Accelerated Successive Substitution Schemes for Bubble-Point and Dew-Point Calculations

DING- YU PENG Department of Chemical Engineering, University of Saskatchewan, Saskatoon, Saskatchewan, Canada S7N OW0
The accelerated successive substitution (SS) algorithms developed by Mehra et al. for flash calculations have been extended to the prediction of saturation points. A transformation matrix which is used to calculate the acceleration parameter has been rewritten in a form that is applicable at the saturation conditions. Simple equations for estimating the initial values and recursive formulae according to which the iterates can be updated are presented. The proposed schemes were compared with the conventional SS method and a multivariate Newtons method. The comparison suggests that the accelerated SS schemes are more tolerant of poor initial values and sometimes more efficient than Newtons method. Les algorithmes de substitution successive accC16rCe (SS) mis au point par Mehra et al. pour les calculs de flash ont ttC Ctendus a la praiction des points de saturation. Une rnatrice de transformation qui est utilisCe pour calculer le paramhe daccklkration a CtC rekcrite sous une forme qui peut sappliquer aux conditions de saturation. On prCsente des equations simples pour lestimation des valeurs initiales et des formules rCcursives selon lesquelles les itkrations peuvent &re mises a jour. Les schemas proposCs ont CtC cornparks B la mCthode SS traditionnelle et une mCthode de Newton multivariee. La comparaison suggkre que les schkmds SS accklCrCs tolkrent mieux les rnauvaises valeurs initiales et quils sont parfois plus efficaces que la mCthode de Newton. Keywords: phase equilibria, accelerated successive substitution, bubble point, dew point.

hase equilibrium calculations form an important part of the process design operations in the hydrocarbon and petroleum industry. In addition to the class of methods which use Gibbs free energy minimization formulations, which are generally applied to combined phase and chemical equilibria, there are largely two classes of methods for phase equilibrium calculations: the successive substitution (SS) method and Newtons method. The SS method is simple to use but converges very slowly near the critical points of the mixtures. However, the improved convergence of Newtons method is achieved at the expense of the increased function evaluations per iteration. The function evaluations are necessary for the computation of the Jacobian. During the past decade or so, a number of researchers (for example, Risnes et al., 1981; Michelsen, 1982; Nghiem et al., 1983; Mehra et al., 1983;Nghiem and Heidemann, 1982; Rijkers and Heidemann, 1986; Gupta et al., 1988) have proposed acceleration algorithms to promote the convergence of the successive substitution method for flash calculations. Generally, the acceleration schemes retain the simplicity of the SS method but require substantially less computing effort in comparison to the SS method. In particular, Mehra et al. (1983) have shown that there exists a rigorous relation between the conventional successive substitution method for flash calculation and the gradient method for Gibbs free energy minimization. In spite of the progress made in the convergence promotion of the SS method for flash calculations, it appears that the accelerated SS method has not been extended to the prediction of saturation pressures and temperatures. In the open literature, the main algorithms used in the calculation of the saturation points are still the conventional SS method and Newtons method. Nghiem et al. (1985) have recently proposed two new Newton formulations and an accelerated SS algorithm for calculating the bubble points and dew points. These authors have also presented an initialization scheme which leads to convergence to all saturation points for their test mixture. The equation used by Nghiem et al. (1985) in their accelerated SS algorithm to calculate the acceleration parameter is essentially the same as that of Algorithm 3 of Mehra et al.
978

(1983). However, the initial K-values used by Nghiem et al. (1985) were generated from a stability test calculation. Michelsen (1985) has also proposed the use of stability-based procedure for calculating the approximate values of saturation temperatures or pressures. These stability-based methods may show their greatest advantage in the critical region, but they are not always economical to use in regions removed from the critical point. A simpler initialization scheme is desirable. Moreover, in view of the success of the accelerated SS schemes in flash calculations, it is worthwhile to study the performances of the other two accelerated SS schemes of Mehra et al. (1983) in bubble-point and dewpoint calculations. This paper reports the findings of such a study and presents a set of empirical equations for calculating the initial values.

