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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
21

Application Of Vapex (vapour Extraction) Process On Carbonate Reservoirs

Yildirim, Yakut 01 January 2003 (has links) (PDF)
The vapour extraction process, or &amp / #8216 / VAPEX&amp / #8217 / has attracted a great deal of attention in recent years as a new method of heavy oil or bitumen recovery. The VAPEX (vapour extraction) can be visualized as energy efficient recovery process for unlocking the potential of high viscosity resources trapped in bituminous and heavy oil reservoirs. A total of 20 VAPEX experiments performed with Hele-Shaw cell utilizing three different Turkish crude oils. Two different VAPEX solvents (propane and butane) were used with three different injection rates (20, 40 and 80 ml/min). Garzan, Raman and Bati Raman crude oils were used as light, medium and heavy oil. Apart from normal Dry VAPEX experiments one experiment was conducted with CO2 and another one with butane + steam as Wet VAPEX experiment. All experiments were recorded by normal video camera in order to analyze visually also. For both VAPEX solvents, oil production rates increased with injection rates for all crude oils. Instantaneous asphaltene rate for Garzan oil, showed fluctuated performance with propane solvent. Butane showed almost constant degree of asphaltene precipitation. Instantaneous asphaltene rate for Raman and Bati Raman oils gave straight line results with the injection rate of 20 ml/min for both solvent. When the injection rate increased graphs showed the same performance with Garzan oil and started to fluctuate for both solvent. For asphaltene precipitation, propane gave better results than butane in almost all injection rates for Garzan and Raman oil. In the experiments with Bati Raman oil, butane made better upgrading than propane with the injection rate 80 ml/min. With the other two rates, both solvents showed almost same performace.
22

EFFECTS OF WARM MIX ADDITIVES AND DISPERSANTS ON RHEOLOGICAL, AGING AND FAILURE PROPERTIES OF ASPHALT CEMENTS

Paul Samy, Senthil Kumar 26 February 2013 (has links)
Existing specifications for asphalt cement employ insufficient aging and conditioning times prior to testing and low strains during the actual test which are insufficient to predict asphalt performance, especially if the materials are modified with additives such as those used for warm mix technology. However, slightly modified protocols, like increasing the conditioning time in the bending beam rheometer (BBR) test and increasing the aging duration in the pressure aging vessel (PAV), predict asphalt performance better than the current Superpave™ specification. These improved protocols are published as new test standards through the collaborative effort between the Ontario Ministry of Transportation and Queen’s University. In this study, the effects of warm mix and other additives on rheological, aging and failure properties are investigated. The properties are measured by regular tests and by modified protocols. The latter include the extended BBR test (LS-308) and the double-edge-notched tension (DENT) test (LS-299). Changes in ductile strain tolerance within base asphalts due to the various additives as measured with the DENT test were found to be very significant. The DENT results like essential work of fracture, we, plastic work of fracture term, βwp, and critical crack tip opening displacement, CTOD, are usually helped to correlate with the cracking distress survey results of the pavement in service. The addition of amide and polyethylene waxes risks increasing the cracking susceptibility in the pavement. They show a negative effect on strain tolerance in the ductile state, which is likely to show up as premature and/or excessive cracking in service which is similar to their physical hardening behavior from low temperature grading and extended BBR testing. / Thesis (Master, Chemistry) -- Queen's University, 2013-02-26 11:10:41.08
23

Asfalteno: um desafio para indústria de petróleo e a busca de soluções pela nanociência / Asphaltene: a challenge for the oil industry and the search for solutions by nanoscience

