λ
University of Southampton, Highfield, Southampton, SO171BJ, UK
2
Institute of Chemical Engineering, Bulgarian Academy of Sciences,
Sofia 1113, Bulgaria
1. INTRODUCTION
Δί/-ΓΔ5+/>ΔΚ<0 (1)
(4)
AG7,,,<0 (5)
dnf+dn?=Q (6)
dnl+dn%=0 (7)
Taylor series expansion is used to represent the property change for each
phase. The series expansion will be combined to express the total Gibbs free
energy change that must then satisfy:
SGTP>Q (8)
(9)
All intensive variables of parts A and B are equal, and the two first order
terms are zero by virtue of Eq. (6) and (7). To satisfy Eq. (8) the sum of the
second order terms in Eq. (9) must be positive. If we consider a special case
of variation in the mole numbers w,A with n* held constant, it will be
necessary to include only the first second-order term to obtain the desired
stability conditions. Thus we must have:
(10 a)
or
>0 (10 b)
>o (Π)
< + »2e U 14
Taking into consideration that the intensive variables of part A and part B are
identical, we can write:
(12)
Because the term in parentheses will always be positive then the stability
condition for a binary system in terms of mole fractions is:
>0 (13 a)
or equivalently
>0 (13 b)
<0 (14)
->0 (15)
Eq. (13) together with Eq. (14) and Eq. (15) are necessary and sufficient
conditions for the thermal, mechanical and chemical stability in regard to
infinitesimal disturbances of the system state. The boundary surface (line)
determined by the above three criteria separates the unstable from the
metastable states, and is called the spinodal. The boundary between the
metastable and stable states is determined by the equilibrium conditions (Eqs.
2, 3, 4) for the co-existing phases and is called the binodal. At the critical
point the binodal and the spinodal coincide.
Nc-\Ne-l
ΣΣ\# *GldXidXj\>0 (17)
1=1 J=\
This stability criterion requires that the Gibbs energy function must be
convex, as was first shown by Gibbs.
The task of thermodynamics of phase equilibrium is to describe
quantitatively the distribution at equilibrium of every component among all
the phases present. We would like to relate the abstract chemical potential of
a substance to physically measurable quantities such as Τ, Ρ, and
composition. The chemical potential does not have an immediate equivalent
in the physical world and it is therefore necessary to express it in terms of
some auxiliary function, which may be more easily connected with
measurable quantities.
For this purpose Lewis defined a function called fugacity. The definition
of fugacity for any component in the system, whether .solid, liquid or gas,
ideal or not is given by:
(18)
f?=f> (19)
The equation gives a very useful result since it tells that the equilibrium
where <p\ and φ? are fugacity coefficients of the /-th component in the
liquid and vapour phase, respectively.
While in the asymmetric models' scheme:
where γ, and f° denote the activity coefficient and the standard state
fugacity of the /-th component in the liquid phase.
This gives us the possibility to have an expression for the Gibbs energy in
measurable quantities and not in terms of chemical potentials. Furthermore,
provided there is a thermodynamic model available, one can calculate the
Gibbs free energy for any system with any number of components.
3. 1. Equation-solving approaches:
These approaches to phase (and chemical) equilibrium calculations solve
a set of non-linear equations arising from mass balances and phase (and
chemical) equilibrium relations, which satisfy the necessary conditions of
equality of the chemical potentials of every component in each phase. The
best known are the isothermal vapour-liquid calculations, which are probably
the most common in a wide variety of chemical engineering applications. The
objective is to determine the compositions of the vapour and liquid phases.
The underlying flash equations for a two-phase vapour-liquid system
include:
(22)
(23)
If Eq. (22) and Eq. (23) are combined and the flow rates are eliminated in
terms of the vapour fraction α = FV/F, the flash condition may be written:
— -1 = 0 (24)
and
y, = *Λ (25 b)
The above equations give only a necessary (equality of chemical
potentials) but not a sufficient condition for equilibrium.
There are many ways to solve the above flash equations and one
possibility is to use classical successive substitution procedures, because they
are simple and perform well in many cases. The algorithm alternates between
calculation of the thermodynamic properties and the current estimate of the
phase distribution, and a recalculation of phase amounts and compositions,
assuming composition independent thermodynamic properties.
