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Alan C. Pierce, SPE, Amoco Production Co.

Kraemer D. Luks, SPE, U. of Tulsa

Abstract

Equations of state are used to predict or to match vergence pressure correlations and subsequently to the

equilibrium fluid phase behavior for systems as diverse development of more sophisticated equation of state

as distillation columns and miscible gas floods of oil methods for modeling and predicting phase equilibria.

reservoirs. The success of such simulations depends on For adequate description of the compositional effects

correct predictions of the number and the compositions that occur in enhanced oil recovery processes such as

of phases present at a given temperature, pressure, and CO 2 and rich gas flooding, an equation-of-state ap-

overall fluid composition. For example, recent research proach is a virtual necessity.

has shown that three or more phases may exist in The use of equations of state for phase equilibrium

equilibrium in CO 2 floods. prediction is not limited to the petroleum industry. Such

This paper shows why an equation of state can predict equations also find wide use in basic chemical and

the incorrect number of phases or incorrect phase com- physical research, and in the refining and chemical proc-

positions. The incorrect phase descriptions still satisfy essing industries.

the usual restrictions on equality of chemical potentials Solution techniques for phase equilibrium problems

of components in each phase and conservation of moles are varied and depend to some extent on the application

in the system. A new method and its mathematical proof and equation of state used; however, there are three

are presented for determining when a phase equilibrium restrictions that all phase equilibrium solutions must

solution is incorrect. satisfy.

Examples of instances where incorrect predictions First, material balance must be preserved. Second, for

may be made are described. These include a binary phases in equilibrium there must be no driving force to

system in which a two-phase solution may be predicted cause a net movement of any component from one phase

for a single-phase fluid and a multi component to any other phase. In thermodynamic parlance, the

CO 2 /reservoir oil system in which three or more phases chemical potentials for each component must be the

may coexist. same in all phases. Third, the system of predicted phases

at the equilibrium state must have the lowest possible

Introduction Gibbs energy at the system temperature and pressure.

Advances in reservoir oil recovery methods have The requirement that the Gibbs energy of a system, at

necessitated advances in methods for prediction of phase a given temperature and pressure, must be a minimum is

equilibria associated with those methods. It was long a statement of the second law of thermodynamics,

considered sufficient to approximate the reservoir equivalent to the more common version requiring the en-

behavior of oil and gas systems with models in which tropy of an isolated system to be a maximum. The

compositions of the phases in equilibrium were unimpor- equivalence is demonstrated formally in Ref. I, for ex-

tant. In such a model, the amounts and properties of the ample. If the Gibbs energy of a predicted equilibrium

phases are dependent on pressure and temperature only. state is greater than that of another state that also satisfies

Later, experience in production from condensate and Requirements I and 2, the state with the greater Gibbs

volatile oil reservoirs showed that models incorporating energy is not thermodynamically stable.

compositional effects were required to simulate the Requirements I and 2, material balance and equality

phase equilibria adequately. This led to the use of con- of chemical potentials, are used commonly as the sole

0197-7520/82/0010-9806$00.25

criteria for solution of phase equilibrium problems. In

Copyright 1982 Society of Petroleum Engineers of AIME many cases, there is no problem with this usage;

OCTOBER 1982 731

PB

91 I

P2

I 12

P 3fl

9z 1---

4

a..

PI

""

I

I

I

I

I I

I I

PA I I

I I

0 XB-- o XLl FHO Xv

XB--

Fig. 1-Pressure/composition diagram for AS system. Fig. 2-Gibbs energy diagram for A-S system at p 1 .

however, there are important instances when the Gibbs Then we describe a method for detecting false solutions

energy minimization requirement also must be con- and illustrate why it succeeds when other methods fail.

sidered. As discussed later, equality of chemical poten- Finally, we give specific examples of the utility of the

tials is necessary but not sufficient for minimization of method, using a version of the Redlich-Kwong equation

the Gibbs energy. of state.

The iterative solution techniques usually used in find-

ing equilibrium states may lead to a trivial situation (all

Illustration of the Problem

phases present having the same properties) that always

will satisfy the first two requirements but not necessarily Fig. 1 shows the pressure/composition diagram for a

the third. Of more importance perhaps, particularly in system composed of hypothetical Components A and B

enhanced oil recovery, is the possibility of predicting at a fixed temperature. The system exhibits two-phase

false two-phase states in or near a three-phase region. (L I + V) behavior at low pressures; a three-phase region

These states can satisfy material balance and chemical (L I + L2 + V) limited to a single pressure, P 3, for a

potential restrictions while failing to minimize the Gibbs binary system; and regions of L I + L2 and L2 + V two-

energy. This leads to predictions of incorrect phase phase equilibrium at pressures greater than P 3' In some

volumes and properties (density, viscosity, etc.), which pressure and composition ranges, the system is single-

can adversely affect the results of an oil recovery phase L I , L 2 , or V.

simulation. The purpose of using an equation of state is to predict

Several authors 2-7 have reported the occurrence of accurately the phase behavior of such a system. The first

multiple (three or more) phases in rich gas/oil and step in solving a phase equilibria problem can be de-

CO 2 /oil reservoir systems. Others S- IO have shown that scribed mathematically as finding a plane tangent to the

when there are multiple phases, it is possible to predict Gibbs energy surface (g surface), with material balance

equilibria at states that do not minimize the Gibbs energy restrictions. (See Appendix for a more detailed descrip-

of a system. tion.) The slope of the tangent plane corresponds to the

This paper describes such failures in solving the phase component chemical potentials (related to the

equilibria problem in terms of Gibbs energy analysis. It fugacities). The points oftangency of the plane and the g

also presents a method, and a mathematical proof sup- surface correspond to the compositions of the predicted

portive of the method, for identifying false solutions. equilibrium phases. For binary systems, as illustrated

Examples of the technique are given. For an elegant here, the g surface is a curve and the tangent plane is a

treatment of some properties of a Gibbs energy surface, straight line. For multicomponent systems, the g surface

the reader is directed to Coleman, II Dunn and is a hypersurface and the tangent plane is a hyperplane.