Pereira, Maria Luiza de Oliveira 15 February 2018 (has links)
Asfaltenos são constituídos de hidrocarbonetos policíclicos aromáticos que fazem parte de uma das classes de compostos químicos mais poluentes e carcinogênicos. São bem conhecidos por formarem inscrutações que obstruem tubulações, podendo até levar ao fechamento do poço. Estes podem constituir até 20% do petróleo, que ainda remanesce o principal recurso de energia usado em nosso planeta. Atualmente são convertidos em asfalto e coque durante o processo de refino, através de destilação destrutiva, exigindo altas temperaturas e emitindo compostos de enxofre na atmosfera. No entanto, sua conversão em matérias-primas mais valiosas e produtos menos poluentes, por exemplo, por craqueamento fotocatalítico ou oxidativo poderia ser uma opção mais limpa e econômica. A nanotecnologia vem sendo incorporada nas pesquisas com petróleo pelas contribuições positivas que acrescenta tanto do ponto de vista econômico como ambiental, assim como através do melhoramento e recuperação de óleos pesados. Os nanomateriais em geral possuem a vantagem de ter maior grau de dispersão e propriedades diferenciadas em relação ao bulk. Neste trabalho estudaram-se as interações entre os asfaltenos e diferentes nanomateriais com propriedades magnéticas, ópticas e eletrônicas extraordinárias, como as nanopartículas de óxido de ferro (Nmag), os híbridos de nanopartículas de ouro com óxido de grafeno reduzido (RGO@AuNP) e os nanobastões de ouro (AuNRs) respectivamente. As interações entre asfaltenos e Nmags com diferentes ligantes passivantes (C8H20O4Si e C6H17NO3Si) foram feitas através da construção de isotermas e experimentos de adsorção,revelando os tipos de ligação que ocorrem entre esses materiais, cobertura e a capacidade adsortiva. O recobrimento da nanopartícula e a concentração de asfalteno influenciam na adsorção, sendo a interação mais forte com as Nmags livres, indicando coordenação do ferro nos substituintes dos anéis aromáticos do asfalteno, tendo cobertura por monocamada. As Nmags funcionalizadas interagem por forças intermoleculares com os asfaltenos, apresentando cobertura por multicamadas. Em altas concentrações de asfalteno em tolueno, a adsorção foi mais efetiva para as Nmags funcionalizadas, pois a coordenação com o ferro é dificultada devido a formação de micela reversa, prevalecendo as interações hidrofóbicas. Houve uma drástica redução na temperatura de craqueamento dos asfaltenos na presença das Nmags, em mais de 100ºC, demonstrando seu potencial na catálise oxidativa de asfaltenos. As interações dos materiais RGO@AuNP e AuNR em filmes com asfalteno foram investigadas por microscopia hiperespectral de campo escuro. Como resultado observou-se o deslocamento e o alargamento da banda de espalhamento no espectro eletrônico, indicando a ocorrência de transferência de carga entre as espécies. A partir disso, realizaram-se fotocatálises com o RGO@AuNP à temperatura ambiente sob luz visível, utilizando o 9-antraldeído como composto modelo para o asfalteno. A reação levou à formação de endoperóxidos cíclicos, que sofreram clivagens com 90% de rendimento. Por ultimo, realizou-se um estudo mecanístico utilizando um sensor fluorogênico de espécies reativas de oxigênio (ROS) para avaliar a atividade fotocatalítica do RGO@AuNP. Mostrou-se que ocorrem transferências de elétrons fotoinduzidas da AuNP para o RGO em uma escala de tempo de ~11 fs, com eficiência quântica de ~35% e que radicais superóxidos (O2•-) podem ser gerados pelos efeitos sinérgicos da fotoexcitação do híbrido. / Asphaltenes are composed by polycyclic aromatic hydrocarbons that belong to one of the most polluting and carcinogenic chemical classes. They are well known for forming hard scales that obstruct pipelines and may even lead to the well shut down. They can constitute up to 20% of petroleum, which still remains the main source of energy used in our planet. At the present time, asphaltenes are converted into asphalt and coke by destructive distillation, in spite of the high cost and polluting technology involved, which employs high temperatures and releases sulfur compounds into the atmosphere. However, their conversion into more valuable raw materials, for instance, by photocatalytic or oxidative cracking using suitable catalysts, would be a better, more economic option. In recent years, nanotechnology has been incorporated into oil research, opening new economic and environmental perspectives, including the improvement and recovery of heavy oils. In general, nanomaterials have the advantage of being better dispersed and exhibiting differentiated properties in relation to the bulk. In this study the interactions between asphaltenes and different nanomaterials exhibiting remarkable magnetic, optical, and electronic properties, such as iron oxide nanoparticles (Nmag), hybrids of gold nanoparticles with reduced graphene oxide (RGO@AuNP) and the gold nanorods (AuNRs) respectively were investigated. The interactions between asphaltenes and Nmags with different surface-passivating ligands (C8H20O4Si and C6H17NO3Si) were made by performing isotherms curves and adsorption tests, revealing the types of binding between these materials, their coverage and the adsorptive capacity. The nanoparticle coating and the asphaltene concentration influence the adsorption. Theinteraction was stronger using the free Nmag, indicating coordination of the iron with the aromatic rings of the asphaltene, having a monolayer cover. Functionalized Nmags interact by intermolecular forces with asphaltenes, having a multilayer coverage. At high concentrations of asphaltene in toluene, the adsorption was more effective for the functionalized Nmags, since the coordination with the iron was hampered due to the formation of reverse micelle, prevailing the hydrophobic interactions. There was a drastic reduction in the asphaltene cracking temperature in the presence of Nmags, bigger than 100ºC, showing its potential on the oxidative catalysis of asphaltenes. The interactions of RGO@AuNP and AuNR materials with asphaltene films were investigated by dark field hyperspectral microscopy. As a result there was a shift and a broadening of the band in the electronic spectrum, indicating the occurrence of charge transfer between the species. From this, photocatalysis were performed with the RGO@AuNP, at room temperature, under visible light, using 9-antraldehyde (9-ATA) as a model compound for asphaltene. The reaction leads to the formation of cyclic endoperoxides that undergo further reactions, resulting in their cleavage, with 90% yield for the 9-ATA degradation. Finally, a mechanistic study was carried out using a fluorogenic sensor of reactive oxygen species to evaluate the photocatalytic activity of RGO@AuNP. It was showed that photoinduced electron transfer from AuNP to RGO can occur in ~11 fs time scale, with a quantum yield of ~35%, and superoxide radicals anions (O2•-) can be generated by synergistic effects after the hybrid photoexcitation.
24

