Computers and Chemical Enghecring Vol. 6, No. 3, pp. 24S-2% 1982 l-KI98-1354/82/030245-i Is03.

00/0
Printed in Great Britain. @ 1982 Pergamon Press Ltd.

NUMERICAL ASPECTS OF THE IMPLEMENTATION OF

CUBIC EQUATIONS OF STATE IN FLASH
CALCULATION ROUTINES

TRULS GUNDERSEN*
Department of Chemical Engineering, University of Trondheim, Norway

(Received 4 November 1980;received for publication 18 November 1981)

Abstract-It is shown that failures in flash calculations (Ki --, 1.0) when cubic equations of state are
used to estimate equilibrium K-values, result from two main deficiencies. One is the well-known
problem of guessing good starting values of the phase compositions at high pressure. The other is
that regular methods for solving the cubic equation in the compressibility often lead to a wrong
type of root (i.e. vapour or liquid). An algorithm without these deficiencies is presented.

Scope-Cubic equations of state (e.g. Soave-Redlich-Kwong and Peng-Robinson) are the most
popular methods among chemical engineers for estimating K-values of hydrocarbon mixtures at high
pressure. In spite of this, many flash calculation packages and even commercial flowsheet simulators
that have implemented these methods fail to perform properly at pressures exceeding 5040% of the
critical pressure of the mixture. In program manuals this failure is referred to as the problem of all
K-values approaching 1.0. Disappointingly, few seem to have looked behind the curtain to find out
why this is so.
This article discusses why flash calculations fail and how to implement the SRK method for use
at high (near critical) pressure. A system of eight components with 72.8 mole % methane is used to
illustrate the techniques and results, together with a three-component system of ethane, propane and
n-butane. To compare the results, calculations were also carried out with the MINISIM program,
developed at Oklahoma State University.

Conclusions and Significance-There seems to be some kind of confusion in the literature about the
connection between the number of roots arising from the equations of state and the actual number of
phases in the system. This work has shown that the Soave-modified Redlich-Kwong equation of
state becomes monotonic at moderate and high pressure. This may happen for one of the phases or
both and well inside the two-phase region.
In cases where the equation is not monotonic, but still only has one root, failure of the calculation
is avoided by using maximum or minimum points instead of the actual solution if this root is a wrong
type (vapour/liquid) of compressibility.
The proposed algorithm is able to estimate the phase diagram for the two test systems within
from 0.2 to 2.0 atm from the critical point, using a sequential technique with stepwise calculations
from low (1 atm) to high (near critical) pressure. The advantage of this method is the good initial esti-
mate of the phase compositions available from the previous calculation.

INTRODUCTION for reasonableness in all equilibrium calculations. Ac-

Vapour-liquid equilibrium calculations represent an im-
portant field in chemical engineering simulation or design
calculations. The many articles published on this theme
may be classified in two groups. The equation of state
approach tries to estimate equilibria at high pressure, but
for a limited amount of compounds, and the activity
coefficient approach estimates equilibria for a wider
spectrum of compounds at normal pressure levels. Most
of the articles on the equation of state method present
modified and new equations. The advantages of the
equations rather than the regions where they fail to
perform properly are emphasized and the implemen-
tation in flash calculation routines is given little con-
sideration.
In a preliminary draft of the MINISIM program
(developed at Oklahoma State University), Erbar stres-
ses the importance of checking the predicted K-values
*Present address: Norsk Hydro a.s. Research Centre, 3901
Porsgrunn, Norway.
cording to him K-values close to 1.0 are caused by:
(i) poor initial estimate of vapour-to-feed ratio
(ii) flash calculations being attempted in a single
phase region
(iii) combinations of pressure and temperature ap-
proaching the true critical point of the mixture.
He further discusses how to change the calculation
strategy in order to overcome this problem. There is,
however, in his discussion no mention of the significance
of the solution of the cubic equation of state to find
the compressibility factors. This side of the problem
is neither discussed by Soave[l] nor by Peng and
Robinson[Z] in their original articles.
Coward et al. [3] have analysed the Redlich-Kwong
(RK) and the Benedict, Webb and Rubin (BWR) equa-
tions of state in order to demonstrate the changing
behaviour as temperature, pressure and compositions are
varied. The RK (and also SRK) equation of state is much
easier to analyse because of its cubic form than is the
complex BWR equation. In a diagram, Coward, Gale,
and Webb give the relationship between the two

