Calculation of Vapor-Liquid-Liquid Equilibria for the Fischer-

Tropsch Reactor Effluents using Modified Peng-Robinson

Equation of State




Maryam Ghadrdan

















Abstract
A modified PengRobinson equation of state is used to develop the methods for calculating the
thermodynamic equilibrium in FischerTropsch synthesis products ] 1 [ . A group contribution
method allowing the estimation of the temperature dependent binary interaction
parameters (k
ij
(T)) for the widely used Peng-Robinson equation of state (EOS) is
proposed. A key point in our approach is that the k
ij
between two components i and j is a
function of temperature (T) and of the pure components critical temperatures (T
Ci
and
T
Cj
), critical pressures (P
Ci
, P
Cj
) and acentric factors (
i
,
j
). This means that no
additional properties besides those required by the EOS itself (T
C
, P
C
, ) are required. By
using a single binary interaction factor, it is sufficient for this correlation to represent a binary
system over a wide range of temperatures and pressures. The groups which are defined in this
paper are: CH
3
, CH
2
, CH, C, CH
4
(methane), and C
2
H
6
(ethane), Ethylene, CO, CO2, N2
which means that it is possible to estimate the k
ij
for any mixture of saturated
hydrocarbons (n-alkanes and branched alkanes), olefins, water, hydrogen whatever the
temperature. The results obtained in this study are in many cases very accurate.

Introduction
One of the possible methods for processing oil-well gases is based on the process in
which the FischerTropsch method is used to produce high-molecular-weight
hydrocarbons from synthesis gas (syngas) [2]. In this reaction, the total number of
components is as large as several hundreds, the vapor phase contains a considerable
proportion of water, and there are both hydrophobic and hydrophilic compounds among
the resulting hydrocarbons [3]. Obviously, this mixture should be treated as nonideal in
phase-equilibrium calculations.
Different approaches have been presented in the literature to calculate the vapor-liquid
equilibriums [4-11]. The empirical methods for estimating the liquidvapor equilibrium
characteristics in multi-component synthesis products, such as the Henry constants,
cannot be applied because of the complex composition of the products. It is worth noting
that these works used a simplified thermodynamic model for the VLE, in which the liquid
is assumed to be an ideal solution, the hydrocarbon products are assumed to be linear
paraffins and the inorganic gases are considered insoluble in the liquid phase. In other
words, these models ignored the non-ideal phase equilibrium problem of a FT reactor.
The rigorous calculation method is based on the use of state equations with appropriate
mixing rules [12]. It could be used if the critical thermodynamic constants for pure
substances and the Pitzer acentric factor are known. For simple gases and hydrocarbons
with a number of carbon atoms less than 20, these constants can be found in the reference
literature [3, 4]. For heavier hydrocarbons, the data on the critical thermodynamic
properties are fragmentary or not available at all. In this situation, the critical
thermodynamic properties and acentric factors of heavy hydrocarbons should be
estimated by calculation.
Huang et al. [13] showed that the solubility of gas solutes in heavy paraffins can be
described with an extended form of Soave equation of state which was coupled with the
HuronVidal type mixing rule. This model is so extensive attaining relatively high
accuracy. However, the introduction of many new parameters for each binary system
restricts its application to the engineering calculation and the possibility of extending to
other systems. Some researchers even presented several semi-empirical correlations such
as solubility enthalpy model [14].
Cubic equations of state have probably been the most widely used methods in the
petroleum-refining process industries for the calculation of vapor-liquid equilibrium
because they allow accurate prediction of phase equilibrium for mixtures containing non-
polar components and industrial-important gases. However, to apply cubic equations of
state to model petroleum processes, binary interaction parameters are required because
phase equilibrium prediction is sensitive to the parameters in the mixing rules.
The Peng-Robinson equation of state slightly improves the prediction of liquid volumes.
It performed as well as or better than the Soave-Redlich-Kwong equation. Han et al. [15]
reported that the Peng-Robinson equation was superior for predicting vapor-liquid
equilibrium in hydrogen and nitrogen containing mixtures. The advantages of these
equations are that they can accurately and easily represent the relation among
temperature, pressure, and phase compositions in binary and multi-component systems.
They only require the critical properties and acentric factor for the generalized
parameters. Little computer time is required and good phase equilibrium correlations can
be obtained.
Jaubert et al. [16] have shown that the binary interaction coefficient value has a huge
influence on a calculated phase diagram. They have extended the PR EOS to contain
temperature-dependant binary coefficients. Their approach is used in this project and
extended to include the components which are present as GTL products.
The general approach of this work is as follows (as it is shown in Figure 1): First, we
calculate the number of phases using the approach in ] 6 [ . Since convergence of these
algorithms depend on the initial estimates of equilibrium distribution of components
between different phases (K values) and each methodology may fail given poor initiation
values, in each step and for each 2-component pair different initial points are used to
solve the problem and the best result is saved. In the next step, after doing the flash
calculations, the temperature-dependant interaction factors are calculated by optimization
and the parameters A and B are obtained for each pair of components. Besides, since the
number of phases which has been possibly formed in a specified condition is not clear,
the phase stability analysis should be used. The phase stability analysis problems are
complex in nature and are used to check the optimization methods [17-22].