Fosdick, 12 and references in those papers. The material balance restrictions require the overall com-

position of a multiphase system to lie within the region

Discussion bounded by the points of tangency of the g surface and

Equations of state often are used to predict phase the tangent plane.

equilibrium solutions. Gibbs energy analysis is the use of These concepts are illustrated in some detail in Figs. 2

an equation of state to calculate a Gibbs energy surface through 5, which represent the Gibbs energy surface

and to determine whether a predicted equilibrium state (curve) for the A-B system at increasing pressures.

has the lowest possible Gibbs energy. We first illustrate Fig. 2 shows the Gibbs energy diagram (Gibbs energy

the use of a Gibbs energy surface to determine phase vs. composition) for the A-B system at pressure

equilibria and show how false solutions can be obtained. PI <P3' The Gibbs energy surface (curve) is calculated

I

91 ~-

93 -J.---

I

t I

"" I

I

I

I

I

I

I

I

I

0 Xu FEED XL2 Xv

XB--

Fig. 3-Gibbs energy diagram for A-8 system at p', . Fig. 4-Gibbs energy diagram for A-8 system at p 3<1>'

for a hypothetical homogeneous (single) phase at all pair of phases satisfying material balance and equality of

compositions and does not represent the actual Gibbs chemical potentials, but only the lower tangent gives a

energy except in the single-phase region and at the minimum Gibbs energy (g 2 < g 2 ' < g 1 ). Consistent with

equilibrium phase compositions. The g surface is con- our earlier observation, only the lower tangent does not

cave upward except in the two-phase composition lie above the g surface at any point.

region. A tangent to the g surface indicates the Fig. 4 shows the g surface at the three-phase pressure,

equilibrium liquid and vapor compositions (points of P 3</> The phase equilibrium solution for the multiphase

tangency). For a given feed composition (as indicated in region (XLI to xv) is given by a tangent at XLI, XL2, and

Fig. 2), the liquid- and vapor-phase fractions can be Xv. As in Figs. 2 and 3, in the composition range XLI to

determined by application of the lever rule. The Gibbs Xv the upper curve is the (hypothetical) Gibbs energy for

energy, g 2, is the molar sum of the phase Gibbs energies a homogeneous phase (g 1 at the indicated feed), while

(g's at the point of tangency) and'lies on the tangent line the actual Gibbs energy g3 is a mole-weighted sum of

at the feed composition. The two-phase Gibbs energy, the phase molar Gibbs energies at the points of tangency,

g 2, is less than the Gibbs energy, g 1 , of the hypothetical XLI,xL2, andx v

homogeneous phase of this composition, indicating that The relative amounts of phases L I, L 2 , and V are not

the two-phase system is more stable than a single phase. fixed by the compositional lever rule in this binary case,

For all feed compositions outside of the two-phase but they are bounded in that as pressure is increased, L2

region, a tangent to the g surface does not intersect the is formed from L 1 and V until one or the other of these

surface at any other point; however, for any composition phases is consumed.

within the two-phase region, a tangent to the Fig. 5 presents the Gibbs energy surface atp2 >P3</>'

hypothetical g surface at that point does intersect (and lie There are two two-phase regions: XLI -x L2, and X L2' -Xv

above) the g surface at some point in the overall com- For the indicated feed, three possible states satisfying

position range. In the next section and in the Appendix material balance and equality of chemical potentials are

we show that this is a necessary and sufficient condition indicated. Only one of these (xLI-XL2, Tangent Line 2)

for stability of a predicted phase equilibrium solution. has the minimum Gibbs energy, The solutions cor-

For a stable solution, the tangent corresponding to the responding to 2' and 2" both have Gibbs energies less

solution does not lie above the g surface at any than g 1 of the hypothetical single phase but greater than

composition. the Gibbs energy of the true solution.

Fig. 3 shows the Gibbs energy surface for A-B at a A feed with composition between XL2 and xL2' will be

higher pressure, P'I , which is still less than P 3</>. In this single-phase at the temperature and pressure specified.

case, the g surface resembles that at PI, but an additional However, Tangent Line 2' corresponds to a two-phase

lobe (the incipient L2 phase) has appeared at a composi- (false) solution for a feed in this composition range, This

tion between that of the liquid and vapor phases. A is an exception to the heuristic rule of thumb that, for a

tangent to the g surface locates equilibrium phase com- given feed, the more phases present at equilibrium, the

positions xLI and Xv for any feed composition in the lower the Gibbs energy will be. 13

two-phase region. An additional tangent to the g surface An observation may be made here concerning the utili-

at XLI 'and xv' locates a false solution. For the feed in- ty of second derivative tests 9 for determining stability of

dicated, either one of the tangent lines corresponds to a a phase equilibrium solution. Such a test indicates the

OCTOBER 1982 733

~.-----.------.-----.------r-----.

