Asphaltenes In Toluene Research Articles

Influence of the Architecture of Additives on the Stabilization of Asphaltene and Water-in-Oil Emulsion Separation

Amphiphilic chemical additives are widely used to prevent the formation of asphaltene deposits and to promote demulsification of crude oil. Although it is known that the efficiency of these additives is mainly related to their structure and molar mass, this correlation is still not well established, because it is also related to the type of petroleum to be treated. In this work, C10I asphaltenes extracted from two different types of asphaltic residues were used to prepare model systems containing 1 wt % asphaltenes in toluene. Amphiphilic macromolecules, obtained from polymerization of cardanol by polyaddition and polycondensation, were characterized by Fourier transform infrared (FTIR) spectroscopy, proton nuclear magnetic resonance (1H NMR), and size-exclusion chromatography (SEC) and evaluated regarding their influence on the variation of asphaltene precipitation onset of model systems and the variation of volume and separation kinetics of water in model water-in-oil emulsions. The results show that th...

DPD Molecular Simulations of Asphaltene Adsorption on Hydrophilic Substrates: Effects of Polar Groups and Solubility

Adsorption of asphaltenes onto a polar substrate (e.g., a mineral) was modeled with dissipative particle dynamics (DPD) simulations, using continental asphaltene models. The adsorption mechanisms in 10–20% wt, of asphaltene in toluene/ heptane solutions were studied (well above the solubility limit). The structure in the adsorbed layer was highly sensitive to the presence of polar groups in the alkyl side chains and heteroatom content in the aromatic ring structure. Four types of asphaltene models were used: completely apolar (zero adsorption), apolar chains and polar heteroatoms, polar chains and no heteroatoms, and polar chains and heteroatoms (maximum adsorption). One hundred asphaltene monomers were distributed homogeneously in the solvent initially, in a ∼(10 nm)3 domain.Asphaltene monomers adsorbed irreversibly on the substrate via the polar group in the side chains, resulting in an average perpendicular orientation of the aromatic rings relative to the substrate. More frequent π–π stacking of the aromatic rings occurred for less solubility (more heptane), as in aggregates. With apolar side chains, only the heteroatoms in the aromatic ring structure had affinity to the substrate, but the ring plane did not have any preferred direction.An important finding is that the aromatic ring assemblies “shielded” the substrate and polar groups that were anchored to the substrate, resulting in an effective non-polar surface layer seen by asphaltenes in the bulk, leading to much lower adsorption probability of the remaining asphaltenes. This “adsorption termination” effect leads to mono-layer formation. Continued adsorption with multilayering and reversible nanoaggregate adsorption occurred when both side chains in the model asphaltene (located on opposite sides of the aromatic sheet) contained polar groups, with a higher probability of exposing further polar groups to the bulk asphaltene. The general conclusion is that the number and position of the polar groups in side chains determine to a large degree the adsorption and aggregation behavior/efficiency of (continental) asphaltenes, in line with experimental evidence. The heteroatoms in the aromatic ring structure plays a more passive role in this context, only by providing organization via more π–π stacking in the adsorbed layer, and in aggregates.

COMPARISON BETWEEN ASPHALTENES (SUB)FRACTIONS EXTRACTED FROM TWO DIFFERENT ASPHALTIC RESIDUES: CHEMICAL CHARACTERIZATION AND PHASE BEHAVIOR

Asphaltenes are blamed for various problems in the petroleum industry, especially formation of solid deposits and stabilization of water-in-oil emulsions. Many studies have been conducted to characterize chemical structures of asphaltenes and assess their phase behavior in crude oil or in model-systems of asphaltenes extracted from oil or asphaltic residues from refineries. However, due to the diversity and complexity of these structures, there is still much to be investigated. In this study, asphaltene (sub)fractions were extracted from an asphaltic residue (AR02), characterized by NMR, elemental analysis, X-ray fluorescence and MS-TOF, and compared to asphaltene subfractions obtained from another asphaltic residue (AR01) described in a previous article. The (sub)fractions obtained from the two residues were used to prepare model-systems containing 1 wt% of asphaltenes in toluene and their phase behavior was evaluated by measuring asphaltene precipitation onset using optical microscopy. The results obtained indicated minor differences between the asphaltene fractions obtained from the asphaltic residues of distinct origins, with respect to aromaticity, elemental composition (CHN), presence and content of heteroelements and average molar mass. Regarding stability, minor differences in molecule polarity appear to promote major differences in the phase behavior of each of the asphaltene fractions isolated.

