Estudo das propriedades físico-químicas do biodiesel e suas influências na deterioração dos elastômeros aplicados no sistema de injeção dos motores diesel

The biodiesel use has become important due to its renewable character and to reduce environmental impacts during the fuel burning. Theses benefit will be valid if the fuel shows good performance, chemistry stability and compatibility with engines. Biodiesel is a good fuel to diesel engines due to its lubricity. Then, the aimed of this study was to verify the physicalchemistry properties of biodiesel and their correlations with possible elastomers damage after biodiesel be used as fuel in an injection system. The methodology was divided in three steps: biodiesels synthesis by transesterification of three vegetable oil (soybean, palm and sunflower) and their physical-chemistry characterization (viscosity, oxidative stability, flash point, acidity, humidity and density); pressurized test of compatibility between elastomers (NBR and VITON) and biodiesel, and the last one, analyze of biodiesels lubricity by tribological test ball-plan( HFRR). Also, the effect of mixture of biodiesel and diesel in different concentrations was evaluated. The results showed that VITON showed better compatibility with all biodiesel blends in relation to NBR, however when VITON had contact with sunflower biodiesel and its blends the swelling degree suffer higher influences due to biodiesel humidity. For others biodiesels and theirs blends, this elastomer kept its mechanical properties constant. The better tribological performance was observed for blends with high biodiesel concentration, lower friction coefficient was obtained when palm biodiesel was used. The main mechanisms observed during the HFRR tests were abrasive and oxidative wear

Caracterização do óleo de carnaúba para uso como biolubrificante

Lubricant is responsible for reducing the wear on the friction protect the metal against oxidation, corrosion and dissipates excess heat, making it essential for the balance of a mechanical system, consequently prolonging the useful life of such a system. The origin of lubricating oils is usually mineral being extracted from the petroleum. But the search for a new source of production of lubricants and fuels it is necessary to meet future demands and reduce the possible environmental damage. For this reason, looking alternative means to produce certain products derived from petroleum, such as biodiesel, for example. Returning to the realm of lubricants, also one realizes this need for new raw materials for their production. Vegetable oil is a renewable resource and biodegradable, and its use entails advantages in environmental, social and economic. The development of this project aims to characterize the carnauba oil as a lubricant plant, or biolubricant. To analyze the oil carnauba tests as checking density, flash point, fire point, viscosity, viscosity, acid number, pH, copper corrosion, thermal conductivity and thermal resistivity were developed. In addition, for conducting the wear on the friction and the gradient of the system temperature, the analysis equipment is designed for wear on the friction. Based on these results, it is observed that the oil carnauba show good correlation to its application as biolubricant

Estudo da incorporação de resíduo industrial polimérico ao CAP

This work presents the incorporation of an industrial polymeric waste into a petroleum asphalt cement with penetration grade 50-60 (CAP 50-60). The main goal of this research is the development of a polymer-modified asphalt, with improvements in its physical properties, in order to obtain a more resistant material to the traffic loads. Furthermore, the use of this polymeric waste will result in economic and environmental benefits. The CAP 50-60 used in this research was kindly supplied by LUBNOR Lubrificantes e Derivados de Petróleo do Nordeste (produced in Fazenda Belém Aracati - Ceará) and the industrial polymeric waste was provided by a button manufacturer industry, located in Rio Grande do Norte state. This polymeric waste represents an environmental problem due to its difficulty in recycling and disposal, being necessary the payment by the industry to a landfill. The difficulty in its reuse is for being this material a termofixed polymer, as a result, the button chips resulting from the molding process cannot be employed for the same purpose. The first step in this research was the characterization of the polymeric waste, using Differential Scanning Calorimetry (DSC) Infrared spectroscopy (IR spectroscopy), and Thermogravimetric analysis (TGA). Based on the results, the material was classified as unsaturated polyester. After, laboratory experiments were accomplished seeking to incorporate the polymeric waste into the asphalt binder according to a 23 experimental factorial design, using as main factors: the polymer content (2%, 7% and 14%), the temperature of the mixture (140 and 180 oC) and the reaction time (20 and 60 minutes). The characterization of the polymer-modified asphalt was accomplished by traditional tests, such as: penetration, ring and ball softening point, viscosity, ductility and flash point temperature. The obtained results demonstrated that the addition of the polymeric waste into the asphalt binder modified some of its physical properties. However, this addition can be considered as a feasible alternative for the use of the polymeric waste, which is a serious environmental and technological problem.

