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Computers cl Chemical Enginffring, Vol. 10, No.3, pp.

269-276, 1986
Printed in Great Britain. All rights reserved

0098-1354/86 $3.00 + 0.00

Copyright

1986 Pergamon Journals Ltd

AN ALGORITHM FOR THREE-PHASE


EQUILIBRIUM CALCULATIONS
J.-S. Wut and P. R. BISHNOIt
Department of Chemical and Petroleum Engineering, University of Calgary, Calgary,
Alberta T2N IN4, Canada
(Received 11 February 1985; revision received I October 1985;
received for publication 13 November 1985)

Abstract-A new algorithm is developed for performing liquid-liquid equilibrium, three-phase bubblepoint and three-phase equilibrium flash calculations. Material-balance and equilibrium equations are
rearranged suitably and solved by the Newton-Raphson method. The method of Shah [1] is used for
testing liquid stability and for generating initial values of the component moles required in the
liquid-liquid equilibrium calculation. A procedure for producing initial values of the variables required
in three-phase equilibrium flash is proposed. The partial derivatives of vapor-liquid K -factors required
in the method are calculated using the procedure proposed by Wu and Bishnoi [2]. The reliability and
efficiency of the proposed algorithm are illustrated by solving a number of example problems. The liquid
solution properties are calculated using the UNIQUAC model and the vapor-phase properties are
calculated using the virial equation of state.
Scope-A reliable and efficientalgorithm to perform equilibrium calculations for coexisting three phases
is required in the design and simulation of processes in the chemical and petroleum industry. Heidemann
[3], Gautam and Seider [4], Soares et al. [5] and Mehra [6] have developed calculation methods based on
the minimization of total Gibbs free energy with material-balance constraints. Alternatively, solution of
material-balance and equilibrium equations using iterative schemes has been suggested by Fournier and
Boston [7], Michelsen [8] and Nghiem and Heidemann [9]. Since the equilibrium and material-balance
equations are highly nonlinear, the reliability and efficiency of a solution method depend on the
arrangement of the equations and selection and the "good" initial values of iterative variables.
The algorithm proposed in this paper combines, in a suitable manner, the material-balance and
equilibrium equations and solves the resulting equations and the summation equations for component
moles using the Newton-Raphson method. The partial derivatives of vapor-liquid K-factors required in
the method are calculated by expressing the K -factor as a product of three functions to separate the effects
of temperature, composition and volatility characteristics, as suggested by Wu and Bishnoi [2]. Schemes
are presented to perform liquid-liquid equilibrium, three-phase bubble-point and three-phase equilibrium
flash calculations. A phase is tested for thermodynamic stability before performing the phase equilibrium
calculations. Heidemann [3], Gautam and Seider [4], Shah [1] and Michelsen [10] have discussed the
problem of phase stability. The stability test of Shah [I], when applied to liquid mixtures, produces
estimates of split factor and component mole fractions for the two liquid phases. Hence in the proposed
algorithm the method of Shah [I] is used for the stability test of the liquid phase and for generating initial
values of the component moles required in the liquid-liquid equilibrium calculation. The vapor-phase
stability is tested by performing vapor-liquid isobaric-isothermal flash calculations. For three-phase
calculations, a procedure is formulated to determine whether phases are present or absent and to generate
good initial guesses for the Newton-Raphson method.
The proposed algorithm is used to solve a wide variety of problems. The liquid solution properties are
calculated using the UNIQUAC model [II] and the vapor-phase properties are calculated using the virial
equation of state truncated after the second virial coefficient.
CondusioDs aDd Signiftcaaee-An algorithm is developed for liquid-liquid equilibrium and three-phase
bubble-point and flash calculations. The algorithm solves the material-balance and equilibrium equations
by the Newton-Raphson method and it is found to be reliable and efficienteven when the liquid mixture
is near its plait point or near the liquid-liquid equilibrium boundary curve. A procedure is formulated
for generating initial values for the three-phase equilibrium calculations. The procedure determines
whether phases are present or absent. This allows the Newton-Raphson method to be used advantageously to solve the equations for known combinations of coexisting phases, with good initial guesses,
and without the difficulties caused by disappearing phases. The algorithm and the procedure were found
to be reliable and efficient in solving a wide variety of problems.

following equations:
Component material-balance equations

LIQUID-LIQUID EQUILIBRIUM

Model equations
Liquid-liquid equilibrium can be described by the

1'+W-I/=O (i=l,c);

tVisiting Scholar from the East China Institute of Chemical


Technology, Shanghai, China.
tTo whom all correspondence should be addressed.

