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Ph. D. Thesis / In order to compute more realistic production plans and schedules, techniques using nonlinear programming (NLP) and mixed-integer nonlinear programming (MINLP) have gathered a lot of attention from the industry and academy. Efficient solution of these problems to a proven ε-global optimality remains a challenge due to their combinatorial, nonconvex, and large dimensionality attributes. The key contributions of this work are: 1) the generalization of the inventory pinch decomposition method to scheduling problems, and 2) the development of a deterministic global optimization method. An inventory pinch is a point at which the cumulative total demand touches its corresponding concave envelope. The inventory pinch points delineate time intervals where a single fixed set of operating conditions is most likely to be feasible and close to the optimum. The inventory pinch method decomposes the original problem in three different levels. The first one deals with the nonlinearities, while subsequent levels involve only linear terms by fixing part of the solution from previous levels. In this heuristic method, infeasibilities (detected via positive value of slack variables) are eliminated by adding at the first level new period boundaries at the point in time where infeasibilities are detected. The global optimization algorithm presented in this work utilizes both piecewise McCormick (PMCR) and Normalized Multiparametric Disaggregation (NMDT), and employs a dynamic partitioning strategy to refine the estimates of the global optimum. Another key element is the parallelized bound tightening procedure. Case studies include gasoline blend planning and scheduling, and refinery planning. Both inventory pinch method and the global optimization algorithm show promising results and their performance is either better or on par with other published techniques and commercial solvers, as exhibited in a number of test cases solved during the course of this work. / Thesis / Doctor of Philosophy (PhD) / Optimal planning and scheduling of production systems are two very important tasks in industrial practice. Their objective is to ensure optimal utilization of raw materials and equipment to reduce production costs. In order to compute realistic production plans and schedules, it is often necessary to replace simplified linear models with nonlinear ones including discrete decisions (e.g., “yes/no”, “on/off”). To compute a global optimal solution for this type of problems in reasonable time is a challenge due to their intrinsic nonlinear and combinatorial nature. The main goal of this thesis is the development of efficient algorithms to solve large-scale planning and scheduling problems. The key contributions of this work are the development of: i) a heuristic technique to compute near-optimal solutions rapidly, and ii) a deterministic global optimization algorithm. Both approaches showed results and performances better or equal to those obtained by commercial software and previously published methods.

Using theoretical relations as a source of econometric specifications might lead a researcher to models that do not adequately capture the statistical regularities in the data and do not faithfully represent the phenomenon of interest. In addition, the researcher is unable to disentangle the statistical and substantive sources of error and thus incapable of using the statistical evidence to assess whether the theory, and not the statistical model, is wrong. The Probabilistic Reduction Approach puts forward a modeling strategy in which theory can confront data without compromising the credibility of either one of them. This approach explicitly derives testable assumptions that, along with the standardized residuals, help the researcher assess the precision and reliability of statistical models via misspecification testing. It is argued that only when the statistical source of error is ruled out can the researcher reconcile the theory and the data and establish the theoretical and/or external validity of econometric models. Through the approach, we are able to derive the properties of Beta regression-like models, appropriate when the researcher deals with rates and proportions or any other random variable with finite support; and of Lognormal models, appropriate when the researcher deals with nonnegative data, and specially important of the estimation of demand elasticities. / Ph. D.