Molecular Dynamics Investigation on the Aggregation of Violanthrone78-Based Model Asphaltenes in Toluene

In order to investigate the aggregation mechanisms of asphaltenes in toluene, a series of molecular dynamics simulations were performed on Violanthrone78-based model asphaltenes with different aliphatic/aromatic ratios. Our simulation results show that the attraction between poly-aromatic cores is the main driving force for asphaltene aggregation in toluene, and that the extent of aggregation is independent of the aliphatic/aromatic ratios. On the other hand, analysis of the aggregated structures indicates that long side chains do hinder the formation of large direct parallel stacking structures. In contrast with water as a solvent, toluene exhibits attractive interactions with both the aliphatic and aromatic regions of the asphaltenes, hence reducing the size and stability of the asphaltene aggregates. Our findings help to elucidate, at a molecular level, the different solubility behaviors of asphaltenes in toluene and in water.

Evaluating steady-state and time-resolved fluorescence as a tool to study the behavior of asphaltene in toluene

A combination of steady-state fluorescence, fluorescence lifetime measurements and the determination of time-resolved emission spectra were employed to characterize asphaltene toluene solutions. Lifetime measurements were shown to be insensitive to the source of asphaltene or the alkane solvent from which asphaltene was precipitated. This insensitivity suggests that either the composition of Athabasca and Cold Lake asphaltene is very similar or that the fluorescence behavior is dominated by the same sub-set of fluorophores for the different samples. These results highlight the limitations in using fluorescence to characterize asphaltene solutions. Different dependencies were observed for the average lifetimes with the asphaltene concentration when measured at two different emission wavelengths (420 nm and 520 nm). This result suggests that different fluorophores underwent diverse interactions with other asphaltene molecules as the asphaltene concentration was raised, suggesting that models for asphaltene aggregation need to include molecular diversity.

Study of Asphaltene Adsorption on Kaolinite by X-ray Photoelectron Spectroscopy and Time-of-Flight Secondary Ion Mass Spectroscopy

The interaction between asphaltenes and clay is crucial in understanding wettability changes in petroleum reservoirs and in oilsands production. In this study, we report the changes in surface properties and composition of kaolin clay as a result of exposure to solutions of asphaltenes. Adsorption experiments were conducted at 25 °C with solutions of asphaltenes in toluene at concentrations ranging from 0.05 to 5 mg/mL. The wettability of the modified kaolinite surface was characterized by contact angle measurement. Chemical composition changes of the surface because of asphaltene adsorption were assessed using time-of-flight secondary ion mass spectroscopy (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), and elemental analysis. The contact angle data indicated that, upon asphaltene adsorption, the clay particles changed from water-wet to bi-wet. Both ToF-SIMS and XPS measurements indicated that the kaolinite surface was never completely covered by asphaltenes based on the concentration of Al and Si on asphaltene-treated kaolinite surfaces. ToF-SIMS analysis indicated that, with more asphaltenes covered on the kaolinite surface, the relative intensities of C3H5+/Al+ and C3H5+/Si+ increased and an inverse linear correlation between the contact angle and surface Si+ concentration was observed. The maximum thickness of adsorbed asphaltenes, assuming complete surface coverage, was estimated to be 11 nm based on XPS depth profile results on a model silica surface, with a mean value of 3 nm. The XPS depth profile also indicated no preferential adsorption of nitrogen- or sulfur-rich species at the interface between asphaltenes and kaolinite.

The influence of asphaltenes subfractions on the stability of crude oil model emulsions

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.

Mesoscale Organization in a Physically Separated Vacuum Residue: Comparison to Asphaltenes in a Simple Solvent

Physical separation of heavy oils and bitumen is of particular interest because it improves the description of the chemical and structural organization in these industrial and challenging fluids (Zhao, B.; Shaw, J. M.Composition and size distribution of coherent nanostructures in Athabasca bitumen and Maya crude oil. Energy Fuels 2007, 21, 2795−2804). In this study, permeates and retentates, differing in aggregate concentrations and sizes, were obtained from nanofiltration of a vacuum residue at 200 °C with membranes of varying pore size. Elemental composition and density extrapolations show that aggregates are best represented as n-pentane asphaltenes, while the dispersing phase corresponds to n-pentane maltenes. Small-angle X-ray scattering (SAXS) measurements are processed, on this basis, to calculate the size and mass of the aggregates. Aggregates in the vacuum residue are similar in size and mass to asphaltenes in toluene, and temperature elevation decreases the size of the aggregates. Wide-angle X-r...