Finding VLE, LLE or
VLLE data Contains T,
P and (xs or ys) from
the Literature
Optimizing Kij for Each Pair at the
Specified Temperature and
Pressure to Minimize the
Difference Between Calculated x
or y and its measured value
Finding A and B of the
Group Contribution
Method for The
Specified Groups
Using Attained Group
Contribution Parameters in
the VLLE Calculations in
order to Estimate Kijs and
Their Changes with
Temperature

Figure 1. General procedure of thermodynamic calculation



The modified Peng-Robinson Model
In 1978, Peng and Robinson [23] published an improved version of their original well-
known equation of state [24] .
For a pure component, the PR78 EOS is:
( ) ( )
( )
i
i i i i
a T RT
P
v b v v b b v b
=
+ +
(1)
1 1
2
2 2
2
2 3
8.314472
0.0777960739
0.457235529 1 1
if 0.491, 0.37464 1.54226 0.26992
if 0.491, 0.379642 1.48503 0.164423 0.016666
ci
i
ci
ci
i i
ci ci
i i i i
i i i i i
R J mol K
RT
b
P
R T T
a m
P T
m
m
e e e
e e e e

=
=
( | |
= + ( |
|
( \ .
s = +
> = + +

where P is the pressure, R the ideal gas constant, T the temperature, v the molar volume,
Tc the critical temperature, Pc the critical pressure and the acentric factor, a denotes
the attractive term and b is the covolume (if the molecules are represented by hard-
spheres of diameter o , then
3
2 3 b N t o = ). The corrective terms a and b are expressed
as functions of the critical coordinates of both the solvent and the solute.
The difference between the original and modified EOS is in the definition of
i
m (equation
(2)). The later work was modified to cover the components heavier than heptanes.
) 76 ( 26992 . 0 54226 . 1 37464 . 0
2
PR m
i i i
e e + =
(2)

To apply such an EOS to mixtures, mixing rules are used to calculate the values of a and
b of the mixtures. Classical mixing rules are used in this study:
( ) ( )
1 1
1
1
N N
i j i j ij
i j
N
i i
i
a z z a a k T
b z b
= =
=
=
=

(3)

where
k
z represents the mole fraction of component k in a mixture and N is the number
of components in the mixture. In Eq. ( 03), the summations are over all chemical species.
kij(T), whose choice is difficult even for the simplest systems, is the so-called binary
interaction parameter characterizing molecular interactions between molecules i and
j. When i equals j, kij is zero. In this paper, in order to obtain a predictive model and to
define the PPR78 model (predictive, 1978 PR EOS), kij, which depends on temperature,
is calculated by a group contribution method [1] through the following expression:
( )
( )( )
( ) ( )
( ) ( )
2
1
1 1
1 298.15
2
2
kl
g g
kl
B
N N
A
j i
ik jk il jl kl
k l i j
ij
i j
i j
a T a T
A
T b b
k T
a T a T
bb
o o o o
| |
|
\ .
= =
| |
| |
|

|
|
\ .
\ .
=



(4)
In which, T is the temperature.
i
a and
i
b are calculated by Eq. (1).
g
N is the number of
different groups defined by the method.
ik
o is the fraction of molecule i occupied by
group k ().
lk kl
A A = and
lk kl
B B = (where k and l are two different groups) are constant
parameters determined after calculating the binary interaction coefficients
( 0 = =
kk kk
B A ).

i molecule in present groups of number total
i molecule in k group of occurence
ij
= o
(5)

Fugacity coefficient is derived from the following equation:
( ) ( )
1
2
2.414
ln 1 ln ln
0.414 2 2
c
i ij
j
i i i
i
y a
f b b A Z B
Z Z B
y P b a b Z B B
=
(
(
+
(
=
(
(

(6)
where Z is the compressibility factor. A and B are defined as below
2 2
aP
A
R T
bP
B
RT
=
=

(7)

It is clear that the equivalence of fugacity coefficients in two phases is the criteria which
should be reached when the phases are in equilibrium.
Because this model relies on the PengRobinson EOS as published by Peng and
Robinson in 1978 and because the addition of a group contribution method to estimate
the kij makes it predictive, the model was called predictive 1978, PengRobinson
(PPR78)[1]. Major components in GTL products are listed in Table 1. Table 2 contains
the sources of binary experimental data used for the calculations.

Table 1. List of components used for the study and their thermodynamic properties
Component
( )
c
T K ( )
c
P MPa
e
Methane 190.6 4.6 0.008
H2O 647.3 22.048 0.3442
H2 33.4397 1.3155 -0.12009
CO2 304.21 7.383 0.223621
CO 132.9490 3.498750 .09300
Ethane 305.32 4.808 0.0995
Propane 369.82 4.2496 0.15176
nC4 425.199 3.79662 0.201
iC4 408.096 3.64762 0.18479
n-Pentane 469.6 3.37512 0.25389
i-Pentane 460.398 3.33359 0.22224
n-Hexane 507.898 3.03162 0.3007
n-Heptane 540.158 2.73678 0.34979
n-Octane 568.598 2.49662 0.40180
n-Nonane 594.598 2.30007 0.44549
n-Decane 617.598 2.107550 0.488480
2-methylbutane 460.398 3.33359 0.22224
2,2,4-Trimethylpentane 543.96 2.56757 0.31
Ethylene 282.34 5.041 0.087
Propene 365.57 4.665 0.1408
1-Butene 419.5 4.02 0.192225
1-Pentene 464.699 3.5287 0.23296

