Asphaltene Adsorption Research Articles

Synthesis of novel green nanocomposites by considering enhanced oil recovery and asphaltene adsorption effectiveness in calcite and dolomite formations

Asphaltene deposition is known as the main issues in reservoirs, which causes formation damage in reservoir. This research investigated the effects of a newly introduced green nanocomposites, namely eucalyptus/CuO/Fe3O4/xanthan nanocomposites (EC-NCs), on the inhibition of asphaltene precipitation in calcite and dolomite formations. First, at two time steps of 48 and 96 h, asphaltene adsorption on EC-NCs surfaces was examined through scanning electron microscope (SEM) tests in both calcite and formation tests. Moreover, asphaltene adsorption on the surface of EC-NCs was confirmed through isotherm models including Langmuir and Freundlich and the interfacial tension between CO2 and oil. Finally, a series of static and dynamic tests were performed at the highest adsorption pressure points, including 4200, 3950, and 3700 psi, and at the highest adsorption time step, i.e., 96 h, and the effects of asphaltene adsorption were seen on permeability reduction and asphaltene precipitation. EC-NCs exhibited superior efficacy in both asphaltene adsorption and precipitation inhibition. Two separate pressure changes were observed, and the ratios of the interfacial tension slope in the 2nd to the 1st regions [1st: 200–2700 psi, 2nd:2700–4200 psi] were changed from 19.44 % to 25.00 % and 29.74 % in 48 and 96 h, respectively, and this confirms that asphaltene had indeed adhered to the surface of the EC-NCs. Moreover, at 48, and 96 h, the size reductions of particles in SEM for calcite and dolomite were (29.27 %, 56.81 %), and (59.09 %, 62.25 %), respectively, which shows asphaltene adsorption was more efficient in dolomite formation, and in 96 h.

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.

Enhancing Asphaltene Adsorption and Dispersion in Crude Oil With Multiwalled Carbon Nanotubes: Optimization via Response Surface Methodology Approach

Enhancing Asphaltene Adsorption and Dispersion in Crude Oil With Multiwalled Carbon Nanotubes: Optimization via Response Surface Methodology Approach

Development of Nanofluid-Based Solvent as a Hybrid Technology for In-Situ Heavy Oil Upgrading During Cyclic Steam Stimulation Applications.

This paper evaluates solvent-based nanofluids for in situ heavy oil upgrading during cyclic steam stimulation (CSS) applications. The study includes a comprehensive analysis of the properties and characteristics of nanofluids, as well as their performance in in situ upgrading and oil recovery. The evaluation includes laboratory experiments to investigate the effects of the nanoparticle's chemical nature, asphaltene adsorption and gasification, heavy oil recovery, and quality upgrading. The results show that alumina-based nanoparticles have a higher efficiency in asphaltene adsorption and catalytic decomposition at low temperatures (<250 °C) than ceria and silica nanoparticles. Specifically, alumina nanoparticles achieved asphaltene adsorption of 48 mg g-1, while ceria adsorbed 42 mg g-1. Alumina and ceria required around 90 and 135 min for 100% asphaltene conversion. Nanofluids were designed by varying nanoparticle and surfactant concentrations dispersed in naphtha, obtaining that the nanofluid containing 0.05 wt % of nanoparticles and 0.05 wt % of surfactant presents the highest yield in increasing API gravity by 5° and reducing oil viscosity by 90% in thermal experiments. Finally, the nanofluid was evaluated under dynamic conditions. The results show that nanofluid-based solvents can significantly improve the recovery and upgrading of heavy oil during CSS applications. When the steam injection technology was assisted by naphtha and nanofluid, 64% and 75% of the original oil in place were recovered, respectively. The effluents obtained in each stage presented lower API gravity values and higher viscosities for those obtained without a nanofluid. Specifically, the API gravity of the recovered oil rose from 11.9° to 34°, and the viscosity decreased to below 100 cP. The paper concludes by highlighting the potential of nanofluid-based solvents as a promising technology for heavy oil recovery and upgrading in the future.

