Computers and Chemical Engineering 26 (2002) 1703
/1724

www.elsevier.com/locate/compchemeng

Multiphase equilibria calculation by direct minimization of Gibbs free

energy with a global optimization method
Dan Vladimir Nichita a,1,*, Susana Gomez b, Eduardo Luna b,2
a
PETROM-Institute for Research and Technology (ICPT), Campina, Romania
b
IIMAS-UNAM, Mexico City, Mexico

Received 23 May 2001; received in revised form 19 June 2002; accepted 1 July 2002

Abstract

This paper presents a new method for multiphase equilibria calculation by direct minimization of the Gibbs free energy of
multicomponent systems. The methods for multiphase equilibria calculation based on the equality of chemical potentials cannot
guarantee the convergence to the correct solution since the problem is non-convex (with several local minima), and they can find
only one for a given initial guess. The global optimization methods currently available are generally very expensive. A global
optimization method called Tunneling, able to escape from local minima and saddle points is used here, and has shown to be able to
find efficiently the global solution for all the hypothetical and real problems tested. The Tunneling method has two phases. In phase
one, a local bounded optimization method is used to minimize the objective function. In phase two (tunnelization), either global
optimality is ascertained, or a feasible initial estimate for a new minimization is generated. For the minimization step, a limited-
memory quasi-Newton method is used. The calculation of multiphase equilibria is organized in a stepwise manner, combining phase
stability analysis by minimization of the tangent plane distance function with phase splitting calculations. The problems addressed
here are the vapor
/liquid and liquid
/liquid two-phase equilibria, three-phase vapor
/liquid
/liquid equilibria, and three-phase
vapor
/liquid
/solid equilibria, for a variety of representative systems. The examples show the robustness of the proposed method
even in the most difficult situations. The Tunneling method is found to be more efficient than other global optimization methods.
The results showed the efficiency and reliability of the novel method for solving the multiphase equilibria and the global stability
problems. Although we have used here a cubic equation of state model for Gibbs free energy, any other approach can be used, as the
method is model independent.
# 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Phase stability; Tangent plane distance; Multiphase equilibria; Global optimization; Equation of state

Nomenclature
B subspace of constraints in Rn defined by inequalities
D tangent plane distance function
/D̄/ dimensionless tangent plane distance function
E defined by Eq. (30)
epsmch machine precision
F mol of feed
f objective function

* Corresponding author. Present address: Div. Chimie et Physico-Chimie Appliquees, Inst. Francais du Petrole, 1 et 4 avenue du Bois-Preau Rucil-
Malmaison, 92852 Cedex, France. Tel.: /33-1-4752-6000; fax: /33-1-4752-7025
E-mail address: d-vladimir.nichita@ifp.fr (D.V. Nichita).
1
Currently with IFP.
2
Currently with University of Manchester.

0098-1354/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 9 8 - 1 3 5 4 ( 0 2 ) 0 0 1 4 4 - 8
1704 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724

fji fugacity of component i in phase j

factr tolerance in Eq. (36)
G Gibbs free energy
g function defined by Eq. (25)
H Hessian matrix
h function defined by Eq. (28)
K equilibrium ratios
kij binary interaction coefficients
L , L1, L2 mol fraction of liquid phases
l lower bound on variables
M molecular weight
n number of independent variables
ni mol number of component i in feed
nji mol number of component i in phase j
nc number of components
np number of phases
ns number of components that may precipitate
p pressure
pgtol tolerance for projected gradients
Q objective function given by Eq. (29)
R universal gas constant
T temperature
T Tunneling function
Tp(x ) Tunneling function with a pole
Tc(x ) classical Tunneling function
Te(x ) exponential Tunneling function
u upper bound on variables
V mol fraction of vapor phase
xij mol fractions of component i in phase j
x independent variable (Section 3)
y mol fractions of vapor phase
xG the global minimum
xm stationary points
xs stationary points of the Tunneling function
z feed composition
Greek letters
bj mol of phase j per mol of feed
d the Kronecker delta
o tolerance in Eq. (38)
8 fugacity coefficient
lm strength of the pole at the point xm
ls strength of the pole at the point xs
m chemical potential
n iteration level
v acentric factor
Subscripts
F feed
i, k component index
j phase index
pure pure component
r reduced
Superscripts
S solid
T transposed
0 initial value
* at stationary points
 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
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1. Introduction
Development of robust and efficient methods for the
calculation of phase equilibria has long been a challenge,
and still it is. The purpose of this work is to develop an
efficient and reliable tool for various multiphase equili-
bria calculations for interest in Chemical Engineering
and Petroleum Engineering.
The difficulty of phase equilibrium calculations con-
sists in the highly non-linear and non-convex form of the
objective function that gives no guarantee that the
global minimum will be found. Complexity of the
problem increases near critical points and phase bound-
aries.
The theoretical basis of multiphase equilibria has been
first stated by Gibbs (1873) pp 382
/404. However, the
spectacular progresses accomplished during the last
decades are strictly related to the development of
thermodynamic models and the increasing performances
of computers.
The formalism given by Baker, Pierce and Luks
(1982) comprises a set of theorems giving the conditions
for phase stability and multiphase equilibria. They
clearly showed why the incorrect number of phases or
phase compositions may be predicted in phase equilibria
calculations.
The classical approach for phase equilibria calcula-
tion is based on the equality of chemical potentials.
Fussel (1979) presents the extension to multiphase
equilibria of the Fussell and Yanosik (1978) Minimum
Variable Newton
/Raphson (MVNR) for two-phase
calculations. Risnes and Dalen (1984) are using the
successive substitutions (SSI) method for multiphase
equilibria. Mehra, Heidemann and Aziz (1982) are using
accelerated SSI, followed by Newton iterations. Nghiem
and Li (1984) used Newton
/Raphson and Quasi-New-
ton successive substitution iterations.
We should note the remarkable work of Michelsen
(1982a,b), whose papers represents a milestone in
the development of phase equilibria calculations.
Michelsen formulated a method for finding the
stationary points of the tangent plane distance (TPD)
function (Michelsen, 1982a), and applied second order
methods for multiphase equilibria calculation (Michel-
sen, 1982b).
The equality of chemical potential represents only the
stationary point conditions for the minimum of thermo-
dynamic potentials. Any method based on these condi-
tions may fail to find the global minimum, being
attracted by local minima. A related feature is the
fractal behavior of robust algorithms, observed by Lucia
et al. (1990), Green, Zhou and Luks (1993).
The modern trend is the treatment of the phase
equilibria problem by the direct minimization of Gibbs
free energy or of the Gibbs TDP function subject to the
linear material balance constraints.
1705
Trangenstein (1985) formulated the two-phase
equilibria reservoir compositional simulation as a con-
strained optimization problem. Vickery and Taylor
(1986), DeGance (1993) used path continuation meth-
ods. The homotopy continuation method was used by
Sun and Seider (1995), for both phase stability analysis
and phase splitting. The approach of Nagarayan, Cullik
and Griewank (1991) is based on the thermodynamic
energy analysis, using a modified ‘semi-local’ stability
test and a higher order initialization procedure in
the two-phase region. A radically different approach
(the Integral Area Method), presented by Eubank,
Elhassan, Barrufet and Whiting (1992) is based on
the integration of the Gibbs energy surface. Bullard
and Biegler (1993) presents a penalty-based approach,
using a linear programming strategy for solving
vapor
/liquid equilibria. A version of their method is
used by Han and Rangaiah (1997) for vapor
/liquid,
and liquid
/liquid equilibria. Wasylkiewicz, Sridhar,
Doherty and Malone (1996) uses ideas from differential
geometry and the theory of differential equations
for solving global stability analysis and LL phase
splitting. The Interval Newton method was used by
Hua, Brennecke and Stadtherr (1996, 1998), Hua et al.
(1999) for stability analysis.
The simulated annealing (SA) algorithm (Corana,
Marchesi, Martini & Ridella, 1987) was used by Pan and
Firoozabadi (1998) for various kinds of phase equilibria,
Nichita, Goual and Firoozabadi, (2001) for wax pre-
cipitation from hydrocarbon mixtures, and Zhu (2000)
for phase stability analysis.
In a series of papers, McDonald and Floudas
solved the phase and chemical equilibrium problem
using different models for the Gibbs free energy
(McDonald & Floudas, 1995a,b) the phase global
stability problem (McDonald & Floudas, 1995c)
and presented the GLOPEQ code (McDonald & Flou-
das, 1997). They used the deterministic branch and
bound method for global optimization. Although
this method guarantees convergence to the global
solution, the computational cost is generally
unaffordable, as the methods used to compute
the lower bound are still inefficient. In many practical
applications, heuristic stochastic methods based on
a space search, that do not need gradient evaluations,
and that have a probability of convergence, have
been successfully used, as genetic algorithms. These
algorithms have the property to descend the
objective function value very fast at the beginning, but
as they loose diversity information of the space, they
tend to be extremely slow to actually get the
global solution (see Gomez, Gosselin & Barker, 2001).
In this paper, we propose the use of the Tunneling
global optimization method for solving the phase
stability and multiphase equilibrium problems. This
method has a hybrid nature. It is deterministic in the
1706 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724

sense that it produces a monotonic sequence of im-
proved local minima (avoiding all the local solutions
above). It also has a stochastic element, as the initial
points to start the search for a point in another valley
(Tunneling phase) are taken in random directions,
allowing the method to perform an intelligent space
search for more promising valleys. The Tunneling
method is able to escape from local minima and saddle
points, and has shown to be able to find efficiently the
global solution for all the academic and industrial
problems tested (Gomez and Romero, 1994; Gomez,
Keeping & Pantelides, 1998; Gomez, Gosselin and
Barker, 2001; Gomez, Solano, Castellanos & Quintana,
2001).
The Tunneling method has two phases. In phase one,
a local bounded optimization method is used to
minimize the objective function. In the second
2. Statement of the phase equilibria problem
2.1. Multiphase equilibria calculation by direct
minimization of the Gibbs free energy
Consider that at given pressure and temperature
conditions, a mixture of nc, components of composition
z /(z1, z2, . . ., znc)T, may split into np phases. We
assume that we have np/1 condensed phases, and the
np phase is the vapor phase. According to the second
law of thermodynamics, at the equilibrium state, the
system has the lowest possible Gibbs free energy from all
possible states. The Gibbs free energy is expressed as:
X
nc X
np
G(n) nji mji (nj ) (1)
i1 j1

phase (tunnelization), either global optimality is ascer- where n/(n1, n2, . . ., nnp)T is a vector of nc /np
tained, or a feasible initial estimate for a new elements, and the nj /(nj 1, nj 2, . . ., nj nc)T; j/1, np
minimization is generated. For the minimization vector contains the component mol fractions in phase j.
step, a limited-memory quasi-Newton method is It is more convenient for EOS calculations to express
used (Zhu, Byrd, Lu & Nocedal, 1994; Byrd, Lu, the Gibbs free energy G in term of fugacities. Eq. (1) can
Nocedal & Zhu, 1995), but any favorite minimizer be rewritten as:
may be used.
The Tunneling method has proved its efficiency and G(n) X
nc X
np
G(n)  nji ln fji (xj ) (2)
reliability on several highly difficult academic and RT i1 j1
industry. The method proposed here does not require
a priori the number of phases existing at equilibrium. where Ḡ is the reduced Gibbs free energy.
The calculation sequence is organized in a stepwise The constrained optimization problem is:
manner. Results from two-phase flash and stability G(n) 0 min (3)
analysis provide good initial guesses for the three-phase
such that the component material balance constraints:
equilibrium. Phase distribution is obtained by solving a
convex unconstrained optimization problem (Michelsen, X
np

