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For the first time, the effect of calcination process on characteristics and catalytic performances of Pd supported on different MOFs (MIL-101(Cr), NH2-MIL-101(Cr), and HKUST-1) was evaluated. Besides, the various orders of calcination process and reduction one on Pd/MOF and Pd/calcinated-MOF were studied, and their performances in CO oxidation reaction were presented to find the effect of H2 and O2. Results showed that the effect of calcination and reduction processes on the catalytic activities and characteristics strongly depends on the nature of MOF. Among MIL-based catalysts, the catalyst with no calcination treatment showed the best activity. Among MNH2-based catalysts, high activity was obtained for Pd/MNH2, Pd/MNH2-C, and Pd/MNH2(RC) samples and Pd/calcinated-MNH2was the best. Catalytic activities of HKUST-1-based catalysts decreased with calcination due to high changes in their structures. The results are useful for predicting the performance of MOFs in oxidation processes, especially reactions in which high oxygen concentrations are involved.

Amine-functionalized MIL-101(Cr) has been synthesized by hydrothermal (MNH2) and post-synthetic modification (MNH2-p) approaches. Pd/MNH2 and Pd/MNH2-p have been tested in CO oxidation reaction as a gas phase reaction to clarify the difference between two synthesis approaches. Their performance has also been compared with that of Pd supported on MIL as a common MOF and CuBTC as a commercial one. The results show the significant difference between Pd/MNH2-p and Pd/MNH2, where CO conversion of 100% was not observed for Pd/MNH2-p, whereas Pd/MNH2 outperformed the others and exhibited the high reaction rate thanks to the active sites created by amorphization during the reduction process because of impressive effect of hydrogen on its structure. The effect of Space Velocity of Reduction Stream (SVr) has also been studied and the results show that the activity of Pd/CuBTC dramatically enhances at higher SVr and its activity further improves as a result of the formation of 8.9 nm CuO nanoparticles during the CO oxidation process.

Acidizing is one of the most effective techniques to remove the formation damage and restore (or even increase) the permeability of the near wellbore region. Although this technique is widely used to resolve the skin problem, it could initiate new damages itself that hinder the fluid flow and decrease the well production, consequently. Acid-oil emulsion and sludge formation are known as two major induced formation damage and the main reasons for the oil well acid treatment failures. Despite its critical effects, no comprehensive study has been addressed this specific type of formation damages in details. In this study, the acid-oil emulsion and asphaltic sludge formation were evaluated quantitatively. Multiple compatibility tests were conducted using HCl and six Iranian acid sensitive crude oil samples. The acid concentration, ferric ion presence, and acid-mixture ratio were selected as the main factors affecting the emulsion stability and the amount of sludge. To mimic the real condition the interference of the effects of these factors was noticed besides the crude oil type which has not been addressed before. The results revealed that controlling the iron ion presence, choosing the best acid concentration, and regulating the acid-mixture ratio would drastically reduce the risk of emulsion and sludge formation without any preventative additives presence. The quantitative values derived from this experimental work showed that the weight of dried asphaltic sludge formed was diminished to 7%, 5.6%, 2.4%, 22%, 7.5% and 10% of the most critical sludging condition for the crude oil samples A, B, C, D, E, and F respectively. Besides, for the first time, the volumetric measurement of the massive asphaltic sludge was performed to approach more realistic damage evaluation. The results confirmed it is possible that the solid sludge occupies 60 vol % of the primitive acid-oil mixture volume at high concentration of HCl and ferric besides high acid-oil ratio condition.

Amino acids partitioning including phenylalanine, glutamic acid, and tryptophan in aqueous and ionic liquid phases at temperature of 298.15 K and atmospheric pressure were measured. 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide used in this work can produce two phases with water immediately. The effect of aqueous solution pH on amino acids partitioning was studied and revealed that amino acid partitioning coefficient was decreased with increasing pH. This phenomenon pertains to the electrostatic interaction between cations of amino acid and the anions of ionic liquid which is decreased when pH increases. Considering the effect of pH, liquid-liquid equilibrium data of amino acids were obtained in a pH owning maximum partitioning coefficient. It was observed that chemical structure of amino acid has an important effect on partitioning of amino acids between two phases. Experimental data indicated that glutamic acid is mostly transferred to aqueous phase while tryptophan moves to the ionic liquid phase. In the modeling section, equilibrium behavior of water, amino acid and ionic liquid system were predicted by SAFT equation of state. Necessary parameters of water and pure ionic liquid for equation of state were measured and amino acid parameters were obtained from literature. Binary interactions of components were optimized by equilibrium data. NRTL model was used in order to analyze cabapility of SAFT EoS to predict the behavior of system. The results indicate that SAFT model anticipates liquid-liquid equilibrium of the system better than NRTL model. The percentage of average absolute deviation for SAFT equiation is 1.9%.

Graphene oxide membranes were prepared by vacuum and pressurized ultrafiltration methods on the 12% modified Polyacrylonitrile (12mPAN) substrate to specify challenges, salient features, future directions, and potential of GO membrane for separation fields using characterization techniques and gas separation test (studied gases are CO2, He and N2), which is an efficient tool for better understanding of GO membrane behavior. GO membrane structure was examined over a wide range of parameters, such as pore size range of substrate and its surface properties, pH of GO dispersion, GO content, synthesis pressure, operating pressure and temperature. The results show that the GO content does not hold a linear relationship with the permeance and selectivity. Film thickness, aggregates, synthesis pressure defects and interlayer spacing have significant effects on the gas separation performance of GO membranes which originate from the synthesis method and its conditions.

