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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 limitedmemory 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
D
/
/D
E
epsmch
F
f
* Corresponding author. Present address: Div. Chimie et Physico-Chimie Appliquees, Inst. Francais du Petrole, 1 et 4 avenue du Bois-Preau RucilMalmaison, 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
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
fji
factr
G
g
H
h
K
kij
L , L1, L2
l
M
n
ni
nji
nc
np
ns
p
pgtol
Q
R
T
T
Tp(x )
Tc(x )
Te(x )
u
V
xij
x
y
xG
xm
xs
z
Greek letters
bj
d
o
8
lm
ls
m
n
v
Subscripts
F
i, k
j
pure
r
Superscripts
S
T
0
*
D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703 /1724
D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703 /1724
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 equilibria calculations for interest in Chemical Engineering
and Petroleum Engineering.
The difficulty of phase equilibrium calculations consists 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 boundaries.
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 calculation 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-Newton 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 (Michelsen, 1982b).
The equality of chemical potential represents only the
stationary point conditions for the minimum of thermodynamic potentials. Any method based on these conditions 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
1706
D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703 /1724
sense that it produces a monotonic sequence of improved 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
phase (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 (Zhu, Byrd, Lu & Nocedal, 1994; Byrd, Lu,
Nocedal & Zhu, 1995), but any favorite minimizer
may be used.
The Tunneling method has proved its efficiency and
reliability on several highly difficult academic and
industry. The method proposed here does not require
a priori the number of phases existing at equilibrium.
The calculation sequence is organized in a stepwise
manner. Results from two-phase flash and stability
analysis provide good initial guesses for the three-phase
equilibrium. Phase distribution is obtained by solving a
convex unconstrained optimization problem (Michelsen,
1994).
The code Tunneling phase equilibria (TUNPEQ)
incorporates the code TUNNEL for the global optimization method, developed at IIMAS-UNAM (Castellanos & Gomez, 1998).
A general form of cubic equations of state (EOS),
(Coats, 1985; Michelsen, 1986), including the Soave/
Redlich /Kwong (SRK) EOS (Soave, 1972), and the
Peng /Robinson (PR) EOS (Peng & Robinson, 1976) is
currently incorporate in TUNPEQ. However, 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.
We will present the multiphase equilibrium problem
in Section 2, the description of the Tunneling
global optimization method will be given in Section 3,
and the results on a set of difficult problems will be
reported and discussed in Section 4. A comparison
with other global methods will be presented in Section 5
and some concluding remarks will be given toward the
end.
nc X
np
X
(1)
i1 j1
G(n)
RT
nc X
np
X
(2)
i1 j1
(3)
np
X
nji ;
i 1; nc
(4)
j1
i 1; nc;
j 1; np
(5)
nji
nc
X
(6)
njk
k1
np
X
nji ;
i 1; nc
(7)
j2
and the optimization problem (3) becomes an unconstrained one, with only bounds on the remaining
nc(np/1) independent variables, n2, . . ., nnp.
D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703 /1724
i1
nji
@ ln fji
@njk;k"i
D(x)
i 1; nc
0;
j 1; np
D(x)
RT
nc
X
(14)
i1
1707
(9)
xnc 1
nc1
X
xi
(15)
i1
the sums in Eq. (8) vanish. Note that Eq. (9) is satisfied
for any mol fractions, not only for the equilibrium mol
fractions. Therefore, it is not necessary to compute the
fugacity derivatives in order to compute the gradient of
the Gibbs free energy:
@G
f
ln ji ; j 2; np; i 1; nc
(10)
@nji
f1i
In this work a Limited Memory Quasi-Newton
minimization technique is used (the L-BFGS-B routine,
Zhu et al., 1994), that requires only the values of the
objective function and of the gradients. Any solver may
be used for minimization; if the elements of Hessian
matrix are required, there are given by:
2
@ G
@ ln fji @ ln f1i
Hik
dik
;
@nji @nlk
@nli
@n1k
(11)
(16)
i 1; nc1
(17)
@2D
@xi @xk
@ ln fi (x)
@xk
@ ln fnc (x)
@xk
(19)
i; k 1; nc1
i; k 1; nc(np1)
where d is the Kronecker delta.
