The Phase Envelope of Multicomponent Mixtures in the Presence of a Capillary Pressure Difference

Confined fluids such as oil and gas mixtures inside tight reservoirs are systems that can experience high capillary pressure difference between the liquid and gas phases. This capillary pressure difference has an effect on the phase equilibrium and in some cases is considerably high. We presented an algorithm which can reliably compute the whole phase envelope for multicomponent mixtures when there is a capillary pressure difference. It uses an equation of state for the phase equilibrium and the Young-Laplace equation for the capillary pressure model. The algorithm proves to be robust and efficient for test mixtures with wide ranges of compositions at different capillary radii and vapor fractions. The calculation results show that the phase envelope changes everywhere except at the critical point. The bubble point and the lower branch of the dew point show a decrease in the saturation pressure, whereas the upper branch of the dew point shows an increase. The cricondentherm is shifted to a higher temperature. We also presented a mathematical analysis of the phase envelope shift due to capillary pressure based on linear approximations. The resulting linear approximation equations can predict the correct direction of the phase envelope shift. Combined with the multicomponent Clapeyron equation, the equations reveal why the shift changes direction for the saturation pressure at the cricondentherm and for the saturation temperature at the cricondenbar. The equations can be used to estimate the magnitude of shift, and the approximation is close for the change in the bubble point pressure.