Phase behaviour of multicomponent mixtures of hydrocarbons : MD simulation

Abstract

We perform a molecular dynamics simulation of a bulk eight-component hydrocarbon mixture that roughly represents a composition of hydrocarbon fluid in a volatile oil reservoir. For that goal, we have developed a method for building molecular models of hydrocarbon mixtures which can include various branched molecules. We have used self-periodical simulation boxes with different aspect ratios. Our main focus here is the phase behavior of a multicomponent mixture in the presence of gas–liquid interfaces of different shapes: spherical, cylindrical, and slab-like gas bubbles. We have developed a method for calculating properties of coexisting phases in molecular simulations of multicomponent systems. In particular, it allows us to analyze the local composition of the mixture and to calculate the molar densities of components in liquid and gas phases, and inside the interface layer between them. For the values of model parameters that we have used so far, the mixture is homogeneous at a high pressure and undergoes liquid–gas phase separation upon decreasing the pressure. We have kept the same temperature T = 375.15 K , the same composition and the same number of molecules in all systems and used several combinations of the simulation box size and shape to control the overall density, and therefore also the pressure, as well as the presence or absence of a liquid–gas interface and its shape. The gas bubble that appears in the system is mainly composed of methane. There is also a small number of ethane and butane molecules, a tiny number of hexane molecules, and no molecules of heavier components at all. In the liquid phase, all components are present. We also show that inside the gas–liquid interface layer, which is actually quite broad, the molar density of methane is also higher than that of other components and even reaches a maximum value in the middle of the interface. Ethane behaves similarly: its molar density also reaches a maximum inside the interface. The molar density of heavier components grows monotonically from the inner part of the interface towards its outer part and shows a very small (almost not visible) maximum at the outer side of the bubble.