Phase transition and viscosity behavior of emulsified systems were studied after modifying their physicochemical formulation. Effects of concentration and nature of salts and n-alcohols, and water/oil relation on the rheological properties of emulsions were also studied. Pre-equilibrated systems were emulsified according to an agitation procedure, and the viscosity (cP) was measured at different shear rates ranging from 1 to 300 s-1. The phase behavior, as well as the emulsion type based on electrolytic conductivity, was observed. Several interpretations of the flow and viscosity curves of emulsions were made through the estimation of rheological parameters such as consistency index "k" and behavior index "n".

The phase behavior of an alcohol polyethoxylated surfactant with decane and dodecane oil phase varying the water proportion from 5 to 90% to determine compositions in which the formation of liquid crystals and microemulsions ocurred was investigated. Pseudoternary phase diagrams were built to represent the regions of liquid crystals, biphases and microemulsions. Polarized light optical microscopy was used for the analysis and characterization of the separate phases. The micrographs obtained showed characteristics of hexagonal and lamellar phases of liquid crystal, isotropic phases, microemulsions and vesicles. This study is important to propose hypothesis regarding the factors determining the formation and stability of phases composed by surfactant/oil/water systems.

The use of fatty acids (FAs) as amphiphiles is very important because they have a behaving similar to surfactants. The formulation for the preferential partition of these species was studied by varying the amount of salt at constant acid concentration. As the salt concentration increases, a Winsor I→III→II transition is observed for all the systems studied. Furthermore, the electrolyte concentration required to obtain the optimum formulation varies inversely with the chain length of the acid. The partition coefficient of the surfactant allows one to obtain thermodynamic information on the acid transfer process between the phases of the system.

Los crudos pesados presentan problemas en la deshidratación debido a la presencia de emulsiones estables, con un contenido de agua mayor a 1%. En este trabajo se propone la aplicación del calentamiento con radiación microondas (CMW) para favorecer la separación del agua emulsionada en un crudo pesado, como método alternativo al calentamiento convencional estándar (CCE). Los resultados obtenidos mostraron que ambos métodos son efectivos para la deshidratación del crudo ya que el contenido de agua fue menor de 1,0%, no obstante, la metodología aplicada en el método termoquímico empleando CMW requirió de menor tiempo de análisis comparado con el CCE, ventaja importante en la disminución de costos y en los análisis de campo en la industria petrolera.

The heavy crude oil presents problems in the dehydration due to the presence stable emulsions, with water content more than to 1.0%. In this work is proposed the application of microwaves heating (MWH) to favor the separation of emulsioned water in this crude oil, as alternative method to the standard conventional heating (SCH). The obtained results showed that both methods are effective for the crude oil dehydration since the content of water was smaller than 1.0%, nevertheless, the applied methodology in the thermal chemical methods using MWH required lower analysis time compared with the SCH, important advantage for the decrease of production costs and in the field analyses in the oil industry.

En el presente trabajo se estudiaron las propiedades tensoactivas de las fracciones obtenidas mediante degradación oxidativa asistida por microondas con peróxido de hidrógeno de dos ligninas de pino (LAA y LKM). Las reacciones fueron llevadas a cabo en recipientes cerrados, empleando diferentes cantidades de agente oxidante, en un horno microondas doméstico. Las reacciones se completaron rápidamente, generando agua como subproducto. Los productos de oxidación fueron caracterizados por espectroscopia UV-Vis y FTIR. Al compararlos con las muestras originales de lignina se observó una disminución de la absorción cerca de los 280 nm debido a la oxidación de los anillos aromáticos. En el análisis por FTIR se observó el aumento de las señales correspondientes a los grupos C=O entre 1.700-1.720 cm-1 y entre 1.650-1.700 cm-1 atribuidas a la oxidación de las cadenas laterales y de los anillos aromáticos, respectivamente. Esto último se evidenció por la disminución de la señal C=C aromática, alrededor de los 1.600 cm-1. Se comprobó la eficiencia y versatilidad de la radiación microondas para promover este tipo de reacciones. Las ligninas oxidadas mostraron un aumento de la tensión superficial debido a la aparición de nuevos grupos polares.

In this work the fractions obtained by microwave-assisted oxidative degradation with hydrogen peroxide of two pine lignins (LAA y LKM) and its tensoactive properties were studied. The reactions were carried out using different quantities of the oxidant agent in a domestic microwave oven in closed reactors. The reaction was completed quickly with the generation of water as by-product. The oxidation products were characterized by UV and FTIR spectroscopy. When comparing them with the original lignin samples in UV analysis, the absorption decreased near the 280nmdue to the oxidation of the aromatic rings. In the analysis by FTIR the signals corresponding to the groups C=O increased among 1,700-1,720 cm-1 and 1,650-1,700 cm-1 attributed to the oxidation of the lateral chains and aromatic rings, respectively. This results were evidenced because of the aromatic signal C=C around the 1,600 cm-1 decreased. It was proven the efficiency and versatility of the radiation microwaves to carry out this type of reactions. The surface tension of the oxidized lignin increased due the new hydrophilic groups.

