A method to extend the domain of convergence for difcult

multicomponent, multistage separation problems

Yoshikazu Ishii
a
, Fred D. Otto
b,
*
a
Fraxon Technology Ltd., 2-18-6 Tanaka, Isogo, Yokohama, Japan
b
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Canada T6G 2G6
Received 13 February 2002; received in revised form 21 October 2002; accepted 2 December 2002
Abstract
A new computational procedure is presented to attain convergent solutions for multistage, multicomponent separation problems
for non-ideal fluid mixture systems when starting from very crude initial assumptions. The procedure incorporates a gradual non-
ideality enhancing method into the Ishii /Otto pseudo-binary-mixture (PBM) algorithm [Comput. Chem. Eng. 25 (2001) 1285].
Shifting K-values from ideal to non-ideal in the course of iterative calculations gradually approaches the correct solution to a
problem. The domain of convergence with the proposed procedure is greatly extended and very difficult problems where both non-
ideality of fluid systems and very rough assumptions for initial variables are involved can be solved with the same ease as one solves
problems with ideal physical properties. An innovative method, made possible because of the PBM concept, to simplify the Jacobian
matrix and significantly reduce the computing time for evaluation of the Jacobian is also presented. The effectiveness of the methods
is illustrated with example problems.
# 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Separation; Distillation; Non-ideal systems; Process simulator; Jacobian
1. Introduction
It is well known that solutions to multistage separa-
tion calculation problems with ideal fluid mixture
systems are easily obtainable. For such problems, the
domain of convergence is usually very large. Even for
problems with moderately non-ideal systems, conver-
gence is not a problem for many of the equation-solving
methods (e.g. Naphtali & Sandholm, 1971; Ishii & Otto,
1973), provided that extremely remote assumptions for
initial variables are not made. However, for severely
non-ideal fluid systems and often for systems where the
non-ideality of both phases must be taken into con-
sideration, identification of suitable initial assumptions
is crucial for successful convergence. The domain of
convergence for such systems is limited and narrow.
The most sophisticated approaches to extending the
domain of convergence are the homotopy-continuation
methods in which the solution is gradually approached
via a step-wise integration along so-called homotopy
paths starting with an easy initial problem. Examples
are Salgovic, Hlavacek and Ilavsky (1981), Hlavacek
(1985), Byrne and Baird (1985), Chavez, Seader and
Wayburn (1986), Vickery and Taylor (1986), Kovach
and Seider (1987), Lin, Seader and Wayburn (1987).
However, the homotopy continuation methods are very
time consuming and their use does not always ensure
convergence. The thermodynamic homotopy method
proposed by Vickery and Taylor (1986) is worthwhile
mentioning in that it was successful in coping with many
problems that could not be solved with other homotopy
continuation methods. A notable feature of the method
of Vickery and Taylor (1986) is the fact that both
ideality and non-ideality for each physical property, K-
value and enthalpy are combined as a thermodynamic
homotopy and physically meaningless solutions during
the course of integration are prevented. In accordance
with their homotopy, idealities are replaced by non-
ideality gradually with the progress of integration along
the homotopy path.
* Corresponding author.
E-mail address: fotto@interbaun.com (F.D. Otto).
Computers and Chemical Engineering 27 (2003) 855/868
www.elsevier.com/locate/compchemeng
0098-1354/02/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0098-1354(02)00271-5
Nomenclature
A Coefficient in Peng/Robinson equation of state
a Coefficient in Peng/Robinson equation of state
B Coefficient in Peng/Robinson equation of state
b Coefficient in Peng/Robinson equation of state
C Component balance function defined by Eq. (5) (kmol/h)
E enthalpy balance function defined by Eq. (11) (kJ/h)
F feed rate (kmol/h) or general function in Eq. (12)
F vector of function F defined by Eq. (12)
f function defined by Eq. (14)
G Equilibrium balance function defined by Eq. (7) (mole fraction)
h enthalpy of liquid (kJ/kmol)
H enthalpy of vapor (kJ/kmol)
H
F
enthalpy of feed (kJ/kmol)
DH Isothermal enthalpy departure from the ideal gas state (kJ/kmol)
K Equilibrium ratio, K0/Y/X
K* modified equilibrium ratio based on PBM concept
L flow rate of liquid (kmol/h)
M material balance function defined by Eq. (3) (kmol/h)
N total number of equilibrium stages
n number of variables (Eq. (13)); parameter in Eq. (49)
NC total number of components
P pressure (kPa)
Q heat input to stage (kJ/h)
R universal gas constant (kJ/kmol per K)
S
X
Summation function defined by Eq. (9a) (mole fraction)
S
Y
Summation function defined by Eq. (9b) (mole fraction)
SL flow rate of liquid side product (kmol/h)
SV flow rate of vapor side product (kmol/h)
T Temperature (K)
t damping factor
V flow rate of vapor (kmol/h)
v molar fluid volume (m
3
/kmol)
x Normalized liquid composition or phase composition in Eq. (48) (mole fraction), or general
variable in Eq. (13)
x
c
liquid composition of pseudo-binary component (mole fraction)
X liquid composition (mole fraction)
x vector of variable x
y Normalized vapor composition (mole fraction)
Y
c
vapor composition of pseudo-binary component (mole fraction)
Y vapor composition (mole fraction)
Z feed composition (mole fraction)
Z Compressibility factor
Greek letters
a Coefficient of Eq. (22)
b coefficient of Eq. (22)
g constant of Eq. (22) or activity coefficient
d numerical constant defined by Eq. (26)
o
M
convergence criterion for material balance
o
T
overall convergence criterion
u non-ideality enhancing parameter
8 fugacity coefficient in mixture
n pure component fugacity coefficient
L Wilson parameter
F vector of zeros
Y. Ishii, F.D. Otto / Computers and Chemical Engineering 27 (2003) 855/868 856
Ishii and Otto (2001) recently improved the original
formulation of their simultaneous correction procedure
(Ishii & Otto, 1973) by incorporating the pseudo-binary-
mixture (PBM) concept to account for the composition
dependence of the equilibrium K-values. The method
assumes that the pseudo-component derivative of the K-
value is the composition weighted average of the
composition derivatives for all the components repre-
sented by the pseudo-component. The PBM concept
makes it possible to account for compositional effects
and yet retain the advantages and simplicity of the
original formulation of the Ishii and Otto algorithm, i.e.
the Jacobian is simplified by replacing a large number of
cross-component elements by a single element. This
greatly reduces computational time because of very
efficient matrix manipulations. The Ishii /Otto PBM
procedure also enjoys a large domain of convergence
even for difficult problems with non-ideal mixture
systems (Ishii & Otto, 2001). However, difficulties in
obtaining convergent solutions are encountered when
very poor guesses are made for the initial variables.
For multicomponent separation calculation problems
with non-ideal fluid mixture systems, the bulk of the
computing time, typically more than 80%, is consumed
for the evaluation of the thermodynamic properties
when Newtons method or any of its variants is used
(Westman, Lucia & Miller, 1984; Byrne & Baird, 1985).
This means that most of the time for the calculation is
spent in the evaluation of the Jacobian and the majority
of this time is used to obtain all the compositional
partial derivatives of each K-value.
Many studies directed to reducing the computing time
for the evaluation of the Jacobian have been published.
Quasi-Newton methods such as represented by the
method of Tomich (1970) a hybrid approach presented
by Lucia and Macchietto (1983), and Westman et al.
(1984), the dogleg method of Chen and Stadtherr (1981)
are typical examples. The major purpose of model
simplification approaches proposed by such as Perre-
gaard (1993), Ferraris (1983) is also for the reduction of
the computational burden associated with the evalua-
tion of the Jacobian.
These methods have contributed to improvement in
handling of the Jacobian. However, it should be noted
that this improvement is generally attained at the
expense of the quality of calculations, i.e. the stability
of convergence or the domain of convergence.
The present paper presents enhancements to the
Ishii /Otto PBM algorithm that extend the domain of
convergence for separation problems involving non-
ideal fluid mixture systems and reduce the time required
to evaluate the Jacobian without degradation of the
quality of calculations. The enhanced PBM method can
be employed to successfully solve difficult problems
starting from very crude initial assumptions and offers a
significant advantage over other methods with respect to
stability of convergence and computational time.
2. Linearization of model equations
The generalized multistage model is shown in our
previous paper, Ishii and Otto (2001). The model
represents a complex column configuration in which
multiple feeds, side streams and/or side heat exchangers
are considered. For linearization, all the model equa-
tions are Taylor series expanded with respect to the
unknown variables and truncated after the linear terms.
The linearized material balance, equilibrium relation-
ship, summation and enthalpy balance (MESH) equa-
tions for any component i and any stage j are expressed
as follows:
Overall material balance
DL
j(1
'DV
j'1
(DL
j
(DV
j
0(M
j
(1)
from which it follows that
DL
j
0