269

(I)

Total material-balance equation


L1+LII-L =0;

(2)

270

J.-S. Wu and P. R. BISHNOI

aMI
-L
il
aLI = (LI)2KII7;

Equilibrium relationships

W l}
LII = KnLI

(i

= 1, c),

(3)

where [11L I and l}1/L II represent mole fractions xl and


xP, respectively;
Mole-fraction summation equation

~ (21- i~l) = O.

(4)

Combining equations (I}-(3) to eliminate


dividing by [I gives

Mi=(I+L~ILIKn)i-I=O

ill and

(aKa)

I aP
aif=-VL I 2J
k
,
i
k

(k

= I,e)

(11)

and

aSI

-1 ~

aLI = (L I)2

7 (1 -

Kn)[1

S.

(12)

= - LI'

where aKn/all are calculated as

xli "II
=xl "IP

(13)

and
all -

(6)

Equations (5) and (6) are model equations for


liquid-liquid equilibrium calculations; l} and L I are
selected as (e + 1) iterative variables; M I and SI are
(e + 1) residual functions and they are driven to zero
when the solution is reached.
Method of solution

The model equations (5) and (6) are solved simultaneously by the Newton-Raphson method, namely

= _~m

Xu.

(10)

aK11_ Ka(ln "II-In "IP)

Similarly, combining equations (2}-(4) gives

J1m~Zm+1

1-

= 1, c),

Ku =-

(i-I,e). (5)

1
SI = LI~(1-Ku)il-O.

aS I

(i

(7)

all

_ (0 In "11

aIn "Ill)

x; ~+ a[f

(14)

The partial derivatives

aIn "II

~ and

aIn "IP
0111

may be calculated from a suitable model describing


the activity coefficient. In this paper the UNIQUAC
model is chosen and the equation for the partial
derivative is given by Wu and Bishnoi [2J.
Computation procedure

The computation procedure is outlined as follows:

and

zm+.

= Zm + "~Zm+I,

(8)

where ~ is a vector of the residual functions,


~

= [M I , M 2, , M., SIJT,

and Z is a vector of the variables,

Z = [[~, [!, ... ,[~, LlJT.


The Jacobian matrix JI of the Newton-Raphson
method is as follows:

1. Perform a stability test on the liquid mixture


using the method developed by Shah [IJ. If the
liquid mixture is stable, only one liquid phase
exists, and hence skip the rest of the calculations. If the liquid mixture is unstable, the
test produces the values of split factor fl, xl
and xp. Using these values calculate L I and [1
and use them as initial values for the subsequent calculations.
2. Using xl and xp calculate "I:, "IP and
K u( = "Il1"1p).
3. Calculate residual functions. If

err J1=

oM.
a[~

oM. oM.
... a[~ aLI

as.
a[~

...

as.

OSI

a[~

aLI

The partial derivatives in the Jacobian matrix are


calculated by the following equations:
I

aMI [
L-L
all = 011< +
KnOll<

-u

+ (L

-LI)il(aKII)J!
LI
0[1 [I (i, k - I, c),

(9)

[~I"'II JI (e + 1) EO 10-

6
,

the calculations are completed. Otherwise go


on.
4. Form the Jacobian matrix, and solve equation
(7) by the Gauss elimination method with
column pivoting. Then update the variables L I
and l} using equation (8) and taking e = 1. If
err" +1 > 2 err", the value of " is halved and
enm+ is recalculated. The reduction of e is
continued until enm+1 EO err". A maximum of
six attempts are allowed to satisfy this criterion. In addition, the step size of every variable
is restricted so that I~X7'+11 EO 0.9x7', and every
variable is kept within its physical limit, i.e.
oE; LIE; Land 0 EO il EO [I'

Three-phase equilibrium. calculations

5. Update I}I, xl and x? using the relations


1=1/-1},

11

xI=II/~1}
and

and then return to Step 2.

mE mREE-PHASE BUBBLE-POINT CALCULATION

Model equations

The three-phase bubble-point calculation can be


described by the following equations:
Component material-balance combined
liquid-liquid equilibrium relationships

L-LI

)1}

with

M/= ( 1 +----v-KIt 1;-1 =0 (I = l,c); (15)


Vapour-liquid equilibrium relationships

II

Yt=KI ~I (i

= I,c);

=iL
(1- KIt)/1 = 0;
L /

(16)

(17)

Mole-fraction summation equation for vapor and


liquid phases
I
8 2 = LI~(I-KDI}=O.

