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Michelsen - Critical Point - 1979
Michelsen - Critical Point - 1979
Michelsen - Critical Point - 1979
MICHAEL L. MICHELSEN
ABSTRACT
Michelsen, M.L., 1980. Calculation of phase envelopesand critical points for multicompo-
nent mixtures. Fluid Phase Equilibria, 4: l-10.
INTRODUCTION
Assume that one mole of composition (zi. 2s. . . .. z,) is split into phase 1
containing 1 - F moles and of composition (x1, x2, . . . . x,) and phase II con-
taining F moles of composition ( yi, y2, . . . . y,). The following set of equations
must be satisfied at equilibrium:
f;’ - fi’ = 0 i = 1, 2, . . . . n (1)
&~Yi~xi~=O (2)
Elimination of the xi and yi using (3) and (4) reduces this set to (n + 1)
equations in (n + 2) variables:
In the following the complete set of solutions a is called the phase envelope,
and a particular solution corresponds to one point on the phase envelope.
A particular solution is obtained, adding a specification equation for one
of the dependent variables
choice of specification variable and the quality of the initial estimate, a(O).
The method to be described is intended to yield automatically a specification
that leads to a unique solution of (10) and a very accurate initial estimate
corresponding to this specification.
In conventional flash calculations P is specified. This works well in the low
pressure region, in particular for bubble point calculations (F = 0), since the
vapour phase fugacity coefficients depend only weakly on vapour phase com-
position and temperature.
To initiate calculations a pressure specification an+a = S1 (= e.g. 20 atm) is
used here. As suggested by Mollerup (1979) the K-factors in predominantly
hydrocarbon systems are reasonably well approximated by
Kd = (PCi/P) exp{5.42[1- (TCj/T)] j (13)
in the low pressure region. Solving (6) for T using (13) for the K-factors
yields an initial estimate of temperature and phase compositions, from which
convergence of the full set of eqns. (10) normally takes place in 3--5 itera-
tions. One point on the phase envelope, as1 is hence available.
The derivative of the solution vector with respect to the specification S is
easily determined by differentiation of (12):
J d(a)/dS + a&)/as = 0 (14)
where
a(g)/aS = (0, 0, .., 0, -I) (15)
since S enters only in gn+a.
J is known from the Newton-Raphson iteration. Provided (11) is solved for
Aa by triangular decomposition only an extra back substitution is required to
provide d(a)/dS.
The pressure specification is now changed to a,+s = Sa (= e.g. 25 atm), and
(10) is resolved using as initial estimate the linear extrapolation.
To put the elements of a on a comparable basis these elements are here taken
as
aT = (ln(K1), .._, ln(K,), In T, In P) (13)
For the continued construction of solutions to (10) the extrapolation
polynomials (17) are always based on the two last points on the phase enve-
lope. The stepsize, that is, the difference between two subsequent specifica-
tions, is chosen within prescribed limits such that an increase takes place if
less than 3 iterations are used to solve (lo), and a decrease if more than 4 itera-
tions are used. The convergence criterion used is that the norm of Aa is less
than lo-‘.
The automatically chosen step variable is normally the K-factor of the
least volatile component on the bubble point side and the K-factor of the
most volatile component on the dew point side.
For F = 0 the phase envelope is constructed at increasing P on the bubble
point side, through the critical point and back at decreasing P on the dew
point curve. For F = 1 the identical phase envelope is traversed in the oppo-
site direction provided the phase envelope is continuous. Finally, for F = 0.5
the “bubble point” and “dew point” curves are identical, and the critical
point coincides with a maximum in temperature and pressure.
No difficulties are encountered in passing the critical point, and the critical
temperature and pressure, usually accurate to 0.01 K/0.01 atm, are easily
found from the interpolation polynomials (17), based on points on each side
of the critical. Extrema in T or P areindicated by sign changes of dT/dS or
dP/dS and their values are evaluated by differentiation of (17) and solving for
dT/dS = 0 or dP/dS = 0.
A wide variety of examples have been tested, including the 32 systems
analyzed by Peng and Robinson (1977). Here we shall only present two sets
of results, the first being of the type encountered in the majority of cases and
the second a rather unusual type with two separate branches of the phase
envelope.