j
k01
M
k
'DV
j'1
(DV
1
(2)
where
Subscripts
i component number
j stage number, component number
k component number
Superscripts
A actual
I ideal
k iteration number
L liquid
V vapor
T transpose of vector
Y. Ishii, F.D. Otto / Computers and Chemical Engineering 27 (2003) 855/868 857
M
j
F
j
'L
j(1
'V
j'1
((L
j
'SL
j
)((V
j
'SV
j
) (3)
Component material balance
L
j(1
DX
i;j(1
'V
j'1
DY
i;j'1
((L
j
'SL
j
)DX
i;j
((V
j
'SV
j
)DY
i;j
'X
i;j(1
DL
j(1
'Y
i;j'1
DV
j'1
(X
i;j
DL
j
(Y
i;j
DV
j
0(C
i;j
(4)
where
C
i;j
F
j
Z
i;j
'L
j(1
X
i;j(1
'V
j'1
Y
i;j'1
((L
j
'SL
j
)X
i;j
((V
j
'SV
j
)Y
i;j
(5)
Equilibrium relationship
DY
i;j
(K
i;j
DX
i;j
(X
i;j

NC
k01
_
@K
i;j
@X
k;j
_
DX
k;j
(X
i;j

NC
k01
_
@K
i;j
@Y
k;j
_
DY
k;j
(X
i;j
_
@K
i;j
@T
j
_
DT
j
0(G
i;j
(6)
where
G
i;j
Y
i;j
(K
i;j
X
i;j
(7)
Summation equation

NC
i01
DX
i;j
0(S
X
j
(8a)
or

NC
i01
DY
i;j
0(S
Y
j
(8b)
where
S
X
j

NC
i01
X
i;j
(1:0 (9a)
or
S
Y
j

NC
i01
Y
i;j
(1:0 (9b)
Enthalpy balance
L
j(1

NC
k01
_
@h
j(1
@X
k;j(1
_
DX
k;j(1
((L
j
'SL
j
)

NC
k01
_
@h
j
@X
k;j
_
DX
k;j
((V
j
'SV
j
)

NC
k01
_
@H
j
@Y
k;j
_
DY
k;j
'V
j'1

NC
k01
_
@H
j'1
@Y
k;j'1
_
DY
k;j'1
'L
j(1
_
@h
j(1
@T
j(1
_
DT
j(1
(
_
(L
j
'SL
j
)
@h
j
@T
j
'(V
j
'SV
j
)
@H
j
@T
j
_
DT
j
'V
j'1
_
@H
j'1
@T
j'1
_
DT
j'1
'h
j(1
DL
j(1
(H
j
DV
j
(h
j
DL
j
'H
j'1
DV
j'1
0(E
j
(10)
where
E
j
F
j
H
F
j
'Q
j
'L
j(1
h
j(1
'V
j'1
H
j'1
((L
j
'SL
j
)h
j
((V
j
'SV
j
)H
j
(11)
The Ishii and Otto PBM algorithm is an efficient
simultaneous correction procedure for solving these
linearized equations for severely non-ideal systems.
The following sections describe (i) a gradual enhance-
ment of non-ideality procedure which can be employed
to achieve a greater domain of convergence when using
the PBM concept; and (ii) a procedure made possible by
the PBM concept to significantly reduce the computing
time required to evaluate the Jacobian.
3. Gradual enhancement of non-ideality
This procedure uses the concept of combining ideality
and non-ideality but in a way that is different from that
which was employed by Vickery and Taylor (1986) for
their thermodynamic homotopy.
Let
F(F
1
; F
2
; . . . . . . ; F
n
; f )
T
0F (12)
and
x(x
1
; x
2
; ; x
n
; u)
T
(13)
where F is a vector of zeros, and F is a vector of
functions whose variables are represented by a column
vector x. In contrast to typical and customary expres-
sions for the Newton/Raphson equations, function f
and variable u are introduced into Eqs. (12) and (13),
respectively.
Y. Ishii, F.D. Otto / Computers and Chemical Engineering 27 (2003) 855/868 858
Provided that f is only a function of variable u as,
f 0f (u) (14)
then the Newton/Raphson equations are obtained by
expanding Eq. (12) through the linear terms only in a
Taylor series as follows,
@F
1
=@x
1
@F
1
=@x
2
@F
1
=@x
n
@F
2
=@x
1



