O objetivo desta pesquisa foi o desenvolvimento de métodos para: determinação simultânea de Cr/Fe/Ni/V em óleo cru; determinação simultânea de Co/Cu/Pb/Se em óleo cru, gasolina e diesel; determinação monoelementar de Si em óleo cru, gasolina e diesel; e determinação de espécies porfirínicas de Fe/Ni/V em óleo cru, utilizando ultracentrifugação e extração em ponto nuvem, por espectrometria de absorção atômica com forno de grafite e detecção simultânea (SIMAAS). Foram estudadas as condições de preparo das amostras por emulsão, empregando Triton X-100® como surfactante e hexano ou clorofórmio como solventes diluentes do óleo cru. Nas melhores condições, as emulsões foram preparadas em 6% (m v-1) de Triton X-100® com o óleo cru previamente diluído com 125 µL de hexano (nos métodos para as determinações totais dos elementos) ou diluído com 400 µL de clorofórmio (no método para a determinação das espécies porfirínicas). No método envolvendo a determinação simultânea total de Cr/Fe/Ni/V não foi utilizada agitação ultrassônica devido à pequena massa de óleo necessária (50 mg) para análise. Por outro lado, a agitação ultrassônica foi essencial para possibilitar a estabilização de maiores massas de óleo cru (200 mg e 400 mg) na emulsão. A estabilidade da emulsão só foi melhorada com agitação ultrassônica, antes da etapa de diluição com água. Nessa condição, foi possível obter emulsões estáveis com 200 mg ou 400 mg de óleo cru, por 30 min ou mais de 8 h, respectivamente. O programa de aquecimento do forno de grafite foi avaliado em cada caso, com e sem uso de diferentes modificadores químicos (Pd e Mg), especialmente nos métodos de determinação simultânea, em que foi necessário adotar condições de compromisso. Para a determinação monoelementar de Si foi verificado melhora nos parâmetros analíticos (sensibilidade e repetibilidade) com o uso de NbC como modificador permanente combinado com 20 µg de Pd como modificador químico co-injetado. Os LODs estimados para Cr (0,07 µg g-1), Fe (2,15 µg g-1), Ni (1,25 µg g-1), V (1,25 µg g-1), Co (0,02 µg g-1), Cu (0,03 µg g-1), Pb (0,04 µg g-1), Se (0,11 µg g-1) e Si (0,16 µg g-1) foram suficientemente baixos para permitir as determinações dos elementos com boas precisão e exatidão. Análises de materiais de referência forneceram resultados a um nível de confiança de 95%, quando aplicado o teste t>/i> de Student. O fracionamento de porfirinas de Fe/Ni/V foi feito em emulsão de óleo cru combinando com a extração por ponto nuvem (CPE) e ultracentrifugação. Nesse estudo, foi verificado a necessidade do uso de 0,1 mol L-1 de HCl para extração dos elementos associados a espécies organometálicas não porfirínicas. Após a ultracentrifugação da emulsão de óleo cru, os alfaltenos e material particulado foram separados e no sobrenadante permaneceram espécies inorgânicas, compostos organometálicos leves e porfirinas de Fe, Ni e V. Após CPE de outra emulsão de óleo cru permaneceram na fase aquosa espécies inorgânicas e composto organometálicos leves. As concentrações das porfirinas de Fe, Ni e V foram determinadas após a subtração dos resultados obtidos no primeiro (ultracentrifugação) e segundo (CPE) procedimentos. / The objective of this research was the methods development for: simultaneous determination of Cr/Fe/Ni/V in crude oil; simultaneous determination of Co/Cu/Pb/Se in crude oil, gasoline and diesel; determination of Si in crude oil, gasoline and diesel; and determination of porphyrin species of Fe/Ni/V in crude oil using graphite furnace atomic absorption spectrometry with simultaneous detection (SIMAAS). It was studied the conditions for the emulsion sample preparation, employing Triton X-100® as surfactant and hexane or chloroform as diluent of the crude oil. Under the best conditions, the emulsions were prepared in 6% (m v-1) of Triton X-100® with crude oil previously diluted with 125 µl of hexane (in methods for total determination of elements) or diluted with 400 µl of chloroform (in the method for determination of porfhyrin species). In the method for the simultaneous determination of Cr/Fe/Ni/V it was not necessary to use ultrasonic agitation due to the small mass of oil needed (50 mg) for analysis. On the other hand, ultrasonic agitation was essential to enable the stabilization of larger masses of crude oil (200 mg and 400 mg) in emulsion. The emulsion stability was improved with ultrasonic agitation, before dilution step with water. In this condition, it was possible to obtain stable emulsions with 200 mg or 400 m;g of crude oil, for 30 min or more than 8 h, respectively. The heating program of graphite furnace was evaluated in each case, with and without use of different chemical modifiers (Pd and Mg), especially in the methods for simultaneous determination, in which was necessary to adopt compromise conditions. For Si determination, was verified significant improvement in analytical parameters (sensitivity and repeatability) with the use of NbC as permanent modifier, combined with co-injected 20 µg of Pd as chemical modifier. The LODs estimated for Cr (0.07 µg g-1), Fe (2.15 µg g-1), Ni (1.25 µg g-1), V (1.25 µg g-1), Co (0.03 µg g-1), Cu (0.03 µg g-1), Pb (0.04 µg g-1), Se (0.11 µg g-1) and Si (0.16 µg g-1) were low enough to allow measurements of the elements with great precision and accuracy. Analysis of reference materials provided results at confidence level of 95%, when applied to the Student\'s t-test. The Porphyrin fractionation of Fe/Ni/V was done on crude oil emulsion by combining cloud point extraction (CPE) and ultracentrifugation. In this method, 0.1 mol L-1 of HCl must be used for extraction of elements associated with the organometallic species different of porfhyrins. After the ultracentrifugation of crude oil emulsion, asfalthene and particulate matter were separated and in the supernatant remained inorganic species, organometallic compounds and porphyrins of Fe, Ni and V. After CPE of another emulsion of crude oil, remained in the aqueous phase only the inorganic and organometallic compound species. The porphyrin concentrations of Fe, Ni and V were determined after the subtraction of the results obtained in the supernatant from the first (centrifugation) and second (CPE) procedures.

