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269-276, 1986
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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);
269
(I)
(2)
270
aMI
-L
il
aLI = (LI)2KII7;
Equilibrium relationships
W l}
LII = KnLI
(i
= 1, c),
(3)
~ (21- i~l) = O.
(4)
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'
xli "II
=xl "IP
(13)
and
all -
(6)
The model equations (5) and (6) are solved simultaneously by the Newton-Raphson method, namely
= _~m
Xu.
(10)
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)
aIn "II
~ and
aIn "IP
0111
and
zm+.
= Zm + "~Zm+I,
(8)
= [M I , M 2, , M., SIJT,
err J1=
oM.
a[~
oM. oM.
... a[~ aLI
as.
a[~
...
as.
OSI
a[~
aLI
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
,
11
xI=II/~1}
and
Model equations
L-LI
)1}
with
II
Yt=KI ~I (i
= I,c);
=iL
(1- KIt)/1 = 0;
L /
(16)
(17)
Model equations
Method of solution
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.
271
with
(19)
I II
II I}I
/="1/ L I-"It LII=O (i= l,c);
(20)
(21)
~ (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
272
J.-8. Wu and P. R.
oMc
all
J=
(i
= I, c),
(32)
=0
(k
= 1, e ),
(33)
aT
OSI
all
es, ~ 0
aMI
01
BISHNOI
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,
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'
(27)
(28)
and
(24)
(25)
(42)
al"l
(39)
OS2
1 ~
I I
S2
aLI = - (L I)2 7' (1 - K;)li = - LI'
a In yl
oEI
aLI =
(38)
01/
I'll) .
(k = I,e),
aLI
et
0 In
x ( alP
(36)
011
all '"
II
OSI
aT =0,
01/
es;
= (L II)2L/i'
(43)
(29)
(30)
(31)
and
(45)
s; = exp[~ (yt'ln KD
(46)
oKb _
/G
oT -
P2
(48)
T2"
oKI
oT
I P2
= K 1 ' T2"
(49)
Computation procedure
err
= [~I"'dJ!(2C +
2) ~
10-
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
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
275
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
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