@F
n
=@x
1
@F
n
=@x
n
_

_
_

_
Dx
1
Dx
2

Dx
n
_

_
_

_
0(
F
1
'(@F
1
=@u)Du
F
2
'(@F
2
=@u)Du

F
n
'(@F
n
=@u)Du
_

_
_

_
(15)
In place of Eq. (14), introduce the following equation,
f 01:0(u (16)
then Du in Eq. (15) is determined by Eq. (16) indepen-
dently of the rest of the equations and is expressed as,
Du01:0(u (17)
Although u is actually a variable to be sought in a
similar manner to the rest of the variables, x?s, we have
chosen to use u as a parameter which controls the
degree of non-ideality of the model equation system at
each iteration level. As will be illustrated later, u is given
particular values as the calculation progresses.
Suppose the following equation for a vapor/liquid
equilibrium relationship as a function of u,
K
i
0(1:0(u)K
I
i
'uK
A
i
(18)
where K
i
I
stands for the ideal K-value of a pure
component i and K
i
A
is the actual K-value in a fluid
mixture system for which non-ideality is prevailing. By
means of Eq. (18), a hypothetical K-value can be
evaluated as a combination of ideality and non-ideality.
The value of u, which varies from zero through unity,
represents the degree of non-ideality for the hypothetical
K-value. K-values at both ends of the spectrum are
identical to an ideal K-value and a non-ideal K-value,
respectively, as follows,
K
i
0K
I
i
when u00:0 (19)
K
i
0K
A
i
when u01:0 (20)
By the introduction of Eq. (18), the linearized model
equations expressed by Eqs. (1) /(7), (8a), (8b), (9a),
(9b), (10) and (11) may be transformed into a general-
ized form of Eq. (15). However, only Eqs. (6) and (7) are
subject to corrections by the introduction of Eq. (18).
The remaining equations are unchanged, since terms
containing a K-value are not present, and thus most of
@F
1
/@u, @F
2
/@u, . . . in Eq. (15) are set to zero. The
modified form of Eq. (6) follows as,
DY
i;j
(K
i;j
DX
i;j
(X
i;j

NC
k01
_
@K
i;j
@X
k;j
_
DX
k;j
(X
i;j

NC
k01
_
@K
i;j
@Y
k;j
_
DY
k;j
(X
i;j
_
@K
i;j
@T
j
_
DT
j
0(
_
G
i;j
'
_
@G
i;j
@u
_
Du
_
(21)
Eq. (21) can be converted to Eq. (22) by applying a
linearization based on the PBM concept. Details of the
PBM concept were reported in our previous paper, Ishii
and Otto (2001).
DY
i;j
0a
i;j
DX
i;j
'b
i;j
DT
j
'g
i;j
(22)
where
a
i;j

