As correntes pesadas do refino de petróleo podem ser utilizadas para a produção de óleos combustíveis para uso industrial ou marítimo, sendo esse último conhecido como óleo bunker. Para tal, é necessária a diluição dessas correntes pesadas com frações de refino mais leves para ajuste da viscosidade. Enquanto o uso industrial do óleo combustível vem sendo significativamente reduzido em função de restrições ambientais, o mercado de óleo bunker apresenta crescimento importante face a expansão do comércio marítimo mundial. No Brasil, há um aumento da produção de petróleos pesados, extrapesados e asfálticos, que exigem complexos esquemas de refino para a sua conversão em frações mais leves. Dessa forma, ocorre uma redução da quantidade de correntes disponíveis para a produção de bunker, além da variação da qualidade das correntes usadas na sua formulação. Esta dissertação avalia a utilização de petróleos pesados e asfálticos na produção de bunker, sem a necessidade do processamento tradicional em refinarias de petróleo. A comparação da qualidade de ignição e de combustão da nova formulação deste produto com o combustível marítimo preparado a partir de correntes residuais é realizada por duas metodologias diferentes. Após a realização de um pré-tratamento, a mistura formulada a partir dos cortes dos petróleos apresenta melhor desempenho que os combustíveis formulados com as correntes residuais. Além disso, este trabalho compara o efeito de diferentes diluentes e a contribuição da corrente pesada utilizada na qualidade de ignição e de combustão do produto / Heavy streams from crude oil refining can be used to prepare fuel oils for industrial or maritime purposes, the latter known as bunker fuel. In order to prepare them, it is necessary to set viscosity to its appropriate value by dilution with lighter fractions from petroleum refining. While industrial usage of fuel oils is decreasing significantly due to environmental restrictions, the bunker fuel market shows an important increasing face to the growing in world maritime trading. Production of heavy, extra heavy and asphaltic crude oils in Brazil is rising and more complex refining process are required to convert them into lighter petroleum products. Because of that, the amount and the quality of available streams to prepare bunker fuel are decreasing. The present dissertation evaluates the feasibility of using heavy and asphaltic crude oils to prepare bunker fuel without traditional processing into petroleum refineries. The comparison of ignition and combustion quality considering the bunker fuel prepared from residual streams are made considering two different methodologies. After pre-treating the crude oils to prepare bunker fuels, that mixture shows a better ignition and combustion performance than those prepared with residual streams. Finally, this study compares the effect of different diluent streams and the heavy fraction contribution to products ignition and combustion quality

[pt] A cromatografia líquida de alta eficiência hifenada por injeção em fluxo com espectrometria de massa com plasma indutivamente acoplado (HPLC-FI-ICP-MS) foi utilizada para investigar vanádio ligado a porfirinas presente em frações de óleo cru. Em primeiro lugar, a amostra de óleo cru foi submetida a um fracionamento por meio de cromatografia líquida preparativa com detecção em UV-Vis, no comprimento de onda da banda Soret da porfirina (400 nm). As frações de porfirina obtidas foram então separadas numa coluna única de 250 mm, no HPLC e eluídas com fases móveis diferentes, metanol ou metanol:tolueno (80:20; v:v). A quantificação de V-porfirinas nas frações eluídas do HPLC foi feita pela medida do isótopo 51V no ICP-MS, usando-se soluções-padrão de octaetil-porfirina de vanádio (VO-OEP), preparados no mesmo solvente usado na fase móvel, e injetados pós-coluna diretamente no plasma. Um padrão de Ge em metanol (20 microgramas L−1) foi utilizado como padrão interno para minimizar interferências não-espectrais, tais como oscilações devido à injeção. O tratamento matemático do sinal com base no algoritmo de suavização do tipo Transformada Rápida de Fourier (FFT) foi utilizado para melhorar a precisão. As concentrações de V como V-porfirinas foram entre 2,7 e 11 mg kg-1 nas frações, valores próximos à concentração total de V nas frações de óleo cru estudadas. / [en] High performance liquid chromatography hyphenated by flow injection to inductively coupled plasma mass spectrometry (HPLC–FI–ICP-MS) was used to investigate vanadium linked to porphyrins present in fractions