RESUMEN
The phase behavior of hydrocarbon fluids confined in porous media has been reported to deviate significantly from that in the bulk environment due to the existence of sub-10 nm pores. Though experiments and simulations have measured the bubble/dew points and sorption isotherms of hydrocarbons confined in both natural and synthetic nanopores, the confinement effects in terms of the strength of fluid-pore interactions tuned by surface wettability and chemistry have received comparably less discussion. More importantly, the underlying physics of confinement-induced phenomena remain obfuscated. In this work, we studied the phase behavior and capillary condensation of n-hexane to understand the effects of confinement at the molecular level. To systematically investigate the pore effects, we constructed two types of wall confinements; one is a structureless virtual wall described by the Steele potential and the other one is an all-atom amorphous silica structure with surface modified by hydroxyl groups. Our numerical results demonstrated the importance of fluid-pore interaction, pore size, and pore morphology effects in mediating the pressure-volume-temperature (PVT) properties of hydrocarbons. The most remarkable finding of this work was that the saturation pressure predicted from the van der Waals-type adsorption isothermal loop could be elevated or suppressed relative to the bulk phase, as illustrated in the graphical abstract. As the surface energy (i.e., fluid-pore interaction) decreased, the isothermal vapor pressure increased, indicating a greater preference for the fluid to exist in the vapor state. Sufficient reduction of the fluid-pore interactions could even elevate the vapor pressure above that of the bulk fluid.
RESUMEN
A parallel implementation of the three-dimensional Shan-and-Chen multicomponent, multiphase lattice Boltzmann method (LBM) was used to simulate the equilibrium distributions of two immiscible fluids in porous media. The simulations were successfully validated against cone-beam x-ray microtomographic data on the distribution of oil (decane), water, and air phases in a 5-mm cube of porous medium composed of packed quartz sand grains. The results confirm that LBM models allow for the straightforward incorporation of complex pore space geometry determined from x-ray microtomography measurements and that simulated wetting and nonwetting phase distributions are consistent with x-ray observations on both macroscopic and microscopic scales.
RESUMEN
Asphaltenic solids formed in the Rangely field in the course of a carbon dioxide flood and heptane insolubles in the oil from the same field were used in this study. Four different solvents were used to dissolve the asphaltenes. Near-infrared (NIR) spectroscopy was used to determine the onset of asphaltene precipitation by heptane titration. When the onset values were plotted versus asphaltene concentrations, distinct break points (called critical aggregation concentrations (CAC) in this paper) were observed. CACs for the field asphaltenes dissolved in toluene, trichloroethylene, tetrahydrofuran, and pyridine occurred at concentrations of 3.0, 3.7, 5.0, and 8.2 g/l, respectively. CACs are observed at similar concentrations as critical micelle concentrations (CMC) for the asphaltenes in the solvents employed and can be interpreted to be the points at which rates of asphaltene aggregations change. CMC values of asphaltenes determined from surface tension measurements (in pyridine and TCE) were slightly higher than the CAC values measured by NIR onset measurements. The CAC for heptane-insoluble asphaltenes in toluene was 3.1 g/l. Thermal gravimetric analysis (TGA) and elemental compositions of the two asphaltenes showed that the H/C ratio of the heptane-insoluble asphaltenes was higher and molecular weight (measured by vapor pressure osmometry) was lower.