fK
i;j
(x
i;j
(@K
i;j
1=@x
c
i;j
)g
d
i;j
(23)
b
i;j

X
i;j
(@K
i;j
=@T
j
)
d
i;j
(24)
and
g
i;j
(
fG
i;j
'(@G
i;j
=@u)Dug
d
i;j
(
fS
X
j
x
2
i;j
(@K
i;j
1=@x
c
i;j
) 'S
Y
j
X
i;j
y
i;j
(@K
i;j
1=@y
c
i;j
)=(1:0 'S
Y
j
)g
d
i;j
(25)
further
d
i;j
1:0'X
i;j
(@K
i;j
1=@y
c
i;j
)
(1:0 'S
Y
j
)
(26)
and
G
i;j
'
_
@G
i;j
@u
_
Du0Y
i;j
(K
A
i;j
X
i;j
(27)
The modification to be made by the introduction of
Eq. (18) is limited to the first term in Eq. (25). As a
result, K
i ,j
in Eq. (7) is modified to K
i ,j
A
as expressed by
Eq. (27) where Du is eliminated at the end result. The
equation solving procedure described in our previous
paper (Ishii & Otto, 2001) can be employed to solve the
newly derived equations. Actual rather than hypothe-
tical K-values must be used for Eq. (27).
The basic concept used to extend the domain of
convergence for difficult problems is to approach
solutions through the hypothetical K-values by shifting
equilibrium relations gradually from ideal to actual K-
values as the calculation progresses. This gradual shift is
made via a change of u in Eq. (18) from zero through
unity. When this parameter reaches unity, then K-values
are identical to non-ideal K-values of the actual fluid
system and strict calculations follow thereafter.
Y. Ishii, F.D. Otto / Computers and Chemical Engineering 27 (2003) 855/868 859
Similar functional relations that combine ideal and
non-ideal enthalpies can be developed. However, our
experience (Ishii & Otto, 2001) is that the non-linearity
caused by enthalpy relations is insignificant compared
with that of equilibrium relations so that enthalpy
relations are all evaluated based on actual fluid condi-
tions throughout the computational procedure.
Intermediate solutions are always sought so as to
satisfy not a transient and hypothetical condition but
the final non-ideal condition even before u reaches
unity. This is understood by the fact that u behaves as
one of the variables and always advances toward unity,
whatever the value of u at the previous iteration level is,
u'Du0u'(1:0(u)01:0 (28)
Thus, corrections to all other variables for the model
equations are sought simultaneously in order to meet a
condition given by Eq. (28), which is the final non-ideal
condition.
Corrections to the variables of Eq. (12), i.e. Dx?s to be
obtained from Eq. (15) and Du from Eq. (17) at the kth
iteration should be used to improve all the variables for
the succeeding iteration as,
x
k'1
j
0x
k
j
't Dx
j
15j 5n (29)
and
u
k'1
0u
k
't Du (30)
where a damping factor, t, is introduced in order to
prevent the variables from correcting excessively. The
variables in Eq. (29), i.e. x?s, correspond to the phase
compositions, flow rates and temperatures associated
with the problem. The recommended criterion to
determine the damping factor for non-ideal systems is
jDT
j
j 5/20 8C. If the factor becomes unity, and this is
most likely to be the case, Eq. (30) is identical to Eq. (28)
and u
k'1
also becomes unity. When improving the
variables for the succeeding iteration, however, we
intentionally do not use Eq. (30) and set the value of
u so as to delay its approach to unity at the early stages
of the iteration process. The state of u is predetermined
by Eq. (28) and it always advances towards unity.
Furthermore, the other variables are entirely governed
by Eq. (15) wherein they are directly influenced by the
value of u. Thus, u is used as a parameter to control the
whole equation system via Eq. (15). Negative values for
the variables are avoided by confining changes to flow
rates to a region one-half to two times the value at the
previous iteration level and by setting any negative
phase compositions to zero.
Difficulties in solving multistage equilibrium separa-
tion problems involving non-ideal mixture systems and/
or remote initial assumptions are obviously incurred
because of a non-linearity effect that is attributable to
such problems. And this degrades the quality of
compositional and often temperature derivatives for
K-values in the Jacobian. A significant feature with
the proposed method is the fact that the extent of non-
linearity accompanying the equilibrium relationship can
be alleviated in the intermediate calculation stage (0.0B/
u B/1.0), where the solution is searched to meet the final
non-ideal condition even though the value of u is yet less
than unity. For example, the partial derivatives of all K-
values with respect to composition which appear in the
Jacobian are moderated by multiplying by u (0.0B/u B/
1.0) as follows,
@K
@x
0(1:0(u)
@K
I
@x
'u
@K
A
@x
0u
@K
A
@x
(31)
In other words, even for calculations at the inter-
mediate stage, a solution is always sought to satisfy the
final condition (u'/Du0/1.0), by using the moderated
compositional derivatives, i.e. u @K
A
/@x. This is also the
case when @K/@y is concerned. By the same token, K-
value itself and @K/@T, which are evaluated in a
hypothetical form at u (0.0B/u B/1.0) are also moder-
ated and influence the Jacobian through a in Eq. (23)
and b in Eq. (24). However, g in Eq. (25) does not
influence the evaluation of the Jacobian, since it is not a
coefficient of any unknown variable.
Prior to entering into the calculation based on
hypothetical K-values combined with ideal and non-
ideal, it is recommended that several calculations using
ideal K-values be initially made. The domain of
convergence for problems with ideal fluid mixture
systems is large and convergence is sufficiently insensi-
tive to initial values so that the solution can be easily
obtained for a wide range of initial values. If the
calculation starts with ideal K-values, it will advance
with ease in the direction of convergence because the
model equations behave more linearly and are thus
easier to solve. But it will not be meaningful to achieve
convergence in this manner, since this solution is
imaginary. Even if the solution based on ideal K-values
is used for the initial guess, it does not guarantee
convergence for actual problems. Thus it will be
necessary to change the direction of convergence by
shifting the quality of K-values from ideal to non-ideal
gradually prior to arriving at a solution based on ideal
K-values.
Thus the computational procedure consists of the
following three calculation stages.
1) Initial stage (u0/0.0).
Initiate the calculation by using ideal K-values and
proceed with several iterations until the convergence
criterion reaches a certain value.In this stage, the
calculation advances toward an imaginary solution
based on ideal K-values.
2) Intermediate stage (0B/u B/1.0).
Switch the equilibrium relationship from ideal K-
values to combined (hypothetical) K-values. Calcu-
Y. Ishii, F.D. Otto / Computers and Chemical Engineering 27 (2003) 855/868 860
lations for a few additional iterations are made
using the hypothetical K-values. The degree of non-
ideality increases gradually based on the increase in
u for which particular values are given as the
calculation progresses.
3) Final stage (u0/1.0).
Continue calculations based on actual K-values
setting u equal to unity until the convergence
criterion meets the final specification.
A recommended and more detailed procedure is as
follows,
1) Initial stage (u0/0.0).
a) Assume initial temperature and overall flow
rate profiles (e.g. see Table 1) for the entire
column and estimate the initial phase compo-
sitions using ideal K-values.
b) Continue the calculations using ideal K-values
until the following criterion is satisfied,
o
M
50:01)N (32)
where o
M
is defined as
o
M

N
j01
f(S
X
j
)
2
'(S
Y
j
)
2
g (33)
This represents a degree of convergence for the
material balance calculation.
2) Intermediate stage (0B/u B/1.0).
a) Conduct the first run by setting u equal to
0.25.
b) Continue with two more runs changing u to
0.5 and 0.75, respectively.
3) Final stage (u0/1.0).
a) Continue the calculations by using actual K-
values until the overall convergence criterion,
Eq. (34), is satisfied,
o
T
510
(6
)N (34)
where o
T
is defined as,
o
T
o
M
Table 1
Problem statements and solutions
Problem number 1 Problem number 2
Type of column Extractive distillation Reboiled absorption
Number of components 4 12
Number of stages 42 30
Pressure (kPa) 101.3 3275.4
Top product (kmol/h) 260.0 1520.0
Reflux ratio 3.0
Feed(s) (kmol/h) 500.0 1820.0
Stage/temperature (8C) (6/48.9) (1/(/20.0)
1000.0 2890.0
(21/37.8) (15/(/20.0)
2960.0
(22/(/20.0)
Final temperature (8C)
Condenser 56.2
Column top 56.3 (/13.5
Reboiler 71.8 95.5
Final vapor (kmol/h)
Condenser 0.0
Column top 1040.0 1520.0
Reboiler 966.8 5959.0
Case A B A B
Initial assumptions
Temperature (8C)
Condenser 40.0 20.0
Column top -35.0 80.0
Reboiler 90.0 110.0 110.0 80.0
Vapor rate (kmol /h)
Condenser 0.0 0.0
Column top 1040.0 1040.0 1520.0 1520.0
Reboiler 1040.0 1040.0 3000.0 1520.0
Y. Ishii, F.D. Otto / Computers and Chemical Engineering 27 (2003) 855/868 861
'

