Nuid Phase Equilibria, 11 (1983) 127-135

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

127
A SIMPLE METHOD FOR CONSTRUCTING PHASE ENVELOPES
FOR MULTICOMPONENT MIXTURES
R.G. ZIERVOGEL and B.E. POLING
Chemical Engineering Department, University of Missouri, Rolla, MO 65401 (U.S.A.)
(Received June 29, 1982; acceptecl in final form October 14, 1982)
ABSTRACT
Ziervogel. R.G. and Poling, B.E., 1983. A simple method for constructing phase envelopes for
multicomponent mixtures. Fluid Phase Equilibria, 11: 1277 135.
A simple method for constructing vapor-liquid equilibrium phase envelopes is described.
Dew and bubble points are calculated throughout the critical and retrograde regions by
stepping around the envelope in suitably small increments of T or P. The technique is simpler
than previous methods because the dew and bubble points are determined by iterating on a
single variable through the entire critical region. Criteria are presented which allow de-
termination of whether this iteration variable should be T or P. Phase envelopes, together
with critical points, cricondentherms and cricondenbars, have been calculated using this
method for ten different mixtures.
INTRODUCTION
This paper presents a simple method for constructing complete phase
envelopes for multicomponent hydrocarbon mixtures. Critical points and the
points of maximum pressure and temperature are also determined by the
method. The Soave (1972) modification of the Redlich-Kwong equation of
state is used to generate equilibrium ratios for all components. Values for the
interaction coefficients k,,, the pure-component properties and other con-
stants are taken from Reid et al. (1977).
The method uses the established technique of calculating dew and bubble
points by stepping around the phase envelope in suitably small increments of
T or P. These dew and bubble points are calculated by iterating on a single
variable, T or P. This is the normal procedure for calculating dew and
bubble points at low to moderate pressures, but multivariable New-
ton-Raphson schemes have generally been proposed for calculations in the
critical and retrograde regions (Asselineau et al., 1980; Michelsen, 1980). The
method described herein, i.e., iteration on a single variable, represents a
0378-3812/83/$03.00 0 1983 Elsevier Science Publishers B.V.
128
considerable simplification over these multi-variable schemes, and converges
reliably provided that the right variable is chosen as the iteration variable.
Criteria are presented to make this choice.
CALCULATION PROCEDURE
In the procedure for constructing the phase envelope, the bubble-point
portion of the curve is first generated from some low pressure up to the
critical point. Then the dew-point portion is generated. To start the process,
a variable is chosen which we will refer to as the independent variable, say T.
Then P becomes the iteration variable, and bubble-point pressures are
calculated at successively higher temperatures along the phase envelope until
either the critical point is reached, or until the iteration and independent
variables must be switched. The first bubble point is obtained at a tempera-
ture and pressure sufficiently low that convergence is easily obtained. The
result for the first bubble point is used as the initial guess for the second
calculation. Thus, the entire phase envelope is generated by a process in
which initial guesses are the result of previous calculations. Trivial root
problems (Asselineau et al., 1980; Poling et al., 1981; Gundersen, 1982) have
never been encountered using this initial guess procedure. Dew and bubble
points are calculated using Newtons method in the form
0 new = %M - f/(df/de)
where 6, the iteration variable, is T or P. For bubble points,
f= Cx,K, - 1
and
df/de = &;(dK,/dt)
For dew points,
f=b,/K,- 1
and
df/de = - c (.w4%%d~)
Other functions, such as f = In Xx; K, , possess superior convergence char-
acteristics at low pressures (King, 1980). The behavior of this type of
function in the retrograde and critical regions has not been evaluated in this
study. Analytic expressions for dK,/d8 were obtained using a procedure
similar to that described by Shah and Bishnoi (1978).
129
The success of the entire method depends upon determination of whether
8 should be T or P. The parameter /3, a dimensionless slope of the phase
envelope, is defined as Id(ln P)/d(ln T)j. In Fig. 1, in the region of the
cricondentherm, j3 passes through infinity and the temperature is relatively
constant over a large pressure range. Thus, dew-point temperatures are
nearly constant for all pressures in this vicinity and are easily calculated. The
procedure is to choose P as the independent variable and T as the iteration
variable, i.e., 0 = T, and calculate dew-point temperatures at successively
higher pressures. Near the cricondenbar, the opposite situation applies, i.e.,
pressure is relatively constant over a large temperature range. Thus, 8 = P,
and the top of the curve in Fig. 1 is generated by calculating dew-point
pressures at successively lower temperatures. We have arrived at the follow-
ing, rather arbitrary guidelines for choosing the iteration variable:
[Mixture
4
c, -
c, -
60 I c3 -
0.9430
0.0270
0.0074
nc, - 0.0049
nC,- 0.0010
C;, - 0.0027
N>- 0.0140
60
P
( o t m)
T(K)
Fig. 1. Phase boundary diagram for Mixture 4 (natural gas). Regions are shown where the
iteration variable 0 must be P ( /? i 2) and where 0 must be T (/3 > 20). In other regions, 0
may be either P or T (/3 = Id(ln P)/d(ln T)I).
130
for p < 2, use e = P;
for B > 20, use 8 = T.
When p is between 2 and 20, convergence is obtained regardless of whether 8
is T or P. The values 2 and 20 are rather arbitrary; any two values which
identify those portions of the phase envelope where temperature or pressure
is relatively constant would work.
Details of the calculation procedure are illustrated by Figs. 1 and 2.
Figure 1 shows regions where /3 is less than 2, between 2 and 20, and greater
than 20 for one of the mixtures studied. This illustrates the regions where 8
must be P, can be T or P, or must be T, respectively. The step sizes in the
independent variable that were actually used to progress along the phase
envelope during its construction are shown in Fig. 2. The numbers of
iterations required for convergence for the bubble points at 56.0, 56.5 and
57.0 atm. were 7, 9 and 11, respectively. All other points in Fig. 2 converged
60
AP =O.Ol .
I AP=O.d/ I
50-
I I 4
225 250 275
T(K)
1
Fig. 2. Phase boundary diagram for Mixture 4 (natural gas). Step sizes in T or P at which
successive dew or bubble points were calculated are shown.
131
in six iterations or less. The convergence criterion was that the change in 8
had to be less than 0.001 K (or atm.).
Construction of the phase envelope identifies the cricondentherm,
cricondenbar and critical point. These points can be determined to a desired
accuracy either by interpolation or by repeating the calculations with smaller
increments of the iteration variable. The critical points are located by the
intersection of the dew- and bubble-point curves, with points being calcu-
lated on both sides of the critical point for both curves (Michelsen, 1980).
Points of maximum temperature and pressure are located more easily, as the
points where /3 passes through infinity and zero, respectively.
RESULTS
Phase envelopes were constructed for the ten multicomponent systems
listed in Table 1. The number of components ranged from two to seven.
Several systems contained non-hydrocarbon species, such as N,, CO, and
H,S. Phase envelopes constructed for two of the ten mixtures are shown in
Figs. 1-3. Tables 2 and 3 list the critical points, cricondentherms and
cricondenbars calculated using the present method for the ten mixtures.
Experimental values together with references are also listed. For Mixture 4,
7
Mixture no.3
C, - 0.2654
50-
nC, - 0.7346
P,,, = 45.23 T, = 520.32
40-
P
(atm)
20-
_L __A
425 450 475 500 525
T (K)
Fig. 3. Phase boundary diagram for Mixture 3.
1
3
2