It has been generally presumed that the successive substitution procedures
will be well behaved and "safe", even if slow to converge in some regions
(Heidemann and Michelsen, 1995). However, the procedures can be
nonconvergent for some systems, far from any points where either of the
equilibrium phases can become unstable or approach criticality. The
nonconvergent behavior is associated with large negative deviations from the
ideal solution model and results when one or more eigenvalues of the matrix
( Qf\
E = -^-
la*, ι . are
\ J Xi=i
less than -1. The consequence will be an oscillatory
Another problem may arise when the algorithm progresses into the domain of
non-physical parameters), such as negative mole fractions.
The intrinsic difficulties of the application of Newton and quasi-Newton
methods to the solution of the phase equilibrium problem include: lack of a
priori criteria for determining the number of possible phases; non-uniqueness
and the impossibility to determine with certainty if the algorithm does not
find solution whether this is the case in reality or whether this is a result of
some numerical or software issue. The non-uniqueness is a particular
problem and is a result of the mathematical presence of local minima and
maxima in the Gibbs energy surface. This, in turn, relates to convergence to a
local rather than global minimum, and to the impossibility to distinguish
among thermodynamically stable, metastable and unstable equilibrium states.
Despite the above limitations, equation-solving methods have been
extremely popular, and many robust algorithms are available for simple
vapour-liquid equilibrium calculations. Ohanomah and Thompson (1984 a-c),
Cairns and Furzer (1990), Seider, Brengel and Widagdo (1991), Seider and
Widagdo (1996) provide extensive studies of the implementation of the best
equation-solving algorithms known for the phase and chemical equilibrium
problem, and we will not review them here. We single-out as deserving
special interest and attention the "inside-out algorithms" advocated by
Boston and Britt (1978) and the thermodynamically consistent hybrid-method
of Lucia et al. (1985) and Venkataraman and Lucia (1986).
Finally, we would like to emphasise once again the extreme importance
of good initial estimates (starting points) for the equation-solving methods
and the employment of efficient procedures for their generation.
min G(n)
s.t An-b = 0 (26)
τ
0 < η <η
(27)
The equality An-b = 0 corresponds to the mass balances, and can take
either of the following two forms depending on whether reaction occurs in
the system:
α
Λ»=^ k = \,...,E (28)
=H T /=!,...,# (29)
There are essentially two routes that can be followed to obtain or confirm
that an equilibrium solution corresponds to a global minimum of the Gibbs
free energy. The two optimisation problems associated with these approaches
are: direct minimisation of the Gibbs free energy and minimisation of the
tangent plane distance function (TPDF).
White et al. (1958) were the first to minimise the Gibbs free energy for an
ideal system. They tested two methods - a steepest descent method and a
linear-programming technique method, which later became known as the
RAND algorithm. An excellent and most extensive review of the early
contributions in this area can be found in Seider et al. (1980).
To minimise directly the Gibbs free energy a variety of optimisation
methods can be used. However, because the number and identity of phases
present at equilibrium are not known a priori the application of optimisation
methods to the solution of this particular phase equilibrium problem may
cause severe computational difficulties. Although the phase rule supplies an
obvious upper bound on the maximum number of phases that can be present
at equilibrium, it is of limited use as it can lead to a large number of potential
phases that need be considered in the system. Thus, there has to be a strategy
to circumvent this problem and several have been proposed.
The first strategy requires fixing the number of phases (two or three
usually because this is the most common circumstance) and using nonlinear
programming to minimise the Gibbs energy function among those phases.
George et al. (1976) used an allocation function to eliminate equality
constraints and minimised an unconstrained Gibbs free energy function by
the method of Powell (1970). Ohanomah and Thompson (1984 c) proposed a
geometric programming method to transform the minimisation problem into
a Newton-Raphson procedure. Their approach proved to be successful in
establishing multiphase behavior of many polar systems with the Wilson
activity coefficient model. Other examples of this approach are the works of
Castillo and Grossmann (1981), who used a projected-variable metric method
that does not require second derivatives of the objective function with respect
to the optimisation variables (Hessian matrix), Lantagne et al. (1988), who
proposed a penalty function approach to include nonnegative inequality
constraints in the objective function. Boston and Fournier (1978) illustrated
this approach for splitting a non-ideal liquid phase into two liquid phases, and
after splitting the liquid phase use K-value algorithms to converge the
equilibrium calculations.