Temperature dependency of infrared band intensity for methylene rocking vibration could be used as indication for creation of solid crystals while decreasing temperature. In this work, different experiments were conducted to measure wax appearance temperature, WAT, such as cross polarized microscopy, rheometry and FTIR spectroscopy. Three Iranian crude oils were characterized based on the SARA test and PC-SAFT model was developed to predict WAT. The obtained results by FTIR spectroscopy and PC-SAFT model were in quite agreement. FTIR spectroscopy determined higher WAT values which may be due to its higher sensitivity to smaller wax crystals. Also, the effect of a polymeric crystal modifier (EVA) and an aromatic solvent (toluene) on wax precipitation was investigated. EVA dramatically decreased the pour point of lower waxy crude oils. Toluene dissolved polar compounds such as asphaltene and consequently decreased WAT and pour point. This observation confirmed that asphaltene supports the wax crystallization and its growth.

Asphaltene deposition in porous media, wellbore and surface facilities has been a severe problem in petroleum industry which causes considerable remediation costs annually. Asphaltenes are heavy and polydisperse fractions of crude oil which are insoluble in n-alkanes such as n-heptane. In this work, three Iranian crude oils were prepared for titration experiments with n-pentane, n-heptane and n-dodecane at different solvent ratios and constant temperature. The experimental data were correlated by perturbed chain form of statistical associating fluid theory (PC-SAFT). The association of asphaltene molecules has been considered in this model with adjusting the uncertain parameters (such as association energy and association volume of asphaltene pseudo component) to match the experimental data. PC-SAFT parameters for other non-associating pseudo components have been calculated using the correlations proposed in literature. The present study also evaluated the performance of SVR method as a supervised learning approach in prediction of asphaltene precipitation. Deviation of proposed models has been validated using the statistical evaluation criteria and graphical analysis. The results show that the proposed models have AAD values less than 0.073 and a high potential in prediction of asphaltene precipitation.

Wax precipitation may occur in production or transportation of crude oil form field which is a serious problem in petroleum industry. Flow assurance issues concerning wax precipitation make it necessary to develop a precise thermodynamic model to predict the wax appearance temperature and amount of precipitation at different conditions. In this work a new procedure has been proposed to characterize crude oil based on the SARA test considering the wax and asphaltene as single pseudo components. Two scenarios have been investigated for the survey of the crude oil characterization, with and without asphaltene pseudo component. Also, in this work, the Perturbed Chain form of the Statistical Associating Fluid Theory, PC-SAFT, has been developed to evaluate its ability for modeling of wax precipitation prediction. It is demonstrated that the developed PC-SAFT model can correlate the wax precipitation amount better than basic models (multiple solid, solid solution) typically used in the industry. The results obtained with the proposed model show a remarkable matching with the experimental data for wax precipitation values. The obtained results are very promising in providing better approach to model wax precipitation. The effect of asphaltene molecules on wax precipitation has been investigated by sensitivity analysis using Monte Carlo algorithm and the Artificial Neural Network as the base model. In this work, a three layer FFBP neural network has been constructed using the Levenberg–Marquardt training method to predict the wax precipitation amount at different conditions which are the network input parameters. Positive effect of asphaltene on wax precipitation confirmed that asphaltene molecules act like the nucleation sites for wax crystals. The obtained results in this work show that the asphaltene content of crude oil should be considered in wax precipitation models.

Classical molecular dynamics simulations are used to compute the solvation free energy of two pharmaceutical solids, namely ibuprofen and acetaminophen in carbon dioxide (CO2), over the density range of interest in supercritical processes. In order to examine the influence of the solvent model on the resulting free energies, three popular CO2 models (Zhang, EPM2, and TraPPE) are studied. Relatively large discrepancies for the solvation free energy exist between these CO2 models, suggesting that the former is sensitive to the different balances between dispersive and electrostatic forces used in these models. In particular, for the solvation of the highly polar (dipole moment of ∼5.2 Debye) acetaminophen molecule, such discrepancies are more pronounced than for the moderately polar ibuprofen (dipole moment of ∼1.6 D) molecule. Since there is an exponential relationship between the solvation free energy and solubility, the choice of the solvent model substantially affects the predicted solubility. For the solubility of the studied solutes, the value obtained using the TraPPE model is the highest, that of the EPM2 model is intermediate, and that of the Zhang model is the lowest. Generally, the simulations results show that the model with the largest quadrupole moment leads to a more negative solvation free energy and a higher solubility over the entire density range. Further, the decomposition of the solvation free energy into contributions stemming from electrostatics and dispersion interactions shows that the electrostatic interactions are important for a quantitative prediction of solid solubility, while the Lennard–Jones parameters of the solute and solvent are more important for qualitative agreement. Additionally, the infinite-dilution partial molar volume of the two solutes is estimated from the pressure derivative of the solvation free energies. With density increasing beyond the value corresponding to the zero partial molar volume of the solute (minimum solvation free energy), the repulsive part of Lennard–Jones potential wins over the attractive interactions, and the solvent strength of supercritical CO2 decreases; however, due to the increase in the chemical potential of the pure solid (effect of the Poynting correction), the solubility further increases. Overall, these results demonstrate the importance of a proper choice of quadrupole moment of the solvent model, which is crucial for quantitative predictions of the solid solubility in supercritical CO2.

In this work, PC-SAFT, an equation of state based on perturbation theory, is applied to predict the reservoir fluids phase behavior. PC-SAFT parameters for pure components have previously been assessed, but they cannot be determined for petroleum fractions with unspecified components and composition. In order to remove this difficulty and making use of PC-SAFT model in the reservoir fluids simulations, a new approach is studied which leads to appearing generalized correlations for the estimation of PC-SAFT parameters for petroleum cuts and plus fractions using only their molecular weight and specific gravity, without the essential need for the characterization of petroleum fractions in different homologous hydrocarbon families. The proposed technique is then validated with the reliable experimental PVT data of reservoir fluids, including saturation pressure and differential liberation test (oil formation volume factor, soluble gas oil ratio, and liquid phase density) for 10 oil samples. Subsequently, available experimental data are compared to results calculated by PC-SAFT model for all existing samples. Afterwards, a comparison between PC-SAFT model and two widely used cubic equations of state (PR and SRK EOS) was also conducted. The results demonstrated PC-SAFT model estimation capabilities and ease of use as an effective tool for describing the phase behavior of reservoir fluids in a wide range of scales and applications. Moreover, the effect of parameter tuning process on reduction of error values was investigated and acceptable results were obtained.