N
j01
_
E
j
(F
j
H
F
j
'Q
j
'L
j(1
h
j(1
'V
j'1
H
j'1
)
_
2
(35)
4. A simplied PBM Jacobian matrix
The PBM concept introduced by Ishii and Otto (2001)
uses an overall compositional partial derivative of K-
values in the Jacobian where only a single element
collectively represents all the component derivatives
with respect to every composition as follows,
@K
i
1
@x
c
i
0(
@K
i
@x
i
'
1:0
(1:0 (x
i
)

NC
k01;k"i
_
x
k
@K
i
@x
k
_
(36)
Eq. (36) can be further transformed to the following,
@K
i
1
@x
c
i
0(
1:0
(1:0 (x
i
)
@K
i
@x
i
'
1:0
(1:0 (x
i
)

NC
k01
_
x
k
@K
i
@x
k
_
(37)
On examination, it was found that some of the
correlation equations for predicting vapor/liquid equi-
librium, where activity coefficients are used, conform to
Eulers homogeneous function. For example, the Wilson
equation is a homogeneous function for which the
degree is (/1. Accordingly, the second term in Eq. (37)
can be expressed as,

NC
k01
x
k
_
@K
i
@x
k
_
0(K
i
(38)
The derivation of Eq. (38) is detailed in the Appendix
A. Consequently, when the Wilson equation is em-
ployed, Eq. (36) is equivalent to the following simple
relation which excludes all cross-component derivatives,
@K
i
1
@x
c
i
0(
1:0
(1:0 (x
i
)
_
@K
i
@x
i
'K
i
_
(39)
where
@K
i
@x
i
0(K
i
_
2:0

NC
j01
(x
i
L
i;j
)
(

NC
k01
_
x
k
L
2
k;i
_

NC
j01
x
j
L
k;j
_
2
__
(40)
Thus, Eq. (36) can be calculated with great ease
through the significantly simplified form of Eq. (39).
This equation eliminates the need for the time-consum-
ing calculation of all the cross-component partial
derivatives. By using the new functional form of Eq.
(39) in place of Eq. (36), the relative computational
frequencies required to obtain the compositional deri-
vatives of K-value is reduced to 1/NC where NC
represents the number of components in the mixture
system. When a large number of components is in-
volved, the effect of Eq. (39) is decisively significant
since a huge volume of calculations corresponding to the
square of the number of components is necessary for the
evaluation of the compositional derivatives in the
existing Newtons methods including the Ishii-Otto
(2001) method.
The functional form of the UNIQUAC equation and
the UNIFAC equation is also homogeneous of degree
(/1 and thus Eq. (39) can be used similarly to the case of
Wilsons equation. However, the NRTL equation is of
degree zero so that the following relation can be derived,
@K
i
1
@x
c
i
0(
1:0
(1:0 (x
i
)
@K
i
@x
i
(41)
However, for equations of state such as the Peng/
Robinson equation, all the functions for correlating
vapor/liquid equilibrium are not homogeneous so that
simplified equations based on Eulers theorem such as
Eqs. (39) and (41) can not be used. When equations of
state are used, @K
i
1
/@x
i
c
and @K
i
1
/@y
i
c
are expressed as
follows (Ishii & Otto, 2001),
@K
i
1
@x
c
i
0(
K
i
(1:0 (x
i
)
@ ln 8
L
i
@x
i
'
K
i
(1:0 (x
i
)

NC
k01
_
x
k
@ ln 8
L
i
@x
k
_
(42)
@K
i
1
@y
c
i
0
K
i
(1:0 (y
i
)
@ ln 8
V
i
@y
i
(
K
i
(1:0 (y
i
)

NC
k01
_
y
k
@ ln 8
V
i
@y
k
_
(43)
The following relation is obtained for the second term
in Eq. (42) when the Peng/Robinson Equation of State
is used.
Table 2
Feed streams for problem number 1
Problem number 1
Feed stage 6 21
Component
Acetone 0.0 250.0
Methanol 0.0 650.0
Ethanol 0.0 50.0
Water 500.0 50.0
Y. Ishii, F.D. Otto / Computers and Chemical Engineering 27 (2003) 855/868 862
@ ln 8
L
i
@x
k
0
b
k
b
_
b
i
b
(1
_
'
_
1
z (B
(
b
i
b
__
b
k
b
z(
@z
@x
k
_
(
A
(z '2:414)(z (0:414)
_
2

NC
j01
(x
j
a
j;i
)
a
(
b
i
b
_

_
b
k
b
z(
@z
@x
k
_
(
A

2
p
B
ln
_
z '2:414B
z (0:414B
_

_
a
k;i
a
'
b
k
b
i
b
2
(
b
i
b

NC
j01
(x
j
a
j;k
)
a
(
b
k
b

NC
j01
(x
j
a
j;i
)
a
_
(44)
where
The value of @K
i
1
/@x
i
c
can be obtained by substituting
Eq. (44) into Eq. (42). However, this calculation,
especially when many components are involved, is very
time-consuming. By taking advantage of mutual com-
pensation and/or complementarity among the composi-
tional partial derivatives of all components in the second
term of Eq. (42), this term can be simplified as follows,

