Sharif Digital Repository

This research aims to propose a thermodynamic model for predicting asphaltene precipitation upon diluting a crude oil with a paraffinic solvent. To this end, a thorough mathematical formulation was carried out to derive a novel micellization model based on the associative properties of asphaltenic compounds. It was assumed that asphaltenes exist in the oil both as monomeric molecules and aggregated cores; with stabilization latter by attachment of resin on its periphery. The aggregation equilibrium was established by taking into account asphaltene's lyophobic tendency, heat of resin adsorption, and interfacial tension between micelle and oil media which is the main driving factor... 

Asphaltene precipitation is a major assurance problem posing significant technical and economic loss on petroleum industry. To tackle this issue, various treatments have been proposed and applied by industry. Amongst, inhibiting or retarding the asphaltene precipitation has been understood as the most efficient approach. In this regard, blending crude oil with chemical additives could appreciably heighten its stability. Surfactants, owing to amphiphilic nature, could keep asphaltene dissolved in crude oil by precluding self-tendency of those particles to making agglomerates. Despite importance of this subject, there is still lack of sufficient experimental data to evaluate effectiveness of... 

Nanoemulsion is a novel type of emulsified solutions holding great promises for utilizing in industrial applications. Although microemulsions have been the subject of numerous studies in past decades, however, nanoemulsions are quite virgin and merit detailed investigation to scrutinize their characteristics specific to reservoir engineering, in particular, Enhanced Oil Recovery (EOR). To this end, the present study is an attempt to evaluate the effectiveness of a specific nanoemulsion for oil displacement through porous media. In this regard, flooding experiments were designed and Hexa decyl trimethylammonium bromide (CTAB), which is a cationic surfactant, was used as the emulsifying agent.... 

Molecular dynamics (MD) simulation was utilized to study the role of asphaltene extracted from Gachsaran (an Iranian oilfield) at the synthetic oil-water interface. In agreement with experimental data, IFTs predicted by MD simulation for heptol/brine system showed a minima at around 50 vol.% n-heptane, reflecting the highest contribution of asphaltene into the interface. At greater n-heptane fractions, IFT was increased steadily. Simulation results suggest the asphaltene propensity for remaining in the bulk heptol phase rather related to the fraction of toluene in the mixture. Heptol ingredients, i.e., toluene and heptane, act differently with respect to asphaltene, where former tends to... 

Despite previous researches on ion-engineered waterflooding (IEWF), its underlying mechanisms are not fully understood, particularly in presence of additives, like surfactants. This paper concerned with the contribution of Ca 2+ , Mg 2+ , SO 4 2- and Na + into altering wettability of oil-wet carbonate minerals towards water preferred state. As a mechanistic study, an experiment workflow was conducted to probe the impact of ions' concentrations in SW, either with or without sodium dodecylbenzene sulfonate (SDBS) which is an anionic surfactant. At first, contact angle (CA) measurement was carried out to evaluate the degree of wettability reversal upon treating the oil-aged calcite slabs with... 

This paper concerns extending applicability of Dehaghani association equation of state (in short DA-EOS) to model non-ideality in phase behavior caused by hydrogen bonding. Advantageously, this equation only needs two and one parameters to treat self- and cross association, respectively, which were determined for methanol/water and ethanol/water mixture in this study. In this respect, DA was coupled with PR and SRK EOS to account for physical interaction between molecules. Notably, DA-PR persistently provides more accurate prediction than DA-SRK for both aqueous methanol and ethanol solutions  

Molecular dynamics simulation was applied in this study to scrutinize the interfacial properties of water nano-film confined between calcite mineral and hydrocarbon layer, as two intrinsically different media. Such system resembles the environment experienced by water molecules in the pore spaces of underground carbonate reservoirs. The interplay between water film and confining phases, oil and mineral, strongly influences hydrocarbon production process; however, there is a lack of detailed understanding of the involved interactions. MD simulations indicate development of several layers with different water densities in the confined brine. Water molecules form well-ordered structure in three... 

The thin brine film that wets rock surfaces governs the wettability of underground reservoirs. The ionic composition and salinity of this nanosized brine film influence the wetting preference of the rock pore space occupied by hydrocarbons. Despite numerous investigations over the last decades, a unanimous fundamental understanding that concerns the contribution of ions in the original wetting state of the reservoir is lacking and hence the mechanisms responsible for the wettability reversal of the mineral are still unclear. This wettability reversal is the main consequence of ion-Tuned waterflooding. Although the method is widely accepted in practice, there is no universal consensus on the... 

Connate water has been coexisting with oil and mineral for centuries within underground reservoirs. The oil recovery techniques, such as low salinity water injection, disturb this prolonged equilibrium state of oil/brine/rock system. However, a thorough understanding of this complex equilibrium in the reservoir is still lacking. In this study, we performed molecular dynamics simulations to provide quantitative comprehension of the thin brine film characteristics that wets carbonate reservoir rocks at molecular level. While an electric double layer is formed at the interface of calcite/low salinity water, the ions in the high saline water form several aggregates of ions. We found that these... 

This study aims to elucidate the impact of salinity on the interactions governing the adsorption of polar aromatic oil compounds onto calcite. To this end, molecular dynamics simulations were employed to assess adsorption of a model polar organic molecule (deprotonated benzoic acid, benzoate) on the calcite surface in NaCl brines of different concentration levels, namely, deionized water (DW), low-salinity water (LS, 5000 ppm), and sea water (SW; 45,000 ppm). Calcite was found to be completely covered by several well-ordered water layers. The top hydration layer is very compact and prevents direct adsorption of benzoates onto the substrate. Instead, Na+ ions form a distinct positively... 

This paper resolve the salinity-dependent interactions of polar components of crude oil at calcite-brine interface in atomic resolution. Molecular dynamics simulations carried out on the present study showed that ordered water monolayers develop immediate to a calcite substrate in contact with a saline solution. Carboxylic compounds, herein represented by benzoic acid (BA), penetrate into those hydration layers and directly linking to the calcite surface. Through a mechanism termed screening effect, development of hydrogen bonding between –COOH functional groups of BA and carbonate groups is inhibited by formation of a positively-charged Na+ layer over CaCO3 surface. Contrary to the common... 

The efficiency of water flooding methods is known to improve by applying ion-tuned water injection. Although there is a consensus that such improvement happens through reversing reservoir wettability characteristics to more water-wet state, the true impact of ions is still ambiguous among contradictory debates. The well-known molecular dynamics (MD) simulation techniques would shed light on such ambiguities to gain deep atomic-scale understanding of the process. Results from MD simulations show that the presence of Na+ and Cl¯ ions leads to the formation of an electrical double layer in adjacency of calcite surface while Mg2+ ions dominantly make complexes with hydrocarbons throughout the...