Las emulsiones de crudo en agua se han utilizado para producir y transportar hidrocarburos pesados. En estudios anteriores se determinó que las emulsiones de crudo en agua preparadas con mezclas de surfactantes no-iónicos y aniónicos son más estables y menos viscosas que las emulsiones preparadas con un único surfactante, y que adicionando aminas de cadena corta se logra incrementar la estabilidad de dichas emulsiones. En este artículo se discute el efecto de aminas alifáticas de cadena corta en la estabilidad y las propiedades reológicas de emulsiones de crudo pesado en agua, preparadas a una relación crudo/agua 70/30. Se utilizaron surfactantes no-iónicos polietoxilados, tanto individualmente como mezclados con un surfactante aniónico del tipo aril benceno sulfonato. Se emplearon como co-surfactantes aminas alifáticas de 2, 4 y 6 átomos de carbono, tanto de cadena lineal como ramificada. Los resultados mostraron que las aminas primarias de cadena lineal producen emulsiones más estables y con mayor viscosidad que las emulsiones preparadas con aminas secundarias o terciarias de igual número de átomos de carbono. Se concluyó que las aminas alifáticas cortas son excelentes co-surfactantes, ya que estabilizan las emulsiones formadas en el sistema surfactante-agua-crudo.

The crude oil in water emulsions have been used to produce and to transport heavy hydrocarbons. More stability and less viscosity than the emulsions prepared with an only surfactant was obtained for the crude oil in water emulsions prepared with non-ionic and anionic surfactant mixtures, in previous studies. The stability of these emulsions could be increased, adding short chain amines. In this work, the effect of aliphatic short chain amines in the stability and the rheological properties of heavy crude oil in water emulsions, prepared at crude oil/water relationship of 70/30, is discussed. Polyethoxylated non-ionic surfactants were used, individually or in a mixture with an anionic surfactant of aryl benzene sulfonate type. Aliphatic short chain amines of 2, 4 and 6 atoms of carbon were used as co-surfactants, so much of lineal chain and ramified chain. The results showed that the primary amines of lineal chain produce more stable emulsions and with more viscosity that the emulsions prepared with secondary or tertiary amines of the same number of atoms of carbon. It was concluded that aliphatic short chain amines are excellent co-surfactants, because they stabilize micelles formed inside the system surfactant-water-crude oil.

En el presente trabajo se evaluaron formulaciones para emulsionar crudo pesado en agua, a una relación crudo/agua 70/30. Se utilizaron surfactantes no-iónicos y aniónicos, mientras que aminas de cadena corta se emplearon como co-surfactantes. Se evaluaron la estabilidad, la viscosidad, la conductividad, el tamaño promedio de gota y la distribución de tamaño promedio de gota. Se obtuvieron emulsiones estables para sistemas simples y múltiples, cuyas viscosidades son considerablemente menores a la viscosidad original del crudo, todas de fase externa agua y con una amplia zona de inversión. El tamaño mínimo promedio de gota obtenido fue de 23 mm, con distribuciones polidispersas, tanto unimodales como bimodales. Se concluyó que las mezclas de surfactantes no-iónicos y aniónicos originan una sinergia positiva incrementando la estabilidad de las emulsiones de crudo en agua, y que las aminas de cadena corta son excelentes co-surfactantes, ya que estabilizan las micelas formadas dentro del sistema surfactante-agua-crudo

In the present work, formulations to emulsify heavy crude oil in water, at crude oil/water relationship of 70/30, were evaluated. Non-ionic and anionic surfactants were used with amines of short chain as co-surfactants. Stability, viscosity, conductivity, drop size and size distribution, were evaluated. Stable emulsions were obtained with simple and multiple systems which smaller viscosities than the original crude oil, all them with external phases of water and “extended inversion zone”. The minimum drop size obtained was of 23 µm, with polydisperses distributions, unimodals and bimodals. It was concluded that non-ionic and anionic surfactants mixtures originate a positive synergy, increasing the stability of the crude oil emulsions, and as well as that short chain amines are excellent co-surfactants, because they stabilize micelles formed inside the surfactant-water-crude oil system

Diferentes fracciones de un crudo pesado soportado en alúmina neutra, ácida y básica, se aislaron aplicando extracción Soxhlet utilizando como solventes acetonitrilo, metanol, n-heptano, tolueno y tetrahidrofurano. Los surfactantes naturales (SN) de las fracciones con alúmina neutra se extrajeron usando mezclas de aceite y agua a diferentes pH. Las fracciones y SN aislados se caracterizaron utilizando espectrometría UV-Visible, infrarrojo, tensiometría y cromatografía de permeación de geles (GPC). Los resultados indicaron que la mayor cantidad de SN se obtuvo a pH 8 con una proporción agua/aceite 30:70. Utilizando tetrahidrofurano se logró extraer los SN retenidos en las alúminas ácida y básica con una recuperación entre 5 y 7%, las cuales fueron mayores a las obtenidas por la extracción líquido-líquido (entre 3 y 4%).

Different fractions of a heavy crude oil supported in neutral, acid and basic alumina, were isolated by Soxhlet extraction using solvent such as acetonitrile, methanol, n-heptane, toluene and tetrahydrofuran. The natural surfactants (SN) of the neutral fractions were extracted using mixtures of oil and water at different pH. The extracted fractions and isolated SN were characterized using UV-VIS and IR spectroscopy, tensiometry and gel permeation chromatography. The results indicate that the largest SN amount is obtained at pH 8 with a water/oil 30:70 ratio. Using tetrahydrofuran it was possible to extract the SN retained in the acid and basic alumina with a recovery between 5 and 7%, i.e. values similar to those obtained by liquid-liquid extraction (between 3 and 4%).