6000

L

+

""

is:! 4000

::>

Vl

Vl

.....

Q::

0..

2000

Fig. 5-Gibbs energy diagram for A-B system at P2' Fig. 6-Pressure/composition diagram for C0 2 /toluene at

38.1C.

direction of curvature of the g surface. For a stable solu- associated tangents must be examined concurrently with

tion, the g surface must be concave upward at the points the solution of mass flow equilibria equations (material

of tangency. Downward curvature indicates definite in- balance and equality of chemical potentials) to ensure

stability. The solution (tangent) labeled as 2" is unstable that the minimum Gibbs energy has been found.

by this criterion because the g surface at the point of We also have indicated that the tangent corresponding

tangency near Xv is concave downward. The g surface is to an equilibrium solution qnnot lie above the Gibbs

concave upward for both tangency points of Solution 2', energy surface for any composition. This is described in

however, and this solution would be considered stable by more detail and extended to multicomponent systems in

the second-derivative criterion. the next section and in the Appendix.

At pressure P3 shown in Fig. I, the lobe of the g sur-

face corresponding to the V phase will have vanished. The Gibbs Energy Analysis

The Gibbs energy curve will resemble that of Fig. 2, The general phase equilibria problem for a feed of I com-

with L I and L2 phases forming from a feed. ponents consists of finding a stationary state that is an

We have shown schematically, and for very simple equilibrium state. A stationary state corresponds to an

systems, that false solutions (not corresponding to the extremum or saddle point in the total Gibbs energy of a

minimum Gibbs energy) to phase equilibrium problems system (Appendix, Definition 2), where the system is a

can be generated for compositions in and around set of phase compositions satisfying the mass balance re-

multi phase regions. The nature of the g surface and quirement. An equilibrium state is a stationary state cor-

nRT An2

P=----- . Fluid Properties

V -nB T'h V(V +nB) T

Tc Pc

Component (K) (kPa) (0C) na nb

I I

CO 2 304.16 7398.1 -25.0 0.42564 0.08003

A= L; L; X,XJCl'.;j' 35.0 0.43776 0.08886

1= 1 j= 1

38.1 0.43776 0.08886

toluene 591.77 4067.9 38.1 0.44485 0.07986

f

n-decane 617.55 2096.0 -25.0 0.46432 0.07042

B= L; x/3;. iodobenzene 721.11 4529.9 35.0 0.41931 0.08213

i= 1

Interaction Parameters, C Ii

C0 2 /toluene 0.080

C0 2 /n-decane 0.095

CO 2liodobenzene 0.1365

2000 , - - - - - , - - - - - - - , - - - - y - - - , - - - - - - - ,

1750 r------r---..,.,.-----,-----r---,

1500 1700

"0

E

:::; 1000

>-- ~ 1650

<.:>

a::: ... -----

UJ

z

UJ 500 I

Vl

<0

I

<0 1

<.:> 1 FALSE

o

-- ---

--I V/

1550

1- L1 +L2 ------..,~;

I

1

-----+1- L1 +V-------t---

-- L+V

-500L-_ _ _ _ _ _ _ _ _ _ _

~ ~ ~ ~ ~ 1500L-~_~_ _ _-u_ _ _~_~L_~

o O. 2 O. 4 O. 6 O. 8 D. 6 D. 7 D. 8 D. 9

MOLE FRACTI ON CO MOLE FRACTION CO

2 2

Fig. 7-Gibbs energy of mixing of CO 2 /toluene at 38.1C, Fig. 8-Pressure/composition diagram for CO 2 /n-decane at

1379 kPa. -25C.

responding to the global minimum in the total Gibbs In the following examples, Gibbs energies of mixing

energy of a system. The mathematical criteria for deter- are calculated by using a version 14 of the Redlich-

mining the equilibrium state are developed in detail in Kwong equation of state. Other equations of state will

the Appendix. Briefly, it is shown that the equations of produce similar results. The equations of state, mixing

mass flow equilibria are satisfied at a stationary state rules, and the component parameters used for the binary

(Theorem I). Solution of these equations-i.e., finding examples to follow are given in Table 1.

the compositions of the coexisting phases-is equivalent Calculation of the Gibbs energy for a system is based

to finding the hyperplane that is tangent to the Gibbs on the relation

energy surface at the J points denoting the composition

of the phases in equilibria (Theorem 2). However, this

condition of tangency does not guarantee that the sta- G=pV+ J(lO (nRT)

p - - - dV-RT ~

I (V)

n;ln - . -

tionary state is an equilibrium state. v V 1=1 nlRT

Theorems 3 and 4, with their associated lemmata,

show that the equilibrium state-i.e., the state in which

the Gibbs energy is a global minimum under the conser- + ~ n;(U;'-TSn. . .................. (1)

vation of mass constraints imposed by the feed-is the ;=1

condition in which the Gibbs energy surface is

everywhere either on (tangent to) or above the tangent Insertion of the equation of state to be used into Eq. I

plane. (as illustrated by Baker and Luks 15 or by Peng and

The implication is, once the mass flow equilibrium Robinson 16) leads to an expression that can be evaluated

problem for I components is solved and the J phases are at the pressure, temperature, and composition of a given

identified, that one must verify that this (stationary) state fluid phase.

