[pt] Diferentes métodos espectrométricos de análise, incluindo ICP OES, ICP-DRCMS e Q-ICPMS com técnicas hifenadas (geração de hidreto, vaporização eletrotérmica ou cromatografia de íons), foram aplicados na caracterização química de 16 óleos e 41 amostras de efluentes aquosos de uma refinaria de petróleo. O objetivo específico deste estudo foi o de entender o comportamento do selênio (Se) e de suas espécies químicas ao longo do processo de geração e tratamento dos efluentes desta unidade industrial. A caracterização química multielementar das amostras por ICP-MS revelou uma composição muito complexa da maioria deles, com altas salinidades e potenciais interferentes espectrais e não espectrais presentes. Por isso, foi necessária uma reavaliação crítica das técnicas analíticas para a determinação de Se e de suas espécies. As técnicas de ICP-DRC-MS, utilizando CH4 como gás de reação, e de ETVICPMS mostraram o seus potencial para a determinação de Se com melhores limites de detecção (cerca de 0,05 ug L-1 para ambas), mas também as suas limitações na análise de efluentes com altas salinidades. Nas 16 amostras de petróleo analisadas, verificou-se uma grande variabilidade nas concentrações de Se total, cobrindo uma faixa de < 10 ug kg-1 até 960 ug kg- 1, a qual poderia explicar também a carga muito variável deste elemento nos efluentes das diferentes unidades de tratamento. As maiores concentrações de Se total foram encontradas nas águas ácidas, com concentrações de até 1714 ug L-1. Confirmou-se a predominância de SeCN - na maioria das amostras analisadas, mas observaram-se também outras espécies com tempos de retenção diferentes das espécies Se(IV), Se(VI) e SeCN-, especialmente nos efluentes da estação de tratamento de despejos industrais (E.T.D.I.). Em amostras ácidas, identificou-se Se coloidal (Seº) formado pela decomposição de SeCN-, ou de outras espécies pouco estáveis nestas condições. Experiências de bancada com soluções de SeCN- apoiaram esta hipótese. Foi constatada, que o perfil de especiação de amostras coletadas num mesmo local de processamento, mas em épocas diferentes, pode variar significativamente, o que torna difícil a comparação de dados obtidos neste trabalho com os de outros autores. / [en] Different spectrometric methods of analysis, including ICP OES, ICP-DRC-MS and Q-ICP-MS, the latter hyphenated to hydride generation, eletrothermal vaporization or ion chromatography have been appliesd to the chemical characterization of 16 crude oils and 41 effluents samples from a petroleum refinery. The specific objective of this study was to get information on the behavior of selenium (Se) and its species along the different processes of generation and treatment of the effluents.Multielemental characterization of effluents by ICP-MS revealed a complex composition of most of them, with high salinity and potential spectral and non spectral interferents present. For this reason, a critical reassessment of the analytical techniques for the determination of total Se and its species was necessary. DRC-ICP-MS and ETV-ICPMS, using CH4 as cell reaction gas, showed their potential for the determination of Se with better detection limits (about 0,05 ug L-1), but also their limitations for the analysis of effluents with high salinity. A large variability in the concentration of Se was observed in the 16 analysed crude oil samples (< 10 ug kg-1 Se until up to 960 ug kg-1), which may explain also the varying concentrations measured in the effluents. Highest concentrations of selenium were measured in samples from the treatment unit for acid waters (up to 1.714 ug L-1). The predominance of selenocyanate (SeCN-1) was confirmed in most of the effluent samples analysed, but also several other species with retention times different from Se(IV), Se(VI) e SeCN - were observed, especially in samples from the treatment plant. Colloidal Se (Seº) was identified in acid waters, probable formed by decomposition of SeCN - or other unstable species under these conditions. Laboratory experiments with selenocyanate solutions confirmed this hypothesis. The speciation profile of samples collected at the same point, but at different time intervals, showed significant variations, not allowing easy comparison of the results obtained in this work with those of other authors.