Model equations

Three-phase equilibrium flash is described by the


following equations:
Component material-balance combined
vapor-liquid equilibrium relationships
I
I
II
F - L - L" III)
M/= (I /+1/ +
LI
K/ /
I

Method of solution

The model equations are rearranged into two


groups. First, equations (15) and (17) are solved
simultaneously by the Newton-Raphson method for
the variables II and L I. Then, equations (16) and (18)
are solved for the variables Y/ and T (if P is specified)
or P (if T is specified). The computation procedure
for the bubble-point calculations is outlined as
follows:
I. Assume P (if T is specified) or T (if P is
specified). The initial values of P or T can be
chosen by assuming only two phases and carrying out the bubble-point calculations.
2. Solve equations (15) and (17) by following the
procedure given previously for liquid-liquid
equilibrium calculations for the variables II and

Xlt-1=0 (1=I,c);

(18)

Thus, there are 2c + 2 equations and 2c + 3 independent variables: I}, Y/, L I , T and P; if P is specified,
it is a bubble-point temperature calculation; otherwise if T is specified, it is a bubble-point pressure
calculation.

L I.

3. Solve equations (16) and (18) for the variables


y/ and T or P. The solution is achieved by
following the procedure of two-phase bubblepoint calculations. The variable T or P is
calculated using the secant method applied to
equation (18)and the variables Y/ are calculated
using equation (16).
4. For the bubble-point pressure calculations, the
value of pressure obtained in Step 3 is the
desired solution because the activity
coefficients given by the UNIQUAC model are
independent of pressure. For the bubble-point
temperature calculations, check to see if the
absolute difference between the T calculated in
Step 3 and its assumed value is less than the
tolerance level of 10- 2 If the tolerance criterion is satisfied the calculations are completed.
Otherwise, assume the value of T to be equal
to that calculated in Step 3, and go to Step 2.
Since Kit are very weak functions of temperature, only a small number of iterations of
Steps 2-4 is expected to meet the criterion.
mREE-PHASE EQUILIBRIUM FLASH

Mole-fraction summation equation for liquid phases


8.

271

with

(19)

Liquid-liquid equilibrium relationships

I II
II I}I
/="1/ L I-"It LII=O (i= l,c);

(20)

Mole.jraction summation equation for liquid phases


1
8 1 = 1 - I i I? = 0;
L /

(21)

Mole-fraction summation equation for vapor and


liquid phases

~ (1 - K I/) II/=0.
(22)
8 2 = i 1 L..
L /
Two types of flash calculations are discussed here,
i.e, the isothermal-isobaric flash and the isobaric
specified V IF flash.
Method of solution

There are 2c + 2 model equations. Hence, the


following 2c + 2 variables are chosen as independent:
Z = [Ii, I~, ... , I~, If, If, ... , I~I, L I, ,,]T

where " is L II for the isothermal-isobaric flash, and


" is T for the isobaric specified V IF flash. The model

272

J.-8. Wu and P. R.

equations (I9}-(22) are solved simultaneously by the


Newton-Raphson method. The corresponding residual functions are

oMc
all

J=

(i

= I, c),

(32)

=0

(k

= 1, e ),

(33)

aT

OSI
all

The Jacobian matrix is


oM. aMI
allc 01~1

es, ~ 0

'" = [M I , M 2, .. , M c' E I, E2, . . . , Ee> SI' S2]T.

aMI
01

BISHNOI

aMI aMI aMI


ol~ aLI
01/

OSI
oIP=-L II (k=l,e),

(34)

OSI
OLI=O,

(35)

OSI
aLII
oM eu,
... eu, eu,
. .. c aLI
01~1
alII
ol~

oEI
all

oEI
ol~

oEI
alII

oEI
ani

oEI
aLI

oMc

es,

es, ee, es,

ol~

01~1

01~1

es,

OSI

OSI

ol~

01~1

OS2
OS2
all ... ol~

OS2
olf

ol~

...

(37)

7'

aS2
alP = 0 (k

es, es,

= I, c),

(40)

OSI

es,

01~1

aLI

OSI
01/

OS2 =0
aLII

(41)

OS2

OS2
aLI

OS2
01/

ol~

and
OS2

= _-.!..-I ~ II (OK})
L 7' I er .