is the actual equilibrium state. This can be done by deter- Throughout this discussion, we refer to the Gibbs

mining whether the tangent hyperplane lies above the energy of mixing, which is the phase Gibbs energy less

Gibbs surface at any composition. The tangent plane cor- the mole-weighted sum of the pure component Gibbs

responding to the equilibrium state lies entirely below or energies. This treatment makes the choice of the pure

tangent to the Gibbs energy surface. The numerical ap- component standard states immaterial. For convenience,

plication of this technique is not described here. In prin- we may choose U? and S? to be zero for all components.

ciple, any technique for finding roots of the equation

G( r) - L(T) = 0 < a should suffice to find points where Example I: CO 2 /Toluene System at IOO.6F

the Gibbs energy surface lies below the tangent plane (38.I O C). The pressure/composition diagram 17 for

corresponding to a predicted phase equilibrium solution, CO 2 /toluene is shown in Fig. 6; the Gibbs energy of

if any such points exist. mixing at 200 psia (1379 kPa) (noted by the dashed line)

is plotted as a function of CO 2 concentration in Fig. 7.

Examples of Gibbs Energy Analysis In this case, there are no three-phase phenomena. The

For ease of illustration, we chose binary systems tc two-phase region at 200 psia (1379 kPa) is spanned by

demonstrate the range of possibilities of phase equilibria the tangent to the Gibbs energy curve, namely, the range

solutions. As shown later in this section, the problem of of 12 to 99% CO 2 , The regions outside this two-phase

false phase equilibrium solutions is encountered also in region are one-phase. In the region of 65 to 87 % CO 2 ,

more complex systems (such as CO 2 ireservoir oil). The there is more than one possible Gibbs energy at each

principles described by the theorems in the Appendix ap- composition because there are three real compressibility

ply equally well to these more complex mixtures. solutions for the equation of state. In calculating a Gibbs

OCTOBER 1982 735

0.2 0.4 0.6 0.8

MOU FRACTIOO CO

2

Fig. 9-Gibbs energy of mixing of CO 2 In-decane at - 25C, Fig. 11-Gibbs energy of mixing of CO 2/n-decane at - 25C,

1610.6 kPa. 1620.3 kPa.

- JIm !:--:'-=---::'-:_-:!-:_::'-::-----:

o 0.2 0.4 0.6 0.8

MOU FRACTIOO CO

2

Fig. 10-Gibbs energy of mixing of C0 2 /n-decane at - 25C, Fig. 12-Gibbs energy of mixing of CO 2 In-decane at - 25C,

1613.4 kPa. 1723.7 kPa.

energy curve, where there are multiple real com- possible false solutions, an L, ' + L 2 ' and an L2 " + V

pressibility solutions of the equation of state, only the solution, as evidenced by the dashed lines tangent to the

solution giving the lowest Gibbs energy should be con- Gibbs energy surface at L, ' and L 2 ' and at L 2 " and V.

sidered, and that is the one shown in Fig. 7. We em- These solutions are shown in Fig. 8 as dashed line exten-

phasize again that the solid Gibbs energy curves plotted sions (into the L, + V region) of the L, + L2 and L2 + V

in the two-phase region (12 to 99% CO 2 ) do not repre- solutions that exist at pressures greater than P 3</>

sent the equilibrium Gibbs energy of the system; the For each of the possible solutions shown in Fig. 9, the

dashed line tangent to the Gibbs energy surface Gibbs energy curve is concave upward at the points of

represents the true equilibrium Gibbs energy in the two- tangency of the solution lines. Thus, tests of the second

phase region. The solid curves are the Gibbs energies derivatives of G, (a2Glanianj), as recommended by

calculated as if the system were a single homogeneous Sorensen et al., '0 could not distinguish the true solution

phase at the pressure, temperature, and composition from the false solutions. However, for each of the false

specified. solutions, the tangent line (solution line) lies above the

Gibbs energy surface at some point. The tangent line for

Example 2: CO 2 /n-decane at -l3F (-25C). The the true solution does not lie above the Gibbs energy

pressure/composition diagram for this system is shown curve at any point, in accordance with the theorems

in Fig. 8. Both CO 2 and decane are subcritical in this proved in the Appendix.

case. In the pressure range considered, the system ex- Fig. 10 shows the Gibbs energy curve at the three-

hibits one-phase, two-phase (L, + V, L, + L 2 , L2 + V) phase pressure, p=234 psia (1613.4 kPa). In this case, it

and three-phase (L, + L2 + V) behavior. The three-phase would be possible to determine L, + L 2 , L2 + V,

region for a binary is limited to a single pressure (at fixed L, +V, or L, +L2 +V solutions; however, the two-

temperature), in this case 234 psia (1613.4 kPa). The phase solutions simply correspond to the case of absence

solid lines are the equation of state predictions, and they of a third phase, which (if it existed) would be in

closely mimic experimental data. '8 Gibbs energy of equilibrium with the other two. This may occur physical-

mixing predictions are shown in Figs. 9 through 12. In Iy. Depending on factors such as the system enthalpy,

Fig. 9, atp=233.6 psia (1610.6 kPa) (P<P3</, the two- there may be L, +L 2 , L, +V, L2 +V, <1r L, +L2 +V.

phase liquid and vapor equilibrium compositions are An increase in system enthalpy will drive the equilibrium

shown as L, and V and are connected by a line tangent to L, + L2 or L2 + V, depending on the composition,

to the Gibbs energy surface. In this case, there are two while a decrease in enthalpy will drive the equilibrium to

736 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

L I + V. The case is analogous to that of a pure liquid at 10000 I I

its boiling point, where liquid and vapor may coexist in

9500

any proportion.