of crude oil. First, the crude oil sample was submitted to fractionation by preparative liquid chromatography with UV-Vis detection, at the porphyrin Soret band wavelength (400 nm). The obtained porphyrin fractions were then separated in a 250 mm single column, in the HPLC, and eluted with different mobile phases, methanol or methanol:toluene (80:20; v:v). The quantification of V-porphyrins in the fractions eluted from HPLC was carried out by online measuring the 51V isotope in the ICP-MS, against vanadyl octaethylporphine standard solutions (VO-OEP), prepared in the same solvent as the mobile phase, and injected post-column directly into the plasma. A 20 micrograms L−1 Ge in methanol was used as internal standard for minimizing non-spectral interference, such as short-term variations due to injection. The mathematical treatment of the signal based on Fast Fourier Transform (FFT) smoothing algorithm was employed to improve the precision. The concentrations of V as V-porphyrins were between 2.7 and 11 mg kg−1 in the fractions, which were close to the total concentration of V in the fractions of the studied crude oil.

Orientador: Antonio Carlos Bannwart / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica e Instituto de Geociencias / Made available in DSpace on 2018-08-12T08:12:48Z (GMT). No. of bitstreams: 1 Karcher_Viviane_M.pdf: 1731022 bytes, checksum: 355de3e34591ff15d14ab367330328f8 (MD5) Previous issue date: 2008 / Resumo: Durante a produção de petróleo, é comum o aparecimento de água sob a forma de gotas finamente dispersas no óleo. A água pode ser oriunda de métodos de recuperação avançada e/ou do próprio reservatório (água conata). O cisalhamento turbulento produzido durante o escoamento destes fluidos através de dutos ou dispositivos, como bombas, ou até mesmo no reservatório, pode causar a formação de emulsões de água em óleo (A/O). Para os óleos pesados,estas emulsões permanecem estáveis por um período longo devido à presença de agentes emulsificantes naturais no petróleo cru. Por essa razão, a separação dessas emulsões necessita de equipamentos específicos, o que contribui para o aumento do custo do processo. O objetivo deste estudo é investigar as propriedades interfaciais de emulsões A/O compostas por água e petróleo pesado brasileiro. Para tanto, um aparato experimental foi construído com o objetivo de calcular a energia interfacial dessas emulsões. As emulsões A/O foram geradas através de um aparelho homogeneizador rotativo imerso em um vaso calorimétrico. Dois métodos foram empregados: o método calorimétrico, baseado no balanço de energia da emulsificação, e o método padrão, baseado na medida do tamanho e distribuição das gotas através da técnica de microscopia óptica. As incertezas nas medidas experimentais, em ambos os métodos, foram estudadas a fim de avaliar a viabilidade de cada um. Como principais resultados deste estudo, as magnitudes relativas dos termos do balanço de energia durante a emulsificação foram obtidas. O comportamento reológico destas emulsões também foi estudado. / Abstract: In petroleum production operations, water is commonly present within the oil phase as a finely dispersed phase. This situation originates from enhanced oil recovery methods and/or the presence of connate water inside the own reservoir. The turbulent shear associated with fluid flow during of heavy crude transportation through pipelines may cause the formation of water-in-oil emulsions (W/O). These remain stable for a long time, due the presence of naturally emulsifying agents in the crude oil phase. Therefore, emulsion separation requires specific equipments which contribute to increase the processes costs. The main purpose of this study is to investigate the interfacial properties of W/O emulsions composed by water and a Brazilian heavy crude oil. For that purpose an experimental set-up was built in order to measure the interfacial energy of the emulsions. The W/O emulsions were prepared in a calorimeter vessel by using a rotating impeller. Two methods were used, namely, the calorimetric method based on the energy balance for the emulsification and the standard method of the droplet size and distribution by means of a digital microscope. The uncertainty in experimental measurements was determined for both methods, in order to evaluate their feasibility. The main result of this research is the determination of the relative magnitudes of the different terms in the energy balance during emulsification. Results for the rheological behavior of W/O emulsions are also reported. / Mestrado / Explotação / Mestre em Ciências e Engenharia de Petróleo