245
246 Trms GUN~IER~EN

parameters Q and R of the cubic equation and the by Asbj$msen [ 151:

number (and type) of roots. In a more recent article [4]
Coward and Webb discuss the problem of non-unique
dew- and bubble-points in the Chao-Seader correlation
because of the use of the Redlich-Kwong equation of
state. This discussion also concentrates on the to an accuracy of 0.001 for a given set of 4, Ki (i =
significance of the values of the parameters (Q, R) of the l,NC). The number of iterations depends on the
equation. linearity of f(f).
Michelsen[lO] has presented an algorithm for the con- At conditions close to critical, f(5) may have such a
struction of complete vapour-liquid phase envelopes, shape that the limited numerical resolution of the com-
capable of accurately determining the critical point of the puter prevents proper solution. In these cases, f(l) is
system. A multivariable Newton-Raphson iteration is very close to zero in the main part of the region 0 d l d
used to solve the flash problem, but neither in this article 1. The third order method was chosen and a maximum
nor in the referenced work by Christiansen et al. [ll] is (for most off-critical conditions) of 4 iterations were
the solution of the cubic equation of state used to find the satisfactory.
compressibility factors discussed. The advantage of the
method presented by Michelsen is the assurance of good EQUATION-OF-STATEAPPROACH
initial estimates of the K-values (and then also the mole When the equilibrium ratios (K-values) are estimated
fractions from the material balances) created by the by this approach, the same equation of state is used for
linear extrapolation from the two previous points on the both phases. A fugacity coefficient can be estimated for
phase envelope. both vapour (V) and liquid (I-) phase and the K-values
Khoury[lZ] discusses the problem that the cubic are given by:
equation of state sometimes give rise to physically un-
acceptable compressibility factors. In cases where a Ki = +i/c&. (3)
vapour or liquid type solution is lost, he perturbates
the temperature in order to get a physically more ac- Reid et al.[7] give the following thermodynamic expres-
ceptable solution. sion for the fugacity coefficients:
Only Boston and Mathias [ 131have solved the problem
that one of the roots does not exist, in a way similar to
the algorithm presented here. In their work with the
process simulator called ASPEN, they have found that
because of the iterative character of the unit operation
calculations either the vapour or the liquid compres- The actual equation of state gives an expression for the
sibility root may not exist at the start, and they use pressure P as a function of V, T and Ni. Possible equations
pseudo properties to enable convergence. of state may be:
The users of equilibrium packages built on the equa- The Soave-modified Redlich-Kwong equation of state:
tion of state approach complain that the high pressure
capabilities of these methods are not as good as stated in p,R.T 0. b.R.T F
the literature. This fact initiated a project where the v-z*o(o+ .
basic objective was to find out whether these inabilities
were caused by the actual equation of state, or by the The Peng-Robinson equation of state:
practical implementation of these methods in flash cal-
culation packages. p,R.T
-- a(T)
In this work, a minicomputer (ABC-80) was used with u-b u(u+b)tb(u-b) (6)
test systems from Kurata and Katz[5] (eight components)
and from Coward and Webb141 (three components). The The SRK equation can be written as the following third
SRK equation of state was chosen, as the equation with degree equation in compressibility:
a wide range of application.
For isothermal flash calculations, Rachford and Z2-Zt(A-B-Bp.Z-A-B=0 (7)
Rice[6] have suggested that the vapour to feed ratio,
[ = V/F, may be computed by iteration from the equa- where
tion: A,& .-P.b*F 0-W
fib R-T
P-b
B=R.T
The function f(c) has two important advantages:
(i) f(J) is monotonically decreasing as l increases. b = 2 xi . b,
(The first derivative with respect to the vapour-to-feed i=*
ratio is always negative.) There is, therefore, just one
solution possible in the region 0 G 6 d 1 and this makes i
b=fi m
the computation safe. b Pci
(ii) f(5) can be solved in (4)-(6) iterations by a second
order Newton method: x x xi . xl . (1 - ki,) *.[(T,i . T,1IP,i . P,J . Fi . Fj]12

