Asphaltene Aggregation Research Articles

Different mechanisms of two oil-soluble additives to reduce heavy crude oil viscosity

The depletion of light crude oil resources necessitates the efficient development of heavy crude oil, characterized by high density and viscosity. In this work, we used molecular dynamics (MD) simulations to investigate the mechanisms by which two oil-soluble viscosity reducers (VRs) reduce the viscosity of heavy crude oil. Our results reveal that direct interaction between VRs and asphaltene (ASP) aggregates is not the sole pathway for viscosity reduction. Instead, targeting resin (RES) emerges as a critical strategy. The first kind of VR (VR1), with its polar acrylamide head, binds effectively to ASP, reducing the exposure of ASP to other heavy oil components and thereby decreasing the friction between ASP and these components. In contrast, the second kind of VR (VR2), with a maleic anhydride head, tends to disperse away from ASP aggregates, reducing viscosity by weakening the intermolecular interactions between RES and lighter components. These findings elucidate distinct mechanisms by which VRs mitigate the viscosity of heavy crude oil and provide insights for the design of more effective oil-soluble VRs for future heavy oil exploitation.

Application of MgO based‐nanofluid for controlling the growth of asphaltene flocs under static and micromodel dynamic conditions

AbstractIn this study, the impact of magnesium oxide (MgO) nanoparticles on the control of asphaltene aggregates growth was examined. The investigation began with static testing, followed by dynamic testing, where nanofluid was injected into a constructed glass micromodel simulating a porous medium. The results obtained from light microscopy and asphaltene dispersant tests demonstrated that the MgO nanoparticles with an average diameter of 50 nm postpone the asphaltene onset point (AOP) and delay the growth of asphaltene aggregates in crude oil. Also, the results obtained from these experiments illustrated the performance of synthesized nanoparticles in various concentrations on inhibition of asphaltene deposit in the crude oil medium, in the order of 750 > 1500 > 100 > 1000 > 500 ppm. The results from both microscopy and ADT experiments strongly validate the effectiveness of MgO nanoparticles across varying concentrations, highlighting the optimal dosage of 750 ppm. Images of nanofluid flooding at the optimal concentration in the glass micromodel demonstrate effective nanoparticle inhibition and enhanced oil recovery from the porous medium. These findings corroborate the results obtained from ADT and microscopy tests. The results of FT‐IR analysis show the adsorption of asphaltene particles on the surfaces of MgO nanoparticles in wavelengths of 2900–3000 cm−1. Moreover, dynamic light scattering (DLS) analysis results indicated that the average diameter of suspended particles was 3580 nm before adsorption and 6230 nm after adsorption, indicating the controlled adsorption of asphaltene onto the surface of MgO nanoparticles. The findings from this study can be applied to manage asphaltene formation across all stages of oil processing and production.

Investigation of the aggregation behavior of rubber asphalt components induced by short-term Aging: A perspective from molecular dynamic simulations and microscopic tests

The distribution characteristics of different rubber asphalt components remain a subject of debate, particularly under the influence of asphalt short-term aging. This paper leverages the visualization advantages of molecular dynamics (MD) simulation and integrates them with microscopic testing methods to observe morphological variations and property changes in the aggregation of different components induced by short-term aging. Short-term aging of rubber asphalt is simulated using a thin-film oven test (TFOT). By conducting Fluorescence microscope (FM) and scanning electron microscope (SEM) tests, the aggregation behavior of components under changes in fluorescence phase and microstructure before and after short-term aging is revealed. MD simulation is employed to analyze the degree of aggregation between different components before and after short-term aging. SEM test results indicate that the structure becomes looser and forms distinct pits as the rubber asphalt ages. FM test results reveal that the particle size of rubber powder particles in aged rubber asphalt decreases and aggregates gradually. Concurrently, the asphalt phase in rubber asphalt becomes more uniform after aging. MD simulation results demonstrate significant aggregation between asphaltene-asphaltene molecules and asphaltene-rubber powder molecules in aged rubber asphalt. A higher degree of asphaltene aggregation leads to reduce asphalt penetration and increase softening point and viscosity. Furthermore, rubber powder molecular chains can inhibit “π-π stacking,” and “offset π-π stacking” of the asphaltene molecules. Therefore, the accumulation effect in aged rubber asphalt is mitigated compared with aged base asphalt. The research outcomes provided a foundation for further studies on the aging and rejuvenation of rubber asphalt.

