Fast and robust phase stability testing at isothermal-isochoric conditions

Abstract

In this paper, a robust and efficient phase stability testing procedure at isotherm-isochoric conditions is proposed. The tangent plane distance function is expressed in terms of component molar densities. Convergence behavior using various sets of independent variables is analyzed and it is shown that the choice of independent variables is very important for both robustness and computational speed. A particular attention is paid for conditions in which the Hessian matrix is notoriously ill-conditioned, that is, in the vicinity of the stability test limit locus (STLL) and of the spinodal, where the convergence is slow and problematic. It is found that poor conditioning occurs also at certain conditions in the two-phase region at low temperatures and towards high densities. A modified Cholesky factorization (to ensure a descent direction) and a line search procedure are used in Newton iterations. The equation of state (EoS) must not be solved for volume and any pressure explicit EoS can be used; only expressions of pressure, fugacity and their partial derivatives with respect to mole numbers are required. The proposed method is tested on several examples from the literature, using a refined grid in the temperature-molar density plane. The variables obtained by scaling the ideal part of the Hessian matrix lead by far to the most robust formulation, with no failure observed for the investigated mixtures, and much faster than previous methods, with a low average number of iterations required for convergence for all mixtures.