Basic equations
The condition for vapor-liquid equilibrium (VLE) is given by

f;(T,P,x,,...,xN-l)=fiv(r,P,YI , . . . ,Y N - I ) ,
(1 5 i 5 N ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
(1)

From the material balance relations, the mole fractions of the components in the equilibrating phases are given by
xi =

z i / [1

+ (K; - 1 ) a ]

. . . . . . . . . . . . . . . . . . . (2)
(3)

yj

= KiXj

..................................

where the vapor fraction a is obtained from the well-known Rachford and Rice (1952) equation

C(K; - 1)z; / [ l

+ (K; - l ) a ] = 0

. . . . . . . . . . (4)

Successive substitution method

In the conventional SS method, a set of K-values is assumed and Equation (4) is solved for a . The mole fractions obtained

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69, AUGUST, 1991

from Equations (2) and (3) are then used to calculate the component fugacities, which are dependent on the temperature, the pressure, and the composition. The K-values are revised and new values of the mole fractions are obtained. The iterative process continues until Equation (1) is satisfied. The initial K-values are usually calculated from some simple empirical equations. For example, Wilson (1968) proposed the following equation for estimating the initial I(-values for the hydrocarbon systems

where
6~

T(")/(5.373 C (1

+ w i ) T,
{1 - C

Dew point temperature prediction:

T ( " + ' )= T(")(1 where

fD

z, l K / " + I ) ] ))

. . (13)

K p
where

Ps, lP'O' . . . . . . . . . . . . . . . . . . . . . . . . . . . .

(5)
Similar to the situation in which two dew-point pressures correspond to a given temperature, retrograde behavior may also involve two dew-point temperatures at a given pressure. In this case the iteration scheme given by Equations (13) and (14) tends to yield the higher-temperature dew point. The lower-temperature dew point may be obtained if the eD calculated from Equation (14) is multiplied by - l . Similar treatment may be applied to f E if retrograde behavior extends to the bubble-point region. It should be noted that in the bubble-point and dew-point calculations one does not solve Equation (4) for the value of a . In such cases the composition of the finite phase is set equal to that of the feed. The mole fractions of the components in the incipient phase are calculated according to

pS, = P,, exp 15.373 (1

+
(1

0,)

(I - T,, /T"')] . (5a)

The algorithm of correcting the K-values is based on the ratios of the fugacities of the components and has the form

K,("+')= K,'").r,'"),
where

I i IN )

. . . . . . . . . (6)

r,

I = j. l

/ f iv . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

(7)

Prausnitz et al. (1967) were among the first researchers to have used this algorithm in their work. Mehra et al. (1983) have shown that Equation (6) can be derived from an application of the gradient method to the minimization of the Gibbs free energy at constant T and P.

y!")

ziKY'IC zi K,@) . . . . . . . . . . . . . . . . . . . . . zi / K?)

I C

(15)

Bubble point and dew point calculations

In bubble-point and dew-point calculations, in addition to the composition of the incipient phase, either the temperature or the pressure is also unknown. An algorithm is needed to guide the trial-and-error process of estimating this unknown. Although interpolation/extrapolation techniques may be used, it is best to have some ideas of the dependency of the K-values on the iterates so that simple yet robust recurrence formulae may be developed. The assumption that the K-values are inversely proportional to the pressure at constant temperature, such as indicated by Equation (5), leads to the following equations which are generally satisfactory for the hydrocarbon systems: Bubble point pressure prediction:

for bubble-point predictions and

x!"' =

[zil K f " ] . . . . . . . . . . . . . . . (16)

for dew-point predictions, respectively.

Initial pressure and initial temperature

In bubble-point and dew-point predictions it is necessary to provide an initial value for either the pressure or the temperature which is to be predicted. Due to the numerous differences among the real systems, it is very unlikely that a non-iterative procedure can be developed to generate the initial values that will lead to convergence for all kinds of mixtures. However, Equation (5) may be used to yield the following empirical equations which, in general, are satisfactory for hydrocarbon systems over a wide range of conditions: Bubble point prediction:

P ( " + ' J= P ( r f )[2

- 1/C

z i K!"+l'] . . . . . . . . . . . .

(8)

Dew point pressure prediction:

P("+') = P'"'/C

[Zj/K!"+l)] . . . . . . . . . . . . . . . . . .

(9)

P(O) -

c xi pi

0 .........................