A5 = -flf (W
or in (2)-(4) iterations by a third order method presented
 Numerical aspects of the implementation of cubic equations of state in flash calculation routines
..
WI
The Peng-Robinson equation can be transformed in the
same manner:
Z3-(l-B).Z2t(A-3-B2-2.B)-Z
-(A.B-B2-Bq=O.
The parameters A and B are the same for the SRK and
PR equations apart from some small deviations in the
constants listed in Table 1. Packages that have already
implemented the SRK method can therefore most easily
be extended to cover the PR method with a change of
the five constants in Table 1 and some adjustments in the
routine that finds the roots (compressibility factors) of
the cubic equation.
The fugacity coefficients and the K-values can be
estimated from either the SRK or the PR method. In the
following discussion, although we concentrate on the
SRK method, most of the ideas and conclusions also
apply to the PR method. The PR equation of state is
more complex because of the coefficients (Eq. 9) and the
technique described in the next section is therefore more
cumbersome.
SOLUTION
OF THE CUBICEQUATION
Equation (7) can be solved analytically or by numerical
iterative methods. Edmister[l7] has presented an analy-
tical solution for deriving charts for compressibility fac-
tors and fugacity coefficients. He does not, however,
Fig. l(a). SRK equation at low pressure.
241
Table 1. Constantsin the SRK and PR equationsof state
SRK PR
0.42747 0.45724
"a
0.06664 0.07760
*b
a 0.48 0.37464
is74 1.54226
6
(9)
Y 0.176 0.26992
discuss the problem when the phase compositions are
unknown. Because the solution strategy is different
depending upon the actual phase (vapor or liquid) and
the fact that maximum or minimum points instead of the
actual roots are accepted in some cases, the numerical
method has been chosen and it is governed by parameter
checks.
Depending upon the coefficients Q = A - B - B2 and
R = A *B, the cubic equation has one or three real roots.
Since it is the composition of one of the phases and not
the total composition of the system that is used to
determine the coefficients Q and R, the number of roots
bears no relation to the number of phases in the system.
The correct interpretation of the existence of three
roots is that the actual composition can exist both as a
vapour and as a liquid, but not necessarily in equilibrium.
The strategy is therefore to pick up the largest root when
the cubic equation is solved for the vapour phase com-
pressibility and the smallest root when the cubic equa-
tion is solved for the liquid phase compressibility. The
248 TRULSGUNDERSEN
Fig. l(b). SRK equation at highpressure.
derivatives of the function
F(Z)=z3-ZZtQ~Z-R (10)
and in particular the first and second
F(Z)=3.Z*-2.Z+Q (11)
F(Z)=6.Z-2 (12)
will indicate the possibility of one or more roots in the
range of Z from 0 to 1.0.
At low pressure, Eq. 10 will take a form as given by
Fig. l(a), while increasing pressure will make the func-
tion monotonically increasing as shown in Fig. l(b).
The point of inflection (F(Z) = 0) for the SRK equa-
tion is at Z = l/3 for all values of xi, yi, P and T. The
Z-values of the extreme points (F(Z) = 0) are given by:
(13)
Obviously, if Q = l/3 the extreme points and the point of
inflection coincide at Z = l/3. If Q > l/3 then F(Z) is
monotonically increasing (Fig. l(b)) and there is only
one root possible. Coward et al.[3] have found the values
of Q and R that give rise to one or three solutions. If
Q < l/3 there is still a possibility of finding just one root.
This is illustrated in Fig. 2. When seeking a vapour
compressibility with F(Z) of the shape A, most solution
routines select 2, as ZVAP. In the same manner, when
looking for a liquid compressibility with F(Z) of the
shape B, a general routine finds ZLIQ = Z,.
An alternative approach is to say the the vapour-like
solution of case A has slipped from the point Z,, and
that the liquid-like solution of case B has slipped from
the point Zr. The values of Z, and Z2 are given by Eq.
13. The cases A and B occur only at low and moderate
pressure levels and result basically from poor starting
values of the phase compositions. It is found from
experience that choosing Z2rather than Z, (ZVAP) and Z,
rather than Z, (ZLIQ) has a positive effect on the iteration
procedure. As a matter of fact, the iteration otherwise
breaks down with the typical solution ZLIQ = ZVAP and
K, --) 1.0(i = 1, NC). Cases A and B can easily be detected
by evaluating the function F(Z) (Eq. 10) at Z, and Z2.
In the general case, the solution is found by a third-
order method, (Eq. 2(b)) which is very fast (2-3 itera-
tions) because of the straightforward nature of the first
(Eq. 11) and thesecond (Eq. 12) derivatives and the
linear nature of F(Z) to the left of Z1 and to the right of
Z2. Starting values are Z = 0 for liquid phase and Z = 1
for vapour phase.
Algorithms for the solution of the cubic equations of
state are seldom published, and this is an indication that
analytical solution techniques are most common. One
numerical algorithm is suggested by Buthod et al. [8], but
this is hardly the most time-saving routine. They chose a
method of ten steps of interval halving followed by
application of Newtons method.
PRoFWErlALGoRrm.M
Estimation of compressibility factors should be done
by a subroutine whose input data are the parameters Q
 Numerical aspects of the implementation of cubic equations of state in flashcalculationroutines 249

