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Fluid Phase Equilibria, 4 (1980) l-10 0 Elsevier Scientific Publishing Company,

1 Amsterdam Printed in The Netherlands





Instituttet for Kemiteknik, Lundtofteuej 100, DK-2800

(Received July 7th, 1979;

Technical Lyngby

University (Denmark)

of Denmark,



in revised form September

ABSTRACT Michelsen, M.L., 1980. Calculation of phase envelopesand critical points for multicomponent mixtures. Fluid Phase Equilibria, 4: l-10. An algorithm for the construction of complete vapour-liquid phase envelopes, capable of accurately determining the critical points and maxima in temperature and pressure is described. Recently developed methods for direct calculation of critical points are critically examined, and a computationally more convenient formulation is suggested.


Calculation of vapourliquid equilibria for multicomponent mixtures using a single equation of state is difficult in the near critical region, as it may not be known in advance whether a given set of specifications corresponds to a single solution, to multiple solutions or to no solution (Erbar, 1975; Heidemar-m and Khalil, 1979). It is therefore of interest to be able to locate certain key-points on the phase envelope, such as the critical point, the temperature maximum and the pressure maximum. In this paper a method for rapid and accurate construction of the complete phase envelope for a specified total composition and phase ratio is described. In addition a significant simplification in a recently developed method for direct determination of the critical point is discussed. The present work is based entirely on the Soave-Redlich-Kwong equation of state for representing vapour-liquid equilibria (Soave, 1972; Christiansen et al., 1979), but the methods may equally well be applied to any other equation of state provided an algorithm for evaluation of component fugacities and their first order partial derivatives with respect to temperature, pressure and composition for specified temperature, pressure, composition and fluid state. The algorithm used in the present work is described fully in Christiansen et al. (1979).

CALCULATION OF PHASE ENVELOPE 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 containing F moles of composition ( yi, y2, . . . . y,). The following set of equations must be satisfied at equilibrium: f; fi = 0
i = 1, 2, . . . . n



(yi/zi)-Ki/[l (xi/zi) l/[l

+ (Ki-l)F] + (Ki l)F]


i = 1, 2, . . . . n i = 1, 2, . . . . n

(3) (4)

= 0

Elimination of the xi and yi using (3) and (4) reduces this set to (n + 1) equations in (n + 2) variables: g&,8) = f?(a,B)--_fi(a,B) = 0,


, . ..) n


gn+l(a, B) =




where a is the vector of dependent variables,

a T = (K,,
K2, T, P)


and p is the vector of fixed specifications, BT =

(Zlr 22, '--,Zrtr 0 (8)

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
gn+2(a, b)=ak-s= 0 (9)

and solving the resulting (n + 2) equations

&a, 8,s) = 0 (10)

by Newton-Raphson iteration: given an estimate a() of the solution vector, an improved estimate acm+l) is found from J(m)Aa +&m) = 0 a(m+l) =(x(m) + Aa where J is the Jacobian matrix at acm), Jii = (dgi/aai). The effectiveness of this approach depends mainly on two factors: the (11) (12)

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 composition 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


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 iterations. 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
a(g)/aS = (0, 0,

= 0


.., 0, -I)


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.
a$:) = a s1 + 6% -%) d(ah,/dS (16)

The components of a and d(a)/dS are now known at points S = S, and S = S,. These values are fitted to a third degree polynomial in S a,(S) = Dlie+ CujlS+ (Yi2S2+ (Yi3S3 (17)

which is used to provide initial estimates corresponding to the subsequent specification S = Ss. If the calculations were to proceed in this manner with specifications of still higher pressures, one would rapidly enter a region where the elements dai/dS became large in magnitude, making the extrapolations (17) inaccurate and finally inapplicable. To avoid this the specification variable is automatically selected in each step as that element of the e-vector with the numerically largest rate of change, that is, the numerically largest value of dai/dS.

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)


For the continued construction of solutions to (10) the extrapolation polynomials (17) are always based on the two last points on the phase envelope. The stepsize, that is, the difference between two subsequent specifications, 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 iterations 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 opposite 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 investigated 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 equilibrium, judging from the compressibility factors of the two phases. For systems 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 compressibility factors for both phases near the pressure minimum, and the compressibility 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.

Fig. 2. 5-component mixture, rich in H2S.

Fig. 3. 5-component

mixture, rich in H,S.

A slight change in composition yields a system with two critical points and two intersecting branches as shown in Fig. 3. The construction of part (a) is initiated easily with a low pressure bubble or dew point calculation as described above, but a point on part (b) cannot be obtained in this manner. Here the construction is started, specifying both phases as liquid and using as initial estimate for the dependent variables those obtained for a corresponding point on Fig. 2. The remaining portion of the curve is constructed without problems. The presence of this branch is suggested by the results obtained in Fig. 2, and it cannot be excluded that other isolated branches may exist. On part (a), phase I is unstable on the bubble point branch below 30 atm, while both phases of part (b) are unstable up to the temperature and pressure maxima. The critical point of this branch is hence located in an unstable region. On the remaining portion the stability criterion is only violated for phase II on a short section extending from the maximum to close to the intersection point.