1994). ni  nji ; i 1; nc (4)

j1
The code Tunneling phase equilibria (TUNPEQ)
incorporates the code TUNNEL for the global optimi- and bounds of independent variables:
zation method, developed at IIMAS-UNAM (Castella-
0 5nji 5ni ; i 1; nc; j 1; np (5)
nos & Gomez, 1998).
A general form of cubic equations of state (EOS), where ni /Fzi are the feed component mol numbers for
(Coats, 1985; Michelsen, 1986), including the Soave
/ F mol of feed.
Redlich
/Kwong (SRK) EOS (Soave, 1972), and the Fugacities depends on mol numbers by means of mol
Peng
/Robinson (PR) EOS (Peng & Robinson, 1976) is fractions xj /(xj 1, xj 2, . . ., xj nc); j/1, np:
currently incorporate in TUNPEQ. However, the
nji
method is general and model independent; although an xji  (6)
X
nc
EOS formulation is used here for the Gibbs free energy, njk
any other thermodynamic model can be used for various k1
kinds of thermodynamic equilibria.
In Eq. (2), one can eliminate the mol numbers of one
We will present the multiphase equilibrium problem
phase:
in Section 2, the description of the Tunneling
global optimization method will be given in Section 3, X
np

and the results on a set of difficult problems will be n1i ni  nji ; i 1; nc (7)
j2
reported and discussed in Section 4. A comparison
with other global methods will be presented in Section 5 and the optimization problem (3) becomes an uncon-
and some concluding remarks will be given toward the strained one, with only bounds on the remaining
end. nc(np/1) independent variables, n2, . . ., nnp.
 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
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The gradient of the objective function is: The expression of the reduced TPD in terms of
  X nc   fugacities is:
@G f @ ln fjk @ ln f1k
ln ji  njk n1k ; X
nc
@nji f1i @nji @n1i (8) D(x)
k1 D(x)  xi [ln fi (x)ln fi (z)] (14)
j 2; np; i  1; nc RT i1

According to the Gibbs
/Duhem equation: If one of the mol fractions is eliminated:

X
nc X
nc1
@ ln fji xnc 1 xi (15)
nji  0; j 1; np (9)
i1 @njk;k"i i1

the sums in Eq. (8) vanish. Note that Eq. (9) is satisfied the optimization problem to be solved is:
for any mol fractions, not only for the equilibrium mol D(x) 0 min (16)
fractions. Therefore, it is not necessary to compute the
fugacity derivatives in order to compute the gradient of for nc/1 mol fractions as independent variables
the Gibbs free energy: bounded by:
  0 5xi 5 1; i 1; nc1 (17)
@G f
ln ji ; j 2; np; i 1; nc (10)
@nji f1i This is an unconstrained optimization problem. The
elements of the gradient vector are:
In this work a Limited Memory Quasi-Newton    
minimization technique is used (the L-BFGS-B routine, @D fi (x) fnc (x)
 ln ln ; i 1; nc1 (18)
Zhu et al., 1994), that requires only the values of the @xi fi (z) fnc (z)
objective function and of the gradients. Any solver may
be used for minimization; if the elements of Hessian and elements of the Hessian matrix are given by:
matrix are required, there are given by: @2D @ ln fi (x) @ ln fnc (x)
Hik    ;
@ G 2
@ ln fji @ ln f1i @xi @xk @xk @xk (19)
Hik  dik  ;
@nji @nlk @nli @n1k (11) i; k 1; nc1
i; k 1; nc(np1)
where d is the Kronecker delta.

2.3. Stepwise organization of multiphase equilibria

2.2. Phase stability analysis by minimization of the
tangent plane distance function
Phase stability testing is not only an important and
intricate problem per se, but the stability analysis
routine is a key sequence in the stepwise organization
of multiphase equilibria calculation program. Stability
analysis provides equilibrium phase status and good
initial estimates for flash calculations.
The TDP function is defined as:
X
nc
D(x)G(x)T(x; z) xi [mi (x)mi (z)]
i1
The TPD function is given by the difference between
the Gibbs free energy surface in x, and the tangent plane
to this surface in z, where, x is the composition of a trial
phase, and z is the composition of the phase whose
stability is to be asserted.
The necessary and sufficient condition for phase
stability is given by Theorems 3 and 4 of Baker et al.
(1982). The mixture is stable if and only if the TPD
function is nonnegative at all stationary points, or:
D(x)]0()x
calculation
Convergence to the correct solution of the problem
(global minimum) can be obtained irrespective to initial
guesses, provided a feasible initial estimate is given. This
is one of the strengths of the Tunneling global optimiza-
tion method. However, for computational efficiency,
improved initial estimates are required.
The sequential approach for stability/flash calculation
has been used by Michelsen (1982b), Nghiem and Li
(1984).
(12) Basically, the idea is that one can take advantage in
the np-phase flash on the results of (np/1)-flash and of
the stability testing for one of the equilibrium phases.
The sequence of calculations is as follows:
1) stability analysis is tested for a phase with overall
composition z ;
2) results of stability testing are used to initiate the
two-phase flash;
3) two-phase flash calculations are performed;
4) stability analysis of one of the equilibrium phases
(say, the liquid phase) from two-phase flash is
(13) tested;
1708 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
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5) results from step 3 and 4 are used to initiate the zi

xnpi  yi  ;
three-phase flash; X
np1

6) three-phase flash calculations are performed; 1 bj ((1=Kji )  1) (24)

7) one can check the results of three-phase flash by j1

testing the stability of equilibrium phases. There is i 1; nc

no need to test the stability of all phases, because
and the mol fractions of the remaining phases, xji ,
the points representing equilibrium phases must
i/1, nc, j/1, np/1 are obtained from Eq. (23).
have a common tangent plane, according to the
The gj functions are defined:
necessary condition of equilibrium.
X
nc
The TUNPEQ code is currently developed for three- gj (b) [xji (b)yi (b)]; j 1; np1 (25)
phase; extension to four-phase equilibria VLLL is being i1
investigated.
Taking into account that:
2.4. Initialization X
nc
xji 1; j 1; np (26)
i1
2.4.1. Initialization of phase splitting calculations
we obtain a set of np/1 equations with the
For the initialization of two-phase flash, the proce-
unknowns b1, b2, . . ., bnp1.
dure of Michelsen (1982b) is used here. Let us discuss
initiation of three-phase flash (Step 5). X
nc
 
(1=Kji  1)zi
The independent variables are the component mol gj (b) 0;
i1
X
np1
numbers for np/1 phases. From the stepwise approach 1 bj (1=Kji  1) (27)
we have component mol fractions from flash and j1
stability. We need the molar fractions of phases (mol j  1; np1
of phase j per mol of feed) b/(b1, . . ., bnp)T to calculate
the mol numbers of component i in phase j:
If the vapor phase disappears Eq. (27) cannot be
nji  bj xji ; i 1; nc; j 1; np (20)
applied; in this case, in a similar manner the
The problem is to find the phase distribution. This following set of equations is obtained:
can be achieved either by: (a) solving a non-linear X
nc
system of np/1 equations (the extension of the hj (b) [xji (b)x1i (b)]; j  2; np (28)
Rachford
/Rice equation to the multiphase case), or i1
(b) by solving an optimization problem.
and solved for the unknowns b2, . . ., bnp.
a) Extension of Rachford
/Rice equation to the multi- The nonlinear systems of Eqs. (27) and (28) can
phase case. be easily solved by a globally convergent Newton
The component material balance, Eq. (4), can be method (Press, Flannery, Teukolski & Vetterling,
written: 1989).
However, some problems may arise with vanish-
X
nc
ing phases during iterations. Bunz, Dohrn and
bj xji ni ; j 1; np (21) Prausnitz (1991) suggests that a three-phase flash
i1
should be performed only if the outcome of prior
with the overall material balance: single-phase tests and two-phase flashes indicates a
X
np three-phase distribution.
bj 1 (22) In order to avoid problems of disappearing
i1 phases during iterations for solving Eqs. (27) and
(28), we have chosen to be included in TUNPEQ the
The definition relationship for the equilibrium procedure described next.
constants is: b) The technique suggested by Michelsen (1994) for
calculation of phase distribution. The objective
yi 8 function Q is defined by Michelsen:
Kji   ji ; i 1; nc; j 1; np1 (23)
xji 8 npi
X
np X
nc
Q(b) bj  ni ln Ei (29)
j1 i1
By combining Eqs. (22)
/(24), the mol fraction of
the gas phase can be expressed as: where
 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
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X
np
bj 2.5. Convergence criteria
Ei  ; i 1; nc (30)
j1 8 ij
There are two stopping criteria for the minimization
and the fugacity coefficients are calculated using routine. The first is given by:
mol fractions provided by two-phase flash, and the (f n  f n1 )
mol fraction of the trial phase from stability analysis Bfactrepsmch (36)
of two-phase equilibrium liquid. max(½f n1 ½; ½f n ½; 1)
We have to solve an unconstrained optimization where epsmch is the machine precision (automatically
problem: generated by the code), factr is provided by the user to
Q(b) 0 min (31) get desired tolerance; here f denotes the objective
s:t: 05 bj 5 1 ; j 1; np (32) function.
The second criteria checks on the norm of projected
gradients:
The gradient vector is given by:
maxf½½projgri ½½; i  1; ng 5pgtol (37)
@Q X
nc
ni
1 ; j 1; np (33) We have set a high restrictive value for the tolerance
@bj i1 8 ij Ei pgtol (1.d-8) for all examples.
The Euclidean norm on fugacities is also recorded,
and a third additional criteria is set for flash calculations
The objective function is a convex function only
defined on the convex set b , therefore the minimum
of Q is unique. One can eliminate one variable from X
np X
nc 0:5
Eq. (22) and use np/1 independent variables in Eq. S (fji f1i )2 Bo (38)
(29), but it is more convenient to maintain the full j2 i1

set of equations (Michelsen, 1994).