The P-T curves for F = 0 and F = 0.5 for a ‘I-component system investi-
gated by Heidemann and Khalil (1979) are shown in Fig. 1. For the F = 0
curve 15 points were constructed, the total computing time on the IBM 3033
being 0.2 sec. A similar typical natural gas mixture with 13 components
required 0.6 sec.
A 5-component mixture rich in HzS, very similar to that described by
Heidemann and Khalil (1979) is shown in Fig. 2. The phase envelope consists
of two separate branches, one extending to infinite pressure, and the mixture
has no critical points.
The bubble point branch in Fig. 2 consists of part (a) corresponding to
vapour-liquid equilibrium and part (b) corresponding to liquid-liquid equi-
librium, judging from the compressibility factors of the two phases. For sys-
tems with a single critical point a clearcut distinction between vapour and
liquid phases can be based on the critical compressibility, but for systems
Fig. 1. Nalural gas mixture, 7 components.
with no critical point (or with multiple critical points) no clear distinction is
available. In the present case the compressibilities for the point at 30 atm on
part (a) are 0.09 and 0.67, respectively, indicating a liquid and a vapour
phase, while the compressibilities at the corresponding pressure on part (b)
are 0.09 and 0.15. The dew point branch exhibits a minimum in compressibil-
ity factors for both phases near the pressure minimum, and the compressibil-
ity factors increase to infinity along the branch extending to infinite pressure.
A stability analysis as described in the next section shows that phase I of
part (a) and both phases of part (b) are thermodynamically unstable, while
the stability criterion is not violated on the F = 1 branch.
C= F cc ~iANjANk(a3A/aNiaNjaNk)T,v = 0 (25)
i k
where
Qij= (a2AIaNiaNj)T,V
=RT(a(h-~f~)/aNj)~,~ (26)
Evaluation of the elements of Q and the cubic form C hence requires ex-
pressions for the first order and second order partial composition derivatives
of the fugacities at constant temperature T and total volume V. These deriva-
tives are more easily evaluated than those required by Peng and Robinson
and expressions for all derivatives needed are given by Heidemann and
Khalil. It is easily shown that the cubic form C corresponding to a given AN
can be reduced to very simple terms, the evaluation requiring essentially only
two double summations. The main computational effort required in solving
(24, 25) is that of determining conditions where a homogeneous solution to
the set of linear algebraic eqns. (24) exists.
To evaluate Tc and PC (or rather Vc), Ileidemann and Khalil used nested
iterations. In an inner loop at fixed V, Newton iteration is used to determine
a value of T such that det(Q) = 0. The AN vector is determined and normal-
ized, and C is evaluated to correct V in the outer loop. The procedure is
repeated until convergence is achieved.
With their recommendations for facilitating the solution of (24, 25) we
found this approach very efficient. A single determination of the critical
point by this procedure typically requires 30-50% of the computing time
needed for the phase envelope construction.
It is, however, of interest to point out that the cubic form C and hence the
need to evaluate all second order partial composition derivatives can be
avoided completely, since C can be rewritten:
C = C C ANiANj[q ANk(a3A/aNiaNjaNh)]
i i
CONCLUSION
NOTATION
Superscripts
I, II phase I or phase II
m m-th iteration
10
Subscripts
i, i, k component numbers
Greek
REFERENCES
Christiansen, L.J., Fredenslund, Aa. and Michelsen, M.L., 1979. Successive approximation
distillation calculations using the SRK equation of state. Computers and Chemical
Engineering (in press).
Erbar, J.H., 1975. Thermodynamic property predictions in process design, Vapor-Liquid
Equilibria in Multicomponent Mixtures, Jablonna, Poland.
Heidemann, R.A. and Khalil, A.M., 1979. The calculation of critical points, Paper
presented at 86th AIChE meeting, Houston, USA.
Mollerup, J., 1979. Private communication, Instituttet for Kemiteknik.
Peng, D.Y. and Robinson, D.B., 1977. A rigorous method for predicting the critical prop-
erties of multicomponent systems from an equation of state. AIChE J., 23: 137.
Soave, G., 1972. Equilibrium constants from a modified Redlich-Kwong equation of
state. Chem. Eng. Sci., 27: 1197.