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Abstract
The statistical associating fluid theory (SAFT) equation of state is employed for the correlation and prediction of vaporliquid equilibrium (VLE) of eighteen binary mixtures. These include water with methane, ethane, propane, butane, propylene, carbon dioxide, methanol,
ethanol and ethylene glycol (EG), ethanol with ethane, propane, butane and propylene, methanol with methane, ethane and carbon dioxide and finally EG with methane and ethane. Moreover, vaporliquid equilibrium for nine ternary systems was predicted. The systems
are water/ethanol/alkane (ethane, propane, butane), water/ethanol/propylene, water/methanol/carbon dioxide, water/methanol/methane, water/methanol/ethane, water/EG/methane and water/EG/ethane. The results were found to be in satisfactory agreement with the experimental
data except for the water/methanol/methane system for which the root mean square deviations for pressure were 6068% when the methanol
concentration in the liquid phase was 60 wt.%.
2004 Elsevier B.V. All rights reserved.
Keywords: Vaporliquid equilibrium; SAFT; Alcohol; Alkane; Water
1. Introduction
The modeling of phase behavior and the calculation of
thermodynamic properties of aqueous solutions involving alcohols, hydrocarbon, water and carbon dioxide is of considerable industrial importance. For example, such information is needed for the design of facilities for the extraction
of alcohols from aqueous solutions using near critical light
hydrocarbons as solvents [1,2]. Another application is the inhibition of gas hydrate formation in the oil and gas industry
[3]. Mixtures containing associating compounds are also of
interest from a theoretical point of view for testing molecular
thermodynamic models.
One successful modelling approach is the statistical associating fluid theory (SAFT), which is based on Wertheims
first-order thermodynamic perturbation theory for associating fluids [4-8]. SAFT has been used to model successfully a
Corresponding author. Tel.: +1 604 822 6184; fax: +1 604 822 6003.
E-mail address: englezos@interchange.ubc.ca (P. Englezos).
0378-3812/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2004.06.052
wide variety of the thermodynamic properties and phase equilibria for industrially important fluids [9]. Huang and Radosz
[6] applied the original SAFT to calculate the phase equilibria of water/n-alkane, water/methane and water/ethane, and
hydrocarbon/alcohol mixtures. It is noted that for the water/methane and water/ethane systems they only calculated
the solubility of water in the hydrocarbon-rich phase. Kraska
and Gubbins [10] proposed the LennardJones (LJ)-SAFT,
in which the chain segments were treated as LennardJones
spheres, to correlate the solubility of water in methane and
in ethane and the equilibria in 1-alkanol/n-alkane systems.
The results with LJ-SAFT exhibited better agreement with
experimental data than the original SAFT [10]. Galindo et al.
[11] applied the hard-sphere (HS)-SAFT to model the critical behaviour of n-alkane/water mixtures, and good agreement with experimental data was obtained. In this equation,
molecules are treated as chains of hard-sphere segments with
van der Waals interactions. Garcia-Lisbona et al. [12] also
used HS-SAFT to predict the high-pressure phase equilibria
of binary aqueous solutions of 1-butanol, n-butoxyethanol
112
2. Equation of State
The residual Helmholtz free energy for an n-component
mixture of associating chain molecules can be expressed as
the sum of hard sphere repulsion, hard chain formation, dispersion and association terms as follows
Ares = A Aid = Ahs + Achain + Adisp + Aassoc
(1)
where Aid is the free energy of an ideal gas with the same
density and temperature as the system, Ahs the free energy of a hard-sphere fluid relative to the idea gas. The
Ahs term is calculated with the BoublikMansoori
CarnahanStarlingLeland equation [17,18] and the
BarkerHenderson perturbation theory [19]. Detailed
expressions for this and the other free energy terms in Eq.
(1) are given elsewhere [15]. Achain is the free energy when
chains are formed from hard spheres. This chain term was
derived by Chapman et al. [7]. Adisp and Aassoc are the
contributions to the free energy of dispersion and association
interactions, respectively. This dispersion term is calculated
by using an expression based on the LennardJones potential
[19]. The following combining rules are used for the cross
parameters between different segments, ij and ij
ii + jj
2
ij = (1 kij ) ii jj
ij =
(2)
(3)
Aj Bi = Ai Bj =
(4)
Aj Bi = Ai Bj
(5)
113
Table 1
Estimated segment parameters for pure fluids
Fluid
T (K)
(1010 m)
/k (k)
AB /k (K)
AB
Water
Methanol
Ethanol
EG
Methane
Ethane
Propane
Butane
Propylene
CO2
283483
295489
303503
375496
523
523.15
369.65
313.15
377.59
323.15
0.982
1.124
1.402
1.043
1.1864
1.437
2.367
2.669
2.287
1.833
2.985
3.642