Formulação de novos combustíveis base diesel: avaliação de desempenho e emissões

The industry, over the years, has been working to improve the efficiency of diesel engines. More recently, it was observed the need to reduce pollutant emissions to conform to the stringent environmental regulations. This has attached a great interest to develop researches in order to replace the petroleum-based fuels by several types of less polluting fuels, such as blends of diesel oil with vegetable oil esters and diesel fuel with vegetable oils and alcohol, emulsions, and also microemulsions. The main objective of this work was the development of microemulsion systems using nonionic surfactants that belong to the Nonylphenols ethoxylated group and Lauric ethoxylated alcohol group, ethanol/diesel blends, and diesel/biodiesel blends for use in diesel engines. First, in order to select the microemulsion systems, ternary phase diagrams of the used blends were obtained. The systems were composed by: nonionic surfactants, water as polar phase, and diesel fuel or diesel/biodiesel blends as apolar phase. The microemulsion systems and blends, which represent the studied fuels, were characterized by density, viscosity, cetane number and flash point. It was also evaluated the effect of temperature in the stability of microemulsion systems, the performance of the engine, and the emissions of carbon monoxide, nitrogen oxides, unburned hydrocarbons, and smoke for all studied blends. Tests of specific fuel consumption as a function of engine power were accomplished in a cycle diesel engine on a dynamometer bench and the emissions were evaluated using a GreenLine 8000 analyzer. The obtained results showed a slight increase in fuel consumption when microemulsion systems and diesel/biodiesel blends were burned, but it was observed a reduction in the emission of nitrogen oxides, unburned hydrocarbons, smoke index and f sulfur oxides

Novas formulações de fluidos de corte: otimização, propriedades e recuperação do óleo usado

Cutting fluids are lubricants used in metal-mechanical industries. Their complex composition varies according to the type of operation carried out, also depending on the metals under treatment or investigation. Due to the high amount of mineral oil produced in Northeastern Brazil, we have detected the need to better use this class of material. In this work, two novel formulations have been tested, both based on naphthenic mineral oil and additives, such as: an emulsifying agent (A), an anticorrosion agent (B), a biocide (C) and an antifoam agent (D). Each formulation was prepared by mixing the additives in the mineral oil at a 700-rpm stirring velocity for 10 min, at 25°C, employing a 24 factorial planning. The formulations were characterized by means of density, total acid number (TAN), viscosity, flash point and anticorrosion activity. In a subsequent study, oil-in-water emulsions were prepared from these novel formulations. The emulsions were analyzed in terms of stability, corrosion degree, percentage of foam formation, conductivity, accelerated stability and particle size. The samples were appropriately labeled, and, in special, two of them were selected for featuring emulsion properties which were closer to those of the standards chosen as references (commercial cutting oils). Investigations were undertaken on the ability of NaCl and CaCl2 to destabilize the emulsions, at concentrations of 2%, 5% and 10%, at an 800-rpm stirring velocity for 5 min and temperatures of 25º, 40º, 50º and 60ºC. The recovered oils were chemically altered by reincorporating the same additives used in the original formulations, followed by preparation of emulsions with the same concentrations as those of the initial ones. The purpose was to assess the possibility of reusing the recovered oil. The effluents generated during the emulsion destabilization step were characterized via turbidity index, contents of oil and grease, pH, and contents of anions and cations, observing compliance with the parameters established by the current environmental legislation (Brazil s CONAMA 357/05 resolution). It could be concluded that the formulations presented excellent physicochemical properties as compared to commercial cutting fluids, showing that the quality of the newly-prepared fluids is superior to that of the formulations available in the market, enabling technically and environmentally-safe applications