A high compression type engine operates far more satisfactorily on gasoline than on kerosene. Frequent oil changes are necessary when kerosene is used. When burning gasoline the engine operated on fuel-air mixtures varying from 1 - 17.5 to 1 - 7.48 by weight. The most economical ratio was 1 - 15.2, with the intake air at 135° F. The most powerful mixture was a ratio of 1 - 12.3*, and intake air at 86.2° F. Kerosene mixtures varied. from 1 - 7.41 to 1 - 16.75. Greatest economy was secured on a mixture of 1 - 15.62, air intake at 134° F. The most power was developed from kerosene on a mixture of 1 - 13.3*, and an air temperature of 80° F. The efficiency of the engine on the most powerful mixtures was 19.75% for gasoline at 23.05 H.P.,and 25.7% for kerosene at 22.85 H.P. The engine developed as much power from a pound of kerosene as from a pound of gasoline. Gasoline and kerosene require practically the same external conditions for optimum operation. Kerosene does not deposit a great deal more carbon than gasoline. Heat added to the intake air gives greater engine economy, but at the same time decreases its capacity. 135° F. gave the most economy in both fuels. Hot air and lean mixtures makes the engine knock on gasoline. The engine knocked with kerosene at all heats on practically all mixtures. Speed above 1350 R.P.M.,and low water temperatures *Average of three mixtures used on power curve. minimize the “pinging” The outlet water must be kept above 180° F when burning kerosene. Oil “stands up” better while burning gasoline. Nine gallons of kerosene produce power equivalent to that produced by ten gallons of gasoline. / M.S.

[pt] Muitos contaminantes orgânicos, incluindo derivados do petróleo, como por exemplo a gasolina, têm baixa solubilidade em água e migram na subsuperfície como uma fase separada da água sendo referidos como NAPLs (non aqueous liquid phases). Em seu processo de migração na subsuperficie os NAPLs deixam para trás segmentos de líquidos disconectados na forma de gânglios ou lentes que constituem a fase residual do contaminante. A presença do contaminante residual constitui-se numa das maiores dificuldades para a implementação de uma técnica adequada de limpeza ou recuperação de locais contaminados, uma vez que tais contaminantes representam uma fonte lenta e continua de contaminação de solos e água subterrânea, especialmente por sua dissolução na água. Nesta tese, estudou-se o efeito do etanol na dissolução de gasolina residual. Tal estudo foi motivado pela necessidade de se obter um melhor entendimento de um cenário de contaminação envolvendo gasolina e etanol uma vez que gasolina com 20 por cento de etanol em sua constituição e etanol puro estão sendo utilizados como combustível, no Brasil, nos últimos 20 anos. O uso de aditivos oxigenados à gasolina, tais como álcoois, objetiva aumentar o desempenho do motor dos automóveis bem como diminuir a emissão de CO2 destes para a atmosfera e este uso vem aumentando em muitos países. Experimentos tipo equilíbrio em lote e experimentos de coluna foram realizados para investigar efeitos do etanol na solubilidade de constituintes da gasolina e no coeficiente de transferência de massa da gasolina para fase aquosa. Colunas de solo arenoso com gasolina em saturação residual foram percoladas por soluções aquosas com diferentes teores de etanol. Os resultados das concentrações efluentes de contaminante ao longo do tempo, obtidas destes ensaios, foram interpretados segundo o modelo de dissolução proposto por Frind et al. (1997), modificado nesta tese para considerar os efeitos de cosolvência do etanol na solubilidade dos constituintes da gasolina. Os resultados experimentais obtidos indicam que um cenário de contaminação envolvendo etanol e gasolina deverá ser bastante diferente daquele de contaminação usual de gasolina.Em um cenário de contaminação envolvendo etanol e gasolina, concentrações mais altas de contaminantes na água serão esperadas bem como diferentes constituintes da gasolina, além do tradicional grupo BTEX (benzeno, tolueno, etilbenzeno e os isômeros xilenos) deverão estar presentes na água em concentrações nocivas ao meio ambiente. / [en] Many organic contaminants, including petroleum products, such as gasoline, have low aqueous solubilities and migrate through the subsurface as a separated phase called NAPLs (non aqueous liquid phases). In its flow path into the porous media the NAPLs let behind disconnected segments of organic liquids entrapped as ganglia or lenses that form the residual phase of the contaminant. The presence of the residual contaminant has been reported as one of the most difficulties in the development of an appropriate cleanup strategy as the residual phase represents a long and continuum source of contamination of soils and groundwater, specially by its dissolution into the water.In this thesis the effect of ethanol on dissolution of residual gasoline was studied, aiming at a better understanding of a scenario of groundwater contamination involving gasoline and ethanol, since 20 percent of ethanol has been added to the Brazilian gasoline in the last 20 years and also ethanol has been used as fuel in Brazil in these years. The use of oxygenated additives into the gasoline, such as alcohols, has the advantage of improving engine performance and reducing the air impact pollution by CO2 and its use has increasing in many countries.Equilibrium batch tests and column experiments were carried out to investigate the effect of ethanol on solubility of gasoline constituents and on the mass transfer coefficient from gasoline to aqueous phase. The results of the column experiments were interpreted with a dissolution numerical model proposed by Frind et al.