Asfalteno: um desafio para indústria de petróleo e a busca de soluções pela nanociência / Asphaltene: a challenge for the oil industry and the search for solutions by nanoscience

Maria Luiza de Oliveira Pereira 15 February 2018 (has links)
Asfaltenos são constituídos de hidrocarbonetos policíclicos aromáticos que fazem parte de uma das classes de compostos químicos mais poluentes e carcinogênicos. São bem conhecidos por formarem inscrutações que obstruem tubulações, podendo até levar ao fechamento do poço. Estes podem constituir até 20% do petróleo, que ainda remanesce o principal recurso de energia usado em nosso planeta. Atualmente são convertidos em asfalto e coque durante o processo de refino, através de destilação destrutiva, exigindo altas temperaturas e emitindo compostos de enxofre na atmosfera. No entanto, sua conversão em matérias-primas mais valiosas e produtos menos poluentes, por exemplo, por craqueamento fotocatalítico ou oxidativo poderia ser uma opção mais limpa e econômica. A nanotecnologia vem sendo incorporada nas pesquisas com petróleo pelas contribuições positivas que acrescenta tanto do ponto de vista econômico como ambiental, assim como através do melhoramento e recuperação de óleos pesados. Os nanomateriais em geral possuem a vantagem de ter maior grau de dispersão e propriedades diferenciadas em relação ao bulk. Neste trabalho estudaram-se as interações entre os asfaltenos e diferentes nanomateriais com propriedades magnéticas, ópticas e eletrônicas extraordinárias, como as nanopartículas de óxido de ferro (Nmag), os híbridos de nanopartículas de ouro com óxido de grafeno reduzido (RGO@AuNP) e os nanobastões de ouro (AuNRs) respectivamente. As interações entre asfaltenos e Nmags com diferentes ligantes passivantes (C8H20O4Si e C6H17NO3Si) foram feitas através da construção de isotermas e experimentos de adsorção,revelando os tipos de ligação que ocorrem entre esses materiais, cobertura e a capacidade adsortiva. O recobrimento da nanopartícula e a concentração de asfalteno influenciam na adsorção, sendo a interação mais forte com as Nmags livres, indicando coordenação do ferro nos substituintes dos anéis aromáticos do asfalteno, tendo cobertura por monocamada. As Nmags funcionalizadas interagem por forças intermoleculares com os asfaltenos, apresentando cobertura por multicamadas. Em altas concentrações de asfalteno em tolueno, a adsorção foi mais efetiva para as Nmags funcionalizadas, pois a coordenação com o ferro é dificultada devido a formação de micela reversa, prevalecendo as interações hidrofóbicas. Houve uma drástica redução na temperatura de craqueamento dos asfaltenos na presença das Nmags, em mais de 100ºC, demonstrando seu potencial na catálise oxidativa de asfaltenos. As interações dos materiais RGO@AuNP e AuNR em filmes com asfalteno foram investigadas por microscopia hiperespectral de campo escuro. Como resultado observou-se o deslocamento e o alargamento da banda de espalhamento no espectro eletrônico, indicando a ocorrência de transferência de carga entre as espécies. A partir disso, realizaram-se fotocatálises com o RGO@AuNP à temperatura ambiente sob luz visível, utilizando o 9-antraldeído como composto modelo para o asfalteno. A reação levou à formação de endoperóxidos cíclicos, que sofreram clivagens com 90% de rendimento. Por ultimo, realizou-se um estudo mecanístico utilizando um sensor fluorogênico de espécies reativas de oxigênio (ROS) para avaliar a atividade fotocatalítica do RGO@AuNP. Mostrou-se que ocorrem transferências de elétrons fotoinduzidas da AuNP para o RGO em uma escala de tempo de ~11 