Distillation systems consist of one or more distillation columns, in which a mixture is separated into higher-value products, and a heat exchanger network (HEN) that recovers and reuses heat within the system. For example, crude oil distillation systems comprise crude oil distillation units (CDU), in which crude oil is distilled into products for downstream processing, a HEN and a furnace. Heat-integrated distillation systems present complex interactions between the distillation columns and HEN. These interactions, together with the many degrees of freedom and process constraints, make it challenging to retrofit or modify the operating conditions of existing distillation processes to accommodate changes in process operating conditions. Retrofit designs aim to re-use existing equipment when process objectives change, for example to increase throughput, improve product quality, or reduce energy consumption or environmental impact. To achieve these retrofit objectives, operational, structural and/or flowsheet modifications to the overall system (distillation columns and HEN) may be considered, subject to specifications and system constraints. This work proposes an optimisation-based approach to retrofit design for the capacity expansion of heat-integrated distillation systems, with a particular focus on crude oil distillation systems. Existing retrofit approaches found in the open research literature consider operational optimisation, replacing column internals, adding preflash or prefractionation units and HEN retrofit to increase the capacity of existing systems. Constraints considered usually relate to the distillation column hydraulic limits, product quality specifications and heat exchanger performance (e.g. minimum temperature approach and, pressure drop). However, no existing methodologies consider these possible modifications simultaneously; thus, beneficial interactions between flowsheet modifications, operational changes, heat integration and equipment modifications may be missed. In this work, retrofit design solutions for crude oil distillation are developed using a stochastic optimisation framework implemented in MATLAB to optimise the system operating parameters and to propose flowsheet, column and HEN modifications. Within the framework, the optimiser can propose addition of a preflash unit, modifications to the CDU internals and changes to its operating conditions; the separation system is then simulated using Aspen HYSYS (via the MATLAB interface) and the hydraulic performance of the column is analysed using published hydraulic correlations. The optimiser also proposes modifications to the HEN (i.e. installed heat transfer area, HEN structure and operating conditions), which is then simulated to evaluate heating and cooling utility demand. Either simulated annealing and global search optimisation algorithms are applied to identify the optimal design and operating conditions that meet the production requirements and product specifications. Industrially relevant case studies demonstrate the effectiveness and benefits of using the proposed retrofit approach. The case studies illustrate that combined structural and operational modifications can be effectively and systematically identified to debottleneck an existing crude oil distillation system with a relatively short payback time, while simultaneously reducing energy consumption per barrel of crude oil processed.