Table 2. Experimental data used for the calculations
Ref. No. of Points Data Type P range(MPa) T range (K) Component
[25-28] 74 T-P-x 0.190 - 9.333 274.14 353.1 CO2 H2O
[29-32] 46
T-P-y & T-
P-x
0.491 - 9.082 274.19 - 318.12 CH4 H2O
[32-35] 50
T-P-y & T-
P-x
0.373 4.952 274.26-343.06 C2H6 H2O
[36, 37] 32 T-P-x 0.1043 - 4.13 298.15 - 423.15 nC4H10 H2O
[37-39] 67
T-P-y & T-
P-x
0.357-3.915 277.62-368.16 C3H8 H2O
[37] 8 T-P-x 0.354 1.712 298.23- 363.19 iC4H10 H2O
[37, 40] 10 T-P-x 0.498 - 0.508 298.28 - 343.15 nC5H12 H2O
[41-43] 32 T-P-x 0.207 - 3.241 298.09 - 477.59 nC6H14 H2O
[40] 10 T-P-x 0.101 279.15- 294.95 2MButane H2O
[44] 38 T-P-x 14.18 - 70.91 573.15 - 628.15 2-MPentane H2O
[44] 25 T-P-x 17.22 - 70.91 295 - 355 nC7H16 H2O
[45] 5 T-P-x 6.5 298- 473 nC8H18 H2O
[41, 45] 9 T-P-x 0.5-6.5 298.15 - 473 2,2,4-tmPentane H2O
[46] 15 T-P-x 0.52- 9.36 423.15- 583.15 nC10H22 H2O
[47, 48] 52
T-P-y & T-
P-x
0.2-8 310-410 Propylene H2O
[49, 50] 47
T-P-y & T-
P-x
1.37-10.3 310-410 Ethylene H2O
[51] 59 BP 1.74 12.06 313 - 393 CO2 1-hexene
[51] 27 BP 2.43 11.55 313 - 373
CO2 2-ethyl-1-
butene
[52, 53] CO2- 1-Hexene
[52] CO2- 1-Heptene
[54] 58
T-P-x
T-P-y
0.97-6.02 283-298 Propylene-CO2
[54, 55] 86
T-P-x
T-P-y
1.03-5.38 283-298 Propylene-Ethylene
[19] 46
T-P-x
T-P-y
0.79 8.51 293 - 373
Ethylene - 4-Methyl-
1-pentene
[56] 30 T-P-x 0.44 2.32 323 - 423 Ethylene - 2,2,4-
T-P-y Trimethylpentane
[57] 106 BP 1.5-9.09 391-495 Ethylene + Hexane
[58] 48
T-P-x
T-P-y
0.6 6.6 293 - 374 Ethylene -1-Butene
[58] 20
T-P-x
T-P-y
1 8.9 303 - 342 Ethylene 1-Octene
[59] 33 T-P-x 1 15 290 - 323 Ethylene n-Eicosane
[60] 20
T-P-x
T-P-y
0.44 2.42 323 423
Ethylene 2,2,4-
Trimethylpentane

[61] 130 BP 1.5 8.5 390 - 450 Ethylene Hexane
[62] 60
T-P-x
T-P-y
0.35 0.86 310 - 338 Butane 1-Butene
[63] 25
T-P-x
T-P-y
0.6 6.06 293 - 375 Ethylene 1-Butene
[54] 50
T-P-x
T-P-y
0.89-4-07 283-298 Propylene-Ethane
[14, 64,
65]
350
T-P-x
T-P-y
0.47-3.51 273-350 Propylene-Propane
[19] 11
T-P-x
T-P-y
0.4 1.4 373 1-Butene 1-Hexene
[66] 13 T-P-x 0.101 293 - 323 1-Butene H2O
[67, 68] 60
T-P-x
T-P-y
6.9-34-48 377.6-477.6 H2 nHexane
[67] 20
T-P-x
T-P-y
2.01-25 524-664 H2 nHexadecane
[67] 8 T-P-x 4.3-8.9 423-453
H2
2,3-dimethylbutane
[69] 15
T-P-x
T-P-y
1 5.07 373 - 573 H2 n-Eicosane
[70, 71] 38 T-P-x .101 273 - 300 H2 H2O
[72] 49
T-P-x
T-P-y
1.26 10.5 293 - 473 CO Hexane
[69] 15 T-P-x 1.02 5.03 373 - 573 CO Eicosane
[73] 18 T-P-x 2.84 10.2 310 - 377 CO n-decane
[73] 41
T-P-x
T-P-y
0.67 3.9 463 - 533 CO C8H18


Figure 2. Calculation of binary interaction coefficient parameters for each pair
Figure 2 shows the procedure of calculating the binary interaction coefficient variables.
As it was mentioned before, since the calculations are sensitive to the initialization,
different points were chosen as the initial value and the best result was reported. Wilson
equation was used for the initial guess of distribution factor (the equation below) in flash
calculations:
( ) ( )
exp 5.37 1 1
c c
i
P T
K
P T
e
| |
= +
|
\ .

(8)

The groups which are defined in this work are: group 1=CH3; group 2 =CH2; group 3 =
CH; group 4 =C; group 5=CH4, i.e. methane; group 6 =C2H6, i.e. ethane; group 7: H2O,
group 8: CO2, group 9: CO, group 10: H2, group 11: Ethylene, group 12: CH=, group 13:
CH2=. These groups are chosen as representatives of the components which are present
in the GTL process. Figure 3 shows the procedure of calculating A and B parameters
from the set of temperatures and K
ij
values.



