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Fluid Phase Equilibria, 72 (1992) 15-24 15

Elsevier Science Publishers B.V., Amsterdam



D.-H. Xu, A. Danesh and A. C. Todd

Department ofPetroleum Engineering, Heriot-Watt University

Riccarton, Edinburgh EH14 4AS, (U. K.)

(Received July IO, 1991; accepted in final form October 28, 1991)


An accelerated successive substitution (ASS) method for bubble and dew point
pressure calculations has been developed. The method iterates on a single variable,
pressure, which represents a considerable simplification over multivariable
schemes. The proposed ASS method has been compared with other commonly used
methods to predict the saturation pressures of a number of fluids. The results
indicate that the ASS method is more rapid and robust than the other evaluated


Vapor-liquid equilibrium (VLE) calculations at high pressures are commonly

performed by using a single equation of state (EOS) to model both phases. The
calculations of bubble or dew point pressures of multicomponent mixtures involve
a set of nonlinear equations that must be solved iteratively. The conventional
successive substitution (CSS) method which iterates on a single variable is
commonly used at low or moderate pressures, but it exhibits divergence or poor
convergent rate at high pressures (Prausnitz, et al, 1980). Another relatively
simple method, Newton-Raphson, is more rapid than the CSS method, but its
convergence strongly depends on the initial values (Anderson and Prausnitz,l980).
Newton type methods (Fussell et al, 1978 and Guehria et al, 1990) have been
extensively used to solve the nonlinear equations for equalizing the fugacities of
both vapor and liquid phases, they can be time consuming for multicomponent
mixtures as a complicated Jacobian matrix and its inverse have to be computed or
updated at almost every iteration. Furthermore, the radius of the Newton type
methods is relatively small when compared to that of the CSS method, hence a good
initial guess is required before the convergence can be achieved.

In recent years a number of authors have improved the calculations of saturation

points in the retrograde region, particularly around circondentherms or
circondenhars (Nghiem and Li 1985; Michelsen, 1985), and also have focussed on

037%3812/92/$05.00 0 1992 Elsevier Science Publishers B.V. All rights reserved


improving the successive substitution method for flash calculations (Risnes et al,
1981; Mehra et alJ983; Michelsen, 1985; Rijkers and Heidemann, 1986). In this
paper, we propose an accelerated successive substitution (ASS) method for
improving the convergence of saturation nressure calculation. The method has
been compared with CSS and Newton type methods for a number of
multicomponent mixtures and its rapid and robust convergence has been


The equilibrium state of a closed system is that state for which the total Gibbs free
energy is minimum with respect to all possible changes at the given temperature
(T) and pressure (P). This criterion provides a general method for determination
of equilibrium states. For a vapor-liquid system, this criterion leads to the
requirement that the fugacity of each component must be the same in both phases,

f; = f; (i = 1,2,--.,N)
where fi is the fugacity of component i which can be calculated by EOS, the
superscripts V and L express vapor and liquid phases respectively, N is the total
number of components.

For a mixture comprising N components in the equilibrated vapor and liquid

phases, the number of degree of freedom is equal to N according to the phase rule.
Although saturation point problems with other combinations of variables can be
envisaged, those of interest in petroleum engineering usually fall into two classes:

I. Bubble point Pressure: Find P,y,,yz ,..., yN at given T,xi,x2 ,..., xN

II. Dew point Pressure: Find P,xt,x2 ,..., xN at given T,y,,y, ,..., yN

where yi and xi are the mole fractions of component i in the vapor and liquid
phases respectively.

For the bubble point, the equilibrium criterion in equation (1) must be satisfied, as
well as the following equation,

Kixi = 1
where xi is equal to the mole fraction of component i in the mixture when the first
bubble of vapor phase appears.

For the dew point, similarly we get,

i=l i=l (3)

where yi is the mole fraction of component i in the mixture when the first drop of
liquid phase appears.

The above nonlinear equations can be solved iteratively by obtaining the fugacity of
each component using an initial pressure and initial guesses of the equilibrium
ratios, Ki , defined as:

xi (4)

The value of Ki is corrected by


where $1 is the fugacity coefficient of component i and an EOS is used to calculate

the fugacities and fugacity coefficients.


According to equations (2) and (3), we may set up the following forms for

S = C Kixi (for buble point), S=l/xyi /Ki (fordewpoint)
i=l i=l

At low or moderate pressures, the following successive substitution method can be

used in calculating the bubble or dew point pressure (Prausnitz et al, 1980),

p(r+i) = p(r)S(r) (7)

where P is the pressure, and the superscript r expresses the iteration time.

The above method, however, is usually very slow at high pressures. Now we
propose an accelerated successive substitution (ASS) method to speed up the
convergence rate.