We use the same solver (L-BFGS-B) to minimize
the objective function Q . Usually, few iterations are
required for convergence.

3. The Tunneling global optimization method

2.4.2. Initialization of stability analysis calculations
The initialization procedure for stability analysis, as
suggested by Michelsen (1982a), and by Sun and Seider
(1995), is based on the equations:
Yi zi Ki
zi
Yi 
Ki
where estimates for equilibrium constants are obtained
from the Wilson (1969) empirical relationship:
Ki pri exp[5:37(1vi )(1Tri1 )]
A slightly modified initialization is used in this work.
The composition of the trial phase is first estimated
from Eqs. (34a) and (34b). The normalized values of mol
fractions are then used to calculate the fugacities, then
with K -values from fugacities, corrected values of the
mol fractions follows from Eqs. (34a) and (34b).
Basically, this is equivalent to performing one SSI.
This initialization procedure brings the equilibrium
constants at more realistic (close) values. We designate
the initialization of being of Type L (for liquid stability
testing), or type V (for vapor stability testing), whether
Eqs. (34a) and (34b) is used.
The aim of the ‘global’ optimization method is to
track down the global minimum skipping every un-
wanted local minimum. In this work we test the benefits
of using a global optimization method called the
(34a) Tunneling method (Barron & Gomez, 1991; Levy &
Gomez, 1985; Levy & Montalvo, 1985) for the calcula-
(34b) tion of multiphase equilibria, and improving results
obtained using standard local methods.
This method has been designed to find the global
optimum of a general non-convex smooth function f,
and in this work the objective is to find the global
(35) solution xG of:
min f (x) (39)
xB
with B /{x jl 5/x 5/u }, f:Rn 0/R , x  /Rn , f  /C2, n being
the number of independent variables.
In this study the objective function f is either the TDP
function (for phase stability analysis), or the Gibbs free
energy (for phase splitting calculations).
It is necessary to use a global optimization method,
whose computational cost is affordable. The cost in this
context is determined by the number of times the
objective function has to be calculated, including its
gradient.
1710 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724
Fig. 1. The basic idea of the Tunneling method.
3.1. The global optimization method
The code that we are using in this work has recently
been developed (Castellanos & Gomez, 1998), and
incorporates the numerical experience obtained in recent
years (Gomez, Levy, & Calderon, 1987; Barron &
Gomez, 1991; Gomez & Romero, 1994). It has already
proven to be very efficient to solve highly difficult
problems, both academic and real (see for instance
Gomez et al., 1998; Gomez et al., 1999; Gomez et al.,
2001).
The basic idea of these methods (see Fig. 1) is to
‘tunnel’ from one valley of the objective function to
another, to be able to find a sequence of local minima
with decreasing function values:
f (x1 )]f (x2 )]. . .]f (xG )
where xG is the global minimum of f(x ), ignoring all the
local minima with larger objective function values than
the best already found. This characteristic of ‘ignoring’
minima makes the algorithm faster and more efficient
than other general purpose methods, like SA, random
search, clustering, and genetic algorithms (see Gomez et
al., 2001).
3.2. The Tunneling method
The Tunneling method has two phases. In the
minimization phase, starting from an initial point x0, a
local minimum x1 is found with f1 /f (x1), using any
local bounded optimization method. From x1 in phase 2
it obtains a feasible point x1 in another valley with
f(x1 )5/f1, which will be taken as the initial point for the
next minimization phase.
3.2.1. Minimization phase
The problem here is to find a local bounded mini-
mum:
Find xm  arg(min f (x))
xB
To perform the minimization phase any algorithm
designed to solve local optimization problems with
bounds on the variables can be used. We use a
limited-memory Quasi-Newton method (Zhu et al.,
1994; Byrd et al., 1995). Any favorite optimizer can
also be used.
3.2.2. Tunneling phase
Once a local minimum has been obtained, we want to
find a point in another valley, that is we need to solve
the following inequality problem:
Find xm  B such that f (x)5
m f (xm ) (42)
To accomplish this goal using gradient-type methods
(40) (Newton-like iterative algorithms), it is necessary to
destroy the minimum, placing a pole at the minimum
point xm, and then to start Tunneling (solving inequality
Eq. (42)), from an initial point near the minimum.
As we are trying to find a point xm in another valley
with less or equal value than fm , we first create the
Tunneling function Tp(x ), such that, if f(x )5/fm then
Tp(x )5/0, for x "/xm.

Tp (x) (f (x)f (xm ))P(x; lm ; xm ) if ½½xxm ½½51
Tp (x) f (x)f (xm ) if ½½xxm ½½]1
(43)
where, we have placed a pole P at xm using one of the
following alternatives:
1) Classical Tunneling function (Levy & Montalvo,
1985),
P(x; lm ; xm )½½xxm ½½lm (44)
2) Exponential Tunneling function (Barron & Gomez,
1991),
 
lm
P(x; lm ; xm )exp (45)
½½x  xm ½½
(41)
where lm is the strength of the pole.
 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724

Solving problem Eq. (44) now consists of finding xm
such that:
Tp (x)50 (46)
m
The role of lm is crucial for the algorithm. In the
classical method its value is an integer that depends on
the multiplicity of the minimum. In the exponential
method a small real value is enough to place a pole
destroying the minimum. However, if the minimum was
not computed exactly, for both methods in the direction
towards the exact minimum, a small value would not
create a pole, and a larger lm has to be used. Also,
increasing lm has the effect of smoothing the Tunneling
function, as it inherits the multimodality of the original
function f. Although in principle, it would be desirable
to take a large lm so that T does not have stationary
points, a large lm gives larger values of the Tunneling
function T further away from the solution to problem
Eq. (46). Thus, in practice, lm is computed just to
destroy the minimum, that is the strength of the pole lm
is computed so that a descent direction can be gener-
ated, and mobile poles are used whenever a stationary
point of T is encountered, as will be described in Section
3.4. The code TUNEL manages poles and mobile poles
automatically. For further details in the actual imple-
mentation, the reader is referred to Castellanos and
Gomez (1998).
We need to take descent directions to solve the
inequality Eq. (46), and thus we use the same algorithm
used to solve Eq. (41), with appropriate stopping
conditions to check convergence for Eq. (46).
As the original objective function f is a general
nonlinear function only assumed to belong to C2 for
x  /B , it could have many local and global minima and
convergence to minima at the same level is possible, that
is f (x1m*) /f(x2m*) /. . ./f (xtm*) as xtm* would be ac-
ceptable solutions of Eq. (46). In order to avoid cycling
and going back to these minima at the same level
already found, it is important to preserve the poles used
to destroy them, until a better minimum xt1 m * with
lower value of the objective function is found. To
achieve this goal it is necessary to modify the definition
of the Tunneling function:
 
Y t
lt
m
Te (x)(f (x)f (xm )) exp (47)
i1 ½½x  xt
m ½½
and making t/1 as soon as an xm is found with smaller
value than fm.
3.3. Initial point for the Tunneling phase
Once a local minimum xm has been found, we
generate an initial point x0m to start the Tunneling
process. This point is generated along a random
direction in a neighborhood of xm, to preserve local
1711
information. Then from this point, the local minimiza-
tion code will generate descent directions and step
lengths to force descend of the Tunneling function, until
it finds a point where inequality Eq. (46) is satisfied. It is
important to recall, that the random direction is only
used to produce the initial point in the neighborhood of
the local minimum xm, to be able to start from there, the
local descent method.
If Tunneling is not successful from there, we generate
a new initial point, until 2n (n being the dimension of
the problem) initial points have been tried. We then
generate initial points at random in the entire feasible
region, until the maximum number of function evalua-
tions (FE) given by the user, has been used. The
Tunneling search is not successful when:
. A corner of admissible region has been reached.
. The strength of the pole is greater than a maximum
value given, without having obtained a descent
direction.
. No further precision for x is possible.
. The maximum number of FE allowed for this phase
has been reached.
3.4. Stationary points of T (x )
The Tunneling function T inherits the non-convex
nature of the original objective function f. It is then
possible that during Tunneling phase we reach station-
ary points xs of the Tunneling function T (x ), that is
points where the gradient of T with respect to x is zero
(up to a tolerance). As we use a gradient type method to
find xm that satisfies Tp(xm)5/0, to be able to continue
the search we place mobile poles that we turn on and off,
and the Tunneling function is modified multiplying by
the mobile pole:
Tp (x) (f (x)
   