Fig. 11 shows the calculated Gibbs energy curve for 900l L1 . L1 + L2

~-

p=235 psia (1620.3 kPa). There is an LI +L2 region,

an L 2 ' + V region, and an intervening single phase (L 2 ) 8500

region (as seen in Fig. 8). The tangent lines for the cor-

CRITICAL POINT-

rect solutions are shown. Also shown is a false L I + V

prediction obtained for a feed composition in the single-

L1+~+V,\ V

phase region. At the points of tangency of this unstable

solution, the Gibbs energy curve is concave upward; se-

cond derivative tests could not determine stability of the

solution. However, the tangent line intersects a lobe of

6500

I FALSE CRITICAL POINT .--/"

iii

the Gibbs energy curve, as theory predicts it should for 6000 ~L1+V

an unstable solution. This is also a prime example con- 5500 I

tradicting the heuristic rule proposed by Gautam and 0.4 0.5 0.6 0.7 0.8 0.9

Seider 13 that a P-phase solution, if it exists, has a lower MOLE FRACTION CO

2

Gibbs energy than a P-I phase solution.

Fig. 12 presents the Gibbs energy curve for CO 2 /n-

decane atp=250 psia (1723.7 kPa) (p> >P3q,). In this Fig. 13-Pressure!composition diagram for CO 2!iodo-

case, the vapor lobe of the curve has disappeared, leav- benzene at 35C.

ing only an L I + L2 two-phase region and L I and L2

single-phase regions.

CO 2 /iodobenzene system is interesting because it FALSE CRITICAL

critical point. Experimental data on this system are not

available, so the specific description of the phase

behavior may be regarded as somewhat conjectural.

However, we also have observed the illustrated

phenomenon in other, more complex, systems in which

the presence of a predicted critical point was not sup- -~~~~~~~--~~

o 0.2 0.4 0.6 0.8

ported by experimental data. MOLE FRACTION CO

2

The predicted pressure/composition diagram for

CO 2 /iodobenzene at 95F (35C) is shown in Fig. 13.

There is a liquid/vapor (L I + V) region, a liquid/liquid

(L I + L 2 ) region, a liquid/vapor (L2 + V) region bound- Fig. 14-Gibbs energy of mixing of CO 2!iodobenzene at

ed above by a critical point, and a three-phase pressure. 35C, 6847.2 kPa.

At a slightly higher temperature [98.4F (36.9C)], the

L2 + V region disappears, with a two-phase K-point

(L I + L2 = V critical fluid) solution.

The most interesting aspect of this diagram is the 26000

critical point solution indicated at 96.8% CO 2 , 993.1

24500

psia (6847.2 kPa).

The Gibbs energy curve in the region of this critical 21000

point is shown in Fig. 14. The mathematical criteria for a

binary system critical point, ;;:, 17500

"'"

l5!' 14000 L1

(::~) (:~~)

:::>

T,p.n2 = T.p.n2 =0, ......... (2) '"

~ 10500 UPPER BO~D OF L + V SOLUTIONS

c.. J

LJ + ~ + V

are satisfied. However, the inequality (a G/an I 4h.P.n, J

3500

> 0 that ensures stability is not satisfied. Consequently:

the dashed line tangent to the curve at the predicted O~~L-~L-~__~__~

critical point lies above the curve almost everywhere out- o 0.2 0.4 0.6 O. 8

MOLE FRACTION CO

side the immediate vicinity of the point. The curvature of 2

the Gibbs energy surface at this point is caused by the in-

cipient L2 lobe, which grows downward as pressure is

increased. The true liquid/vapor phase equilibrium is in- Fig. 1S-C0 2!Leveliand oil phase behavior at 41.1 C.

dicated by the dashed line tangent to the g surface at L I

and V of Fig. 14.

OCTOBER 1982 737

Similar false critical points for this system can be the tangent plane lies above the Gibbs energy surface at

calculated (with the equation of state and parameters any point, the predicted equilibrium solution is false.

shown in Table I) over a temperature range of 70 to Conversely, if the plane lies entirely below or tangent to

116F (21 to 47C). the Gibbs energy surface, the solution does describe the

equilibrium state.

Example 4: CO 2 /Levelland Oil at 106F (41.1C).