The solubility of carbon dioxide and hydrogen sulfide gases in the ionic liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([C2mim][OTf]) was measured at temperatures from (303.15–353.15) K and pressures up to about 3.0 MPa. The Henry's law constants were determined from the new experimental data, which in turn were used to derive the change of some thermodynamic functions of dissolution of the gases in that particular ionic liquid. The new experimental data were correlated by a combination of the extended Henry's law and Pitzer's model for the excess Gibbs energy. The average relative percent deviation (ARD%) of correlated molality values from experimental data are within experimental uncertainties, which indicate quite good correlative accuracy of the Pitzer's model for the systems under investigation. Results show that at the same temperature and pressure, the solubility of H2S in [C2mim][OTf], expressed on the molality scale, is more than four times that of CO2. Comparison of the obtained experimental data indicates that the solubility of H2S, expressed on the molality scale, in [C2mim][OTf] is much more than its magnitude in the high-capacity ionic liquids 1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate ([C2mim][eFAP]) and 1-ethyl-3-methylimidazolium bis(trifluoromethyl) sulfonylimide ([C2mim][Tf2N]). For example the molality of H2S at 303.15 K and 2.0 MPa is 2.5 times and 1.3 times that of [C2mim][eFAP] and [C2mim][Tf2N], respectively. Solubility of CO2 in the ionic liquids follows the order [C2mim][OTf]

Parameters of the PC-SAFT Equation of State (EoS) for pure components are generally determined by matching the saturation pressure and liquid density experimental data. These experimental data are unavailable for petroleum cuts and plus fractions of the petroleum reservoir fluids. In this work, new correlations as functions of specific gravity and molecular weight were developed to estimate the PC-SAFT parameters of petroleum cuts with unknown composition. It was shown that the proposed correlations accurately estimate the PC-SAFT parameters of the pure components published in the literature. Then, the obtained correlations were used and the PVT experimental data for various real reservoir fluids was modeled using the PC-SAFT EoS and the results were compared to the modeled results using the Peng-Robinson EoS. The obtained results showed that the PC-SAFT EoS along with the proposed correlations presents acceptable results for phase behavior modeling of the reservoir petroleum fluids.

In recent times, single layer graphene oxide (GO) has been of intense interest for a broad spectrum of applications. Size and surface charge of GO sheets are two key factors in the most of these fields. These structural properties can be tuned by adjusting pH manipulating the content of oxygen-containing groups. Furthermore, the pH value extremely affects on the surface chemistry and functional groups of GO sheets which are crucial in providing a high stable solution and chemical activity of particles. In this study, Graphene oxide is synthesized by improved hummer method and characterized by XRD, AFM, FTIR, DLS and zeta potential. pH value can be tuned trough titration with NaOH and HCl and effect of pH on GO dispersion stability and optical properties is investigated.

In this work, a new model based on multilayer kinetic adsorption mechanism has been proposed to account asphaltene adsorption in porous media under dynamic condition and the model was verified using experimental data obtained in this work and also with those reported in the literature. In the proposed model two steps are considered for asphaltene adsorption. The first step is taken as adsorption of asphaltenes on the surface of the porous media and the second step is taken as adsorption of asphaltenes on the asphaltenes already adsorbed on the porous media. The Crank-Nicholson method, central difference in space and trapezoidal rule in time, giving second order convergence in time was applied to develop a computer program using MATLAB software. Also, the Rung-Kutta fourth order scheme has been applied to calculate the volume fraction of asphaltene adsorption. The results show that the proposed model based on multilayer adsorption kinetic mechanism of aphaltene with the absolute average deviation 0.7% can predict more accurately the asphaltene adsorption experimental data in comparison to the previous models based on the monolayer adsorption kinetic and equilibrium mechanism. Sensitivity analysis shows that the proposed model is more sensitive to the first step of adsorption than the second step of adsorption. Also, a series of experiments was carried to investigate the asphaltene adsorption using UV–vis spectroscopy in order to study the effect of different parameters on asphaltene adsorption mechanisms during dynamic condition in porous media such as concentration, asphaltene composition, flow rate and type of porous media. The experimental results show that adsorption is controlled by the type of porous media rather than the asphaltene concentration of solution. Also, it was found that the adsorption process in porous media is controlled by kinetics mechanism during dynamic condition.

In this work, the thermodynamic behavior of aqueous solutions containing the solutes NaCl, glucose, and/or urea is investigated. These substances are vital components for living bodies and further they are main components of blood serum. Osmotic coefficients were determined by cryoscopic measurements in single-solute and multi-solute aqueous solutions containing salts (NaCl, KCl, CaCl2), glucose, and/or urea. The results show that NaCl determines the osmotic coefficients in the urea/glucose/NaCl/water system. Investigation of the effect of different salts on osmotic coefficients revealed ion-specific effects. At physiologically important solute concentrations in typical blood serum solutions, the osmotic coefficients were found to be in the range of 0.90–0.93. In a second step, the state of water in different glucose/salt/water and urea/salt/water systems was investigated. Depending on the kind of salt, the chemical potential of water in urea/salt/water is either higher or lower than in glucose/salt/water systems at equal nonelectrolyte concentrations. This result was found to be independent of the salt molality. Finally, the investigated systems were modeled with the Pitzer model and the ePC-SAFT equation of state, which allowed predicting of the properties of these multi-solute aqueous solutions.

