Asphaltene is the compound with the most complex structure and the most difficult degradation in oily sludge, which is the key to limit the efficiency of supercritical water oxidation treatment of oily sludge. In this paper, the supercritical water oxidation process of asphaltene was investigated in terms of free radical reaction, degradation pathway, and product generation mechanism using ReaxFF molecular dynamics simulation method. The results showed that increasing temperature, increasing O2, and increasing H2O have different effects on HO2·generation. Benzene rings undergo fusion and condensation through hydrogenation abstraction and oxygen addition reactions, subsequently breaking down into long-chain alkanes. Increasing O2 can effectively promote the ring-opening of nitrogen-containing heterocycles. -COOH is the most important intermediate fragment for CO and CO2 generation, and there is a reaction competition with -CHO3 and -CO3. When the number of oxygen molecules increases from 300 to 700, the reaction frequency of -CHO3 and -CO3 to generate CO and CO2 increases by 17.14 % and 12.77 %·H2O determines the production of H2 by controlling the number of H·radicals present. As the amount of H2O increases from 500 to 1500, the product ratio of H2 increases from 12.73 % to 21.31 %. ENVIRONMENTAL IMPLICATION: Asphaltene is the most structurally complex organic matter in oily sludge, and its presence makes it difficult for oily sludge to be completely degraded by conventional treatment methods such as pyrolysis and incineration. Polycyclic aromatic hydrocarbons (PAHs) represented by asphaltene increase the carcinogenicity and mutagenicity of oily sludge, and even irreversibly pollute soil and groundwater. Supercritical water oxidation, as an efficient organic waste treatment technology, can realize harmlessness in a green and efficient way. So the study on the mechanism of supercritical water oxidation of asphaltene is of great significance for environmental protection.

Using smart or low salinity waters known as green processes gained increasing attention due to their unique features and their positive impacts on the environment. In light of this fact and since there is limited knowledge about the effects of salts under engineered concentrations or binary mixtures and crude oil fractions on the interfacial tension (IFT) reduction and wettability alteration of the resinous (RSO) and asphaltenic synthetic oil (ASO), the current investigation is designed and performed for the first time. Moreover, the dynamic behavior of the IFT variation was carefully investigated and the relaxation time was obtained and modeled to see the impact of mono and divalent salts individually and in binary conditions. The relaxation times revealed that the lowest adsorption times were obtained for NaCl/CaCl2 brine regardless of the examined oil types of ASO and RSO due to the high movement affinity of the polar functional groups toward the interface consequently reducing the required time for coverage and packing of active agents at the interface. Finally, the measured contact angle values revealed a significant effect of binary salts on the wettability alteration toward strongly water-wet conditions, especially for the RSO and ASO compared with crude oil.

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.

Miscible gas injection in tight/shale oil reservoirs presents a complex problem due to various factors, including the presence of a large number of nanopores in the rock structure and asphaltene and heavy components in crude oil. This method performs best when the gas injection pressure exceeds the minimum miscibility pressure (MMP). Accordingly, accurate calculation of the MMP is of special importance. A critical issue that needs to be considered is that the phase behavior of the fluid in confined nanopores is substantially different from that of conventional reservoirs. The confinement effect may significantly affect fluid properties, flow, and transport phenomena characteristics in pore space, e.g., considerably changing the critical properties and enhancing fluid adsorption on the pore wall. In this study, we have investigated the MMP between an asphaltenic crude oil and enriched natural gas using Peng-Robinson (PR) and cubic-plus-association (CPA) equations of state (EoSs) by considering the effect of confinement, adsorption, the shift of critical properties, and the presence of asphaltene. According to the best of our knowledge, this is the first time a model has been developed considering all these factors for use in porous media. We used the vanishing interfacial tension (VIT) method and slim tube test data to calculate the MMP and examined the effects of pore radius, type/composition of injected gas, and asphaltene type on the computed MMP. The results showed that the MMP increased with an increasing radius of up to 100 nm and then remained almost constant. This is while the gas enrichment reduced the MMP. Asphaltene presence changed the trend of IFT reduction and delayed the miscibility achievement so that it was about 61% different from the model without the asphaltene precipitation effect. However, the type of asphaltene had little impact on the MMP, and the controlling factor was the amount of asphaltene in the oil. Moreover, although cubic EoSs are particularly popular for their simplicity and accuracy in predicting the behavior of hydrocarbon fluids, the CPA EoS is more accurate for asphaltenic oils, especially when the operating pressure is within the asphaltene precipitation range.