The second strategy adds sequentially an extra phase in the computations
and tests the stability of the resulting phase configuration (Gautaum and
Seider, 1979; Scares et al. 1982; Nghiem and Li, 1984; Wu and Bishnoi,
1986; Walraven and Rompay, 1988; Gastier et al. 1989). An example is the
work of Gautam and Seider (1979) who use Wolfe's Quadratic Programming
algorithm, and eliminate phases as the algorithm progresses. They compared
its performance to some other methods for the minimisation of the Gibbs free
energy. This approach, however, could lead either to convergence to
constrained minima if too many phases are assumed, or to convergence to
trivial or local extrema. In their review Ohanomah and Thompson (1984
a,b,c) highlight in detail the difficulties generated when a large number of
excessive phases is assumed, and this question will not be pursued further
here. It is important to underline, however, that even if the number of phases
is assumed correctly, the solution obtained may be at a local minimum.
Hence, it is necessary to address the problem of multiplicity within the
solution space, especially near phase boundaries and in the critical region.
i
min F(x) = g(x)-L(x) = f>, {M(x)-//,(z)}
/=!
(30)
If the tangent plane lies completely below the Gibbs surface (that means
that F(x) is nonnegative for all ranges of χ ), then the postulated solution
corresponds to a global minimum of the Gibbs free energy. If not, a phase
equilibrium configuration with lower Gibbs energy exists and must be found.
Recently, Smith et al. (1993) and Jiang et al. (1996) have provided
important new insights into stability analysis and extended the tangent-plane
criterion to apply to reacting mixtures in a reaction tangent-plane criterion.
The application of this criterion was presented in great detail by Smith et al.
(1993) and Seider and Widagdo (1996), and will not be discussed here.
The motivation for using the tangent-plane stability criterion arises from
an assumption that must be made in order to formulate the Gibbs free-energy
minimisation problem, i.e. to specify the number and identity of the phases at
equilibrium. However, for a given number and type of phase, the global
minimum of the Gibbs free energy is not a sufficient condition for the true
equilibrium. This is because a different set of phases may contain a solution
that has a lower value for the Gibbs energy. Given a candidate equilibrium
solution, the advantage of the tangent-plane criterion is that it provides an
unambiguous means of determining if the proposed solution is stable or
unstable.
Minimisation of the TPDF has been found to be more reliable and robust
than minimising the Gibbs function directly, since theoretically to guarantee
a global .minimum for G, using global optimisation, the formulation must
contain a large number of variables, making a global optimisation algorithm
computationally expensive, particularly for larger systems. For these reasons,
the minimisation of the TPDF presents many advantages.
Baker et al. (1982) formalised the concepts of thermodynamic stability
for multicomponent mixtures, the fundamental principles of which had first
been studied by Gibbs. They proved that a necessary and sufficient condition
for an equilibrium solution to correspond to a global minimum of the Gibbs
free energy is that the tangent plane corresponding to this solution lies on or
below the Gibbs free energy surface for all possible values of the
compositions. (See Figure 1 for a two component system). The key
characteristic is that if a tangent plane that lies completely below the Gibbs
free energy surface does exist, then the equilibrium solution, which
corresponds to the global minimum of the Gibbs free energy, is given by the
compositions at the points of tangency and ß. In other words Baker et al.
(1982) proved that a necessary and sufficient condition for a postulated
solution to be equilibrium one is that the TPDF is non-negative for all
possible phases represented in the system. However, in the general
multicomponent, multiphase problem there is no rigorous approach to
determine where the tangent plane touches the Gibbs free energy surface so
that it always lies below it.
Mole Fraction
Fig. 1: Tangents to the curve of the Gibbs free energy versus mole fraction
(constant temperature and pressure).
6. MICHELSEN'S APPROACH
G =!>,/', (32)
1=1
It is assumed that the mixture is split into two phases, I and II, with mole
numbers (Ν-έ) and ε respectively, where ε is a very small amount of the
second phase.
Stability of the original mixture requires that its Gibbs free energy be at
the global minimum. Therefore, a necessary condition for stability is that:
Γ(ι)= 1=1
negative at all stationary points where its derivatives with respect to all of the
independent variables vanish. Differentiation with respect to the mole
*
•s
I
ui
e
u.
H
Λ
Λ
Ο
I
Fig. 2: The vertical distance F from the tangent plane to the molar Gibbs
energy of mixing at composition z to the tangent at composition y,
for a binary mixture.
