O principal objetivo deste estudo foi estimar um modelo analítico que explicasse a relação entre os mercados de etanol hidratado e de gasolina C, incluindo, também, efeitos de outros fatores, como o preço de açúcar nos mercados doméstico e internacional e a renda. Por sua capacidade de captar efeitos dinâmicos, utilizou-se o Modelo de Auto-Regressão Vetorial com Correção de Erro VEC. A análise das funções de demanda dos combustíveis mostrou que o consumo de etanol responde de forma expressiva a variações contemporâneas no próprio preço e no preço da gasolina, produto substituto nesse segmento de mercado. Já com relação à demanda de gasolina C, verifica-se que suas vendas respondem menos tanto ao próprio preço como ao do etanol. De maneira geral, a análise das funções de respostas a impulsos permite verificar que os efeitos dos choques não antecipados sobre as variáveis do modelo são de curta duração, desaparecendo, na maior parte das vezes, após o terceiro mês. A renda mostrou-se importante variável explicativa tanto para o consumo de etanol hidratado quanto de gasolina C. Um choque exógeno no preço internacional de açúcar resulta em um efeito elevado no preço do produto no mercado doméstico. De outro lado, um choque no preço doméstico de açúcar tem impacto significativo no preço do etanol anidro (elasticidade acumulada de 0,57), sendo que esses produtos concorrem pela mesma matéria-prima na indústria. Como este preço, por sua vez, representa uma variável proxy para o preço do etanol hidratado no segmento produtor, pode-se afirmar que 60% das variações de preço neste segmento são transmitidas ao preço do combustível no mercado varejista. A análise da decomposição das variâncias do erro de previsão evidenciou que a variável que tem maior impacto sobre o preço do etanol hidratado combustível no varejo é o preço do etanol anidro (proxy do preço do etanol hidratado no segmento produtor). Os principais determinantes da venda de etanol hidratado no varejo são a renda, o preço do etanol hidratado combustível no varejo e o do etanol anidro no segmento produtor. Já com relação às vendas de gasolina C no varejo, o principal determinante é a renda, enquanto as demais variáveis pouco contribuem para explicar suas variações. Finalmente, a análise da previsão dentro da amostra para o preço do etanol hidratado no segmento varejista sugere que este preço assumiria um patamar mais elevado, não fosse a atual política de controle de preços dos derivados do petróleo adotada no Brasil. Nas duas últimas safras do período estudado, o preço praticado está, em média, 23,7% abaixo do previsto pelo modelo estimado neste estudo. Vale ressaltar que o modelo estimado capta o padrão médio do comportamento da série, dados os fundamentos de mercado considerados, os quais explicam pelo menos 76% das variações do preço do etanol hidratado no varejo. / The main objective of this study was to estimate an analytical model to explain the relationship between the markets of hydrated ethanol fuel and gasoline C, including effects of other factors such as sugar prices in the domestic and the International markets and income. Because of its ability to capture dynamic effects, the Auto-regression Model with Vector Error Correction VEC was used. Analysis of the demand function showed ethanol fuel consumption significantly responds to contemporary variations of its price and gasoline price, replacement product in this market segment. Regarding the demand for gasoline C, it appears that sales respond less to its price and ethanol price. In general, analysis of the response functions to impulses allows to verify that the effect of unanticipated shocks on model variables are of short duration and disappears, in most cases, after three months. Income proved to be important in ethanol and gasoline C consumption. An exogenous shock in the international sugar price results in a large effect on the product price in the domestic market. Therefore, a shock in the domestic sugar price has a significant impact on the anhydrous ethanol price (accumulated elasticity of 0.57), once these products compete for raw material in the sector. Given that this price represents a proxy variable for the hydrous ethanol price for the industry, 60% of the price in this segment is transmitted to the fuel price in the retail market. A decomposition analysis of forecast error variance showed that the variable with greater impact on the hydrated ethanol fuel price in the retail market is the anhydrous ethanol price (proxy of the hydrated ethanol price in the industry). The main determinants of hydrated ethanol sales in the retail market are the income, the hydrated ethanol fuel price and the anhydrous ethanol fuel price in the industry. Gasoline C sales in the retail market are mostly determined by income, while the other variables contribute little to explain its variations. Finally, the analysis of the in-sample forecast for the hydrated ethanol price in the retail market suggests that this price would assume a higher level, if there were not the current policy of controlling prices of petroleum derivatives adopted in Brazil. In the last two seasons of the analysis, the price was on average 23.7% below that predicted by the model estimated in this study. It is noteworthy that the estimated model captures the average standard of the series, given the market fundaments considered, which explain at least 76% of the variations in the hydrated ethanol price in the retail market.

