A novel method for detecting and computing univolatility curves in ternary mixtures

•3D generalized univolatility surfaces are defined.•Ternary RCM univolatility curves are the loci of relative composition critical points.•Ordinary differential equations describe the univolatility curves.•A new algorithm based on an initial value problem is proposed.•The method finds univolatility curves not connected to any azeotrope.

Residue curve maps (RCMs) and univolatility curves are crucial tools for analysis and design of distillation processes. Even in the case of ternary mixtures, the topology of these maps is highly non-trivial. We propose a novel method allowing detection and computation of univolatility curves in homogeneous ternary mixtures independently of the presence of azeotropes, which is particularly important in the case of zeotropic mixtures. The method is based on the analysis of the geometry of the boiling temperature surface constrained by the univolatility condition. The introduced concepts of the generalized univolatility and unidistribution curves in the three dimensional composition - temperature state space lead to a simple and efficient algorithm of computation of the univolatility curves. Two peculiar ternary systems, namely diethylamine - chloroform - methanol and hexane - benzene - hexafluorobenzene are used for illustration. When varying pressure, tangential azeotropy, bi-ternary azeotropy, saddle-node ternary azeotrope, and bi-binary azeotropy are identified. Moreover, rare univolatility curves starting and ending on the same binary side are found. In both examples, a distinctive crossing shape of the univolatility curve appears as a consequence of the existence of a common tangent point between the three dimensional univolatility hypersurface and the boiling temperature surface.