Organization of Asphaltenes in a Vacuum Residue: A Small-Angle X-ray Scattering (SAXS)–Viscosity Approach at High Temperatures

Temperature-dependent rheological behavior of heavy oils and bitumen is usually modeled with a colloidal approach, taking into account a temperature-dependent solvation effect (Storm, D. A.; Barresi, R. J.; Sheu, E. Y.Rheological study of Ratawi vacuum residue in the 298–673 K temperature range. Energy Fuels 1995, 9, 168−176). In addition to viscosity measurements for vacuum residue at various asphaltene contents, in the present study, we make use of small-angle X-ray scattering (SAXS) data on the 80–240 °C temperature range to propose an interpretation on asphaltene aggregation, consistent with both approaches. The radius of gyration Rg and molecular weight MW of asphaltenes in a vacuum residue are measured and are of the same magnitude as asphaltenes in toluene. Dimensions and masses decrease with the temperature, while the small length scale remains unchanged, reinforcing the hierarchical aggregation scheme previously described in toluene. These findings enrich the viscosity data interpretation. A solvation factor has to be accounted for, as noticed in previous works. Its signification is made clear by SAXS data: lose asphaltene clusters in maltenes dissociate with temperature, decreasing their solvation.

Role of Asphaltenes in Inhibiting Corrosion and Altering the Wettability of the Steel Surface

Abstract Asphaltenes (heptane insolubles) from a variety of crude oils have been identified previously as contributors to inhibition of internal corrosion of mild steel pipelines. However, the mechanism of inhibition is unknown. To explore the mechanism, carbon dioxide (CO2) corrosion rates and wettability (oil/water contact angles) have been measured using Arab Heavy crude oil and its asphaltenes. Inhibition of CO2 corrosion rates for carbon steel was measured using electrochemical methods in a glass cell; wettability was assessed using contact angle measurements in a multiphase goniometer. The phase behavior of asphaltenes in corrosion and wetting was evaluated in the crude, toluene (C7H8), or heptol (70:30 mixture of heptane [C7H16] and toluene). Inhibition on steel exposed to a hydrocarbon phase increased with the concentration of asphaltenes in toluene. Inhibition by asphaltenes dissolved in toluene appears to be more effective than in the whole crude, at equivalent concentrations of asphaltenes. At 5 wt% in toluene, asphaltenes form a strong protective layer on the carbon steel surface, which reduces the corrosion rate and makes the surface hydrophobic. When the solubility of the oil is altered to the point where asphaltenes start to flocculate, it enhances the corrosion inhibition greatly. However, the inhibition is not as persistent as for the fully dissolved asphaltenes, and the surface needs to be periodically wetted with the oil phase to maintain the protection.

Effect of the Particle Size on Asphaltene Adsorption and Catalytic Oxidation onto Alumina Particles

In this study, the adsorption and catalytic oxidation of asphaltenes, problematic heavy hydrocarbons present in heavy oil, onto two aluminas with different particle sizes and comparable surface acidity were investigated. Equilibrium batch adsorption experiments were conducted at 25 °C with solutions of asphaltenes in toluene at concentrations ranging from 100 to 3000 mg/L. Adsorption data were fit to the Langmuir and Freundlich isotherm models. Nano-alumina fit better to the Langmuir model, while micro-alumina fit well to the Freundlich model. On a surface area basis, nano-alumina has higher adsorption capacity for asphaltenes than micro-alumina. Interestingly, micro-alumina has higher catalytic activity toward asphaltene oxidation than nano-alumina, at the same asphaltene loading, thus exhibiting the significance of textural properties during catalytic oxidation of asphaltenes that dominated over the effect of the particle size.

Integration of rotational algorithms into dissipative particle dynamics: modeling polyaromatic hydrocarbons on the meso-scale

Heavy crude oil consists of thousands of compounds, a significant fraction of which have fairly large molecular weights and complex structures. Our work aims at constructing a meso-scale platform to explore this complex fluid in terms of microstructure, phase behavior, stability and rheology. In the present study, we focus on the treatment of the structures of fused aromatic rings as rigid body fragments in fractions such as asphaltenes and resins. To derive the rotational motion of rigid bodies in a non-conservative force field, we conduct a comparison of three rigid body rotational algorithms integrated into a standard dissipative particle dynamics (DPD) simulation. The simulation results confirm the superiority of the Quaternion method. To ease any doubt concerning the introduction of rigid bodies into DPD, the performance of the Quaternion method was tested carefully. Finally, the aggregation dynamics of asphaltene in very diluted toluene was investigated. The nanoaggregates are found to experience forming, breaking up and reforming. The sizes of the asphaltene monomer and nanoaggregate are identified. The diffusion coefficient of diluted asphaltene in toluene is similar to that found experimentally. All these results verify the rotational algorithm and encourage us to extend this platform to study the rheological and colloidal characteristics of heavy crude oils in the future.