lm ls
f (xm ))exp exp (48)
½½x  xm ½½ ½½x  xs ½½
These poles are placed where the stationary point is
detected and while needed and we turn it off when the
iterand is out of the zone of attraction of the stationary
point (making ls /0).
3.5. General stopping conditions
To check for global optimality, either a lower bound
for the objective function is known and has been
attained or the search for the solution T (x )5/0 has to
be exhaustive.
In general the value of the objective function at the
global solution is not known, but when the global
solution has been found, there is not a point xm in
another valley with f(xm)5/f(xm). Consequently, the
1712 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724
algorithm has to spend some time checking for global
optimality, by performing unsuccessful Tunneling
searches, starting from all the initial points allowed.
The user decides then, how much computer effort he
wants to spend to check for global optimality through
the maximum number of initial points to start the
Tunneling phase, or through the maximum number of
FE.
The algorithm stops when any of the following global
criteria is satisfied:
. In the Tunneling phase the given maximum number
of initial points to start the search for xm has been
reached. The last minimum found is the putative
global minimum.
. The given maximum number of FE has been reached.
. The lower bound of the objective function given by
the user has been attained. The last minimum found
is the putative global minimum.
. All the global minima at the same level required by
the user have been found.
3.6. Features of the code
We have developed an in-house FORTRAN prototype
to perform the minimization iteration with calls to the
TUNPEQ code providing gradient information, calls to
the local optimizer and to the Tunneling module, in a
way giving to the user flexibility to design the numerical
experiments. Some of the options are:
1) The user can incorporate the local optimization
method more suitable for his problem. However, if
not decided otherwise, the Tunneling code uses a
Limited Memory Quasi-Newton Method.
2) The number of cycles min
/tun
/min, and/or the
maximum number of FE the user wants to spend in
the process.
3) The tolerances to control:
. The precision for the local optimization (see Eqs.
(36)
/(38)).
. the desired decrease in the objective function
imposed to the Tunneling phase. This can help
the user to force the code to search for another
valley with sufficiently lower objective function.
. The precision to find minima at the same level.
This can be interesting if a sufficiently good value
of the objective function has already been
attained, and the user is interested in finding
alternative solutions within certain range (/ or
/) of this objective value.
4) The number of tries from different initial points in
the Tunneling phase.
5) The code is programmed to save all the files
containing partial results at every local minimum
the method finds along the way. Reverse commu-
nication allows the user even to save every iteration
points within the local minimization (if the local
minimizer has also reverse communication).
4. Results
This section presents the results of phase stability
analysis and multiphase equilibria calculation for sev-
eral representative systems. The problems addressed
here are vapor
/liquid, liquid
/liquid, vapor
/liquid
/
liquid, vapor
/solid, liquid
/solid, and vapor
/liquid
/
solid calculations.
4.1. Stability analysis
The reliability of the phase stability testing module of
TUNPEQ is first investigated separately. We have
chosen a set of five examples from the literature, for
binary and ternary mixtures. These simple mixtures
exhibit several stationary points of the TPD function,
among them local minima and saddle points that may
attract the minimizer. TUNPEQ finds the global
minima of the TPD for all examples.
For all examples considered, both kinds of initial
estimates (V and L) are used. For some cases, initial
guesses other than those given by V or L initialization
are provided, in order to test the ability of our approach
to escape certain local minima that are not found with
the V or L initializations.
The following test examples (Eqs. (1)
/(5)) are ad-
dressed by Hua, Brennecke and Stadtherr (1998). For all
cases results are consistent with their results. The
problem of stability testing will be also addressed in
the next sections in a multiphase context.
4.1.1. Problem 1. Hydrogen sulfide
/methane binary
mixture
This is a mixture of methane and hydrogen sulfide at
T /190 K and p /40.53 bar. Calculations are per-
formed using the SRK EOS, with the BIC 0.08. This
example is taken from Michelsen (1982a), and it
represents a very difficult problem. Sun and Seider
(1995); Hua, Brennecke and Stadtherr (1998) have also
tested their proposed methods for stability analysis on
this example.
The TPD function is plotted in Fig. 2a versus the trial
phase composition for an equimolar mixture. Fig. 2b
provide a detail of the region between z1 /0.9 and 1. A
third branch corresponding to the intermediate Z -factor
root of the EOS, with a local minimum at z1 /0.968 is
disregarded here.
There are four stationary points, three minima and a
maximum corresponding to the trivial solution. The
global minimum corresponds to 0.9254 methane, and
has a negative value, indicating instability.
 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724 1713

For any initial guess comprised between z1 /0.5 and

Fig. 2. (a) TDP function for the methane
/hydrogen sulfide binary
mixture. (b) TPD function for the methane
/hydrogen sulfide binary
mixture (detail).
0.954, and between z1 /0.982 and 1, the global mini-
mum is found by the first minimization step. This is true
for the minimizer we use; for example, the Newton
/
Raphson algorithm will find the local minimum for
initial guesses z1 /0.98. The local minimum at 0.98 is
first found by the minimizer only for initial guesses
falling between z1 /0.954 and 0.982. For z1 B/0.5, the
local minimum at z1 /0.118 is first found. This is an
illustration of the fractal behavior of solution techniques
for solving the stationary point problem observed by
Green et al. (1993); Lucia et al. (1990). For the latter two
cases, after a tunnelization phase the second minimiza-
tion leads to the global minimum.
Two-phase VL split gives y1 /0.98 and x1 /0.11.
Stability analysis of these two feeds indicates again
instability. A liquid
/liquid phase split gives the correct
equilibrium state, consisting in two liquid phases with
x11 /0.92 and x21 /0.11, respectively. Stability analysis
of these two feeds gives positive or zero values of
minimum TPD.
Table 1 provides for different feed compositions: the
stationary points of the TPD function found by the
minimizer, the corresponding values of the objective
function, the number of FE, norms of projected
gradients at the solution, number of minimization
phases, and initial guesses. Note that in column 4
from Tables 1
/6 the number of FE required in the
minimization step is given in parenthesis. Type of
initialization is also given in the last column.
For this binary mixture, for all feeds considered, the
number of FE is less than half than the number of root
inclusion tests for FCSM, and one order of magnitude
less than F versions of the interval analysis method of
Hua et al. (1998).

Table 1
Problem 1: C1/H2S SRK-EOS at p 40.53 bar and T  190 K

Feed composition Stationary points of the TPD function Objective function FE NT Initial guess

(0.50, 0.50) (0.925382, 0.074618) 8.2521e2 696 (38) 1 L(0.982223, 0.017777)

/ (0.118133, 0.881867) 5.6893e2 647 (87) 2 V(0.070334, 0.929666)

/ (0.925382, 0.074618) 8.2521e2
/
/
/

/ (0.981559, 0.018441) 7.9352e2 853 (832) 2 *(0.955, 0.045)

/ (0.925382, 0.074618) 8.2521e2
/
/
/
(0.9885, 0.0115) (0.9885, 0.0115) 0 512 (6) 1 L(0.988860, 0.011140)

/ (0.9885, 0.0115) 0 581 (17) 1 V(0.432088, 0.567912)
(0.9813, 0.0187) (0.923314, 0.076686) 3.9565e3 645 (8) 1 L(0.982297, 0.017703)

/ (0.115208, 0.884792) 1.09098e2 693 (237) 2 V(0.214960, 0.785040)

/ (0.923314, 0.076686) 3.9565e3
/
/
/

/ (0.9813, 0.0187) 0 690 (4755) 2 *(0.97, 0.03)

/ (0.923314, 0.076686) 3.9565e3
/
/
/
(0.112, 0.888) (0.920821, 0.079179) 2.4623e3 630 (7) 1 L(0.937174, 0.062826)

/ (0.112, 0.888) 0 632 (85) 2 V(0.066633, 0.933367)

/ (0.920821, 0.079179) 2.4623e3
/
/
/
(0.11, 0.89) (0.919132, 0.080868) 5.6076e3 681 (76) 2 L(0.936020, 0.063980)

/ (0.11, 0.89) 0
/
/

/ (0.11, 0.89) 0 667 (8) 1 V(0.066010, 0.933990)
1714 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724

Table 2
Problem 2: C1/C3 SRKEOS at p 50 bar and T  277.6 K

Feed composition Stationary points of the TPD function Objective function FE NT Initial guess

(0.10, 0.90) (0.10, 0.90) 0 692 (9) 1 L(0.606896, 0.393104)

/
/ 0 637 (6) 1 V(0.093568, 0.996106)
(0.40, 0.60) (0.865478, 0.134522) 0.152987 864 (6) 1 L(0.879067, 0.120933)

/
/
/ 987 (13) 1 V(0.294238, 0.705762)
(0.60, 0.40) (0.192783, 0.807217) 0.2226 2369 (9) 1 L(0.784372, 0.215628)

/
/
/ 2417 (6) 1 V(0.171736, 0.828264)
(0.90, 0.10) (0.90, 0.10) 0 1060 (6) 1 L(0.909399, 0.090601)

/
/ 0 1023 (13) 1 V(0.387085, 0.612915)

4.1.2. Problem 2. Methane
/propane binary mixture
This is a mixture of methane and propane at T /
277.6 K. Calculations are performed with the SRK
EOS at p/50 bar (Table 2) and p /100 bar (Table 3).
The BIC is set at 0.029.
Feeds 2 and 3 at 100 bar are difficult problems
because of the near-criticality. Note the low absolute
values of the TPD function at the global minimum. The
method correctly predicts instability in both cases.
4.1.3. Problem 3. Ethane
/nitrogen binary mixture
This is a mixture of ethane and nitrogen at p /76 bar
and T /270 K. The PR EOS with k12 /0.08 is used.
Results are given in Table 4 for four feeds. Feed 2 is near
the bubble point locus and feed 3 is near the dewpoint
locus. With both L and V initial estimates, convergence
to the global minimum is observed. For the feed with
z1 /0.56, an extra initial guess is provided; for this case,
two minimization steps are required (the first finds the
trivial solution; after tunnelization, the second one
converge to the global minimum).
4.1.4. Problem 4. Carbon dioxide
/methane binary
mixture
This is a mixture of methane and carbon dioxide at
T /220 K and p/60.8 bar. The PR EOS is used with
k12 /0.095. Calculations are performed for five feeds.
For z1 /0.90 and 0.40 (see Table 5), the mixture is stable
vapor and liquid, respectively.
For z1 /0.80, the mixture is stable and close to the
dewpoint locus. The minimizer avoids the trivial solu-
tion for both initial estimates. For z1 /0.57 the mixture
is unstable and near the bubble point locus. For one of
initial estimates, two minimization phases are required.
4.1.5. Problem 5. Methane, ethane, and nitrogen ternary
mixture
This is a mixture of methane, ethane, and nitrogen at
T /270 K and p /76 bar. The PR EOS is used, with
k12 /0.021, k13 /0.038, k23 /0.08. Four feeds are
considered. Results are given in Table 6.
Feed 1 is unstable, and close to the dewpoint locus.
With V initialization the method converge to global
minimum. With L initialization it converge first to a
stationary point (close to the trivial solution), then the
second minimization converge to the global minimum.
Feed 2 is in the two-phase region and close to the critical
point. The correct answer is given by the method for
both initial estimates. Feed 3 is at near-critical condi-
tions, in the single-phase vapor region. Convergence of
the method to the trivial solution indicates stability.
Feed 4 is also stable; convergence to the trivial solution
is obtained.
For most of the problems considered in this section,
the number of FE is less then the number of root
inclusion tests (Hua et al., 1998) for the constrained
space plus monotonic interval extensions case (FCSM),
and up to one order of magnitude less than their F case.