Probing the interactions between asphaltenes and a PEO-PPO demulsifier at oil–water interface: Effect of temperature

HypothesisAsphaltenes are primary stabilizers in water-in-oil (W/O) emulsions that cause corrosion and fouling issues. In oil sands industry, oil/water separation processes are generally conducted at high temperatures. A high temperature is expected to impact the interactions between asphaltenes and emulsion breakers (EBs), consequently influencing demulsification performance. ExperimentsThe adsorption and interactions of asphaltenes and a PEO-PPO type EB (Pluronic F68) at the oil–water interface were investigated at various temperatures, using tensiometer, quartz crystal microbalance with energy dissipation (QCM-D), and atomic force microscopy (AFM). The effect of temperature on EB’s demulsification performance was explored through bottle tests. Additionally, demulsification mechanisms were studied using direct force measurements with the droplet probe AFM technique. FindingsDynamic interfacial tension and QCM-D results demonstrate that the PEO-PPO type EB exhibits higher interfacial activity than asphaltenes and can disrupt rigid asphaltene films at the oil–water interfaces. Elevated temperatures accelerate the displacement of adsorbed asphaltenes by EB molecules, leading to sparse interfacial films, rapid droplet coalescence, and improved demulsification efficiency (supported by AFM and bottle test results). This work provides valuable insights into interfacial interactions between asphaltenes and EB at different temperatures, enhancing the understanding of demulsification mechanisms and offering useful implications for the development of efficient EBs to enhance oil/water separation performance.

TECHNOLOGICAL COMPLICATIONS (FORMATION DAMAGE) DURING CO2 INJECTION FOR ENHANCED OIL RECOVERY. Part 2. INTERACTION OF CO2 WITH FORMATION OIL: WETTABILITY CHANGE, ASPHALTENE PRECIPITATION AND DEPOSITION IN THE FORMATION

In the second part of the review (the first part was published in [1]) the processes of formation damage at CO2 injection due to the oil phase stability disturbance are considered. Changes in reservoir temperature, pressure or fluid composition due to CO2 dissolution can provoke asphaltene precipitation and deposition. Their adsorption on the reservoir pore surface leads to a change in decrease in rock permeability. The currently ac wettability and a cepted numerical models describe well the experimental results on colmatation of pore media by asphaltenes in the presence of CO2, with different equations for asphaltene adsorption and kinetics of their occurrence being used in the models. Asphaltenes precipitated in pore volumes migrate with formation fluids to production wells and can form deposits that complicate oil production.

Computational Study of Asphaltene Adsorption on Carbonate Surface: Role of Molecular Structure and Oil Phase

Computational Study of Asphaltene Adsorption on Carbonate Surface: Role of Molecular Structure and Oil Phase

Influence of CO2 on asphaltene adsorption dynamics at the Oil-Gas Interface: New insights into precipitation and aggregation processes

To investigate the effect of CO2 on the precipitation of asphaltene in oil, and verify the advantages of CO2 flooding, this work designs interfacial tension experiments and PVT system experiments to create the experimental environment under different temperature and pressure conditions that make CO2 contact with oil. The results indicate that CO2 can affect the oil morphology, and the trend of oil volume increase and decrease depends on the dynamic balance between the expansion effect and the component extraction effect of CO2 on oil. Under low pressure, the oil expansion caused by dissolved CO2 dominates the experiments, increasing the oil volume. Under high pressure, sufficient CO2 in the oil activates its component extraction effect, and the asphaltene in the oil precipitates and accumulates at the interface between the oil and CO2 due to the disruption of the component equilibrium of the system, exerting a surface activity effect, leading to a decrease in oil volume. Due to the movement of asphaltene towards the system interface and the formation of an asphaltene film during this stage, which hinders the entry of CO2 into the oil, the interfacial tension shows three linear decreasing trends with increasing pressure. This mechanism also changes the variation trend of the oil volume in CO2 during the pressure increase. Moreover, the components of the oil extracted by CO2 will be transferred to CO2, making its properties similar to oil. With the reduction of interfacial tension, this process promotes the miscibility between the two. These effects verify that CO2 can improve the fluidity and quality of oil during reservoir development, and reduce or even eliminate the adhesion work required for the working fluid to displace the oil. These conditions are conducive to improving reservoir development efficiency, reflecting the great application value of CO2 flooding.