Adequate wastewater management is a crucial element to achieve water sustainability in the petroleum refining sector, as their operations produce vast quantities of wastewater with potentially harmful contaminants. Treatment technologies are therefore pivotal for stopping these chemicals from entering the environment and protecting receiving environments. However, refining effluents are still linked to serious pollution problems, partly because little progress has been made in determining the causative agents of the observed biological effects, resulting in non-targeted treatment. Here it is shown that naphthenic acids, which have been reported as toxic and recalcitrant, are important components of refining wastewater resulting from the processing of heavy crude oil and that they have a significant contribution to the toxic effects exerted by these effluents. Furthermore, it was found that their chemical stability makes them highly resistant to remediation using Pseudomonas putida and H2O2/Fe-TAML (TetraAmido Macrocyclic Ligands) systems under laboratory conditions, and only sequential aliquots of Fe-TAML catalysts and H2O2 showed to partially degrade naphthenic acids (50 mg/L) within 72 hours. Results suggest that a combinatorial approach of Fe-TAML/H2O2 followed by biodegradation might improve current treatment options, but further optimisation is required for the biological treatment. These results can serve as a starting point for better environmental regulations relevant to oil refining wastewater resulting from heavy crude oil, as naphthenic acids are not currently considered in the effluent guidelines for the refining sector. Furthermore, the degradation of naphthenic acids under mild conditions using Fe-TAML/H2O2 systems indicates that these catalysts hold promise for the remediation of refining wastewater in real-life scenarios.

The aim of this thesis is to show that news analytics data can be utilised to improve the predictive ability of existing models that have useful roles in a variety of financial applications. The modified models are computationally efficient and perform far better than the existing ones. The new modified models offer a reasonable compromise between increased model complexity and prediction accuracy. I have investigated the impact of news sentiment on volatility of stock returns. The GARCH model is one of the most common models used for predicting asset price volatility from the return time series. In this research, I have considered quantified news sentiment as a second source of information and its impact on the movement of asset prices, which is used together with the asset time series data to predict the volatility of asset price returns. Comprehensive numerical experiments demonstrate that the new proposed volatility models provide superior prediction than the "plain vanilla" GARCH, TGARCH and EGARCH models. This research presents evidence that including news sentiment term as an exogenous variable in the GARCH framework improves the prediction power of the model. The analysis of this study suggested that the use of an exponential decay function is good when the news flow is frequent, whereas the Hill decay function is good only when there are scheduled announcements. The numerical results vindicate some recent findings regarding the utility of news sentiment as a predictor of volatility, and also vindicate the utility of the new models combining the proxies for past news sentiments and the past asset price returns. The empirical analysis suggested that news augmented GARCH models can be very useful in estimating VaR and implementing risk management strategies. Another direction of my research is introducing a new approach to construct a commodity futures pricing model. This study proposed a new method of incorporating macroeconomic news into a predictive model for forecasting prices of crude oil futures contracts. Since these futures contracts are iii iv more liquid than the underlying commodity itself, accurate forecasting of their prices is of great value to multiple categories of market participants. The Kalman filtering framework for forecasting arbitrage-free (futures) prices was utilized, and it is assumed that the volatility of oil (futures) price is influenced by macroeconomic news. The impact of quantified news sentiment on the price volatility is modelled through a parametrized, nonlinear functional map. This approach is motivated by the successful use of a similar model structure in my earlier work, for predicting individual stock volatility using stock-specific news. Numerical experiments with real data illustrate that this new model performs better than the one factor model in terms of accuracy of predictive power as well as goodness of fit to the data. The proposed model structure for incorporating macroeconomic news together with historical (market) data is novel and improves the accuracy of price prediction quite significantly.