(1997), modified in this thesis to include the cosolvent effects of the ethanol on the solubility of gasoline constituents.In terms of soil and groundwater contamination related to gasoline spills, chemicals like benzene, toluene, ethylbenzene and xylenes (BTEX group) have acute toxicity or carcinogenicity, are the most water- soluble and mobile gasoline components, receiving the greatest concern. In this work, an enormous enhancement of gasoline constituents solubility due to ethanol was observed, and it was also noticed that the mass transfer coefficient diminished due to ethanol. The highest increase in solubility were for the less water soluble components. Therefore, gasoline components, other than BTEX, are expected in significant concentrations, in a scenario of contamination involving ethanol and therefore more concern about this potential threat should be addressed.

Le moteur essence à allumage par compression (GCI), reposant sur la combustion partiellement prémélangée de l'essence (GPPC), peut potentiellement assurer des opérations efficaces et propres. Le moteur GCI s'est avéré efficace à forte charge, mais l'indice d'octane élevé de l'essence limite considérablement les opérations à faible charge. Le présent travail étudie le potentiel de l'utilisation de l'ozone, fort agent oxydant, pour améliorer la réactivité de l'essence et permettre le fonctionnement à faible charge de GCI. L'ozone peut être produit on board en équipant le moteur d'un générateur d'ozone, sans impact dramatique sur le coût du moteur et sur la complexité du contrôle du moteur. Les essais effectués avec un moteur monocylindre ont montré que l'ozone favorise la combustion HCCI de l'essence, permettant d'étendre la limite d’auto-inflammation et de réduire la température minimale nécessaire de celle-ci. Les diagnostics optiques ont montré que ces propriétés sont liées à une prolifération radicale accrue, amenées par des réactions à basse température induites par l'ozone. En parallèle, le processus de combustion GCI a été étudié dans des conditions de faible charge. Sans ozone, la température d'admission doit être considérablement augmentée pour permettre l'auto-inflammationdes mélanges essence-air pauvres. De plus, les résultats indiquent que le monoxyde d’azote (NO) contenu dans les gaz brûlés résiduels peut, dans certaines conditions, favoriser fortement la combustion GCI. Ensuite,l'effet de l'ozone a été étudié dans des conditions d'injection directe GCI. Les résultats démontrent qu’une stratégie avec double injection est nécessaire pour maximiser l’effet promoteur de l’ozone et pour contrôler le processus de combustion GCI. Enfin, l'utilisation d’une forte concentration d’ozone a permis d’atteindre des opérations à faible charge en mode GCI, avec des faibles émissions de NOx et de suie, et cela, sans avoir besoin d'augmenter la température ou la pression d'admission. / Gasoline Compression Ignition (GCI) engine, relying on Gasoline Partially Premixed Combustion (GPPC) has potential for efficient and clean operations. GCI engine showed to be effective at high load, however, the highoctane number of gasoline dramatically limits low load operations. The present work investigates the potential of using ozone, a strong oxidizing agent, to improve gasoline reactivity and enabling low load GCI operation.Ozone can be produced in-situ and on-demand by equipping the engine with an ozone generator, without a dramatic impact on the engine cost and the engine control complexity. Experiments in a single cylinder engine showed that ozone promotes gasoline HCCI combustion, making possible to extend the lean limit and reducing the minimum temperature needed for autoignition. Optical diagnostics showed that these properties are related to an increased radical proliferation related to ozone-induced low temperature reactions. In parallel, GCI combustion process was investigated under low load conditions. Without ozone, the intake temperature should be considerable increased to enable auto ignition of lean gasoline-air mixtures. Moreover, results indicated that the NO contained into residual burnt gases can strongly promote GCI low load combustion. Finally, the effect of ozone was investigated under GCI direct-injection conditions, demonstrating that low load GCI operation with low NOx and Soot emission can be achieved by seeding the intake of the engine with ozone without needing of increasing the intake charge temperature or boosting the intake pressure.

