Estudo de sistemas microemulsionados utilizando água do mar na recuperação avançada de petróleo

Petroleum exists in the nature in certain underground formations where it is adsorbed into the rocks pores. For the conventional recovery methods usually only 30% of the oil is extracted and this can be credited, basically, to three aspects: high viscosity of the oil, geology of the formation and high interfacial tensions between the reservoir s fluids. The enhanced recovery methods use the injection of a fluid or fluids mixture in a reservoir to act in points where the conventional process didn't reach the recovery rates. Microemulsion flooding, considered an enhanced method, has the purpose to desorb the oil from the rock formation and to attain an efficient displacement of the oil emulsion. With this in mind, this work was accomplished with two main objectives: the study of the parameters effect that influence a microemulsified system (surfactant and cosurfactant types, C/S rate and salinity) and the evaluation of displacement efficiency with the microemulsions that showed stability in the rich aqueous area. For the analyzed parameters it was chose the microemulsions composition used in the recovery stage: 25% water, 5% kerosene, 46.7% of butanol as cosurfactant and 23.3% of BC or SCO cosurfactant. The core plugs of Assu and Botucatu sandstones were appraised in porosity and permeability tests and then submitted to the steps of saturation with seawater and oil, conventional recovery with water and enhanced recovery with the selected microemulsions. The Botucatu sandstone presented better recovery parameters, and the microemulsion composed with BS surfactant had larger recovery efficiency (26.88%)

Microemulsões aplicadas ao tratamento de Óleos isolantes

Naphthenic lubricating oils are used in transformers with the purpose of promoting electrical insulation and dissipating heat. The working temperature range of these oils typically lies between 60°C and 90°C and their useful life is 40 years in average. In that temperature range, the oils are decomposed during operation, whereby a small fraction of polar compounds are formed. The presence of these compounds may induce failure and loss of physical, chemical and electrical properties of the oil, thus impairing the transformer operation. By removing these contaminants, one allows the oxidized insulating oil to be reused without damaging the equipment. In view of this, an investigation on the use of surfactants and microemulsions as extracting agents, and modified diatomite as adsorbent, has been proprosed in this work aiming to remove polar substances detected in oxidized transformer oils. The extraction was carried out by a simple-contact technique at room temperature. The system under examination was stirred for about 10 minutes, after which it was allowed to settle at 25°C until complete phase separation. In another experimental approach, adsorption equilibrium data were obtained by using a batch system operating at temperatures of 60, 80 and 100°C. Analytical techniques involving determination of the Total Acidity Number (TAN) and infrared spectrophotometry have been employed when monitoring the decomposition and recovery processes of the oils. The acquired results indicated that the microemulsion extraction system comprising Triton® X114 as surfactant proved to be more effective in removing polar compounds, with a decrease in TAN index from 0.19 to 0.01 mg KOH/g, which is consistent with the limits established for new transformer oils (maximal TAN = 0.03 mg KOH/g). In the adsorption studies, the best adsorption capacity values were as high as 0.1606 meq.g/g during conventional adsoprtion procedures using natural bauxite, and as high as 0.016 meq.g/g for the system diatomite/Tensiofix® 8426. Comparatively in this case, a negative effect could be observed on the adsorption phenomenon due to microemulsion impregnation on the surface of the diatomite

Estudo de uma coluna de absorção recheada para desidratação do gás natural utilizando microemulsão como absorvente