(34)
(35>
1=1
l + ln<pl(y)-\nzl-\n<pl(z) = K (36)
/ = 1,..., Nc (37)
Σ^· - ' ' a"d conversely, the phase is unstable if a stationary point is located
where ΣΥ>>1·
»=l
Before proceeding further we would like to point out that for liquid
mixtures at low to moderate pressures the stability test can be rewritten using
activity coefficients instead of the chemical potential. If the activity of any
component zy,(z) in the initial overall system is greater than unity then the
system is unstable (see for example Heidemann, 1983; Cairns and Furzer,
1990). This is because the TPDF calculated at the point, corresponding to
pure component / , is negative, if z,y,(z) >1. If this happens, then there is at
least one point in the composition space where the TPDF is negative. This
simple stability test is very fast but not absolute. The phase of composition z
is certainly unstable if the above is true for any pure component. However, it
may still be unstable even if the inequality is satisfied at all points
corresponding to pure components.
There are other alternative stability tests, which require the evaluation of
the sign definiteness of the Hessian matrix of the Gibbs free energy with
respect to Nc -1 independent mole fractions (van Dongen et al., 1983). It
should be noted that the Hessian matrices of the TPDF and the Gibbs free
energy are identical and equal to the Jacobian of the gradients of the TPDF.
Thus the Hessian matrix of the Gibbs free energy is positive definite at
stationary points corresponding to a minimum in the TPDF, and these
stationary points are stable or metastable phases. Conversely, all minima and
saddles of the TPDF lie in the region of unstable phases. Therefore, if the
Hessian matrix of the Gibbs free energy is positive definite, the mixture will
be either metastable or globally stable. It is important to underline that
Michelsen's approach does distinguish absolutely stable from metastable
regions.
Michelsen's stability method requires initial guesses, and it is
recommended to use as many initial guesses as there are components. The
pure components of the mixture act as such (Michelsen, 1982 a). However,
they prove to be insufficient in many cases of multiphase equilibria, since
solutions of Eq. (37) that are found will correspond to stationary points lying
All methods for global optimisation assume that a bounded set S c R",
containing the global optimum in its interior, is given in advance. Thus, with
χ = (Xf,...,xn) and /:S -> R, the problem will be to find:
?.= min
ΛΕ.Ι
{/(*)} (38)
/ x =0 (40)
(42)
H(x f ,l) = g(x f ) = 0 (43)
Newton homotopy.
(44)
Fixed-point homotopy:
(45)
Affine homotopy:
(46)
where
0 at / = 0 Λ=1 (48)
H(x f ,o) = /(x f ) = 0 at t = \ A=Q (49)
and use multiple starting points in an attempt to find all stationary points of
TPDF along a single path.
The application of homotopy-continuation methods (e.g. Wayburn &
Seader, 1987; Kuno & Seader, 1988; Sun & Seider, 1995; Jalali-Farahani &
Seader, 2000) to the minimisation of the TPDF often provides much
improved reliability and the capability for locating multiple solutions.
However, these methods are still initialisation dependent, and variable
bounds and inequality constraints cannot be handled directly. More
importantly, no theoretical guarantee of identifying all solutions of the TPDF
can be given, as the formulation of TPDF always contains logarithmic terms.
Such guarantees can only be claimed for special cases like polynomial
systems of equations with no constraints.
minf(x) (51)
s.txeA/ (51 a)
(52)
(54)
energy models, and focussed on the NRTL and UNIQUAC models. They
examined larger problems using these two models and considered means of
enhancing further the efficiency of the technique, based on sharpening the
range of interval function evaluations.
The (IN/GB) method (Hua et al., 1996 a, b, c; 1998 b; 1999) gives an
important practical advantage since it does not require elaborate and smart
initial guesses. Furthermore, it represents a powerful and general-purpose
approach, which can be used successfully to solve a number of difficult
global optimisation and nonlinear equation solving problems, such as arise in
chemical engineering (e.g. Maier et al., 1998; 1999), in addition to the
minimisation of the TPDF. However, the (IN/GB) method cannot give
complete certainty of finding all stationary points because of rounding errors
and dependence problem of TPDF. Moreover, as discussed by Hansen et al.
(1992), Maranas and Floudas (1995) and Harding and Floudas (2000) it is not
possible for interval methods to exactly locate all finite stationary points.
Instead, it is possible to enclose all stationary points, that is, to construct tight
intervals around the stationary points. Thus, the (IN/GB) approach encloses
all stationary points of the TPDF within intervals of some tolerance ε.