(23)

(26)
(i

= 1, c),

(i, k

(I,k=l,e),

y}l}.
(LI)2 (I = 1, c),

oEI
y}IW .
aLII = (LII)2 (I=l,e),

= 1, c),

oK I

a In y?
alP

oKl

o~ and OIl'

the suggestion of Wu and Bishnoi [2] is used to


express the K -factors as a product of three functions
separating the effects of temperature, composition
and apparent volatility as follows:

(27)
(28)

and

required in equations (28) and (29) is discussed


previously under the section Liquid-Liquid Equilibrium. In order to calculate the partial derivatives

(24)
(25)

(42)

In deriving equation (32), oyl/oT and fjyll/oT are


neglected. The calculation of the partial derivatives

al"l

(39)

OS2
1 ~
I I
S2
aLI = - (L I)2 7' (1 - K;)li = - LI'

a In yl

oEI
aLI =

(38)

01/

The partial derivatives in the Jacobian matrix are


calculated by the following equations:

I'll) .

(k = I,e),

aLI

et

0 In
x ( alP

(36)

OS2 = 1 - Kl_ -.!..- ~ II (OK})


all
LI
LI
I
all

011

all '"

II

OSI
aT =0,

01/

es;

= (L II)2L/i'

(43)

where Kb is primarily a function of temperature, 1'1 is


the activity coefficient, influenced primarily by composition, and !XI is an apparent volatility of the
component and it may be considered independent of
temperature and composition. Thus,

(29)
(30)
(31)

and
(45)

Three-phase equilibrium calculations


As recommended by Boston and Britt (12] the
factor K b is defined as

s; = exp[~ (yt'ln KD

(46)

and may be approximated as follows:


(47)

The coefficients PI and P2 are constants, only weakly


dependent on composition.
From equation (47),

oKb _

/G

oT -

P2

(48)

T2"

Combining equations (45) and (48) gives

oKI
oT

I P2
= K 1 ' T2"

(49)

Computation procedure

The computation procedure is outlined below:


l. Establish whether three phases exist by following the procedure given in the next section
Production ofinitial values. If three phases exist
the procedure would generate the initial values
of 11,111, L I and '1 and the values of K1. 1'1, I'~,
K/I and Yi'
2. The factors Kt, and al are calculated from
equations (46) and (43). For the isobaric
specified V/F flash P2 is calculated from equation (47).
3. Calculate the residual functions M/, E/, 8 1 and
8 2 , If

err

= [~I"'dJ!(2C +

2) ~

10-

the calculation is completed. Otherwise go on.


4. Form the Jacobian matrix JJ. Calculate ~Xm+1
and update the X variables following the procedure given in Step 4 of the computation
procedure for liquid-liquid equilibrium. The
step size for temperature in specified V /F flash
calculations is restricted so that ~T ~ 10 K.
5. Using the thermodynamic models calculate KI,
1'1 and I'll. Then return to Step 2.
Production of initial values
It is quite important, for the Newton-Raphson
method, to produce good initial values, especially for
highly nonlinear objective functions. The following
procedure is proposed to establish whether three
phases exist and to generate the initial values for the
isothermal-isobaric calculations:

l. Perform a three-phase bubble-point temperature calculation for the feed mixture. If the
specified temperature T is less than the bubblepoint temperature Tb , only liquid phases could
exist.

273

2. Perform a two-phase dew-point temperature


calculation for the feed mixture using an iterative scheme. The equilibrium equations are
solved for the mole fractions in the liquid phase
and the mole-fraction summation equation is
solved for Td using the secant method. If the
specified temperature T is larger than the dewpoint temperature Td , only a vapor phase could
exist.
3. Perform an L-V isothermal flash calculation
for the feed mixture to produce a new vapor
phase V' and liquid phase L ',
4. Test the stability of vapor V' by performing an
L-Visothermal flash calculation again for V'.
Ifno liquid is generated, V' is stable. Otherwise
the vapor V' is unstable and the new vapor
phase V" and liquid phase L" are produced.
5. Perform liquid-liquid equilibrium calculations
for the liquid mixture L m obtained by combining L' and L". If the liquid mixture L m is
stable (possible only when L" = 0 and L' is
stable), the calculation is an L-V isothermal
flash and it is completed. Otherwise the initial
two liquid phases are produced. The amounts
and compositions of these two liquids are used
as initial values.