Gas injection into reservoirs can be used to increase oil recovery. However, reservoir heterogeneity and high gas mobility reduce sweep efficiency and decrease recovery. Using foam can reduce gas mobility and therefore increase sweep efficiency. Foam is thermodynamically unstable, so it is important to predict the foam stability. In order to understand the influence of oil presence on foam stability, static experiments performed on foam by varying the type and amount of added oil and molecular weight of added alkane. Also static foam properties have been investigated by varying the surfactant concentration, ionic strength, composition of different salts in the sample, and addition of polymer.

In this work, experimental studies were conducted to determine the effect of asphaltene deposition on the permeability reduction and porosity reduction of carbonate, sandstone and dolomite rock samples using an Iranian bottom hole live oil sample which is close to reservoir conditions, whereas in the majority of previous work, a mixture of recombined oil (a mixture of dead oil and associated gas) was injected into a core sample which is far from reservoir conditions. The effect of the oil injection rate on asphaltene deposition and permeability reduction was studied. The experimental results showed that an increase in the oil injection flow rate can result in an increase in asphaltene deposition and permeability reduction. Also, it can be observed that at lower injection flow rates, a monotonic decrease in permeability of the rock samples can be attained upon increasing the injection flow rate, while at higher injection rates, after a decrease in rock permeability, an increasing trend is observed before a steady-state condition can be reached. The experimental results also showed that the rock type can affect the amount of asphaltene deposition, and the asphaltene deposition has different mechanisms in sandstone and carbonate core samples. It can be seen that the adsorption and plugging mechanisms have a more important role in asphaltene deposition in carbonate core samples than sandstone core samples. From the results, it can be observed that the pore volumes of the injected crude oil are higher for sandstone cores compared with the carbonate cores. Also, it can be inferred that three depositional types may take place during the crude oil injection, i.e., continuous deposition for low-permeability cores, slow, steady plugging for high-permeability cores and steady deposition for medium-permeability cores. It can be seen from the experimental results that damage to the core samples was found to increase when the production pressures were increased. The experimental results show that the amount of remaining asphaltene in carbonate core samples is higher than those in sandstone core samples. Also, SEM (Scanning Electron Microscopy) micrographs of carbonate core samples showed the formation of large clusters of asphaltene in comparison with sandstone core samples during natural depletion. It can be seen from the modeling results that the proposed model based on the multilayer adsorption equilibrium mechanism and four material balance equations is more accurate than those obtained from the monolayer adsorption equilibrium adsorption mechanism and two material balance equations, and is in agreement with the experimental data of natural depletion reported in this work and with those reported in the literature.

New experimental results are presented for the solubility of carbon dioxide, hydrogen sulfide in the ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate ([C8mim][PF6]) at temperatures range from (303.15 to 353.15) K and pressures up to about 2 MPa. The solubility of the mixture of CO2/H2S in [C8mim][PF6] under various feed compositions were also measured at temperatures of (303.15, 323.15 and 343.15) K and the pressure up to 1 MPa. The solubility of carbon dioxide and hydrogen sulfide increased with increasing pressure and decreased with increasing temperature and the solubility of H2S is about three times that of CO2 in the particular ionic liquid studied. The measured data were correlated using extended Henry’s law included Pitzer’s virial expansion for the excess Gibbs energy, and the generic Redlich–Kwong cubic equation of state proposed for gas/ionic liquid systems. The correlations from the two models show quite good consistency with the experimental data for CO2/IL and H2S/IL binary mixtures within experimental uncertainties. For CO2/H2S/IL ternary mixtures, the RK model shows better correlation with the experimental values. We also studied the effect of cation alkyl chain length on the CO2 and H2S solubility by comparison of the experimental data of this study with those of previous reports. As the cation alkyl chain length became longer, the solubility of CO2 and H2S increased in the ionic liquid. Additionally, the influence of the anion on the solubility is studied by comparing the solubility of CO2 and H2S in [C8mim][PF6] with those in [C8mim][Tf2N]. As a result, CO2 and H2S have higher solubility in the IL with [Tf2N]− as the anion.

Rheological behavior of two crude oils and their surfactant-stabilized emulsions with initial droplet sizes ranging from 0.5 to 75 µm were investigated at various temperatures under steady and dynamic shear testing conditions. In order to evaluate the morphology and Stability of emulsions, microscopic analysis was carried out over three months and average diameter and size distribution of dispersed droplets were determined. The water content and surfactant concentration ranged from 10 to 60% vol/vol and 0.1 to 10% wt/vol, respectively. The results indicated that the rheological properties and the physical structure and stability of emulsions were significantly influenced by the water content and surfactant concentration. The crude oils behaved as Newtonian fluids over a wide range of shear rates, whereas the emulsions behaved as non-Newtonian fluids, indicating shear-thinning effects over the entire range of shear rates. The viscosity, storage modulus and degree of elasticity were found to be significantl...

The strong bases statistical associated fluid theory (SAFT) equations of state allow modeling for a wide range of scales and applications. The equilibrium calculations are very time-consuming in SAFT-based family of equations of state; therefore the number of components used in describing a fluid mixture must be reduced by grouping. On the other hand, in some applications it is required to retrieve the detailed fluid description from equilibrium calculation performed on the lumped fluid description. The purpose of this paper is to develop a systematic approach for lumping and delumping with equilibrium calculations using the Perturbed Chain (PC)-SAFT equation of state. The methodology proposed by this paper is to calculate some delumping coefficients from flash calculations performed on the lumped system. Later on those delumping coefficients will be used to retrieve the detailed compositions of the fluid phases from the lumped mixture. To prepare the lumped system, the components are classified into groups through a clustering algorithm and the group properties are calculated according to mixing rules. To examine the accuracy and efficiency of the suggested methodology, it is applied to four synthetic gas samples and two real samples, one being a natural gas condensate and the other one is an oil reservoir fluid. It will be shown that based on the proposed method the delumped equilibrium ratios are close to detailed equilibrium ratios. The observed deviations are small and can be accepted.