The pressure/composition diagram for the CO 2 / Nomenclature

Levelland oil system 7 is shown in Fig. 15. We cannot

A = temperature-, pressure,- and composition-

represent rigorously either the pressure/composition sur-

face or the Gibbs energy surface for this system because dependent phase parameter (Table I)

such a representation would require N dimensions, B = temperature-, pressure-, and composition-

where N is the number of components in the system. dependent phase parameter (Table I)

However, the regions of multiphase (L I + V, L I + L 2 , C ij = interaction parameter for component i with

L I + L2 + V) solutions are shown, with an indication of component j (Table I)

the regions where unstable solutions also may be found. D = G- L, the difference between the Gibbs

In general, with complex systems such as these, L I + V energy surface and a tangent plane

solutions may be obtained not only in the actual L I + V (function of composition)

region but also in the L I + L2 region and the three-phase F = function defined in Lemma 2 (Appendix)

(L I + L z + V) region. Similarly, L I + L z solutions also

G = Gibbs energy surface

may be found in all three regions. Three-phase solutions

g = molar Gibbs energy

are found only in the region marked L I + L z + V. Gibbs

energy analysis is as successful in detecting false solu- I = number of components

tions for this system as it is in the binaries of Examples I J, K = number of phases

through 3. e = hypothetical phase vector

It is usually possible to obtain L I + V solutions in the L = liquid phase (subscripted)

L I + L z region for only a (relatively) small pressure in- L = plane tangent to Gibbs energy surface, G

terval above the three-phase region, while L I + L2 solu- m ij = composition variable, composition of

tions often may be found in the L I + V region at

component i in phase j

pressures far below the three-phase region. This results

from the variation in shape of the Gibbs energy curve,

mj = vector (mlj' m2j . .. mlj), composition of

with an L2 lobe persisting at quite low pressures, while phase j

the vapor lobe disappears rapidly with pressure increas- m= state, set of phase composition vectors mj

ing above the three-phase pressure. This is not surpris- n = number of moles

ing, because the properties of a liquid phase are more in- n = state, set of phase composition vectors

sensitive to pressure variation than the properties of a p = pressure, psia (kPa)

vapor phase. r = phase composition vector (r I , r 2 . . r I)

Since false phase equilibrium predictions can be ob- R = gas law constant

tained over a wide range of pressure and composition, it S7 = standard state molar entropy of component i

is important to confirm that the correct solution is found. T = temperature

For the CO 2 /Levelland oil system, the properties (densi-

ty, viscosity) of the L I liquid phase are similar in the

U7 = standard state molar internal energy of

component i

L I + V and the L I + L2 regions. However, the proper-

ties of the vapor (V) and the L2 liquid phases are strik- V = vapor

ingly different. For example, the L z phase density is x = mole fraction

commonly two or more times the density of the vapor IX ij = temperature-dependent component

the L I + L2 region of the phase diagram could lead to a {3 i = temperature-dependent component

much different performance in a reservoir model of a parameter

COz flood. Similarly, the third phase present in the o = negative number

L I + L2 + V region could have a marked effect on the Ej = positive number

fluid flow behavior and relative permeabilities. Unless T = variable parameterizing a curve in com-

the model recognizes the possibility of a third phase, a

position space

two-phase (L I + V or L 1 + L 2 ) equilibrium would be

11- = chemical potential

predicted, with possibly adverse consequences.

e = variable defined in Lemma 2 (Appendix)

Conclusions na, nb = generalized component parameters, func-

For fluid systems that exhibit multiple phases, an equa- tion of the reduced temperature and the

tion of state may predict false phase equilibrium component Pitzer acentric factor

solutions.

This paper presents a self-consistent method for deter- Subscripts

mining whether a predicted equilibrium state is false.

The method makes use of the equation of state to c = critical

calculate the Gibbs energy surface and the tangent plane i = component i

corresponding to the predicted equilibrium solution. If j = component j (Table I); phase j elsewhere

738 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

k phase k stream is represented by (nl, n2'" n1), we say the

total phase r is admissible if 0 < r i < n i' This discussion is

v = component v limited to systems of admissible phases, in which each

cf> phase component is present (at least in a trace amount) in each

1,2,3 phase identification phase. The results are not strictly applicable to a system

in which any component is excluded from one or more

References phases.

A possible state of a system of I species and J phases

I. Callen, H.B.: Thermodynamics, John Wiley and Sons Inc., New resulting from a feed n is designated m=[mj] wheremj

York City (1960). is thejth phase. Conservation of mass requires

2. Huang, E.T.S. and Tracht, J.H.: "The Displacement of Residual

Oil by Carbon Dioxide," paper SPE 4735 presented at the SPE J

Third Symposium on Improved Oil Recovery, Tulsa, April 22-24,

1974.

L: mij=ni ............................ (A-I)

3. Shelton, J.L. and Yarborough, L.: "Multiple Phase Behavior in j=1

Porous Media During CO z or Rich-Gas Flooding," J. Pet. Tech.

(Sept. 1977) 1171-78. for each i, I $. i $. I. Herein, it is assumed that one has a

4. Gardner, J.W., Orr, F.M., and Patel, P.D.: "The Effect of Phase

nonreacting system.

Behavior on CO) Flood Displacement Efficiency," J. Pet. Tech.

(Nov. 1981) 206-7-81. At a given pressure and temperature, the Gibbs energy

5. Henry, R.L. and Metcalfe, R.S.: "Multiple Phase Generation function for a phase is G=G(r). The Gibbs energy is a

During CO 2 Flooding," paper SPE 8812, presented at the First continuous first-order function in accordance with

Joint SPE/DOE Symposium on Enhanced Oil Recovery, Tulsa, classical thermodynamics (e.g., see Callen I). The total

April 20-23, 1980.