NC
k01
_
x
k
@ ln 8
L
i
@x
k
_
0
_
b
i
b
(1
_
'
_
1
z (B
(
b
i
b
__
z(

NC
k01
_
x
k
@z
@x
k
__
(
A
(z '2:414B)(z (0:414B)
_
2

NC
j01
(x
j
a
j;i
)
a
(
b
i
b
_

_
z(

NC
k01
_
x
k
@z
@x
k
__
(46)
where

NC
k01
_
x
k
@z
@x
k
_
0B'
2(B (z)(A '2Bz) (4Bz
(A (3B
2
(2B) 'z(3z '2B (2)
(47)
Eq. (46) together with Eq. (47) clearly indicates that
the same degree of simplification can be obtained when
using the Peng/Robinson Equation of State even
though Eulers theorem cannot be applied. To be more
specific, the evaluation of all the individual cross-
component derivatives is not needed and they can be
represented by a single value obtained from Eq. (46). A
similar relation can be obtained for @K
i
1
/@y
i
c
by repla-
cing liquid composition with vapor composition in Eqs.
(44) /(47).
Other equations for the correlation of vapor/liquid
equilibrium, where Eulers theorem is not applicable,
including Chao/Seader, Soave/Redlich/Kwong,
Scatchard/Hildebrand, Margules, van Laar and
ASOG were examined in the same way. As a result,
the compositional derivatives for all the equations
examined to date, which cover essentially all of the
existing equations for vapor/liquid equilibrium correla-
tion, can be expressed in simplified forms so that the
evaluation of all individual derivatives are not required
whenever the PBM concept is employed. Several equa-
tions such as ASOG contain Eulers homogeneous
function therein partly and such cases can be more
easily simplified. Whichever correlation equation is
used, the reduction in the computing time required to
obtain the derivatives is decisively significant in that the
greater part of the computing time is spent for the
evaluation of the Jacobian in the existing methods. This
is a significant outcome of the introduction of the PBM
concept, since the greatest drawback with any of the
Newton-type methods is this huge time requirement for
the evaluation of the Jacobian.
It is our experience that even though the composi-
tional derivatives of K-value are neglected completely,
i.e. neglecting Eqs. (42) and (43), it is possible to solve
the problems with moderately non-ideal mixtures for
which the Peng/Robinson Equation of State is used.
Any detrimental effect on convergence has not been
experienced, at least for cases when the gradual non-
ideality enhancing method is applied. Further studies to
@z
@x
k
0
2A(B (z)

NC
j01
(x
j
a
j;k
)=a 'Bf(A (3B
2
(2B) (z(z (6B (2)gb
k
=b
(A (3B
2
(2B) 'z(3z '2B (2)
(45)
Y. Ishii, F.D. Otto / Computers and Chemical Engineering 27 (2003) 855/868 863
establish the criteria to determine cases where the
compositional derivatives of K-value can have negligible
effect are warranted. Though it is conservative, our
present recommendation for moderately non-ideal mix-
ture systems is to evaluate the overall derivatives by
using a simplified equation such as Eq. (46) since their
evaluation can be made very quickly.
5. Illustrative examples
Two test problems are presented in this paper to
demonstrate the effectiveness of the proposed method.
Problem number 1 is identical to the example 1 of our
previous paper (Ishii & Otto, 2001). Problem number 2
is a three-feed demethanizer used to separate hydrogen
rich feeds in a reboiled absorber. Shah and Bishnoi
(1978) reported the details of this problem. The compo-
nents for Problem number 2 cover a wide range of
boiling points from light ones including hydrogen,
nitrogen and methane through heavy lean oils. It is
interesting to test this problem for the following reasons:
1) The column is operated in the vicinity of the critical
pressure and its fluid system is non-ideal both in
liquid and vapor phases.
2) A wide range of components in terms of boiling
point is involved in the system
3) Molar enthalpy values for individual components
are distributed very widely.
4) A broad temperature profile in the column is
expected.
5) A broad flow rate profile is expected.
6) Sudden changes in temperature and flow rate
profiles will be caused by a large quantity of sub-
cooled feed.
7) Convergence is very sensitive to the assumed initial
variables.
Problem statements are presented in Table 1, and
initial temperatures and flow rates are compared with
those of converged solutions for all problems in the
same table. Two cases (Case A and Case B where Case B
is more difficult) are presented for each problem. Initial
temperature and flow rate profiles were assumed to be
linear by interpolating values given at the top and
Table 3
Feed streams for problem number 2
Problem number 2
Feed stage 1 15 22
Component
Hydrogen 0.0 0.0 562.40
Nitrogen 0.0 0.0 207.20
Methane 0.0 28.90 651.20
Ethylene 0.0 57.80 414.40
Ethane 0.0 144.50 414.40
Propylene 0.0 491.30 384.80
Propane 23.66 317.90 118.40
1-Butene 196.56 520.20 88.80
Cis -2-Butene 444.08 173.40 14.80
n-Butane 777.14 982.60 59.20
n-Pentane 331.24 158.95 35.52
Heptane 47.32 14.45 8.88
Table 4
Convergence characteristics for problem number 1
Iteration number Case A Case B
u e
T
u e
T
0 0.0 0.529)/10
3
0.0 0.876)/10
6
1 0.0 0.546)/10
3
0.0 0.922)/10
6
2 0.0 0.482)/10
3
0.0 0.906)/10
6
3 0.0 0.466)/10
3
0.0 0.856)/10
6
4 0.0 0.353)/10
3
0.0 0.892)/10
6
5 0.0 0.331)/10
3
0.0 0.780)/10
6
6 0.0 0.142 0.0 0.773)/10
6
7 0.25 0.808 0.0 0.666)/10
6
8 0.5 0.120)/10
2
0.0 0.393)/10
6
9 0.75 0.434)/10
(1
0.0 0.270)/10
6
10 1.0 0.426)/10
(3
0.0 0.110)/10
6
11 1.0 0.116)/10
(3
0.0 0.294)/10
4
12 1.0 0.330)/10
(4
0.0 0.308)/10
3
13 1.0 0.474)/10
(6
0.0 0.113)/10
3
14 0.0 0.147)/10
15 0.0 0.250)/10
(1
16 0.25 0.462
17 0.5 0.664)/10
18 0.75 0.371)/10
(2
19 1.0 0.114)/10
(1
20 1.0 0.220)/10
(2
21 1.0 0.620)/10
(4
22 1.0 0.135)/10
(5
Table 5
Convergence characteristics for problem number 2
Iteration number Case A Case B
u e
T
u e
T
0 0.0 0.394)/10 0.0 0.153)/10
2
1 0.0 0.302)/10 0.0 0.109)/10
2
2 0.0 0.274)/10 0.0 0.552)/10
3 0.0 0.101)/10 0.0 0.489)/10
4 0.25 0.184)/10
(1
0.0 0.491)/10
5 0.50 0.150)/10
(2
0.0 0.431)/10
6 0.75 0.124)/10
(3
0.0 0.261)/10
7 1.0 0.525)/10
(3
0.0 0.295)/10
2
8 1.0 0.766)/10
(3
0.25 0.481)/10
9 1.0 0.702)/10
(4
0.50 0.313
10 1.0 0.810)/10
(5
0.75 0.224)/10
(1
11 1.0 0.308)/10
(2
12 1.0 0.105)/10
(1
13 1.0 0.513)/10
(2
14 1.0 0.331)/10
(3
15 1.0 0.310)/10
(4
16 1.0 0.191)/10
(5
Y. Ishii, F.D. Otto / Computers and Chemical Engineering 27 (2003) 855/868 864
bottom of each column, e.g. see Table 1. Regarding
problem number 2, computed results are detailed
graphically in the paper of Shah and Bishnoi (1978).
Feed stream information for problem number 1 is given
in Table 2, and that for problem number 2 is given in
Table 3. It is noted for problem number 2 that the
specified column pressure is greater than at least 80% of
the pure component critical pressures for components
making up 75% of the first feed stream and 60% of the
second feed stream on a molar basis.
The Wilson equation was used to generate K-values
and their partial derivatives for problem number 1. For
problem number 2, equilibrium relations were calculated
by using the Peng/Robinson Equation of State. Re-
quired partial derivatives of K-values were evaluated
analytically without resorting to numerical differentia-
tion. Initial composition profiles for all the problems
were estimated by using ideal K-values. For problem
number 2, liquid fugacity coefficients of pure compo-
nents correlated by Chao and Seader (1961) were used to
calculate ideal K-values. Enthalpies and their partial
derivatives can also be evaluated analytically with the
Peng/Robinson Equation of State through the follow-
ing isothermal enthalpy departure from ideal gas,
(
DH
RT
0T
g