(17)

Because the controlling K-values in dew point calculations are those of the less-volatile components and because these K-values increase with an increase in the pressure in the retrograde region, an equation for the calculation of the retrograde dew-point pressure takes the form

Dew point prediction:

PcO' C y; / p i - IIp:' = 0 . . . . . . . . . . . . . . . . . . (18)

where

P("+l' = P c n J ( 2 - 1 / C [zi/ K ( " + ' ) ] . . . . . . . . (10)

Empirical equations can also be obtained for the temperature predictions. Assuming Equation ( 5 ) provides the correct temperature dependency of the K-values, we obtain the following recurrence relations: Bubble point temperature prediction:

p i = Psi when T(O) I T,.; . . . . . . . . . . . . . . . . (1 9a)

= (Psi Pc;)0,5 when

T'O'

> T,,

. . . . . . . . . (1 9b)

Accelerated successive substitution

Accelerated SS algorithms are generally characterized by the use of the suitably calculated step length X such that the K-values are updated according to the equation
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THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69, AUGUST, 1991

K ! ~ + '= ) K!") . [r?)]',

(1 ~i

IN)

. . . . . . . (20)

TABLE1 Compositions of the Test Mixtures

Mole Fraction

For example, Risnes et al. (1981) have assumed that the rvalues given by Equation (7) approach monotone after a finite number of iterations and proposed that the step length h be estimated from the ratio of the logarithms of the ri between two successive iterations. These authors also stated that a constant value of 2 may be used for X after ten iterations. In their study of the relationship between the S S algorithm described by Equation (6) and the gradient method for Gibbs free energy minimization at constant T and P, Mehra et al. ( 1983) have presented three different algorithms for calculating the optimal or near-optimal step lengths. Specifically, their Algorithm 1 has the form

Component Nitrogen Methane Ethane Propane n-Butane n-Pentane n-Hexdne n-Heptane n-Octane n-Nonane n-Decane

Mixture 1

Mixture 2
0.0140 0.9430 0.0270 0.0074 0.0049 0.0010 0.0027

Mixture 3 0.6436 0.0752 0.0474 0.0412 0.0297 0.0138 0.0303 0.0371 0.0415 0.0402

0.39842 0.29313 0.20006 0.07143 0.03696

(g(n-l)

g ( 9 1 1 X ( n - 1 ) ....................

(21)

for bubble-point calculations and

w;,
= X ; ~j

where the elements of the matrix U-' are given by

u.71 1 , -

. . . . . . . . . . . . . . . . . . . (22) (an,!'/aln K,)T,P,K

+ 6 i j ~ i[ C ( X ; / Z ~)

11 . . . . . . . . . . (29)

The acceleration is initiated after the initial guess and one ss step; i.e., A"' = 1. Mehra et al. (1983) and Rijkers and Heidemann (1986) have shown that
Ui,Tl

= [LV/(L

+ v)] (XiYIlZi)

[tiij+ X j Y j / ( Z j S ) ]
(23)

.......................................
where S is given by
S = 1 - C
( ~ k ~ k / ~ k )

for dew-point calculations, respectively. The three formulae developed by Mehra et al. (1983), with the formula for Algorithm 1 modified as outlined above, were applied to the calculation of bubble points and dew points. The schemes are referred to as Accl, Acc2, and Acc3, respectively. The accelerated S S scheme proposed by Rijkers and Heidemann (1986) is similar to the Algorithm 1 of Mehra et al. (1983) but requires more computational effort. It was not tested in this study.

Numerical examples

......................

(24)

Because the leading product term LV vanishes at the bubble-point and the dew-point conditions, it appears that Equation (23) has limited the application of Algorithm 1 to only those cases where the amounts of liquid and vapor are both nontrivial. One also may erroneously conclude that u;,: * vanishes when either V or L vanishes. However, it can be shown that
LV/(L

+ v)* = S/C

[(Yk -

Xk)Z/Zk]

........

and that Equation (23) may therefore be rewritten as

u,,-'

= L y, y,/

[C ( Y Z l Z k ) - 11 . . . . . . . . . . . . (26)
[ E ( X ~ / Z , ) - 11

at the bubble-point conditions and as

u,J'
= V X , x,/

. . . . . . . . . . . . . (27)

at the dew-point conditions, respectively. Consequently, the Algorithm 1 of Mehra et al. (1983) is also valid when the specified temperature and pressure for a flash calculation happen to be exactly the same as the conditions of either a bubble point or a dew point. Unfortunately, the performance of the accelerated bubblepoint and dew-point calculations using Equation (2 1) with the u,;' given by Equations (26) and (27) was found to be inferior to that of the same calculations using the other two algorithms of Mehra et al. (1983). However, an empirically obtained matrix W may be substituted for the matrix U-' to improve the convergence behavior. The elements of the matrix W are given by
w,, = y, y,
980