200℃ ТЕМПЕРАТУРАДА АУЫР МҰНАЙДЫ БУМЕН ТЕРМИЯЛЫҚ ӨҢДЕУДІҢ ТИІМДІЛІГІН АРТТЫРУ ҮШІН БЕТТІК БЕЛСЕНДІ ЗАТТАРДЫ ҚОЛДАНУ

In the presented work influence of surfactants on of the oil transformation regularities in hydrothermal conditions was studied. The oil with density 0,9727 g/cm3 was chosen as objects of research. It has been established that the introduction of surfactants reduces the content of resinous asphaltenes as a result of peptizing action on asphaltene aggregates. As a result, more carbon-heteroatom bonds in asphaltenes are involved in the processes of destructive hydrogenation. According to the results of SARA - and chromato-mass-spectral analysis, a change of mass fractions of each fraction is observed. When using the surfactant "SA-3" the content of saturated hydrocarbons is 20% higher than in the original sample, while in the oil sample with the surfactant "SBG" the content is almost unchanged. The content of aromatic hydrocarbons increased significantly with the addition of "SBG" by 19%, and with the addition of "SA-3" by 10%, which is due to the newly formed low molecular weight saturated and aromatic hydrocarbons. Asphaltene content also changed significantly, the sample with the addition of "SA-3" showed a decrease of 12% and with the addition of "Biolub green" a decrease of 9% relative to the original oil. The dynamic viscosity at 20℃ of the original oil is 3000 mPa∙s at a shear rate of 1.3 s-1. When using non-ionic surfactants of GK "Mirrico" of "Biolub green" type after the experiments, the viscosity decreases by 22%, and when adding "SA-3" surfactants by 30%. The use of surfactants in the development of heavy oil fields by steam-heat methods will increase the oil recovery factor.

Adsorption behavior of asphaltene aggregates generated by self-association at the oil/water interface

The formation of emulsions is undesirable yet unavoidable in petroleum production. Researchers suggest that asphaltenes adsorb at the oil/water interface, forming a protective film that stabilizes emulsions. This study investigates how asphaltene aggregates, formed through intermolecular interactions, affect emulsion stability and the properties of the oil/water interface. First, the effects of asphaltene concentrations, components, and temperatures on emulsion stability and the association state of asphaltenes were explored using the bottle test method and dynamic light scattering, respectively. The promotion of asphaltene aggregation by higher asphaltene concentrations and liquid paraffin content was confirmed by comparing the average size of aggregates, while higher temperatures were found to inhibit aggregation. Higher temperatures destabilize emulsions containing asphaltenes by increasing water droplet collisions, whereas higher asphaltene concentrations and liquid paraffin content stabilize emulsions. Subsequently, the effects of these conditions on expansion modulus were thoroughly investigated using the pendant drop technology. Pendant drop experiments demonstrate that increasing asphaltene concentration, along with the introduction of liquid paraffin, enhances asphaltene aggregation, thereby reinforcing the structural stability of the interfacial film. Spinning drop experiments were conducted to obtain dynamic interfacial tension (IFT) and analyze the adsorption behavior of aggregates at the oil/water interface. The adsorption process of asphaltenes driven by intermolecular interactions, occurs in three regimes: a short-term diffusion-controlled process, a transition process, and a long-term low-speed descent process, referred to as Regimes I, II, and III. The diffusion coefficient in Regime I increases with temperature, while the equilibrium IFT in Regime III decreases with temperature. In Regime II, adsorbed asphaltene aggregates from Regime I tend to prevent further adsorption, reducing the rate of dynamic IFT decrease. In Regime III, dynamic IFT decreases slowly, primarily due to the continued adsorption of asphaltene aggregates into the sublayer and their subsequent reconfiguration. These findings have significant implications for improving the understanding of oil/water interface properties and emulsion behavior in oil production, transportation, and refining systems.