Another important theoretical and computational issue that arises is that
since the (IN/GB) method ends up with intervals, it is not certain that within
an interval there exist one or multiple stationary points, that is, the
uniqueness issue. A theoretical condition for uniqueness that needs to be met
in the interval Newton methods is that the interval Jacobian matrix is a
regular Lipschitz matrix. As a result, the key issue becomes whether it is
possible to (1) state a priori whether the Jacobian matrix is regular (that is,
consider necessary and sufficient conditions for regularity), or (2) check a
posteriori whether within an interval there exists a unique solution (that is,
consider sufficient conditions for regularity).
The most significant drawback of the currently used interval methods is
the potentially high computational cost that must be paid to obtain the
mathematical and computational guarantees of certainty. New methodologies
are described for improving the efficiency of the interval approach. In
particular, a new hybrid preconditioning strategy, in which a simple pivoting
preconditioner is used in combination with the standard inverse-mid-point
method and a new scheme for selection of the real point used in formulating
the interval-Newton equation has been recently advocated by Gau and
Stadther (2002).
W, Ne
5>,.//,.(x,z)-5>,//,F (56)
1=1 »=l
s.t.£OS(x,z) = 0 (57 a)
=1 ( 57b >
1=1
0<*,<1 (57 c)
z>0 (57 d)
31
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Vol. 20, Nos. 1-2, 2004 Numerical Solution of the Isothermal, hobaric
Phase Equilibrium Problem
liquid equilibrium (Zhu and Xu, 1999 b, d). However, the asymptotic
convergence of the SAA strongly depends on the suitable choice of its
"cooling schedules", otherwise it tends to get stuck in locally optimal
solutions (Zhu and Inoue, 2001). Rangaiah (2001) applied GA and SA to
phase equilibrium and stability problems, evaluated their reliability and
computational efficiency for locating the global minimum of the Gibbs free
energy and TPDF, and advocated a hybrid algorithm combining GA and SA
for difficult phase equilibrium problems. To the best of our knowledge, with
the above two exceptions, there has been no report on a detailed study on the
application of GA and SA to phase equilibrium and stability problems.
In a new development, Balogh et al. (2001, 2003) applied a stochastic
sampling and clustering method to locate the minima of a modified TPDF
(Stateva and Tsvetkov, 1991 a, b; 1994) and compared its reliability with
those of the most promising global optimisation methods. Their optimisation
algorithm GLOBAL is a modification of the method originally introduced by
Boender et al. (1982) with two local search procedures for finding a local
minimiser - either a quasi-Newton procedure with the Davidon-Fletcher-
Powell (DFP) update formula (Gill et al., 1981) or a random walk direct
search method UNIRANDI (Järvi, 1973). Both are derivative-free, i.e. they
do not use the partial derivatives of the objective functions (although in the
case of the DFP method an assumption of differentiability is made).
The optimisation algorithm GLOBAL can be described concisely as
follows:
Step 1. Draw M points with uniform distribution in the region of interest
5 (=[0,1]" ' ) , and add them to the current sample C. Construct the
transformed sample D by taking the percent of the points in C with the
lowest function values.
Step 2. Apply the clustering procedure to D. If all points of D can be
assigned to a cluster, go to Step 4.
Step 3. Apply the local search procedure to the points in D not yet clustered.
Repeat Step 3 until every point has been assigned to a cluster. If a new
local minimiser has been found, go to Step 1.
Step 4. Determine the smallest local minimum values found, and stop.
Balogh et al. (2001, 2003) chose the single linkage clustering procedure,
whose purpose is to recognise a priori those sample points starting from
which the local search might result in an already found local minimiser.
Clusters are grown around either local minimisers or points of the local
search procedure from which an already known local minimum was reached.
These are known as seed points. A distance d(x,\') is defined for the
clustering between two points χ and χ in the neighbourhood of a local
minimiser x* by:
Γ 1 + -'
'(«•0 (59)
Here H(X*)| denotes the determinant of H(X*) , m(S) is a measure of the set
5, N' is the total number of sampled points, and 0 < α < 1 is a parameter of
the clustering procedure.
Balogh et al. (2001, 2003) demonstrated the robustness, efficiency and
effectiveness of their method on the example of two of the most widely used
systems in the literature - the methane+hydrogen sulphide system and the
nitrogen+methane+ethane system. They compared their results on the basis
of the roots found with the results of some of the best representatives of the
above discussed methods (Hua et al., 1998 a; 1999; Sun and Seider, 1995;
Harding and Floudas, 2000 a; Zhu and Xu, 1999 a).