If only a determination of critical properties is required, the procedure used in the previous section may appear unnecessarily complicated since repeated solution of n + 2 equations rather than a single solution of two simultaneous non-linear equations as formulated by Gibbs, is used. Until recently, however, the effort involved in setting up, evaluating and solving these two equations far exceeded that of constructing the phase envelope. The first major attempt to develop a general procedure for direct determination of Tc and PC was that of Peng and Robinson (1977) who used the

criterion of Gibbs in the form:

F,(T, F,(T, P) = det(U)


(19) (20) (i, j) = 1, 2, .. .. n 1

P) = det(M) = 0

the matrices U and M being (n - 1) X (n- 1) with elements Uij = (aG/aXiaXj)T,r Mlj = a(det( U))/axj
Mij = Uij i = 2, .., n 1

(21) (22) (23)

where G is the Gibbs molar free energy. The computationally expensive part of using (19, 20) is that of evaluating the elements Mlj. For analytic evaluation as used by Peng and Robinson, analytic expressions for (a3G/axiaxjax k)T,e (or, equivalently, for (a2(ln fi)/ aNjaNk),,e) are required, and about (n - 1)2 determinants of order (n - 1) must be computed. The derivation of analytic expressions for the second order partial composition derivatives of the fugacity coefficients of constant temperature and pressure is unattractive and tedious, and errors are easily made. For simple two-constant equations of state, this procedure is certainly possible. However, the large number of determinant evaluations makes the method extremely expensive when n is large, since the computational effort increases as n5. The recent modification by Heidemann and Khalil(l979) is far superior. Their criterion is formulated in terms of the Helmholtz free energy A: at the critical point, a mixture of total composition N must satisfy




C= F cc ~iANjANk(a3A/aNiaNjaNk)T,v i k where

= 0


Qij (a2AIaNiaNj)T,V = =RT(a(h-~f~)/aNj)~,~


Evaluation of the elements of Q and the cubic form C hence requires expressions for the first order and second order partial composition derivatives of the fugacities at constant temperature T and total volume V. These derivatives 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 normalized, 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 i i = FE where
Q* = ; (Q(N + SAN, T, V)),,, (28)

ANk(a3A/aNiaNjaNh)] = ANr QA N (27)


The matrix Q is a partial composition derivative of Q in the AN-direction. Since only a single derivative is required, numerical differentiation becomes much more attractive, e.g.

Q* =(lle)[QW
or Q* = (1/2e)[Q(N

+ e AN, T, VI - QW, T, VI + O(E)

+ EAN, T, V) Q(NEAN, T, V)] + O(E)


where e is chosen suitably small. This modification is particularly attractive for more complicated equations of state, where it may not be possible to derive compact expressions for C, or where the evaluation of the second order composition derivatives of the fugacities is too cumbersome. The approach described above can also be used in connection with partial derivatives of fugacities, taken at constant T and P (which are the derivatives normally required for phase equilibrium calculations), the only difference being that Q has dimension n - 1 rather than n, that is Qij = RT(a and A@ = (AN,, . . . . AN,_,, 0) (32) In filaNj),,p (i, j) = 1 , . . . . n 1 (31)

In the present work this Q-matrix wad used to test the fluid phases found in the phase envelope construction for thermodynamic stability, a necessary (but not sufficient) criterion for stability being that Q is positive definite.


An algorithm for rapid construction vapour-liquid phase envelopes has been developed. The algorithm is based on the Newton-Raphson solution of the non-linear equation, automatic selection of the most convenient specification variables and the use of previously calculated solutions to obtain initial estimates. No difficulties are encountered in the critical region, and the critical point as well as regions of retrograde behaviour are determined accurately. Recent methods for direct determination of the critical point are discussed, and a modification, in which second order partial derivatives of the component fugacities are not needed, is presented.

c :

Helmholtz free energy cubic form fraction of phase II fugacity of component Gibbs free energy


J Ki

Ni i:



Yi zi

see eqns. (5), (6), W, (10) Jacobian matrix, Jij = (ag,/aej) equilibrium factor for component i matrix of partial derivatives, eqns. (22), (23) amount of component i in mixture number of components in mixture pressure critical pressure matrix of partial derivatives, eqn. (26) directional derivative of Q gas constant specification parameter of eqn. (28) temperature critical temperature matrix of partial derivatives, eqn. (21) volume molar fraction of component i, phase I molar fraction of component i, phase II molar fraction in combined mixture

I, II phase I or phase II m-th iteration


Subscripts i, i, k Greek i-th dependent variable, eqn. (7) i-th specification variable increment for numerical differentiation
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 properties 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.

component numbers