Fluid Phase Equilibria 371 (2014) 614

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Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

Prediction of solubility of CO2 in ethanol[EMIM][Tf2N] ionic liquid

mixtures using articial neural networks based on genetic algorithm
Meysam Mirarab a, , Maysam Shari a , Mohammad Ali Ghayyem b , Fatemeh Mirarab c
a
b
c

Department of Chemical Engineering, Iran University of Science and Technology, Tehran, Iran
Petroleum University of Technology, Ahwaz, Iran
Mathematics and Computer Science Department, Amirkabir University of Technology, Tehran, Iran

a r t i c l e

i n f o

Article history:
Received 19 July 2013
Received in revised form 24 February 2014
Accepted 25 February 2014
Available online 5 March 2014
Keywords:
Ionic liquid
CO2 capture
Solubility
Articial neural network
Genetic algorithm

a b s t r a c t
This paper proposes articial neural networks (ANNs) technique as a new approach to predict solubility
of CO2 in ethanol[EMIM][Tf2 N] ionic liquid mixtures. The solubility equilibrium data of CO2 were measured at 0, 20, 50 and 80 and 100 wt.% mixture of [EMIM][Tf2 N] ionic liquid, temperatures of 313.2 and
333.2 C, and pressure range of 07 MPa. A feed-forward multilayer perceptron (MLP) neural network
with Levenberg-Marquardt learning algorithm was developed for prediction task. The ANN model was
trained, validated and tested using 70%, 15% and 15% of all solubility data, respectively. An optimization
procedure was performed based on genetic algorithm to select the best ANN architecture. Therefore,
a three layer feed-forward neural network with Levenberg-Marquardt back-propagation training algorithm was developed and designed with four variables as inputs and one variable as output, 15 neurons
in the hidden layer, log-sigmoid transfer function in the hidden layer and linear transfer function in the
output layer. Based upon statistical analysis, results obtained demonstrated that there is a very little
difference between predicted and experimental data of CO2 capture rate giving very low value of average
absolute deviation (AAD) and high value of least square (R2 ) very close to one, indicating high accuracy of
this model to predict output variable. The results also proved that the developed ANN model outperforms
the Peng-Robinson model.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Many industrial processing operations such as natural gas
purication produce a large amount of carbon dioxide (CO2 ) which
is suspected to be a major contributor to the greenhouse effect
and global warming. A wide range of technologies have been proposed to capture CO2 including absorption, adsorption, cryogenic
distillation and membrane separation. Among these technologies,
absorption is the most common method for CO2 capture [1].
The absorption process is fundamentally utilized to reduce the
global warming problem by separating CO2 from industrial waste
gases which would otherwise be vented to the atmosphere. In the
absorption process, CO2 in gas streams is absorbed into liquid solvents, which can be classied into physical and chemical categories
[2,3]. Chemical solvents are preferred for the process because they
have higher absorption capacity at low partial pressures of CO2 [1].

Corresponding author. Tel.: +98 911 2794239.

E-mail address: meysam mirarab@chemeng.iust.ac.ir (M. Mirarab).
http://dx.doi.org/10.1016/j.uid.2014.02.030
0378-3812/ 2014 Elsevier B.V. All rights reserved.

Recently, the interest towards the development of new ionic

liquids (ILs) to capture CO2 has risen signicantly. Ionic liquids,
which are the generic names of a broad category of salts with
melting point less than 373.15 K that usually composed of large,
asymmetric and loosely coordinating organic cations and inorganic or organic anions, have attracted a considerable attention due
to their unique properties such as extremely low vapor pressure,
wide liquid temperature range, high thermal and chemical stability,
and their capability of dissolving a variety of chemical compounds
[47].
Considerable amount of theoretical and experimental studies
have been conducted for the application of ionic liquids for CO2 capture [818]. Bates et al. [19] were the rst group that applied amine
factor in cation of liquid and synthesized [NH2 p-bim][BF4 ] substance. Based upon their study, CO2 capture was feasible reversibly
in amine section without any reduction in stability of ionic liquid. Exposing ionic liquid to CO2 at atmospheric temperature and
pressure by three hours, it absorbed CO2 with approximate ratio of
0.5 mol CO2 /1 mol IL. Their ionic liquid remained stable even after
ve cycles of adsorption and desorption of gas without any dramatic drop in efciency. Sumon and Henni [20] studied the effect