During natural gas processing, water removal is considered as a fundamental step in that combination of hydrocarbons and water favors the formation of hydrates. The gas produced in the Potiguar Basin (Brazil) presents high water content (approximately 15000 ppm) and its dehydration is achieved via absorption and adsorption operations. This process is carried out at the Gas Treatment Unit (GTU) in Guamaré (GMR), in the State of Rio Grande do Norte. However, it is a costly process, which does not provide satisfactory results when water contents as low as 0.5 ppm are required as the exit of the GTU. In view of this, microemulsions research is regarded as an alternative to natural gas dehydration activities. Microemulsions can be used as desiccant fluids because of their unique proprieties, namely solubilization enhancement, reduction in interfacial tensions and large interfacial area between continuous and dispersed phases. These are actually important parameters to ensure the efficiency of an absorption column. In this work, the formulation of the desiccant fluid was determined via phases diagram construction, employing there nonionic surfactants (RDG 60, UNTL L60 and AMD 60) and a nonpolar fluid provided by Petrobras GMR (Brazil) typically comprising low-molecular weight liquid hydrocarbons ( a solvent commonly know as aguarrás ). From the array of phases diagrams built, four representative formulations have been selected for providing better results: 30% RDG 60-70% aguarrás; 15% RDG 60-15% AMD 60-70% aguarrás, 30% UNTL L60-70% aguarrás, 15% UNTL L60-15% AMD 60-70% aguarrás. Since commercial natural gas is already processed, and therefore dehydrated, it was necessary to moister some sample prior to all assays. It was then allowed to cool down to 13ºC and interacted with wet 8-12 mesh 4A molecular sieve, thus enabling the generation of gas samples with water content (approximately 15000 ppm). The determination of the equilibrium curves was performed based on the dynamic method, which stagnated liquid phase and gas phase at a flow rate of 200 mL min-1. The hydrodynamic study was done with the aim of established the pressure drop and dynamic liquid hold-up. This investigation allowed are to set the working flow rates at 840 mL min-1 for the gas phase and 600 mLmin-1 for the liquid phase. The mass transfer study indicated that the system formed by UNTL L60- turpentine-natural gas the highest value of NUT

Desenvolvimento de tensoativos e sistemas microemulsionados para recuperação de petróleo

The high concentration of residual oil is one of the greatest problems found in petroleum mature fields. In these reservoirs, different enhanced oil recovery methods (EOR) can be used, highlighting the microemulsion injection. The microemulsion has showed to be efficient in petroleum recovery due to its ability to promote an efficient displacement of the petroleum, acting directly in the residual oil. In this way, this research has as objective the study of microemulsion systems obtained using a commercial surfactant (TP), determining microemulsion thermal stabilities and selecting points inside the pseudoternary phases diagram, evaluating its efficiencies and choosing the best system, that has the following composition: TP as surfactant (S), isopropyl alcohol as co-surfactant (C), kerosene as oil phase, water as aqueous phase, C/S ratio = 1, and 5% sodium p-toluenesulfonate as hydrotope; being observed the following parameters for the selection of the best pseudoternary phases diagram: C/S ratio, co-surfactant nature and addition of hydrotope to the system. The efficiency in petroleum recovery was obtained using two sandstone formation systems: Assu and Botucatu. The study of thermal stabilities showed that as the concentration of active matter in the system increased, the thermal stability also increased. The best thermal stability was obtained using point F (79.56 0C). The system that presented the best recovery percentile between the three selected (3) was composed by: 70% C/S, 2% kerosene and 28% water, with 94% of total recovery efficiency and 60% with microemulsion injection, using the Botucatu formation, that in a general way presented greater efficiencies as compared with the Assu one (81.3% of total recovery efficiency and 38.3% with microemulsion injection)

Estudo da cristalização de parafinas em sistemas solventes/tensoativos/água

The WAT is the temperature at the beginning of the appearance of wax crystals. At this temperature the first wax crystals are formed by the cooling systems paraffin / solvents. Paraffins are composed of a mixture of saturated hydrocarbons of high molecular weight. The removal of petroleum from wells and the production lines means a surcharge on produced oil, thus solubilize these deposits formed due to modifications of thermodynamics has been a constant challenge for companies of oil exploration. This study combines the paraffin solubilization by microemulsion systems, the determination of WAT systems paraffin / solvent and performance of surfactant in reducing the crystallization. We used the methods: rheological and the photoelectric signal, validating the latter which was developed to optimize the data obtained due to sensitivity of the equipment used. Methods developed for description of wax precipitation are often in poor agreement with the experimental data, they tend to underestimate the amount of wax at temperatures below the turbidity point. The Won method and the Ideal solution method were applied to the WAT data obtained in solvent systems, best represented by the second interaction of Won method using the solvents naphtha, hexane and LCO. It was observed that the results obtained by WAT photoelectric signal when compared with the viscosity occur in advance, demonstrating the greatest sensitivity of the method developed. The ionic surfactant reduced the viscosity of the solvent systems as it acted modifying the crystalline structure and, consequently, the pour point. The curves show that the WAT experimental data is, in general, closer to the modeling performed by the method of Won than to the one performed by the ideal solution method, because this method underestimates the curve predicting the onset of paraffin hydrocarbons crystallization temperature. This occurs because the actual temperature measured was the crystallization temperature and the method proposes the fusion temperature measurement.