v
_
@z
@T
_
v;x
dv
v
'(1(z)
0
1
2

2
p
A
B
_
1(
T
a
@a
@T
_
ln
z '(1 '

2
p
)B
z '(1 (

2
p
)B
'(1(z) (48)
In general, all example problems are difficult to attain
convergence unless the initial assumptions are reason-
ably close to the final solution. We attempted to solve
them by our previous procedure (Ishii & Otto, 2001),
with the following results.
Case A Case B
Problem number 1 16 iterations not converged
Problem number 2 not converged not converged
Except for the converged cases (Case A of problem
number 1), our previous procedure was far from
convergence at the end of 30 trials. The converged
case is described in our previous paper (Ishii & Otto,
2001) where the same initial assumptions were used for a
temperature sensitivity test.
All the cases were solved smoothly by the new
method. Tables 4 and 5 show the behavior of the
convergence criterion o
T
for each problem with relation
to the value of u.
Example problem number 1 was solved using both
Eqs. (36) and (39) based on the Wilson equation, and
there was complete agreement using either equation.
Table 5 shows the convergence characteristics for cases
A and B for problem 2. Both cases were solved by
applying the gradual non-ideality enhancing method
and neglecting the compositional derivatives, i.e. by
setting Eqs. (42) and (43) to zero.
In addition to non-ideality of the mixture systems,
initial assumptions are all remote from the final solu-
tions so that the problems are examples for which it is
normally very difficult to achieve convergence. How-
ever, all the problems were solved easily by applying the
present method.
Columns should be operated at a pressure lower than
the critical pressure of each internal stream for V/L
separation to occur. During the course of iterative
calculations in many of the solving methods, variables
often stray off into or near the vicinity of the critical
condition, such as problem number 2. As a result
divergence occurs in the absence of excessively good
initial values. Though further study is required, our
procedure was very effective in avoiding this problem.
As an alternative, when using the gradual non-ideality
enhancing method, it is possible to attain the solution by
setting Du equal to zero in place of (1.0(/u). Based on
this approach, intermediate solutions are always sought
so as to meet the condition at the value of u. This is a
simple replacement of individual solutions by changing
u successively. We solved several examples by setting Du
equal to zero and this alternative method worked.
However, it took many trials so that this alternative is
not efficient. When three sets of u (0.25, 0.5 and 0.75) in
combination with Du equal to 0.0 were successively
specified for cases-B, all the problems were far from the
convergence at the end of 30 trials.
6. Discussion
In our experience, the standard procedure, where u is
changed from 0.25 through 0.75 together with the
resultant Du(0/1.0(/u), is very reliable and seems to
always ensure convergence. However, there may be
more effective ways to reduce the computational burden
by a better parameterization of u. Furthermore, an even
more reliable procedure can be implemented by repla-
cing Eq. (16) with the following equation.
f 0exp((nu) (49)
Then u advances as follows,
u'Du0u(
f
@f
@u
0u'
1
n
(50)
where n is a parameter to determine the step size in the
intermediate stage of calculation. The larger the value of
n the more stable the convergence. For example, when
f 0exp((4u) (51)
Y. Ishii, F.D. Otto / Computers and Chemical Engineering 27 (2003) 855/868 865
the values for u calculations in the intermediate stage
are as follows,
u u'/Du
0.0 0.25
0.25 0.5
0.5 0.75
0.75 1.0
Although the method presented in this paper is
seemingly similar to homotopy-continuation methods
it is actually a modified version of the Newton/
Raphson method in which the Newton/Raphson calcu-
lations are made by using a modified Jacobian matrix.
The method has several distinguishing features superior
to homotopy-continuation methods. In the homotopy-
continuation methods the solution is approached by
successive integration of the homotopy differential
equations. At a given parameter level many iterations
are required until convergence is attained. Intermediate
solutions are, in many cases, physically meaningless, and
the Jacobian often becomes singular so that a counter-
measure to cope with the difficulties is required. The
new computational procedure does not require the
integration of differential equations and no iteration-
wise convergence is required at each parameter level.
Basing initial assumptions on ideal K-values and
gradually introducing non-linearity as the solution
procedure progresses is effective in avoiding the problem
of a singular or near singular Jacobian matrix which
may occur when dealing with non-linear functions and
the initial variables are remote from the true solution. If
such a problem does occur the recommendation is to
step back the calculation to a point halfway between the
present and previous parameter levels representing the
degree of non-ideality.
Flow sheet simulation is very instrumental in design-
ing and analyzing complex chemical processes where
many separation and/or reactor units are involved. It is
especially effective when many interconnected streams
are involved and loops exist by recycle streams. Most
commercial process simulators employ computational