Table 3
Problem 2: C1/C3 SRKEOS at p 100 bar and T  277.6 K

Feed composition Stationary points of the TPD function Objective function FE NT Initial guess

(0.40, 0.60) (0.40, 0.60) 0 592 (6) 1 L(0.426354, 0.573646)

/ (0.40, 0.60) 0 586 (6) 1 V(0.093997, 0.906003)
(0.68, 0.32) (0.68, 0.32) 0 1196 (137) 2 L(0.881459, 0.118541)

/ (0.772465, 0.227535) 3.346e4
/
/
/

/ (0.772465, 0.227535)
/ 1113 (7) 1 V(0.410751, 0.589249)
(0.73, 0.27) (0.650287, 0.349713) 2.948e4 1539 (9) 1 L(0.881402, 0.118598)

/ (0.757048, 0.242952) 2.081e5 1473 (915) 2 V(0.411153, 0.588847)

/ (0.650287, 0.349713) 2.948e4
/
/
/
(0.90, 0.10) (0.90, 0.10) 0 1214 (7) 1 L(0.921832, 0.078168)

/ (0.90, 0.10) 0 1259 (11) 1 V(0.530911, 0.469089)
 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724 1715

Table 4
Problem 3: C2/N2 PREOS at P 76 bar and T  270 K

Feed composition Stationary points of the TPD function Objective function FE NT Initial guess

(0.90, 0.10) (0.90, 0.10) 0 1033 (7) 1 L(0.505716, 0.494284)

/
/ 0 1167 (7) 1 V(0.920178, 0.079822)
(0.82, 0.18) (0.505590, 0.494410) 9.746e3 1048 (10) 1 L(0.381899, 0.618101)

/
/
/ 1092 (8) 1 V(0.884377, 0.115623)
(0.70, 0.30) (0.510582, 0.489418) 1.379e2 1247 (12) 1 L(0.370731, 0.629269)

/
/
/ 1282 (8) 1 V(0.883679, 0.116321)
(0.56, 0.44) (0.845281, 0.154719) 1.553e2 1502 (7) 1 L(0.381497, 0.618503)

/
/
/ 1318 (7) 1 V(0.888463, 0.111537)

/ (0.56, 0.44) 0 1329 (86) 2 *(0.5, 0.5)

/ (0.845281, 0.154719) 1.553e2
/
/
/
(0.40, 0.60) (0.40, 0.60) 0 1469 (6) 1 L(0.305497, 0.694503)

/
/ 0 1524 (9) 1 V(0.845406, 0.154594)

The number of initial points in the Tunneling phase was
set to 20 for all examples; same results would be
obtained with much less computer time for less initial
points. Note that for Eqs. (2)
/(5) results are also
consistent with results from Prausnitz, Lichtenthaler
and Gomez de Azevedo (1986).
4.2. Two-phase vapor
/liquid equilibria
Two-phase vapor
/liquid equilibria calculations were
carried out for two hydrocarbon mixtures, with empha-
sis to the near-critical region.
4.2.1. The Yarborough 8 mixture
Two-phase vapor
/liquid equilibria calculation were
performed with the Tunneling method for a synthetic
mixture of six normal-alkanes (feed mol fractions:
0.8097 C1, 0.0566 C2, 0.0306 C3, 0.0457 nC5, 0.033
nC7, 0.0244 nC10), referred in the literature as the Y8
mixture (Yarborough, 1972). The Peng
/Robinson EOS
is used, with all BIC’s zero.
The phase envelope is given in Fig. 3. Saturation
pressures were calculated with the MVNR method,
using PX iterations for dewpoints, and PY iterations
for bubblepoints (Fussell & Yanosik, 1978). The critical
point temperature (293.78 K) and pressure (210.668 bar)
were calculated based on Heidemann and Khalil (1980)
criteria, using a different solution procedure (Nichita,
Minescu, & Cretu, 1996; Nichita, 1996).
To decide whether one or two phases exists at
equilibrium, one can perform stability analysis. If
TPD B/0 results from stability are used to initiate flash.
If flash calculations are carried out in the single-phase
region, the two-phase code returns the trivial solution.
Intensive testing has shown that both approaches give
the correct answer, even for the most difficult points.
Equilibrium constants obtained from flash calcula-
tions on the critical isotherm are presented in Fig. 4. In
the immediate vicinity of the critical point (for pressures
between about 210.66 bar and the critical pressure), our
method has no problems in finding the correct solution.
For these conditions, the convergence radius of the
classical MVNR method is extremely small, therefore,
the switch from SSI to MVNR iterations has to be
performed at very small values of the Euclidean norm of
the error vector, otherwise divergence occurs.

Table 5
Problem 4: C1/CO2 PREOS at p 60.8 bar and T  220 K

Feed composition Stationary points of the TPD function Objective function FE NT Initial guess

(0.90, 0.10) (0.90, 0.10) 0 1063 (6) 1 L(0.908073, 0.091927)

/
/ 0 1125 (10) 1 V(0.541701, 0.458299)
(0.80, 0.20) (0.502644, 0.497356) 7.427e3 1739 (8) 1 L(0.838722, 0.161278)

/
/
/ 1831 (6) 1 V(0.270924, 0.729076)
(0.70, 0.30) (0.642304, 0.357696) 1.876e4 1353 (85) 2 V(0.237605, 0.762395)

/ (0.815263, 0.184737) 7.003e3
/
/
/

/ (0.815263, 0.184737) 7.003e3 1301 (7) 1 L(0.845278, 0.154722)
(0.57, 0.43) (0.57, 0.43) 0 1284 (75) 2 V(0.205001, 0.794999)

/ (0.808873, 0.191127) 1.3098e3
/
/
/

/ (0.808873, 0.191127) 1364 (7) 1 L(0.839429, 0.160571)
(0.40, 0.60) (0.40, 0.60) 0 1836 (9) 1 V(0.171840, 0.828160)

/ (0.40, 0.60) 0 1711 (8) 1 L(0.819257, 0.180743)
1716 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724

Table 6
Problem 5 C1/C2/N2 PREOS at p 76 bar and T 270 K

Feed composition Stationary points of the TPD functiona Objective function FE NT Initial guessa

(0.10, 0.60, 0.30) (0.101617, 0.586727) 5.88659e6 3079 (1814) 2 L(0.118613, 0.380627)

/ (0.067797, 0.799168) 1.48288e2
/
/
/

/
/
/ 3474 (12) 1 V(0.055818, 0.853433)
(0.30, 0.55, 0.15) (0.245094, 0.658130) 0.011746 4831 (16) 1 L(0.373190, 0.360265)

/
/
/ 4779 (13) 1 V(0.181211, 0.766340)
(0.38, 0.54, 0.08) (0.38, 0.54) 0 2929 (18) 1 L(0.491972, 0.356744)

/
/ 0 3006 (39) 1 V(0.242737, 0.725904)
(0.05, 0.90, 0.05) (0.05, 0.90) 0 4717 (19) 1 L(0.121698, 0.611101)

/
/ 0 4727 (11) 1 V(0.045620, 0.912190)
a
x1, x2.

unstable for these conditions (TPD //6.914e/5).

Using L initialization, only one minimization is re-
quired. For V initialization, a local minimum with
TPD //4.008e/5 is first found. A second minimiza-
tion finds the global solution. Compositions for the two
minima are close to the equilibrium liquid and vapor
phases. The two-phase flash gives L /0.534; the solu-
tion (Euclidean norm on fugacities of 4.3e/7) is found
with only 43 FE. The results are consistent with those
obtained for this mixture by Nagarajan et al. (1991);
Sun and Seider (1995). PR EOS has been used in
calculations, with BIC’s and properties of the two heavy
pseudocomponents as given by Nagarajan et al. (1991).

Fig. 3. Phase envelope of Y8 system. 4.3. Three-phase vapor
/liquid
/liquid equilibria

4.3.1. Ternary mixture CO2/C1/n C16

The first example for VLL calculations is for a ternary
mixture containing carbon dioxide, with methane and
normal-hexadecane in equimolar participation. At low
temperatures this mixture presents three-phase VLL
equilibria, and exhibit a Type II phase behavior
according to Orr, Yu and Lien (1980).
The PR EOS is used with BIC’s: kC1
C16 /0.078, kC1

/ /

CO2 /0.100, and kCO2
C16 /0.125 (from Pan & Firoo-
/

zabadi, 1998). Fig. 5 depicts the calculated amount of

Fig. 4. Equilibrium constants for the Y8 system on the critical
isotherm.
4.2.2. Eight-component mixture
Calculations have been performed for the eight-
component mixture of Nagarayan, Cullik and Griewank
(1991) at near critical conditions (T /353 K, p /385
bar). Results are given in Table 7.
For phase stability analysis of the feed, using both
initial estimates, the method finds the mixture to be
phases versus pressure for a 90% carbon dioxide mixture
at T /294.3 K. A three-phase region exists at this
temperature between a lower consolute pressure of 64.07
bar and an upper consolute pressure of 69.45 bar.
Results are in excellent agreement with results presented
by Risnes and Dalen (1984), using SSI and by Pan and
Firoozabadi (1998), using SA.
Table 8 presents the results (mol fractions) of VLLE
calculations for these conditions. Results of stability of
the feed (TPD//0.1663), two-phase flash, and stabi-
lity of the equilibrium liquid from two-phase flash
(TPD//0.0097) are also given in Table 8. One can
notice that good initial estimates were available for the
VLL flash.
 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724 1717

Table 7
Stability testing and two-phase flash for the eight component mixture

Component Feed composition Stability Two-phase flash

Mol fractions of trial phase Vapor mol fraction Liquid mol fraction
a
Type V initialization Type L initialization

C1 0.6883 0.6532 0.7298 0.7177 0.6628

C2 0.0914 0.0902 0.0917 0.0920 0.0909
C3 0.0460 0.0471 0.0438 0.0447 0.0471
n C4 0.0333 0.0351 0.0304 0.0315 0.0349
n C5 0.0139 0.0150 0.0123 0.0128 0.0148
n C6 0.0152 0.0170 0.0131 0.0138 0.0164
C7-16 0.0896 0.1077 0.0677 0.0741 0.1032
C17 0.0222 0.0349 0.0112 0.0133 0.0299
a
Local minimum found by first minimization.