Formulação de novos combustíveis base diesel: avaliação de desempenho e emissões

The industry, over the years, has been working to improve the efficiency of diesel engines. More recently, it was observed the need to reduce pollutant emissions to conform to the stringent environmental regulations. This has attached a great interest to develop researches in order to replace the petroleum-based fuels by several types of less polluting fuels, such as blends of diesel oil with vegetable oil esters and diesel fuel with vegetable oils and alcohol, emulsions, and also microemulsions. The main objective of this work was the development of microemulsion systems using nonionic surfactants that belong to the Nonylphenols ethoxylated group and Lauric ethoxylated alcohol group, ethanol/diesel blends, and diesel/biodiesel blends for use in diesel engines. First, in order to select the microemulsion systems, ternary phase diagrams of the used blends were obtained. The systems were composed by: nonionic surfactants, water as polar phase, and diesel fuel or diesel/biodiesel blends as apolar phase. The microemulsion systems and blends, which represent the studied fuels, were characterized by density, viscosity, cetane number and flash point. It was also evaluated the effect of temperature in the stability of microemulsion systems, the performance of the engine, and the emissions of carbon monoxide, nitrogen oxides, unburned hydrocarbons, and smoke for all studied blends. Tests of specific fuel consumption as a function of engine power were accomplished in a cycle diesel engine on a dynamometer bench and the emissions were evaluated using a GreenLine 8000 analyzer. The obtained results showed a slight increase in fuel consumption when microemulsion systems and diesel/biodiesel blends were burned, but it was observed a reduction in the emission of nitrogen oxides, unburned hydrocarbons, smoke index and f sulfur oxides

Utilização de microemulsões como agentes modificadores de superfícies para remoção de íons metálicos

The heavy metals are used in many industrial processes and when discharged to the environment can cause harmful effects to human, plants and animals. The adsorption technology has been used as an effective methodology to remove metallic ions. The search for new adsorbents motivated the development of this research, accomplished with the purpose of removing Cr (III) from aqueous solutions. Diatomite, chitosan, Filtrol 24TM and active carbon were used as adsorbents. To modify the adsorbent surface was used a bicontinuous microemulsion composed by water (25%), kerosene (25%), saponified coconut oil (10%) and as co-surfactant isoamyl or butyl alcohols (40%). With the objective of developing the best operational conditions the research started with the surfactant synthesis and after that the pseudo-ternary diagrams were plotted. It was decided to use the system composed with isoamyl alcohol as co-surfactant due its smallest solubility in water. The methodology to impregnate the microemulsion on the adsorbents was developed and to prepare each sample was used 10 g of adsorbent and 20 mL of microemulsion. The effect of drying time and temperature was evaluated and the best results were obtained with T = 65 ºC and t = 48 h. After evaluating the efficiency of the tested adsorbents it was decided to use chitosan and diatomite. The influence of the agitation speed, granule size, heavy metal synthetic solution concentration, pH, contact time between adsorbent and metal solution, presence or not of NaCl and others metallic ions in the solution (copper and nickel) were evaluated. The adsorption isotherms were obtained and Freundlich and Langmuir models were tested. The last one correlated better the data. With the purpose to evaluate if using a surfactant solution would supply similar results, the adsorbent surface was modified with this solution. It was verified that the adsorbent impregnated with a microemulsion was more effective than the one with a surfactant solution, showing that the organic phase (kerosene) was important in the heavy metal removal process. It was studied the desorption process and verified that the concentrated minerals acids removed the chromium from the adsorbent surface better than others tested solutions. The treatment showed to be effective, being obtained an increase of approximately 10% in the chitosan s adsorption capacity (132 mg of Cr3+ / g adsorbent), that was already quite efficient, and for diatomite, that was not capable to remove the metal without the microemulsion treatment, it was obtained a capacity of 10 mg of Cr3+ / g adsorbent, checking the applied treatment effectiveness