6. Orr, F.M., Yu, A.D., and Lien, c.L.: "Phase BehaviorofCO z

Gibbs energy for a system of J phases is

and Crude Oil in Low Temperature Reservoirs," Soc. Pet. Eng. J.

(Aug. 1981) 480-92.

7. Turek, E.A. et al.: "Phase Equilibria in Carbon Dioxide-Multi-

component Hydrocarbon Systems: Experimental Data and Im- J

proved Prediction Technique," paper SPE 9231 presented at the

SPE 1980 Technical Conference and Exhibition, Dallas, Sept. L: G(mj), ..................... (A-2)

21-24. j=1

8. Heidemann, R.A.: "Three Phase Equilibria Using Equations of

State," AIChE J. (1974) 20,847-55. which is the sum of the Gibbs energies of the constituent

9. Evelein, K.A., Moore, R.G., and Heidemann, R.A.: "Correla-

tion of the Phase Behavior in the Systems Hydrogen Sulfide-Water phases.

and Carbon Dioxide-Water," I&EC Proc. Des. Dev. (1976) 15, An equilibrium state for a system will exhibit a global

423-28. minimum in the Gibbs energy. The following definitions

10. Sorensen, J.M. et al.: "Liquid-Liquid Equilibrium Data: Their are made to distinguish between phase states correspond-

Retrieval, Correlation and Prediction," Fluid Phase Equilibria

(1979) 3, 47-82.

ing to local and global minima.

II. Coleman, B.D.: "On the Stability of Equilibrium States of

General Fluids," Arch. Rational Mech. Anal. (1979) 36, 1-32. n

Definition 1. A state of J admissible phases satisfying

12. Dunn, J.E. and Fosdick, R.L.: "Morphology and Stability of conservation of mass is an equilibrium state if

Phases," Arch. Rational Mech. Anal. (1980) 74, 1-99. Gt(n)=min Gr(m) where the minimum is taken over all

13. Gautam, R. and Seider, W.D.: "Computation of Phase and

Chemical Equilibrium: Part II-Phase Splitting," AIChE J. states mof K admissible phases satisfying conservation

(1979) 25, 999-1006. of mass (K not necessarily equal to 1).

14. Yarborough, L.: "Application of a Generalized Equation of State

to Petroleum Reservoir Fluids," Equations of State in Engineering

and Research, K.C. Chao and R.L. Robinson Jr. (eds.) ACS,

Definition 2. Let n be a state of J admissible phases

Washington, D.C. (1979) 385-439.

satisfying conservation of mass and let G be differen-

15. Baker, L.E. and Luks, K.D.: "Critical Point and Saturation tiable at each phase in n. Suppose that for every differen-

Pressure Calculations for Multicomponent Systems," Soc. Pet. tiable curve m(7)=[mj(7)], which is defined for 7 in

Eng. J. (Feb. 1980) 15-24. some open interval containing 0 and which satisfies con-

16. Peng, D.Y. and Robinson, D.B.: "A Rigo~ous Method for servation of mass-i.e.,

Predicting the Critical Properties of MUlticomponent Systems

from an Equation of State," AIChE 1. (1977) 23, 137-44.

J

17. Ng, H.-J. and Robinson, D.B.: "Equilibrium Phase Properties of

the Toluene-Carbon Dioxide System," 1. Chern. Eng. Data

(1978) 23, 325-27.

L: mij(7)=ni, ......................... (A-3)

j=1

18. Kulkarni, A.A. et al.: "Phase Equilibrium Behavior of System

Carbon Dioxide-n-Decane at Low Temperatures," J. Chern. Eng.

Data (1974) 19, 92-94. and for which mjCO) = n j, I $.j $.J, we have

APPENDIX d A

-G r [m(7)]I7=O =0. . .................... (A-4)

Theorems Related to Gibbs Energy Analysis d7

The following terminology and definitions are needed in Then we say that n is a stationary state.

the development of the theorems. A stationary state corresponds to an extremum (local

Let a hypothetical phase of I components be or global minimum or maximum) or saddle point of the

represented by r=(rl, r2 ... r/), where ri is the total Gibbs energy. These two definitions suggest that

number of moles of species i in the phase. If a feed out of the stationary states found, the equilibrium state

OCTOBER 1982 739

must be identified. The purpose of the theorems n

Thus, is a stationary state. Conversely, stationarity

presented is to develop criteria for this determination. of a state n implies that the conditions of mass flow

We show in Theorem I that the conditions of mass equilibria apply. This can be demonstrated by consider-

flow equilibria, ing special curves, along each of which the only varia-

tion is in one component in two different phases.

fLij=fLib l~i~I, l~(j, k)~J, ............ (A-5) Central to the development of the Gibbs energy

n

analysis is recognizing that can be determined by the

are equivalent to the condition of stationarity of the points of tangency of a hyperplane tangent to the surface

system. G.

be a state of J admissible phases

satisfying conservation of mass. The state n

is a sta- [n)] satisfying conservation of mass. Then G r is sta-

tionary state if and only if G is differentiable at each n) tionary at n if and only if G is differentiable at each n)

and the chemical potentials, fLij, do not vary with the and the surface G has the same tangent plane at each of

phase-i.e., fLij =fLib as in Eq. A-5. the points [n ) ] .