Molecular-atomic scale insights into polymer-asphalt interactions induced by the oxidation of reactive oxygen species via computational simulation and multifield microscopy characterization

The objective of this study is to investigate the intermolecular interactions between polymers and asphalt components due to the oxidation of reactive oxygen species (ROS). Quantum chemistry (QC) and molecular dynamics (MD) were employed to simulate the molecular properties and intermolecular interactions between SBS and asphalt components during ROS aging. Multifield optical microscopy was utilized to analyze the microstructural characteristics and validate intermolecular interactions of SBS and asphalt components during ROS aging. The results show that asphaltenes have the most uneven electrostatic potential (ESP) distribution, followed by resins and aromatics, while saturates exhibit the most uniform ESP distribution. ROS aging leads to a more uneven ESP distribution and a higher polarity for HiMA molecules, especially for asphaltenes and resins with increased formation of polar functional groups. SBS and saturates exhibit small energy gaps and electronic softness, indicating good resistance to ROS oxidation, whereas asphaltenes and resins are prone to free radical oxidation reactions with ROS. The potential ROS oxidation site of asphaltenes and resins are mainly distributed in benzene ring regions and heteroatoms, while that of SBS are primarily located at the polybutadiene chains. The interactions between SBS and asphalt components are primarily driven by van der Waals forces. However, the hydrogen bonding appears after ROS aging, enhancing the intermolecular interactions. The interaction energies of SBS-asphaltenes and SBS-resins are significantly enhanced, and the intermolecular distances are shortened as ROS aging progresses. Multifield microscopy observation reveals that the development of bee structures in polymer regions is significantly faster than that in asphalt regions, indicating a significantly enhanced adsorption of asphaltenes by polymers after ROS aging. This is attributed to the uneven charge distribution, increased polarity, and enhanced reactivity of asphaltenes and SBS due to ROS aging. This study contributes to a molecular-atomic-level understanding of the intermolecular interactions between polymers and asphalt components during ROS aging.

External electric field effects on asphaltene adsorption on Kaolinite-water interface: A molecular dynamics study

Applying electric fields to promote water/oil recovery efficiency is gaining increasing attention in downstream of heavy oil development. In this work, molecular dynamics simulations were performed to study the motion of N-(1-Hexylheptyl)-N′-(5-carboxylicpentyl) perylene-3,4,9,10-tetracarboxylic bisimide (C5Pe) between kaolinite (Kaol) surfaces mediated by external electric field in water under different pH. Aggregation of C5Pe was mainly mediated by pH and not affected by the electric field, while adsorption responded to both pH and the electric field. In neutral and alkaline solutions, C5Pe was deprotonated, and its distribution between two Kaol surfaces was mainly mediated by the Coulombic force exerted by the electric field. In acidic solutions, C5Pe carried zero charge, and yet its distribution was still affected by the electric field. The external electric fields mediated the wettability of the two Kaol surfaces in different extents, and C5Pe preferred to adsorb on the more hydrated surface. The mediation of the electric fields on the wettability of surfaces was achieved in two stages. In the first stage, when the electric field of a low strength was applied, diffusion of water enhanced. The hydration of both Kaol surfaces became increased as water molecules formed more hydrogen bonds with the surfaces. As the electric field strength became sufficiently high, diffusion showed no further enhancement, and the re-orientation of water dipoles started dominating the hydrogen bonding with the surfaces. Carrying opposite charges, the hydrogen bond donors and acceptors of water were differently regulated by the electric field, and therefore water molecules conformed in a certain manner under the electric field of high strength. As a result, the hydrogen bonding between water and the two Kaol surfaces (placed on two sides of the simulated box under the electric field) varied with their positions. Due to the structural hindrance of the hydroxyl groups on the surface, the surface could provide more hydrogen bonding donors formed more hydrogen bonds with water, and thus became more hydrophilic and had stronger attraction to C5Pe.

Study on the effect and mechanism of temperature and shear on the stability of water–in–oil emulsion stabilized by asphaltenes

As a complex component of crude oil, asphaltenes determine the stability of emulsion. However, the mechanism of asphaltenes stabilize emulsion is still insufficient recognition due to the complexity of the molecular structure of asphaltenes. In this paper, the experiments and dissipative particle dynamics simulations were used to study the interfacial properties of asphaltenes. The adsorption of asphaltenes at the oil–water interface was studied by interfacial tension (IFT) experiments. A realistic molecular structure of asphaltene was constructed on the results of the characterization of the asphaltenes. The effects of asphaltenes concentration, temperature, and shear on the formation and stability of emulsion based on this molecular structure were investigated by simulations. The results show that the IFT decreases as asphaltenes concentration increases, while the droplet size of the emulsion decreases and becomes more uniformly distributed. Increasing the temperature enhances the interfacial activity of the asphaltenes, but also promotes its dissolution in the oil phase, which has a negative effect on reducing the IFT value and the stability of the emulsion. As the shear rate increases, the configuration of the emulsion changes from droplets to ellipsoids and rods, and the structure of the interfacial film is disrupted. This work provides useful insights into the mechanisms of asphaltenes concentration, temperature, and shear on the stability of the emulsion.