Orientador: Ronei Jesus Poppi / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T02:05:14Z (GMT). No. of bitstreams: 1 Filgueiras_PauloRoberto_D.pdf: 5218504 bytes, checksum: f307cad15b41230e15e9d018c384a91d (MD5) Previous issue date: 2014 / Resumo: O petróleo é constituído por uma mistura complexa de composição química heterogênea. Sua completa avaliação envolve cerca de 700 ensaios físico-químicos, consumindo de 10 a 70 litros de amostra em aproximadamente 1 ano de análises. Visando reduzir tempo e quantidade de amostra, nesta Tese, métodos espectroscópicos aliados à Regressão por Vetores de Suporte (SVR) foram aplicados na determinação de algumas propriedades físico-químicas de petróleos e biocombustíveis. Diferentes abordagens para otimização e interpretação dos modelos SVR foram desenvolvidas: técnica para determinar as variáveis mais importantes na construção dos modelos, estimativa de intervalos de confiança nas previsões e avaliação de tendências nos resíduos. Foram realizadas quatro aplicações com diferentes técnicas instrumentais. A primeira aplicação foi direcionada a interpretação dos modelos SVR construídos a partir de espectros de infravermelho médio (MIR) na determinação da gravidade API, viscosidade cinemática e teor de água em petróleos. Na segunda aplicação foi desenvolvido um método para estimar o intervalo de confiança de modelos SVR aplicados a espectros de Ressonância Magnética Nuclear de próton (RMN de 1H) na determinação das temperaturas equivalentes a 10%, 50% e 90% de volume destilado de petróleo. Na terceira aplicação foi desenvolvido um método para selecionar variáveis espectrais e otimizar os parâmetros do modelo SVR simultaneamente por algoritmo genético, aplicado a espectros de Ressonância Magnética Nuclear de carbono 13 (RMN de 13C) na determinação de saturados, aromáticos, resinas e asfaltenos (SARA) em petróleos. Na última aplicação, procurou-se selecionar variáveis espectrais utilizando o método de sinergismo de intervalos, aplicado a espectros de infravermelho próximo (NIR) para quantificar biodiesel de gordura animal em mistura com biodiesel de soja e diesel B20. Os resultados apontam o SVR como excelente ferramenta para calibração multivariada aplicada a dados complexos como petróleo e biocombustíveis / Abstract: Crude oil is composed by a complex mixture of heterogeneous chemical composition. Its full evaluation involves about 700 physicochemical experiments, consuming about 10-70 liters of sample in there about 1 year of analysis. In order to reduce time and amount of sample, in this Thesis, spectroscopic methods combined with Support Vector Regression (SVR) were applied in determination of physicochemical properties of petroleum and biofuels. Different approaches for optimization and interpretation of SVR models were developed: techniques to determine the most important variables in the model development, determination of confidence intervals in predictions and assessment of trends in residuals. Four applications with different instrumental techniques were performed. The first application was directed to interpretation of SVR models built from mid infrared (MIR) spectra to determination of the API gravity, kinematic viscosity and water content in petroleum. In the second application, it was developed a method to estimation of the confidence interval of SVR models applied in spectra of proton nuclear magnetic resonance (1H NMR) for the determination of equivalent temperatures to 10%, 50% and 90% of distillate volume in petroleum. In the third application it was developed a method for spectral variables selection and optimization the SVR model parameters simultaneously by genetic algorithm, applied to nuclear magnetic resonance spectra of carbon 13 (13C NMR) in determination of saturates, aromatics, resins and asphaltenes (SARA) in petroleum. In the last application, it was proposed a method for spectral variables selection using the synergism of intervals, applied to near-infrared (NIR) spectra to quantify biodiesel from animal fat in blend with biodiesel from soybean and diesel B20. The results indicate the SVR as an excellent tool for multivariate calibration applied to complex dataset such as petroleum and biofuels / Doutorado / Quimica Analitica / Doutor em Ciências