For the (r+m) iteration , we may rewrite equation (7) as:

p(r+m) = p(r)S(r)S(r+l) . . . s(r+m)


Taking the logarithm of the two sides in equation (8), we get,

h p(r+m) = h p(r) + h s(r) + h s(r+l) +. . . + h $+m)


which still is a conventional successive substitution method.

Now in order to accelerate the iterative process we may replace the remaining part
of the series in equation (9) by a geometric series,


where q is the ratio between the two consecutive terms, and

If the iterative process is to be convergent, q must be less than unity as S should
approaches unity when m + 00.

Hence, we may get an accelerating step as follows:

p = p(r)S(rF (12)
The convergence of this iterative process therefore entirely depends on the form of
the sequence function.

In practice, it was found that the required solution is achieved when a tolerance
equal to 1.0x10-6 for the average absolute difference of vapor and liquid fugacities,
as an objective function, is used.


In a recent comparative study of EOS to predict the phase behavior of petroleum

reservoir fluids (Danesh et al 1991), the modified Patel-Teja EOS by Valderrama
(1990) (VPT) was found to be superior to others. It was, therefore, selected for
this study, although the method can be used with any EOS. The binary interaction
parameters of the VPT EOS were assigned to be zero except for the systems
containing CO2. Initial equilibrium ratios were calculated by the Wilson
correlation (1968).


Compositions of Multicomponent Pluids

Component. 1 2 3 4 5 6 7 8 9 10
$2 2.20 1.40 24.41 0.12 0.57
0.91 4.00 3.82
31.60 94.30 76.90 68.70 46.78 74.18 75.44 77.82 75.95 76.32
Ethvlene 0.02
C2- 38.80 2.70 7.90 3.33 8.77 5.32 2.79 2.28 2.00 1.91
Propylene 0.02
C3 22.30 0.74 5.20 1.44 7.44 4.67 2.52 2.06 1.80 1.72
ic4 0.30 1.12 0.92 0.80 0.76
nC4 4.30 0.49 0.40 4.01 2.58 1.40 1.14 0.10 0.94
Cyc pent 0.06 0.05 0.04 0.04
iC5 0.16 0.84 0.69 0.60 0.57
Neopentane 0.92 0.80 0.76
nC5 0.80 0.10 4.00 0.10 2.56 0.97 0.56 0.46 0.40 0.37
Benzene 0.18 0.17
2-Met Pent 1.12 0.92 0.80 0.76
nC6 0.27 0.11 1.77 0.68 0.84 0.69 0.60 0.57
Met cyc Pent 2.25 0.87 0.09 0.08 0.08
Cyc Hex 2.20 0.86 0.21 0.18 0.17
nC7 0.06 0.46 0.18 1.23 1.01 0.88 0.84
Met Cycl Hex 2.36 0.94
Met Hex 0.12 0.23 0.20 0.19
Eth Cyc Pent 0.34 0.30 0.29
Toluene 0.72 0.28 0.18 0.19
nC8 0.08 1.02 0.41 1.20 0.98 0.86 0.82
Eth Cyc Hex 0.37 0.20 0.31
Eth benzene 0.15
o-Xylene 1.79 0.72 0.14 0.13
m-Xylene 0.10
p-Xylen 0.04
nC9 1.66 0.66 1.17 0.96 0.84 0.80
nG0 2.80 2.73 1.11 1.12 0.92 0.80 0.76
nCl1 2.37 0.961 1.09 0.89 0.78 0.74
nCl2 2.04 0.83 1.06 0.87 0.76 0.72
nCl3 1.77 0.73 1.01 0.82 0.72 0.69
nCl4 1.53 0.63 0.98 0.80 0.70 0.67
nC15 1.34 0.56 0.92 0.76 0.66 0.63
la6 3.20 1.15 0.48 0.89 0.73 0.64 0.61
nC17 0.99 0.42 0.87 0.71 0.62 0.59
nC18 0.87 0.36 0.84 0.69 0.60 0.57
nCl9 0.75 0.32 0.56 0.46 0.40 0.38
nC20 0.65 0.27 0.28 0.23 0.20 0.19
No. of Comp. 6 7 6 12 25 25 25 30 35 40
Temperature,K 310.0 200.0 310.9 190.0 373.2 373.2 360.0 360.0 360.0 360.0
Crit. Temp., K 313.7 201.1 188.9
Pressure,MPa 7.88c 5.58c 6.67c 2o.3b 32.8b
Source VI 111 [31 Ul PI VI 131 131 131 r31
b: bubble point d c: crltlcal polnt
Source: [l] Peng a$ i$r.ttt (1977); [2] Danesh et al (1991); [3] Xu (1990)

In this study, we compared the performance of the ASS with the Newton-Raphson
method for solving one equation with one unknown and two Newton type methods
(Dennis and Schnabel, 1983), a Newton-Quassi method and a Broyden method
which replaces the Jacobian matrix by an approximated matrix, for solving a set of
equations with multivariables. The Broyden method was modified in this work by
calculating the Jacobian matrix after every 5 iterations as this improved the
convergence of the method when solving a large number of non-linear equations.