Nesse trabalho foi estudada uma técnica para a detecção de OHTC na água salina. Descobriu-se que certos complexos de rutênio em determinados valores de pH reagem com a molécula de OHTC e isto é detectável por espectrofotometria UV-Vis. Foram estudados os complexos fac-[RuCl2(S-DMSO)3(O-DMSO)] (complexo 1), {[(DMSO)2H][trans-RuCl4(DMSO)2]} (complexo 2) e cis-[RuCl2(bpy)2].2H2O (complexo 3). O complexo 1 possui um dos ligante (O-DMSO) que pode ser substituído pelo OHTC. Já o complexo 2 possui um dos ligantes (S-DMSO) na posição trans um ao outro, e o complexo 3 possui os 2 íons Cl- para tal finalidade. Determinou-se que o complexo 1 é viável, mesmo em presença de sais presentes na água do mar. Assim a reação foi realizada em função do tempo, variação do pH, temperatura e concentração de OHTC. Nos outros dois complexos os estudos foram realizados sem a variação da temperatura e concentração de OHTC. / p>In this work we studied a technique for detection of OHTC in water. It was discovered that complexes involving ruthenium, on determined pH values, react with the OHTC molecule and this is detectable by UV-VIS spectroscopy. The complexes fac-[RuCl2(S-dmso)3(O-dmso)] (complex 1), {[(DMSO)2H][trans-Ru(DMSO)2Cl4]} (complex 2), and cis-[RuCl2(bpy)2].2H2O (complex 3) were studied. The complex 1 present one position ( O - DMSO) which can be substituted by the OHTC. Additionally, the complex 2 present two ligands ( S- DMSO) trans between each other, and the complex 3 present two chloride ions for the same porpose of complex 1 respectively. It was determined that the complex 1 was able to react with OHTC even in presence of the salts present in sea water. Thereby, the reaction involving complex 1 and OHTC was monitored in function of the time, pH, temperature, and finally concentration of OHTC. On the other two complexes, the reaction was studied without variation of temperature and concentration of OHTC.

Nesse trabalho foi estudada uma técnica para a detecção de OHTC na água salina. Descobriu-se que certos complexos de rutênio em determinados valores de pH reagem com a molécula de OHTC e isto é detectável por espectrofotometria UV-Vis. Foram estudados os complexos fac-[RuCl2(S-DMSO)3(O-DMSO)] (complexo 1), {[(DMSO)2H][trans-RuCl4(DMSO)2]} (complexo 2) e cis-[RuCl2(bpy)2].2H2O (complexo 3). O complexo 1 possui um dos ligante (O-DMSO) que pode ser substituído pelo OHTC. Já o complexo 2 possui um dos ligantes (S-DMSO) na posição trans um ao outro, e o complexo 3 possui os 2 íons Cl- para tal finalidade. Determinou-se que o complexo 1 é viável, mesmo em presença de sais presentes na água do mar. Assim a reação foi realizada em função do tempo, variação do pH, temperatura e concentração de OHTC. Nos outros dois complexos os estudos foram realizados sem a variação da temperatura e concentração de OHTC. / p>In this work we studied a technique for detection of OHTC in water. It was discovered that complexes involving ruthenium, on determined pH values, react with the OHTC molecule and this is detectable by UV-VIS spectroscopy. The complexes fac-[RuCl2(S-dmso)3(O-dmso)] (complex 1), {[(DMSO)2H][trans-Ru(DMSO)2Cl4]} (complex 2), and cis-[RuCl2(bpy)2].2H2O (complex 3) were studied. The complex 1 present one position ( O - DMSO) which can be substituted by the OHTC. Additionally, the complex 2 present two ligands ( S- DMSO) trans between each other, and the complex 3 present two chloride ions for the same porpose of complex 1 respectively. It was determined that the complex 1 was able to react with OHTC even in presence of the salts present in sea water. Thereby, the reaction involving complex 1 and OHTC was monitored in function of the time, pH, temperature, and finally concentration of OHTC. On the other two complexes, the reaction was studied without variation of temperature and concentration of OHTC.