In this work, a new model based on the multilayer adsorption kinetic mechanism and four material balance equations for oil, asphaltene, gas, and water phase has been developed to account for asphaltene deposition in porous media under dynamic conditions and the model was verified using experimental data obtained in this work and also with those reported in the literature. The results showed that the developed model based on multilayer adsorption kinetic mechanism can correlate more accurately the oil flooding experimental data in comparison to the previous models based on the mechanical plugging mechanism, in particular in carbonate core samples. Also, a series of experiments was carried to determine the permeability reduction of carbonate, sandstone, and dolomite core samples due to asphaltene deposition using an Iranian bottom hole live oil sample which is close to reservoir conditions in order to study the effect of different parameters on asphaltene deposition mechanisms during dynamic conditions in p...

In this paper, oil recovery and permeability reduction of a tight sandstone core sample in miscible CO2 flooding processes due to asphaltene deposition were studied using an Iranian bottom hole live oil sample in order to distinguish between the mechanical plugging and adsorption mechanisms of asphaltene involved in the interfacial interaction of the asphaltene/mineral rock system. A novel experimental method was designed and proposed to measure the amount of deposited asphaltene due to different mechanisms using the cyclohexane or toluene reverse flooding and spectrophotometer. In this work, the bottom hole live oil sample was injected first to a long core and then CO2 injection was performed which is close to reservoir conditions, whereas in the majority of previous works, the mixture of recombined oil (mixture dead oil and associated gas) and CO2 was injected in a short core sample which is far from reservoir conditions. Then, the cyclohexane and toluene reverse flooding was performed, and the amount o...

Urea and inorganic ions are present in some of the physiological systems, e.g. urine. Understanding the interactions in urea/salt/water is a preliminary step to shed light on more complicated behavior of multi-component physiological systems. State-of-the-art models as well as thermophysical properties can be applied to understand the interactions in these systems. In order to determine such interactions densities, mean ionic activity coefficients (MIACs), osmotic coefficients, and solubility were measured in aqueous solutions of urea and different salts. Densities were determined at temperatures 293.15, 303.15, and 313.15 K for urea concentrations up to 3 molal and up to 1 molal for NaCl. Osmotic coefficients and MIACs were obtained at 310.15 K by using the vapor-pressure osmometry and potentiometry methods, respectively. Ternary aqueous urea solutions containing NaCl, KCl, NaBr, KBr, LiBr, NaNO3, and LiNO3 at two different concentrations of urea (0.3 and 1 molal) as well as at three salt concentrations (0.25, 0.5, and 0.75 molal) were considered. Moreover, urea solubility was also measured at 310.15 K in 3 and 5 molal NaCl solutions in the present work. Experimental data obtained in this work showed that the salt primarily dictates the volumetric properties and the MIAC while the solute with higher concentration determines the behavior of osmotic coefficients in these solutions. The ePC-SAFT model (without any adjustable mixture parameter) was used to accurately predict the experimental densities, activity and osmotic coefficients, and solubilities of the studied mixtures.

The solubility of acetaminophen in SuperCritical-Carbon Dioxide (SC- CO 2 ) with and without menthol as a cosolvent was measured at various temperatures (313, 328 and 343) K, and within pressures ranging from (10 to 25) MPa. It should be stated that the cosolvent, menthol, has chiral isomers with different melting points. Therefore, the effects of both menthol (I) with a lower melting point and menthol (II) with a higher melting point, as cosolvents on the solubility of acetaminophen in SC- CO 2 , were studied. The experimental data collected in this work were obtained using a static flow apparatus. The experiments were replicated at least three times and the data reported are the average of the replicas. Finally, the data reduction for the solubility of acetaminophen in SC- CO 2 in the presence and in the absence of menthol (I) and menthol (II), were correlated, using the semi-empirical equations proposed by Chrastil and Mendez-Santiago & Teja. The results obtained from these equations were in good agreement with the experimental data.

Changes in thermodynamic properties such as pressure, temperature, and composition may result in asphaltene precipitation and deposition in porous media. In addition, asphaltene deposition can cause wettability alteration, permeability reduction, and ultimately a decrease in the productivity of a reservoir. Natural depletion is one of the most common processes of asphaltene deposition in which pressure changes destabilize the dissolved asphaltene in the oil and settle them onto the rock surface. In this work, natural depletion experiments in consolidated core samples were performed under simulated reservoir conditions to obtain reliable data and analyze the asphaltene deposition mechanisms. A mass balance equation, momentum equation, asphaltene deposition, and permeability reduction models were applied to model the process of permeability changes as a result of asphaltene deposition. MATLAB programming language was used to calculate the numerical form of the above equations iteratively. A genetic...

A depleted naturally fractured gas condensate reservoir with extremely tight matrix permeability in the center of Iran is used for gas storage. Due to the tightness of the matrix, simulation of this process may present a unique challenge in terms of the importance of diffusion process in flow behavior of the injected gas in matrix blocks. This article presents a multimechanistic (Darcian-type flow and Fickian-type flow) mathematical model to investigate the importance of diffusion process as a function of important rock and fluid parameters. The authors' approach consists of the following steps: (a) development of a 1-D governing equations for a single matrix block consists of a gas condensate mixture considering multimechanistic approach and (b) numerical solution of the highly nonlinear governing equations using Newton-Raphson technique in conjunction with Broyden updating approach. The model developed is validated against an analytical model applying the simplifying assumptions behind the anal...