2.3. Stepwise organization of multiphase equilibria
calculation
nc
X
(12)
i1
(13)
1708
D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703 /1724
zi
xnpi yi
1
np1
X
bj ((1=Kji ) 1)
(24)
j1
i 1; nc
and the mol fractions of the remaining phases, xji ,
i/1, nc, j/1, np/1 are obtained from Eq. (23).
The gj functions are defined:
gj (b)
nc
X
j 1; np1
(25)
i1
nc
X
xji 1;
j 1; np
(26)
i1
i 1; nc;
j 1; np
(20)
bj xji ni ;
j 1; np
(21)
i1
(22)
bj 1
i1
yi
8
ji ;
xji 8 npi
i 1; nc;
j 1; np1
(23)
i1
(1=Kji 1)zi
0;
np1
X
1
bj (1=Kji 1)
(27)
j1
j 1; np1
If the vapor phase disappears Eq. (27) cannot be
applied; in this case, in a similar manner the
following set of equations is obtained:
hj (b)
nc
X
j 2; np
(28)
i1
nc
X
np
X
j1
where
bj
nc
X
i1
ni ln Ei
(29)
D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703 /1724
Ei
np
X
bj
j1
8 ij
i 1; nc
(30)
j 1; np
(31)
(32)
1
1709
nc
X
ni
i1
8 ij Ei
j 1; np
(33)
(36)
i 1; ng 5pgtol
(37)
X
np X
nc
(fji f1i )2
0:5
Bo
(38)
j2 i1
zi
Ki
(34a)
(34b)
(35)
(39)
D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703 /1724
1710
(40)
f (xm )
xm B such that f (x)5
m
(42)
xm arg(min f (x))
xB
(41)
(44)
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
m
(46)
1711
information. Then from this point, the local minimization 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 evaluations (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 stationary 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)
ls
exp
x xm
x xs
f (xm ))exp
lm
(48)
1712
D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703 /1724
4. Results
This section presents the results of phase stability
analysis and multiphase equilibria calculation for several 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 addressed 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 performed 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
Fig. 2. (a) TDP function for the methane /hydrogen sulfide binary
mixture. (b) TPD function for the methane /hydrogen sulfide binary
mixture (detail).
1713
Table 1
Problem 1: C1/H2S SRK-EOS at p 40.53 bar and T 190 K
Feed composition
Objective function
FE
NT
Initial guess
(0.50, 0.50)
/
/
/
/
(0.9885, 0.0115)
/
(0.9813, 0.0187)
/
/
/
/
(0.112, 0.888)
/
/
(0.11, 0.89)
/
/
(0.925382, 0.074618)
(0.118133, 0.881867)
(0.925382, 0.074618)
(0.981559, 0.018441)
(0.925382, 0.074618)
(0.9885, 0.0115)
(0.9885, 0.0115)
(0.923314, 0.076686)
(0.115208, 0.884792)
(0.923314, 0.076686)
(0.9813, 0.0187)
(0.923314, 0.076686)
(0.920821, 0.079179)
(0.112, 0.888)
(0.920821, 0.079179)
(0.919132, 0.080868)
(0.11, 0.89)
(0.11, 0.89)
8.2521e2
5.6893e2
8.2521e2
7.9352e2
8.2521e2
0
0
3.9565e3
1.09098e2
3.9565e3
0
3.9565e3
2.4623e3
0
2.4623e3
5.6076e3
0
0
696 (38)
647 (87)
/
853 (832)
/
512 (6)
581 (17)
645 (8)
693 (237)
/
690 (4755)
/
630 (7)
632 (85)
/
681 (76)
1
2
/
2
/
1
1
1
2
/
2
/
1
2
/
2
/
1
L(0.982223, 0.017777)
V(0.070334, 0.929666)
/
*(0.955, 0.045)
/
L(0.988860, 0.011140)
V(0.432088, 0.567912)
L(0.982297, 0.017703)
V(0.214960, 0.785040)
/
*(0.97, 0.03)
/
L(0.937174, 0.062826)
V(0.066633, 0.933367)
/
L(0.936020, 0.063980)
/
V(0.066010, 0.933990)
667 (8)
D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703 /1724
1714
Table 2
Problem 2: C1/C3 SRKEOS at p 50 bar and T 277.6 K