nÃo hà / This work contributes to a better understanding of the phenomenon of adulteration of fuel, in order to identify possible economic determinants related to this practice. With the objective of a complete description of the problem, there is the need to preliminarily study the oil industry, which was done transpiring succinctly, from the birth of the oil industry to the current stage of it, featuring and highlighting its most important aspects for the economy. Then it approaches the question of asymmetric information present in the fuel retail markets, and finally through the construction of econometric models that take into account assumptions formalized in works related to the problem of adulteration of fuel, then the evidence to economic determinants. / Este trabalho contribui para um melhor entendimento do fenÃmeno da adulteraÃÃo de combustÃveis, visando à identificaÃÃo de possÃveis determinantes econÃmicos, relacionados a tal prÃtica. Tendo por objetivo uma perfeita caracterizaÃÃo do problema, verifica-se, preliminarmente, a necessidade de estudar o setor petrolÃfero, e assim foi feito transcorrendo de maneira sucinta, do nascimento da indÃstria do petrÃleo ao atual estÃgio da mesma, caracterizando e ressaltando seus aspectos mais importantes para a economia. Posteriormente, aborda-se a questÃo da assimetria de informaÃÃes presente nos mercados varejistas de combustÃveis, e, finalmente, atravÃs da construÃÃo de modelos economÃtricos que levem em conta pressupostos formalizados nos trabalhos relacionados ao problema da adulteraÃÃo de combustÃveis, evidenciando-se entÃo os determinantes econÃmicos.

A contaminação de ambientes aquáticos decorrente de acidentes com gasolina, álcool combustível e misturas binárias representa um risco crescente, tendo em vista as projeções do setor para os próximos 50 anos. O objetivo do presente estudo foi avaliar a toxicidade aguda da Gasolina C, Gasolina P e álcool combustível isoladamente e em misturas binárias, assim como de suas respectivas Frações Solúveis em Água (FSA) e Frações Dispersas em Água (FDA) sobre Daphnia similis. O estudo ainda incluiu a avaliação da toxicidade aguda remanescente na matriz água de uma contaminação antiga (intemperismo) com a Gasolina C. Paralelamente, foram conduzidos ensaios de toxicidade aguda com amostras ambientais (água subterrânea, superficial e elutriato a partir de sedimentos) de uma área alagada com histórico de contaminação antiga. O cultivo e os ensaios com D. similis foram de acordo com a NBR 12.713 (2009). Tanto a gasolina C quanto a P foram extremamente tóxicas para os organismos, apresentando valores médios de CE50% em 48 h de 0,00113% e 0,058% respectivamente. As diferenças entre os resultados obtidos com a Gasolina C e aqueles obtidos com suas frações FSA e FDA foram significativas (p < 0,05), sendo que não houve diferença significativa entre a toxicidade aguda da FSA e da FDA (p < 0,05). Os resultados obtidos com os ensaios com Gasolina P e FDA não apresentaram diferenças significativas entre si (p < 0,05), mas, foram significativamente diferentes daqueles obtidos com FSA (p < 0,05). Os resultados dos ensaios de toxicidade aguda com misturas binárias sugeriram efeito menos que aditivo (antagonismo). Os resultados da simulação de uma contaminação antiga demonstraram redução acentuada da toxicidade para D. similis ao longo de apenas 28 dias. Entretanto, com relação aos ensaios com as amostras ambientais da área com histórico de contaminação, apesar da ausência ou baixa toxicidade nas amostras de água superficial (sugerindo intemperismo), toxicidade alta foi observada em amostras de água subterrânea e no elutriato de sedimentos, sugerindo condições de adsorção aos sedimentos com alto teor de argila e/ou aprisionamento dos compostos em zona saturada. / The contamination of aquatic environments due to accidents with gasoline, alcohol fuel and their mixtures represents an increasing risk due to the projections made by the petroleum-based fuels industry for the next 50 years. The objective of the present study was to assess the acute toxicity of gasoline C, gasoline P, ethanol fuel separately and in mixtures, as well