The mean spherical approximation (MSA) model, coupled with two hard sphere models, was used to predict the activity coefficients of mixtures of electrolyte solutions at different temperatures and concentrations. The models, namely the Ghotbi-Vera-MSA (GV-MSA) and Mansoori et al.-MSA (BMCSL-MSA), were directly used without introducing any new adjustable parameters for mixing of electrolyte solutions. In the correlation step, the anion diameters were considered to be constant, whereas the cation diameters were considered to be concentration dependent. The adjustable parameters were determined by fitting the models to the experimental mean ionic activity coefficients for single aqueous electrolytes at fixed temperature. The results showed that the studied models predict accurately the activity coefficients for single electrolyte aqueous solutions at different temperatures. In the systems of binary aqueous electrolyte solutions with a common anion, the GV-MSA model has slightly better accuracy in predicting the activity coefficients. Also, it was observed that the GV-MSA model can more accurately predict the activity coefficients for ternary electrolyte solutions with a common anion, especially at higher concentrations.

Equations of state based on the statistical associating fluid theory for potentials of variable range (SAFT-VR) and the perturbed chain statistical associating fluid theory (PC-SAFT) have been used to model the PVT behavior of ionic liquids and the solubility of H2S in six imidazolium-based ionic liquids. The studied systems included [bmim][PF6], [hmim][PF6], [bmim][BF4], [hmim][BF4], [bmim][NTF2] and [hmim][NTF2] at various temperatures and pressures. For pure components, parameters of the models have been obtained by fitting the models to experimental data on liquid densities; the average relative deviation between the calculated and experimental densities for ionic liquids is less than 2.42% in the PC-SAFT model and 5.44% in the SAFT-VR approach, the latter which incorporates the square-well potential for short-range interactions. In both models an additional term has been added to account for dipole–dipole interactions between solute molecules resulting from the permanent charges on the chain molecules of the solvents. The model parameters have also been correlated as functions of the molecular weight of the solvents. For binary mixtures of ionic liquids and H2S, the association interactions between H2S molecules and between the ionic liquids and H2S molecules have also been taken into account in both approaches, using binary interaction coefficients. The results show an average deviation of less than 5% in the calculation of the mole fraction of H2S in the ionic liquids. The effect of inclusion of the polar term has been studied for binary systems in both models.

Densities and viscosities of aqueous solutions containing sulfolane and ternary aqueous solutions of sulfolane and triethanolamine and ternary aqueous solutions containing sulfolane and disopropanolamine and also equilibrium surface tensions of the above ternary aqueous solutions were measured at temperatures ranging from (303.15 to 343.15) K and atmospheric pressure. The overall concentration of sulfolane, triethanolamine, and diisopropanolamine in solutions varied in the range of 0 to 16.5, 0 to 43, and 0 to 40 mass percent, respectively. Using the density, viscosity, and surface tension of pure water as the solvent, the corresponding experimental values obtained for the investigated solutions were correlated with temperature and concentration by a modified Setchenow equation.

Recently, ultrasonic wave technology has received much attention as a method for removal of asphaltene deposits from the near wellbore region. However, very little is known about another feature of this technology on the kinetics of asphaltene molecules aggregation. In this work, the kinetics of asphaltene flocculation in several crude oil samples exposed to ultrasonic waves for different time intervals is studied by confocal microscopy. The colloidal structural evolutions of flocks are described by analysis of size distribution of flocculated asphaltene particles. The results show that for the first 90 min of flocculation time, the size of aggregates increases rapidly, and a reaction-limited aggregation model matches well with the experimental data for all samples. But, after 90 min, a reduction in aggregate size of sonicated samples is observed, whereas the aggregate size of nonsonicated oil samples increases in close agreement with the diffusion-limited aggregation model. It has been found tha...

In this work, PEG 1500, MgSO4 and water were used to create an aqueous two-phase system and the effect of temperature was surveyed by obtaining binodal data and equilibrium data at 35, 40 and 45°C; compositions of mixture were obtained by atomic absorption spectrometer and refractometery method. Results showed that with increasing temperature, the solution tends to attain a two-phase region and the slope and length of tie lines increases. Modified Wilson equation was used to correlate this system, adjustable parameters were evaluated directly from experimental data and good agreement with experimental data was obtained. The overall average relative deviation was found to be less than 6%.

Gas-oil relative permeability is essential for performance predictions of reservoirs with solutions for gas drive, gas cap expansion, or gas injection. The nature of flow in reservoir is determined by the interplay of relative permeability and viscous, gravity, and capillary forces. Displacement experiments of the gas-oil system are performed on long core scale models by varying the petrophysical properties and flow conditions. Experiments are conducted in situations where capillary, gravity, and viscous forces are comparable. The effect of destabilized front velocity on relative permeability and residual saturation is investigated. The results indicate that the relative permeability varies with the balance between the gravity and viscous forces. The relative permeabilities determined by analytical and numerical approaches indicate that higher displacement velocity leads to a higher gas relative permeability and lower oil relative permeability. The residual oil saturation was increased by increas...

In order to relate the wetting properties at the pore scale to the macroscale prevailing forces, a series of experiments was performed in vertical porous media under forced gas invasion at various wettability conditions with partially spreading oil. To describe the dynamics of oil recovery in a three-phase flow condition, the downward gas flood experiments were continued by water injection from the bottom. Experimental results obtained in situations where the magnitudes of viscous, capillary, and gravity forces are comparable. We study the transition from flow configurations where the interface is stable with respect to viscous instability to flow configurations where viscous fingering occurs. The results also have been analyzed using a dimensionless number.