Sistemas microemulsionados aplicados à remoção da cor de efluente têxtil

Effluent color resulting from textile dyeing processes has been one of the biggest environmental problems faced by the textile industry. In particular, reactive dyes are highly resistant to conventional wastewater treatment methods. New technologies have been contemplated, some of which have been applied in industrial treatment plants, but color removal has not been efficiently attained. Since microemulsion systems provide good results in heavy metals and proteins extraction processes, their use in dyes extraction has been suggested and investigated. In this work, a real textile wastewater from an exhaustion dyebath has been treated, which contains the following reactive dyes: Procion Yellow H-E4R (CI Reactive Yellow 84), Procion Blue H-ERD (CI Reactive Blue 160) and Procion Red H-E3B (CI Reactive Red 120), in addition to auxiliary compounds normally found in dyeing processes with reactive dyes. The dyes Remazol Blue RR and Remazol Turquoise Blue G (Reactive Blue 21) have also been examined in view of the presence of heavy metals in these molecules. The microemulsion system comprised dodecyl ammonium chloride (as a cationic surfactant), water or wastewater as aqueous phase, kerosene as oil phase, and one of the following alcohols as cosurfactant: isoamyl alcohol, n-butyl alcohol and n-octyl alcohol. The pseudo-ternary diagrams were constructed in order to define Winsor s equilibrium regions. The influence of parameters such as pH, C/S (cosurfactant/surfactant) ratio, distribution coefficient, initial dye concentration, salinity, temperature, phases relative amounts, loading capacity of the microemulsion phase and dye reextraction rate has also been investigated. An experimental planning (Scheffé Net) was used to optimize the extraction process. The removal of color and metals reached levels as high as 99%

Estudo da influência de tensoativos em sistemas microemulsionados na extração de gálio e alumínio

Gallium is an important material used in the electronic industry whose demand in the world market is increasing in view of its potential applications. A selective technique is required to allow for the production of the metal, separated from aluminium. Due to the fact that microemulsions constitute an attractive alternative to metal extraction procedures, microemulsified systems have been employed as gallium-selective extraction agents. Two surfactants have been synthesized: sodium 12-N,N-diethylamino-9,10-dihydroxyestearate (AMINE) and saponified coconut oil (SCO), both produced from raw materials readily available in Northeastern Brazil. Also, the commercial extraction agent KELEX-100, conventionally used with the same purpose, has been used in this work for comparison. The optimization of the extraction process with microemulsions was carried out by investigating the influence of some parameters, namely the type of cosurfactant, the cosurfactant/surfactant (C/S) ratio, the pH and concentration of metals in the aqueous phase. Pseudoternary diagrams, which are representative of the microemulsified systems under study, have been constructed in order to establish the boundaries of the regions where the several Winsor systems are formed. An experimental planning methodology (Scheffé Net) has been used to optimize the extraction. The extraction percentage values were as high as 100% for gallium and 99.99% for aluminium for the system with KELEX-100; 96.6% for gallium and 98.8% for aluminium for the system containing AMINE; and 88% for gallium and 85% for aluminium for the system with SCO. The microemulsified system chosen for presenting the best results in gallium extraction was composed by SCO/isoamyl alcohol/kerosene/Bayer licquor with a C/S ratio of 28 and pH of the original aqueous phase of 6.0. The selectivity that has not been observed in the extraction stage was accomplished in the reextraction process using HCl. For the KELEX-100 system, gallium was reextracted at 100% with 6M HCl and aluminium was reextracted at 100% with 0.8M HCl. For the AMINE system, the reextraction percentages were also 100% for both metals, using 6M HCl for gallium and 0.5M HCl for aluminium. On the other hand, the reextraction percentages for the system with SCO were as high as 84% for gallium and 92% for aluminium, with HCl in the same concentrations as those used in the AMINE system. Finally, an optimized system was applied in the gallium extraction process employing a reciprocating perforated-plates extractor. As a result, the metal content was extracted at a recovery rate of 95% for gallium and 97% for aluminium

Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões

The diesel combustion form sulfur oxides that can be discharged into the atmosphere as particulates and primary pollutants, SO2and SO3, causing great damage to the environment and to human health. These products can be transformed into acids in the combustion chamber, causing damage to the engines. The worldwide concern with a clean and healthy environment has led to more restrictive laws and regulations regulating the emission levels of pollutants in the air, establishing sulfur levels increasingly low on fuels. The conventional methods for sulfur removal from diesel are expensive and do not produce a zero-level sulfur fuel. This work aims to develop new methods of removing sulfur from commercial diesel using surfactants and microemulsion systems. Its main purpose is to create new technologies and add economic viability to the process. First, a preliminary study using as extracting agent a Winsor I microemulsion system with dodecyl ammonium chloride (DDACl) and nonyl phenol ethoxylated (RNX95) as surfactant was performed to choose the surfactant. The RNX95 was chosen to be used as surfactant in microemulsioned systems for adsorbent surface modification and as an extracting agent in liquid-liquid extraction. Vermiculite was evaluated as adsorbent. The microemulsion systems applied for vermiculite surface modification were composed by RNX95 (surfactant), n-butanol (cosurfactant), n-hexane (oil phase), and different aqueous phases, including: distilled water (aqueous phase),20ppm CaCl2solution, and 1500ppm CaCl2solution. Batch and column adsorption tests were carried out to estimate the ability of vermiculite to adsorb sulfur from diesel. It was used in the experiments a commercial diesel fuel with 1,233ppm initial sulfur concentration. The batch experiments were performed according to a factorial design (23). Two experimental sets were accomplished: the first one applying 1:2 vermiculite to diesel ratio and the second one using 1:5 vermiculite to diesel ratio. It was evaluated the effects of temperature (25°C and 60°C), concentration of CaCl2in the aqueous phase (20ppm and 1500ppm), and vermiculite granule size (65 and 100 mesh). The experimental response was the ability of vermiculite to adsorb sulfur. The best results for both 1:5 and 1:2 ratios were obtained using 60°C, 1500ppm CaCl2solution, and 65 mesh. The best adsorption capacities for 1:5 ratio and for 1:2 ratio were 4.24 mg sulfur/g adsorbent and 2.87 mg sulfur/g adsorbent, respectively. It was verified that the most significant factor was the concentration of the CaCl2 solution. Liquid-liquid extraction experiments were performed in two and six steps using the same surfactant to diesel ratio. It was obtained 46.8% sulfur removal in two-step experiment and 73.15% in six-step one. An alternative study, for comparison purposes, was made using bentonite and diatomite asadsorbents. The batch experiments were done using microemulsion systems with the same aqueous phases evaluated in vermiculite study and also 20ppm and 1500 ppm BaCl2 solutions. For bentonite, the best adsorption capacity was 7.53mg sulfur/g adsorbent with distilled water as aqueous phase of the microemulsion system and for diatomite the best result was 17.04 mg sulfur/g adsorbent using a 20ppm CaCl2solution. The accomplishment of this study allowed us to conclude that, among the alternatives tested, the adsorption process using adsorbents modified by microemulsion systems was considered the best process for sulfur removal from diesel fuel. The optimization and scale upof the process constitutes a viable alternative to achieve the needs of the market

Síntese e caracterização de tensoativos e estudo de equilíbrio de fase dos sistemas CnH2n+2/H2O/CnH2n+1COONa/But-OH