This research investigates the interactions between a novel environmentally friendly chemical fluid consisting of Xanthan gum and bio-based surfactants, and crude oil. The surfactants, derived from various leaves using the spray drying technique, were characterized using Fourier-transform infrared (FTIR) spectroscopy, zeta potential analysis, Dynamic light scattering, and evaluation of critical micelle concentration. Static emulsion tests were conducted to explore the emulsification between crude oil and the polymer-surfactant solution. Analysis of the bulk oil FTIR spectra revealed that saturated hydrocarbons and light aromatic hydrocarbons exhibited a higher tendency to adsorb onto the emulsion phase. Furthermore, the increased presence of polar hydrocarbons in emulsion phases generated by polar surfactants confirmed the activation of electrostatic forces in fluid-fluid interactions. Nuclear magnetic resonance spectroscopy showed that the xanthan solution without surfactants had a greater potential to adsorb asphaltenes with highly fused aromatic rings, while the presence of bio-based surfactants reduced the solution\'s ability to adsorb asphaltenes with larger cores. Microfluidic tests demonstrated that incorporating surfactants derived from Morus nigra and Aloevera leaves into the xanthan solution enhanced oil recovery. While injection of the xanthan solution resulted in a 49.8% recovery rate, the addition of Morus nigra and Aloevera leaf-derived surfactants to the xanthan solution increased oil recovery to 58.1% and 55.8%, respectively.

In the enhanced oil recovery (EOR) process, interfacial tension (IFT) has become a crucial factor because of its impact on the recovery of residual oil. The use of surfactants and biosurfactants can reduce IFT and enhance oil recovery by decreasing it. Asphaltene in crude oil has the structural ability to act as a surface-active material. In microbial-enhanced oil recovery (MEOR), biosurfactant production, even in small amounts, is a significant mechanism that reduces IFT. This study aimed to investigate fluid/fluid interaction by combining low biosurfactant values and low-salinity water using NaCl, MgCl2, and CaCl2 salts at concentrations of 0, 1000, and 5000 ppm, along with Geobacillus stearothermophilus. By evaluating the IFT, this study investigated different percentages of 0, 1, and 5 wt.% of varying asphaltene with aqueous bulk containing low-salinity water and its combination with bacteria. The results indicated G. Stearothermophilus led to the formation of biosurfactants, resulting in a reduction in IFT for both acidic and basic asphaltene. Moreover, the interaction between asphaltene and G. Stearothermophilus with higher asphaltene percentages showed a decrease in IFT under both acidic and basic conditions. Additionally, the study found that the interaction between acidic asphaltene and G. stearothermophilus, in the presence of CaCl2, NaCl, and MgCl2 salts, resulted in a higher formation of biosurfactants and intrinsic surfactants at the interface of the two phases, in contrast to the interaction involving basic asphaltene. These findings emphasize the dependence of the interactions between asphaltene and G. Stearothermophilus, salt, and bacteria on the specific type and concentration of asphaltene.

The effects of sulfate salts under low and high salinity conditions and pH of 3.5-11 on interfacial tension (IFT) reduction and IL adsorption using resinous (RSO) and asphaltenic (8 wt/wt%) synthetic oils are investigated. The measurements showed the increasing effect of pH on the IFT of RSO/DW from 23.5 to 27.3 mN/m (pH = 3.5 → 7) in the first place and a reducing effect (0.4 mN/m) if pH = 7 → 11. Using a high concentration of 50,000 ppm for MgSO4, and Na2SO4 revealed an extensive IFT reduction for a pH value of 11 with the value of 0.20 mN/m for Na2SO4. The measured IFT values showed the significant impact of IL (500 ppm) on the IFT (minimum value of 0.01 mN/m for RSO/50,000 Na2SO4 + 500 ppm 1-decyl-3-methyl imidazolium triflate ([C10mim][TfO])) for pH = 11. The IL adsorption measurements showed the role of in-situ surfactant production (saponification process) on the 1-decyl-3-methyl imidazolium chloride ([C10mim][Cl]) and [C10mim][TfO] adsorption reduction from 3.67 to 2.33 and 4.21 to 3.34 mg IL/g rock, respectively. The performed core flooding experiments using the optimum chemical formulation showed the possibility of tertiary oil recovery with maximum oil recovery of 28.8% based on original oil in place in the presence of 500 ppm.