fs, com eficiência quântica de ~35% e que radicais superóxidos (O2•-) podem ser gerados pelos efeitos sinérgicos da fotoexcitação do híbrido. / Asphaltenes are composed by polycyclic aromatic hydrocarbons that belong to one of the most polluting and carcinogenic chemical classes. They are well known for forming hard scales that obstruct pipelines and may even lead to the well shut down. They can constitute up to 20% of petroleum, which still remains the main source of energy used in our planet. At the present time, asphaltenes are converted into asphalt and coke by destructive distillation, in spite of the high cost and polluting technology involved, which employs high temperatures and releases sulfur compounds into the atmosphere. However, their conversion into more valuable raw materials, for instance, by photocatalytic or oxidative cracking using suitable catalysts, would be a better, more economic option. In recent years, nanotechnology has been incorporated into oil research, opening new economic and environmental perspectives, including the improvement and recovery of heavy oils. In general, nanomaterials have the advantage of being better dispersed and exhibiting differentiated properties in relation to the bulk. In this study the interactions between asphaltenes and different nanomaterials exhibiting remarkable magnetic, optical, and electronic properties, such as iron oxide nanoparticles (Nmag), hybrids of gold nanoparticles with reduced graphene oxide (RGO@AuNP) and the gold nanorods (AuNRs) respectively were investigated. The interactions between asphaltenes and Nmags with different surface-passivating ligands (C8H20O4Si and C6H17NO3Si) were made by performing isotherms curves and adsorption tests, revealing the types of binding between these materials, their coverage and the adsorptive capacity. The nanoparticle coating and the asphaltene concentration influence the adsorption. Theinteraction was stronger using the free Nmag, indicating coordination of the iron with the aromatic rings of the asphaltene, having a monolayer cover. Functionalized Nmags interact by intermolecular forces with asphaltenes, having a multilayer coverage. At high concentrations of asphaltene in toluene, the adsorption was more effective for the functionalized Nmags, since the coordination with the iron was hampered due to the formation of reverse micelle, prevailing the hydrophobic interactions. There was a drastic reduction in the asphaltene cracking temperature in the presence of Nmags, bigger than 100ºC, showing its potential on the oxidative catalysis of asphaltenes. The interactions of RGO@AuNP and AuNR materials with asphaltene films were investigated by dark field hyperspectral microscopy. As a result there was a shift and a broadening of the band in the electronic spectrum, indicating the occurrence of charge transfer between the species. From this, photocatalysis were performed with the RGO@AuNP, at room temperature, under visible light, using 9-antraldehyde (9-ATA) as a model compound for asphaltene. The reaction leads to the formation of cyclic endoperoxides that undergo further reactions, resulting in their cleavage, with 90% yield for the 9-ATA degradation. Finally, a mechanistic study was carried out using a fluorogenic sensor of reactive oxygen species to evaluate the photocatalytic activity of RGO@AuNP. It was showed that photoinduced electron transfer from AuNP to RGO can occur in ~11 fs time scale, with a quantum yield of ~35%, and superoxide radicals anions (O2•-) can be generated by synergistic effects after the hybrid photoexcitation.
25