[pt] O mercado brasileiro de derivados de petróleo está sendo aberto para competição este ano, saindo de um ambiente de preços regulados pelo Governo Federal para um ambiente onde os preços são estabelecidos pelas leis de oferta e demanda. Neste contexto, existe a preocupação de como serão estes preços, e seus impactos sobre os consumidores e sobre os produtores locais. Esta Tese propõe alguns modelos matemáticos para estimar preços, níveis de produção, níveis de consumo (demanda), e importação e exportação de derivados de petróleo nas diversas regiões do mercado brasileiro. O fornecimento de derivados de petróleo não é considerado um mercado competitivo, e sim oligopolizado, principalmente no curto prazo, devido à capacidade instalada de refinarias e aos altos custos envolvidos na construção de novas refinarias. Estes modelos são multi- produto, considerando um fato importante na produção de derivados que é a impossibilidade de produzir apenas um derivado. Assim, existem restrições onde a oferta de um derivado é relacionada a oferta dos outros. O primeiro modelo considera um mercado de oligopólio fechado, com um número fixo de firmas. Tal modelo é formulado como um problema de equilíbrio a Nash. Um segundo modelo é apresentado expandindo o primeiro para o caso em que existem preços teto de demanda definidos politicamente. O terceiro modelo relaxa a suposição do mercado fechado, com número fixo de firmas, e considera a possibilidade de competição de novas firmas no mercado. Um quarto modelo é discutido, onde assume-se que existe uma firma líder no mercado, que consegue definir sua estratégia antes das demais firmas, semelhante ao problema econômico de Stackelberg. Todos os modelos foram formulados como problemas de inequações variacionais, sendo que o último modelo é ainda um problema de programação binível. Algoritmos de solução são propostos para os três primeiros modelos. Simulações sobre o mercado brasileiro de derivados são apresentadas. / [en] The Brazilian petroleum refined products market is being opened to competition this year, leaving an environment of regulated prices to another one where the prices are defined by the supply demand interactions. Considering this new scenario, there is a concern about how high the prices will be, and about their impact on the consumers and on the local producers. This thesis proposes some mathematical models to predict prices, production, consumption, and import and export levels of petroleum-refined products in all the sub-regions of the Brazilian market. Instead of a competitive market, the supply of refined products is considered an oligopoly market, especially in the short term, given the already installed refining capacity and the high costs involved in building new refineries. These models are multi-products, and they consider an important characteristic of the production of refined products, the impossibility of producing only one refined product. Hence, constraints where the production of one refined product is related to the production of the others are considered. The first model considers a closed oligopoly market, with a fixed number of firms. This problem is formulated as a Nash equilibrium problem. A second model is presented generalizing the first one to consider the possibility of ceiling demand prices politically defined. The third model relaxes the assumption of a fixed number of firms in the first model, and considers the possibility of competition by new entrants. A fourth model is discussed, where it is assumed that there is a leader firm in the market, which can define its strategy before the other firms, similar to the economic problem of Stackelberg. All the models are formulated as variational inequalities problems, and the last model is also a bi-level programming problem. Solution algorithms for the three first models are proposed. Some analyses of the Brazilian petroleum refined- products market are presented.

Thermal recovery methods are frequently used to enhance the production of heavy crude oils. Steam-based processes are the most economically popular and effective methods for heavy oil recovery for several decades. In general, there are various mechanisms over steam injection to enhance and have additional oil recovery. However, among these mechanisms, steam distillation plays pivotal role in the recovery of crude oil during thermal recovery process. In this study, an experimental investigation was carried out to investigate the role of various minerals present in both sandstone and carbonate formations as well as the effect of steam temperature on steam distillation process. Two different types of dead-heavy crude oils were tested in a batch autoclave reactor with 30 % water and the content of the reactor (crude oil, 10 % rock and mineral). The results were compared as the changes in the density, viscosity and chemical composition (SARA and TPH analyses) of heavy crude oil. Five different mineral types (bentonite, sepiolite, kaolinite, illite and zeolite) were added into the original crude oil and reservoir rocks to observe their effects on the rheological and compositional changes during steam distillation process. Analysis of the results of experiments with Camurlu and Bati Raman heavy crude oils in the presence of different minerals such as Bentonite, Zeolite, Illite, Sepiolite, and Kaolinite in both sandstone and limestone reservoir rocks indicate that steam distillation produces light end condensates which can be considered as solvent or condensate bank during steam flooding operation. It was also illustrated that minerals in reservoir formations perform the function of producing distilled light oil compounds, resulting in enhancement of heavy crude oils recovery in steam flooding. Measurements showed that the remaining oil after steam distillation has higher viscosity and density. On the other hand, the effect of steam distillation is more pronounced in limestone reservoirs compared to sandstone reservoirs for the given heavy crude oil and steam temperature. Among the five different minerals tested, kaolinite found to be the most effective mineral in terms of steam distillation.