Different effects of resins and asphaltenes concentration of crude oil on sandstone wettability

The influence of asphaltenes in crude oil on sandstone wettability is widely acknowledged. Although asphaltenes are recognized for their stronger polarity compared to resins, resins also contain the similar acidic and nitrogen-containing compounds to those found in asphaltenes. Nevertheless, the impact of resin adsorption on altering sandstone wettability, the different effects of vary concentrations of resins and asphaltenes, and their microscopic mechanisms influencing sandstone surfaces remain ambiguous. Thus, in this study, resins and asphaltenes were isolated from crude oil individually to investigate the different effects of their concentrations on sandstone wettability and the specific reasons. The contact angle measurements, atomic force microscopy (AFM), energy dispersive spectroscopy (EDS), and Cryo-environmental scanning electron microscopy (ESEM) were used to examine and explain the wettability changes of Berea sandstone slices before and after exposure to varying concentrations kerosene solutions of resins and asphaltenes. The results reveal that sandstone wettability could not be changed from strongly water-wet to oil-wet, even at resin concentrations as high as 50.0 mg/mL kerosene. In contrast, lower concentrations of asphaltenes, equivalent to a 5.0 mg/mL kerosene threshold, can facilitate the wettability transition process. After the adsorption of resins and asphaltenes, the roughness of the clay surface changes much more significantly than that of the quartz surface. Combined with the observation of ESEM and the results of EDS, it is believed that the resins and asphaltenes preferentially adsorb to clay surfaces, especially chlorite, rather than quartz surfaces. Clay could provide favorable sites for the accumulation of oxygen-containing compounds, leading to enduring clay-organic complexes that serve as anchor molecules for the adsorption of other compounds, ultimately causing the sandstone surface to an oil-wet state. These results may provide theoretical support for better core aging process in the laboratory, surfactant development and enhanced oil recovery procedure optimization in the oilfield.

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.

Asphaltene Adsorption on Solid Surfaces Investigated Using Quartz Crystal Microbalance with Dissipation under Flow Conditions.

Asphaltenes can cause operational challenges in petroleum production facilities and adversely affect production by adsorption on mineral surfaces and alteration of the oil wettability of reservoirs. Therefore, understanding asphaltene adsorption mechanisms and their effects is crucial to improving the efficiency of oil production and reducing costs. In this study, we focus on understanding the impact of asphaltene concentration and the depositing environment of asphaltene adsorption on solid surfaces using the quartz crystal microbalance with dissipation (QCM-D) technique. The initial and long-term kinetics of adsorption at different concentrations were examined on three different solid surfaces including silicon dioxide to represent quartz mineral, stainless steel, and gold. The frequency-dissipation data showed evidence of monolayer adsorption initially, followed by multilayer formation. At short times, the adsorbed mass increased linearly with time, suggesting that the process was kinetically controlled rather than diffusion-controlled. The results were reproducible and did not depend on convection velocity but did depend on the surface material. At later stages, the monolayer development appeared to follow the random sequential adsorption (RSA) theory. Once multilayer adsorption commenced, the rates agreed well with the two-layer model of Zhu and Gu, 1990. The impact of asphaltene adsorption on the wettability of the surface was examined using contact angle studies, which showed decreasing water wettability with an increase in the adsorbed mass. The contact angle of water after 12 h of adsorption leveled off at around 100° on all three surfaces. Contact angle measurements were also used to evaluate if brine salinity causes the wettability alteration of surfaces with the adsorbed asphaltene. The results indicate that at 3% NaCl solution, the contact angle decreased only slightly by less than 2°.

Performance Investigation of Asphaltene Adsorption at a Carbonate Rock Surface: Spectroscopy Experiment and Molecular Simulation.