3.731
4.232
2.990
3.193
3.078
3.068
3.082
2.654
433.91
309.90
263.70
354.65
160.84
199.73
174.07
184.12
171.13
165.80
1195.20
2320.77
2616.50
2375.26
0.038
0.019
0.016
0.020
Table 2
Comparison of the segment parameters of the pure compounds obtained form fitting mixture data in this work with those given by Huang and Radosz [5]
Compound
CH4
C2 H6
C3 H8
C4 H10
C3 H6
CO2
(1010 m)
/k (K)
This work
Reference [5]
This work
Reference [5]
This work
Reference [5]
1.186
1.437
2.367
2.669
2.287
1.833
1.000
1.941
2.696
3.458
2.223
1.417
2.990
3.193
3.078
3.068
3.082
2.654
3.701
3.239
3.162
3.093
3.325
3.171
160.84
199.73
174.07
184.12
171.13
165.80
190.29
191.44
193.03
195.11
213.90
216.08
114
Table 3
Estimated binary interaction parameters from regression of binary VLE experimental data
Systems
T (K)
kij
kijAB
RMSD (y)a
Data source
T (K)
RMSD (y)a
377.59
394.26
410.93
427.59
0.0141
0.0216
0.0310
0.0412
4.1
3.8
4.0
6.5
[24]
298.15
343.15
0.0453
0.0260
4.9
19.9
[25]
344.26
410.93
0.0036
0.0172
23.5
14.4
[26]
348.15
0.0058
13.2
[27]
283.2
293.2
18.2
14.5
[28]
283.2
293.2
303.2
32.0
26.3
21.3
[28]
350.10
325.10
0.0221
0.0176
14.6
12.2
[32]
323.75
298.45
0.0082
0.0090
19.9
20.7
[33]
333.10
0.0121
12.2
[34]
308.15
303.18
298.16
291.15
0.0064
0.0068
0.0067
0.0056
8.8
10.8
8.6
14.2
[30]
283.2
293.2
19.0
16.3
[28]
283.2
293.2
8.6
6.2
[28]
a
RMSD
RMSD
(y) =
N
exp 2
Data source
Fig. 4 shows the calculated results for the water/EG system at 371.15 K. As seen, it exhibits a good agreement between data and calculated values. Table 4 presents VLE calculations for the water/ethanol and water/methanol mixtures
in which a good agreement between data and computed values is also obtained.
115
116
Table 5
Predicted VLE results for ternary mixtures
Systems
T (K)
P (MPa)
RMSD (y)a
y1
y2
Data source
313.15
323.15
5.0
5.0
0.0067
0.0038
0.0097
0.0079
34.5
35.7
[37]
333.0
363.0
383.0
1.12.0
1.13.7
1.14.1
0.0054
0.0099
0.0153
0.0084
0.0139
0.0259
10.0
5.8
8.6
[38]
353.2
0.671.1
0.0208
0.0185
15.2
[38]
333.2
1.82.5
0.0052
0.0089
13.8
[38]
313.15
308.15
303.15
298.15
7.0
6.011.0
7.0
5.07.0
0.0011
0.0033
0.0011
0.0011
0.0031
0.0159
0.0036
0.0017
16.2
6.5
13.7
6.8
[39]
[40]
[40]
[40]
a
RMSD
RMSD
(y) =
N
exp 2
5.4. Water/ethanol/propylene
High-pressure vaporliquid equilibrium for the ternary
system at 333.2 K is shown Fig. 8. The predictions compare
very well with the experimental data.
The predictions of the vaporliquid phase equilibria for other four systems, water/methanol/methane,
water/methanol/ethane, water/ethylene glycol/methane and
water/ethylene glycol/ethane, were also made and given. We
117
Table 6
Predicted VLE results for ternary mixtures at two alcohol liquid phase compositions
Systems
T (K)
P (MPa)
RMSD (y)
y1
x2
y2
80a
wt.%
Data source
x2
60a
wt.%
303.2
293.2
283.2
5.0540.05
5.0540.05
5.0540.05
24.87
24.04
28.99
68.1
59.7
66.6
[28]
303.2
293.2
283.2
0.54.0
0.53.0
0.53.0
11.78
8.15
9.38
30.8
29.7
36.5
[28]
303.2
293.2
283.2
303.2
5.0540.06
5.0540.05
5.0540.06
0.54.0
38.84
15.55
16.43
24.23
30.0
16.8
15.5
19.1
[28]
293.2
283.2
0.53.0
0.53.0
17.62
14.19
17.1
15.4
[28]
only compared the predicted pressure values with the experimental data, because the experimental data of vapor phase
composition for these ternary systems were unavailable from
literature. The agreement was satisfactory except ones at
x2 = 60 wt.% for water/methanol/methane as indicated in
Table 6 from the root mean square deviation values.
6. Conclusions
The SAFT equation of state is employed to predict the
phase equilibria for nine hydrocarbon/alcohol/water ternary
systems. Binary interaction parameters estimated from the
vaporliquid equilibrium data of the constituent binary subsystems were employed. A satisfactory agreement between
predicted values and experimental data was found except for
the water/methanol/methane system at the low methanol concentration in the liquid phase (60 wt.%).
List of symbols
A
Helmholtz free energy (J)
d
hard-sphere diameter (1 1010 m)
g
radius distribution function
k
Boltzmann constant (J K1 )
m
effective number of segments
M
number of associate sites
N
number of molecules
NA
Avogadro constant (6.02217 1023 mol1 )
R
gas constant (8.3143 J mol1 K1 )
S
ethanol loading in supercritical phase
T
absolute temperature (K)
x
mole fraction in liquid phase
xi
mole fraction of component i
118
xethanol
ethanol weight fraction in the aqueous phase (hydrocarbon free basis)
XiA
mole fraction of molecule i not bonded at site A
y
mole fraction in vapor phase
Z
compressibility factor
Greek letters
1/kT
/k
energy parameter of dispersion (K)
AB /k energy parameter of association between sites A and
B (K)
AB
bonding volume
AB
association strength between sites A and B
chemical potential
Acknowledgements
The financial support from National Science and Engineering Research Council of Canada (NSERC) is greatly appreciated.
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