Fig. 5. Phase distribution of the ternary system CO2/C1/n C16 at T / Fig. 6. Detail of the p
/z phase diagram of the ternary system CO2/C1/
294.3 K. n C16 at T/294.3 K.

Three-phase distribution calculated with Michelsen
(1994) procedure, using fugacities calculated for mol
fractions from stability, is: V /0.2466, L1 /0.6105,
L2 /0.1429. Phase distribution from three-phase VLL
flash is: V /0.2962, L1 /0.5645, L2 /0.1393.
A detail of the p
/z phase envelope at T /294.3 K is
presented in Fig. 6, showing lower and upper consolute
pressures and critical points. Critical points are located
at 73.5 and 99.5% CO2. Construction of Fig. 6 does not
require three-phase VLLE calculations. For a given CO2
mol fraction, once a phase boundary is located, extra-
polation of TPD (for stability testing of liquid phase
resulting from two-phase flash) from three-phase region
gives a good approximation, then the exact pressure is
refined to the desired accuracy.
4.3.2. A sour gas system
The second example for VLLE is for the six compo-
nent synthetic mixture of Robinson et al. (1978), which
exhibits a three-phase region at T /178.8 K for a wide
pressure range. Feed composition is given in Table 9.
Peng
/Robinson EOS is used, with BIC’s from Pan and

Table 8
Results for CO2/C1/n C16 system at p 67 bar and T 294.3 K

Component Feed stability Two-phase flash stability Three-phase flash

a a
Z x y x x y x1 x2

C1 0.05 0.040511 0.050832 0.044778 0.099791 0.078112 0.036181 0.038707

n C16 0.05 0.466839 0.004166 0.337496 0.000048 0.000069 0.340224 0.004609
CO2 0.90 0.492650 0.945002 0.617726 0.900161 0.921819 0.623595 0.956683
a
Trial phase composition.
1718 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724

Table 9 Firoozabadi (1998) shown in Table 10. This is a difficult

Calculated mol fractions for the sour gas system at T  178.8 K, problem due to the very small amounts in the hydrogen
p 21.9 bar
sulfide-rich phase.
Component Feed composi- Phase mol fractions Calculated phase mol fractions at p /21.9 bar are
tion given in Table 9. The mol percent of different phases
HC-rich li- Vapor H2S-rich li- versus pressure are plotted in Fig. 7.
quid quid For most of the points, the global minimum is found
C1 0.70592 0.5282 0.8577 0.0666 by the first minimization. However, local minima are
C2 0.06860 0.1598 0.0113 0.0261 found for both stability and flash calculations. For flash
C3 0.02967 0.0760 0.0006 0.0075 calculations, local mimima are found only in the
H2S 0.10559 0.1879 0.0094 0.8688 immediate vicinity of the consolute pressures.
CO2 0.01996 0.0371 0.0082 0.0304
N2 0.07026 0.0110 0.1129 0.0006
For example, stability of the liquid phase from two-
phase flash at p /30 bar: there are two local minima,
one nontrivial with positive TPD, and one trivial (both
wrongly indicating a stable phase). The convergence to
Table 10 the global minimum corresponding to a negative value
BIC for the sour gas system of TPD is achieved by the third minimization phase, and
Component C2 C3 H2S CO2 N2
then the system is correctly asserted as being in three-
phase VLL state (third tunnelization).
kC j 0.000 0.000 0.100 0.125 0.031 Calculation results at p/35 bar are given in Table 11.
1
kC j
/ 0.000 0.080 0.135 0.042 The TPD for two-phase flash liquid composition is /
2
kC j
/
/ 0.080 0.150 0.091
3
kH Sj
/
/
/ 0.120 0.200
0.0185, indicating a three-phase state. The phase dis-
2
KCO j
/
/
/
/ 0.020 tribution resulting from three-phase VLLE flash is V /
2
0.0407, L1 /0.9447, and L2 /0.0146.

4.3.3. Quaternary mixture C1/n C6/H2S/CO2

The third example for VLLE presents the results for
the quaternary mixture studied by Kohse and Heide-
mann (1992). Same input data and version of the SRK
EOS (Graboski & Daubert, 1978) were used. BIC’s are
given in Table 12. Three-phase flash calculations were
performed at T /175 K and p /15 bar (Table 13). For
these conditions, our results correspond to the global

Table 12
BIC for the quaternary system

Component C6 H2S CO2

kC1-j 0.036 0.080 0.093

kC6-j
/ 0.050 0.118
kH2S-j
/
/ 0.099
Fig. 7. Phase distribution for the sour-gas system at T /178.8 K.

Table 11
Results for the sour gas system at p 35 bar and T 178.8 K

Component Feed Stability Two-phase flash Stability Three-phase flash

z x
y x x y x1 x2

C1 0.70592 0.060303 0.715787 0.064426 0.705964 0.726129 0.714973 0.065262

C2 0.06860 0.011263 0.069469 0.012099 0.006233 0.006352 0.072154 0.012393
C3 0.02967 0.003438 0.030069 0.003697 0.000489 0.000466 0.031333 0.003738
H2S 0.10559 0.904991 0.093383 0.899205 0.008382 0.008596 0.097494 0.897742
CO2 0.01996 0.018229 0.019979 0.018734 0.004765 0.004933 0.020621 0.019166
N2 0.07026 0.001776 0.071312 0.001839 0.274167 0.253524 0.063425 0.001699
 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724 1719

Table 13
Results for the quaternary system at p 15 bar and T  175 K

Component Feed Stability Two-phase flash Stability Three-phase flash

z x
y x x y x1 x2

C1 0.50000 0.082317 0.979116 0.118005 0.286047 0.977599 0.308646 0.068425

n C6 0.02627 0.001380 0.000001 0.047214 0.349603 0.000001 0.227252 0.007764
H2S 0.41633 0.878809 0.007984 0.741901 0.293955 0.007900 0.363484 0.833419
CO2 0.05740 0.037836 0.012899 0.092880 0.070395 0.014499 0.100618 0.090391

minimum found by Sun and Seider (1995), with the
phase distribution: V /0.4482, L1 /0.1002, L2 /
0.4516.
At T /200 K and p/42.5 bar the system splits into
two phases, with L /0.6741. Stability analysis of the
liquid phase finds TPD /0. Same results were obtained
by Sun and Seider (1995). At slightly different condi-
tions (T/199 K and the same pressure), the equilibrium
state is three-phase VLL. These are particularly difficult
conditions for this system, in the vicinity of a two-phase
liquid
/liquid critical point located on the three-phase
boundary. The results are presented in Table 14. The
extent of the three-phase region for p /42.5 bar is about
5 K.
4.4. Three-phase vapor
/liquid
/solid equilibria
Wax precipitation from hydrocarbon mixtures is an
important problem for the oil industry, which implies
vapor
/liquid
/solid equilibria calculations. Two exam-
ples, including vapor
/liquid
/solid equilibria, vapor
/
solid, and liquid
/solid equilibria for wax precipitation
are presented, one for a synthetic gas-condensate, the
other for a North Sea crude oil (at Stock-Tank and
reservoir conditions).
4.4.1. The SHF4 mixture
The first example is a synthetic gas condensate fluid of
Ungerer et al. (1995), designated by the acronym SHF4
(Synthetic Hyperbaric Fluid), containing seven compo-
nents. The thermodynamic multisolid model for wax
precipitation from hydrocarbon mixtures of Nichita et
al. (1999) is used. BIC’s used with the PR EOS are given
in Table 15.
The p
/T phase diagram of this mixture is given in
Fig. 8, showing the vapor
/liquid and vapor
/solid phase
boundaries as well as the vapor
/liquid
/solid/vapor
/
solid and vapor
/liquid
/solid/vapor
/liquid phase
boundaries. Results are identical with the results ob-
tained with the SA method (Nichita et al., 2001).
Construction of the phase envelope does not require
carrying out three-phase VLS calculations.
For a multisolid model, the condition of solid stability
as a pure phase is obtained from Eq. (12) (Firoozabadi,
1998):
S
fi (p; T; z)fpure; i ]0; i 1; ns (49)
where ns is the number of components that may
precipitate.
This relationship is used to locate the V/VS phase
boundary (cloud point locus); it is also used to locate the
VL/VLS phase boundary, for z/x, where, x is the
liquid mol fraction resulted from the two-phase VL
flash.
For several conditions, local minima are observed
near the VL/VLS and V/VS phase boundaries. Table 16
gives the results obtained with the Tunneling method for
some of the points considered for the construction of the
phase diagram by Nichita, Goual and Firoozabadi,
2001. The total number of FE is reported, including
those required by the tunnelization phases. The number
of FE for the minimization step(s) is given in parenth-
esis. The computational effort required by the SA
algorithm is also given for comparison. For all points,

Table 14
Results for the quaternary system at p 42.5 bar and T  199 K

Component Feed Stability Two-phase flash Stability Three-phase flash

z x y x x y x1 x2

C1 0.50000 0.961720 0.956278 0.289556 0.244579 0.956229 0.331272 0.250611

n C6 0.02627 0.000023 0.000021 0.038376 0.029114 0.000021 0.046211 0.030348
H2S 0.41633 0.024470 0.025186 0.596733 0.653089 0.025179 0.545958 0.645240
CO2 0.05740 0.013787 0.018515 0.075334 0.073218 0.018571 0.076560 0.073801
1720 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724

Table 15
BIC for the SHF4 mixture

Component C2 C3 C7H8 n C8 n C16 n C36

kC j 0.0000 0.0384 0.0439 0.0475 0.0658 0.0960

1
kC j
/ 0.0417 0.0000 0.0358 0.0242 0.0050
2
kC j
/
/ 0.0000 0.0221 0.0104 0.0188
3
kC H8j
/
/
/ 0.0000 0.0000 0.0000
7
Kn C j
/
/
/
/ 0.0002 0.0294
8
Kn C j
/
/
/
/
/ 0.0172
16

Fig. 9. Phase compositions of SHF4 fluid at p/400 bar.