as their respective water-soluble fractions (WSF) and water-disperse fraction (WDF) on the bioindicator Daphnia similis. The study also included the assessment of the remaining acute toxicity in an aged gasoline C-contaminated water matrix with aging simulation for a 28-day period. Parallel to that, toxicity assays were conducted with environmental samples, including surface water, elutriate of sediments and groundwater from an aged contaminated area. The cultivation and the assays with D. similis were carried out according to NBR 12.713 (2009). Both gasoline C and P were highly toxic to D. similis, with CE50% in 48 h of 0.00113% e 0.058% respectively. The differences in acute toxicity between Gasoline C and its fractions WSF and WDF were significant (p <0.05). However, no significant difference was found between WSF and WDF fractions. Gasoline P and its WDF fraction had no significant differences (p < 0.05), but their toxicity were significant different from that one obtained with the FSA fraction (p < 0.05). Acute toxicity assays carried out with gasoline C and P mixed with ethanol fuel suggested effect less than additive (antagonism). The results obtained with the simulation of an aged contamination with Gasoline C showed sharp reduction in toxicity along 28 days. However, regarding the assays with environmental samples from an aged contamination, although absence or low toxicity was observed in the superficial water, severe toxicity was found in the sediments elutriate and in the groundwater, which was confirmed by the high concentrations of gasoline hydrocarbons in both matrixes. The results suggest that the contaminant was entrapped in the saturated zone and/or adsorbed to the sediments with high clay content.

A contaminação de ambientes aquáticos decorrente de acidentes com gasolina, álcool combustível e misturas binárias representa um risco crescente, tendo em vista as projeções do setor para os próximos 50 anos. O objetivo do presente estudo foi avaliar a toxicidade aguda da Gasolina C, Gasolina P e álcool combustível isoladamente e em misturas binárias, assim como de suas respectivas Frações Solúveis em Água (FSA) e Frações Dispersas em Água (FDA) sobre Daphnia similis. O estudo ainda incluiu a avaliação da toxicidade aguda remanescente na matriz água de uma contaminação antiga (intemperismo) com a Gasolina C. Paralelamente, foram conduzidos ensaios de toxicidade aguda com amostras ambientais (água subterrânea, superficial e elutriato a partir de sedimentos) de uma área alagada com histórico de contaminação antiga. O cultivo e os ensaios com D. similis foram de acordo com a NBR 12.713 (2009). Tanto a gasolina C quanto a P foram extremamente tóxicas para os organismos, apresentando valores médios de CE50% em 48 h de 0,00113% e 0,058% respectivamente. As diferenças entre os resultados obtidos com a Gasolina C e aqueles obtidos com suas frações FSA e FDA foram significativas (p < 0,05), sendo que não houve diferença significativa entre a toxicidade aguda da FSA e da FDA (p < 0,05). Os resultados obtidos com os ensaios com Gasolina P e FDA não apresentaram diferenças significativas entre si (p < 0,05), mas, foram significativamente diferentes daqueles obtidos com FSA (p < 0,05). Os resultados dos ensaios de toxicidade aguda com misturas binárias sugeriram efeito menos que aditivo (antagonismo). Os resultados da simulação de uma contaminação antiga demonstraram redução acentuada da toxicidade para D. similis ao longo de apenas 28 dias. Entretanto, com relação aos ensaios com as amostras ambientais da área com histórico de contaminação, apesar da ausência ou baixa toxicidade nas amostras de água superficial (sugerindo intemperismo), toxicidade alta foi observada em amostras de água subterrânea e no elutriato de sedimentos, sugerindo condições de adsorção aos sedimentos com alto teor de argila e/ou aprisionamento dos compostos em zona saturada. / The contamination of aquatic environments due to accidents with gasoline, alcohol fuel and their mixtures represents an increasing risk due to the projections made by the petroleum-based fuels industry for the next 50 years. The objective of the present study