Table I summarises the information about the local minima determined
for six feed compositions of the methane+hydrogen sulphide system at T=
190 K, and P= 40.53 bar. (The thermodynamic model applied is the SRK
CEOS). It must be noted that owing to a lack of space only the results
obtained with the application of the quasi-Newton local search method are
shown. For all candidate phases tried, the locations of the local minima are
identical to those reported in the literature.
It must be noted that the CPU time required to find all roots for a feed
composition is given in Table I as an information rather than as a basis for
comparison with global optimisation methods. The reason behind this is that
global optimisation methods give different results than stochastic methods or
local methods. In a global optimisation approach, the global solution is found
usually at an early stage and subsequently CPU time spent is to prove that
this solution is global. In other words, the main computational cost of a
global optimisation method lies in guaranteeing that the global solution has
been found.
Furthermore, stochastic optimisation methods do not provide a theoretical
guarantee that all solutions will be found by all independent program
executions. Their reliability is measured by their success rate, and the CPU
time requirements of any stochastic method will increase in order to
guarantee a 100 % success rate.
Finally, as pointed out by Balogh et al. (2003), a particular problem
associated with the implementation of stochastic methods is the dependence
of the results obtained on the algorithmic parameters chosen. Thus, in
principle, the CPU time requirements of a stochastic method include also the
time to experiment with different parameter values until the best (most
suitable) set for a particular case study is found. That is why it is very
difficult to report the actual CPU time requirements for a stochastic method.
The section now concludes the review of some of the methods advocated
for locating the solutions of the TPDF with a brief description of a novel and
original approach introduced by Wasylkiewich et al. (1996). They used ideas
from differential geometry and the theory of differential equations for solving
global stability analysis and LL phase splitting. A remarkable feature of their,
method is the possibility to establish the number of local minima and saddle
points from a topological criterion. The authors point out that the major
difficulty in implementing the stability test is that the number of the minima
of the TPDF or the number of points satisfying Kuhn-Tacker condition is not
known a priori. They advocate an algorithm to locate all stationary points of
the TPDF (minima, maxima, and saddle points) by tracking the ridges and
valleys in the TPDF and continuing the exploration of the function domain
until the results are globally consistent with a topological relationship, which
they introduce. For a ternary mixture the topological criterion is given by
Nm + Nmia - N^ = 1 and represents the number of maxima, minima and the
saddles of the TPDF. Wasylkiewich et al. (1996) did a systematic exploration
of the function domain rather than repeated calculations starting from various
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points generated using heuristics. The authors conjectured that the ridges and
the valleys connect every stationary point of the TPDF and that they can be
completely explored using a line search no matter how many components
there are present in the system. The approach of Wasylkiewich et al. (1996)
has the advantage that the topological constraint reveals that sometimes one
or more stationary points remain to be found - a situation which often occurs
in difficult problems (Zhu and Inoue, 2001).
Finally, recently Wasylkiewich and Ung (2000) advocated a global
algorithm for stability analysis in multi-component, multiphase reactive
mixtures based on the Gibbs tangent plane stability test. They located all
stationary points of the TPDF expressed in terms of transformed coordinates.
The algorithm is independent of the specific fluid model, is self-starting and
significantly improves the robustness and reliability of multiphase reactive
equilibrium calculations. The method is implemented and tested on a variety
of problems, in which solutions for the entire phase diagram were found
without fail, and difficult cases were successfully calculated.
where:
4 /=1,2,...A (60 a)
(60 b)
then O(y*) = 0, which is its minimum value. The zeros y* of the function
<I>(y) are its minima, and from a computational point of view it is more
advantageous to search for minima with known zero minimum value. The
zeros of the objective function correspond with points on the Gibbs energy
surface, where the local tangent hyperplane at each y* is parallel to that at z.
To each y*, a quantity A* corresponds, such that:
(62)
This quantity can be either positive or negative. When all calculated k' are
positive, the system is stable.
As pointed out in the previous sections, it is a challenging task to locate
all zeros of the TPDF (O(y) in this particular case) because a search over the
entire composition space is required. The search is further complicated by the
existence of a number of trivial solutions, corresponding with the number of
equilibrium phases present. The specific form of <I>(y) (its zeros are its
minima) and the fact that it is easily differentiated analytically, allows the
application of a non-linear minimisation technique for locating its stationary
points, and Stateva and Tsvetkov used the BFGS method with a line-search
(Fletcher, 1987). The implementation of any non-linear minimisation
technique requires a set of "good" initial estimates, and the BFGS method is
no exception. All details of the organisation and implementation of the
initialisation strategy employed by the stability analysis procedure are given
by Stateva and Tsvetkov (1991) and will not be discussed here.
