Asphaltene Self-Association: Modeling and Effect of Fractionation With A Polar Solvent

The self-association of asphaltenes in toluene is believed to occur step-wise, rather than by the formation of micelles. A number of step-wise models have been used to fit the calorimetric titration of asphaltenes in dried toluene solutions, with excellent results. All the models are based on chemical reactions equivalent to the ones found in polymerization. The study shows that the choice of the average properties of asphaltenes, such as the molecular weight, is critical in the final value of the parameter of interest, namely the average heat of self-association ΔH_a. The low values of ΔH_a obtained suggest that a fraction of asphaltenes is not active in the calorimetric experiments. Asphaltenes from Venezuela (LM1) and Mexico (KU) have been fractionated by precipitation with a mixture of acetone and toluene. It is considered that the most polar compounds are collected in the soluble fraction. A calorimetry study was performed on the two fractions, and the results show that the soluble fraction (SOL) has a much higher heat developed than the insoluble fraction (INS). This suggests again that a fraction of asphaltenes is not active in the calorimetric experiments, either because it does not self-associate or because the dilution effect is not strong enough to break the aggregates. Fluorescence and IR spectroscopy experiments confirm there is self-association in INS fraction, leading to the conclusion that asphaltene aggregates are formed by bonds of different strengths. The stronger aggregates would be predominantly in INS fraction and would be inactive in the calorimetric experiments.     

Asphaltene Self-Association: Modeling and Effect of Fractionation With A Polar Solvent

Abstract

The self-association of asphaltenes in toluene is believed to occur step-wise, rather than by the formation of micelles. A number of step-wise models have been used to fit the calorimetric titration of asphaltenes in dried toluene solutions, with excellent results. All the models are based on chemical reactions equivalent to the ones found in polymerization. The study shows that the choice of the average properties of asphaltenes, such as the molecular weight, is critical in the final value of the parameter of interest, namely the average heat of self-association ΔH _a . The low values of ΔH _a obtained suggest that a fraction of asphaltenes is not active in the calorimetric experiments. Asphaltenes from Venezuela (LM1) and Mexico (KU) have been fractionated by precipitation with a mixture of acetone and toluene. It is considered that the most polar compounds are collected in the soluble fraction. A calorimetry study was performed on the two fractions, and the results show that the soluble fraction (SOL) has a much higher heat developed than the insoluble fraction (INS). This suggests again that a fraction of asphaltenes is not active in the calorimetric experiments, either because it does not self-associate or because the dilution effect is not strong enough to break the aggregates. Fluorescence and IR spectroscopy experiments confirm there is self-association in INS fraction, leading to the conclusion that asphaltene aggregates are formed by bonds of different strengths. The stronger aggregates would be predominantly in INS fraction and would be inactive in the calorimetric experiments.     

减压渣油微观相结构特性的分子模拟

选用4种模型化合物代表减压渣油四组分(SARA),采用分子动力学模拟了减压渣油微观相结构,发现不同结构分子间相互作用的差异是减压渣油微观非均匀分布的本质原因,并通过电子分布特性分析了不同结构分子间相互作用差异的本质原因。沥青质分子间强相互作用使得沥青质分子自缔合形成聚集体;而多个胶质分子与沥青质分子的强相互作用封闭了沥青质分子自身进一步发生相互作用的活性位;同时,与胶质分子、饱和烃分子具有强相互作用的芳香烃分子将沥青质 胶质分子形成的聚集体分散在由芳香烃 饱和烃分子构成的连续相内,其中芳香烃分子更靠近胶质分子。因此,增加沥青质、饱和烃分子的含量会促进沥青质聚集,降低减压渣油稳定性;增加胶质、芳香烃分子的含量会阻碍沥青质聚集,提高减压渣油稳定性。     

Interfacial and Thermal Characterization of Asphaltenes Separated from Crude Oils Having Different Geological Origins

Abstract

Three crude oils having different geological origins, namely, DK from Eocene (Sylhet limestone and Langpar), SL from Barail (Oligocene), and JN from Tipam (lower Miocene), were selected. Asphaltenes were separated and characterized. Fourier transform infrared (FTIR) spectroscopy showed the presence of polar groups. Interfacial tension studies of the asphaltenes between benzene–water, toluene–water, and xylene–water showed the lowest interfacial tension with SL asphaltenes in a toluene–water system. Thermogravimetric analysis of asphaltenes indicates greater thermal degradation for DK asphaltenes. Asphaltenes were pyrolyzed and the pyrolyzed products were analyzed by gas chromatography/mass spectrometry (GC/MS). Based on the distribution pattern of n-alkanes in pyrolyzed product of asphaltenes, crude oils, and kerogens, it was concluded that crude oil and asphaltenes originate from the same source and asphaltenes are the unconverted parts of kerogens.     