Advanced equation of state modeling for compositional simulation of gas floods

Mohebbinia, Saeedeh 10 February 2014 (has links)
Multiple hydrocarbon phases are observed during miscible gas floods. The possible phases that result from a gas flood include a vapor phase, an oleic phase, a solvent-rich phase, a solid phase, and an aqueous phase. The solid phase primarily consists of aggregated asphaltene particles. Asphaltenes can block pore throats or change the formation wettability, and thereby reduce the hydrocarbon mobility. The dissolution of injected gas into the aqueous phase can also affect the gas flooding recovery because it reduces the amount of gas available to contact oil. This is more important in CO₂ flooding as the solubility of CO₂ in brine is much higher than hydrocarbons. In this research, we developed efficient and fast multi-phase equilibrium calculation algorithms to model phase behavior of asphaltenes and the aqueous phase in the compositional simulation of gas floods. The PC-SAFT equation of state is implemented in the UTCOMP simulator to model asphaltene precipitation. The additional computational time of PC-SAFT is substantially decreased by improving the root finding algorithm and calculating the derivatives analytically. A deposition and wettability alteration model is then integrated with the thermodynamic model to simulate dynamics of precipitated asphaltenes. Asphaltene deposition is shown to occur with pressure depletion around the production well and/or with gas injection in the reservoir domain that is swept by injected gas. It is observed that the profile of the damaged area by asphaltene deposition depends on the reservoir fluid. A general strategy is proposed to model the phase behavior of CO₂/hydrocarbon/water systems where four equilibrium phases exist. The developed four-phase reduced flash algorithm is used to investigate the effect of introducing water on the phase behavior of CO₂/hydrocarbon mixtures. The results show changes in the phase splits and saturation pressures by adding water to these CO₂/hydrocarbon systems. We used a reduced flash approach to reduce the additional computational time of the four-phase flash calculations,. The results show a significant speed-up in flash calculations using the reduced method. The computational advantage of the reduced method increases rapidly with the number of phases and components. We also decreased the computational time of the equilibrium calculations in UTCOMP by changing the sequential steps in the flash calculation where it checks the previous time-step results as the initial guess for the current time-step. The improved algorithm can skip a large number of flash calculation and stability analyses without loss of accuracy. / text
26

Development of a non-isothermal compositional reservoir simulator to model asphaltene precipitation, flocculation, and deposition and remediation

Darabi, Hamed 25 June 2014 (has links)
Asphaltene precipitation, flocculation, and deposition in the reservoir and producing wells cause serious damages to the production equipment and possible failure to develop the reservoirs. From the field production prospective, predicting asphaltene precipitation, flocculation, and deposition in the reservoir and wellbore may avoid high expenditures associated with the reservoir remediation, well intervention techniques, and field production interruption. Since asphaltene precipitation, flocculation, and deposition strongly depend on the pressure, temperature, and composition variations (e.g. phase instability due to CO2 injection), it is important to have a model that can track the asphaltene behavior during the entire production system from the injection well to the production well, which is absent in the literature. Due to economic concerns for asphaltene related problems, companies spend a lot of money to design their own asphaltene inhibition and remediation procedures. However, due to the complexity and the lack of knowledge on the asphaltene problems, these asphaltene inhibition and remediation programs are not always successful. Near-wellbore asphaltene inhibition and remediation techniques can be divided into two categories: changing operating conditions, and chemical treatment of the reservoir. Although, the field applications of these procedures are discussed in the literature, a dynamic model that can handle asphaltene inhibition and remediation in the reservoir is missing. In this dissertation, a comprehensive non-isothermal compositional reservoir simulator with the capability of modeling near-wellbore asphaltene inhibition and remediation is developed to address the effect of asphaltene deposition on the reservoir performance. This simulator has many additional features compared to the available asphaltene reservoir simulators. We are able to model asphaltene behavior during primary, secondary, and EOR stages. A new approach is presented to model asphaltene precipitation and flocculation. Adsorption, entrainment, and pore-throat plugging are considered as the main mechanisms of the asphaltene deposition. Moreover, we consider porosity, absolute permeability, and oil viscosity reductions due to asphaltene. It is well known that the asphaltene deposition on the rock surface changes the wettability of the rock towards oil-wet condition. Although many experiments in the literature have been conducted to understand the physics underlying wettability alteration due to asphaltene deposition, a comprehensive mathematical model describing this phenomenon is absent. Based on the available experimental data, a wettability alteration model due to asphaltene deposition is proposed and implemented into the simulator. Furthermore, the reservoir simulator is coupled to a wellbore simulator to model asphaltene deposition in the entire production system, from the injection well to the production well. The coupled reservoir/wellbore model can be used to track asphaltene deposition, to diagnose the potential of asphaltene problems in the wellbore and reservoir, and to find the optimum operating conditions of the well that minimizes asphaltene problems. In addition, the simulator is capable of modeling near-wellbore asphaltene remediation using chemical treatment. Based on the mechanisms of the asphaltene-dispersant interactions, a dynamic modeling approach for the near-wellbore asphaltene chemical treatments is proposed and implemented in the simulator. Using the dynamic asphaltene remediation model, we can optimize the asphaltene treatment plan to reduce asphaltene related problems in a field. The results of our simulations show that asphaltene precipitation, flocculation, and deposition in the reservoir and wellbore are dynamic processes. Many parameters, such as oil velocity, wettability alteration, pressure, temperature, and composition variations influence the trend of these processes. In the simulation test cases, we observe that asphaltene precipitation, flocculation, and deposition can occur in primary production, secondary production, or EOR stages. In addition, our results show that the wettability alteration has the major effect on the performance of the reservoir, comparing to the permeability reduction. During CO2 flooding, asphaltene precipitation occurs mostly at the front, and asphaltene deposition is at its maximum close to the reservoir boundaries where the front velocity is at its minimum. In addition, the results of the coupled reservoir/wellbore simulator show that the behavior of asphaltene in the wellbore and reservoir are fully coupled with each other. Therefore, a standalone reservoir or wellbore simulator is not able to predict the asphaltene behavior properly in the entire system. Finally, we show that the efficiency of an asphaltene chemical treatment plan depends on the type of dispersant, amount of dispersant, soaking time, number of treatment jobs, and the time period between two treatment jobs. / text
27