The features of the acceleration schemes and those of the empirical equations developed in this study can be illustrated using three hydrocarbon mixtures. The compositions of the test mixtures are given in Table 1. The first system is a five-component mixture of n-alkanes. The experimental data for this system were first reported by Etter and Kay (1961). The second mixture is a typical natural gas system (Gonzalez and Lee, 1968). The third is a volatile oil (Nghiem et al., 1983). The Peng-Robinson equation of state (Peng and Robinson, 1976a) was used to model all three mixtures. The calculated phase envelopes are plotted in Figure 1 to show the characteristically different two-phase regions of the three mixtures. A multivariate Newton's method (Peng and Robinson, 1976b, 1977) was also used in this study to make the calculations. The Jacobian matrices were calculated from analytical expressions for the derivatives of the fugacity, and Crout's LU decomposition algorithm was used to calculate the correction vector, To guard against excessive number of occurrences of early divergence, which may be due to poor initial values, one S S step was always applied before Newton's method was used. This iteration is included in the counting of the number of iterations for Newton's method. The convergence criterion used in all schemes was
gTg

< 10-l0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

(30)

which is the same as that used by Mehra et al. (1983).

Mixture 1
As shown in Figure 1, the critical point of this mixture is almost at the extreme temperature and pressure of the

+ A,,

y1 [ E ( Y ; / Z ~ ) - 11

. . . . . . . . . . (28)

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25

CRITICAL POINT
0-

MIXTURE 1 P = 3 MPa T(O)= 326 K

-2n
I -

----

CT,

-+
-6-

____-_-_______ Acc 1 - - - - - Acc3

Newton
\ \

ss

m
0

t i 0

r n Y
U

MlXTURE 2

6
0 -

"r\

MIXTURE 1

-8-

\ \
\ \

5j ;j,n
0100
180

340

450

T E M ~ ~ R A T U R EK ,

4
5cio

-10-

\
\

-12

NUMBER OF ITERATIONS
Figure 2 - Iteration performance for Mixture 1 at 3 MPa.

Figure I - Phase envelopes for the test mixtures. TABLE 2 Performances of the Various Schemes for Mixture 1 at Selected Temperatures T
pl01

MIXTURE 1 P = 3 MPa 326 K

p(n)
SS

Number of Iterations Accl Acc2 Acc3 5 5 6 6 7 9 8 10 8 9 14 Newton 3 4 4 4 4 3 4 4 4 5 5 12 4 4 4 4 4 4 4 4 4 4 3 4 5

(K)
270 280 290 300 310 320 330 340 350 360 370 380 270 280 290 300 310 320 330 340 350 360 370 380 390
~~

(M Pa) 1.044 1.339 1.690 2.101 2.487 2.804 3.149 3.523 3.930 4.369 4.843 5.239 0.189 0.189 0.272 0.381 0.691 0.889 1.125 1.402 1.722 2.089 2.503 2.915 3.362

. LLI
C K
L t

331

Bubble-point prediction 0.925 6 4 5 1.166 7 4 5 6 6 1.446 8 1.765 9 5 6 6 7 2.124 1 0 2.524 11 6 7 2.961 12 7 8 3.433 12 7 8 3.931 15 7 8 4.443 22 8 9 4.945 37 9 13 5.384 100 25 19 Dew-point 0.076 4 5 0.121 5 0.185 6 0.276 0.398 7 0.560 7 0.773 8 1.047 10 11 1.398 1.848 13 2.428 15 3.199 24 4.365 70 prediction 3 4 4 4 4 4 5 5 5 5 5 5 5 6 6 5 6 6 7 7 7 7 8 9 16 13

2
W

329

a
I
327

325

I Y
'

NUMBER OF ITERATIONS
Figure 3 - Effect of iteration number on an iterated variable for Mixture 1 at 3 MPa.

i l

12

15

.I

4 4 4 5 5 5 6 6 6 7 7 9 15

*The calculation diverged.

phase envelope. The initial pressures or temperatures calculated from Equations (17) and (18) were very close to the converged values. The initial and converged values and the number of iterations required for the prediction of the bubble-point and dew-point pressures at selected

temperatures are given in Table 2. As expected, the SS method is quite efficient in the region which is far from the critical point but its performance gradually deteriorates as the specified temperature gets closer and closer to the critical region where the K-values approach unity. It is also evident that all three accelerated SS schemes are faster than the S S method; the improvement is especially noticeable from the results for the critical region. The convergence behavior of a bubble-point temperature prediction is illustrated in Figure 2 which is a plot of error versus iteration number for a pressure of 3 MPa. It is seen that four iterations were required when Newton's method was used but seven iterations were required when either the Accl or the Acc3 was used. However, as shown in Figure 3, the temperature values calculated from the accelerated SS schemes after four iterations were essentially the same as the converged value. It can also be seen that eight SS iterations were required in order to attain the same level of precision. For this mixture, the performance of Acc2 was
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THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69, AUGUST, 1991