Thus, a method has been created which leads, in practice, to an
"extensive" search in the multidimensional composition space. It has proved
to be extremely reliable in locating almost all zeros of <S(y) at a reasonable
computational cost (Stateva and Tsvetkov, 1991 a, b; 1994). The term
"almost all" zeros is used because there is no theoretically - based guarantee
that the scheme will always find them all. If, however, a zero is missed, the
method is self- recovering, as will be demonstrated later. This unique feature
is a characteristic that distinguishes this procedure from the equation solving
methods, which can eventually fail to determine correctly the phase
identification of the system. Furthermore, the TPDF is minimised once only,
which is a distinct difference from the approach that stage-wise methods
generally adopt. Since stability analysis on its own cannot determine
unequivocally which is the stable phase configuration of a system (identified
as unstable at the given temperature and pressure), it is suggested to run a
sequence of two-phase flash calculations to determine the correct number of
the phases at equilibrium, and the distribution of the components among the
phases.
To assure a steady and non-oscillatory convergence of the flash
calculations, with no tendency towards a strong attraction to the trivial
solution, a reliable initialisation scheme is generated. All possible y* pairs are
taken together as initial estimates since there is no way of telling which
minima of 4>(y) will lead to the global solution. Such application of initial
estimates guarantees a highly diversified search for the phase configuration
with the minimum Gibbs energy. Thus, the chance of using guesses that may
in the end lead to either local optima or solutions already determined or even
to infeasible solutions is greatly reduced. It is possible that some guesses may
lead to a phase configuration physically inconsistent with the overall
composition specified for the mixture and they are rejected. For the
remaining pairs, two-phase flash calculations (in any order) are performed by
any available technique. These calculations lead to different values of the
Gibbs energy and that with the lowest value is selected for further processing,
which determines whether the inclusion of a third phase leads to further
stability. If not, then the two-phase result is the final, stable solution. The
three phase system can be subjected to a further test of the same kind if
1. Given ζ, Γ and P.
2. Run a stability analysis upon z. If the initial solution is stable, the system
is a homogeneous mixture. END. Otherwise, continue with step 3.
5. Run a LLL flash upon z. Use as initial estimates the converged mole
fractions of the solutions determined in step 4. END.
NHromethane 0.0 0.1 0.2 0.3 0.4 0.5 o.e 0.7 o.» 0.9 1.0 Ethylene glycol
Table 2
Ethylene glycol, lauryl alcohol, nitromethane system
at T = 295 K and P = 0.1 MPa.
Feed conditions of case (2). Application of the algorithm, step 3.
Converged mole fractions of solution 1.
Table 3
Ethylene glycol, lauryl alcohol, nitromethane system
at Ύ =295 Κ and Ρ = 0.1 MPa.
Feed conditions of case (2). Application of the algorithm, step 4.
Component Liquid2 ζ LI
C2H602 0.285030 0.689103 0.252575
C,2H260 0.540228 0.0748627 0.577605
CH3NO2 0.1747420 0.2360340 0.169819
α = 0.9235
45
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solution (Table 4). The resulting set of the initial estimates is given in Table
5. Applying these initial estimates, the LLL flash converges in three
iterations. The component distribution for the global solution is given in
Table 6.
Table 4
Ethylene glycol, lauryl alcohol, nitromethane system
at T= 295 K and P = 0.1 MPa.
Feed conditions of case (2). Application of the algorithm, step 4.
Component ς Ϊ 4
C2H602 0.689103 0.096779 0.690811
C12H260 0.0748627 0.035292 0.074977
CH3NO2 0.2360340 0.867929 0.234212
Tables
Ethylene glycol, lauryl alcohol, nitromethane system
at Γ = 295 Κ and Ρ = 0. l MPa.
Feed conditions of case (2). Application of the algorithm, step 4.