Application of thermogravimetric analysis to the renewable energy sources is a novel study and it has been becoming attractive by the researchers in recent years. In this thesis, thermal and kinetic properties of biodiesel as new energy source, diesel and canola oil have been analyzed by using very popular thermogravimetric analysis methods which are / Differential Scanning Calorimetry (DSC) and Thermogravimetry (TGA/DTG). The main aim of the study is to observe the combustion and pyrolysis behaviour of methanol route biodiesel and diesel blends at different blending rates. Additionally, combustion and pyrolysis behaviour of canola oil, the origin of biodiesel have been analysed to observe the transesterification reaction effect on biodiesel. Therefore, biodiesel, diesel, canola oil and blends of diesel and biodiesel at different percentages are exposed to isothermal heating under nitrogen and air atmosphere with a constant heating rate of 5, 10 and 15

Diferentes etapas do refino do petróleo resultam na geração de resíduos oleosos que possuem em sua composição substancias que imprimem periculosidade aos mesmos, que, caso venham a contaminar o solo, podem impactar a biota da área, atingir os lençóis freáticos, rios e lagos da região, agredindo diretamente ou indiretamente a saúde humanae gerando custos ambientais, sociais e monetários muito altos. O objetivo do presente trabalho foi avaliar a gestão dos resíduos sólidos perigosos gerados na atividade de refinarias de petróleo no Brasil, descrevendo processos, caracterizando a geração dos mesmos em cada etapa do refino e avaliando técnicas de tratamento e de destinação final. Ao longo do texto, foram abordados conceitos de gestão ambiental e de logística reversa, com o objetivo de ressaltar benefícios ambientais e sócio- econômicos advindos de umatravés do processo de gestão. Sobre a gestão dos resíduos, são apreciados os conceitos básicos desta, compondo-se uma abordagem prática e simplificada, sendo avaliadas estratégias de minimização de resíduos com base nos 3Rs, algumas metodologias de tratamento e a utilização de aterros industriais como local de destinação final para os resíduos. Para a estruturação da dissertação proposta, foi executada uma revisão bibliográfica, além da construção de uma linha de coesão entre os objetos estudados. Conclui-se que atualmente não existe metodologia de gestão tão eficiente que seja totalmente sustentável, nem gestão que possa ser baseada em apenas uma prática ou metodologia. A integração de conceitos e práticas, incluindo programas de minimização de resíduos, logística reversa, tratamento e destinação final faz-se necessária para uma gestão mais eficiente dos resíduos oleosos. Porém, deve-se destacar as novas oportunidades gerenciais associadas à logística reversa, bem como a necessidade de utilização dos aterros industriais em alguma etapa da gestão, assim como a atual tendência à adoção do co-processamento como metodologia de tratamento que apresenta a melhor relação custo x benefício para a gestão dos resíduos perigosos gerados nas refinarias de petróleo. / Different stages of the petroleum refining generate oil wastes that have hazardous substances. When oil waste contaminates the soil it may cause impacts on living resources, reaching groundwater, rivers and lakes in the region, affecting directly or indirectly the human health, with environmental, social and economic costs that can be very high. The objective of this study was to assess the management of hazardous solid wastes generated at petroleum refineries, describing processes and characterizing the way these wastes are generated in different stages of the refining process. The study also included assessment of treatment options and final disposal strategies. Principles of environmental management and reverse logistics were addressed with the objective of highlighting the environmental and socio-economic benefits added by a suitable management scheme. The basic concepts related to solid waste management are discussed in a practical and simplified language, and the minimization strategies are evaluated based on 3Rs principle. Treatment methodologies and the relevance of utilizing industrial landfills as final disposal solution are presented. Besides the literature survey, the construction of a red thread connecting the issues is presented. It was concluded that currently, there is no management scheme for oil waste efficient enough to be considered sustainable, neither management option that can be based on a single technology or methodology. An integration of concepts and different practices including waste minimization, reverse logistics, treatment and final disposal is needed in order to achieve a more efficient oil waste management. However, it is worth to highlight new managerial opportunities related to reverse logistics, as well as the need to make use of industrial landfills in some point of the process and the current trend of co- processing as the option that presents the best cost-benefit for management of oil hazardous wastes generated by petroleum refineries.