TABLE 3

Performances of the Various Schemes for Mixture 2 at Selected Temperatures

T
(K) 140 150 160 170 180 190 200 210 220 230 240 250 260 265 210 220 230 240 250 260 265 210

pro,

pm
SS 6 7 9 10 I1 28 252 4 5 6
7

(MPa)
0.672 1.074 1.626 2.354 3.278 4.414 5.106 0.491 0.759 1.124 1.603 2.209 2.945 3.362 0.491 0.759 1.124 1.603 2.209 2.945 3.362 5.774 0.708 1.112 1.660 2.374 3.273 4.355 5.583 0.023 0.058 0.133 0.287 0.601 1.292 2.038

Number of lterations Accl Acc2 Acc3 Newton

5 3 6 6 6 7 37 3 4 4 5 6 8 10 4 5 6 7 5 14 4 6 6 7 5 14 20 4 4 5 5 6 9 8 37 29 18 15 12 3 4 4 4 4 5 10 5 6 6 7 8 9 9

Accl

ss

I I
I
I

Newton

Bubble-point prediction

t
LL

Ll
/

CIL
W

m I
3 Z

Dew-point prediction
4 4 5 5 6 8 10

10 15 24

PRESSURE, MPa

Retrograde dew-point prediction 6.984 88 36 28 8.052 43 24 23 8.664 29 13 18 8.733 22 16 12 8.259 18 14 12

Figure 4 - Performances of the various schemes in dew-point temperature predictions for Mixture 2. When divergence in the prediction of retrograde dew points is due to poor initial values, the problem may be somewhat alleviated by using the values calculated from Equation (17) as the initial values. As shown in the last row of Table 3 for the prediction of the retrograde dew-point at 210 K, the calculation based on Newtons method converged in eight iterations using initial values based on Pcot = 5.774 MPa. The performances of the other schemes were also improved by using this initial value for the pressure. The capabilities of the SS scheme, the Accl scheme, and Newtons method in dew-point temperature calculations for this mixture are shown in Figure 4. The dew points are those whose temperatures are greater than the temperature corresponding to the cricondenbar. The initial temperatures were calculated from Equation (18). It is obvious that, as far as the number of iterations is concerned, Newtons method was the fastest among the three schemes. However, more iterations were required with the Accl scheme (as well as the other two accelerated SS schemes) than with the conventional SS method over an extended range of pressures at low pressure conditions. All schemes failed to yield the correct results when the initial values based on Equation (18) were used in the prediction of the lower-value dew-point temperatures of the retrograde region where there are two dew-point temperatures for each pressure value. The initial values were simply too poor to result in adequate corrections during the early stage of the iterations. Convergence was generally obtained when the cricondenbar temperature was used as the initial temperature for all dew-point temperature calculations.

* * * *
7 6 6 8

7.023 5.866 6.984

19 28 84

14 14 25

12 13 19

14 12
29

*The calculation diverged. similar to that of Acc3 and was therefore omitted from the figures.

Mixture 2
This mixture exhibits retrograde behavior over a very broad range of pressure and temperature conditions of its VLE region. As methane is the predominant component of this mixture, the bubble-point locus tends to assimilate with the vapor pressure locus of pure methane. Therefore the initial values calculated from Equation (17), which in general provides good estimates for vapor pressures, were very close to the converged bubble-point values over a wide range of temperatures. Unfortunately, because of the pronounced retrograde region of this mixture, Equation (18) can not be expected to yield good initial values over the entire dew-point region of this mixture. In particular, Equation (18) is meant for only the low-pressure dew points. Nevertheless, this equation was used in both normal dew-point and retrograde dew-point calculations. Table 3 shows the initial values, the predicted results, and the number of iterations required for selected bubble-point and dew-point calculations. It is interesting to note that for a number of temperature conditions the Accl scheme was faster than Newtons method in the prediction of the normal dew-point pressures. Moreover, for a wide range of temperatures Newtons method diverged when the initial values calculated from Equation (18) were used to predict the retrograde dew-point pressures. It appears that the accelerated SS schemes, which are based on the gradient method, were not so seriously affected by the same poor initial values.
982

Mixture 3
This mixture was first used by Nghiem et al. (1983) to illustrate the application of Powells method in flash calculations. The critical pressure and critical temperature calculated in this study are 19.17 MPa and 425.14 K, respectively. These values are based on the assumption that the binary interaction parameters are all zero and are therefore different from those reported by Nghiem et al. (1983).

