx) during a combustion process is difficult to avoid because of the large exotherm and the consequent problem of avoiding local high-temperature spikes. Consequently, for many applications, such as for automotive power generation, there will be a continuing need to use catalytic after-treatment to reduce harmful emissions. The investigation of the mechanisms of the key catalytic reactions in environmental catalysis can provide an insight into the action of the catalyst, and time-resolved methods offer a powerful means to study these processes under realistic conditions. The use of Temporal Analysis of Products (TAP) and Steady State Isotopic Transient Kinetic Analysis (SSITKA) methods to investigate the reduction of NOx under various experimental conditions is described. From a detailed analysis of the SSITKA profiles, it is shown that at low temperatures the mechanism for the formation of N-2 and N2O from NO may differ from the conventional high-temperature mechanism. This is supported by density functional theory calculations, which show that the barrier to the formation of N2O from the reaction of N(ads) and NO(ads) may be too high to allow this process to occur at low temperatures. The alternative reaction of NO(ads) + NO(ads) = N2O(g) + O(ads) is shown to be much more favorable and is consistent with the SSITKA analysis. The remarkable effect of hydrogen as a reductant at low temperatures is described, and alternative interpretations of the role of hydrogen are discussed.

The use of short time-on-stream in situ spectroscopic transient kinetic isotope techniques to investigate the mechanism of hydrocarbon selective catalytic reduction (HC-SCR) of NOx at low temperatures

The problem of differentiating between active and spectator species that have similar infrared spectra has been addressed by developing short time-on-stream in situ spectroscopic transient isotope experimental techniques (STOS-SSITKA). The techniques have been used to investigate the reaction mechanism for the reduction of nitrogen oxides (NOx) by hydrocarbons under lean-burn (excess oxygen) conditions on a silver catalyst. Although a nitrate-type species tracks the formation of isotopically labeled dinitrogen, the results show that this is misleading because a nitrate-type species has the same response to an isotopic switch even under conditions where no dinitrogen is produced. In the case of cyanide and isocyanate species, the results show that it is possible to differentiate between slowly reacting spectator isocyanate species, probably adsorbed on the oxide support, and reactive isocyanate species, possibly on or close to the active silver phase. The reactive isocyanate species responds to an isotope switch at a rate that matches that of the rate of formation of the main product, dinitrogen. It is concluded that these reactive isocyanates could potentially be involved in the reduction of NOx whereas there is no evidence to support the involvement of nitrate-type species that are observable by infrared spectroscopy.

Low-Temperature Selective Catalytic Reduction (SCR) of NOx with n-Octane Using Solvent-Free Mechanochemically Prepared Ag/Al2O3 Catalysts

Low-temperature (<200 degrees C) hydrocarbon selective catalytic reduction of NOx has been achieved for the first time in the absence of hydrogen using a solvent-free mechanochemically prepared Ag/Al2O3 catalyst. Catalysts prepared by this ball-milling method show a remarkable increase in activity for the reduction of nitrogen oxides with octane by lowering the light-off temperature by up to 150 degrees C compared with a state-of-the-art 2 wt %Ag/Al2O3 catalyst prepared by wet impregnation. The best catalyst prepared from silver oxide showed 50% NOx conversion at 240 degrees C and 99%, at 302 degrees C. The increased activity is not due to an increased surface area of the support, but may be associated with a change in.the'defeet structure of the alumina surface, leading to the formation of the small silver clusters necessary for the activation of the octane without leading to total combustion. On the other hand, since one possible role of hydrogen is to remove inhibiting species from the silver, we cannot exclude some change in the chemical properties of the silver as a result of the ball-milling treatment.

A review of biomass co-firing in North America

Biomass fuels have long been accepted as useful renewable energy sources, especially in mitigating greenhouse gases (GHG), nitrogen oxides, and sulfur oxide emissions. Biomass fuel is carbon neutral and is usually low in both nitrogen and sulfur. For the past decade, various forms of biomass fuels have been co-combusted in existing coal-fired boilers and gas-fired power plants. Biomass is used as a supplemental fuel to substitute for up to 10% of the base fuel in most full commercial operations. There are several successful co-firing projects in many parts of the world, particularly in Europe and North America. However, despite remarkable commercial success in Europe, most of the biomass co-firing in North America is limited to demonstration levels. This review takes a detailed look at several aspects of biomass co-firing with a direct focus on North America. It also explores the benefits, such as the reduction of GHG emissions and its implications. This paper shows the results of our studies of the biomass resources available in North America that can be used in coal-fired boilers, their availability and transportation to the power plant, available co-firing levels and technologies, and various technological and environmental issues associated with biomass co-firing. Finally, the paper proffers solutions to help utility companies explore biomass co-firing as a transitional option towards a completely carbon-free power sector in North America.

Computational scheduling methods for integrating plug-in electric vehicles with power systems: a review

Traditional internal combustion engine vehicles are a major contributor to global greenhouse gas emissions and other air pollutants, such as particulate matter and nitrogen oxides. If the tail pipe point emissions could be managed centrally without reducing the commercial and personal user functionalities, then one of the most attractive solutions for achieving a significant reduction of emissions in the transport sector would be the mass deployment of electric vehicles. Though electric vehicle sales are still hindered by battery performance, cost and a few other technological bottlenecks, focused commercialisation and support from government policies are encouraging large scale electric vehicle adoptions. The mass proliferation of plug-in electric vehicles is likely to bring a significant additional electric load onto the grid creating a highly complex operational problem for power system operators. Electric vehicle batteries also have the ability to act as energy storage points on the distribution system. This double charge and storage impact of many uncontrollable small kW loads, as consumers will want maximum flexibility, on a distribution system which was originally not designed for such operations has the potential to be detrimental to grid balancing. Intelligent scheduling methods if established correctly could smoothly integrate electric vehicles onto the grid. Intelligent scheduling methods will help to avoid cycling of large combustion plants, using expensive fossil fuel peaking plant, match renewable generation to electric vehicle charging and not overload the distribution system causing a reduction in power quality. In this paper, a state-of-the-art review of scheduling methods to integrate plug-in electric vehicles are reviewed, examined and categorised based on their computational techniques. Thus, in addition to various existing approaches covering analytical scheduling, conventional optimisation methods (e.g. linear, non-linear mixed integer programming and dynamic programming), and game theory, meta-heuristic algorithms including genetic algorithm and particle swarm optimisation, are all comprehensively surveyed, offering a systematic reference for grid scheduling considering intelligent electric vehicle integration.

Levantamento ambiental de uma indústria conserveira nos Açores

Dissertação de Mestrado em Ambiente, Saúde e Segurança.