The growing utilization of surfactants in several different areas of industry has led to an increase on the studies involving solutions containing this type of molecules. Due to its amphiphilic nature, its molecule presents one polar part and one nonpolar end, which easily interacts with other molecules, being able to modify the media properties. When the concentration in which its monomers are saturated, the airliquid system interface is reached, causing a decrease in interfacial tension. The surfactants from pure fatty acids containing C8, C12 and C16 carbonic chains were synthesized in an alcoholic media using sodium hydroxide. They were characterized via thermal analysis (DTA and DTG) and via infrared spectroscopy, with the intention of observing their purity. Physical and chemical properties such as superficial tension, critical micelle concentration (c.m.c), surfactant excess on surface and Gibbs free energy of micellization were determined in order to understand the behaviour of these molecules with an aqueous media. Pseudo-ternary phase diagrams were obtained aiming to limit the Windsor equilibria conditions so it could be possible to understand how the surfactants carbonic chain size contributes to the microemulsion region. Solutions with known concentrations were prepared to study how the surfactants can influence the dynamic light scattering spectroscopy (DLS) and how the diffusion coefficient is influenced when the media concentration is altered. The results showed the variation on the chain size of the studied surfactant lipophilic part allows the conception of surfactants with similar interfacial properties, but dependent on the size of the lipophilic part of the surfactant. This variation causes the surfactant to have less tendency of microemulsionate oil in water. Another observed result is that the n-alcanes molecule size promoted a decrease on the microemulsion region on the obtained phase diagrams

On the incorporation of the non-steroidal anti-inflammatory naproxen into cationic O/W microemulsions

Microemulsions (ME) containing hexadecyltrimethylammonium bromide (HTAB)/ethanol as surfactant, isopropylmyristate (IM) or butylstearate (BS) as oil phase and aqueous buffer were studied. Pseudo-ternary phase diagrams of the investigated systems were obtained at constant surfactant/cosurfactant molar ratio (1:5) by titration in order to characterize the proportions between the components to obtain clear systems. Oil in water microemulsions were prepared in a wide range of phase volume (phi). UV-vis absorption spectra of naproxen at pH 5.5 showed that the solubility of Np increases significantly in the presence of O/W ME in high phase volumes. For both, IM and BS microemulsions, the dynamic light scattering experiments showed that the size of the oil droplets remains constant in low values of phi, increasing abruptly in high phi values. Phase solubility study revealed that for both IM and BS microemulsions, the drug incorporation followed a straight-line profile in all range of phi. The data could be analyzed through the phase-separation model and the association constants (K) calculated varied from 27 to 90 M-1, depending on the pH and on the microemulsion oil phase. (c) 2005 Elsevier B.V. All rights reserved.

Nanotechnology-based Drug Delivery Systems for Dermatomycosis Treatment

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Rheological, Mechanical and Adhesive Properties of Surfactant-Containing Systems Designed as a Potential Platform for Topical Drug Delivery

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Thermal characterization of solid lipid nanoparticles containing praziquantel

Solid lipid nanoparticles (SLNs), loaded and unloaded with praziquantel (PRZ-load SLN and PRZ-unload SLN) were prepared by two different procedures: (a) oil-in-water hot microemulsion method, obtaining at 70 degrees C an optically transparent blend composed of surfactant, co-surfactant, and water; and (b) oil-in-water microemulsion method, dissolving the lipid in an immiscible organic solvent, emulsified in water containing surfactants and co-surfactant, and then evaporated under reduced pressure at 50 degrees C. The mean diameter, polydispersity index (PdI), and zeta potential were 187 to 665 nm, 0.300 to 0.655, and -25 to -28 mV respectively, depending on the preparation method. The components, binary mixture, SLNs loaded and unloaded with PRZ, and physical mixture were evaluated by differential scanning calorimetry (DSC) and thermogravimetry (TG). The non-isothermal isoconversional Flynn-Wall-Ozawa method was used to determine the kinetic parameters associated with the thermal decomposition of the samples. The experimental data indicated a linear relationship between the apparent activation energy E and the pre-exponential factor A, also called the kinetic compensation effect (KCE), allowing us to determine the stability with respect to the preparation method. Loading with PRZ increased the thermal stability of the SLNs.