Unified flash calculations with isenthalpic and isochoric constraints

Abstract

In the unified flash procedure, a persistent set of unknowns and equations are solved in equilibrium calculations, allowing for simultaneous phase stability and split calculations. For fluids in a subcritical thermodynamic state characterized by pressure and temperature, modeling both liquid and gas phases with inequality conditions for phase fractions has been shown to incorporate the tangent-plane criterion and results in a consistent formulation of compositions for both present and absent phases. However, applications such as high-enthalpy systems in subsurface flow require a state definition using other state variables than pressure and temperature, as well as the capability to represent supercritical phases. Furthermore, the robustness of the flash across a wide range of state values is required if equilibrium dynamics are to be included in a flow and transport problem.

This work introduces constraints in terms of enthalpy and volume to allow pressure and temperature to vary in the unified setting. The constraints are shown to arise from equilibrium conditions for the relevant state functions to be minimized. To increase the range of applicability, a modified extension procedure for the compressibility factor was devised, as well as procedures for the flash initialization.

The unified formulation is extendable to allow isenthalpic and isochoric flash calculations. The initialization was devised using methodologies from the negative flash and Rachford–Rice equations. Extensive numerical tests with multiple equilibrium definitions in terms of state variables were performed. Gas–liquid, binary and a multicomponent mixture using Peng–Robinson EoS showed consistency of results which are verified using third-party code.