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arXiv · 2003.06236

Confinement-mediated phase behavior of hydrocarbon fluids: Insights from Monte Carlo simulations

Jiaoyan Li·Qi Rao·Yidong Xia·Michael P. Hoepfner·Milind Deo
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Abstract

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-10nm 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.

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Jiaoyan Li, Qi Rao, Yidong Xia, Michael P. Hoepfner, Milind Deo. 2020-03-06. Confinement-mediated phase behavior of hydrocarbon fluids: Insights from Monte Carlo simulations. https://arxiv.org/abs/2003.06236

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