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69, AUGUST. 1991

TABLE 4 Performances of the Various Schemes for Mixture 3 at Selected Temperatures T (K) 370 380 390 400 410 420 430 440 450 460 410 480 480 410 460 450 440 430
p0,

0 1 0 J:

p(n)
SS

Number of Iterations Accl

Acc2 Acc3

0
Newton

I
5-

(MPa) 0.780 0.967 1.184 1 436 1.722 2.047 2.408 2.807 3.247 3.127 4.247 4.800 4.800 4.247 3 727 3 241 2.801 2.408

- - - ss

1
/
/
/
/
/
/

Dew-point prediction 0.127 5 4 4 0.185 6 4 5 0.264 6 5 5 0.371 7 5 6 0.512 8 6 6 9 6 6 0.699 10 6 1 0.946 1.272 12 6 1 1.708 14 7 7 8 2.304 18 7

4 5 5 6 6 6 6 7 7 8

3.164 24 9 9 1 4.576 35 9 9 9 Retrograde dew-point prediction 11.928 150 19 23 * * 20 22 14.134 171 15.721 260 43 21 22 16.975 475 50 32 31 17.994 1000 55 32 * 18.826 1043

5 5 5 6 6 6 6 6 6 6 5 4
4+ 8+

2 w

Accl Newton

2-

10

i t
290

2to

320

3dO

TEMPERATURE, K
* * * *

do

Figure 5 - Performances of the various schemes in bubble-point pressure predictions for Mixture 3.

13

85

+The calculation converged to a normal dew-point. *The calculation diverged. TABLE 5 Performances of the Various Schemes for Mixture 3 at Selected Pressures

p
(MPa) 3 6 9 12 15 18

~((1

T(n)

Number of Iterations
SS

(K) 400 400 400 400 400 400

Act1

Acc2 Acc3 Newton

11 13 14 18 57 81

Dew-point prediction 468.4 14 11 10 485.3 24 21 13 486.9 42 18 13 16 23 479.7 87 464.9 253 30 36 86 439.9 >2000 55

5 5 8

*
*

*The calculation diverged.

The calculated phase envelope indicates that this mixture exhibits both isothermal retrograde behavior at temperatures above the critical temperature and isobaric retrograde behavior at temperatures below the critical point. This kind of complex phase behavior tends to adversely affect the quality of the description of the pressure and temperature dependency of the K-values as given by the empirical formulae. It also makes the calculation of a single saturation point in the high pressure region particularly challenging, although the construction of the complete VLE phase envelope can be easily accomplished by using a marching algorithm such as that proposed by Michelsen (1980). Because of the very high critical pressure and critical temperature, the initial values calculated from Equations (1 7) and ( 18) were substantially different from the converged values. These initial values were, however, still used for dewpoint and bubble-point pressure predictions. But an arbitrarily selected temperature (400 K) instead of the values calculated from Equation (18) was used as the initial temperature for the prediction of all dew-point temperatures. The performances of the various schemes in the prediction of dew

points are presented in Tables 4 and 5 . The results show that the accelerated SS schemes are generally superior to the conventional SS scheme. We note again that Newtons method not only sometimes required more iterations but also was less reliable than the accelerated SS schemes. The convergence behavior of different schemes in the prediction of bubble-point pressures is shown in Figure 5 . The performances of the Acc2 and Acc3 schemes were considerably worse than that of the Accl scheme and, for clarity, are not shown. The SS method converged for all temperatures up to the critical point, although the number of iterations became very large as the specified temperature approached the critical temperature. Newtons method, on the other hand, diverged when the specified temperature was greater than 413 K; when convergence was obtained, it required between a low of nine iterations and a high of thirteen iterations for the range of temperatures tested. The performance of the Accl scheme is seen to be very good for temperatures below 280 K. However, the performance became unpredictable when the specified temperature was greater than about 350 K; the number of iterations varied irregularly with temperature and, in a number of cases, the scheme failed.