Calculating A and B for Pairs or
Groups
Read Physical
Properties of
Components (Tc, Pc, )
Read (T, Kij) for
Each Pair of
Component
Calculate
ij
for
Each Component
Calculate Tr and a
i
for Each Component
at the Specified
Temperature
Minimize error by
Changing A* and
B* Matrixs
Get A* and B*
Matrix from the
Optimization
Procedure
Make Complete A and
B Matrixs Using Input
A* and B* and Previous
Valuse
Calculate Kij Using
A and B Matrixs,

ij ,
T and Physical
Properties
Resid = Kij_calcd
Kij_opt
Is This the Last
Pair
No
error =
sum( abs (Resid))
Report A* and B*
Yes

Figure 3. Calculation of A and B parameters for each pair of components

Stability Analysis
The stability analysis test is possible through two approaches: solving the nonlinear
system of equations and minimization. We have used the second approach for our work.
The function to be minimized is as below
( ) min ( ) ln ln ( ) ln ln ( )
: 1 0 1
i i i i i
i
i i
i
F x x x x z z
subject to x x
| | = +
= s s

(9)
In fact, a mixture with the mole fraction z is in equilibrium when for every value for x,
the above expression results in a positive value. By performing an optimization we can
get the minimum value which results in positive value of F. If the obtained minimum
value is negative, this means the system is unstable. So, in order to get the number of
phases which are in equilibrium in a specified operating point, it is sufficient to do the
flash calculations for two phases and if the criterion is not satisfied, the number of phases
will be increased.

Results and Discussions
As summarized in the flowcharts (Figures 1-3), the approach of this work consists of two
stages: First, the binary interaction for each pair of components is optimized so that the
difference between the resulting compositions from flash calculations and the
experimental ones will be minimum. Second, A and B parameters are optimized in order
to minimize the difference between the calculated binary interaction from the previous
step and the one which is derived from equation (4).
There isnt any clue about the initial guesses for the binary coefficient factor. So, we start
with different random initial points. Then, successive substitution method is used to do
the flash calculation. The initial guess for this stage is derived from Wilson equation for
the distribution factor and the experimental data for compositions of the phases. In this
manner, we can have a good guess for the amount of vapor. After reaching to the point
which we dont see any improvement (the change in the distribution coefficient value in
two subsequent iterations is less than some specified tolerance) or when the maximum
number of iteration is reached, we switch to the other approach of flash calculations,
which is solving a system of equations (1 total mol balance, n-1 component balance, two
equations for summation of mole fractions in two phases and n equi-fugacity of
components in two phases). We use the solution from the previous approach as an initial
point in this step.
Figures 4-13 show some of the cases the P-x-y diagrams in different temperatures. It was
observed that for a few cases the error tolerance for higher pressures were more,
especially in higher temperatures. However, in our case the points near the operational
conditions in GTL process are of more importance. There are also a few graphs (Figures
15, 16) which shows the functionality of the binary interaction coefficient of some pairs
as a function of temperature.



0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 5 10 15 20 25 30 35 40 45
P(MPa)
m
o
l
e

f
r
a
c
.

o
f

H
2

i
n

l
i
q
.

o
r

v
a
p
.

Figure 4. H
2
/n-C
6
H
14
: black: experimental ( and ) and calculated data @ 377.6,
red: experimental ( and ) and calculated data @ 444.3, blue:
experimental ( and ) and calculated data @ 477.6



0
0.2
0.4
0.6
0.8
1
1.2
0 2 4 6 8 10 12
P(MPa)
m
o
l
e

f
r
a
c
.

o
f

H
2

i
n

l
i
q
.

o
r

v
a
p
.
X exp-542.3
X calc-542.3
Y exp. 542.3
Y calc. 542.3
X exp 664.1
X calc. 664.1
Y exp 664.1
Y calc. 664.1

Figure 5. H
2
/n-C
16
H
34
: black: experimental ( and ) and calculated data @ 542.3,
red: experimental ( and ) and calculated data @ 664.1


0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
4 5 6 7 8 9 10 11
P(MPa)
m
o
l
e

f
r
a
c
.

o
f

H
2

i
n

l
i
q
.

o
r

v
a
p
.

Figure 6. H
2
/ 2,3-dimethylbutane: black: experimental () and calculated data @
423.2, red: experimental () and calculated data @ 453.2


0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 2 4 6 8 10 12 14 16
P(MPa)
m
o
l
e

f
r
a
c
.

o
f

H
2

i
n

l
i
q
.

o
r

v
a
p
.

Figure 7. H
2
/n-C
6
H
14
: black: experimental ( and ) and calculated data @ 344.3,
red: experimental ( and ) and calculated data @ 377.6, blue:
experimental ( and ) and calculated data @ 410.9



0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 2 4 6 8 10 12 14 16
P(MPa)
m
o
l
e

f
r
a
c
.

o
f

C
O

i
n

l
i
q
.

o
r

v
a
p
.

Figure 8. CO/n-C
6
H
14
: black: experimental () and calculated data @ 373, red:
experimental () and calculated data @ 423, blue: experimental () and
calculated data @ 473


0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 1 2 3 4 5 6 7
Pr essur e(MPa)
m
o
l

f
r
a
c
.

C
O

i
n

V
a
p
.

o
r

L
i
q
.

Figure 9. CO/n-C
6
H
14
: black: experimental ( and ) and calculated data @ 483,
red: experimental ( and ) and calculated data @ 503, blue: experimental
( and ) and calculated data @ 523


0
0.2
0.4
0.6
0.8
1
0.3 0.8 1.3 1.8 2.3
P(MPa)
M
o
l

f
r
a
c
.