Fig. 8. Phase diagram of the SHF4 fluid.
TUNPEQ is at least one order of magnitude faster than
SA.
These minima are not a problem for the SA algorithm
if some code parameters are properly set (Pan &
Firoozabadi, 1998), but a local minimizer can be
attracted (this is the case of L-BFGS-B as shown in
Table 16). TUNPEQ is able to escape and finally finds
the global minimum. Results are identical with the
results obtained with SA.
As expected, only the heavy hydrocarbon component
(normal-hexatriacontane) precipitates. The variation of
the amount of precipitated solid and the molar fraction
of the liquid and vapor phases at p/400 bar are
illustrated in Fig. 9. A narrow three-phase region from
328 to 333 K exists at this pressure.

Table 16
VLS equilibria for SHF4 mixture

T (K), p (bar) conditions Equilibrium state Gibbs free energy function FE SA FE TUNPEQ Tunneling phases

332, 600 VS 9.220000 130 201 4869 (15) 1

335, 400
/ 8.683763
/
/
/

/ VL 8.677826 270 201 20 181 (7916) 2
333, 400 VL 8.659164 268 801 20 178 (62) 1
332, 400 VLS 8.649628 268 801 21 024 (67) 1
331, 400 VLS 8.645886
/
/
/

/
/ 8.639555 273 001 28 527 (7223) 2
330, 400 8.635533
/
/
/

/ VLS 8.629042 266 001 26 333 (6613) 2
329.5, 400 VLS 8.623662 463 401 25 895 (92) 1
329, 400 8.624830
/
/
/

/ VLS 8.618213 378 001 13 196 (130103) 2
328.5, 400 VS 8.612708 263 201 14 596 (63) 1
328, 400 VS 8.607162 267 401 12 613 (53) 1
326, 400 VS 8.584619 263 201 13 821 (50) 1
325, 400 8.580098
/
/
/

/ VS 8.573146 266 001 12 265 (4358) 2
320, 400 VS 8.513939
/ 11 945 (58) 1
 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724 1721

Fig. 10. Retrograde solid behavior and liquid dropout at T/330 K

for SHF4 fluid.