Thesis submitted in fulfilment of the requirements for the degree of Master of Technology: Chemical Engineering, In the Faculty of Engineering, Cape Peninsula University of Technology 2014 / Energy efficiency has become an important feature in the design of process plants due to the rising cost of energy and the more stringent environmental regulations being implemented worldwide. In South Africa as in other African countries, most of the chemical plants were built during the era of cheap energy with little emphasis placed on energy efficiency due to the abundance of cheap utility sources such as coal and crude oil. In most of these plants, there exists significant potential for substantial process heat recovery by conceptual integration of the plant’s heat exchangers. Pinch Technology (PT) has been demonstrated to be a simple and very effective technique for heat integration and process optimization. This study applies the PT approach to retrofit the heat exchangers network of the Crude Distillation Unit (CDU), of a complex petroleum refinery with the aim to reduce utilities requirement and the associated gaseous pollutants emission. This objective is accomplished by firstly conducting an energy audit of the unit to scope for potential energy saving. The existing Heat Exchanger Network (HEN) was re-designed using the remaining problem analysis (RPA) to achieve improved process energy recovery while making maximum use of the existing exchangers. The aim is to maintain the existing plant topology as much as possible. This network was later relaxed trading heat recovery with number of heat transfer unit so as to optimize the capital cost. These were implemented in AspenPlus v7.2 environment. The cost implications of the retrofitted and evolved networks including the capital and operating costs were determined on a 5 years payback time basis. The Problem Table (PT) analysis revealed that the minimum utilities requirements are 75 MW and 55 MW for the hot and cold utilities respectively. Compared to the existing utilities requirements of 103 MW for hot utility and 83 MW for cold utility, this represent a potential savings of about 26 % and 33 % savings for the hot and cold utilities respectively. The target utilities usage in the re-designed network after applying Remaining Problem Analysis (RPA) was found to be 55 MW for the cold utility and 75 MW for hot utility. The relaxed HEN required a cold utility of 62.5 MW and hot utility of 81 MW. From the total cost estimation, it was found that, although an energy saving of 34% can be achieved by the re-designed network before relaxation, the capital cost, US$ 1670000 is significantly higher than for the existing network (about US$ 980000). The final relaxed network gave an energy saving of 34% and with total cost of US$ 1100000. It was recommended from the study after cost comparisons of the four different networks (the original network, the MER network, the relaxed network and a grass-root design) that the best network for the retrofit purpose was the relaxed HEN, because there is no major shift in deviation from the topology of the original network. From the analysis it was found that a 34% saving in energy cost could be achieved from this retrofit. The Total Annual Cost (TAC) for this network gives credence to the fact that this retrofit which applied the rules of pinch analysis can bring about real saving in energy usage.

Thesis (MTech (Electrical Engineering))--Cape Peninsula University of Technology, 2012. / Electric motors consume over 60% of the world's generated electricity. In South Africa approximately 65% of the energy generated is consumed by electric motors (Niekerk, 2009). About 95% of motors in use in South Africa are Standard-Efficient Motors (SE-motors) that operate at an average efficiency of 84% to 90%, depending on the size of the motor and the load driven by them. High-Efficient motors (HE-motor) run at an efficiency of 2% to 8% higher than that of SE-motors. In recent years, a drive to replace SE-motors with HE-motors has been promoted for the purpose of Demand Side Management (DSM). The rationale of using HE-motors as a tool of DSM is to harness a small difference in operating efficiency per motor, which can result in a huge reduction in electricity consumption, depending on the number of HE-motors that will replace SE-motors. Reducing the demand for electricity is the key driving factor for DSM in South Africa, so as to relieve the already stressed power generation capacity. Other consequential factors of DSM are to reduce the amount of pollutant gases emitted into the atmosphere. To the electricity users DSM will be a great incentive, as reduced consumption of electricity will decrease the amount of money spent on electricity. Much has been written on the ability of HE-motors to reduce electricity consumption, cost of electricity and global pollution. ESKOM has even demonstrated the faith they have in these motors by giving rebates to motor users who are willing to exchange their existing SE-motors with new HE-motors. The rebates are paid by ESKOM through a newly established DSM program. However, it must be mentioned that savings through HE-motors is not a perfect guarantee. HE-motors have inherent design limitations that may inhibit the saving of energy. To achieve higher efficiency, HE-motors are designed to operate on a smaller slip that consequently increases their speed compared to that of SE-motors (Cheek et al., 1995). Higher rotor speed impacts energy saving abilities of HE-motors when they are used to drive fans, pumps and compressors, normally referred to as centrifugal loads. An increase in speed results in a proportional increase in flow. Power consumed by a motor goes up as a cube of the speed, and the flow rate increases linearly with speed. Motor loads in the petrochemical industry are generally centrifugal, and that is why this thesis focuses on refineries.