A: Vapour phase
Z3: unacceptable root ZZ: chosen value
B: Liquid phase
s1
. chosen value
Z6: unacceptable root z,:

z
I I I I I
kI.0 .2 .4 .6 .8 4.0

Fig. 2. Possible shapes of the SRK equation.

and R together with a key (IPH) for actual phase. become zero if the following equation is satisfied:
(IPH = O+ liquid, IPH = 1+ vapour). The algorithm,
which has been tested and found to perform properly, is Z,-Z,tQ.Z2-R..,=O. (1%
presented in Fig. 3. The basic idea has been presented in
the previous section, and only a few details about the We already have:
algorithm is mentioned below:
(i) If Q 2 l/3, then F(1/3) is calculated in order to Z,-Z,2tQ~Z2-R,,,~=F2. (16)
determine whether the (only) solution is to the left or to
the right of the point of inflection. A proper starting This leads to a simple correction scheme:
point, Z,, is found to be:

F(1/3)>O+Z<1/3+Zo=0 B CW = Bou (17)

F(1/3)<O+Z> l/3+5= 1 In case B, there should be a change in B:

(ii) If Q < l/3, but R 2 l/27, there is also just one

solution possible. It can be easily veritied that this solu-
tion must be greater than l/3 looking at F(Z) (Eq. 10)
when Q = l/3. Then F(Z) has a maximum value of
1/27-R for Z = l/3. If R > l/27, then F(Z) c 0 for all
Z < l/3, and the solution must therefore be to the right of
the point of inffection. The starting point is therefore
chosen to be Z,, = 1.
(iii) In cases A and B of Fig. 2, where Z, and Z2 are
chosen instead of the straightforward solutions Zs and
5, one should change the parameter B (Eq. 8(b)) until
the function F(Z) is satisfied at the points Z, or Zz. This
is done to avoid negative arguments in logarithmic func-
tions in the expression for In 4, developed for the actual
equation of state from Eq. 4 (see Reid et al.[7j).
In case A, this can be illustrated as follows: F(Z)- can
be moved vertically by a change in the parameter R.
First, it is assumed that parameter B may be changed
without changing the shape of the function. F(Z)
B c\u
= Bold 1+. (18)
( old 1
A change of the parameter B will also change the
parameter Q, but since B is substantially less than the
parameter A, the effect on Q will be much less than it is
on R, and the shape of the function will remain roughly
the same. This is only a mathematical manipulation and
the mole fractions xi and yi (i = 1, NC) are not changed.
Nuh5ucALREsLnTs
Flash calculations were carried out for the mixture in
Table 2, based on the experimental data of Kurata and
Katz [5].
The experimental critical point is reported[5] to be at
172.6atm and 316.1 K.
About 300 flash calculations were performed to est-
ablish the phase diagram of Fig. 4. These computations
indicate that the critical point is in the region 176