Discussion and conclusions

The overall performances of the five schemes are shown in Table 6, which is a summary of the total CPU time expended on those iterative calculations for which all algorithms were successful. The computation loads in terms of CPU time per iteration for the saturation-pressure predictions are shown in Figure 6 for the SS method, the Accl scheme, and Newtons method. It can be seen that the computation load of Newtons method increases very rapidly as the number of components increases. The CPU time per Newton iteration can be reduced by applying Broydens algorithm (Broyden, 1965). However, the number of iterations required will be more than that for the rigorous Newtons method. The above results (which were based on the use of Microsoft Fortran and an AT & T PC6300, with 8087-2
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THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69, AUGUST, 1991

0.6

2 0.5 0
F
Q
W

0.4

t
0.3
W

o_

w 0.2 I -I

NUMBER OF COMPONENTS
Figure 6 - Computation loads of three selected schemes.
TABLE 6 Performances of the Various Schemes at Conditions Where All Schemes Converged

Scheme

CPU Time / Number of Iterations, seconds Mixture 3 Overall Mixture 1 Mixture 2

9.82 6.01 5.88 6.10 5.88
/ / / /

ss
Accl Acc2 Acc3 Newton

334 150 162 168 I 96

11.23 8.34 6.21 6.72 11.31

/ / / / I

291 140 139 150 101

16.57 I 13.46 / 8.72 / 8.80 / 18.30 /

234 125 114 114 84

37.62 27.81 20.80 21.63 35.49

I
/ / / /

859 415 415 432 281

The SS iterations used in initialization are included in all the tables. The numbers shown here include 24 for Mixture 1, 17 for Mixture 2. and 15 for Mixture 3.

coprocessor) show that the proposed acceleration schemes all gave noticeable improvement in the convergence speeds of bubble-point/dew-point calculations. The improvement is similar to that found by Mehra et al. (1983) for their accelerated SS algorithms in flash calculations. The extra mathematical operations required to carry out the acceleration schemes for the prediction of saturation points are also comparable to that for the flash calculations. Although the phase behavior of the example mixtures does not represent that of all the possible hydrocarbon systems, the problematic features that are generally encountered in phase equilibrium calculations have been manifested by these mixtures. In particular, the results show that the SS method is the most reliable and that the accelerated SS schemes are generally more reliable than Newtons method in getting a correct solution. The results also show that, while the SS method usually takes the greatest number of iterations, Newtons method may take more iterations than the accelerated SS schemes and that the accelerated schemes may become inferior to the conventional SS scheme under certain unpredictable conditions. Because of the complexity of the phase behavior of naturally occurring systems, it is difficult to devise a general strategy for switching from the SS scheme to an accelerated
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SS scheme and/or from an accelerated SS scheme to Newtons method. Nghiem et al. (1983) have proposed a set of criteria which must be satisfied before switching from the SS method to Powells method (Powell, 1970) in flash calculations. To adapt their criteria to the prediction of bubble points and dew points requires that the conditions placed on the vapor mole fraction be replaced with comparable conditions on the pressure or temperature, whichever is the iterate. On the other hand, a set of general criteria must be based on the results of the calculations for a large number of different systems. For these reasons, no attempt has been made in this study to determine the optimal conditions under which a calculation should be switched from the SS method to an accelerated SS scheme or Newtons. method. The authors experience suggests that in most cases it is advantageous to switch to Newtons method if five SS iterations followed by five accelerated SS iterations have not resulted in convergence. When attempting a saturation-point calculation, one may have a priori information to decide the type of saturation point that is to be calculated. Alternatively, one may base on empirical rules to select the proper calculation. For hydrocarbon systems, the empirical correlations for calculating the true critical points may be used to help to decide whether the calculation should be for a bubble point or for a dew point. For example, the critical temperatures of Mixture 1 and Mixture 2 calculated from the correlation presented by Peng (1986) are 388.7 K and 204.9 K, respectively. These values compare very well with the rigorous values of 388.9 K and 202.4 K. However, empirical correlations may fail and, for calculations in the near-critical region, one may have to resort to stability-based initialization procedures. This paper presents a set of initial-value formulae which may be used in bubble-point and dew-point predictions for mixtures of hydrocarbons and related fluids. Empirical formulae according to which the iterates may be efficiently corrected are also given. Furthermore, it is shown that the acceleration algorithms developed by Heidemann and coworkers for use in flash calculations are all applicable to saturation point calculations. In particular, the transformation matrix of their Algorithm 1 can be rewritten in a form that has nontrivial value at a saturation point. In conclusion, the accelerated SS schemes represent a set of useful alternatives to the multivariate Newtons method when an efficient algorithm is needed in bubble-point and/or dew-point calculations.

Acknowledgement
The author gratefully acknowledges the financial assistance received from the Natural Sciences and Engineering Research Council of Canada.