M. Mirarab et al. / Fluid Phase Equilibria 371 (2014) 614

of structure, properties and molecular interactions of ionic liquids

on solubility and selectivity for CO2 capture using the thermodynamic method COSMO-RS. The relationships between the Henrys
law constants and the properties of ionic liquids were also investigated. Based on their work, the Henrys law constants of CO2
decreased with increase in molar volume, and decreased in polarity
of ILs. Moreover, both the solubility of CO2 and selectivity decreased
as temperature increased. Sistla et al. [21] examined a number
of ionic liquids (ILs) for CO2 capture and its separation from ue
gas mixture based on Hildebrand solubility parameter () that was
computed through molecular dynamic simulations using Material
Studio. The () values obtained by correlation matched well with
the () values obtained by direct molecular simulations, suggesting
that correlation equation was reliable to predict the () values of
several ILs. Hwang et al. [22] conducted a theoretical and experimental work to study absorption of carbon dioxide into organic
solvents such as DMA, NMP, DMSO, and DMF with the 2-hydroxy
ethylammonium lactate (HEAL). A mathematical model for the
CO2 absorption accompanied by its reaction with HEAL was developed based upon the lm theory with a nonlinear reaction rate
equation according to the zwitterions mechanism. The proposed
model could t the experimental data of the enhancement factor
as a result of the chemical absorption of CO2 in different solvents,
temperatures, and HEAL concentrations. many other investigations
have been done about CO2 capture using ionic liquids including:
CO2 capture by enzymatic bioconversion in a membrane contactor
with task specic ionic liquids [23], a supported liquid membrane
(SLM) based on a task-specic ionic liquid to achieve the selective and facilitated CO2 transport through the membrane [24], The
carbon dioxide separation performance of polymeric ionic liquid
composite membranes based on poly (diallyldimethylammonium)
bis (triuoromethylsulfonyl) imide, poly ([pyr11 ][NTf2 ]) [25], CO2
capture by a dual amino ionic liquid with amino-functionalized
imidazolium cation and taurine anion [26], performance of multiple CO2 binding organic liquids (CO2 BOLs) as solvent systems for
post combustion CO2 capture [27], the effects of zeolite imidazolate
framework-8 (ZIF-8) nanoparticles in miscible ionic liquid blend
systems for natural gas sweetening and post-combustion CO2 capture [28] and new criteria combined of efciency, greenness, and
economy for screening ionic liquids for CO2 capture [29].
Methanol, ethanol and acetone, are the most widely used physical solvents for CO2 capture from synthesis gas with high partial
pressures [3032]. Physical solvents do not interact powerfully
with the gas to be captured, which decreases the energy needed
to recover the agent. However, for any physical solvent to be profitably feasible, it should meet the following criteria: (i) low vapor
pressure to prevent solvent loss; (ii) high selectivity for acid gases
compared to CH4 , H2 , and CO; (iii) low viscosity; (iv) high chemical
and thermal stability; (v) benign impact on the environment; and
(vi) non-corrosive behavior [33,34].
Although ethanol as a polar but non-corrosive solvent is commonly utilized for CO2 capture in industry, its high volatility makes
the separation process and solvent recycle hardly viable. Therefore,
in this work, we add [EMIM][Tf2 N] into ethanol to make the mixture as separating agent for capturing CO2 , which combines the
advantages of organic solvents and ionic liquids because ethanol
possesses low viscosity and surface tension, promoting mass transfer, and the ionic liquid provides non-volatility, decreasing the
amount and loss of ethanol.
In a classical approach, exact determination of the CO2 capture
rate requires the resolution of thermodynamic equations of state,
which are time-consuming and not suitable for real-time applications and iterative solvers. Inspired by thermodynamic systems,
ANN approach has demonstrated to be powerful tools to model
non-linear systems [35]. This modeling technique creates a connection between input and output variables and keeps the underlying