Estudo da influência do biodiesel de mamona como aditivo antioxidante para o biodiesel de girassol e soja

Biodiesel is a fuel made up by mono-alkyl-esters of long chain fatty acids, derived from vegetable oils or animal fat. This fuel can be used in compression ignition engines for automotive propulsion or energy generation, as a partial or total substitute of fossil diesel fuel. Biodiesel can be processed from different mechanisms. Transesterification is the most common process for obtaining biodiesel, in which an ester compound reacts with an alcohol to form a new ester and a new alcohol. These reactions are normally catalyzed by the addition of an acid or a base. Initially sunflower, castor and soybean oil physicochemical properties are determined according to standard test methods, to evaluate if they had favorable conditions for use as raw material in the transesterification reaction. Sunflower, castor and soybean biodiesel were obtained by the methylic transesterification route in the presence of KOH and presented a yield above 93% m/m. The sunflower/castor and soybean/castor blends were studied with the aim of evaluating the thermal and oxidative stability of the biofuels. The biodiesel and blends were characterized by acid value, iodine value, density, flash point, sulfur content, and content of methanol and esters by gas chromatography (GC). Also studies of thermal and oxidative stability by Thermogravimetry (TG), Differential Scanning Calorimetry High Pressure (P-DSC) and dynamic method exothermic and Rancimat were carried out. Biodiesel sunflower and soybean are presented according to the specifications established by the Resolution ANP no 7/2008. Biodiesel from castor oil, as expected, showed a high density and kinematic viscosity. For the blends studied, the concentration of castor biodiesel to increased the density, kinematic viscosity and flash point. The addition of castor biodiesel as antioxidant in sunflower and soybean biodiesels is promising, for a significant improvement in resistance to autoxidation and therefore on its oxidative stability. The blends showed that compliance with the requirements of the ANP have been included in the range of 20-40%. This form may be used as a partial substitute of fossil diesel

Produção de biodiesel a partir de óleo residual reciclado e realização de testes comparativos com outros tipos de biodiesel e proporções de mistura em um moto-gerador

Pós-graduação em Engenharia Mecânica - FEIS

Análise multivariada no monitoramento do processo de produção de óleo diesel numa refinaria de petróleo

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Uso da técnica de análise de óleo lubrificante em motores diesel estacionários, utilizando-se misturas de biodiesel e diferentes níveis de contaminação do lubrificante

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Desenvolvimento de modelos quimiométricos associados à espectroscopia no infravermelho para determinação de parâmetros físico-químicos do óleo diesel

Pós-graduação em Química - IQ

Desenvolvimento, aperfeiçoamento e validação de método cromatográfico para previsão da qualidade e propriedades físico-químicas do óleo diesel tipo B

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Craqueamento termocatalítico da borra de neutralização do óleo de palma (Elaeis guineensis) em escala piloto