CACE Vol. 6, No. 2-E

250 TRULS GUNDERSEN

F3 = F(1/3)

P-
Yes no
F,>O

3. order method z = z, z = 22

to find 2. B = B(l+Fl/R) B = B(l+Fz/R)

4

CL3 END

Fig. 3. Algorithmfor the solution of the cubic SRK equationof state.

Table 2. Compositionof test mixtureI The number of iterations increases as we approach the
critical point:
Component mole 9:
l- 50 atm: 2-4 iterations
Nitrogen 0.54 50-100 atm: 4-8 iterations
Methane 72.80 100-150 atm: 8-12 iterations
150-170 atm: 12-30 iterations,
Ethane 5.46

Propane 3.02 About 50 vapour-liquid equilibrium calculations were

run on the MINISIM program, developed at Oklahoma
n-Butane 3.07 State University, in order to compare the results. As can
n-Pentane 6.88 be seen from Table 3, MINISIM predicts pure vapour
instead of pure liquid in the region 32-160 atm. In these
Hexane 4.36
cases all K-values were close to 1.0. Attempts were also
Heptane 3.75 made to establish the boiling point curve (fixed pressure
and phase condition, calculate boiling point temperature),
but even at 16 atm pressure the K-values collapsed (K, +
180atm and 320-340 K. Deviations between experimental 1.0). However, being in the two-phase region, MINISIM
and predicted results could be a result of the treatment performed properly up to 172atm.
of the heavy ends and should be of no concern. The In the following, some of the results are plotted to
proposed algorithm works well up to about 174atm. demonstrate that the proposed algorithm gives physically
 Numerical aspectsof the implementation
of cubicequationsof statein flash calculation routines 251

TEMPERATURE (K)

Fig. 4. Phase diagram for test mixture I (8 components). The curves show vapour fractions of 0,20,40,60,80 and
100mole %.

Table 3. Comparison between MINISIM and proposed algorithm

r Estimated vapour to feed ratio

MINISIM Prop. algorithm

1
P (am) T (0

1 100 0.0 0.0

1 180 0.7725 0.7725
1 260 0.8860 0.8864
1 340 1.0 1.o
8 140 0.0 0.0
8 220 0.7566 0.7566
a 300 0.8690 0.8693
a 380 1.0 1.0

32 180 1.0 (8) 0.0

32 260 0.7249 0.7251
32 340 0.8615 0.8618
32 400 1.0 1.o
128 250 1.o () 0.0 -
128 320 0.6163 0.6178
128 400 1.0 1.0

160 280 1.0 (*) 0.0

160 320 0.4852 0.4806
160 360 0.7619 0.7739
160 370 0.8844 0.8934

172 300 0.0297 0.0

172 320 0.3431 0.3500
172 340 0.5529 0.5722
172 360 0.8539 1.o

(1 represent conditions where MINISIM failed to perfon properly.

252 TRULS
GUNDERSEN

8
2.