Mechanism study on rheological response of thermally pretreated waxy crude oil

Pre-heating treatment significantly influences the low-temperature flow characteristics of waxy crude oil, yet its underlying mechanism warrants further investigation. This study explores the effects of pre-heating temperatures (60–110 °C) on the rheological characteristics of waxy crude oil from Nanyang using 1H NMR, DSC, Microscopic Observation, and Rheological Property Test. Findings reveal that asphaltenes increasingly dissolve at the pre-heating temperature of 70 °C, improving their capacity to act as nucleation sites for wax crystals. Consequently, the wax appearance temperature (WAT) increases. Meanwhile, the rheological parameters of the crude oil decrease and wax crystals exhibit smaller and tighter rod-like structures. Further growing the pre-heating temperature to 80 °C induces a comprehensive effect: alterations in asphaltene polarity, hindrance of asphaltene aggregation by alkyl side chains, and self-aggregation of alkyl side chains. This results in decreased WAT, along with the lowest rheological parameter values, with wax crystals appearing as the smallest and tightest dot-like shapes. At 80 °C, the optimal ratio between asphaltene polarity and alkyl side chain characteristics promotes strong nucleation and co-crystallization between asphaltene and wax crystals, maximizing asphaltene's ability to enhance the crude oil's low-temperature flowability. However, as the pre-heating temperature continues to rise, WAT decreases slightly and the rheological response starts to deteriorate.

Nuclear Magnetic Resonance (NMR) Assessment of Bio and Crude Oil-Based Rejuvenation

Asphalt binders in pavements lose their stability through aging and eventually fail in the field. Using nuclear magnetic resonance (NMR) to monitor the primary longitudinal relaxation time of asphalt samples and the ratio of material that carries this primary relaxation time has been shown to indicate the impact of ultraviolet (UV) radiation on the aging of asphalt pavements. Longitudinal NMR relaxation was used to investigate two types of proposed asphalt rejuvenators, a bio-oil-based rejuvenator and a crude-oil-based rejuvenator. Two different binders with the performance grades (PG) 64-22 and 76-22 were considered for their interactions with the rejuvenators. After 72 h of exposure to intense UV radiation, specifically designed NMR relaxometry experiments were applied to compare the rejuvenation capabilities of the two rejuvenator samples. The crude oil-based rejuvenator was found to exhibit relaxation times similar to the binder samples while the bio-based material showed relaxation times that pointed to different nuclear hydrogen environments. Both rejuvenators reduced the primary relaxation time of the PG 76-22 binder, which indicates that their stiffness was reduced. Both types of rejuvenators also seemed to prevent the effects of UV aging. Two mechanisms of rejuvenation were identified by NMR relaxometry. The primary relaxation time can be used to indicate a change in stiffness while the primary ratio of the material is tied to oxidative aging. Oxidative aging creates distinct hydrogen environments due to asphaltene aggregation. The bio-based rejuvenator only reduced the binder’s stiffness, while the crude oil-based rejuvenator also reduced the aggregation of asphaltenes. Consequently, the bio-based rejuvenator could be classified as an asphalt softener, while the oil-based material acted like a true rejuvenator.

Hydroxyl-Functionalized Carbon Nanoparticles Alter the Asphaltene Aggregate Structure and Reduce the Viscosity of Heavy Oil

Hydroxyl-Functionalized Carbon Nanoparticles Alter the Asphaltene Aggregate Structure and Reduce the Viscosity of Heavy Oil

Large-scale molecular dynamics simulation and aggregate behavior research on asphalt

In this comprehensive study, a molecular dynamics (MD) model consisting of approximately 150,000 atoms was developed within the Strategic Highway Research Program (SHRP) framework to investigate the behavior of AAA asphalt, focusing on asphaltene aggregate dynamics behavior over a simulation time span of 0.282 microseconds. The findings reveal that the model achieves a stable state in terms of both energy and microstructure without significant changes or the formation of densely clustered molecules, despite the extensive simulation period. Notably, the patterns of asphaltene aggregation were found to significantly influence the MD system energy, with variations ranging from loosely organized structures due to dispersed asphaltenes to more structured, energy-efficient clusters formed by encapsulated asphaltene pentamers. The size of asphaltene aggregates emerged as a pivotal factor, affecting their encapsulation and leading to distinct formation patterns. Furthermore, the research highlighted that increasing shear rates prompt the depolymerization of asphaltene aggregates, shifting from large-scale structures to smaller ones and adapting dynamically to the flow conditions by aligning parallel to the shear direction. This study underscores the critical impact of asphaltene aggregate behavior and shear rates on the structural integrity and distribution within the asphalt model, offering profound insights into the MD of asphalt materials.