procedures in a sequential modular fashion where each
unit accepts the information necessary to initiate
calculation from outside and its output streams are
transferred sequentially to other connected units. For
these simulators reasonably good initial estimates for all
input parameters in a chemical process such as a
complex distillation system have to be provided to
insure convergence, especially for highly non-ideal
mixtures (Wasylkiewicz & Alva-Argaez, 2002). For
downstream units in a complex distillation separation
system good initial assumptions are often not known
and/or are subjected to the changes of other units so that
it is often difficult and very time consuming to achieve
convergence. The improved Ishii /Otto algorithm with
the non-ideality enhancement method, for which the
convergence is less-dependant on initial assumptions,
can be an effective tool for flow-sheet simulation where
difficulties are anticipated. It is also noted that the
algorithm does not require a huge amount of storage
memory and it is able to achieve convergence very
quickly.
Both the PBM concept and the gradual non-ideality
enhancing method are applicable to other types of
separation problems such as three-phase distillation,
liquid/liquid extraction and even to reactive distillation.
In the papers authored by us to date, the model
equations have been exclusively grouped by equation
type rather than stage location. This is to avoid the
toilsome manipulation of a large number of block
matrices where elements in each constituent matrix are
scattered widely. However, it is worthwhile to apply the
PBM concept alone or together with the gradual non-
ideal enhancing method to cases where the equations are
grouped by stage location. The following situations will
bias the choice in favor of grouping by individual stages:
/ A large number of theoretical stages, such as a
propylene-propane splitter where more than 200
stages are specified and the number of components
involved is quite limited. In such cases, relative
memory storage required becomes smaller and thus
the computing time can be lessened accordingly.
/ Reactive distillation where relations among compo-
nents governing the chemical reactions can be speci-
fied with ease. All chemical species can be present in
the same stage-wise matrix when the equations are
formulated in accordance with stage location.
7. Conclusions
Incorporating the gradual non-ideality enhancing
method into the Ishii /Otto PBM algorithm provides a
method that works well for difficult problems even when
starting with very crude initial assumptions. This
significant expansion of the domain of convergence is
meaningful in that very difficult problems can be solved
with the same ease as if they are identical to problems
where ideal mixture systems are involved. It was also
observed that the proposed method is effective for
problems where the influence of critical pressures may
become significant. The method is, in effect, a modified
version of the Newton/Raphson method and does not
require the integration of differential equations and
iteration-wise convergence at each parameter level such
as is required when using homotopy-continuation meth-
ods.
Provided that the linear approximation based on the
PBM concept is applied, the number of the composi-
tional derivatives of K-value required in the Jacobian
matrix can be greatly reduced for problems for essen-
Y. Ishii, F.D. Otto / Computers and Chemical Engineering 27 (2003) 855/868 866
tially all the correlating equations for non-ideal vapor/
liquid equilibrium. The significant reduction in the
computing time due to the above fact is meaningful in
that Jacobian evaluation is a major consumer of
computational effort for multicomponent, multistage
separation problems.
When equations of state are involved for the predic-
tion of K-values, no compositional derivatives may be
required in the Jacobian, provided that the gradual non-
ideality enhancing method is employed. More specifi-
cally, the following can be assumed when the method is
employed for problems with moderately non-ideal
mixture systems.
@K
i
1
@x
C
i
00:0 and
@K
i
1
@y
C
i
00:0
Appendix A
Derivation of Eq. (38)
The activity coefficient for any component i in the
Wilson equation is expressed by,
g
i
0exp
_
(ln

NC
j01
(x
i
L
i;j
)'1:0(

NC
k01
_
x
k
L
k;i

NC
j01
x
j
L
k;j
__
(A1)
Introducing the following variables,
x?
1
0lx
1
; x?
2
0lx
2
; . . . ; x?
NC
0lx
NC
and substituting them into Eq. (A1), we can obtain a
new relation as,
g?
i
0exp
_
(ln l(ln

NC
j01
(x
i
L
i;j
)'1:0
(

NC
k01
_
x
k
L
k;i

NC
j01
x
j
L
k;j
__
0g
i
l
(1
(A2)
Thus Eq. (A1) conforms to Eulers homogeneous
function in which its degree is (/1. Differentiating Eq.
(A2) with respect to l gives
@g?
i
@l
0(
g
i
l
2
0

NC
j01
_
@x?
j
@l
__
@g?
i
@x?
j
_
0

NC
j01
x
j
_
@g?
i
@x?
j
_
(A3)
If l is set equal to 1.0, then x
j
?
0/x
j
and Eq. (A4)
follows,

NC
j01
x
j
_
@g
i
@x
j
_
0(g
i
(A4)
K
i
is expressed by the following fundamental relation,
K
i
g
i
_
n
0
i
8
V
i
_
(A5)
where, n
i
0
is the fugacity coefficient of pure liquid
component i and 8
i
V
is the fugacity coefficient of
component i in the vapor mixture. Thus, n
i
0
/8
i
V
is
independent of liquid composition so that the following
relation can be derived,

NC
j01
x
j
_
@K
i
@x
j
_
0(K
i
(A6)
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