The set of the initial estimates obtained (mole fractions)
Component L\ L\ LI
C2H602 0.096779 0.690811 0.252575
C12H260 0.035292 0.074977 0.577605
CH3N02 0.867929 0.234212 0.169819
Table 6
Ethylene glycol, lauryl alcohol, nitromethane system at T = 295 K and P =
0.1 MPa. Feed conditions of case (2). Application of the algorithm, step 5.
The actual global LLL solution, mole fractions
^^^»^^^^^^^^^— >*^^^^— ^^^^to·^^
Component L, L2 L3
C2H602 0.096766 0.691110 0.252738
C12H260 0.035232 0.074737 0.578284
CH3NO2 0.868002 0.234153 0.168978
= 0.0466; ψ2 = 0.4692; ψ3 = 0.4842
where at equilibrium
(64)
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then no phase split is possible, and the system is homogenous at the specified
conditions.
In a new development, Elhassan et al. (1998) extended the original AREA
method into the case of an Nc - component, two-phase system, and provided a
rigorous mathematical proof that the maximum AREA criterion gives a
necessary and sufficient condition for equilibrium in the case of a two
component, two-phase system. The proof demonstrates that with the
exception of a single point, which is the trivial solution, the only points that
maximise the objective function (satisfy the AREA criterion) are the
equilibrium points. Elhassan et al. (1998) proved also for the first time that
the maximum AREA criterion is a necessary but not a sufficient condition for
equilibrium in the case of an Nc component, two-phase system.
Recently, Elhassan et al. (2000), following some discussion in the
•literature (Barton and Hwang, 2000), using classical prepositional logic
demonstrated that for the two-component, two-phase case a stable phase split
always makes the objective function F stationary (maximum, minimum or a
saddle point). Further they argued that because only the maxima satisfy the
material stability criterion, the minima and the saddle points have to be
excluded, and thus proved that a connection between the AREA criterion and
phase stability had been established.
The AREA approach has been used successfully in different kinds of
phase equilibrium calculations (Stateva et al., 199S), especially in the critical
region (Eubank and Hall, 1995; Hanif et al. 1996 a, b; Shyu et al. 1995,
1996).
The goal of the present review was to highlight the application of a wide
variety of numerical methods and optimisation techniques to the solution of
the phase equilibria problem. The methods we have reviewed inevitably have
their merits and disadvantages and our purpose has been to present them in as
non-biased a manner as we can.
In the future, it is expected that there will be a further development of
new methods and evolution of the existing ones. The reason behind this is
that there is still not an effective general method, which can be applied to
perform phase equilibrium calculations, and that will guarantee a
mathematically stable solution for any arbitrary equation of state at elevated
pressures or activity coefficient model. This does indeed prompt the question
whether there can exist a general solution because more thermodynamic
models with higher accuracy are now appearing for all sorts of systems.
However, there is no proof that developing a general method is not possible.
We would like to point out that the need to develop a more reliable
numerical implementation of phase equilibria calculations is pressing also in
other chemical engineering applications. In the introduction we referred to
experimental data regression as an important but till recently neglected area.
One of the key problems in deriving thermodynamic models is adjusting the
model parameters to match experimental data. A failure to do that has a
profound influence on the ability of the model to predict correctly the phase
behaviour. In fact failure to converge to "difficult" experimental points often
causes some points to be ignored in regression even to the extent that the data
for some mixtures cannot be treated at all by the existing algorithms (Gau
and Stadtherr, 2000; Gau et al., 2000). Another important area, which was
not covered in the present review but also requires reliable phase equilibria
calculations, is the determination of homogeneous and heterogeneous
azeotropes (see for example Maier et al. 1998; 1999; Harding and Floudas,
2000b; Tolsma and Barton, 2000 a,b).
It is quite clear that the numerical solution of the phase equlibrium
problem presents considerable challenges and there still remains much to be
done.
LIST of SYMBOLS
Greek letters
α phase split for a two-phase flash
0<a< 1 parameter of the clustering procedure
ε specified global tolerance
φ Gibbs energy of mixing, Eq. (63)
φ, fugacity coefficient, component /
<D(y) modified TPDF, Eq. (60)
γ, activity coefficient, component /
λ homotopy parameter, Eq. (47 - 49)
μ, chemical potential, component /
π number of phases, Eq. (2 - 4)
•ψ phase split for a three-phase flash
Subscripts
L liquid
V vapour
max maximum
min minimum
sad saddle
Superscripts
L liquid
F feed
V vapour
Abbreviations
EOS equation of state
LL liquid-liquid
LLL liquid-liquid-liquid
VL vapor-liquid
VLL vapor-liquid-liquid
TPDF tangent-plane distance function
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