Proof. Suppose that the chemical potentials do not vary

with phase. Consider nl(T) as in Definition 2. By the

chain rule,

Also,

...................... (A-6) follows that

Then aG

I

L)(r)= ~ -a (n)ri = ~ fLijri' ....... (A-l3)

i=1 ri i=1

J

state (Theorem I), L) (r) is the same tangent plane for

~ ~ aG[m)(O)] x dmij(O) , each of the} phases. Conversely, if all L j are the same,

LJ LJ ......... (A-7) differentiation shows that the fL U' s do not depend on}.

amij dT

)=1 i=1

We now sho)V that a stationary state, n, is an

equilibrium state if and only if the corresponding com-

but mon tangent plane of Theorem 2 never lies above the

surface G at any point. Let D be the difference between

aG[m)(O)] aG(n) G and the tangent plane L :

=---=fLij, ................ (A-8)

amu ami} .

D(r)= G(r) -L(r). . .................... (A-14)

and fLij does not depend on the label}. Thus,

D(r)=G(r)- ~ fLijri

i=1

I

=G(r)- ~ fLilri ................ (A-15)

~

i=1

dmij(O) --0

~ fLi} LJ ............... (A-9)

i=1 )=1 dT ' for a stationary state n. It is clear from this that

D(n )=0, 1s,}s,J. We now show in the next few

J n

results that is an equilibrium state if and only if D is

since ~ mij(T)=ni = fixed feed constraint, and so never negative.

)=1

n

Lemma 1. Let be a stationary state with J admissible

J phases [n]. Let liz be a collection of K admissible

~

dmij(O)

----''--- = -

dT

dni

dT

=0. . ................ (A-IO) i

phases [m) satisfying conservation of mass (K and J are

)=1 not necessarily equal). Then

740 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

K Proof. Recall that

G{(m)-G{(n)= b D(mj)' .............. (A-16)

j=i D(r)=G(r)-L(f)

=G(r)-G(n j)-

J K

j=i j=i

...................... (A-23)

Also, J1.ij =J1.iI for 1:5 i :5/, 1 :5}:51. Now,

G{(n)= b GUi j)

j=i

J D(r)/ b Irv-n'jl ..................... (A-24)

= b b

j=i ;=i

J1.iI n ij v=i

b

j=i

bJ1.;i m ij

;=i

approaches nj. Let

K f

j=i v=i

so Then

I f

K ;=i v=i

b [G(mj)-L(mj)] f

ISlsf v=i

b Ir

"

- nVj I

K

j=i =F/(f-n j ) m;lx Ir;-n;/1. ....... (A-26)

. ISlsf .

n

Theorem 3. Let be a stationary state and suppose that

G lies on or above the common tangent plane-i.e., Theorem 4. Let n be an equilibrium state with J ad-

D( r) ~ 0 for all admissible phases r. Then n is an missible phases-z at each of which G is differentiable, and

equilibrium state. suppose that f is an admissible hypothetical phase.

Then D(f) 2: O.

Proof. Consider any state mcontaining K phases 1mj J.

Then each D(mj) 2: 0, and . Proof. Assume D( f) < O. Note that since n is an

equilibrium state, it is also a stationary state.

K Choose the set of positive numbers [Ej J so that

b D(mj)2:0 ......................... (A-20)

j=i nij-E/;>O, ........................... (A-27)

ciently small that, when Lemma 2 is applied to

G{(m)-G{(n)2:0 ....................... (A-2I) r= n j -E? j ' F(r

j j satisfies

- n)

I Sisl

Next we prove that D, as the difference between a

function and its tangent plane, is (roughly speaking) of

second order in its argument. Construct a state mof J + 1 phases by

Lemma 2. Let n

be a stationary state with J nonzero

phases [n jJ. Then, for 1 :5}:5J, there is a functi(),n Fj

which approaches 0 as its argument approaches 0 and and

for which

J

. . ISlsf .

mJ+i = b EJ ........................ (A-30)

j=i

This state, m,

satisfies conservation of mass with J J

respect to the feed composition. Furthermore, each mij < ~ [D()[Ej+( ~ Ej)D()

is positive and each mj is admissible. It follows that j=! j=!

J+! J J

J

~ D(mj)= ~ D(mj)+D( ~ E/) ..... (A-31) =( ~ Ej)[[D()[+D()J

j=! j=! j=! j=!

J J

~ D(n j -E/)+( ~ Ej)D(f) =0, .................................. (A-33)

j=! j=!

J J

if D()<O. Thus,

~ ~ [D(n j-E/)[+( ~ Ej)D(l\

j=! j=! J+!

~ D(mj)<O .

. . . . . . . . . . . . . . . . . . . . . . (A-32) j=!

Using Lemma 2, state. However, we have specified that n~ is an

equilibrium state; therefore, the assumption D( e)< 0 is

incorrect.

J

OF (OF-32)/1.8 =oC

+( ~ Ej)D()]

psi x 6.894 757 E+OO =kPa

j=!

SPEJ

J J Original manuscript received in Society of Petroleum Engineers office Dec. 17, 1980.

~ F ( - E r)E ( m;lx ei ) + ( ~ E )D( ) Paper accepted for publication May 2, 1982. Revised manuscript received July 6,

LJ } } } 1$ [ $ / LJ! J 1982. Paper (SPE 9806) first presented at the 1981 SPE/DOE Enhanced Oil Recovery

j=! J= Symposium held in Tulsa April 5-8.

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