G
r:.

t2
I?.
- i 40 400 i 000

PRESSURE CATM I

Fig. 5. K-v&es for methane(A), n-butane (0) and heptane (t) in the mixtureof 8 componentsat 320K.

acceptable results. Figure 5 shows K-values for
methane, n-butane and heptane in mixture I at 320K.
The shapes of the curves agree well with theory, and the
K-values approach 1.0 when the pressure comes close to
its critical value.
In Fig. 6, compressibility factors of the two phases are
plotted against pressure at 320K. When the pressure
approaches its critical value, the two compressibility
factors meet at a value of about 0.68.
At high pressure, the K-values do not behave normally
outside the two-phase region. At pressures exceeding 60
per cent of the critical pressure, the iteration outside the
two-phase region fails. For example, at temperatures
above the dew-point, the mole fractions of the liquid
phase and the K-values tend to continue changing until
all K-values come close to 1.0 and the compositions of
the two phases become identical. It was found that the
only possible way of reaching the critical region of the

100 150 2

PRESSURE t ATrl I

Fig. 6. Compressibilityfactors for vapour(V) and liquid(A).

 Numericalaspects of the implementationof cubic equationsof state in flash calculationroutines
mixture was to do a sequential calculation, starting at low
pressure (1 atm) and then increasing the pressure step-
wise until the actual pressure was reached. The equili-
brium compositions of the previous calculation are used
as starting values of the new calculation. The tem-
perature for each calculation is chosen in a way that
keeps the mixture at each calculated point in the two-
phase region. This can be illustrated by the following: A
flash calculation at 170atm and 340K was successfully
carried out after having done two initial calculations
(1 atm, 200 K and 140atm, 340 K).
The critical region of the ethane (0.4)-propane (0.4)-
n-butane (0.2) mixture investigated by Coward and
Webb[4], was analysed. According to them, the Chao-
Seader correlation using the Redlich-Kwong equation of
state gave disturbing and physically unacceptable results
for pressures exceeding 40atm. Using the Orye[9] vari-
ant of the Benedict-Webb-Rubin equation, Coward and
Webb estimated the critical pressure and temperature to
be 50.5 atm and 365.4 K.
With the proposed algorithm, high-pressure flash cal-
culations were performed and the results are given in
Fig. 7. The SRK method estimated the critical tem-
perature to be in the region 366.8-367.1 K and the critical
pressure to be 50.7 f 0.1 atm.
DISCUsslON
The algorithm in Fig. 3 has shown the great influence
that the choice of roots in the solution of the cubic
equations of state has on flash calculations. The physical
interpretation of the number of roots of the equation
seems to vary in the literature. According to Peng and
Robinson[2], their equation of state yields one or three
roots depending on the number of phases in the system.
The authors experience with the SRK equation of state
is that it is only at low pressure levels that the function
F(Z) (Eq. 10) is shaped as in Fig. l(a) with three roots
for both phases.
TEMPEFtATURE
Fig. 7. Phase diagramfor test mixtureII (3 components).The curves show vapourfractionsof 0,20,40,60,80 and
100mole %.
253
Numerical investigation of the g-component system
showed that F(Z) for the liquid phase became monotonic
for pressures above lOatm, while the vapour phase
resulted in a monotonic F(Z) for pressures above
145atm. The number of phases in the system therefore
has nothing to do with the number of roots of the SRK
equation of state. This trend should also apply to the PR
equation of state. Maddox and Erbar[l4] present the
typical behaviour of cubic equations of state as having
three roots in the two-phase region and one root (mono-
tonic function) in the single phase regions, but this is not
correct.
Results have proved the advantage of using the
extreme points Z1 and Z, in Fig. 2 as roots whenever the
correct root gives physically unacceptable values of
the compressibility factors. This is what Coward et al. [3]
characterize as embarrassing without telling the reader
what actions to take. Boston and Mathias[13] have
reported a similar technique when roots are lost, and
in their work with the ASPEN program, they have
experienced the same advantage as in the work with the
proposed algorithm. They do not mention that this
mathematical manipulation in some cases can lead to
negative arguments of the logarithmic expressions in the
formula for the fugacity coefficients. A change of the
parameter B according to Eqs. (17) and (18) is sometimes
necessary to avoid failure in the calculation when the
extreme points rather than the mathematical roots are
used as compressibility factors.
The reason why flash calculations fail at high pressure
has been found to be the lack of good initial estimates of
the phase composition. Attempts have been made to find
methods for this estimation, but with poor results
because the connections between the phase compositions
and the Q and R parameters are too complex. The result
of poor starting values of the phase compositions may be
that the first estimate of the vapour phase compres-
sibility is less than the liquid phase compressibility. The
I 1
366 369
IKI
254 TRULSGUNDERSEN