It is worth noting that in our findings both or either


of the vapor V' and the liquid L' could be unstable.
We found that the objective function for the isobaric specified V/F flash calculation has a wider
convergence
domain
than
that
of
the
isothermal-isobaric flash. Hence the requirement of
having good initial values is not very strict. Initial
values can be obtained by the following procedure:
l. Perform a two-phase isobaric specified V/F
flash calculation for the feed mixture and generate vapor phase V' and liquid phase L'.
2. Perform a three-phase bubble-point temperature calculation for the liquid L' and
generate P, xl, xii, T, K/I and KI. The initial
values of II, 111, L I and T are thus obtained.
EXAMPLE PROBLEMS

The application of the algorithm is demonstrated


by solving a variety of problems. The specifications
and results of the problems are given in Tables I and
2 for bubble-point and flash calculations, respectively. The UNIQUAC parameters used in the
calculations are taken from Ref. [II] and the second
virial coefficients are calculated using the Hayden and
O'Connell correlation [13]. The computations were
performed on a Honeywell DPS 8/70M computer.
In Table I first the temperature is specified and the
bubble-point pressure is calculated. Then, for every
example the pressure is specified and the bubble-point
temperature is calculated. The two results are found
to be the same as expected. The number of iterations
in the table are those required for Step 2 of the

Table I. Specifications and results for bubble-point calculations


Mole fractions

Case
No.

2
3

7
8

9
10

11
12
13
14

Temp
(K)

Pressure
(bar)

Mole fractions
of feed

333

0.592

333

0.605

333

0.707

298

0.119

298

0.098

298

0.099

298

0.083

298

0.089

298

0.089

318.15

0.425

298.15

0.181

298.15

0.181

370.46

1.013

370.46

1.013

0.6000
0.1300
0.2700
0.6000
0.1500
0.2500
0.6000
0.3500
0.0500
0.1000
0.3000
0.4000
0.2000
0.3000
0.4000
0.2000
0.1000
0.3000
0.4000
0.3000
0.4000
0.4000
0.2000
0.2700
0.4000
0.3300
0.2500
0.4000
0.3500
0.5000
0.3000
0.2000
0.4000
0.3000
0.3000
0.4000
0.4000
0.2000
0.9000
0.1000
0.2500
0.7500

Components
Water
Acrylonitrile
Acetonitrile
Water
Acrylonitrile
Acetonitrile
Water
Acrylonitrile
Acetonitrile
2,2,4-TMP"
Furfural
Cyclohexane
Benzene
2,2,4-TMP
Furfural
Cyclohexane
Benzene
2,2,4-TMP
Furfural
Cyclohexane
2,2,4-TMP
Furfural
Benzene
2,2,4-TMP
Furfural
Benzene
2,2,4-TMP
Furfural
Benzene
Acetonitrile
a-Heptane
Benzene
Benzene
Water
Ethanol
Benzene
Water
Ethanol
Water
Furfural
Water
Furfural

fJ

Liquid I

Liquid II

Vapor

0.2863

0.8082
0.0463
0.1455
0.8368
0.0431
0.1201
0.9520
0.0341
0.0139
0.0314
0.6044
0.1770
0.1872
0.0435
0.8139
0.0545
0.0881
0.0276
0.9141
0.0583
0.0794
0.7399
0.1807
0.1439
0.5368
0.3193
0.1644
0.4930
0.3426
0.6337
0.1851
0.1812
0.6765
0.0872
0.2363
0.8201
0.0443
0.1356
0.9445
0.0555
0.9444
0.0556

0.5165
0.1636
0.3199
0.4689
0.2092
0.3219
0.2140
0.6964
0.0896
0.1315
0.1603
0.5023
0.2059
0.4945
0.0862
0.3103
0.1090
0.4816
0.0573
0.4611
0.6719
0.1117
0.2164
0.4575
0.1966
0.3459
0.4145
0.2212
0.3643
0.3497
0.4292
0.2211
0.0798
0.5464
0.3738
0.0305
0.7129
0.2566
0.2038
0.7962
0.2037
0.7963

0.3082
0.3497
0.3421
0.3039
0.3847
0.3114
0.2727
0.6709
0.0564
0.0970
0.0313
0.6621
0.2096
0.3617
0.0426
0.4414
0.1543
0.3325
0.0454
0.6221
0.6040
0.0473
0.3487
0.4866
0.0395
0.4739
0.4724
0.0385
0.4891
0.5860
0.2622
0.1518
0.6664
0.1516
0.1820
0.6738
0.1562
0.1670
0.8889
0.1111
0.8889
0.1111

0.3563
0.5231

0.3146

0.4312

0.4000
0.4589
0.5979

0.6577
0.5293

0.5366
0.4680

0.9399
0.0625

No. of
iteration
5

5
5
6

3
5
6
6

7
5
5
5

2,2,4-TMP = 2,2,4-trimethyl-pentane.
Table 2. Specifications and results for flash calculations
No. of iterations
specified

Mole fractions
Case
No.