was to assess the acute toxicity of gasoline C, gasoline P, ethanol fuel separately and in mixtures, as well as their respective water-soluble fractions (WSF) and water-disperse fraction (WDF) on the bioindicator Daphnia similis. The study also included the assessment of the remaining acute toxicity in an aged gasoline C-contaminated water matrix with aging simulation for a 28-day period. Parallel to that, toxicity assays were conducted with environmental samples, including surface water, elutriate of sediments and groundwater from an aged contaminated area. The cultivation and the assays with D. similis were carried out according to NBR 12.713 (2009). Both gasoline C and P were highly toxic to D. similis, with CE50% in 48 h of 0.00113% e 0.058% respectively. The differences in acute toxicity between Gasoline C and its fractions WSF and WDF were significant (p <0.05). However, no significant difference was found between WSF and WDF fractions. Gasoline P and its WDF fraction had no significant differences (p < 0.05), but their toxicity were significant different from that one obtained with the FSA fraction (p < 0.05). Acute toxicity assays carried out with gasoline C and P mixed with ethanol fuel suggested effect less than additive (antagonism). The results obtained with the simulation of an aged contamination with Gasoline C showed sharp reduction in toxicity along 28 days. However, regarding the assays with environmental samples from an aged contamination, although absence or low toxicity was observed in the superficial water, severe toxicity was found in the sediments elutriate and in the groundwater, which was confirmed by the high concentrations of gasoline hydrocarbons in both matrixes. The results suggest that the contaminant was entrapped in the saturated zone and/or adsorbed to the sediments with high clay content.

The design and optimisation of a modern gasoline direct injection (GDI) engine requires a thorough understanding of the fuel sprays characteristics and atomisation process.Therefore this thesis presents a detailed optical analysis of atomisation, penetration and interaction of multi-stream GDI sprays under engine relevant pressures and temperatures. The characteristics of the fuel spray in a GDI engine have a great influence on the fuel-air mixing and combustion processes as fuel injectors must provide adequate atomisation for vaporisation of the fuel to take place before combustion is initiated, whilst also avoiding spray impingement on the cylinder walls or piston crown. In this study multi-stream injectors, to be used within GDI engines, are quantified using Laser Doppler Anemometry (LDA) on an atmospheric bench. This process allowed for highly detailed spray analysis of droplet velocities and diameter at precise locations, using a three dimensional traverse, within the injector spray. The aim of the study was to analyse plume interaction between separate plumes of multi-stream injectors. Three multi-stream injectors were subjected to testing; two six-hole injectors and one three-hole injector. The injectors differed by having different distances between the plumes. The effect of fuel type on the liquid break-up and atomisation was investigated using Phase Doppler Anemometry (PDA) and Mie imaging. Mie imaging was also performed to capture images of fuel from a multi-stream injector as it was sprayed into a pressure chamber which was used to recreate the conditions found in an engine likely to cause flash boiling. In total, five variables were investigated: fuel pressure, ambient pressure, ambient temperature, fuel composition and injector geometry. Once processed, the recorded images allowed measurement of spray tip penetration and cone angle. Qualitative data on the change in shape of the spray was also available. The results showed that flash boiling has potential to reduce droplet diameters and improve fuel vaporisation, however, the associated change in spray shape must be taken into account to avoid problems with spray impingement. Keywords: Gasoline Direct Injection, multi-stream injector, atomisation, penetration, cone angle, Mie imaging, Phase Doppler Anemometry, flash boiling.