Investigation of asphaltene adsorption at rock surfaces plays an important role in enhanced oil recovery (EOR) for the petroleum industry. In this work, the interaction performances of asphaltene adsorption at carbonate dolomite and calcite surfaces are investigated based on experimental and simulation insights. On the one hand, macroscopic interaction performances were investigated by spectroscopy experiments to obtain the Langmuir thermodynamic model and pseudo-second-order (PSO) kinetic model. The results indicated monolayer molecular asphaltene adsorption for both dolomite and calcite, while they showed 'slow adsorption-slow desorption' for dolomite but 'fast adsorption-fast desorption' for calcite. Meanwhile, dolomite showed a higher adsorption capacity with qm(dol1) = 5.35 mg/g > qm(cal1) = 1.28 mg/g and a stronger adsorption spontaneity with ΔGm(dol1)θ = -7.76 kJ/mol < ΔGm(cal1)θ = -4.76 kJ/mol. On the other hand, microscopic interaction performances were investigated for three asphaltene molecules by molecular dynamics simulation (MDS) with ∼8 Å distance-placing and 500 ps time-running. According to the results, dolomite showed higher system stability than calcite with a lower final energy of ΔEdol-cal = -58 kJ/mol, and archipelago asphaltene showed higher adsorption stability with the smallest equilibrium energy of Earch(dol) = -147 kJ/mol for albite and Earch(cal) = -89 kJ/mol for calcite. The model of molecular orientation and force dominance was proposed as the interaction mechanism for asphaltene adsorption, which "lie sideways" at low concentrations but "stands upright" at high concentrations. This work allows the performance investigation and mechanism illustration of asphaltene adsorption at rock surfaces, which can help gain a fundamental understanding of the EOR during reservoir exploitation.

Insights into Asphaltene Adsorption on Sandstone Surface by Experiment and Simulation: Performance and Mechanism Investigation

Insights into Asphaltene Adsorption on Sandstone Surface by Experiment and Simulation: Performance and Mechanism Investigation

A novel method for examining the influence of molecular and structural properties of the asphaltene fraction on the wettability change of the calcite surface

Asphaltene deposition in the porous media of the reservoir during the production life causes serious challenges with significant economic cost. From the point of view of proactive action to prevent the formation of such precipitates, today asphaltene inhibitors are widely used in the oil industry. The successful performance of inhibitors strongly depends on molecular structure of asphaltene. This study investigates the effect of molecular-structural properties of asphaltene in four crude oil samples on calcite surface wettability. The wettability of the calcite surface is evaluated with contact angle test and micromodel. The crude oil properties are determined using DHA (Detailed Hydrocarbon Analysis) and FTIR (Fourier Transform Infrared Spectroscopy) tests, while the molecular-structural properties of asphaltene are assessed using elemental analysis, FESEM (Field Emission Scanning Electron Microscopy), NMR (Nuclear Magnetic Resonance), and FTIR techniques. Based on FTIR analysis of oil samples, the higher polarity of samples B and G compared to samples F and A can be attributed to the presence of C = O carboxylic acid stretches. In addition, DHA analysis indicates that sample B, which contains heavier compounds comprising 27.4220 % of the C14+ compounds by weight, exhibits distinct characteristics. The FESEM images demonstrate a uniform and smooth spread surface morphology of the asphaltene samples. However, the elemental analysis does not establish a correlation between the heteroelement ratios of N/C, O/C, and S/C and asphaltene adsorption tendency. FTIR and NMR analyses suggest that the wetting properties observed on the surface are mainly attributed to the high aromatic and aliphatic compounds present in the asphaltene of sample B, while the polar compounds are less influential. The results reveal that crude oil sample B exhibits the highest percentage of damage to the porous medium caused by asphaltene deposition, with a rate of 36.18 % and a contact angle of 163.53 degrees. This indicates a wetter surface of the oil compared to other samples. Samples G and A follow with contact angles of 157.34° and 153.60°, respectively. On the other hand, sample F shows the lowest wettability change on the calcite surface with a contact angle of 144.77° and only 0.08 % damage to the porous medium.

A mechanistic study of asphaltene formation and aggregation in presence of metallic-based nanoparticles