Impact of various aggregation kinetics on thermophoretic velocity of asphaltene deposition.

Asphaltene deposition may pose serious challenges to flow assurance of crude oil in well columns. Different aggregation kinetics would partly be responsible for asphaltene particle growth ending in deposition on the surface of well columns. This work primarily investigates the thermophoretic deposition velocity caused by temperature gradients inside well columns for various asphaltene aggregation kinetics, including crossover behaviour, sedimentation, reaction-limited aggregation (RLA), and diffusion-limited aggregation (DLA). To do so, the experimental observations of size distribution for a live crude oil was performed at 80°C and pressure range of 4500-5500 psia. Moreover, various patterns of different size distributions were gathered from the literature for the sake of comparison. Next, a well column in southern Iran was selected to study the kinetic behaviour of thermophoretic velocity of deposition, with a difference between geothermal and static temperatures of around 5 to 50°C. The non-isothermal deposition velocity was shown to decrease from the top to the bottom of the well column, according to the findings of the study. The results also revealed that the thermophoretic velocity decreases as particle size increases and vice versa. This was confirmed by examining a comparably large range of asphaltene particle sizes, ranging from approximately 100 nm to roughly 9 µm. Practical implications of these findings were also discussed which would provide guidance for mitigation of asphaltene deposition in well columns.

Microscopic behavior of heteroatom asphaltene in the multi-media model: The effect on heavy oil properties

The high viscosity and surface adsorption of heavy oil pose significant challenges for its exploration. Asphaltenes, the most polar and heaviest components of crude oil, play a crucial role in these properties. Heteroatom asphaltenes (A-X, S-Y) exhibit stronger interaction energy compared to non-heteroatom asphaltenes A-C. The self-assembly of A-X/S-Y forms ordered "reinforcement-cement" aggregates, whereas A-C aggregates are more chaotic. The presence of heteroatoms, particularly the sulfur atom in the side chains, may significantly influences asphaltene aggregation structures. The diffusion coefficient of heteroatom asphaltene in oil droplet is smaller than that of A-C, and these heteroatom compound can bind other oil components, reducing the overall fluidity. Notably, the adsorption energy of asphaltenes on solid surfaces exceeds their interaction energy. Surface aggregation of A-X/S-Y is more dispersed compared to A-C adsorption system. Additionally, the existence of heteroatom asphaltenes can shorten the distance between oil droplets and the solid surface by 16.20 Å compared with non-heteroatom system. These phenomena, caused by A-X/S-Y, further complicate the detachment of crude oil components from surfaces. This study aims to share some new insights into the micro-mechanisms of heteroatom asphaltenes self-assembly and the behavior in the oil-sludge process, which may contribute to the theoretical foundation for the targeted and efficient exploitation of heavy oil.

Mechanism exploration of the modified asphalt binders with sustainable rapeseed-based derivatives using multi-scale evaluation method