Understanding Molecular Interactions of Asphaltenes in Organic Solvents Using a Surface Force Apparatus

A surface force apparatus was used to study the intermolecular forces of asphaltenes in toluene and heptane. The repulsive interaction forces measured between two asphaltene surfaces in toluene were shown to have a steric nature and could be described by the Alexander–de Gennes theory on steric repulsion between two interacting polymer layers in good solvents at short separation distances under high compression forces. On the other hand, the adhesion forces measured between asphaltenes in heptane can be described by van der Waals forces, which are responsible for asphaltene aggregation and precipitation in paraffinic solvents. The asphaltene films adsorbed on mica were found to swell significantly in toluene but only moderately in heptane. In addition, an adhesion force was observed between an asphaltene surface and a mica surface in toluene. The results from this study provide an insight into the basic interaction mechanisms of asphaltenes in organic media and hence in crude oil and bitumen production.

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.

Distribution of Ni and V in A1 and A2 Asphaltene Fractions in Stable and Unstable Venezuelan Crude Oils

Asphaltenes are a complex mixture of compounds grouped as the colloidal phase in crude oils. Two fractions, A1 and A2, have been isolated from them. A1 is defined as the mayor and practically insoluble fraction, while A2 has a similar solubility to the original asphaltenes in toluene. The studies on the molecular structure, organic compound distribution, and metal content can help to better understand the chemical behavior of these two fractions. In this sense, the concentration of Ni and V and elemental analysis (C, H, N, and S) were determined in asphaltenes and their fractions. The samples were analyzed using inductively coupled plasma atomic emission spectrometry and elemental combustion analysis. Results show that A1 presents higher Ni and V concentrations than A2, in both stable and unstable crude oils. These results can be explained by strong interactions, such as covalent bonds between the petroporphyrins and the asphaltene molecules. V/V + Ni ratios suggest differences in the distribution of meta...

Effect of surface acidity and basicity of aluminas on asphaltene adsorption and oxidation

This study investigates the effect of surface acidity and basicity of aluminas on asphaltene adsorption followed by air oxidation. Equilibrium batch adsorption experiments were conducted at 25°C with solutions of asphaltenes in toluene at concentrations ranging from 100 to 3000g/L using three conventional alumina adsorbents with different surface acidity. Data were found to better fit to the Freundlich isotherm model showing a multilayer adsorption. Results showed that asphaltene adsorption is strongly affected by the surface acidity, and the adsorption capacities of asphaltenes onto the three aluminas followed the order acidic>basic and neutral. Asphaltenes adsorbed over aluminas were subjected to oxidation in air up to 600°C in a thermogravimetric analyzer to study the catalytic effect of aluminas with different surface acidity. A correlation was found between Freundlich affinity constant (1/n) and the catalytic activity. Basic alumina that has the lowest 1/n value, depicting strongest interactions, has the highest catalytic activity, followed by neutral and acidic aluminas, respectively.

Surface Chemistry and Spectroscopy of UG8 Asphaltene Langmuir Film, Part 2

While there has been much focus on asphaltenes in toluene, there has been much less focus on asphaltenes in other solvents. It is important to quantify characteristics of asphaltenes in solvents besides toluene in order to better assess their molecular architecture as well as their fundamental aggregation characteristics. The present work focuses on the investigation of UG8 asphaltene Langmuir films at the air-water interface using chloroform as spreading solvent. The results are compared to the results recently obtained using toluene as spreading solvent. Surface pressure-area isotherms and UV-vis spectroscopy indicate that asphaltenes form smaller nanoaggregates in chloroform than in toluene in similar concentration ranges. Still these nanoaggreates share common features with those in toluene. From the surface pressure-area and compression-decompression isotherms, Brewster angle microscopy, and p-polarized infrared reflection-absorption spectroscopy, it was concluded that small size aggregates are spread on the water surface and the compression of the film leads to formation of large aggregates. The films (Langmuir-Schaefer and Langmuir-Blodgett) studied by atomic force microscopy reveal the existence of nanoaggregates spread on the water surface that coexist with large aggregates formed during compression. In addition to these findings, the spreading solvent, chloroform, allows the determination of asphaltene absorption bands using in situ UV-vis spectroscopy at the air-water interface after 15 min waiting time period. The absorbance data carried out after waiting a time period of 1 h shows similar features with the ones carried out after only 15 min; therefore, there is no need to wait 1 h as in the case when toluene is used as spreading solvent. A comparison of the data obtained from chloroform and toluene shows that smaller aggregate sizes are obtained from chloroform as suggested from the surface pressure-area isotherm, in situ UV-vis spectroscopy, and atomic force microscopy. Nevertheless, the similarity of these nanoaggregates in different solvents suggests this formation is a fundamental property of asphaltenes. Moreover, the lack of the isolated absorption band for one-ring aromatics and only a small peak for two-ring aromatics in the UV spectrum of asphaltenes indicate that these groups are not present in asphaltenes in significant quantities.