AGGREGATION OF ASPHALTENES OBTAINED FROM A BRAZILIAN CRUDE OIL IN AROMATIC SOLVENTS

Surface and interfacial tensions in model systems formed by a Brazilian crude oil n-pentane insolubles (C5I) and n-heptane insolubles (C7I) in three different aromatic solvents: toluene, pyridine and nitrobenzene, were measured at room temperature, employing an automatic tensiometer and using the ring method. The results obtained indicated possible asphaltene aggregation and allowed the determination of critical micelle concentrations (c.m.c) for both C5I and C7I fractions in each of the three solvents considered. In toluene and pyridine solutions, the C5I fraction consistently presented higher c.m.c. values indicating a lower tendency of association for the organic fraction contained in the C5I, and absent in the C7I. In nitrobenzene solutions, this extra organic fraction appears to facilitate asphaltene association, possibly due to the formation of mixed aggregates. Average molecular areas for asphaltenes adsorbed at different interfaces were estimated using measured tensions and found to be in agreement with literature values and suggest a the flatwise surface adsorption of asphaltene molecules. This is consistent with the currently accepted stacking aggregation mechanism of asphaltenes.     

SEPARATION OF ASPHALTENES BY POLARITY USING LIQUID-LIQUID EXTRACTION

In order to investigate the nature of petroleum asphaltenes in terms of polarity a process was developed using initial liquid-liquid extraction of the oil phase followed by precipitation of the asphaltenes using n-heptane. The liquid-liquid extraction was performed using toluene-methanol mixtures with increasing content of toluene. Although large fractions of the crude oil (Alaska '93) was extracted in the higher polarity solvents (high concentration of methanol), the asphaltene content of the dissolved material was low As the toluene content increased more asphaltenes were transferred to the solvent phase. The asphaltenes were analysed using FTir, Elemental analysis, and HPLC-SEC with a diode array detector. With increasing content of toluene in the methanol the molecular weight distribution of the asphaltenes significantly move to higher molecular weights. The content of nitrogen and sulfur of the mallene phase also increase while H/C decreases. The content of heteroatoms in the asphaltenes are relatively higher and apparently increase with the polarity of the solvent. It is concluded that these asphaltenes are indeed dominated by high molecular weight substances that cannot be extracted in the high polarity solvents     

原油乳状液稳定机理的分子模拟研究

沥青质在稳定原油乳状液方面发挥重要的作用,采用分子动力学研究了沥青质分子在甲苯 水界面的吸附聚集行为,用量子化学方法研究了沥青质和水分子间以及沥青质分子之间的相互作用能,探讨了沥青质稳定乳状液的作用机理。结果表明,沥青质分子和水分子间氢键的形成是沥青质能够在油 水界面吸附的主要原因,沥青质分子之间的氢键和π π作用使得沥青质构成超分子结构,此超分子结构将水分子包围在内,阻止了水滴的聚并。此外,模拟研究了一种化学破乳剂的破乳过程,结果发现,破乳剂可以通过沥青质分子的间隙,为后续的破乳过程提供了可能。     

AGGREGATION OF ASPHALTENES OBTAINED FROM A BRAZILIAN CRUDE OIL IN AROMATIC SOLVENTS

Abstract

Surface and interfacial tensions in model systems formed by a Brazilian crude oil n-pentane insolubles (C5I) and n-heptane insolubles (C7I) in three different aromatic solvents: toluene, pyridine and nitrobenzene, were measured at room temperature, employing an automatic tensiometer and using the ring method. The results obtained indicated possible asphaltene aggregation and allowed the determination of critical micelle concentrations (c.m.c) for both C5I and C7I fractions in each of the three solvents considered. In toluene and pyridine solutions, the C5I fraction consistently presented higher c.m.c. values indicating a lower tendency of association for the organic fraction contained in the C5I, and absent in the C7I. In nitrobenzene solutions, this extra organic fraction appears to facilitate asphaltene association, possibly due to the formation of mixed aggregates. Average molecular areas for asphaltenes adsorbed at different interfaces were estimated using measured tensions and found to be in agreement with literature values and suggest a the flatwise surface adsorption of asphaltene molecules. This is consistent with the currently accepted stacking aggregation mechanism of asphaltenes.     