Feed composition
Objective function
FE
NT
Initial guess
(0.10,
/
(0.40,
/
(0.60,
/
(0.90,
/
(0.10, 0.90)
/
(0.865478, 0.134522)
/
(0.192783, 0.807217)
/
(0.90, 0.10)
/
0
0
0.152987
/
0.2226
/
0
0
692 (9)
637 (6)
864 (6)
987 (13)
2369 (9)
2417 (6)
1060 (6)
1023 (13)
1
1
1
1
1
1
1
1
L(0.606896,
V(0.093568,
L(0.879067,
V(0.294238,
L(0.784372,
V(0.171736,
L(0.909399,
V(0.387085,
0.90)
0.60)
0.40)
0.10)
0.393104)
0.996106)
0.120933)
0.705762)
0.215628)
0.828264)
0.090601)
0.612915)
Table 3
Problem 2: C1/C3 SRKEOS at p 100 bar and T 277.6 K
Feed composition
Objective function
FE
NT
Initial guess
(0.40,
/
(0.68,
/
/
(0.73,
/
/
(0.90,
/
(0.40, 0.60)
(0.40, 0.60)
(0.68, 0.32)
(0.772465, 0.227535)
(0.772465, 0.227535)
(0.650287, 0.349713)
(0.757048, 0.242952)
(0.650287, 0.349713)
(0.90, 0.10)
(0.90, 0.10)
0
0
0
3.346e4
/
2.948e4
2.081e5
2.948e4
0
0
592 (6)
586 (6)
1196 (137)
/
1113 (7)
1539 (9)
1473 (915)
/
1214 (7)
1259 (11)
1
1
2
/
1
1
2
/
1
1
L(0.426354,
V(0.093997,
L(0.881459,
/
V(0.410751,
L(0.881402,
V(0.411153,
/
L(0.921832,
V(0.530911,
0.60)
0.32)
0.27)
0.10)
0.573646)
0.906003)
0.118541)
0.589249)
0.118598)
0.588847)
0.078168)
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
Objective function
FE
NT
Initial guess
(0.90,
/
(0.82,
/
(0.70,
/
(0.56,
/
/
/
(0.40,
/
(0.90, 0.10)
/
(0.505590, 0.494410)
/
(0.510582, 0.489418)
/
(0.845281, 0.154719)
/
(0.56, 0.44)
(0.845281, 0.154719)
(0.40, 0.60)
/
0
0
9.746e3
/
1.379e2
/
1.553e2
/
0
1.553e2
0
0
1033 (7)
1167 (7)
1048 (10)
1092 (8)
1247 (12)
1282 (8)
1502 (7)
1318 (7)
1329 (86)
/
1469 (6)
1524 (9)
1
1
1
1
1
1
1
1
2
/
1
1
L(0.505716,
V(0.920178,
L(0.381899,
V(0.884377,
L(0.370731,
V(0.883679,
L(0.381497,
V(0.888463,
*(0.5, 0.5)
/
L(0.305497,
V(0.845406,
0.10)
0.18)
0.30)
0.44)
0.60)
0.494284)
0.079822)
0.618101)
0.115623)
0.629269)
0.116321)
0.618503)
0.111537)
0.694503)
0.154594)
Objective function
FE
NT
Initial guess
(0.90,
/
(0.80,
/
(0.70,
/
/
(0.57,
/
/
(0.40,
/
(0.90, 0.10)
/
(0.502644, 0.497356)
/
(0.642304, 0.357696)
(0.815263, 0.184737)
(0.815263, 0.184737)
(0.57, 0.43)
(0.808873, 0.191127)
(0.808873, 0.191127)
(0.40, 0.60)
(0.40, 0.60)
0
0
7.427e3
/
1.876e4
7.003e3
7.003e3
0
1.3098e3
1063 (6)
1125 (10)
1739 (8)
1831 (6)
1353 (85)
/
1301 (7)
1284 (75)
/
1364 (7)
1836 (9)
1711 (8)
1
1
1
1
2
/
1
2
/
1
1
1
L(0.908073,
V(0.541701,
L(0.838722,
V(0.270924,
V(0.237605,
/
L(0.845278,
V(0.205001,
/
L(0.839429,
V(0.171840,
L(0.819257,
0.10)
0.20)
0.30)
0.43)
0.60)
0
0
0.091927)
0.458299)
0.161278)
0.729076)
0.762395)
0.154722)
0.794999)
0.160571)
0.828160)
0.180743)
D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703 /1724
1716
Table 6
Problem 5 C1/C2/N2 PREOS at p 76 bar and T 270 K
Feed composition
Objective function
FE
NT
Initial guessa
(0.10,
/
/
(0.30,
/
(0.38,
/
(0.05,
/
(0.101617, 0.586727)
(0.067797, 0.799168)
/
(0.245094, 0.658130)
/
(0.38, 0.54)
/
(0.05, 0.90)
/
5.88659e6
1.48288e2
/
0.011746
/
0
0
0
0
3079 (1814)
/
3474 (12)
4831 (16)
4779 (13)
2929 (18)
3006 (39)
4717 (19)
4727 (11)
2
/
1
1
1
1
1
1
1
L(0.118613,
/
V(0.055818,
L(0.373190,
V(0.181211,
L(0.491972,
V(0.242737,
L(0.121698,
V(0.045620,
0.60, 0.30)
0.55, 0.15)
0.54, 0.08)
0.90, 0.05)
0.380627)
0.853433)
0.360265)
0.766340)
0.356744)
0.725904)
0.611101)
0.912190)
x1, x2.