Orientador: Célio Pasquini / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-18T09:40:06Z (GMT). No. of bitstreams: 1 Bueno_AerentonFerreira_D.pdf: 13715052 bytes, checksum: 49ac649190d25c5991f45b0564f4df65 (MD5) Previous issue date: 2011 / Resumo: O trabalho trata do desenvolvimento de um analisador de processo utilizando a espectroscopia no infravermelho próximo (NIR) para prever propriedades de derivados de petróleo, como gasolina e querosene de aviação. O instrumento foi projetado para ser instalado diretamente em uma linha de processo numa unidade industrial, realizando, de maneira automatizada, a coleta, análise e descarte da amostra, envio dos resultados obtidos, além de operações como limpeza da célula e diagnósticos funcionais. Um protótipo de um espectrofotômetro NIR de bancada foi construído, a partir do qual, foi montado um espectrofotômetro de laboratório plenamente funcional. O espectrofotômetro foi instalado num gabinete com sistema de pressurização (para estar de acordo com a classificação da área industrial), controlador de temperatura e dispositivos para a seleção da amostra e limpeza da célula, tornando-se, assim, um analisador de processo. Um programa de computador em linguagem Visual Basic foi desenvolvido para a operação automatizada do analisador. Foram obtidos espectros e desenvolvidos modelos de calibração multivariados para prever uma série de parâmetros de qualidade de gasolina (como destilação, octanagem e concentrações de aromáticos, olefinas e saturados) e querosene de aviação (massa específica e ponto de congelamento), que apresentaram resultados compatíveis com os valores de precisão dos métodos de referência utilizados. O analisador foi instalado num sistema de mistura para produção de gasolina de uma refinaria de petróleo, visando prever, em tempo real, vários parâmetros de qualidade desse produto, para a otimização do processo produtivo / Abstract: The work deals with the development of a process analyzer using near infrared spectroscopy (NIR) to predict properties of petroleum products like gasoline and jet fuel. The instrument was designed to be mounted directly on a line in an industrial process, performing automatically the collection, analysis and disposal of the sample, transmission of results, as well as operations such as cleaning the cell and functional diagnosis. A prototype of a benchtop NIR spectrometer was built, from which a fully functional laboratory spectrophotometer was assembled. The spectrophotometer was installed in a cabinet with a pressurization system (to be consistent with the classification of the industrial area), temperature controller and devices for sample selection and cleaning of the cell, becoming thus a process analyzer. A computer program written in Visual Basic was developed for the automated operation of the analyzer. Spectra were acquired and multivariate calibration models were developed to predict a series of gasoline (such as distillation, octane and concentrations of aromatics, olefins and saturated) and jet fuel quality parameters (specific gravity and freezing point), who presented results compatible with the precision values of the reference methods used. The analyzer was installed in a blending system for production of gasoline in an oil refinery, aimed to provide, in real time, various quality parameters of the product, to optimize the production process / Doutorado / Quimica Analitica / Doutor em Ciências