Diferentes etapas do refino do petróleo resultam na geração de resíduos oleosos que possuem em sua composição substancias que imprimem periculosidade aos mesmos, que, caso venham a contaminar o solo, podem impactar a biota da área, atingir os lençóis freáticos, rios e lagos da região, agredindo diretamente ou indiretamente a saúde humanae gerando custos ambientais, sociais e monetários muito altos. O objetivo do presente trabalho foi avaliar a gestão dos resíduos sólidos perigosos gerados na atividade de refinarias de petróleo no Brasil, descrevendo processos, caracterizando a geração dos mesmos em cada etapa do refino e avaliando técnicas de tratamento e de destinação final. Ao longo do texto, foram abordados conceitos de gestão ambiental e de logística reversa, com o objetivo de ressaltar benefícios ambientais e sócio- econômicos advindos de umatravés do processo de gestão. Sobre a gestão dos resíduos, são apreciados os conceitos básicos desta, compondo-se uma abordagem prática e simplificada, sendo avaliadas estratégias de minimização de resíduos com base nos 3Rs, algumas metodologias de tratamento e a utilização de aterros industriais como local de destinação final para os resíduos. Para a estruturação da dissertação proposta, foi executada uma revisão bibliográfica, além da construção de uma linha de coesão entre os objetos estudados. Conclui-se que atualmente não existe metodologia de gestão tão eficiente que seja totalmente sustentável, nem gestão que possa ser baseada em apenas uma prática ou metodologia. A integração de conceitos e práticas, incluindo programas de minimização de resíduos, logística reversa, tratamento e destinação final faz-se necessária para uma gestão mais eficiente dos resíduos oleosos. Porém, deve-se destacar as novas oportunidades gerenciais associadas à logística reversa, bem como a necessidade de utilização dos aterros industriais em alguma etapa da gestão, assim como a atual tendência à adoção do co-processamento como metodologia de tratamento que apresenta a melhor relação custo x benefício para a gestão dos resíduos perigosos gerados nas refinarias de petróleo. / Different stages of the petroleum refining generate oil wastes that have hazardous substances. When oil waste contaminates the soil it may cause impacts on living resources, reaching groundwater, rivers and lakes in the region, affecting directly or indirectly the human health, with environmental, social and economic costs that can be very high. The objective of this study was to assess the management of hazardous solid wastes generated at petroleum refineries, describing processes and characterizing the way these wastes are generated in different stages of the refining process. The study also included assessment of treatment options and final disposal strategies. Principles of environmental management and reverse logistics were addressed with the objective of highlighting the environmental and socio-economic benefits added by a suitable management scheme. The basic concepts related to solid waste management are discussed in a practical and simplified language, and the minimization strategies are evaluated based on 3Rs principle. Treatment methodologies and the relevance of utilizing industrial landfills as final disposal solution are presented. Besides the literature survey, the construction of a red thread connecting the issues is presented. It was concluded that currently, there is no management scheme for oil waste efficient enough to be considered sustainable, neither management option that can be based on a single technology or methodology. An integration of concepts and different practices including waste minimization, reverse logistics, treatment and final disposal is needed in order to achieve a more efficient oil waste management. However, it is worth to highlight new managerial opportunities related to reverse logistics, as well as the need to make use of industrial landfills in some point of the process and the current trend of co- processing as the option that presents the best cost-benefit for management of oil hazardous wastes generated by petroleum refineries.