3
4

6
7

Components
Water
Acrylonitrile
Acetonitrile
Water
Acrylonitrile
Acetonitrile
Water
Acrylonitrile
Acetonitrile
2,2,4-TMP"
Furfural
Cyclohexane
Benzene
2,2,4-TMP
Furfural
Benzene
2,2,4-TMP
Furfural
Benzene
2,2,4-TMP
Furfural
Cyclohexane
Benzene
Water
Ethanol
Benzene
Water
Ethanol

Pressure
(bar)

Mole fractions
of feed

Temp
(K)

fJ

Liquid I

Liquid II

Vapor

VjF

1.013

0.3004
0.5923
0.1073
0.6000
0.2500
0.1500
0.6000
0.3500
0.0500
0.3000
0.4000
0.2000
0.1000
0.4000
0.4000
0.2000
0.2700
0.4000
0.3300
0.3000
0.4000
0.3000
0.4500
0.5000
0.0500
0.4000
0.5000
0.1000

343.15

0.6167

0.9286

0.9873

339.65

0.4605

0.8885

300.05

0.5542

0.9728

299.00

0.5291

0.9686

298.30

0.2158

0.7899

300.20

0.5992

0.9934

298.80

0.4238

0.2383

14

298.30

0.3702

0.2314

0.2969
0.6112
0.0919
0.2921
0.4773
0.2306
0.2889
0.6376
0.0735
0.4919
0.0487
0.3303
0.1291
0.6789
0.0525
0.2686
0.5070
0.0409
0.4521
0.4754
0.0516
0.4730
0.7267
0.1932
0.0801
0.6975
0.1692
0.1333

0.4773

0.9375
0.0374
0.0251
0.3701
0.3422
0.2877
0.2358
0.6493
0.1149
0.6288
0.0768
0.2135
0.0809
0.7573
0.0901
0.1526
0.5067
0.1725
0.3208
0.6259
0.0582
0.3519
0.0042
0.9631
0.0327
0.0075
0.9009
0.0916

332.60

0.2555
0.6040
0.1405
0.8877
0.0386
0.0737
0.9447
0.0360
0.0193
0.0456
0.8580
0.0331
0.0633
0.0649
0.8132
0.1219
0.1246
0.5856
0.2898
0.0339
0.9270
0.0391
0.9798
0.0048
0.0154
0.9408
0.0137
0.0455

0.627

0.90
0.098

0.083

0.089
0.099
0.176

0.179

2,2,4-TMP = 2,2,4-trimethyl-pentane.