A gasolina que é comercializada no Brasil sofre a adição de álcool etílico anidro, também conhecido como etanol, em frações que podem variar de 20 a 24%. O uso desse composto adicionado à gasolina serve para aumentar a octanagem e reduzir a emissão de monóxido de carbono para a atmosfera. Esta pesquisa teve como objetivo verificar e comparar a relação existente entre a espessura encontrada nos poços de monitoramento e no meio poroso, tanto para gasolina pura quanto para a gasolina com 20 % de etanol (E-20), após a simulação de um vazamento em subsuperfície, utilizando colunas de areia em laboratório, visto que esta relação é de extrema importância para o cálculo preciso do volume do contaminante a ser bombeado, no caso de vazamentos de combustível. As colunas foram confeccionadas utilizando-se 2 tubos de acrílico transparente com 100 cm de comprimento e 23cm de diâmetro interno que foram fixados a uma base de acrílico transparente com 0,60 cm de espessura. Um tubo de PVC branco com 100 cm de comprimento e 3,50 cm de diâmetro interno, com ranhuras horizontais de 0,10 cm de largura foi cortado longitudinalmente e cada metade foi fixada nas paredes dos tubos de acrílico para representar o poço de monitoramento. As colunas foram preenchidas com areia de granulometria muito fina (0,088 mm). Os resultados obtidos mostraram que a espessura aparente da gasolina pura foi 2,6 vezes superior à espessura real da fase livre e a espessura aparente da E-20 foi 0,6 vezes superior a espessura real da fase livre. A tensão interfacial da E-20 foi 67% inferior à tensão interfacial da gasolina pura, possibilitando que uma quantidade maior de poros fosse acessada, refletindo em valores de saturação total 54% superiores ao da gasolina pura. Parte da fase gasolina da E-20 deve ter sido depositada como glóbulos desconectados nos poros caracterizando uma saturação residual, devido ao particionamento preferencial do etanol para a água subterrânea e o conseqüente enriquecimento em gasolina na fase gasolina. Esta saturação residual deve ter dificultado o fluxo e consequentemente reduzido a permeabilidade relativa para a fase aquosa, causando o retardamento da chegada da E-20 no poço de monitoramento. / Commercial gasolines sold in Brazil are added ethanol from 20 to 24% by volume. This oxygenated additive raises the octane level and reduces carbon monoxide emissions to the atmosphere. Underground storage tanks and gasoline lines are a major potential problem for soil and groundwater contamination. Since ethanol has cosolvent properties that alter the behavior of phase distribution in subsurface, this research compares the existing relationship of apparent and actual thicknesses of free phase gasoline and E-20 (80% gasoline and 20% ethanol by volume) found respectively in monitoring wells and medium porous material using two column experiments. Two cylindrical plexiglass columns were used (100 cm long and 23 cm in internal diameter). The bottom ends were capped using two 35 x 35 cm plexiglass plates. A spout-like connection of PVC was fitted near the base of each column as an inlet/outlet end. One well screen (100 cm long and 3,5 cm in internal diameter) in white PVC was cut in half lengthwise and attached to the inside walls of columns to be used as monitoring wells. The columns were then filled with 0,088 mm grain size sand (very fine).The apparent thickness of pure gasoline was 2.6 times thicker than the actual thickness in the aquifer while it was only 0.6 thicker for E-20. The interfacial tension of E-20 is 67% lower than the that of the pure gasoline, allowing a larger quantity of pores to be accessed, which was reflected in an oil saturation 54% higher than that of pure gasoline. Part of the gasoline phase of E-20 must have been precipitated as disconnected doplets within the pores creating a residual saturation and consequently reducing the permeability with respect to the aqueous phase delaying the breakthrough of E-20 in the monitoring well.

A presente pesquisa trata de calibrar, a ferir e utiliza em laboratório um detetor de fotoionização (método de campo) proveitoso na caracterização de áreas contaminadas por vazamentos de gasolina; comparar as informações do detetor com os resultados obtidos com balança analítica; comparar os resultados de fluxo de massa medido com o previsto pelo modelo JURY contido no software APIDSS 2.0 O detetor mostrou-se útil como primeira ferramenta na caracterização de áreas contaminadas recentemente (até 100 dias). Para áreas onde a contaminação esteja em uma fase mais avançada o aparelho mostrou-se útil na detecção de alterações; os modelos desenvolvidos com base nos resultados obtido com balança e com o detetor de fotoinização apresentaram resultados satisfatórios para o período de ensaio; as comparações realizadas com o software APIDSS 2.0 serviram para a confirmação dos resultados obtidos. / The present research aims at gauging, checking and using a photoionization detector (field method) in laboratory advantageous to the characterization of areas polluted by leaks of gasoline; to compare the information of the detector with the results obtained in the analytic scale; to compare the results of the measured mass flow with those foreseen by the model JURY of the software APIDSS 2.0. The detector showed to be useful as a first tool in the characterization of areas recently contaminated (up to 100 days). To areas where the contamination is in a more advanced phase, the apparel showed to be useful in the detection of alterations; the development of models based on the results obtained with a scale and with the photoionization detector presented satisfactory results for the rehearsal period; the comparisons accomplished by the software APIDSS 2.0 confirmed the obtained results.