Study of the Asphaltene Aggregation Structure by Time-Resolved Fluorescence Spectroscopy

Asphaltene is defined as a fraction of petroleum that is insoluble in light linear alkane solvents, such as pentane or heptane, and soluble in toluene. This fraction of petroleum is responsible for serious problems in petroleum extraction, transportation, and refining. It aggregates and precipitates in well pipes and pipelines, reducing flow and increasing downtime for cleaning and removal. Fluorescence spectroscopy has been used to evaluate asphaltene size and aggregation. The time-resolved fluorescence decay profile of complex mixtures, such as asphaltenes, can be better evaluated by a distribution analysis method rather than the use of two exponential decays. Further, the time-resolved fluorescence decay profiles of asphaltene show that, even at a concentration of 0.08 g/L of asphaltene in toluene, the asphaltene compounds are aggregated, and using a simple kinetic model, we can conclude that the asphaltene compounds are dimerized via π−π stacking or other intermolecular forces.

Critical Nanoaggregate Concentration of Asphaltenes by Direct-Current (DC) Electrical Conductivity

The critical nanoaggregate concentration (CNAC) of asphaltenes in toluene has been studied by a variety of methods recently. Here, we explore low-frequency electrical impedance measurements to detect and quantify nanoaggregate formation of asphaltenes. The Nyquist and Bode plots confirm the frequency range necessary for the dominance of (organic) ion conduction as opposed to reactive impedance. Impedance measurements are made as a function of the asphaltene concentration in toluene. We perform ionic conduction measurements at low frequency to avoid electrode polarization effects and then extrapolate to obtain direct-current (DC) conductivity. In a plot of DC conductivity versus asphaltene concentration, we see a clear break between two linear regions that is attributed to nanoaggregate formation. Very close agreement with high-Q ultrasonic measurements is shown for two petroleum asphaltenes with different CNACs. In addition, this work is shown to be consistent with previous alternating-current (AC) conductivity measurements. Measurements on aqueous salt solutions are used to validate measurements of the mole fraction of asphaltenes ionized in toluene, which is ∼10−5. The plausible identity of these ions is discussed. A comparison of conductivity at concentrations below and above CNAC indicates that the aggregation number is small (<10) in agreement with previous findings. Resin shows no aggregation and is also much less conductive than asphaltenes. We also observe a break in the slope at higher asphaltene concentrations, where nanoaggregate clustering has been observed.

Electrodeposition of Asphaltenes. 1. Preliminary Studies on Electrodeposition from Oil−Heptane Mixtures

We investigated the behavior of asphaltic solids in an unstable crude oil Y3, its mixtures with heptane, and its isolated asphaltenes with respect to electrodeposition onto metal electrodes in direct current (DC) electric fields. Asphaltic material from the neat oil Y3 was found to possess a net negative charge, whereas its isolated asphaltene had a net positive charge when suspended in heptane. The negative charge of the deposit from the oil reversed to positive when the electrodes with the deposit were transferred from the oil to heptane, which was manifested in the movement of the particles from the anode to the cathode. Mixing the oil with heptane prior to application of a DC electric field resulted in a gradual decrease of the amount of anodic deposit and an increase of the amount of cathodic deposit upon increasing the heptane/oil ratio, but that trend did not hold when small amounts of oil were added to heptane under a DC electric field. Fourier transform infrared (FTIR) spectroscopy and high-performance liquid chromatography−size-exclusion chromatography (HPLC−SEC) data for electrode deposits obtained in the latter experiments showed that the cathodic material was more aromatic and appeared richer in carbonyl and sulfoxide groups than the anodic material. Nevertheless, structural properties of cathodic as well as anodic deposits were distinct from those of resins and asphaltenes isolated from the crude oil Y3. Application of a DC electric field did not cause flocculation of asphaltenes in either a stable oil or a solution of asphaltenes in toluene.