VjF

274

Three-phase equilibrium calculations

275

computation procedure outlined for the three-phase


K, = Liquid-liquid K-factor
L = Total moles of liquid
bubble-point calculations. For the bubble-point temI = Component moles of liquid
perature calculations the number of iterations of
M = Residual function of the component material
Steps 2-4 of the procedure is found to be only two.
balance
This number is small, as expected, because the activP = Pressure
S, = Residual function of the mole-fraction sumity coefficients are very weak functions of temmation for liquid phases
perature. Cases 2-8 are taken from the examples of
S2 = Residual function of the mole-fraction sumliquid-liquid equilibrium given by Prausnitz et al.
mation for vapor and liquid phases
[11]. The split factor p and the compositions of the
T = Temperature
two liquid phases are the same as those reported by
V = Total moles of vapor
x = Mole fraction of liquid
Prausnitz et al. [11]. These authors have reported that
y = Mole fraction of vapor
the number of iterations required in their method
increases substantially for the feed mixtures near their Greek letters
plait points. However, in our method the number of
IX = "Apparent" volatility
P = Split factor, ratio of moles of liquid I to total
iterations is nearly the same for any feed mixture as
moles of liquids
illustrated by Cases 1, 2, 8, 9, 10 and 11 which are
P" P2 = Coefficient in equation (47)
close to the plait points. Cases 13 and 14 are binary
y = Activity coefficient
systems and the calculated results are close to the
~Ik = Kronecker delta, ~ii = I, ~Ik = 0 (i k)
experimental data measured by Mains and reported
e = Damping factor
'1 = Variable, T or P
by Gmehling and Onken [14]. The computation times
X = Independent variable
for the examples ranged from 0.45 to 0.82 s.
z = Vector of independent variables
The examples given in Table 2 are solved first by
'" = Vector of residual functions
specifying temperature and calculating V IF. The
Subscripts
examples are then solved by specifying VIF and
b = Bubble point
calculating temperature. As expected the results are
d=Dew point
the same in both the solutions. The three phases
i, k = Component number
generated by the calculations are tested for stability
and found to be stable. For most of the examples the Supercripts
I, II = Liquid phase number
three phases occur in a narrow range of temperature.
m = Iteration number
For example in Case 3 the three-phase bubble-point
temperature of the feed is 339.40K, and when the
REFERENCFS
mixture is flashed at 339.70K only one liquid phase
is found to be present. The computation times for the
I. V. B. Shah, Ph.D. Thesis, Univ. of Toledo, Toledo,
Ohio (1980).
problems ranged from 2.15 to 3.40s for the
2. J.-S. Wu and P. R. Bishnoi, Comput, chem. Engng
isobaric-isothermal flash calculations and from 1.41 s
(1986).
to 2.21 s for the isobaric specified VIF flash calcu3. R. A. Heidemann, AIChE JI20, 847 (1974).
lations except for Case 8 which required 6.04 s.
4. R. Gautam and W. D. Seider, AIChE JI25, 999 (1979).
Acknowledgements-The authors wish to express their sincere appreciations to Dr R. A. Heidemann for his valuable
suggestions. The financial assistance provided by the Ministry of Education, China and the University of Calgary is
greatly appreciated.
NOMENCLATURE

c = Number of components
E = Residual function of the liquid-liquid equi-

librium relation
F = Total moles of feed
/ = Component moles of feed
JJ = Jacobian matrix
K = Vapor-liquid K-factor
Kb = Base vapor-liquid K-factor function

5. M. E. Soares et al., Chem. Engng Sci. 37, 521 (1982).


6. R. K. Mehra, Ph.D. Dissertation, Univ. of Calgary,
Calgary, Alberta (1981).
7. R. L. Fournier and J. F. Boston, Chem. Engng Commun. 8, 305 (1981).
8. M. L. Michelsen, Fluid Phase Equil. 9, 21 (1982).
9. L. X. Nghiem and R. A. Heidemann, Paper presented
at the 2nd Eur. Symp. on EnhancedOil Recovery, Paris
(1982).
10. M. L. Michelsen, Fluid Phase Equi/. 9, 1 (1982).
II. J. M. Prausnitz et al.; Computer Calculations/or Multicomponent Vapor-Liquid and Liquid-Liquid Equilibria.
Prentice-Hall, New York (1980).
,
12. J. F. Boston and H. I. Britt, Comput, chem.Engng 2, 109
(1978).
13. J. G. Hayden and J, P. O'Connell, Ind. Engng Chem.,
Process Des. Dev. 14, 209 (1975).
14. J. Gmehling and U. Onken, Chemistry Data Series,
Vol. I, Part I. DECHEMA, Frankfurt, F.R.G. (1977).

About tbe autbors-JUN-SHENG Wu: graduated in chemical engineering from East China Institute of
Chemical Technology in 1960. He has been a lecturer at the institute since 1960. During the period
1982-1984 he was a Visiting Scholar at the University of Calgary. He has returned to China, taking up
his previous position with the institute. His major interests include simulation of separation processes and
mass transfer operations.
P. R. BISHNOI: received his B. Chern. Eng. and M.Sc. (Tech.) in Chemical Engineering from the
C.A.C.E. IO/}-Q

276

J.-S. Wu and P. R. BISHNOI


University of Bombay, India and Ph.D. in Chemical Engineering from the University of Alberta,
Edmonton, Alberta, Canada. After having worked as Senior Process Engineer with Ralph M. Parsons
Co. and Fluor Canada Ltd. he is presently Professor of Chemical Engineering at the University of Calgary.
His major research interests are chemical engineering thermodynamics, simulation and design of chemical
processes and natural gas hydrates.