Orientador: Marcos Nogueira Eberlin / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T09:34:26Z (GMT). No. of bitstreams: 1 Lima_MairaFasciottiPinto_M.pdf: 3076235 bytes, checksum: bc4b63f365634b0b6e2e36e84cb49537 (MD5) Previous issue date: 2012 / Resumo: Esta dissertação apresenta uma breve introdução sobre a técnica de mobilidade iônica acoplada a espectrometria de massas (Capítulo 1) e a discussão de resultados aplicados a três subprojetos distintos. A técnica de TWIM-MS é uma técnica de separação na qual a separação em dos íons ocorre em uma cela de mobilidade iônica e é baseada em parâmetros como a seção de choque, carga, polarizabilidade, que é a capacidade de um íon ter sua densidade eletrônica distorcida pela interação com o gás de mobilidade, além de, obviamente, da estrutura tridimensional dos íons em fase gasosa. Sobre o Capitulo 2, objetivo do trabalho em petroleômica foi desenvolver e otimizar um método para a identificação de compostos polares presentes em amostras de petróleo e seus derivados como diesel e gasolina, que fosse capaz de diferenciar amostras distintas com relação essas composições, verificando quais respostas esta técnica pode fornecer nos estudos petroleômicos. Puderam ser identificadas as classes N, O2 e NO, com excelente resolução com a técnica de TWIM-MS. Entretanto, acredita-se que algumas outras classes ainda podem ser elucidadas. O CO2 se mostrou ser o melhor gás de mobilidade a ser utilizado para a resolução destas classes. A técnica de TWIM-MS também se mostrou adequada para a caracterização de gasolina e seus aditivos, entretanto mais amostras de diesel aditivado devem ser investigadas, para se descobrir porque os aditivos não puderam ser detectados através da técnica de ESI-TWIM-MS. Com relação ao estudo das estruturas em fase gasosa dos isômeros do Corrol (Capítulo 3), podese observar que o corrorin tem a estrutura tridimensional mais compacta entre todos os isômeros, enquanto NCC4 e corrol são os isômeros com maiores seções de choque e maiores drift times. Mesmo que o norrole tenha os maiores valores previstos de CCS, seu menor momento de dipolo resulta em interações mais fracas com o gás de mobilidade, e um drift time menor do que o esperado é obtido. Uma melhor resolução entre os isômeros de corrol foi alcançada usando CO2 como gás de mobilidade. Além disso, estes isômeros podem ser diferenciados monitorando íons característicos resultantes de suas fragmentações. Em conclusão, mostrou-se que a diferenciação por TWIM-MS destas estruturas pode ser conseguida através do monitoramento das diferenças entre as suas mobilidades relativas e também pelos espectros distintos de MS/MS obtidos para cada isômero. Já o Capítulo 4, visou avaliar a separação de 4 dissacarídeos isoméricos, em que se observou que a utilização de mais gases polarizáveis, tais como o CO2 na análise realizada com o Synapt G2 permite uma resolução quase na linha de base, o que não foi possível utilizando N2 como gás de mobilidade e nem na primeira geração do equipamento comercial Synapt, mesmo usando CO2 como gás de mobilidade / Abstract: This dissertation presents a brief introduction of the technique of Ion Mobility Mass Spectrometry (Chapter 1) and also the discussion of results applied to three distinct subprojects. The technique of Traveling Wave Ion Mobility Mass Spectrometry, is a separation technique in which the separation of the ions occurs in a mobility cell and is based on parameters such as collision cross-section, charge, polarizability (the capacity of an ion to have its electronic density distorted by interaction with the drift gas) and the three dimensional structure (shape) of ions in the gaseous phase. The main goal of the work performed in petroleomics (Chapter 2), was to develop and optimize a method for the identification of polar compounds present in oil samples and its derivatives, such as diesel and gasoline. The applied method was able to differentiate oil samples based on some polar components. Classes N, O2 and NO could be identified with proper resolution with TWIM-MS technique. However, it is believed that some other classes may be elucidated. CO2 was shown to be the best drift gas to be used for the separation of these classes. The technique of TWIM-MS also proved to be suitable for the characterization of gasoline and its additives, however, more samples of additive diesel must be investigated to find out why the additives could not be detected by the technique of ESI-TWIM-MS. During the study of tridimensional structures in the gaseous phase of five Corrole isomers (Chapter 3), it was observed that significant differences in shape and charge distributions for the protonated molecules lead to contrasting gas phase mobilities, most particularly for corroin, the most "confused¿ isomer. Accordingly, corroin was predicted by DFT and collisional cross section calculations to display the most compact tridimensional structure. NCC4 and corrole, on the other hand were found to be the most planar isomers. Better resolution between the corrole isomers was achieved using the more polarizable and massive CO2 as the drift gas and contrasting labilities towards CID, allowed the prompt differentiation of some isomers. Chapter 4 aimed to evaluate the separation of four isomeric disaccharides, where it was observed that the use of more polarizable gases, such as CO2, in the analysis performed with a Synapt G2 allows almost a baseline resolution for some isomeric pairs. This was not possible using N2 as drift gas with the Synapt G2, and not with the Synapt G1 using either N2 or CO2 / Mestrado / Quimica Analitica / Mestra em Química

Orientador: Marcos Nogueira Eberlin / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T09:31:28Z (GMT). No. of bitstreams: 1 Lalli_PriscilaMicaroni_D.pdf: 7058193 bytes, checksum: bda550a8e643bbf3d082b69bfd94c04e (MD5) Previous issue date: 2012 / Resumo: A espectrometria de mobilidade iônica separa íons de diferentes tamanhos ou formatos (seção de choque) em fase gasosa de acordo com o tempo que levam para atravessar uma câmara preenchida com gás sob a influência de um campo elétrico fraco. O acoplamento dessa técnica à espectrometria de massas (IM-MS) resulta em uma ferramenta extremamente versátil, pois adiciona uma nova dimensão aos dados de MS com informação sobre a estrutura tridimensional das espécies. Assim, a IM-MS tem sido muito utilizada para o estudo conformacional de proteínas, separação de isômeros e análise de misturas complexas. Neste trabalho, investigamos novas aplicações da IMMS, focando na separação de isômeros. Na primeira parte, mostramos que a IM-MS é capaz de separar isômeros posicionais de piridil porfirina mono ou multi substituída com [Ru(bpy)2Cl]+. Os isômeros substituídos em meta mostraram ser mais compactos do que os substituídos em para. Entretanto, os isômeros di-substituídos em cis e trans possuem seção de choque muito parecida e não puderam ser separados. Na segunda parte, mostramos a separação e caracterização de protômeros (espécies protonadas ou desprotonadas em sítios distintos). Apesar da protonação (ou desprotonação) em sítios diferentes não alterar significativamente a seção de choque da espécie, ela pode resultar em íons com distribuição de cargas contrastantes, o que leva a formação de heterodímeros entre os íons e as moléculas do gás (CO2) com forças e tempo de vidas contrastantes, assim assegurando a resolução desses protômeros por IM-MS. Na terceira parte do trabalho, investigamos o potencial da técnica para o detalhamento composicional e estrutural de compostos presentes em petróleo através da análise de cortes de destilação de alto ponto de ebulição / Abstract: Ion mobility mass spectrometry separates ions with different size or shape (collision cross section) in the gas phase according to the time they take to travel through a cell filled with gas under the influence of a low electric field. The coupling of this technique to mass spectrometry (IM-MS) results in an extremely versatile tool, since it adds a new dimension to MS data with information about the species¿ threedimensional structure. Therefore, IM-MS has been extensively used for protein conformation studies, isomer separations and analysis of complex mixtures. In this work, we investigate new applications of IM-MS, focusing on isomer separation. In the first part, we show that IM-MS is able to separate positional isomers of pyridilporhyrins mono or multi-substituted wih [Ru(bpy)2Cl]+. The meta substituted isomers were shown to be more compact than the para substituted isomers. On the other hand, cis and trans di-substituted isomers display very similar collision cross sections and could not be separated. In the second part of this work, we show the separation and characterization of protomers (species protonated or deprotonated in different sites). Although protonation (or deprotonation) in different sites does not change significatly the species collision cross section, it may result in ions with contrasting charge distribution, which leads to the formation of heterodimers between ions and gas molecules (CO2) with contrasting strengths and life times, therefore allowing the resolution of these protomers by IM-MS. In the third part of this work, we investigate the potencial of this technique for the compositional and structural detailing of compounds present in crude oil by the analysis of high boiling point distillation cuts / Doutorado / Quimica Analitica / Doutora em Ciências

