O petróleo é produzido na forma de emulsão água em óleo e os asfaltenos são considerados os principais responsáveis pela estabilização dessas emulsões. O objetivo deste trabalho foi avaliar a influência de diferentes frações asfaltênicas sobre a estabilidade de emulsões modelo de petróleo (salmoura em asfaltenos/tolueno) e sobre a eficiência de desemulsificantes. A estabilidade das emulsões foi acompanhada pelo ensaio de garrafa, com e sem a adição de desemulsificante. Os resultados mostram que a amostra de asfaltenos com larga distribuição de polaridade promove maior estabilidade da emulsão do que a amostra com distribuição mais estreita e polaridade intermediária. Além disso, a eficiência do desemulsificante na separação das emulsões está diretamente relacionada à estabilidade original da emulsão. Resultados de tensão interfacial evidenciaram a eficiência de deslocamento dos asfaltenos pelos tensoativos desemulsificantes, o que ocorreu com maior eficiência para as emulsões contendo frações de asfaltenos com distribuição estreita e polaridade intermediária.

Crude oil is produced as water-in-oil emulsion, and asphaltenes have been considered the main responsible by their stabilization. The aim of this work was to evaluate the influence of the asphaltenes subfractions on the stability of petroleum model emulsions and on the efficiency of demulsifiers. Model water-in-oil emulsions were prepared: aqueous phase of brine and oil phase of asphaltenes in toluene. Different asphaltenes fractions were used. The emulsions' stability was assessed by the bottle test, with and without adding demulsifier. The results show that a sample of asphaltenes with broad polarity distribution promotes greater emulsion stability than a sample with narrow distribution and intermediate polarity. Besides this, the efficiency of demulsifiers in separating the emulsions is directly related to the original stability of the emulsion. Measurements of the interfacial tension revealed the efficiency of displacement of the asphaltenes by the demulsifiers, which occurred more efficiently for the emulsions containing asphaltenes fractions with narrow distribution and intermediate polarity.

Foi realizado um estudo para investigar a interação entre asfaltenos (em soluções de tolueno) e resinas (em soluções de n-heptano). Para entender melhor o tipo de interação entre essas frações, quantificou-se o consumo de resina quando asfaltenos (dissolvidos em tolueno) foram precipitados com uma solução de n-heptano contendo resina. Os resultados indicaram que a precipitação de asfaltenos ocorre juntamente com a redução na concentração de resina. Os perfis das isotermas de ligação indicaram que a saturação ocorreu em um caso, em quanto que o efeito cooperativo com posterior platô inicial foi observado para duas outras amostras. Estes resultados confirmaram a hipótese de que resinas podem adsorver em asfaltenos, mas não podem evitar floculação e precipitação de asfaltenos. Além disso, resultados de microcalorimetria sugeriram que a resina e asfalteno interagem por forças fracas de van der Waals. Estes resultados estão em contraste com a escola de pensamento predominante desde a década de 1940 que advoga que as resinas podem peptizar e estabilizar asfaltenos.

A study was carried out to investigate the interaction between asphaltenes (in toluene solutions) and resins (in n-heptane solutions). To better understand the type of interaction between these fractions, it was quantified the resin uptake when asphaltenes (dissolved in toluene) were precipitated by a resin-containing n-heptane solution. These results indicated the asphaltene precipitation occurs together with a reduction in the resin concentration. The binding isotherm profiles indicated that saturation occurred in one case, while collective association following an initial plateau was observed for the other two samples. These results confirmed the hypothesis that resins can adsorb on asphaltenes but cannot prevent asphaltenes from flocculating and precipitating. Furthermore, microcalorimetric results suggested that the resin and asphaltene interact by weak van der Waals forces. These results are in stark contrast with the school of thought prevalent since the 1940s that resins can peptize and stabilize asphaltenes.

The structure of the various asphaltenic subfractions found in crude oil was evaluated. For this purpose, C5 asphaltenes were extracted from an asphaltic residue using n-pentane as the flocculant solvent. The different subfractions were isolated from the C5 asphaltenes by the difference in solubility in different solvents. These were characterized by infrared spectroscopy, nuclear magnetic resonance, X-ray fluorescence, elementary analysis and mass spectrometry. The results confirmed that the subfractions extracted with higher alkanes had greater aromaticity and molar mass. However, small solubility variations between the subfractions were attributed mainly to the variation in the concentrations of cyclical hydrocarbon compounds and metals.

The objective of this work was to use the high-pressure homogenizer (HPH) to prepare stable oil/water nanoemulsions presenting narrow particle size distribution. The dispersions were prepared using nonionic surfactants based on ethoxylated ether. The size and distribution of the droplets formed, along with their stability, were determined in a Zetasizer Nano ZS particle size analyzer. The stability and the droplet size distribution in these systems do not present the significant differences with the increase of the processing pressure in the HPH). The processing time can promote the biggest dispersion in the size of particles, thus reducing its stability.

In this work, it was studied the behavior of the nonionic surfactant aqueous solutions, containing or not a hydrotropic agent, by resonance magnetic nuclear (NMR). We have studied monofunctional diblock copolymers of poly(propylene oxide-ethylene oxide) (R-PPO-PEO-OH, where R length is linear C4) as nonionic surfactant and sodium p-toluenesulfonate (NaPTS) as hydrotropic agent. The critical micelle concentration (CMC) of the aqueous copolymer solution was obtained from ¹H-NMR. The preliminary study of the interaction between the copolymer, under the unimer and micelle forms, and the hydrotrope, in aqueous solutions, was evaluated by ¹H-NMR and 13C-NMR.

O comportamento de sistemas aquosos contendo copolímeros dibloco monofuncionais de poli(óxido de etileno)-poli(óxido de propileno), bloqueados em uma das extremidades da cadeia com segmento hidrocarbônico linear, foi avaliado através de calorimetria exploratória diferencial (DSC). Transições endotérmicas foram observadas no aquecimento das soluções dos copolímeros e as temperaturas iniciais destas transições estão de acordo com os pontos de turvação dos copolímeros estudados. Nas curvas de resfriamento, são observadas duas transições, e quanto mais rápido é resfriada a solução de copolímero, melhor é observada a transição que deve estar relacionada à formação das micelas. A influência da presença de um agente hidrotrópico também foi avaliada em todas as soluções de copolímeros por meio do aumento no ponto de turvação com o aumento da concentração do agente hidrotrópico, visto que os picos endotérmicos foram deslocados para temperaturas mais altas.

The behavior of aqueous systems containing block copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), coupled to hydrocarbon groups, was evaluated by differential scanning calorimetry (DSC). Endothermic transitions in the copolymer solutions were observed under a linear heating rate and the initial temperatures of these transitions are in agreement with the cloud points of the copolymers studied. Two transitions were observed in the cooling curves; these transitions were better defined at faster cooling rates of the copolymer solutions which can be related to the micelles formation. The effect of the increasing concentration of the hydrotropic agent, sodium p-toluenesulfonate (NaPTS), in the copolymer solutions was observed by the increase in the cloud points given by the dislocation of the endothermic peaks to higher temperatures.