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
0.6883
0.0914
0.0460
0.0333
0.0139
0.0152
0.0896
0.0222
0.7177
0.0920
0.0447
0.0315
0.0128
0.0138
0.0741
0.0133
0.6628
0.0909
0.0471
0.0349
0.0148
0.0164
0.1032
0.0299
Type L initialization
0.6532
0.0902
0.0471
0.0351
0.0150
0.0170
0.1077
0.0349
0.7298
0.0917
0.0438
0.0304
0.0123
0.0131
0.0677
0.0112
Fig. 6. Detail of the p /z phase diagram of the ternary system CO2/C1/
n C16 at T/294.3 K.
Table 8
Results for CO2/C1/n C16 system at p 67 bar and T 294.3 K
Component
C1
n C16
CO2
a
Feed stability
a
0.05
0.05
0.90
0.040511
0.466839
0.492650
Three-phase flash
a
0.050832
0.004166
0.945002
0.044778
0.337496
0.617726
0.099791
0.000048
0.900161
x1
x2
0.078112
0.000069
0.921819
0.036181
0.340224
0.623595
0.038707
0.004609
0.956683
D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703 /1724
1718
Table 9
Calculated mol fractions for the sour gas system at T 178.8 K,
p 21.9 bar
Component Feed composition
C1
C2
C3
H2S
CO2
N2
0.70592
0.06860
0.02967
0.10559
0.01996
0.07026
HC-rich liquid
0.5282
0.1598
0.0760
0.1879
0.0371
0.0110
0.8577
0.0113
0.0006
0.0094
0.0082
0.1129
0.0666
0.0261
0.0075
0.8688
0.0304
0.0006
Table 10
BIC for the sour gas system
Component
C2
C3
H2S
CO2
N2
kC j
1
kC j
2
kC j
3
kH Sj
2
KCO j
0.000
/
/
/
/
0.000
0.000
/
/
/
0.100
0.080
0.080
/
/
0.125
0.135
0.150
0.120
/
0.031
0.042
0.091
0.200
0.020
Component
C6
H2S
CO2
kC1-j
kC6-j
kH2S-j
0.036
/
/
0.080
0.050
/
0.093
0.118
0.099
Table 11
Results for the sour gas system at p 35 bar and T 178.8 K
Component
C1
C2
C3
H2S
CO2
N2
Feed
Stability
0.70592
0.06860
0.02967
0.10559
0.01996
0.07026
0.060303
0.011263
0.003438
0.904991
0.018229
0.001776
Two-phase flash
Stability
Three-phase flash
x1
x2
0.715787
0.069469
0.030069
0.093383
0.019979
0.071312
0.064426
0.012099
0.003697
0.899205
0.018734
0.001839
0.705964
0.006233
0.000489
0.008382
0.004765
0.274167
0.726129
0.006352
0.000466
0.008596
0.004933
0.253524
0.714973
0.072154
0.031333
0.097494
0.020621
0.063425
0.065262
0.012393
0.003738
0.897742
0.019166
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
C1
n C6
H2S
CO2
Feed
Stability
0.50000
0.02627
0.41633
0.05740
0.082317
0.001380
0.878809
0.037836
Two-phase flash
Stability
Three-phase flash
x1
x2
0.979116
0.000001
0.007984
0.012899
0.118005
0.047214
0.741901
0.092880
0.286047
0.349603
0.293955
0.070395
0.977599
0.000001
0.007900
0.014499
0.308646
0.227252
0.363484
0.100618
0.068425
0.007764
0.833419
0.090391
al. (1999) is used. BICs 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 obtained 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)
Table 14
Results for the quaternary system at p 42.5 bar and T 199 K
Component
C1
n C6
H2S
CO2
Feed
Stability
Two-phase flash
Stability
Three-phase flash
x1
x2
0.50000
0.02627
0.41633
0.05740
0.961720
0.000023
0.024470
0.013787
0.956278
0.000021
0.025186
0.018515
0.289556
0.038376
0.596733
0.075334
0.244579
0.029114
0.653089
0.073218