C
2
=

i
n

V
a
p
.

o
r

L
i
q

Figure 10. C
2
H
4
/2,2,4-Trimethylpentane: black: experimental ( and ) and
calculated data @ 373, red: experimental ( and ) and calculated data @
423

0
0.5
1
1.5
2
2.5
0 2 4 6 8 10
P(MPa)
m
o
l
.

f
r
a
c
.

C
O
2

i
n

l
i
q
.

Figure 11. CO
2
/H
2
O: black: experimental () and calculated data @ 318, red:
experimental () and calculated data @ 308, blue: experimental () and
calculated data @ 298

0
0.0001
0.0002
0.0003
0.0004
0.0005
0.0006
0.0007
0.0008
0.0009
0.001
0 1 2 3 4 5 6
P(MPa)
m
o
l
.

f
r
a
c
.

o
f

C
2

i
n

L
i
q
.

Figure 12. C
2
H
6
/H
2
O: black: experimental () and calculated data @ 313, red:
experimental () and calculated data @ 323, blue: experimental () and
calculated data @ 343


0
0.00005
0.0001
0.00015
0.0002
0.00025
0.0003
0.00035
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
P(MPa)
M
o
l
.

f
r
a
c
.

o
f

n
C
4

i
n

L
i
q
.

Figure 13. nC
4
H
10
/H
2
O: black: experimental () and calculated data @ 373, red:
experimental () and calculated data @ 398, blue: experimental () and
calculated data @ 423

0
0.00005
0.0001
0.00015
0.0002
0.00025
0.0003
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
P(MPa)
m
o
l
.

f
r
a
c
.

o
f

C
3

i
n

L
i
q
.

Figure 14. C
3
H
8
/H
2
O: black: experimental () and calculated data @ 338, red:
experimental () and calculated data @ 353, blue: experimental () and
calculated data @ 368






-0.3
-0.25
-0.2
-0.15
-0.1
-0.05
0
270 290 310 330 350
Temperature
K
i
j

v
a
l
u
e
s

Figure 15. Kij values of H2O-Ethane

-0.18
-0.16
-0.14
-0.12
-0.1
-0.08
-0.06
-0.04
-0.02
0
220 270 320 370
Temperature
K
i
j

Figure 16. Kij values for H2O-CO2




As mentioned previously, this work is a development of previous works done by Jaubert
et. al [1, 74] to make it applicable to GTL process. The binary interaction coefficients
between CO2 and Hydrocarbons which is presented in Table 3 is from their work.
Addition of water, CO, CO2, H2, Ethylene and other olefins is our contribution in order
to provide a tool for thermodynamic studies of GTL process. Table 3 presents the
parameter values which are the result of this work. There are some missing data in the
table due to different reasons which is described below:
- The vapor-liquid equilibriums of some groups are not in the range of temperatures and
pressures which are applicable to our case. For example, the equilibrium data which were
found for H2-CH4 are in the range of 103.15-173.65 K and 10-110 MPa for temperature
and pressure respectively. In the operational condition under study, these components
will be in the supercritical state. CH4-Ethylene, CO-H2, H2-Ethylene and carbon
monoxidemethane are other examples.
- It is said that the values of the Kij parameters for the CH4C2H6, CH4C2H4, and
C2H6C2H4 are close to zero, which indicates the near athermal character of these
mixtures [75]. We have used this assumption to calculate the parameters for the last two
pairs due to lack of data.
- Groups C and C= should also be present as two of the groups in the study. However,
due to the lack of experimental data, the group contribution is not calculated in some
cases. There are very few works which have dealt with the equilibrium of different
components with branched hydrocarbons (especially alkenes).
- One other point is that performing the experiments in order to get the VLE data is costly
and there is always a reason to do it. So, its maybe natural that finding the data is so
difficult for every pair of components of interest in different ranges of temperatures and
pressures.
Table 3. A and B parameters which are needed to calculate Kij as a function of temperature
CH3 CH2 CH C CH4 C2H6 CO2 H2O
CH3 0 0
CH2 74.81 165.7 0 0
CH 261.5 388.8 51.47 79.61 0 0
C 396.7 804.3 88.53 315 -305.7 -250.8 0 0
CH4 33.94 -35 36.72 108.4 145.2 301.6 263.9 531.5 0 0
C2H6 8.579 -29.51 31.23 84.76 174.3 352.1 333.2 203.8 13.04 6.863 0 0
CO2 164 269 136.9 254.6 184.3 762.1 287.9 346.2 137.3 194.2 135.5 239.5 0 0
H2O 559.4083 -204.813 0.0288 -0.8781 0.0114 -0.4669 -915.918 -438.848 124.1 2484 691.2692 -109.009 489.797 -399.749 0 0
H2 317.5348 -67.478 51.18 297.4748 -186.083 72.1725 - - - - - - 123.2 60.1
CO 98.0672 -137.8 52.929 398.8686 - - - - - - - - 241 152.32
Ethylene 0.0476 -0.7808 75.2236 313.1654 186.7467 339.2428 171.5267 313.959 5.8826 9.357 0.0052 0.041 - - 638.3672 138.8688
CH= 88.5 51.7943 -0.5604 13.8159 348.8818 -7.7501 263.8316 345.7421 322.24 -145.23
CH2= 102.4364 60.9804 0.6879 29.2979 351.8326 -21.2664 -90.845 564.2252 100.32 54.75

CO Ethylene CH= CH2=
CH3
CH2
CH
C
CH4
C2H6
CO2
H2O
H2 0 0
CO - - 0 0
Ethylene - - - - 0 0
CH= 0.001 0.5949 0 0
CH2= 66.7801 73.9685 91.6826 7.8722 0 0

Conclusion
In this work the dependency of Kij on temperature has been derived for the pairs of
component which are included in the GTL reactor effluents. The calculation of Kij was
done was done with the criteria of maximum 1% difference between the experimental
and calculated mole fractions, while in the next step the error (the difference between the
calculated Kij from the previous step and the current one) is so low.