The above methods were used to calculate the bubble or dew point pressures of a
number of fluids near and remote from critical points as given in Table 1. All
cases were run on a VAX-8700 computer.

The effect of number of components describing a fluid on CPU time is shown in

Figure 1 for fluid 5. The number of components were increased above 25 by
adding 0.1% mole fraction of alkenes to the pertinent carbon number groups, and
decreased by lumping the components using a grouping method proposed by
Danesh et al (1990). Note that the CPU times of the.ASS and CSS methods increase
gradually with the number of components, but the CPU time of the Newton type
methods increase sharply with the number of components, especially for mixtures
with a large number of components.



0 10 20 30 10
Number of Components

Figure 1. Effect of Number of Components on Computational Time, Fluid 5.

Table 2 also gives a comparison of various methods for CPU time on calculating
bubble and dew point pressures. The number of iterations in the Newton type
methods were much less than that in the SS methods in all the cases because the
order of the Newton type methods is higher than that of the SS methods. The
Newton type methods were also more rapid than the successive substitution
methods in the case of the systems with a few components. But for mixtures with

many components, the SS methods were faster than the Newton type methods, and
increasing markedly with increase of number of components, as the Newton type
methods now need to compute a more complicated Jacobian matrix and its inverse.

Table 2

Comparison of Various Methods for CPU Times of Saturation Pressure Calculations

Fluid Initial Cal. CSS ASS Newton- Newton- Broyden CSS ASS Newton- Newton- Broyden

i: 30.00
6.00 32.56
6.62 201
990 400
97 +8 4i si 0.77
1.10 0.33
0.51 0.+12 3.+9 +

5 15.00 19.99 117 56 21 12 17 1.65 1.34 0.91 6.14 :;49

6 20.00 33.68 55 49 41 1.50 1.21 9.42
7 20.00 36.28 89 56 6’5 :; 2: 2.35 2.34 2.+56 11.88 5.52
8 30.00 34.18 66 55 70 6.78 2.52 3.83 15.98
9 30.00 36.20 70 50 + 9 ;‘6 3.66 3.02 + 66.89 48fi2
10 30.00 36.01 80 62 + + + 6.24 5.01 + + +
N.B.:* Dew Point Pressures + Divergence

Table 2 also indicates that the SS methods were more robust in converging to a
solution. Fluid 6 is near its critical point at lOO.O“C. Figure 2 shows the effect of
temperature on the CPU time for fluid 6 using various methods. It demonstrates
that the CPU time increases when the critical point is approached. The Broyden’s
method failed to converge at high temperatures. The increase in the computational

---Q-- css
40 -‘-‘Q--- Newton-Raphson
--‘+- Quasi-Newton
__- *--* BrOyaen
1 30

ks 2o


i 2; 4’0 6; . 6b . 100
’ - 1 0

Temperature, deg C

Figure 2. Effect of Temperature on Computational Time, Fluid 6.


time was much higher for the Newton-Quassi method with the least change for the
ASS method.

Figure 3 shows the effect of the initially guessed saturation pressure on the
computational time. It indicates that the initial value does not influence
significantly the convergence rate of SS methods, whilst the Newton-Quassi method
shows a sharp increase in the CPU time when the initial pressure is much higher
that the converged value.

20 ,
--o-- css
. - ASS
---m- Newton-Raphson t’
15 - _._. *_.-
P Newton-Quasi ;
6 _--t-m. I
E Bubble Point i’
.g 10 /
2 @O.-y ._,._.‘._.*...i
v y’

40 60

Figure 3. Effect of Initial Pressure on Computational Time, Fluid 5.


A simple and rapid new accelerated successive substitution method has been
proposed for calculating the bubble or dew point pressure of m&component fluids
by iterating on a single variable pressure. The proposed method has been
compared against the most commonly used methods for various fluids leading to
the following conclusions:

1. The successive substitution methods exhibited a reduction of CPU time to

Newton type methods for multicomponent mixtures. The ASS method was
superior to others, followed by the Newton-Raphson, CSS, Broyden and
Newton-Quasi methods.

2. The ASS method is quite robust in converging to the solution, even at near
critical conditions.

3. The proposed method is relatively insensitive to the initial value used in the


f fugacity
K equilibrium ratio
N number of components in a mixture
P pressure
T temperature
S iteration function
X liquid mole fraction
Y vapor mole fraction
+ fugacity coefficient


L liquid
V vapor
r iteration time


i component label


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