[pt] Com o intuito de reduzir as emissões e melhorar a combustão em uma maior faixa de rotação e carga de um motor, foi proposto o estudo da combustão por compressão de misturas homogêneas (HCCI), este processo apresenta altas eficiências e baixas emissões, principalmente de NOx e fuligem. Assim, o objetivo do presente trabalho é a determinação das faixas de operação estável em um motor diesel, de alta taxa de compressão (20:1). O combustível utilizado foi gasolina tipo A, tendo em vista a sua grande produção, além das características de auto-ignição. Para atingir o objetivo proposto foram controladas a temperatura de entrada do ar e a quantidade de combustível da mistura, o que foi implementado sem modificação estrutural do motor. Os ensaios foram realizados com uma temperatura de alimentação entre 75 e 95 ºC, com rotação entre 1200 e 2200 RPM. Os valores para o fator lambda variaram, em função de um processo de combustão estável, entre 2 e 4. São apresentados os resultados experimentais obtidos em um dinamômetro de bancada, sobre os quais se fez uma análise do rendimento, para a faixa de melhor estabilidade da combustão. Para a mesma faixa foi realizada uma análise das curvas de pressão x tempo, caracterizando a auto-ignição como função da temperatura do ar e da riqueza da mistura. Os melhores rendimentos encontrados situam-se ao redor de 36,5 %, para uma temperatura de ingresso de 85 °C, para as maiores rotações pesquisadas. / [en] The present study of homogeneous mixture compression ignition (HCCI) was proposed in order to reduce emissions and improve combustion at a higher speed range and load, this process has high efficiency and low emissions mainly NOx and soot. Therefore, the aim of this study was to determine the ranges of stable operation in a diesel engine of high compression ratio (20:1), operating in HCCI. The fuel used was gasoline type A, given its large production, besides the good characteristics of auto-ignition. To achieve this purpose were controlled inlet air temperature and the amount of fuel in the mixture, these were implemented without structural modification of the engine. The tests were conducted with a feed temperature between 75 and 95 ° C, with rotation between 1200 and 2200 RPM. The values for the lambda factor varied between 2 and 4, as a function of a stable combustion process. The experimental results here reported were obtained on a dynamometer bench, on which, it was made a performance analysis for the better stability combustion range. Additionally for this range, an analysis of the curves of pressure vs. time was performed, characterizing the auto-ignition as a function of air temperature and the richness of the mixture. The best results found are located around 36.5% at an intake temperature of 85 ° C for the highest speed studied.

The ternary phase behaviour of the n-heptane-l-propanol-water system was studied and compared with the theoretical prediction based on the UNIQUAC model for non-electrolyte solutions. The results showed that this model adequately approximated experimental studies. The excess enthalpies and excess volumes for several binary mixtures were determined. The excess enthalpies were measured using a LKB flow microcalorimeter and the excess -volumes determined using a PAAR densitometer. The study showed that no significant enthalpy or volume changes occurred when petrol/n-heptane were mixed with alcohols . Ternary phase diagrams, including tie lines have been determined for a number of petrol-alcohol-water systems (including the Sasol blend of alcohols). The tie line results show that the concentration of water in the water-rich layer is strongly dependent on the type of alcohol used. The Sasol alcohol blended with petrol resulted in a high water concentration in the water-rich layer which forms on phase separation. This is believed to contribute significantly to the corrosion problems experienced by motorists using the Sasol blended fuel on the Witwatersrand. The effect of temperature on several of these blends was included in the study. Diesel-alcohol blends and the co-solvent properties of ethyl acetate investigated. Ethyl acetate ensures miscibility at low concentrations for diesel-ethanol blends. Octyl nitrate and two cetane improvers from AECI were assessed in terms of their ability to restore cetane rating of blended diesel fuel to that of pure diesel fuel. The results indicated that all three samples were successful in this application. / KMBT_363

This thesis presents the results of an investigation of the differences in combustion between gasoline and natural gas in a spark-ignition engine. Combustion development is influenced by calorific value, specific heat, flame speed and the gaseous or liquid state of the fuel. Simple simulation programs were set up to investigate the effects of low flame speed and higher specific heat of the fuel-air mixture. Actual performance was measured on a single cylinder test engine using ionization probes as flame detectors and a pressure pick-up. The experimental results show that longer ignition delay and limited flame speed at high pressure and temperature are the main reasons for' the power loss of natural gas at high engine speed; this is in addition to the basic loss due to the replacement of air by gaseous fuel in the cylinder. From calculations, it was learned that specific heat and dissociation differences had little effect on power. / Applied Science, Faculty of / Mechanical Engineering, Department of / Graduate

This thesis describes a fractionation column method of separating isobutane and isobutene to isolate isooctane.