References

1. Jaubert, J.-N. and F. Mutelet, VLE predictions with the PengRobinson equation
of state and temperature dependent kij calculated through a group contribution
method. Fluid Phase Equilibria, 2004. 224: p. 285-304.
2. Storch, H.H., N. Golumbic, and R.B. Anderson, The Fischer-Tropsch and Related
Synthesis. 1951, New York: Wiley.
3. Mikhailova, I.A., et al., Calculating the LiquidGas Equilibrium in the Fischer
Tropsch Synthesis. Theoretical Foundations of Chemical Engineering, 2003.
37(2): p. 167-171.
4. Bunz, A.P., R. Dohrn, and J.M. Prausnitz, Three- Phase Flash Calculations for
Multicomponent Systems Computers and Chemical Engineering, 1991. 15(1): p.
47-51.
5. Nghiem, L.X. and L. Yau-Kun, Computation of Multi-phase Equilibrium
Phenomena with an Equation of State. Fluid Phase Equilibria, 1984. 17: p. 77-95.
6. Lucia, A., L. Padmanabhan, and S. Venkataraman, Multiphase equilibrium flash
calculation. Computers and Chemical Engineering, 2000. 24: p. 2557-2569.
7. Nelson, P.A., Rapid Phase Determination in Multiple-Phase Flash Calculations.
Computers and Chemical Engineering, 1987. 11(6): p. 581-591.
8. Wu, J.S. and P.R. Bishnoi, An Algorithm Equilibrium for Three-Phase
Calculations. Computers and Chemical Engineering, 1986. 10(3): p. 269-276.
9. Soares, M.E. and A.G. Medina, Three Phase Flash Calculations Using Free
Energy Minimization Computers and Chemical Engineering, 1982. 37(4): p. 521-
528.
10. Eubank, P.T., Equations and procedures for VLLE calculations. Fluid Phase
Equilibria, 2006. 241: p. 81-85.
11. Sandoval, R., G. Wilczek-Vera, and J.H. Vera, Prediction of Ternary Vapor-
Liquid Equilibria with the PRSV Equation of State. Fluid Phase Equilibria. 52: p.
119-126.
12. Walas, S., Phase Equilibria in Chemical Engineering. 1985, Boston: Butterworth.
13. Huang SH, et al., Industrial and Engineering Chemistry Research, 1988. 27: p.
162-169.
14. Kuo, C., Two stage process for conversion of synthesis gas to high quality
transportation fuels, in DE-AC22-83PC60019, D. Contact, Editor. 1985.
15. Han, S.J., H.M. Lin, and K.C. Chao, Vapour-Liquid Equilibrium of Molecular
Fluid Mixtures by Equation of State. Chem. Eng. Sci., 1988. 43: p. 2327-2367.
16. Jean-Nol Jaubert, et al., Extension of the PPR78 model (predictive 1978, Peng
Robinson EOS with temperature dependent kij calculated through a group
contribution method) to systems containing aromatic compounds. Fluid Phase
Equilibria, 2005. 237: p. 193-211.
17. Saber, N. and J.M. Shaw, Rapid and robust phase behaviour stability analysis
using global optimization. Fluid Phase Equilibria, 2008. 264: p. 137-146.
18. Rangaiah, G.P., Evaluation of genetic algorithms and simulated annealing for
phase equilibrium and stability problems. Fluid Phase Equilibria, 2001. 187-188:
p. 83-109.
19. Hua, J.Z., J.F. Brennecke, and M.A. Stadtherr, Reliable Computation of Phase
Stability Using Interval Analysis: Cubic Equation of State Models, in 6th
European Symposium on Computer-Aided Process Engineering (ESCAPE-6).
1996: Rhodes, Greece.
20. Harding, S.T. and C.A. Floudas, Phase Stability with Cubic Equations of State: A
Global Optimization Approach, in AIChE Annual Meeting. 1998.
21. Jalali-Farahani, F. and J.D. Seader, Use of homotopy-continuation method in
stability analysis of multiphase, reacting systems. Computers and Chemical
Engineering, 2000. 24: p. 1997-2008.
22. Bausa, J. and W. Marquardt, Quick and reliable phase stability test in VLLE flash
calculations by homotopy continuation. Computers and Chemical Engineering,
2000. 24: p. 2447-2456.
23. Robinson, D.B. and D.Y. Peng, The characterization of the heptanes and heavier
fractions for the GPA Peng-Robinson programs, Gas processors association 1978
(Booklet only sold by the Gas Processors Association, GPA), RR-28 Research
Report
24. Peng, D.-Y. and D.B. Robinson, A New Two-Constant Equation of State. Ind.
Eng. Chem., Fundam., 1976. 15(1): p. 59-64.
25. Chapoy, A., et al., Measurement and Modeling of Gas Solubility and Literature
Review of the Properties for the Carbon Dioxide-Water System. Ind. Eng. Chem.
Res., 2004. 43: p. 1794-1802.
26. Larryn W. Diamond and N.N. Akinfiev, Solubility of CO2 in water from 1.5 to
100 C and from 0.1 to 100 MPa: evaluation of literature data and