Experimental values for surface tension of single and mixed electrolyte solutions were correlated using the models based on the perturbation theory. The Mean Spherical Approximation (MSA) model, coupled with the Ghotbi–Vera (GV) and the Mansoori et al. (BMCSL) equations of state, were used to correlate the experimental values of the surface tension. The results showed that the models can favourably correlate the experimental values for single electrolyte solutions. However, it was observed that the GV–MSA model can more accurately predict the surface tension for single electrolytes, especially at higher concentrations. Two different expressions for concentration dependency of cation hydrated diameters were used. Therefore, in terms of such dependency different forms of the models, i.e ., GV–MSA1, GV–MSA2, BMCSL–MSA1 and BMCSL–MSA2 were introduced. It should be stated that the prediction of the surface tension for the mixed electrolyte solutions were made without introducing any new adjustable parameters. The results showed that GV–MSA2 model can predict more accurately the surface tension of electrolyte mixtures particularly at higher concentrations. Finally, the GV–MSA model was directly used to correlate the experimental results for the surface tension for both single and mixed electrolyte solutions with 2 and 4 adjustable parameters. The results showed that both of the models can accurately predict the experimental data of surface tension. These models can favourably fit and also, predict the surface tension of single electrolyte solutions with less than 1% average absolute relative deviation (AARD). The prediction capability of the proposed models is also acceptable for mixtures of electrolytes.

The solubility of hydrogen sulfide in three ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][Tf2N]), at temperatures ranging from (303.15 to 343.15) K and pressures up to 1 MPa was determined. The solubility data were correlated using the Krichevsky−Kasarnovsky equation, and Henry’s law constants at different temperatures were obtained. From the solubility data, the partial molar thermodynamic functions of solution such as Gibbs energy, enthalpy, and entropy were calculated. Comparison showed that the solubility of H2S in these three ionic liquids was in sequence: [bmim][Tf2N] > [bmim][BF4] > [bmim][PF6].

In this work, the partition coefficients of Cephalexin in aqueous two-phase systems containing PEG [poly(ethylene glycol)] 4000, 10000 and K2HPO4, Na3Citrate (C6H5Na3O7 5, 5H2O) have been measured. The experimental data were obtained in a wide range of temperatures, (28.2 to 37.2) °C. The effects of temperature, pH, polymer concentration, polymer molecular weight, and salt concentration on the partitioning of Cephalexin were also studied. The results showed that salt concentration has a large effect on the partition coefficient, and temperature has an almost negligible effect. The Chen−NRTL Gibbs energy model was used to correlate the experimental results.

The solubility of hydrogen sulfide in three ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF 6 ]), 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF 4 ]), and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][Tf 2 N]), at temperatures ranging from (303.15 to 343.15) K and pressures up to 1 MPa was determined. The solubility data were correlated using the Krichevsky― Kasamovsky equation, and Henry's law constants at different temperatures were obtained. From the solubility data, the partial molar thermodynamic functions of solution such as Gibbs energy, enthalpy, and entropy were calculated. Comparison showed that the solubility of H 2 S in these three ionic liquids was in sequence: [bmim][Tf 2 N] > [bmim][BF 4 ] > [bmim][PF 6 ].

A modified form of the UNIQUAC-NRF activity coefficient model was used to study the phase behaviour of the aqueous two-phase systems (ATPSs) of polyethylene glycol (PEG) and dextran (DEX) with different molecular weights at various temperatures. In the proposed model, a ternary interaction parameter was added to the expression for the excess Gibbs free energy and, in turn, to the corresponding activity coefficient rendered by the UNIQUAC-NRF model. The combinatorial part of the new model takes the same form as that of the original UNIQUAC model and the residual part considers the nonrandomness and also the binary and the ternary interactions among the molecules in mixtures of PEG, DEX, and water. The results show that the new model can more accurately correlate the experimental data for the systems studied in this work than those obtained from the original UNIQUAC and the UNIQUAC-NRF activity coefficient models. In order to favourably compare the results the same minimisation procedure and the same experi...

In this paper, a new Gibbs energy model is proposed to study the thermophysical properties of aqueous electrolyte solutions at various temperatures. The proposed model assumes that the electrolytes completely dissociate in solution. The model also has two temperature-independent adjustable parameters that were regressed using experimental values of the mean ionic activity coefficients (MIAC) for 87 electrolyte solutions at 298.15 K. Results from the proposed model for the MIAC were compared with those obtained from the E-Wilson, E-NRTL, Pitzer and the E-UNIQUAC models, and the adjustable model parameters were used directly to predict the osmotic coefficients at this temperature. The results showed that the proposed model can accurately correlate the MIAC and predict the osmotic coefficients of the aqueous electrolyte solutions better on the average than the other models studied in this work at 298.15 K. Also, the proposed model was examined to study the osmotic coefficient and vapor pressure for a number of aqueous electrolyte solutions at high temperatures. It should be stated that in order to calculate the osmotic coefficients for the electrolyte solutions, the regressed values of parameters obtained for the vapor pressure at high temperatures were used directly. The results obtained for the osmotic coefficients and vapor pressures of electrolyte solutions indicate that good agreement is attained between the experimental data and the results of the proposed model. In order to unequivocally compare the results, the same experimental data and same minimization procedure were used for all of the studied models.