Gasoline is a substance commonly encountered in forensic settings. Unfortunately, gasoline is an easily obtainable ignitable liquid that arsonists commonly use to initiate or expedite the spread of an intentionally set fire. Fires claim the lives of many people each year in addition to causing widespread property damage. Many fire scene investigations result in charges of arson, which has the legal connotation of a committed crime. For this reason, extensive analysis and investigation must be undertaken before any suspected arson scene is deemed an actual case of arson. Although ignitable liquids, including gasoline, may be present at the scene of a fire, it does not necessarily mean they were intentionally used as accelerants. An accelerant is a fuel used to initiate a fire. These realities, in addition to several other factors, demonstrate why a rapid, reliable, gasoline analysis method is crucial to forensic applications. In this thesis, direct analysis in real time – mass spectrometry (DART-MS) is evaluated as a potential method that could better identify, distinguish and classify gasoline brands from one another. Techniques such as DART-MS could enable forensic laboratories to better identify questioned gasoline samples. Many ignitable liquids share similar chemical properties, and forensically relevant evidence is often obtained from a crime scene in less than favorable conditions. Fire debris can encompass various materials, including burnt carpet, flooring, items of furniture and clothing, among others. If gasoline was used as an accelerant, it may be present in trace amounts after the termination of the fire. Materials submitted for laboratory analysis may be substrates with compositions that have components similar to those found in some ignitable liquids. These are just a few of the potential obstacles that could be encountered with analyzing fire debris in a forensic setting. Traditionally, gas chromatography – mass spectrometry (GC-MS) methods are utilized for gasoline analysis in the criminal laboratory setting. While traditional GC-MS methods are sensitive and able to classify samples as gasoline, they are time consuming in terms of both sample preparation and analysis. Additionally, they do not generate differential mass spectral data based on the brand of gasoline. Conversely, gasoline analysis in this research, utilizing the DART-MS method, demonstrated that five different brands of gasoline could be distinguished from one another both by visual examination of mass spectra and with methods of chemometric analysis. Advantageously, the DART-MS method, an ambient ionization technique, requires little sample preparation and a rapid sample analysis time, which could drastically increase the throughput of standard sample analysis with further method development. The goals and objectives of this research were to optimize the DART-MS parameters for gasoline analysis, determine if DART-MS analysis could distinguish gasoline by brand, develop chemometric models to appropriately classify gasoline samples, and finally lay groundwork for future studies that could further develop a more efficient and discriminating DART-MS gasoline analysis method for forensic casework. Each brand of gasoline was observed to have a chemical attribute signature (CAS) consisting of not only low-mass ions, but also a variety of high-mass ions not usually observed with gasoline samples analyzed by GC-MS. Although variables including season, storage time, dilution and age of the gasoline were observed to contribute to the resulting mass spectral data, once the mass spectra are better understood, they could offer even more discriminating power between samples than simple analysis of the gasoline brand. In this research, DART-MS parameters were first optimized for gasoline analysis. Subsequently, the five acquired brands of gasoline: Shell, Sunoco, Irving, Cumberland Farms and Gulf, were analyzed both undiluted (or neat) and diluted utilizing the DART-MS analysis method. GC-MS data was generated and analyzed to show comparisons. After analyzing the data generated by both approaches, it was apparent that the DART-MS method could generate CASs based on the gasoline brand and offer a degree of differentiation that traditional GC-MS does not. Additional chemometric analyses utilizing principle component analysis (PCA) and the construction of models with Analyze IQ Lab software verified that the gasoline brands were distinguishable when samples were analyzed with this ambient ionization method. PCA plots of the neat gasoline demonstrated clustering based on brand. Additionally, models constructed from training samples generated from DART-MS analysis of the various brands were able to accurately classify gasoline samples as "yes" or "no" when a test set of gasoline was compared to all five brands. The lowest associated testing error rate for some of these models was 0%. However, additional analysis with greater sample sizes needs to be further carried out to more accurately evaluate this method of gasoline analysis and classification.

This study compares and contrasts operational expenses of district-owned to privately owned school bus services operated in Wichita, Clay, Montague, Jack, Wilbarger, Throckmorton, Baylor, Palo Pinto, Young, and Archer counties within the state of Texas.