thermodynamic modelling. Fluid Phase Equilibria, 2003. 208: p. 265-290.
27. Valtz, A., et al., Vapourliquid equilibria in the carbon dioxidewater system,
measurement and modelling from 278.2 to 318.2K. Fluid Phase Equilibria, 2004.
226: p. 333-344.
28. Bamberger, A., G. Sieder, and G. Maurer, High-pressure (vapor-liquid)
equilibrium in binary mixtures of (carbon dioxide + water or acetic acid) at
temperatures from 313 to 353 K. Journal of Supercritical Fluids, 2000. 17: p. 97-
110.
29. Chapoy, A., C. Coquelet, and D. Richon, Corrigendum to Revised solubility data
and modeling of water in the gas phase of the methane/water binary system at
temperatures from 283.08 to 318.12K and pressures up to 34.5MPa [Fluid
Phase Equilibria 214 (2003) 101117]. Fluid Phase Equilibria, 2005. 230: p. 210-
214.
30. Knut Lekvam and P. Raj Bishnoi, Dissolution of methane in water at low
temperatures and intermediate pressures. Fluid Phase Equilibria, 1997. 131: p.
297-309.
31. Chapoy, A., et al., Estimation of Water Content for Methane + Water and
Methane + Ethane + n-Butane + Water Systems Using a New Sampling Device. J.
Chem. Eng. Data, 2005. 50(4): p. 1157-1161.
32. Mohammadi, A.H., et al., Experimental Measurement and Thermodynamic
Modeling of Water Content in Methane and Ethane Systems. Ind. Eng. Chem.
Res., 2004. 43(22): p. 7148-7162.
33. Chapoy, A., C. Coquelet, and D. Richon, Measurement of the Water Solubility in
the Gas Phase of the Ethane + Water Binary System near Hydrate Forming
Conditions. J. Chem. Eng. Data, 2003. 48(4): p. 957-966.
34. Mohammadi, A.H., et al., Measurements and Thermodynamic Modeling of
VaporLiquid Equilibria in EthaneWater Systems from 274.26 to 343.08 K. Ind.
Eng. Chem. Res., 2004. 43(17): p. 5418-5424.
35. Coan, C.R. and A.D. King, Solubility of Water in Compressed Carbon Dioxide,
Nitrous Oxide and Ethane. Evidence for Hydration of Carbon Dioxide and
Nitrous Oxide in the Gas Phase. J. Am. Chem. Soc. , 1971. 93: p. 1857-1862.
36. Carroll, J.J., F. Jou, and A. Mather, FLUID PHASE EQUILIBRIA IN THE
SYSTEM N-BUTANE PLUS WATER. Fluid Phase Equilibria, 1997. 140: p. 157-
169.
37. Mokraoui, S., et al., New Solubility Data of Hydrocarbons in Water and Modeling
Concerning VaporLiquidLiquid Binary Systems. Ind. Eng. Chem. Res. , 2007.
46(26): p. 9257-9262.
38. Song, K.Y. and R. Kobayashi, The water content of ethane, propane and their
mixtures in equilibrium with liquid water or hydrates. Fluid Phase Equilibria,
1994. 95: p. 281-298.
39. Chapoy, A., et al., Solubility measurement and modeling for the system propane
water from 277.62 to 368.16K. Fluid Phase Equilibria, 2004. 226: p. 213-220.
40. Black, C., G.G. Joris, and H.S. Taylor, J. Chem. Phys. , 1948. 16: p. 537.
41. Pereda, S., et al., Solubility of hydrocarbons in water: Experimental
measurements and modeling using a group contribution with association equation
of state (GCA-EoS). Fluid Phase Equilibria 2009. 275: p. 52-59.
42. S. D. Burd, J. and W.G. Braun, Proc. Am. Pet. Inst., Div. Refin., 1968. 48: p. 464.
43. De Loos, T.W., W.G. Penders, and R.N. Lichtenthaler, Phase equilibria and
critical phenomena in fluid (n-hexane + water) at high pressures and
temperatures. J. Chem. Thermodyn., 1982. 14(1): p. 83-91.
44. Connolly, J.F., Solubility of Hydrocarbons in Water Near the Critical Solution
Temperatures. J. Chem. Eng. Data, 1966. 11: p. 13-16.
45. Miller, D.J. and S.B. Hawthorne, Solubility of Liquid Organics of Environmental
Interest in Subcritical (Hot/Liquid) Water from 298 K to 473 K. J. Chem. Eng.
Data, 2000. 45(1): p. 78-81.
46. Namiot, A.Y., V.G. Skripka, and Y.G. Lotter, Zh. Fiz. Khim., 1976. 50: p. 2718.
47. Li, C.C. and J.J. McKetta, Vapor-Liquid Equilibrium in the Propylene-Water
System. Journal of Chemical & Engineering Data, 1963. 8(2): p. 271-275.
48. Azarnoosh, A. and J.J. McKetta, Solubility of Propylene in Water. Journal of
Chemical & Engineering Data, 1959. 4(3): p. 211-212.
49. Anthony, R.G. and J.J. McKetta, Phase equilibrium in the ethylene-water system.
Journal of Chemical & Engineering Data, 1967. 12(1): p. 17-20.
50. Bradbury, E.J., et al., SOLUBILITY OF ETHYLENE IN WATER. EFFECT OF
TEMPERATURE AND PRESSURE. Industrial & Engineering Chemistry, 1952.
44(1): p. 211-212.
51. Vapor-Liquid Equilibria Measurement of Carbon Dioxide+1-Hexene and Carbon Dioxide+2-