Nomenclature
f
K L n N p
g
= fugacity
= =

gradient of Gibbs free energy equilibrium ratio = liquid moles = mole number = number of components = a quantity defined in Equations (19a) and (19b) P = pressure r = fugacity ratio S = a quantity defined in Equation (24) T = temperature u - = element of a transformation matrix

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 69, AUGUST, 1991

V w
x

vapor moles mole fraction

= element of an empirically defined matrix = liquid mole fraction

== vapor

y
I

= feed mole fraction

Greek Letters
01

6
t

= vapor-to-feed ratio = Kronecker delta

= =

scaling factor acentric factor

h
w

= acceleration parameter

Subscripts
B = bubble point c = critical state D = dew point i , j , k = component indices S = saturated state

Superscripts
L V (n)
= == =

liquid vapor iteration number

References
Broyden, C. G.. A Class of Methods for Solving Nonlinear Simultaneous Equations, Math. Comp. 19, 577-593 (1965). Etter, D.0. and W. B. Kay, Critical Properties of Mixtures of Normal Paraffin Hydrocarbons, J. Chem. Eng. Data 6,409-414 (196 I). Gonzalez. M. H. and A. L. Lee, Dew and Bubble Points of Simulated Natural Gases, J . Chem. Eng. Data 13, 172-176 (1968). Gupta, A . K., P. R. Bishnoi and N. Kalogerakis, An Accelerated Successive Substitution Method for Single Stage Flash Calculations, Can. J. Chem. Eng. 66, 291-296 (1988). Mehra. R. K.. R. A. Heidemann and K . Aziz, An Accelerated Successive Substitution Algorithm, Can. J. Chem. Eng. 61, 590-596 (1483). Michelsen, M. L., Calculation of Phase Envelopes and Critical Points for Multicomponent Mixtures, Fluid Phase Equilibria 4, I--10 (1980).

Michelsen, M. L., The Isothermal Flash Problem, Parts I and II, Fluid Phase Equilibria 9, 1-40 (1982). Michelsen, M. L., Saturation Point Calculations, Fluid Phase Equilibria 23, 181-192 (1985). Nghiem, L. X., K. Aziz and Y.-K. Li, A Robust Iterative Method for Flash Calculations Using the Soave-Redlich-Kwong or the Peng-Robinson Equation of State, SOC. Pet. Eng. J . 23, 521-530 (1983). Nghiem, L. X. and R. A. Heidemann, General Acceleration Procedure for Multiphase Flash Calculation with Application to Oil-Gas-Water Systems, paper presented at the 22nd European Symposium on Enhanced Oil Recovery, Paris, France, November 8-10, 1982. Nghiem, L. X., Y.-K. Li and R. A. Heidemann, Application of the Tangent Plane Criterion to Saturation Pressure and Temperature Computations, Fluid Phase Equilibria 21, 39-60 (1985). Peng, D.-Y., An Empirical Method for Calculating Vapor-Liquid Critical Points of Multicomponent Mixtures, Can. J . Chem. Eng. 64, 827-830 (1986). Peng, D.-Y. and D. B. Robinson, A New Two-Constant Equation of State, Ind. Eng. Chem. Fund. 15, 59-64 (1976a). Peng, D.-Y. and D. B. Robinson, Users Guide to GPA PengRobinson Program, Gas Processors Association, Tulsa, Oklahoma, U.S.A. (1976b). Peng, D.-Y. and D. B. Robinson, A Rigorous Method for VaporLiquid Equilibrium Calculations, paper presented at the AIChE 1977 Annual Meeting, New York, N.Y., November 13-17, 1977. Powell, M. J . D., A Hybrid Method for Nonlinear Equations, in Numerical Methods for Nonlinear Algebraic Equations, P. Rabinowitz, Editor, Gordon and Breach, London (1970). Prausnitz, J. M., C. A. Eckert, R. V. Orye and J . P. OConnell, Computer Calculations for Multicomponent Vapor-Liquid Equilibria, Prentice-Hall, Englewood Cliffs, N.J. (1967). Rijkers, M. P. W. and R. A. Heidemann, Convergence Behavior of Single-Stage Flash Calculations, ACS Symposium Series 300, 476-493 (1986). Risnes, R., V. Dalen and J . I . Jensen, Phase Equilibrium Calculations in the Near-Critical Region, paper presented at the 1st European Symposium on Enhanced Oil Recovery, Bournemouth, Great Britain, September 21-23, 1981, Dev. Pet. Sci. 13, 329-350 (1981).
~~

Manuscript received October 23, 1989; revised manuscript received April 10, 1990; accepted for publication May 9, 1990.

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