Phase equilibrium distillation curves

A residue curve map (RCM) consists of a plot of the phase equilibrium of a mixture submitted to distillation in a batch vessel at constant pressure. RCM is advantageous for analyzing ternary mixtures. More exactly, a residue curve shows explicitly the evolution of the residual liquid of a mixture submitted to batch distillation. 

Three types of binary phase equilibrium curves are shown in Fig. 13-18. The y-x diagram is almost always plotted for the component that is the more volatife (denoted by the subscript 1) in the region where distillation is to take place. Curve A shows the common case in which component 1 remains more volatile over the entire composition range. Curve B is typical of many systems (e.g., ethanol-water) in which the... 

As illustrated throughout this section, process simulators have extensive facilities for preparing phase-equilibrium diagrams T-x-y, P-x-y, x-y,... ), and residue curve maps and binodal curves for ternary systems. In addition, related but independent packages have been developed for the synthesis and evaluation of distillation trains involving azeotropic mixtures. These include SPLIT by Aspen Technology, Inc., and DISTIL by Hyprotech (now Aspen Technology, Inc., which contains MAYFLOWER developed by M.F. Doherty and M.F. Malone at the University of Massachusetts). 

Fig. 2-14). B is the intersection of the equilibrium curve with the line of slope — Fgj/D starting at point A, The distillate concentration yp = Xp, and distillate residue concentration Xg, are simply the coordinates of B. Provided that the released vapor and distillation residue are in phase equilibrium, this is approximately true in practice. 

However, tie-lines can cross each other. That is why, for phase equilibrium characteristics in the concentration space, it is convenient to use another kind of line, the so-called residue curves. Let s consider a process of open evaporation simple distillation) illustrated in Fig. 1.3. 

In Sections 1.3 to 1.5, the residue curve bundles, which characterize the direction of Uquid-vapor tie-lines in each point of the concentration space (i.e., the phase equilibrium field), were considered. As stated previously, such characteristics of the phase equilibrium field and structural elements related to it (bonds, distillation regions, and subregions) are the most important for one of the distillation modes, in particular, for the infinite reflux mode. 

These are azeotropic points where the azeotropes occur. In other words, azeotropic systems give rise to VLE plots where the equilibrium curves crosses the diagonals. Both plots are however, obtained from homogenous azeotropic systems. An azeotrope that contains one liquid phase in contact with vapor is called a homogenous azeotrope. A homogenous azeotrope carmot be separated by conventional distillation. However, vacuum distillation may be used as the lower pressures can shift the azeotropic point. Alternatively, an additional substance may added to shift the azeotropic point to a more favorable position. When this additional component appears in appreciable amounts at the top of the column, the operation is referred to as an azeotropic distillation. When the additional component appears mostly at the bottom of the column, the operation is called extractive distillation. 

Solute equilibrium between the mobile and stationary phases is never achieved in the chromatographic column except possibly (as Giddings points out) at the maximum of a peak (1). As stated before, to circumvent this non equilibrium condition and allow a simple mathematical treatment of the chromatographic process, Martin and Synge (2) borrowed the plate concept from distillation theory and considered the column consisted of a series of theoretical plates in which equilibrium could be assumed to occur. In fact each plate represented a dwell time for the solute to achieve equilibrium at that point in the column and the process of distribution could be considered as incremental. It has been shown that employing this concept an equation for the elution curve can be easily obtained and, from that basic equation, others can be developed that describe the various properties of a chromatogram. Such equations will permit the calculation of efficiency, the calculation of the number of theoretical plates required to achieve a specific separation and among many applications, elucidate the function of the heat of absorption detector. 

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