Ethyl-1-Butene Systems at High Pressure. Korean J. Chem. Eng., 2004. 21(5): p. 1032-
1037.
52. Vera, J.H., Binary vapor-liquid equilibria of carbon dioxide with 2-methyl-1-
pentene, 1-hexene, 1-heptene, and m-xylene at 303.15, 323.15, and 343.15 K.
Journal of Chemical and Engineering Data, 1984. 29(3): p. 269-272.
53. Byun, H.S.H.S., Vapor-liquid equilibria measurement of carbon dioxiden+1-
hexene and carbon dioxide+2-ethyl-1-butene systems at high pressure. Korean
Journal of Chemical Engineering, 2004. 21(5): p. 1032-1037.
54. Ohgaki, K., et al., Isothermal vapor-liquid equilibria for the binary systems
propylene-carbon dioxide, propylene-ethylene and propylene-ethane at high
pressure. Fluid Phase Equilibria, 1982. 8: p. 113- 122.
55. Kubota, H., et al., Vapor-Liquid Equilibria of the ethylene-propylene system
under high pressure
Journal of Chemical Engineering of Japan
1983. 16(2).
56. Solubility of Ethylene in 2,2,4-Trimethylpentane at Various Temperatures and
Pressures. Journal of Chemical and Englneering Data, 2007. 52(1): p. 102-107.
57. VaporLiquid Equilibrium Data for the Ethylene + Hexane System. Journal of
Chemical and Englneering Data, 2005. 50(4): p. 1492-1495.
58. Ethylene + Olefin Binary Systems: Vapor-Liquid Equilibrium Experimental Data and Modeling.
Journal of Chemical and Engineering Data, 1994. 39(2): p. 388-391.
59. Kohn, J.P., et al., Phase equilibriums of ethylene and certain normal paraffins. J.
Chem. Eng. Data, 1980. 25(4): p. 348/350.
60. Lee, L.-S., H.-Y. Liu, and Y.-C. Wu, Solubility of Ethylene in 2,2,4-
Trimethylpentane at Various Temperatures and Pressures. J. Chem. Eng. Data,
2007. 52(1): p. 102-107.
61. Nagy, I., et al., VaporLiquid Equilibrium Data for the Ethylene + Hexane
System. J. Chem. Eng. Data, 2005. 50(4): p. 1492-1495.
62. Laurance, D.R. and G.W. Swift, Vapor-liquid equilibriums in three binary and
ternary systems composed of butane, 1-butene, and 1,3-butadiene. J. Chem. Eng.
Data, 1974. 19(1): p. 61-67.
63. BAE, H.K., K. NAGAHAMA, and M. HIRATA, MEASUREMENT AND
CORRELATION OF HIGH PRESSURE VAPOR-LIQUID EQUILIBRIA FOR
THE SYSTEMS ETHYLENE-1-BUTENE AND ETHYLENE-PROPYLENE.
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN, 1981. 14(1): p. 1-6.
64. Ho, Q.N., et al., Measurement of vaporliquid equilibria for the binary mixture of
propylene (R-1270) + propane (R-290). Fluid Phase Equilibria, 2006. 245: p. 63-
70.
65. Harmens, A., Propylene-propane phase equilibrium from 230 to 350 K. Journal of
Chemical and Engineering Data, 1985. 30(2): p. 230-233.
66. Serra, M.C.C.M.C.C., Solubility of 1-Butene in Water and in a Medium for
Cultivation of a Bacterial Strain. Journal of Solution Chemistry, 2003. 32(6): p.
527-534.
67. Ferrando, N. and P. Ungerer, Hydrogen/hydrocarbon phase equilibrium
modelling with a cubic equation of state and a Monte Carlo method. Fluid Phase
Equilibria, 2007. 254: p. 211223.
68. Solubilities of Hydrogen in Hexane and of Carbon Monoxide in Cyclohexane at
Temperatures from 344.3 to 410.9 K and Pressures to 15 MPa. J. Chem. Eng.
Data 2001. 46: p. 609-612.
69. Solubility of Synthesis Gases in Heavy n -Paraffins and Fischer-Tropsch Wax. Ind. Eng. Chem.
Res. , 1988. 27: p. 162/169.
70. Crozier, T.E. and S. Yamamoto, Solubility of Hydrogen in Water, Seawater, and
NaCl Solutions. Journal of Chemical and Engineering Data, 1974. 19(3): p. 242-
244.
71. Crozier, T.E., Solubility of hydrogen in water, seawater, and NaCl solutions.
Journal of Chemical and Engineering Data, 1974. 19(3): p. 242-244.
72. Solubility of carbon monoxide in n-hexane between 293 and 473 K and carbon monoxide
pressures up to 200 bar. Journal of Chemical and Engineering Data, 1993. 38(3).
73. Solubilities of Carbon donoxide in Heavy Normal Paraffins at Temperatures from
311 to 423 K and Pressures to 10.2 MPa. J. Chem. Eng. Data, 1995. 40(237/240).
74. Stphane Vitu, et al., Predicting the phase equilibria of CO2 + hydrocarbon
systems with the PPR78 model (PR EOS and kij calculated through a group
contribution method). Journal of Supercritical Fluids, 2008. 45(1): p. 1-26.
75. Ioannidis, S. and D.E. Knox, Vaporliquid equilibria predictions of hydrogen
hydrocarbon mixtures with the HuronVidal mixing rule. Fluid Phase Equilibria
1999. 165: p. 23/40.