TABLE 2
Comparison of calculated critical temperatures and pressures with literature values
Mixture
r, (K)
Calc. Exp.
Absolute
error (%)
PC (atm.) Absolute Reference
error (%)
Calc. Exp.
1 328.2 322.4 1.80 61.88 57.82 7.02
2 424.4 409.3 3.69 87.04 85.92 1.30
3 520.3 - 515.7 0.89 43.20 46.39 6.88
4 202.58 202.32 0.13 57.83 57.53 0.52
5 442.57 438.15 1.01 62.41 65.26 4.37
6 318.02 313.70 1.38 88.41 88.46 0.06
7 541.02 541.26 0.04 30.35 30.53
8 319.80 313.70 1.94 17.63 -??.43
9 321.84 310.92 3.51 87.54 8 I .66 7.20
10 380.7 371.2 0.93
Average absolute error (%) 1.53
73.93 73.31
0.59
0.26
0.85
2.91
Kay (1938)
Kay (I 938)
Kay (1938)
Michelsen ( 1980)
Peng and Robinson (1977)
Yarborough and
Smith (1970)
Hissong ( 1968)
Yarhorough and
Smith (1970)
Robinson and
Bailey ( 1957)
Olds et al. (1949)
^. ^ .- ..___..
134
TABLE 3
Comparison of calculated maximum temperatures and pressures with literature values
Mixture
T,,, (K)
Absolute P
mdX (atm.1
Absolute
error (%) error (%)
Calc. Exp. Calc. Exp.
1 357.5 357.2 0.08 66.41 64.69 2.66
2 450.2 450.4 0.04 87.50 85.92 1.84
3 521.7 521.2 0.10 45.23 48.57 6.88
4 269.9 269.9 0.00 87.6 87.6 0.00
Average absolute error (%) 0.06 2.85
the values labeled as experimental are actually those calculated by Michelsen
(1980) using the Soave-Redlich-Kwong equation. His results should thus be
identical to ours, and they are indeed quite close. Mixtures 559 have also
been studied by Peng and Robinson (1977). The good agreement between
the calculated and experimental results indicates that the present method
converges to the appropriate values for all ten mixtures.
CONCLUSIONS
A simple method for constructing phase envelopes for multicomponent
mixtures has been described. The simplicity results because derivatives with
respect to only one variable, temperature or pressure, are necessary to obtain
convergence in all examples considered. The success of the method depends
on proper choice of the variable upon which to iterate. Thus. in the region of
the cricondentherm, the iteration variable is temperature; near the cricon-
denbar, the iteration variable is pressure. Trivial root problems are avoided
by using the results of previous calculations as initial guesses.
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