complexity of the process. The ability to learn the behavior of data

generated by a system is the neural networks versatility and privilege [36]. Fast response, simplicity, and capacity to learn are the
advantages of ANN compared with classical methods.
So far, however, there has been little discussion about prediction
of CO2 solubility in ionic liquids using articial neural networks.
Pressure, temperature and wt.% of components are three main characteristics for calculation of CO2 capture rate. Due to the direct
effect of these parameters on CO2 capture, their evaluation can
be a crucial issue. Hence, this study aims to evaluate and validate
the accuracy of ANN technique to estimate CO2 capture rate in different concentrations of ethanol and 1-ethyl-3-methylimidazolium
bis (triuoromethylsulfonyl) imide [EMIM][Tf2 N] ionic liquid mixtures. First, the inuence of [EMIM][Tf2 N] concentration over the
range of 0100% by treatment with ethanol solvent on the CO2
capture rate is measured using a jacketed equilibrium cell. Next,
temperature, pressure, wt.% of ethanol and [EMIM][Tf2 N] ionic liquid were set as input variables, while CO2 capture rate was set as
output to ANN network. Then, the best network to predict output was selected based upon an optimization procedure using
genetic algorithm. Finally for the purpose of performance comparison, the predicted results by ANN approach are compared to
the most commonly used thermodynamic models (PengRobinson
and RedlichKowng equation of states). The goodness of t of the
ANN approach and the thermodynamic models is assessed using
statistical analysis.

2. Experimental
[EMIM][Tf2 N] ionic liquid, with mass fraction purity >97%,
thermal decomposition temperature of 440 C, viscosity of 28 cP
(at 25 C), melting point of 19 C and density of 1506 g/cm3 ,
was purchased from SigmaAldrich Co. CO2 was purchased from
Arian Gas Co. with mass fraction purity >99.9%. Ethanol was purchased from Fanavaran Arvand Co. with mass fraction purity 99.8%.
Fig. 1 shows chemical structure of [EMIM][Tf2 N] ionic liquid. The
apparatus used in the measurements of the solubility of CO2 in
ethanol[EMIM][Tf2 N] ionic liquid mixtures has been shown in
Fig. 2. The setup was built of a jacketed equilibrium cell made of
stainless steel with an inner diameter of 3 cm and internal height
of 6 cm, where temperature of the equilibrium cell was adjusted
using a water bath (JULABO F12-ED) with temperature stability
of 0.03 C. To precisely record absorption temperature, a temperature sensor (PASCO High Temperature Type-K Thermocouple)
with resolution of 0.01 C was placed in autoclave. Pressure in
equilibrium cell was measure by a pressure sensor typed G26.600
0100 bar. As shown in Fig. 2, a magnet and magnetic stirrer was
used to mix the solution inside the equilibrium cell. A CO2 gas
container made of stainless steel with a volume of approximately
450 cm3 was placed along CO2 capsule to equilibrium cell. Pressure
of CO2 gas container was also measured by pressure sensor typed
G26.600 0100 bar.
Calibration of equilibrium cell volume: As shown in Fig. 2, equilibrium cell setup was divided into three regions of A, B, and C,
where volume of each section was determined using a calibrated
bulb with given volume.
Calibration of pressure sensors: Pars Sehat Co. calibrated the pressure sensors on the basis of ISO/IEC 17025.
Operational procedure: rst, to reach a uniform temperature of
equilibrium cell wall, temperature of water bath was adjusted to
desired absorption temperature. Next, a given weight of ethanolionic liquid mixture owed into equilibrium cell, followed by
pumping the cell. Then, closing valve No. 8 vacuum condition
was created by discharging the air inside the cell using a vacuum
pump during 3 min. A certain amount of CO2 from gas container