0.956229
0.000021
0.025179
0.018571
0.331272
0.046211
0.545958
0.076560
0.250611
0.030348
0.645240
0.073801
D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703 /1724
1720
Table 15
BIC for the SHF4 mixture
Component
C2
C3
C7H8
n C8
n C16
n C36
kC j
1
kC j
2
kC j
3
kC H8j
7
Kn C j
8
Kn C j
0.0000
/
/
/
/
/
0.0384
0.0417
/
/
/
/
0.0439
0.0000
0.0000
/
/
/
0.0475
0.0358
0.0221
0.0000
/
/
0.0658
0.0242
0.0104
0.0000
0.0002
/
0.0960
0.0050
0.0188
0.0000
0.0294
0.0172
16
Table 16
VLS equilibria for SHF4 mixture
T (K), p (bar) conditions
Equilibrium state
FE SA
FE TUNPEQ
Tunneling phases
332, 600
335, 400
/
333, 400
332, 400
331, 400
/
330, 400
/
329.5, 400
329, 400
/
328.5, 400
328, 400
326, 400
325, 400
/
320, 400
VS
/
VL
VL
VLS
VLS
/
9.220000
8.683763
8.677826
8.659164
8.649628
8.645886
8.639555
8.635533
8.629042
8.623662
8.624830
8.618213
8.612708
8.607162
8.584619
8.580098
8.573146
8.513939
130 201
/
270 201
268 801
268 801
/
273 001
/
266 001
463 401
/
378 001
263 201
267 401
263 201
/
266 001
/
4869 (15)
/
20 181 (7916)
20 178 (62)
21 024 (67)
/
28 527 (7223)
/
26 333 (6613)
25 895 (92)
/
13 196 (130103)
14 596 (63)
12 613 (53)
13 821 (50)
/
12 265 (4358)
11 945 (58)
1
/
2
1
1
/
2
/
2
1
/
2
1
1
1
/
2
1
VLS
VLS
VLS
VS
VS
VS
VS
VS
D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703 /1724
1721
Table 17
Composition of crude oil 2
Component
Stock-Tank oil
Reservoir fluid
N2
CO2
C1
C2
C3
i C4
n C4
i C5
n C5
C6
C7
C8
C9
C10
/
/
/
0.00087
0.00536
0.00301
0.01240
0.01008
0.01730
0.03701
0.08213
0.10623
0.06672
0.65888
0.00225
0.01365
0.51283
0.07344
0.04430
0.00755
0.02037
0.00772
0.01097
0.01967
0.02524
0.03456
0.02101
0.20644
bar, respectively. Results are given for both the multisolid (MS) and ideal solid solution (SS) models.
The number of FE for TUNPEQ (including the
Tunneling phase for checking global optimality) is one
order of magnitude less than for SA. The conditions for
this example are not difficult conditions, but what
makes it interesting is that the mixture is described
with a large components number (37). If only the
minimization step is used, only 15/47 FE were required
by L-BFGS-B to find the solution.
Wax precipitation is a major problem for the oil
industry, because wax deposition may plug the flow
lines. We believe such a code would be extremely
valuable for the industry. For wax precipitation from
crude oils, it is very important that the heavy fractions
distribution between species (paraffins, naphthenes, and
aromatics) is taken into account; this may lead to very
large number of components. The code has proved to be
able to handle such problems.
1722
D.V. Nichita et al. / Computers and Chemical Engineering 26 (2002) 1703 /1724
i)
Acknowledgements
a systematic comparison of the efficiency of TUNPEQ 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 investigated;
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.
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