THE COLLOIDAL STRUCTURE OF CRUDE OILS AND SUSPENSIONS OF ASPHALTENES AND RESINS

A better understanding of colloidal macrostructure of the heavy petroleum products and their complex fractions is of great importance in the context of industrial problems that arise during the crude oil production, refining and transport. Much effort has been devoted to the chemical structure studies, but there is a need for more precise data regarding parameters that characterize those complex systems. For instance, the molecular weight of heavy molecules, the composition and size of aggregates formed during the industrial processing and their evolution upon the variation of temperature, pressure and with the addition of solvent have not been well known. In this paper we present new results obtained using several powerful techniques. Scattering methods (using X-rays and neutrons) are applied to study both the fractionated products (asphaltene and resin solutions in more or less good solvents) and the real systems (Safaniya vacuum residue). The lamellar structural model for asphaltenes and resins is confirmed and the molecular weight of these species determined using a polydisperse size distribution. Discussion is presented concerning the specificity of X-ray and neutron scattering : X-ray experiments are more sensitive to the aromatic-rich regions, whereas the neutron scattering data provide information about all the particle volume. Viscosimetry measurements provide information on the molecular shape of asphaltene and confirm the disk-like model. Critical micellar concentration has been obtained using Vapour Pressure Osmometry (VPO) for asphaltene suspensions in toluene and in pyridine. The resin molecules are smaller than asphaltenes, and appear to be a good solvent for asphaltenes. One of the major conclusions of this work is the wide-spread presence of density heterogeneities in diluted solutions of asphaltenes and resins as well as in the pure product (Safaniya vacuum residue). This was deduced from the scattering experiments and cryo-scanning electron microscopy data. The heating effects. were studied: a temperature increase leads to the decrease of molecular weight, but heterogeneities remain present. The structure of vacuum residue exhibits large density fluctuations which are thermally stable. These dense regions remain connected into a network up to 393°K and determine the yield value of the rheological behaviour.     

SEPARATION OF ASPHALTENES BY POLARITY USING LIQUID-LIQUID EXTRACTION

ABSTRACT

In order to investigate the nature of petroleum asphaltenes in terms of polarity a process was developed using initial liquid-liquid extraction of the oil phase followed by precipitation of the asphaltenes using n-heptane. The liquid-liquid extraction was performed using toluene-methanol mixtures with increasing content of toluene. Although large fractions of the crude oil (Alaska '93) was extracted in the higher polarity solvents (high concentration of methanol), the asphaltene content of the dissolved material was low As the toluene content increased more asphaltenes were transferred to the solvent phase. The asphaltenes were analysed using FTir, Elemental analysis, and HPLC-SEC with a diode array detector. With increasing content of toluene in the methanol the molecular weight distribution of the asphaltenes significantly move to higher molecular weights. The content of nitrogen and sulfur of the mallene phase also increase while H/C decreases. The content of heteroatoms in the asphaltenes are relatively higher and apparently increase with the polarity of the solvent. It is concluded that these asphaltenes are indeed dominated by high molecular weight substances that cannot be extracted in the high polarity solvents     

DIBSOLUTION OF SOLID BOBCAN ASPHALTENES IN MIXED SOLVENTS.

ABSTRACT

Solid petroleum asphaltenes have been fractionated according to solubility in toluene/n-heptane mixtures of increasing toluene content. A large hysteresis was observed between this dissolution and the precipitation from the crude oil. In order to shed light on the solution mechanism, the fractions obtained have been analyzed using size exclusion chromatography (SEC-HPLC-UV-vis), VPO, elemental analysis, UV-vis adsorption spectroscopy and phenol interaction values and methylene content by FTir. Less polar non-associating low molecular weight species are dissolved and a specific extraction of porphyrins is observed. An increased association in the insolubles is indicated. More basic interaction sites are available on the asphaltenes in both fractions relative to the native asphaltene. From the SEC chromatograms it was seen that the soluble fractions did not associate as the insoluble fractions even when making up more than 60 % of the total asphaltenes.     

Small-angle scattering study of colloidal particles in heavy crude oils

The structural and dispersion characteristics of samples of heavy crude oils and fractions isolated from them have been studied. A method of in situ analysis of the aggregation of asphaltenes directly in crude oils on the basis of small-angle X-ray scattering is proposed. It has been shown that the maximum size of scattering particles in all crude oil samples is limited to the value on the order of 8.0 nm; the average diameter is ∼2.0 nm. It has been found that the fraction with sizes of 0.8–2.5 nm is mostly composed of resins. Asphaltenes in crude oils form larger aggregated particles with a size up to 8 nm. A comparative study of model dilute solutions of asphaltenes in toluene (0.23 wt %) has shown that the major part of asphaltenes in the liquid (∼94%) is in the form of individual molecules with a size of 0.4–1.2 nm, and only an insignificant remaining part (∼6%) occurs in the form of large aggregates.     