Les mousses rencontrées dans l’industrie pétrolière comptent parmi les mousses les plus complexes et problématiques. Lors de la production du pétrole brut, la présence de mousses stables peut entraîner de gros problèmes dans les équipements de traitement en surface à cause de la dépressurisation et de la nucléation de bulles provenant du gaz naturellement dissous dans le fluide de réservoir. Cette mousse peut rapidement occuper la moitié du volume des séparateurs et provoquer des dommages opérationnels graves, liés à des difficultés de contrôle des niveaux, à l’entraînement de liquide dans la ligne gaz et à l’entraînement de gaz dans la ligne liquide. Le contrôle de ces mousses pétrolières constitue donc un véritable enjeu, et les diverses solutions proposées sont basées sur l’utilisation de moyens physiques (chauffage, utilisation d’internes spécifiques) mais surtout sur l’utilisation d’additifs antimousses ou démoussants et plus particulièrement de silicones PDMS. Cependant, il n’existe pas encore d’optimisation possible de ces traitements du fait du manque d’études détaillées sur le comportement de ces systèmes complexes. L’objectif principal de ce travail a donc été de contribuer à la compréhension des mécanismes de formation, de stabilisation et de rupture des mousses non aqueuses et plus particulièrement des mousses de pétrole brut. Dans un premier temps, nous avons développé une nouvelle méthodologie expérimentale permettant de former des mousses représentatives des mousses pétrolières afin de comparer quantitativement différents systèmes moussants à base de pétroles bruts ainsi que l’efficacité de différentes familles d’additifs chimiques. Ensuite, nous avons étudié les cinétiques de cassage et développé un modèle de type sigmoïde permettant de décrire les courbes expérimentales de manière satisfaisante, et ouvrant la voie à une analyse quantitative de ces systèmes. Grâce à ce type de modélisation, il est possible de comparer l’efficacité des additifs chimiques en tant que démoussants et/ou antimousses et donc d’optimiser le choix du meilleur additif requis.Enfin ces développements permettent de proposer une première analyse de l’influence des caractéristiques physico chimiques de ces systèmes complexes sur leurs propriétés de moussage. / Crude oil foams are present in most steps of the oil industry, being one of the most complex and problematic non aqueous foams. During the crude oil exploitation, the presence of stable foams may cause major problems on surface equipment because of the depressurisation between the reservoir and the wellhead and the nucleation of the bubbles from the natural gas solubilised in the reservoir oil. These foams can fill up rapidly the half of the volume of the separators and cause serious damages due to the loss of the level control capacity, by dragging gas to the liquid line or liquid to the gas line, which leads to a reduction of the efficiency of the operation. The control of these foams is therefore a real issue. Several methods are used to control the foam based on its physical destruction (by mechanical devices, heating, special design of the unit internals...) but, by far, the most common method is the chemical destruction by adding different chemical compounds (called defoamers and antifoamers), particularly PDMS silicones. However, there is still no possible optimization of these treatments because of the lack of detailed studies on the behaviour of these complex systems. With this work we wanted to contribute to the understanding of the formation, stabilization and breaking mechanisms of this kind of non-aqueous foams. With this in mind, our first objective was the development of a new experimental methodology that allows to form crude oil foams which are representative of the oilfield foams, in order to compare the different foamy systems as well as the efficiency of different families of chemical additives. After that, we used a sigmoid model which describes in a satisfactory way the experimental curves of foam breaking. Besides, this kind of modelling allows to compare the efficiency of the different chemical additives in terms of defoaming and antifoaming effects, leading to the optimal selection of the additive in each case. Finally, these developments allow us to propose a first analysis of the influence of the physicochemical characteristics of these complex systems on their foaming properties.