Os subprodutos das indústrias de refino de óleo e de biodiesel, como a borra de neutralização, são bastante extensivos e devido a sua baixa pureza e valor econômico constituem uma problemática para essas indústrias no descarte e destinação, sendo de fundamental interesse pesquisas para a utilização desse rejeito. Portanto, este trabalho visa investigar uma alternativa viável, econômica e ambiental para o destino deste subproduto usando o Processo de Craqueamento Termocatalítico da Borra de Neutralização do Óleo de Palma (Elaeis guineensis, Jaqc) em escala piloto utilizando-se 5, 10 e 15% de Carbonato de Sódio (Na²CO³) como catalisador e temperaturas finais de 440ºC e 420ºC. A borra foi obtida pelo processo de neutralização e submetida a uma desidratação e caracterizada assim como o catalisador foi desidratado em estufa e caracterizado em relação à Difração de Raio-X, Análise Térmica Gravimétrica (ATG) e à Análise Térmica Diferencial (TDA). Foram realizados cinco testes de craqueamento termocatalítico na Usina Piloto de Craqueamento (THERMTEK/FEQ/UFPA) o qual é constituído em um reator com agitação mecânica e capacidade de 125 litros, além da dinâmica do processo e destilação dos produtos do craqueamento. O produto líquido orgânico (PLO), amostras da dinâmica do processo e frações da destilação foram caracterizados de acordo com cada norma exigida pela ANP N°65 e analisadas por IV e RMN. Após as análises dos resultados verificou-se que a eficiência do processo aumenta com catalisador e temperatura e que a matéria-prima fornece produtos de baixa acidez e com boas características para uso como combustível. Pela análise da termodinâmica do processo percebeu que alguns parâmetros como viscosidade, densidade e ponto de fulgor diminuem com o tempo e aumento da temperatura, formando hidrocarbonetos mais leves. Com relação à destilação, as frações nas faixas mais pesadas se assemelham ao óleo diesel do petróleo na maioria dos parâmetros exigidos pela ANP N°65.

Partial Discharge Phenomena in Converter and Traction Transformers: Identification and Reliability

After the development of power electronics converters, the number of transformers subjected to non-sinusoidal stresses (including DC) has increased in applications such as HVDC links and traction (electric train power cars). The effects of non-sinusoidal voltages on transformer insulation have been investigated by many researchers, but still now, there are some issues that must be understood. Some of those issues are tackled in this Thesis, studying PD phenomena behavior in Kraft paper, pressboard and mineral oil at different voltage conditions like AC, DC, AC+DC, notched AC and square waveforms. From the point of view of converter transformers, it was found that the combined effect of AC and DC voltages produces higher stresses in the pressboard that those that are present under pure DC voltages. The electrical conductivity of the dielectric systems in DC and AC+DC conditions has demonstrated to be a critical parameter, so, its measurement and analysis was also taken into account during all the experiments. Regarding notched voltages, the RMS reduction caused by notches (depending on firing and overlap angles) seems to increase the PDIV. However, the experimental results show that once PD activity has incepted, the notches increase PD repetition rate and magnitude, producing a higher degradation rate of paper. On the other hand, the reduction of mineral oil stocks, their relatively low flash point as well as environmental issues, are factors that are pushing towards the use of esters as transformer insulating fluids. This PhD Thesis also covers the study of two different esters with the scope to validate their use in traction transformers. Mineral oil was used as benchmark. The complete set of dielectric tests performed in the three fluids, show that esters behave better than mineral oil in practically all the investigated conditions, so, their application in traction transformers is possible and encouraged.