Tuning of properties of alkyl phenol formaldehyde resins in petroleum demulsifiers: 1. Emulsion stability test

This research studies the interactions between nonylphenol ethoxylates (10 and 20 moles of ethylene oxide) and two polymeric resins (ethoxylated alkyl phenol formaldehyde resins), and its dehydrating effect on the Furrial and Carabobo crude oils. The demulsification performance of these resins was studied according to the cyclohexane dilution method. Results show that resins can be modulated when mixed with other low molecular nonionic surfactants, fact that enhances their demulsifying performance. The results obtained in this study quantified the effect of polymer resins to counteract the effect of asphaltenes as stabilizers of emulsions of water in oil.     

Steady State Size Distribution of Asphaltenes by Flocculation From Toluene–n-Heptane Mixtures

Abstract

The aggregation mechanisms of asphaltenes have been the subject of several recent studies. In this work, we have studied the effect of inhibitors on size distribution of asphaltene particles, in solutions containing toluene and mixtures of n-heptane and toluene. The asphaltenes used have been extracted from Marlim crude oil, using a modified procedure IP-143/82. Several solutions containing one percent volume of asphaltenes have been prepared in pure toluene and in toluene and n-heptane mixtures with and without inhibitors and have been homogenized during a period of 24 h. The particles sizes were determined by filtering the solutions through a set of standard filters ranging from 0.45 to 0.02 µm pore size. In addition, from the saturated filtered solution of asphaltene in toluene, three other solutions were prepared having 10, 20, and 30% volume of n-heptane and were homogenized for 24 h. Again the size distribution of precipitated particles was obtained by filtering. The concentration of asphaltenes remaining in the solution was measured directly by evaporation or by spectroscopy. The results have shown that large part of asphaltenes remain as colloidal particles in the size range tested in toluene solution without inhibitor. On the solutions in which inhibitors were used, one of the inhibitors effectively prevented flocculation, concentrating the asphaltene particles on the smaller size range even on mixtures containing 20 and 30% volume of n-heptane, which is a strong flocculating agent.     

Montmorillonite surface properties modifications by asphaltenes adsorption

The effects of asphaltenes on the particle size, and the surface charge of two montmorillonite clays having in water various particle sizes, flow behaviours, and cationic exchange capacities (CEC) are investigated. The aim of this work is to contribute to the comprehension of the mechanism by which the asphaltenes alter the mineral wettability in an oil reservoir. Thus, adsorption of asphaltenes onto clays was made from water-saturated toluene, and the resulting asphaltenes covered clays were dried to remove trace of solvent and then dispersed in water. Upon adsorption of asphaltenes onto various clays, the mineral surface charge is reduced and the aggregation of the clay particles is enhanced, as observed, respectively, by microelectrophoresis and scanning electronic microscopy (SEM). Further, the samples aqueous dispersion properties such as the natural pH and the electrical conductivity were found, in all instances, to be lower for the asphaltenes covered clays as compared to the bare minerals, indicating reduction by asphaltenes of the clay's CEC. It is shown that the asphaltenes adsorption from water-saturated toluene onto clay is higher for the solid mineral having in water and at natural pH, the lower surface charge, the highest particle size and presenting the highest yield point for flowing.     

Design of Synthetic Dispersants for Asphaltenes

Synthetic dispersants can greatly increase the solubility of asphaltenes in crude oils at low concentrations. They have one or more head groups that complex with the polynuclear aromatic structures in asphaltenes and long paraffinic tails that promote solubility in the rest of the oil. As a result, synthetic dispersants can be much more effective than the natural dispersants in the oil, the resins. At high concentrations, synthetic dispersants can even make all the asphaltenes soluble in n-heptane and thereby convert asphaltenes to resins. Asphaltene dispersants were optimized according to their ability to reduce the toluene equivalence of 05a crude oil. By synthesizing families of prospective dispersants, one sulfonic acid group was determined to be the most effective head attached to a two ring aromatic structure. As previously reported, a straight chain paraffinic tail is not effective above 16 carbons. We discovered that this was because of decreased solubility in the oil caused by crystallization with other tails and with waxes in the oil. In addition, not previously reported, n-alkyl-aromatic sulfonic acids lose their ability to disperse asphaltenes with time. Both of these problems were solved by using two branched tails of varying length proportions between the two tails. As a result, the effectiveness of the dispersant increases with total tail length, well above 30 carbons and it remains effective with time.     