The advancements in the field of analytical chemistry, and especially mass spectrometry, have been redefining the field of contaminant detection. While more traditional analysis was sufficient to screen for a small number of well-known compounds, new techniques such as high-resolution mass spectrometry, have enabled a fairly comprehensive screening for previously unknown contaminants. This is enormously beneficial with respect to the analysis of water, air, or soil quality in a society that continuously introduces novel anthropogenic compounds into the environment. This dissertation, thus, focused on the analysis of the uncharacterized portion of compounds in two types of complex environmental matrices (i.e., crude oil and wastewater). First, targeted and non-targeted analyses were used in order to characterize a crude oil weathering series. Traditional techniques were used for the analysis of well-known oil components and led to the confirmation of biodegradation and photo-degradation trends. An ultrahigh-resolution mass spectrometric analysis was carried out in conjunction with several visualization plots in order to search for unknown compounds. While the study successfully detected a drastic increase in oxygenated components (likely ketones, quinones, and carboxylic acids), it also revealed severe limitations in the state of the art non-targeted crude oil analysis. Some of these limitations were explored in an in-depth atmospheric pressure ionization study of model petroleum compounds, and the dependence of ionization efficiency on numerous factors (e.g., size, heteroatom content, and methylation level) was shown. Since disregarding these intrinsic limitations leads to severely biased conclusions, these results provide crucial information for future crude oil characterization studies. Lastly, suspected and non-targeted analyses were used to evaluate contamination levels in wastewater-impacted interrelated water samples. A significant number of persistent compounds were tentatively identified, which represents an area of environmental concern that needs to be addressed further. Overall, this dissertation successfully applied non-targeted (in addition to targeted) analysis in order to screen for non-characterized compounds in crude oil and wastewater affected water samples. By doing so, the great potential of the growing field of non-targeted screening in order to expand the range of contaminants to include previously unknown and emerging compounds was highlighted.

This thesis assesses and describes two main current trends appearing at the crude oil market, specifically re-entry of Iran back to the crude oil market after termination of economic sanctions and current oil glut. First part of this thesis is devoted to the crude oil as resource, it focuses mainly on the history, formation and mining of crude oil. Second part of this thesis focuses on the international trade with crude oil. It analyses data regarding reserves, production, consumption, export and import of crude oil, as well as it describes the OPEC organization. Third part is devoted to the organization of the market with crude oil and describes three main motives of entering to the crude oil market. There are analyzed current trends on the crude oil market in the last part of this thesis.

Building relations with China is a topic of broad and current interest, when it comes to establishing and deepening new economic cooperation between Sub-Saharan Africa and other regions. This thesis analyses current economic cooperation between these two regions with the prevailing emphasis on the African partner. The thesis is formally divided into five chapters. The first two chapters focus on selected theoretical and factual starting points related to the main topic of the thesis, which create a foundation stone for the other chapters. In the third chapter of the thesis, selected statistical data about current trade and investment cooperation between both partners are introduced. The main goal of the following fourth chapter is to analyze real impact of mutual cooperation on the selected country of Sub-Saharan region. The last chapter of the thesis analyses a relatively problematic and widely discussed issue: the classification and allocation of financial flows from China in the Sub-Saharan Africa.