This study examined how the concentration of asphaltene and divalent ions in various salinities affects the interfacial tension (IFT) between a model oil/brine using the pendant drop method. The oleic phase consisted of a mixture of toluene and n-heptane (heptol), to which asphaltene was added to investigate how asphaltene molecules affect the surface properties. The base fluid was prepared with a salinity of 40,000 ppm, and two additional solutions with concentrations of 4000 ppm (low salinity) and 80,000 ppm (high salinity) were created. The results revealed that increasing the concentration of asphaltene within certain salinity ranges led to a decrease in IFT. The lowest IFT was observed at the 40,000 ppm salinity level, indicating that at this optimal salinity, the maximum asphaltene concentration migrated to the heptol/brine interface, reducing the IFT from 23 mN/m to 16 mN/m. Additionally, a 0.5 % wt of asphaltene demonstrated a significant concentration of micellization of natural surfactants, suggesting that the interface was nearly saturated with asphaltene. Consequently, concentrations higher than this value did not significantly alter the IFT. In the final part of the study, the impact of divalent ions was investigated, revealing that as the concentration of Ca2+ ions increased up to fourfold, the IFT decreased to 15 mN/m, about 10 % less than the base case. This value represented the lowest IFT compared to Mg2+ and SO42-. Moreover, modeling the results indicated that the relaxation time decreased with increasing salinity, suggesting that higher salinity accelerated the process of asphaltene absorption at the interface.

This study investigates the synthesis of mesophase pitch using low-cost fluid catalytic cracking (FCC) slurry and waste fluid asphaltene (WFA) as raw materials through the co-carbonization method. The resulting mesophase pitch product and its formation mechanism were thoroughly analyzed. Various characterization techniques, including polarizing microscopy, softening point measurement, Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA), were employed to characterize and analyze the properties and structure of the mesophase pitch. The experimental results demonstrate that the optimal optical texture of the mesophase product is achieved under specific reaction conditions, including a temperature of 420 °C, pressure of 1 MPa, reaction time of 6 h, and the addition of 2% asphaltene. It was observed that a small amount of asphaltene contributes to the formation of mesophase pitch spheres, facilitating the development of the mesophase. However, excessive content of asphaltene may cover the surface of the mesophase spheres, impeding the contact between them and consequently compromising the optical texture of the mesophase pitch product. Furthermore, the inclusion of asphaltene promotes polymerization reactions in the system, leading to an increase in the average molecular weight of the mesophase pitch. Notably, when the amount of asphaltene added is 2%, the mesophase pitch demonstrates the lowest ID/IG value, indicating superior molecular orientation and larger graphite-like microcrystals. Additionally, researchers found that at this asphaltene concentration, the mesophase pitch exhibits the highest degree of order, as evidenced by the maximum diffraction angle (2θ) and stacking height (Lc) values, and the minimum d002 value. Moreover, the addition of asphaltene enhances the yield and aromaticity of the mesophase pitch and significantly improves the thermal stability of the resulting product.

The utilization of chemical dispersants as a way of mitigating of oil spills in marine eco-system has been extensively documented worldwide. Hence, in this research we have successfully synthesized two amphiphilic asymmetric Dicaionic Ionic Liquids (DILs). The efficacy of these synthesized DILs as dispersants was assessed using the baffled flask test (BFT). The results indicated a dispersant effectiveness ranging from 47.98 % to 79.76 % for the dispersion of heavy crude oil across various temperature ranges (10-30 °C). These dispersant-to-oil ratios (DOR) were maintained at 3: 100 (V%), showcasing promising dispersant capabilities for mitigating heavy crude oil spills. Additionally, acute toxicity tests conducted on Nile tilapia and Oreochromis niloticus have demonstrated the relatively low toxicity of the IL-dispersants, with Lethal Concentration 50 (LC50) values exceeding 100 ppm after 96 h. This suggests a practically slight toxic effect on the tested fish. In summary, the newly developed IL-dispersants are considered to be conducive to environmentally benign oil spill remediation.