Estudio técnico-económico de una planta de producción de biodiesel

Se explica las posibles razones que han obligado a varias de las plantas de biodiésel en España a cerrar a pesar de estar siendo auspiciadas por la Unión Europea y fomentadas, mediante normativas específicas y ayudas sustanciales en cada uno de los países miembros, a fin de reforzar la utilización de los biocarburantes, como energía alternativa a los combustibles fósiles, debido a las ventajas medioambientales y sociopolíticas que conllevan. Para ello se ha empezado realizando un estudio del sector y de su funcionamiento así como de la evolución reciente del mercado tanto en Europa como en España. Posteriormente se ha modelizado una planta de biodiesel tipo desde las primeras fases de su construcción hasta su puesta en funcionamiento, para, a continuación analizar su desarrollo haciendo especial hincapié en la evolución de las principales variables económicas anteriormente estudiadas que han llevado finalmente a tener que cerrarla por falta de rentabilidad. El proceso de producción del biodiésel desde aceites vegetales y grasas animales mantiene un fuerte crecimiento en los mercados de la Unión Europea al igual que en Estados Unidos y Canadá. La producción de biodiésel se ha incrementado rápidamente en los últimos años, ya que es una alternativa renovable a los carburantes, como el petróleo o el diésel. La producción por trasesterificación de aceites vegetales y grasas animales, dan al biodiésel una densidad, un punto de encendido, viscosidad, estabilidad a la oxidación similares al diésel. Estas propiedades permiten a la mezcla de biodiésel poder usarlo en motores convencionales sin necesidad de grandes modificaciones. El objetivo fundamental de este proyecto es, dentro de un entorno económico hostil, explicar el posible porqué de la situación de las plantas de biodiésel en España, haciendo un análisis de la viabilidad económico – financiera de una planta de producción de biodiésel. La instalación de la que parte el presente proyecto es la de una planta, situada en la provincia de Jaén, con una capacidad de producción de 100 000 t/año, con una previsión de funcionamiento continua y con una vida útil estimada de 15 años. Una vez finalizado el estudio económico, se ha valorado el impacto del mercado en el funcionamiento de la planta, tanto a nivel internacional debido a la competencia desleal, como nacional, debido a las ayudas en los cultivos. Se deduce que la rentabilidad de una planta de biodiésel es relativamente positiva pero viene dada por un gran número de variables internas y externas que hacen un negocio inestable y poco rentable. ABSTRACT It explains the possible reasons that have forced several biodiesel plants in Spain to close in spite of being sponsored by the European Union and promoted by specific regulations and substantial aid in each of the member countries to strengthen the use of biofuels as alternative energy to fossil fuels because of the environmental and sociopolitical involving VII For this we have begun a study of the sector and its operation as well as the recent market developments in Europe and in Spain. Later was modeled biodiesel plant type from the early stages of construction to commissioning, to then analyze its development with particular emphasis on the evolution of the main economic variables that have been previously studied eventually have to close by unprofitability. The processes and production of biodiesel (methyl ester) from vegetable oil and animal fat feedstocks remain a strong growth market in the European Union as well as the United States and Canada. Biodiesel production has increased rapidly in this last years as producers sought a renewable alternative to petroleum fuel. Produced by the trans-esterification of vegetable oils and animal fats, biodiesel has similar density, flash point, viscosity, oxidation stability to petroleum diesel. These similarities enable biodiesel blends to be used in conventional diesel engines without significant modifications. This proyect gives an overview of current developments with regard to biodiesel technology, the Spain biofuel market, and national biofuel policies, looking at closely the economic-financial feasibility of a biodiesel production plant. The installation, situated at Linares (Jaén), has a production capability of 100 000 t/year. The operation estimated is constant and with a product life of 15 years. Finished the part destined to the economic view of this project, it has been considered the adverse effects on the overall performance and the financial situation of the industry. It follows form the study that biodiesel plant´s profitability is relatively high, but it is given by a large numbers of variables, internals and externals, which have made an unviable and unsustainable business.

Biokerosene from Babassu and Camelina Oils: production and properties of their blends with fossil kerosene

Babassu and camelina oils have been transesterified with methanol by the classical homogeneous basic catalysis method with good yields. The babassu fatty acid methyl ester (FAME) has been subjected to fractional distillation at vacuum, and the low boiling point fraction has been blended with two types of fossil kerosene, a straight-run atmospheric distillation cut (hydrotreated) and a commercial Jet-A1. The camelina FAME has been blended with the fossil kerosene without previous distillation. The blends of babassu biokerosene and Jet-A1 have met some of the specifications selected for study of the ASTM D1655 standard: smoke point, density, flash point, cloud point, kinematic viscosity, oxidative stability and lower heating value. On the other hand, the blends of babassu biokerosene and atmospheric distillation cut only have met the density parameter and the oxidative stability. The blends of camelina FAME and atmospheric distillation cut have met the following specifications: density, kinematic viscosity at −20 °C, and lower heating value. With these preliminary results, it can be concluded that it would be feasible to blend babassu and camelina biokerosenes prepared in this way with commercial Jet-A1 up to 10 vol % of the former, if these blends prove to accomplish all the ASTM D1655-09 standards.