Hydrocarbon recovery from waste streams of oil sands processing

Thomas, Tenny Unknown Date
No description available.
28

Flocculation of silica particles in a model oil solution: Effect of adsorbed asphaltene

Zahabi, Atoosa Unknown Date
No description available.
29

Hydrocarbon recovery from waste streams of oil sands processing

Thomas, Tenny 06 1900 (has links)
Bitumen recovery by the water-based extraction process produces waste streams known as tailings. When discharged into the tailing ponds, the coarse solids in the tailings stream settle out quickly, while the fine solids accumulate over years of settling to a solids content of 30-35% by weight. The formed fluid fine solids sludge, known as mature fine tailings (MFT), traps 1-3% by weight hydrocarbons within its stable slurry structure. The remediation of these mature fine tailings is one of the major challenges facing the oil sands industry. This study was intended to investigate the recovery of residual hydrocarbons in the MFT by froth flotation process. Using a laboratory Denver flotation cell operated in a batch mode, the effect of MFT dilution ratio by process water or tap water, the flotation hydrodynamics and aeration rate on hydrocarbon recovery kinetics was studied. It was found that at 1:2 dilution by weight of the MFT with process water, increasing aeration rate has a more favourable effect on recovering more than 85% of the hydrocarbons from the MFT. The hydrocarbon-rich froth produced was treated by naphtha and was found to produce a hydrocarbon product similar to diluted bitumen obtained in bitumen extraction process, suitable for upgrading. Similar approach was applied to the hydrocarbon-rich tailings from the Tailings Solvent Recovery Unit of paraffinic froth treatment. Satisfactory recovery of hydrocarbons from the MFT was obtained using a flotation column operated in a continuous mode, confirmed the results obtained from the batch tests. The tailings produced from the continuous flotation experiments were treated with polymer flocculants such as Magnafloc-1011 and Al-PAM to study the effect of hydrocarbon recovery on the remediation of the MFT. The results from initial tests showed that both flocculants were not as effective on flocculating MFT solids following the recovery of hydrocarbons by froth flotation. / in Chemical Engineering
30

Estudo de agregação em asfaltenos por Ressonância Magnética Nuclear de Alto Campo