Financialization of crude oil and its frequent inclusion into investment portfo- lios raise the demand for proper correlation estimates of this commodity and other financial assets. This thesis particularly examines the co-movement of crude oil price with prices of four other representatives of commodity market (gasoline, natural gas, gold and Industrials Index). It contributes to the exist- ing literature by the results obtained from application of wavelet coherence, which allows uncovering dynamics of interconnection between commodity prices in time as well as over different frequencies. Analysis brings many in- teresting findings and practical implications. Among others, it specifies the investment horizons that should be considered to maximize diversification properties of studied commodities. 1

Este trabalho visa o estudo da viabilidade da redução do uso de água no processo de dessalgação em refinarias de petróleo. Em uma primeira fase, foi necessário o estudo teórico da separação das emulsões água/óleo. Em seguida, foi desenvolvido um modelo matemático baseado nas forças atuantes nas gotas de água, o que possibilitou a determinação do tempo entre as colisões de pares de gotas e o estabelecimento do critério para que ocorra o fenômeno de coalescência. Esse modelo foi empregado em um sistema desenvolvido com base em autômatos celulares, o qual possibilitou o acompanhamento do processo micro e macroscópico, através do cálculo para o conjunto das gotas, e o acompanhamento visual até a separação da fase contínua. Os experimentos de laboratório, para os quais foi usado equipamento ótico para a medição da intensidade de luz transmitida ou espalhada pelas gotas, possibilitaram avaliar a influência da qualidade da água de mistura no tempo de separação das emulsões. Na unidade industrial, foram realizados testes que permitiram analisar o desempenho das dessalgadoras em diferentes situações operacionais. Os resultados obtidos através dos experimentos de laboratório e da simulação usando o modelo matemático desenvolvido mostraram-se compatíveis com os dados obtidos nos testes na unidade industrial. O trabalho mostrou ser possível alterar os esquemas de usos de água nas dessalgadoras, aumentando a taxa de reciclagem e possibilitando a otimização do consumo de água fresca neste processo, o que resultaria em redução substancial no consumo geral de água na refinaria. / The aim of this work is the study of the reduction of water consumption in petroleum desalting processes. The study of the attraction forces acting on the droplets was necessary to know how the emulsion water/oil is separated. A mathematical model based upon these forces was built to calculate the time between each droplets collision and to establish criteria for their coalescence. This model was applied to a system developed based on cellular automata, which allows to follow the process micro and macroscopically. Computations were carried out to the ensemble of droplets and the visual progression, from the start of droplets separation of the continuous phase to the end of the process could be visualized. Laboratory experiments, in which optical equipment was used to measure the light intensity transmitted or scattered by the droplets, allowed to evaluate the influence of the type of mixing water in the separation time of the emulsions. Tests in the industrial unity allowed evaluating the performance of the desalting units at different operating conditions. Conclusions of the laboratory experiments and the results of the mathematical model were compared with results of the industrial tests, showing coherence between them. The work shows that it is possible to simulate the effect of the operating variables and to alter schemes of water use in desalting units, increasing the water recycling rate, allowing optimization of fresh water consumption in this process and reducing the total water consumption in the refinery.

This study attempts to resolve two important issues. First, it investigates the diversification benefit of crude oil for equities. Second, it examines whether or not crude oil derivatives transactions by oil and gas producers can change shareholders' wealth. With these two major goals in mind, I study the risk and return profile of crude oil, the value effect of crude oil derivatives transactions, and the systematic risk exposure effect of crude oil derivatives transactions. In contrast with previous studies, this study applies the Goldman Sachs Commodity Index (GSCI) methodology to measure the risk and return profile of crude oil. The results show that crude oil is negatively correlated with stocks so adding crude oil into a portfolio with equities can provide significant diversification benefits for the portfolio. Given the diversification benefit of crude oil mixed with equities, this study then examines the value effect of crude oil derivatives transactions by oil and gas producers. Differing from traditional corporate risk management literature, this study examines corporate derivatives transactions from the shareholders' portfolio perspective. The results show that crude oil derivatives transactions by oil and gas producers do impact value. If oil and gas producing companies stop shorting crude oil derivatives contracts, company stock prices increase significantly. In contrast, if oil and gas producing companies start shorting crude oil derivatives contracts, stock prices drop marginally significantly. Thus, hedging by producers is not necessarily good. This paper, however, finds that changes in policy regarding crude oil derivatives transactions cannot significantly affect the beta of shareholders' portfolios. The value effect, therefore, cannot be attributed to any systematic risk exposure change of shareholders' portfolios. Market completeness, transaction costs, and economies of scale are identified as possible sources of value effect. The following conclusions have been obtained in this study. Crude oil provides significant diversification benefits for equities. In the presence of market imperfections, crude oil derivatives transactions by oil and gas producers may change shareholders' wealth, even though crude oil derivatives transactions by oil and gas producers do not have significant effect on the systematic risk exposures of companies.