Due to the concerns of sustainability, environment, and economy that are associated with non-renewable petroleum-based additives, there has been a growing interest in bio-additives derived from renewable feedstocks. This study aims to reveal the modification mechanism of three bio-additives derived from rapeseed on the base asphalt. The exploration of modification mechanism helped to explain the distinct rheological properties of bio-modified asphalt binders presented in a previous study. The effect of three bio-additives on the surface morphology, micro-mechanical properties, adhesivity, and chemical structure of base asphalt binders were investigated via Atomic Force Microscopy (AFM) and Fourier Transform Infrared spectrometer (FTIR) tests. The Electrostatic potential distribution and the orbital energy was analyzed via density functional theory (DFT) calculation to explore the inherit polarity of both the three bio-additives and asphalt components. Furthermore, molecular dynamic (MD) methods were used to evaluate the compatibility mechanism and aggregation tendency of asphalt components and bio-additives. The results showed that the electrostatic potential and the orbital energy of three bio-additives predominantly centered around the polar group. Specifically, AERO exhibited highest electrostatic potential distribution and lowest energy gap, indicating its heightened polarity. Moreover, the solution parameter difference value of bio-modified asphalt fell within 0.2 (J/m3)0.5, indicating great compatibility between asphalt and bio-additives, especially for ERO. Additionally, three bio-additives mitigated the aggregation of asphaltene within the asphalt due to their electrostatic interaction, especially notable in the cases of ERO and AERO. Furthermore, a cross-link network was formed within AERO-modified asphalt binders owing to its heightened polarity, fostering hydrogen bonding interactions internally and promoting the aggregation of saturate and resin factions around it. Consequently, this led to enhanced modulus and elasticity in the AERO-modified asphalt binders. Rapeseed derivatives as asphalt additives would be a sustainable and durable material for pavement construction and maintenance. It provides a theoretical basis for advancing the practical application of renewable vegetable oils in road engineering, which has exceptional economic and social benefits.

Mechanistic understanding of asphaltene precipitation and oil recovery enhancement using SiO2 and CaCO3 nano-inhibitors

Asphaltene precipitation in oil reservoirs, well equipment, and pipelines reduces production, causing pore blockage, wettability changes, and decreased efficiency. Asphaltenes, with their unique chemical structure, self-assemble via acid–base interactions and hydrogen bonding. Nano-inhibitors prevent asphaltene aggregation at the nanoscale under reservoir conditions. This study investigates the effect of two surface-modified nanoparticles, silica, and calcium carbonate, as asphaltene inhibitors and oil production agents. The impacts of these nano-inhibitors on asphaltene content, onset point, wettability, surface tension, and oil recovery factor were determined to understand their mechanism on asphaltene precipitation and oil production. Results demonstrate that these nano-inhibitors can significantly postpone the onset point of asphaltene precipitation, with varying performance. Calcium carbonate nano-inhibitor exhibits better efficiency at low concentrations, suspending asphaltene molecules in crude oil. In contrast, silica nano-inhibitor performs better at high concentrations. Wettability alteration and IFT reduction tests reveal that each nano-inhibitor performs optimally at specific concentrations. Silica nano-inhibitors exhibit better colloidal stability and improve oil recovery more than calcium carbonate nano-inhibitors, with maximum oil recovery factors of 33% at 0.1 wt.% for silica and 25% at 0.01 wt.% for calcium carbonate nano-inhibitors.

Formulating stable surrogate wood pyrolysis oil-in-oil (O/O) emulsions: The role of asphaltenes evidenced by interfacial dilational rheology

This work presents a novel methodology to obtain stable bio-oil-in-oil emulsions using crude oil endogenous asphaltenes as emulsifiers. This approach provides new insights into the valorization of wood pyrolysis bio-oils through co-processing with crude oils or by direct incorporation in fuels for marine transportation, contributing to a significant reduction of the carbon footprint of these products. Similar to water-crude oil systems, asphaltenes can form a rigid film at the bio-oil / petroleum-derived oil interface, thus limiting droplets coalescence and increasing the emulsion lifetime without requiring additional emulsifier. The evolution of the interfacial layers with the asphaltene content and the nature of the petroleum-derived oil phase were investigated by interfacial rheology. The results show the consolidation of the interfacial layer and the formation of a solid-like film, referred to as “skin” with appropriate asphaltene content and polarity of the oil phase. Changes in the dilational elasticity depend on the asphaltenes aggregation behaviour according to the Yen-Mullins model, and the mechanisms that account for these phenomena are discussed.