Oliveira, Emanuele Catarina da Silva 25 March 2013 (has links)
Made available in DSpace on 2016-12-23T14:41:50Z (GMT). No. of bitstreams: 1 Emanuele Catarina da Silva Oliveira.pdf: 3488830 bytes, checksum: fc0d45235f94ffa597f9bb41f45af330 (MD5) Previous issue date: 2013-03-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Heavy crude oils have attracted a growing interest from oil industries around the world. In this scenario, asphaltenes, which are molecules known for their low reactivity and high molecular weight, have received special attention in recent decades, due to the problems they cause during oil processing. In an effort to minimize these problems, researchers have increasingly looked for a better understanding of aspects such as molecular structure, stability and physicochemical properties of asphaltenes, as well as for the development of methods to prevent their unwanted precipitation. In recent decades, nuclear magnetic resonance (NMR) has been widely used as a tool for the study of petroleum and its derivatives. The analysis of 1H and 13C NMR spectra allows the direct determination of a series of structural parameters such as the fractions of aromatic carbons and of carbon atoms in alkyl chains. Diffusion-ordered NMR spectroscopy (DOSY), which is based on the results of pulsed-field gradient (PFG) experiments, is a new developed NMR technique highly useful for the elucidation of complex mixtures. This work sought to identify the differences in average molecular parameters of asphaltenes from national crudes and to correlate them with the physicochemical properties of the asphaltene and of the original crude. The aim was also to investigate and to compare the asphaltenes among themselves, using data such as diffusion coefficient, concentration of these compounds in the oil and state of aggregation. Extraction and quantification of the amount of asphaltenes were performed using ASTM D6560-00 standard and the characterization of the asphaltenes was performed using the following analytical techniques: elemental analysis, atomic absorption spectrometry, mass spectrometry, high-resolution 1H and 13C NMR and DOSY. Significant changes were observed in almost all studied parameters. To study the asphaltene aggregation behavior using DOSY, the asphaltenes were diluted in various concentrations of deuterated toluene and the DOSY spectra were correlated with their respective states of aggregation. The diffusion properties were highly dependent on the concentration and type of oil from which the asphaltene was extracted / Os petróleos pesados são de grande interesse das indústrias petroleiras ao redor do mundo. Com isso, os asfaltenos, moléculas conhecidas por sua baixa reatividade e alto peso molecular, têm recebido uma atenção especial nas ultimas décadas, devido aos problemas que causam durante o processamento do óleo. Buscando minimizar estes problemas, pesquisadores têm investido cada vez mais no conhecimento da estrutura molecular e estabilidade dos asfaltenos, no entendimento de suas propriedades físico-químicas e no desenvolvimento de metodologias que impeçam sua precipitação indesejada. Nas últimas décadas, a ressonância magnética nuclear (RMN) tem sido amplamente utilizada como ferramenta no estudo de petróleos e seus derivados. A obtenção de espectros de RMN de 1H e 13C permite a determinação direta de uma série de parâmetros estruturais, tais como a fração de carbonos aromáticos e de carbonos ligados em uma cadeia alquílica. O desenvolvimento de novas técnicas de RMN, como a espectroscopia de RMN ordenada pela difusão (DOSY), baseada na sequência de gradiente de campo pulsado (PFG), têm se mostrado excelentes ferramentas na elucidação de misturas complexas. Neste trabalho, procurou-se identificar as diferenças observadas nos parâmetros moleculares médios dos asfaltenos provenientes de petróleos nacionais, bem como correlacioná-las com as propriedades físico-químicas do próprio asfalteno e do óleo de origem. Pretende-se, ainda, investigar e comparar os asfaltenos, a partir de dados de coeficiente de difusão, concentração desses compostos no óleo e forma de agregação. A extração e quantificação do teor de asfaltenos foram realizadas utilizando-se a norma ASTM D6560-00 e a caracterização dos asfaltenos foi realizada através das técnicas analíticas de: análise elementar, espectrometria de absorção atômica, espectrometria de massas de alta resolução, RMN de 1H e 13C e, RMN DOSY. Foram observadas modificações significativas em praticamente todos os parâmetros estudados. No estudo do comportamento de agregação com a técnica RMN DOSY os asfaltenos foram diluídos em concentrações diferentes de tolueno deuterado e os espectros correlacionados com os seus respectivos estados de agregação. As propriedades de difusão se mostraram altamente dependentes da concentração e do tipo de óleo utilizado para a obtenção dos asfaltenos

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