A model based on the perturbation theory of fluids was proposed to correlate the experimental data for surface tension of pure hydrocarbons in a wide range of temperature. The results obtained for the pure hydrocarbons were directly used to predict the surface tension for binary hydrocarbon mixtures at various temperatures. In the proposed model, a modified form of the square well potential energy between the molecules of the reference fluid was taken into account while the Lennard–Jones dispersion energy was considered to be dominant amongst the molecules as the perturbed term to the reference part of the model. In general, the proposed model has three adjustable parameters which are chain length, m, size, σ, and energy, e/κ, parameters, but in some cases the number of parameters was reduced to two, thereby setting the chain length to be unity for pure hydrocarbons. The regressed values of these parameters were obtained using the experimental data for pure hydrocarbons at different temperatures. The results showed that these parameters can be related to the molar mass of hydrocarbons. The model was also extended to predict the surface tension of binary hydrocarbon mixtures using the parameters obtained for the pure compounds. It is worth noting that no additional parameter has been introduced into the model in the extension of the model to the mixtures studied in this work. The results showed that the proposed model can accurately correlate the surface tension of pure hydrocarbons. Also the results showed that the surface tension for binary mixture of hydrocarbons can be accurately predicted using the proposed model over a wide temperature range.

The Vapor Extraction (VAPEX) process, a newly developed Enhanced Oil Recovery (EOR) process to recover heavy oil and bitumen, has been studied theoretically and experimentally and is found a promising EOR method for certain heavy oil reservoirs. In this work, a simulation study of the VAPEX process was made on a fractured model, which consists of a matrix surrounded by horizontal and vertical fractures. The results show a very interesting difference in the pattern of solvent flow in fractured model compared with the conventional model. Also, in the fractured system, due to differences in matrix and fracture permeabilities, the solvent first spreads through the fractures and then starts diffusing into matrix from all parts of the matrix. Thus, the solvent surrounds the oil bank, and an oil rather than the solvent chamber forms and shrinks as the process proceeds. In addition, the recovery factor is higher at lower solvent injection rates for a constant pore volume of the solvent injected into the model. Also, the diffusion process becomes important and higher recoveries are obtained at low injection rates, provided sufficient time is given to the process. The effect of inter-connectivity of the surrounding fractures was studied by making the side vertical fractures shorter than the side length of the model. It was observed that inter-connectivity of the fractures affects the pattern of solvent distribution. Even for the case of side fractures being far apart from the bottom fracture, the solvent distribution in the matrix was significantly different than that in the model without fractures. Combination of diffusion phenomenon and gravity segregation was observed to be controlling factors in all VAPEX processes simulated in fractured systems. The early breakthrough of the solvent for the case of matrix surrounded by the fracture partially inhibited diffusion of the solvent into the oil and consequently the VAPEX process became the least effective. It is concluded that fractures of poor connectivity improve the effectiveness of VAPEX process. This is a significant finding for the application of the VAPEX process to the fractured reservoirs.

A theoretical and experimental study was conducted to accurately determine the amount of adsorption and desorption of methane by various Granular Activated Carbon (GAC) under different physical conditions. To carry out the experiments, the volumetric method was used up to 500 psia at constant temperature of 25 °C. In these experiments, adsorption as well as desorption capacities of four different GAC in the adsorption of methane, the major constituent of natural gas, at various equilibrium pressures and a constant temperature were studied. Also, various adsorption isotherm models were used to model the experimental data collected from the experiments. The accuracy of the results obtained from the adsorption isotherm models was compared and the values for the regressed parameters were reported. The results shows that the physical characteristics of activated carbons such as BET surface area, micropore volume, packing density, and pore size distribution play an important role in the amount of methane to be adsorbed and desorbed.

In this work, the Ion Pair Modified Ghotbi-Vera Mean Spherical Approximation (IP-MGV-MSA) model was proposed to correlate the mean ionic activity coefficients (MIAC) for a number of symmetric and asymmetric aqueous electrolyte solutions at 25 °C. The new model is based on the recently proposed MGV-MSA model by Mortazavi-Manesh et al. In the IP-MGV-MSA model, the effects arising from the ion pair formation in the electrolyte solution was taken into account. Also, in the proposed model, while the cation diameter as well as the relative permittivity of water was considered to be dependent on electrolyte concentration, the anion diameter was independent of electrolyte concentration. The results obtained from the IP-MGV-MSA model showed that the model can accurately correlate the MIAC of single electrolyte solutions, in which ion pairs are formed. These results were also compared with those obtained from the GV-MSA and MGV-MSA models. The comparison showed that in the electrolyte solutions in which ion pairs are formed, the IP-MGV-MSA model can give more superior results than those obtained from the MGV-MSA and GV-MSA models. In the proposed model, the equilibrium constant of ion pair formation, K , is an adjustable parameter and can be obtained using the experimental data of the MIAC for electrolyte solutions. It should be noted that the values for the MIAC obtained from the IP-MGV-MSA model were converted from the McMillan–Mayer (MM) framework to that of the Lewis–Randall (LR) in order to be compatible with the experimental data.

In this study, water activities for the ternary systems of PEG6000 + sodium citrate (Na3Cit) + H2O and PEG6000 + potassium citrate (K3Cit) + H2O have been measured using an improved isopiestic method over the entire homogeneous mixing range at 298.15 K. From these measurements, values of the vapor pressure of solutions were also determined. The experimental data for the activity of water, collected in this work, were accurately correlated with local composition based models of the NRTL, modified NRTL, Wilson and modified Wilson. The results showed that these models can accurately correlate the water activity data generated in this work.

In this work, the vapour extraction (VAPEX) process is studied experimentally in a rectangular physical model at moderate-high pressure. The solvent was either pure propane or a mixture of propane/methane with different compositions. The solvent and carrier gas were totally mixed before injection, so that a solvent with the desired composition flowed through the injector during experiments, and the solvent mixture was in thermodynamic equilibrium before injection into VAPEX cell. Effects of pressure and composition of solvent were studied. Results showed that at a fixed pressure, the process is more effective with pure solvent compared to the use of solvent mixtures. The main feature of this work is that heavy oil recovery is improved as the approach pressure, defined as the (saturation) pressure minus operating pressure, decreases regardless of solvent composition or operating pressure. These results provide insight into proper field scale implementation of the VAPEX process.