iteration then fails with ZLIQ=ZVAP and Ki + 1.0 F total amount of moles in the mixture (flash cal-
(i = 1, NC). This problem was solved by the sequential culations)
technique mentioned in the previous section. With this F parameter in the SRK equation for mixtures (Eq. 8(e))
strategy the proposed algorithm performed properly Fi parameter in the SRK equation for component i (Eq.
within from 0.2 to 2.0 atm from the critical point. An 8(f))
F(Z) SRK equation written as a third degree equation in
alternative method would be the step-wise technique of compressibiity (Eq. 10)
extrapolating the K-values presented by Michelsen[ lo].
f objective function in flash calculations
The importance of a good estimate of the phase com- IPH key for actual phase (vapour or liquid)
positions increases as the equilibrium calulations are Ki equilibrium ratio for component i @q. 3)
carries out in the critical region. The initial estimate of kii binary interaction parameter of the SRK equation
the phase compositions are given as the equilibrium Ni number of moles of component i
compositions at a point in the neighbourhood of the NC number of components
actual point. This neighbouring region gets smaller as one P pressure
approaches the critical region of the phase diagram. Pci critical pressure for component i
parameter of the SRK equation
The system of three components was a lot easier to ! gas constant
handle than the system of eight components. This can be R parameter of the SRK equation
explained by the fact that mixtures of close-boiling T temperature
components give rise to more linear objective functions T,i critical temperature for component i
(Eq. 1) than mixtures of wide-boiling components. Ano- 4 reduced temperature for component i
ther point is the larger amount of numerical roundoffs V amount of vapour in the mixture (moles)
with eight components and the fact that the computer V volume (Eq. 4)
has a limited accuracy. V specific volume (Eqs. 5 and 6)
xi mole fraction of component i in the liquid phase
The proposed algorithm gives numerical results with
mole fraction of component i in the vapour phase
this classical three-component system that are far ; compressibility factor
better than what Boston and Mathias [13] report with the ZLIQ compressibility of the liquid phase
ASPEN program. As is seen from Fig. 7, the present ZVAP compressibility of the vapour phase
approach works well up to 50.5 atm, while the ASPEN zi mole fraction of component i in the mixture
program gives physically unacceptable results for pres-
sures exceeding 45 atm. Greek symbols
At the exact critical point, all flash calculation routines a constant of the SRK and PR equation
fail because all K-values tend to be 1.0. The function fi constant of the SRK and PR equation
y constant of the SRK and PR equation
(Eq. 1) approaches zero in the whole region 0 d 6 s 1. [ vapour to feed ratio (V/F)
The program is therefore not able to predict the vapour- I$ fugacity coefficient
to-feed ratio. How close to the critical point calculations a, constant of the SRK and PR equation
can be performed depends on the chosen algorithm, the fib constant of the SRK and PR equation
numerical accuracy of the computer and, as it is seen, Oi acentric factor for component i
the number of components in the system. Hydrocarbon
gas processing conditions are often close to the critical Subscripts
point, and the high pressure capabilities of flash cal- i loop index and component identifier
culation routines are therefore important. j loop index and component identifier
c critical property
Another interesting aspect is the use of these some- r reduced property
what sophisticated methods for estimating K-values in
flowsheet simulators. In commercial packages the com- Superscripts
pressibility factors and K-values are regarded as inter- L liquid phase
mediate results, and therefore not printed out. The V vapour phase
chemical engineer is therefore not able to verify the
results. If a sequential technique were applied, as des- RElmRENcm
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8(d))
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25s
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