Table 17
Composition of crude oil 2

Component Stock-Tank oil Reservoir fluid

N2
/ 0.00225
CO2
/ 0.01365
C1
/ 0.51283
C2 0.00087 0.07344
C3 0.00536 0.04430
i C4 0.00301 0.00755
n C4 0.01240 0.02037
i C5 0.01008 0.00772
n C5 0.01730 0.01097 Fig. 11. (a) Wax precipitation from Oil 2 at Stock-Tank conditions.
C6 0.03701 0.01967 (b) Wax precipitation from Oil 2 at reservoir conditions.
C7 0.08213 0.02524
C8 0.10623 0.03456
C9 0.06672 0.02101 bar, respectively. Results are given for both the multi-
C10 0.65888 0.20644 solid (MS) and ideal solid solution (SS) models.
The number of FE for TUNPEQ (including the
Tunneling phase for checking global optimality) is one
The retrograde solid behavior (reported by Nichita et order of magnitude less than for SA. The conditions for
al., 2001) may imply the increase in the amount of the this example are not difficult conditions, but what
precipitated solids with decreasing pressure at constant makes it interesting is that the mixture is described
temperature. Fig. 10 shows the calculated isothermal with a large components number (37). If only the
expansion of fluid SHF4. At T /330 K the amount of minimization step is used, only 15
/47 FE were required
the precipitated solid decreases from about 13% (at the by L-BFGS-B to find the solution.
three-phase dewpoint) to 3% (at p /185 bar). With Wax precipitation is a major problem for the oil
further pressure decrease the precipitation increases at industry, because wax deposition may plug the flow
an increasing rate to over 15 wt.% at atmospheric lines. We believe such a code would be extremely
pressure. valuable for the industry. For wax precipitation from
crude oils, it is very important that the heavy fractions
distribution between species (paraffins, naphthenes, and
4.4.2. Wax precipitation from a north sea crude oil aromatics) is taken into account; this may lead to very
The second example deals with wax precipitation large number of components. The code has proved to be
from a crude oil. The composition of the Oil 2 (Stock- able to handle such problems.
Tank and reservoir fluid, see Table 17) as well as the
characterization of the plus fraction is given by Pan,
Firoozabadi and Fotland (1997). Again, the thermo- 5. Some considerations on computational efficiency
dynamic model, component properties, and BIC’s from
Nichita et al. (2001) are used. Whenever data were available in the literature or
Fig. 11a and b show the calculated amount of software was available for other methods, comparison is
precipitated wax versus temperature at p /1 and 120 given in terms of the number of FE. Some authors
1722 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724
reports CPU time, but a comparison cannot be made
because one should have the same hardware support.
For the limited data we had, the Tunneling method has
shown to be faster than other global optimization
methods reported in the literature, for similar test
problems.
TUNPEQ is definitely more efficient than SA. For
phase stability analysis, it is more efficient than the
Enhanced-Newton-Interval method. It is expected to be
more efficient than branch and bound and homotopy
continuation methods. It would be very useful to test
TUNPEQ against MULPEQ, HOMPEQ, GLOPEQ,
etc. Further investigation of TUNPEQ efficiency is
needed.
A feature of our code is that the user may decide how
much computer time is to be spent on checking
globality. This depends on the particular problem to
be solved, mainly on how far we are from difficult
regions of the phase envelope. More initial points for the
Tunneling phase means more confidence, but also more
computer time. It is, however, essential to keep relia-
bility by making meanwhile a particular run as efficient
as possible.
We have already embarked, or intend to embark on
the following directions:
i) a systematic comparison of the efficiency of TUN-
PEQ with other global optimization methods used
for multiphase equilibria calculations;
ii) development of the code to be able to handle more
than two liquid phases;
iii) since the approach is model independent, the use of
different thermodynamic models will be investi-
gated;
iv) testing the behavior of the method for a wider set of
phase equilibria problems.
The major feature of the method is its reliability.
There is no guarantee that a method would work for
every problem without failure, but so far we have not
experienced any failures with TUNPEQ. Therefore, our
approach is recommended for use as a powerful
diagnostic tool for reservoir compositional simulation
and process design models.
6. Conclusions
. A global optimization method has been developed for
multiphase equilibrium calculations (stability analysis
and phase splitting), and successfully tested for
various kinds of phase equilibria problems, both
hypothetical and real.
. In many of the addressed problems, several local
minima have been found, showing the need for global
optimization approaches.
. The global optimization Tunneling method used here
has shown to be a robust and efficient tool to solve
phase equilibrium problems even for extremely diffi-
cult cases, like calculations at critical points and in
the vicinity of the phase boundaries.
. The method checks global optimality, to be sure that
there is not a better solution and this checking is the
most expensive part of the algorithm. However, the
user can decide on the CPU effort spent for this
globality check.
. If only local optimization is performed, the results
show that the efficiency is comparable with classical
methods based on the equality of chemical potentials.
. The method has shown to be faster than other global
optimization methods reported in the literature, for
similar test problems.
. Our approach can be used as a powerful diagnostic
tool for reservoir compositional simulation and
process design models.
. The method is general and model independent
although an EOS formulation is used here for the
Gibbs free energy, any other thermodynamic model
can be used for various kinds of thermodynamic
equilibria.
Acknowledgements
Partial support for this work was provided by IIMAS,
Intercambio Academico, and project PAPIIT No.
IN11299, UNAM. Partial support from SNP Petrom
SA and the permission to publish this paper are greatly
appreciated. We thanks Dr Bruce Kohse of CMG for
providing the same input data as used by Kohse and
Heidemann (1992) for the quaternary system in example
Section 4.3.3.
References
Baker, L. E., Pierce, A. C. & Luks, K. D. (1982). Gibbs energy analysis
of phase equilibria , pp. 731
/742). SPE Journal .
Barron, C., & Gomez, S. (1991). The exponential Tunneling method,
Technical Report , IIMAS, vol . 1, No. 3.
Bullard, L. G. & Biegler, L. T. (1993). Iterated linear programming
strategies for non-smooth simulation: a penalty based method for
vapor
/liquid equilibrium applications. Computers and Chemical
Engineering 17 (1), 95
/109.
Bunz, A. P., Dohrn, R. & Prausnitz, J. M. (1991). Three-phase flash
calculations for multicomponent systems. Computers and Chemical
Engineering 15 (1), 47
/51.
Byrd, R. H., Lu, P., Nocedal, J. & Zhu, C. (1995). A limited memory
algorithm for bound constrained optimization. SIAM Journal of
Science and Computers 16 , 1190
/1208.
Castellanos, L., & Gomez, S. (1998). An implementation of the
Tunneling methods for bound constrained global optimization,
Tehnical Report , IIMAS.
Coats, K. H. (1985). Simulation of gas condensate reservoir perfor-
mance , pp. 1870
/1885). Journal of Petroleum .
 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724
Corana, A., Marchesi, M., Martini, C. & Ridella, S. (1987). Minimiz-
ing multimodal functions of continuous variables with the ‘Simu-
lated Annealing Algorithm’. ACM Transactions on Mathematical
Software 13 , 265
/274.
DeGance, A. E. (1993). Ab initio equation of state phase equilibria
computations via path continuation. Fluid Phase Equilibria 89 ,
303
/334.
Eubank, P. T., Elhassan, A. E., Barrufet, M. A. & Whiting, W. B.
(1992). Area method for prediction of fluid phase equilibria.
Industrial Engineering and Chemical Research 31 , 942
/949.
Firoozabadi, A. (1998). Thermodynamics of hydrocarbon reservoirs .
McGraw-Hill.
Fussel, L. T. (1979). A technique for calculating multiphase equilibria ,
pp. 203
/210). SPE Journal .
Fussell, D. D. & Yanosik, J. L. (1978). An iterative sequence for phase
equilibria calculations incorporating the Redlich
/Kwong equation
of state , pp. 173
/182). SPE Jounal .
Gibbs, J.W. (1873). A method of geometrical representation of the
thermodynamic properties of substances by mean of surfaces.
Trans. Conn. Acad. 2.
Gomez, S. & Romero, D. (1994). Two global methods for molecular
geometry optimization. In Progress in mathematics , vol. 121, pp.
503
/509). Birkhauser.
Gomez, S., Levy, A. V. & Calderon, A. (1987). A global zero residual
least squares method. In Lecture notes in mathematics , vol. 1230,
pp. 1
/10). Springer.
Gomez, S., Keeping, B. & Pantelides, C. (1998). Tunneling methods for
the time optimal control of high dimensional systems, manuscript .
London: Imperial College.
Gomez, S., Gosselin, O. & Barker, J. W. (2001). Gradient-based
history */matching with a global optimization method, paper SPE
71307 , pp. 200
/208). SPE Journal .
Gomez, S., Solano, J., Castellanos, L. & Quintana, M. I. (2001).
Tunneling and genetic algorithms for global optimization, ad-
vances in convex analysis and global optimization . Kluwer
Academic Publishers.
Graboski, M.S., & Daubert, T.W. (1978). A modified Soave equation
of state for phase equilibrium calculations IEC PDD, vol . 17, No.
4, 1. Hydrocarbon Systems (pp. 443
/448); 2. Systems Containing
CO2 , H2 S, N2 , and CO (pp. 448
/454).
Green, K. A., Zhou, S. & Luks, K. D. (1993). The fractal response of
robust solution techniques to the stationary point problem. Fluid
Phase Equilibria 84 , 49
/78.
Han, G. & Rangaiah, G. P. (1997). A method for calculation of
vapor
/liquid and liquid
/liquid equilibria. Computers and Chemi-
cal Engineering 21 (8), 905
/913.
Heidemann, R. A. & Khalil, A. M. (1980). The calculation of critical
points. American Institute of Chemical Engineering Journal 26 ,
770
/778.
Hua, J. Z., Brennecke, J. F. & Stadtherr, M. A. (1996). Reliable
prediction of phase stability using an interval Newton method.
Fluid Phase Equilibria 116 , 52
/59.
Hua, J. Z., Brennecke, J. F. & Stadtherr, M. A. (1998). Enhanced
interval analysis for phase stability: cubic equation of state models.
Industrial Engineering and Chemical Research 37 , 1519
/1527.
Hua, J. Z., Maier, R. W., Tessier, S. R., Brennecke, J. F. & Stadtherr,
M. A. (1999). Interval analysis for thermodynamic calculations in
process design: a novel and completely reliable approach. Fluid
Phase Equilibria 158 , 607
/615.
Kohse, B. F. & Heidemann, R. A. (1992). Tricritical lines and
multiphase equilibria in quaternary mixtures. Fluid Phase Equili-
bria 75 , 11
/22.
Levy, A. V. & Gomez, S. (1985). The Tunneling method applied to
global optimization. In P. T. Boggs, R. H. Byrd & R. B. Schnabel
(Eds.), Numerical optimization , pp. 213
/244). SIAM.
Levy, A.V., & Montalvo, A. (1985). The Tunneling method for global
optimization. SIAM Science and Computers .
1723
Lucia, A., Guo, X., Richey, P. J. & Derebail, R. (1990). Simple process
equations, fixed-point methods, and chaos. American Institue of
Chemical Engineering Journal 36 , 641
/654.
McDonald, C. M. & Floudas, C. A. (1995). Global optimization and
analysis for the Gibbs free energy function using the UNIFAC,
Wilson, and ASOG equations. Industrial Engineering and Chemical
Research 34 , 1674
/1687.
McDonald, C. M. & Floudas, C. A. (1995). Global optimization for
the phase and chemical equilibrium problem: application to the
NRTL equation. Computers and Chemical Engineering 19 (11),
1111
/1139.
McDonald, C. M. & Floudas, C. A. (1995). Global optimization for
the phase stability problem. Thermodynamics 41 , 1798
/1814.
McDonald, C. M. & Floudas, C. A. (1997). GLOPEQ: a new
computational tool for the phase and chemical equilibrium
problem. Computers and Chemical Engineering 21 (1), 1
/23.
Mehra, R. K., Heidemann, R. A. & Aziz, K. (1982). Computation of
multiphase equilibrium for compositional simulation , pp. 61
/68).
SPE Journal .
Michelsen, M. L. (1982). The isothermal flash problem. Part I.
Stability. Fluid Phase Equilibria 9 , 1
/19.
Michelsen, M. L. (1982). The isothermal flash problem. Part II. Phase
splitting. Fluid Phase Equilibria 9 , 21
/40.
Michelsen, M. L. (1986). Simplified flash calculations for cubic
equations of state. Industrial Engineering and Chemical Process
Design and Development 25 , 184
/188.
Michelsen, M. L. (1994). Calculation of multiphase equilibrium.
Computers and Chemical Engineering 18 (7), 545
/550.
Nagarayan, N. R., Cullik, A. S. & Griewank, A. (1991). New strategy
for phase equilibrium and critical point calculations by thermo-
dynamic energy analysis. Part I. Stability analysis and flash. Fluid
Phase Equilibria 62 , 191
/210.
Nghiem, L. X. & Li, Y.-K. (1984). Computation of multiphase
equilibrium phenomena with an equation of state. Fluid Phase
Equilibria 17 , 77
/95.
Nichita, D.V. (1996). Ph.D. dissertation, University of Ploiesti.
Nichita, D. V., Minescu, F. & Cretu, I. (1996). A new algorithm for the
calculation of mixtures critical point. Romanian Petroleum Journal
(Revista Româna de Petrol in Romanian) 3 , 197
/210.
Nichita, D.V., Goual, L., & Firoozabadi, A. (2001). Wax precipitation
in gas condensate mixtures. SPE Production and Facilities (pp.
250
/259).
Orr, F.M., Jr, Yu, A.D., & Lien, C.L. (1980). Phase behavior of CO2
and crude oil in low temperature reservoir, paper SPE 8813
presented at the first SPE/DOE symposium on enhanced oil
recovery. Tulsa, OK.
Pan, H., & Firoozabadi, A. (1998). Complex multiphase equilibrium
calculations by direct minimization of Gibbs free energy by use of
simulated annealing. SPE Reservoir Evaluation and Engineering
(pp. 36
/42).
Pan, H., Firoozabadi, A., & Fotland, P. (1997). Pressure and
composition effect on wax precipitation: experimental data and
model results. SPE Production and Facilities (pp. 250
/258).
Peng, D. Y. & Robinson, D. B. (1976). A new two-constant equation
of state. I.&E.C. Fundamentals 15 (1), 59
/64.
Prausnitz, J. M., Lichtenthaler, R. N. & Gomez de Azevedo, E. (1986).
Molecular thermodynamics of fluid-phase equilibria . Englewood
Cliffs, NJ: Prentice-Hall.
Press, W. H., Flannery, B. P., Teukolski, S. A. & Vetterling, W. T.
(1989). Numerical recipes */the art of scientific computing . Cam-
bridge University Press.
Risnes, R. & Dalen, V. (1984). Equilibrium calculations for coexisting
liquid phases , pp. 87
/96). SPE Journal .
Robinson, D.B., Kalra, H. & Rempis, H. (1978). The equilibrium phase
properties of a synthetic sour gas mixture and a simulated natural gas
mixture, GPA Research Report , No. RR-31, Tulsa.
1724 D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703
/1724
Soave, G. (1972). Equilibrium constants from a modified Redlich
/
Kwong equation of state. Chemical Engineering and Science 27 (6),
1197
/1203.
Sun, A. C. & Seider, W. D. (1995). Homotopy-continuation method
for stability analysis in the global minimization of the Gibbs free
energy. Fluid Phase Equilibria 103 , 213
/249.
Trangenstein, J.A. (1985). Minimization of Gibbs free energy in
compositional reservoir simulation, paper SPE 13520, presented
at the SPE 1985 Reservoir Simulation Symposium, Dallas, TX.
Ungerer, P., Faissat, B., Leibovici, C., Zhou, H., Behar, E., Mor-
acchini, G. & Courcy, J. P. (1995). High pressure
/high tempera-
ture reservoir fluids: investigation of synthetic condensate gases
containing a solid hydrocarbon. Fluid Phase Equilibria 111 , 287
/
311.
Vickery, D. J. & Taylor, R. (1986). Path-following approaches to the
solution of multicomponent, multistage separation process pro-
blems. American Institute of Chemical Engineering Journal 32 (4),
547
/556.
Wasylkiewicz, S. K., Sridhar, L. N., Doherty, M. F. & Malone, M. F.
(1996). Global stability analysis and calculation of liquid
/liquid
equilibrium in multicomponent mixtures. Industrial Engineering
and Chemical Research 35 , 1395
/1408.
Wilson, G.A. (1969). Modified Redlich
/Kwong equation of state,
application to general physical data calculations, paper no. 15C
presented at the American Institute of Chemical Engineering 65th
National Meeting, Cleveland, OH.
Yarborough, L. (1972). Vapor
/liquid equilibrium data for multi-
component mixtures containing hydrocarbon and non-hydrocar-
bon components. Journal of Chemical Engineering Data 17 , 129
/
133.
Zhu, Y. (2000). High pressure phase equilibrium through the simulated
annealing algorithm: application to SRK and PR equations of
state, paper presented to the 2000 American Institute of Chemical
Engineering Annual Meeting.
Zhu, C., Byrd, R. H., Lu, P. & Nocedal, J. (1994). L-BFGS-B-
FORTRAN subroutines for large-scale bound constrained optimiza-
tion . Department of Electrical Engineering and Computer Science,
Northwestern University.