Fig 13-9

13-10 DISTILLATION
(a)
FIG. 13-9 The K values (K = y/x) in light-hydrocarbon systems. (a) Low-temperature range. (b) High-temperature range.
[DePriester, Chem. Eng. Prog. Symp., Ser. 7, 49, 1 (1953).]
where the mixture fugacity coefficients Φ̂ Li for the liquid and Φ̂Vi for the mixing rules for cubic equations of state now permit such equations to
vapor are derived by classical thermodynamics from the P-V-T expres- be extended to mixtures of organic chemicals, as shown in a reformu-
sion. Consistent equations for enthalpy can be similarly derived. lated version by Orbey and Sandler [AIChE J., 41, 683 (1995)].
Until recently, equations of state that have been successfully applied An alternative K value formulation that has received wide applica-
to Eq. (13-3) have been restricted to mixtures of nonpolar compounds, tion to mixtures containing polar and/or nonpolar compounds is
namely, hydrocarbons and light gases. These equations include those of
Benedict-Webb-Rubin (BWR), Soave (SRK) [Chem. Eng. Sci., 27, γ Li Φ Li
Ki = ! (13-4)
1197 (1972)], who extended the remarkable Redlich-Kwong equation, Φ̂ Vi
and Peng-Robinson (PR) [Ind. Eng. Chem. Fundam., 15, 59 (1976)].
The SRK and PR equations belong to a family of so-called cubic equa- where different equations of state may be used to predict the pure-
tions of state. The Starling extension of the BWR equation (Fluid Ther- component liquid fugacity coefficient Φ iL and the vapor-mixture
modynamic Properties for Light Petroleum Systems, Gulf, Houston, fugacity coefficient, and any one of a number of mixture free-energy
1973) predicts K values and enthalpies of the normal paraffins up models may be used to obtain the liquid activity coefficient γ Li . At low
through n-octane, as well as isobutane, isopentane, ethylene, propylene, to moderate pressures, accurate prediction of the latter is crucial to
nitrogen, carbon dioxide, and hydrogen sulfide, including the cryogenic the application of Eq. (13-4).
region. Computer programs for K values derived from the SRK, PR, When either Eq. (13-3) or Eq. (13-4) can be applied, the former is
and other equations of state are widely available in all computer-aided generally preferred because it involves only a single equation of state
process design and simulation programs. The ability of the SRK corre- applicable to both phases and thus would seem to offer greater con-
lation to predict K values even when the pressure approaches the con- sistency. In addition, the quantity Φ Li in Eq. (13-4) is hypothetical for
vergence pressure is shown for a multicomponent system in Fig. 13-13. any components that are supercritical. In that case, a modification of
Similar results are achieved with the PR correlation. The Wong-Sandler Eq. (13-4) that uses Henry’s law is sometimes applied.
THERMODYNAMIC DATA AND MODELS 13-11
(b)
FIG. 13-9 (Continued)
For mixtures of hydrocarbons and light gases, Chao and Seader (CS) pair of components in the mixture are required for use in Eq. (13-4), as
[AIChE J., 7, 598 (1961)] applied Eq. (13-4) by using an empirical discussed in Sec. 4. Six popular expressions are the Margules, van Laar,
expression for Φ Li based on the generalized corresponding-states P-V-T Wilson, NRTL, UNIFAC, and UNIQUAC equations. The preferred
correlation of Pitzer et al., the Redlich-Kwong equation of state for Φ̂Vi , expressions for representing activity coefficients are the NRTL and
and the regular solution theory of Scatchard and Hildebrand for γ Li . UNIQUAC equations. Extensive listings of binary-interaction parame-
The predictive ability of the last-named theory is exhibited in Fig. ters for use in all but the UNIFAC equation are given by Gmehling and
13-14 for the heptane-toluene system at 101.3 kPa (1 atm). Five pure- Onken (op. cit.). They obtained the parameters for binary systems at
component constants for each species (Tv , Pv , ω, δ, and v L) are required 101.3 kPa (1 atm) from best fits of the experimental T-y-x equilibrium
to use the CS method which, when applied within the restrictions dis- data by setting ΦVi and Φ iL to their ideal-gas, ideal-solution limits of 1.0
cussed by Lenoir and Koppany [Hydrocarbon Process., 46 (11), 249 and P sat/P, respectively, with the vapor pressure P sat given by a three-
(1967)], gives good results. Revised coefficients of Grayson and Streed constant Antonie equation, whose values they tabulate. Table 13-2 lists
(GS) (Paper 20-P07, Sixth World Pet. Conf. Frankfurt, June, 1963) for their parameters for selected binary systems based on the binary sys-
the Φ Li expression permit application of the CS correlation to higher tem activity coefficient equation forms given in Table 13-3.
temperatures and pressures and give improved predictions for hydro- Consistent Antoine vapor pressure constants and liquid molar vol-
gen. Jin, Greenkorn, and Chao [AIChE J, 41, 1602 (1995)] present a umes are listed in Table 13-4. The Wilson equation is particularly
revised correlation for the standard-state liquid fugacity of hydrogen, useful for systems that are highly nonideal but do not undergo phase
applicable from 200 to 730 K. splitting, as exemplified by the ethanol-hexane system, whose activity
For mixtures containing polar substances, more complex predictive coefficients are shown in Fig. 13-15. For systems such as this, in
equations for γ Li that involve binary-interaction parameters for each which activity coefficients in dilute regions may exceed values of

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