Exploring asphaltene aggregation: Model systems based on toluene-heptane mixtures

This work evaluates how chemical characteristics, such as polarity and aromaticity, can affect asphaltene aggregation. The asphaltene fraction was extracted from two different crude oils by precipitation in n-heptane, and these extracted asphaltenes were named A and B. Based on infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) analyses, we found that asphaltenes B present greater aromaticity. According to X-ray photoelectron spectroscopy (XPS), asphaltene B showed higher heteroatom content. Model systems based on toluene/n-heptane/asphaltene (0.05 g/L) were prepared to evaluate the aggregation/precipitation of asphaltenes. Dynamic light scattering (DLS) analysis of aggregation kinetics revealed that aromatic asphaltenes with higher heteroatom content tend to form larger aggregates. Moreover, hydroxyl content exhibits a greater impact on aggregation compared to diffusivity. Furthermore, once the aggregates reach a critical size, the suspension stability is reduced, and the aggregates sediment. The atomic force microscopy (AFM) and DLS results revealed a wide range of particle size distribution. The larger clusters likely consisted of smaller aggregates that adhered together. Still, we highlight that the sizes of these aggregates determined by AFM are not directly comparable to the measurements obtained from DLS. The drying of the samples for the AFM measurements probably affects the asphaltene aggregation process. For this reason, the results obtained from the AFM and DLS techniques are not comparable.

Synthesis and demulsification performance of a novel low-temperature demulsifier based on trimethyl citrate

A significant amount of water-in-oil (W/O) emulsion is generated during petroleum extraction. However, the current commercial demulsifiers are expensive to produce and requires high demulsification temperatures, leading to increased energy and economic consumption. To enhance the efficiency of demulsifiers and reduce the cost of demulsifying W/O emulsions, we have successfully developed a novel demulsifier named TCED through a straightforward two-step process. This demulsifier features trimethyl citrate as the hydrophilic core grafted with three hydrophobic chains. Its structure was characterized using EA, FT-IR and 1H NMR spectroscopy, and the demulsification performance was comprehensively evaluated. At a low demulsification temperature of 40 °C, TCED demonstrated a remarkable demulsification efficiency (DE) of 99.06% and 98.74% in emulsions containing water contents of 70% (E70) and 50% (E50), respectively. Especially, a DE of 100% could be obtained in both E70 and E50 emulsions at a concentration of 600 mg/L. Moreover, TCED displayed a high DE even at high salinity levels of 50,000 mg/L and across a wide pH range of 2–10. Additionally, the phase interface was consistently clear after demulsification. To investigate the demulsification mechanism of TCED, various adsorption kinetics experiments were conducted, including measurements of interfacial tension (IFT), surface tension (SFT), interfacial competitive adsorption, and stability of interfacial film. The results obtained from the experiments indicated that TCED possessed remarkable diffusion and replacement capabilities within the emulsions. As a result, it effectively disrupted the original interfacial active substances, such as asphaltenes aggregates found in crude oil. TCED exhibits a high DE at low concentration and temperature. This characteristic highlights its significant potential for low-temperature demulsification applications in the petroleum industry.

Nonlinear relationship between heavy oil viscosity and asphaltene dispersion: A molecular dynamics simulation study

Theoretically clarifying the sources of viscosity of heavy oil is an essential premise for achieving effective exploitation and viscosity reduction. However, the complicated dispersion behavior of asphaltenes hinders the elucidation of the underlying viscosity mechanisms. Therefore, we investigated the relationship between heavy oil viscosity and asphaltene dispersion, identifying an unconventional nonlinear V-shaped trend. A generalized physical model is then proposed to elucidate the determining sources of heavy oil viscosity. This viscosity model emphasizes the dynamic balance role of external molecular friction and internal structural deformation of asphaltene aggregates in their contribution to viscosity, deepening the understanding of the nature of high viscosity in heavy oil. These results provide valuable theoretical support to enhance our understanding of the microscopic molecular mechanisms underlying heavy oil viscosity, which is expected to contribute to a better comprehension of the intricate viscosity phenomena and the development of more effective viscosity reducers.

Synergistic Effect of Asphaltene, Resin, and Wax Improving the Emulsification and Interfacial Properties of a High-Phase-Inversion Thin Oil.