EFFECT OF EXPERIMENTAL CONDITIONS AND SOLVENTS ON THE PRECIPITATION AND COMPOSITION OF ASPHALTENES

The ASTM D 3279 test method for “n-Heptane Insolubles” is being currently used to determine the asphaltene content of fuel oils as defined by insolubility in normal (n) heptane solvent. Precipitation of n-heptane insolubles can produce sediments which vary in color, morphology and composition. The SEM analysis of n-heptane insolubles indicated that the sediments were heterogeneous containing some large particles >300 μ and the majority of particles to be small, <10 μ, “chained” together forming agglomerates. Significant fractions of n-heptane insolubles were found insoluble in toluene indicating their non-asphaltenic nature (“solids”). FTIR and XRF analyses of “solids” indicated the presence of multiring aromatics, Ni and carboxylate and sulfate salts. FTIR analysis of toluene soluble asphaltenes showed the presence of multiring aromatics. GC/MS analysis of toluene soluble asphaltenes indicated desorption of alkylbenzenes and O-containing molecules but no desorption of N- and S-containing molecules was observed. The tendency for N- and S-containing molecules to remain in the nonvolatile residue during the GC/MS analysis indicates that the N- and S-containing compounds have higher stability. The XRF analysis of the toluene soluble asphaltenes indicated that the molecules are similar to asphaltenes found in crude oils in terms of C, H, N and S contents, however, no presence of V- and Ni-containing molecules was found.     

THE COLLOIDAL STRUCTURE OF CRUDE OILS AND SUSPENSIONS OF ASPHALTENES AND RESINS

ABSTRACT

A better understanding of colloidal macrostructure of the heavy petroleum products and their complex fractions is of great importance in the context of industrial problems that arise during the crude oil production, refining and transport. Much effort has been devoted to the chemical structure studies, but there is a need for more precise data regarding parameters that characterize those complex systems. For instance, the molecular weight of heavy molecules, the composition and size of aggregates formed during the industrial processing and their evolution upon the variation of temperature, pressure and with the addition of solvent have not been well known. In this paper we present new results obtained using several powerful techniques. Scattering methods (using X-rays and neutrons) are applied to study both the fractionated products (asphaltene and resin solutions in more or less good solvents) and the real systems (Safaniya vacuum residue). The lamellar structural model for asphaltenes and resins is confirmed and the molecular weight of these species determined using a polydisperse size distribution. Discussion is presented concerning the specificity of X-ray and neutron scattering : X-ray experiments are more sensitive to the aromatic-rich regions, whereas the neutron scattering data provide information about all the particle volume. Viscosimetry measurements provide information on the molecular shape of asphaltene and confirm the disk-like model. Critical micellar concentration has been obtained using Vapour Pressure Osmometry (VPO) for asphaltene suspensions in toluene and in pyridine. The resin molecules are smaller than asphaltenes, and appear to be a good solvent for asphaltenes. One of the major conclusions of this work is the wide-spread presence of density heterogeneities in diluted solutions of asphaltenes and resins as well as in the pure product (Safaniya vacuum residue). This was deduced from the scattering experiments and cryo-scanning electron microscopy data. The heating effects. were studied: a temperature increase leads to the decrease of molecular weight, but heterogeneities remain present. The structure of vacuum residue exhibits large density fluctuations which are thermally stable. These dense regions remain connected into a network up to 393°K and determine the yield value of the rheological behaviour.     

Design of Synthetic Dispersants for Asphaltenes

Abstract

Synthetic dispersants can greatly increase the solubility of asphaltenes in crude oils at low concentrations. They have one or more head groups that complex with the polynuclear aromatic structures in asphaltenes and long paraffinic tails that promote solubility in the rest of the oil. As a result, synthetic dispersants can be much more effective than the natural dispersants in the oil, the resins. At high concentrations, synthetic dispersants can even make all the asphaltenes soluble in n-heptane and thereby convert asphaltenes to resins. Asphaltene dispersants were optimized according to their ability to reduce the toluene equivalence of 05a crude oil. By synthesizing families of prospective dispersants, one sulfonic acid group was determined to be the most effective head attached to a two ring aromatic structure. As previously reported, a straight chain paraffinic tail is not effective above 16 carbons. We discovered that this was because of decreased solubility in the oil caused by crystallization with other tails and with waxes in the oil. In addition, not previously reported, n-alkyl-aromatic sulfonic acids lose their ability to disperse asphaltenes with time. Both of these problems were solved by using two branched tails of varying length proportions between the two tails. As a result, the effectiveness of the dispersant increases with total tail length, well above 30 carbons and it remains effective with time.