Volatile crude oil prices significantly affect the profitability of crude oil firms. The purpose of this single case study was to explore strategies some crude oil and gas business leaders used to remain profitable during periods of crude oil price volatility. The target population comprised 8 crude oil and gas business leaders located in Calgary, Canada, whose company remained profitable despite crude oil price volatility. The transformational leadership theory formed the conceptual framework for the study. Data were collected through the use of semistructured face-to-face interviews, company reports, and field notes. Data analysis involved a modified Van Kamm method, which included descriptive coding, a sequential review of the interview transcripts, and member checking. Based on methodological triangulation and thematic analysis, 5 themes emerged from the study, including communication and engagement; motivation and empowerment; measurement, monitoring, and control; self-awareness and humility; and efficiency and optimization. The implications for social change include the potential for crude oil and gas companies in Calgary, Canada to manage production costs, ensure earnings and profitability, and thus improve the socioeconomic well-being of Calgary indigenes through improved employment opportunities.

Simulated oil spills were created in S. alterniflora sediment-water microcosms to determine the effects of applied crude oil on S.alterniflora during two 90-day studies. In the first experiment, oil dosage was varied at 0-250 mg crude oil/g wet soil to determine the lethal dosage level. In the second experiment, oil type, dosage, and soil type were varied to determine the effects of oil under multiple scales of resolution. A light, medium, and heavy crude oil at dosages ranging from 0-150 mg crude oil/g wet soil were used in addition to an oiled and non-oiled soil. Following the completion of the 90-day experiment, several key findings were observed: (1) The lethal dosage limit was reached at 250 mg crude oil/g wet soil during the first experiment but not the second, by design; (2) At initial dosages of 10 and 50 mg crude oil/g wet soil, the oiled soil (acclimated for 4 months) was more influential in decreasing cumulative biomass growth rates compared to oil applied at the oil-water interface; (3) At the heaviest dosages applied as a simulated oil slick, concentrations of 150 mg crude oil/g wet soil, evapotranspiration rates were negatively affected by the oil (significant at p=0.05 in a one-tailed t-test); (4) Light, heavy, and then medium crude oil showed the lowest biomass growths, in that order, indicating that light crude oil was the most toxic in these microcosm experiments with S. alterniflora; (5) The 10 mg oil/g wet soil out-performed the 0 mg oil/g wet soil in transpiration and biomass growth.

Light, medium and heavy crude oils were studied at three concentrations and with two different sediments in experimental microcosm settings to determine the ability of Spartina alterniflora and associated microbes to breakdown total extractable hydrocarbons (TEH) in the water. It was a baseline experiment designed to quantify the rates of biodegradation under relatively quiescent conditions from different crude oils at moderate doses ranging from 0-150 mg/kg soil. Upon the completion of the experiment there were several key findings: (1) The lethal dosage for Spartina alterniflora was not reached within the 90 day experiment at these dosages, and all plants survived; (2) More than 97% of the total extractable hydrocarbons (TEH) were shown to be degraded by plants and rhizosphere microorganisms within the 90- day experiment; (3) The dose of oil introduced as a slick (simulated spill) on day zero did not significantly affect the results for TEH degradation within the range of dosages from 50-150 mg/g -- these dosages could be degraded by the marsh cord grass system; (4) A sediment type which was acclimated to oil for several months and one which was non-acclimated did not show significantly different results for TEH degradation in the microcosms -- both sediment systems resulted in TEH degradation over the 90-day experiment; and (5) A mathematical model was developed which simulated experiment results quite closely including TEH diffusion from the crude oil slick into the water and subsequent biodegradation.