Nowadays, high-phase-inversion in situ emulsification technology has shown great potential in enhancing oil recovery from high-water-cut thin-oil reservoirs. However, emulsification characteristics, interfacial properties, and the mechanism of high phase inversion have not been systematically described. In this study, an emulsification experiment was conducted to investigate the effects of shear time, shear rate, and temperature on the phase inversion of thin oil. Furthermore, the influence of resin and wax on the dispersion of asphaltene was studied through microscopic morphology analysis. Interfacial tension measurement and interfacial viscoelasticity analysis were carried out to determine the interaction characteristics of asphaltene, resin, and wax at the interface. The results showed that, at 50 °C, the phase-inversion point of thin oil reached as high as 75%, and even at 60 °C, it remained at 70%. The shear time and shear rate did not affect the phase-inversion point of thin oil, while an increase in temperature led to a decrease in the phase-inversion point. Moreover, compared to the 20% phase-inversion point of base oil, the phase-inversion point increased with different proportions of asphaltene, resin, and wax. Particularly, at the ratio of asphaltene/resin/wax = 1:5:9, the phase-inversion point reached as high as 80%, indicating the optimal state. In this proportion, asphaltene aggregates exhibited the smallest and most uniform size, best dispersion, lower interfacial tension, and higher interfacial modulus. These findings provide reference and guidance for further enhancing oil recovery in medium-to-high-water-cut thin-oil reservoirs.

Density functional theory investigation of the contributions of π-π stacking and hydrogen bonding with water to the supramolecular aggregation interactions of model asphaltene heterocyclic compounds

ContextA complex supramolecular process involving electrostatic and dispersion interactions and asphaltene aggregation is associated with detrimental petroleum deposition and scaling that pose challenges to petroleum recovery, transportation, and upgrading. The homodimers of seven heterocyclic model compounds, representative of moieties commonly found in asphaltene structures, were studied: pyridine, thiophene, furan, isoquinoline, pyrazine, thiazole, and 1,3-oxazole. The contributions of hydrogen bonding involving water bridges spanning between dimers and π-π stacking to the total interaction energy were calculated and analyzed. The distance between the planes of the aromatic rings is correlated with the π-π stacking interaction strength. All the dimerization reactions were exothermic, although not spontaneous. This was mostly modulated by the strength of the hydrogen bond of the water bridge and the π-π stacking interaction. Dimers bridged by two water molecules were more stable than those with additional water molecules or without any water molecule in the bridge. Energy decomposition analysis showed that the electrostatic and polarization components were the main stabilizing terms for the hydrogen bond interaction in the bridge, contributing at least 80% of the interaction energy in all dimers. The non-covalent interaction analysis confirmed the molecular sites that had the strongest (hydrogen bond) and weak (π-π stacking) attractive interactions. They were concentrated in the water bridge and in the plane between the aromatic rings, respectively.MethodsThe density functional ωB97X-D with a dispersion correction and the Def2-SVP basis set were employed to investigate supramolecular aggregates incorporating heterocycles dimers with 0, 1, 2, and 3 water molecules forming a stabilizing bridge connecting the monomers. The non-covalent interactions were analyzed using the NCIplot software and plotted as isosurface maps using Visual Molecular Dynamics.

Adsorption of Asphaltenes at Model Oil/Brine Interface: Influence of Solvent Polarity.

With the exploitation of heavy oil worldwide, the influence of asphaltene aggregation in the oil phase on the stability of crude oil emulsion has been paid more and more attention. Under this background, the effects of solvent polarity on model oil/brine water interfacial properties and emulsion stability are investigated in this study. It is demonstrated that there is a critical asphaltene concentration for the formation of a stable emulsion. This critical concentration is then found to increase from 80 to 500 ppm with the mixing ratio of methylnaphthalene to n-decane changed from 2:3 to 7:3. The dynamic light scattering experiment shows that the average aggregate size increases abruptly from 132.8 to 261.1 nm at 2:3 mixing ratio of methylnaphthalene to n-decane once the asphaltenes are added to above the critical concentration. Accordingly, the diffusion coefficient of the asphaltenes decreases sharply from 4.36 × 10-12 to 5.68 × 10-13 m2/s. Similar conclusions are also found for the other mixing ratios of 1:1, 3:2, and 7:3. Besides, the aggregation degree of asphaltenes weakens, and the diffusion coefficient enlarges at the same asphaltene concentration with the enhancement of the solvent polarity. Further, the interfacial experiments manifest that the equilibrium interfacial dilation modulus decreases from 38.42 to 23.65 mN/m with the mixing ratio of methylnaphthalene to n-decane increased from 2:3 to 7:3. It can thus be inferred that the structural strength of the interfacial film decreases with the enhancement of the solvent polarity.