In this work, the effects of metallic-based nanostructures including iron oxide (Fe2O3), magnesium oxide (MgO) and zinc oxide (ZnO) on asphaltene precipitation and aggregation were explored. The synthesized nanoparticles were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), Fourier-transform infrared spectroscopy (FTIR), and Brunauer, Emmett and Teller (BET) methods. Optical microscopy and asphaltene dispersant tests (ADTs) were utilized to discover the effects of nanoparticles on asphaltene stability and the size-growth of asphaltene aggregates in crude oil medium. The interactions of the asphaltene functional groups with metal oxide nanoparticles were evaluated at molecular scale by thermogravimetric analysis (TGA/DTG), FT-IR, and field emission scanning electron microscopy (FESEM). Results of different experiments exhibited that synthesized nanostructures in general postpone the asphaltene onset of precipitation (AOP) and reduce the size of asphaltene aggregates in unstable crude oil medium. MgO nanoparticles with a concentration of 300 ppm had the greatest effect on controlling the asphaltene precipitation and aggregation. The TGA/DTG analysis showed that the oxidation of pure asphaltenes occurs at a temperature of about 425 °C, while the oxidation temperature of asphaltenes adsorbed on ZnO and Fe2O3 nanoparticles occurs at around 330 °C, and for MgO nanoparticles at about 365 °C. In addition, the spectra obtained from the FT-IR analysis for asphaltenes without and with nanoparticles at the wavelengths of 1450 and 2900 cm−1 show the medium C–H stretching bonds that play the most important role in the adsorption of asphaltene on the surfaces of the nanoparticles. Also, the recorded FESEM images of the asphaltene and nanoparticles demonstrated the proper absorption of asphaltenes in the empty spaces between the structures of nanoparticles. According to the results from different experiments and intermolecular analyses, the performance of synthesized nanoparticles for retarding asphaltene precipitation and dispersing the asphaltene aggregates was in order of MgO (300 ppm) > Fe2O3 (300 ppm) > ZnO (700 ppm). The results of intermolecular analyses established the effective adsorption of the asphaltene particles onto the surface of the nanoparticles, which is caused by strong hydrogen interactions between the active sites of the asphaltene and nanoparticles. The findings of this study prove that metal-oxide nanoparticles can be utilized as an economically and environmentally-effective agents for controlling asphaltene formation and aggregation in crude oil.

Evaluation of rock and fluid intermolecular interaction between asphaltene and sand minerals using electrochemical, analytical spectroscopy and microscopy techniques

Long-time contact of heavy crude oil with rock leads to an adsorption phenomenon, which causes the rock surface to become oil-wet and appears as a barrier to the fluid flow in the porous media. However precise understanding of how asphaltene fractions influence sand wettability is lacking. The wetness of neat and asphaltene-aged sandstone was calculated using two relative permeability and contact angle methods. Then the molecular interaction between asphaltene and sand minerals was systematically analyzed using Fourier-transform infrared spectroscopy. Furthermore, the zeta potential was representative of electrostatic properties and surface charge alteration of the sand after these phenomena. Scanning electron microscopy with energy-dispersive X-ray (EDX) analysis also showed elemental mapping and dispersion of asphaltene particles on the rock surface. According to contact angle and EDX analyses of asphaltene samples, the contact angle rises from 115° to 141° by an increase in carbon adsorption on the sand surface from 8.23 to 41.56%. Spectroscopy results demonstrated that hydrogen-bonding, π-bonding, and sulfur-containing compounds such as sulfoxide improve asphaltene adsorption onto the sand surface. The higher the aromaticity index and hydrogen potential index of asphaltene, the greater the ability of asphaltene to change wettability. Adsorption of surface active components would make the surface charge of the sand more negative. The presence of nitrogen/sulfur-containing functional groups on the sand surface changed the electrostatic properties, as a sand surface coated with asphaltene would reduce the percentage of metal cations.

Water-CO2 wettability on sandstone surface with asphaltene adsorption: Molecular dynamics simulation

The reactions between CO2 slugs and crude oil induce a substantial amount of asphaltene precipitation and adsorption on the rock surface during the CO2 alternative water flooding process. When the subsequent water slug passes through the core pores after asphaltene adsorption, it will displace the previous CO2 slug. The wettability of water and CO2 on the asphaltene-adsorbed rock surface will directly determine the magnitude and direction of the capillary force of the two media, which in turn affects their flow resistance and flow pattern analysis. In this paper, the systems of CO2/water/sandstone and CO2/water/asphaltene adsorption sandstone were established by molecular dynamics simulation technology. The effects of asphaltene adsorption, thickness of the asphaltene adsorption layer, CO2 density, mass fraction and type of salt in water on the wettability of water on sandstone surfaces were studied. The results reveal that asphaltene adsorption significantly reduces the wettability of water on the original powerful water-wetting sandstone surface, making it easier to see how CO2 density affects the wettability of water on the asphaltene-adsorbed sandstone surface. The increased CO2 density will continue to lower the wettability of water on the asphaltene-adsorbed sandstone surface, even causing it to become wet with CO2. The adsorption thickness of asphaltene does not affect the wettability of water and CO2 on the asphaltene-adsorbed sandstone surface, and just a layer of 5A-thick asphaltene adsorption can significantly reduce the wettability of water on sandstone surfaces. Furthermore, a rise in salinity in water has a detrimental impact on the wettability of water on the asphaltene-adsorbed sandstone surface, with divalent salts having a stronger negative effect than monovalent salts.