444 Chapter 11 Enhanced Distillation and Supercritical Extraction
except in the critical region, were obtained using (11-19) and
(11-20), with (11-23) and (11-24), and values of
kij = -0.164 and lij = -0.233 in conjunction with the PR
equation. Similar good agreement with experimental data
was obtained for the systems nitrogen-cyclohexane, carbon
dioxide-n-butane, and carbon dioxide-cyclohexane, and
the ternary systems nitrogen-carbon dioxide-n-butane and
nitrogen-carbon dioxide-cyclohexane.
For high pressures and mixtures containing one or more
strongly polar components, the preceding rules are inade-
quate and it would seem desirable, in those cases, to combine
the equation-of-state method with the activity-coefficient
(free energy) method to handle strong nonidealities in the
liquid phase. The following theoretically based mixing rule
of Wong and Sandler [86] accomplishes such a bridge be-
tween a cubic equation of state and a free-energy or activity-
coefficient equation. If, for example, the PR equation of state
and the NRTL activity-coefficient equation are used, the Wong
and Sandler mixing rule leads to the following expressions
for computing a, and b, to be used in the PR equation:
a, = RTQDI(1-D) (11-25)
bm = Q/(l-Dl (11-26)
where
c c
(11-27)
1=1J=I
C can be made by conventional computer programs, as the fol-
a1
D = ~ X ~ - -
b,RT
+-
GeX(xl)
--
uRT
(11-28)
1=1
(b - +IiJ = [kt - &) (bJ - I)& (1 - kij)
with aij = aji .
From Equations (11-25) to (11-32), it is seen that for a
binary system, using the NRTL equation, there are four
adjustable binary-interaction parameters (BIPs): kg, aij, ~ i j , and which are defined as the mole fraction in the extract divided by
and 7,i. These four parameters, for a temperature and
pressure range of interest, are best obtained by regression of
experimental binary-pair data for VLE, LLE, andlor VLLE.
The parameters can then be used to predict phase equilibria
for ternary and higher multicomponent mixtures. However,
Wong, Orbey, and Sandler [90] show that when values of
the latter three parameters are already available, even at just
i
near-ambient temperature and pressure conditions, from
an experimental-data-compilation source such as that of
Gmehling and Onken [9 11, those parameters can be assumed
to be independent of temperature and used directly to make
reasonably accurate predictions of phase equilibria, even at
temperatures to at least 200C and pressures to 200 bar. Fur-
thermore, regression of experimental data to obtain a value
of k, is not necessary either, because Wong, Orbey, and
Sandler show that it can be determined from the other three
parameters by choosing its value so that the excess Gibbs
free energy computed from the equation of state matches
that computed from the activity-coefficient mode. Thus, the
application of the Wong-Sandler mixing rule to supercritical
extraction conditions is facilitated.
Another phase-equilibrium prediction method applicable
to wide ranges of pressure, temperature, molecular size,
and polarity is the group-contribution equation of state
(GC-EOS) of Skjold-Jldrgensen [92]. This method, which
combines features of the van der Waals equation of state, the
Carnahan-Starling expression for hard spheres, the NRTL
activity-coefficient equation, and the group-contribution
principle, has been successfully applied to supercritical-
extraction conditions. The GC-EOS method is particularly
useful when all of the necessary binary data are not available
to determine all binary interaction parameters.
When experimental K-values are available, or when the
Wong-Sandler mixing rule or the GC-EOS can be applied,
equilibrium-stage calculations for supercritical extraction
lowing example illustrates.
EXAMPLE 11.10
One moVs of 10 wt% ethanol in water is extracted by 3 moVs of
carbon dioxide at 305 K and 9.86 MPa in a countercurrent-flow
extraction column with the equivalent of five equilibrium stages.
Determine the flow rates and compositions of the exiting extract
and raffinate.
SOLUTZON
This problem, which was taken from Colussi, Fermeglia, Gallo,
and Kikic [93],was solved with the Tower Plus model of the Chem-
CAD process simulator, under conditions of constant temperature
and constant pressure, at which composition changes were small
enough that K-values could be assumed constant. The following
K-values, taken from Colussi et al., who used the GC-EOS method,
the mole fraction in the raffinate, are in reasonably good agreement
with experimental data.
Component K-Value
CO2 34.5
Ethanol 0.115
Water 0.00373