M. Mirarab et al. / Fluid Phase Equilibria 371 (2014) 614

Fig. 1. Chemical structure of [EMIM][Tf2 N] ionic liquid.

introduced to the equilibrium cell. The mole injected to equilibrium

cell was calculated as follows [37],

nCO2 =

Vgc
RTgc

P

Zi

Pf
Zf

constant, recorded as equilibrium pressure. The remaining number

of moles in the gas phase was calculated by following equation,
g

(1)

where Vgc is volume of gas container, Tgc is ambient temperature, Pi and Pf are initial and nal pressure, respectively, Zi and
Zf are compressibility factor at initial and nal pressure (Pi and Pf ),
respectively. In this work, compressibility factors were calculated
by PengRobinson equation.
Injecting gas into equilibrium cell followed by mixing
ethanolionic liquid mixture, cell pressure data were continuously
recorded and related diagrams drawn on the monitor. Pressure
diagram of equilibrium cell remained constant after about 3 h,
indicating equilibrium state. Pressure in which diagram remained

nCO =
2

Vg PCO2

(2)

ZCO2 RT

where Vg is volume of the gas phase, T is the equilibrium temperature of the cell, and ZCO2 is compressibility factor of CO2 at the
equilibrium temperature (T) and pressure of CO2 (PCO2 ).
Finally, moles of CO2 capture into ionic liquid was determined
as follows,
g

n1CO = nCO2 nCO

2

(3)

Table 1 presents solubility of CO2 in ethanol and [EMIM][Tf2 N]

mixtures at different temperatures and pressures.

Fig. 2. Experimental setup used for measurement of CO2 capture rate.

M. Mirarab et al. / Fluid Phase Equilibria 371 (2014) 614

Table 1
Experimental data of CO2 solubility in ethanol + [EMIM][Tf2N] at different pressures and temperatures.
ANN

T (K)

P (MPa)

x (mole fraction)a

ANN

100 wt.% Ethanol + 0.00 wt.% [EMIM][Tf2N] ionic liquid

1.22
0.056
313.2
313.2
2.24
0.111
3.03
0.164
313.2
4.21
0.226
313.2
313.2
4.74
0.259
313.2
5.28
0.304
313.2
6.20
0.403

0.055
0.092
0.146
0.225
0.259
0.307
0.401

333.2
333.2
333.2
333.2
333.2
333.2
333.2

0.72
1.84
2.48
3.35
4.49
4.93
6.20

0.028
0.076
0.101
0.143
0.187
0.213
0.269

0.027
0.076
0.108
0.140
0.189
0.212
0.270

80 wt.% Ethanol + 20 wt.% [EMIM][Tf2N] ionic liquid

313.2
1.11
0.057
313.2
2.17
0.124
313.2
2.29
0.121
313.2
3.00
0.176
313.2
3.83
0.217
313.2
4.59
0.265
5.34
0.320
313.2
6.20
0.398
313.2

0.080
0.123
0.126
0.171
0.218
0.266
0.324
0.408

333.2
333.2
333.2
333.2
333.2
333.2
333.2
333.2
333.2

0.83
1.82
2.49
3.32
3.82
4.90
5.30
5.36
6.20

0.033
0.079
0.110
0.149
0.165
0.219
0.236
0.237
0.287

0.034
0.093
0.123
0.149
0.166
0.216
0.239
0.240
0.300

50 wt.% Ethanol + 50 wt.% [EMIM][Tf2N] ionic liquid

1.23
0.082
313.2
1.94
0.127
313.2
2.97
0.193
313.2
3.82
0.252
313.2
313.2
4.48
0.284
313.2
5.30
0.346
313.2
6.20
0.423

0.082
0.125
0.196
0.248
0.297
0.360
0.427

333.2
333.2
333.2
333.2
333.2
333.2

1.30
2.50
3.23
4.47
5.34
6.20

0.069
0.128
0.163
0.219
0.265
0.308

1.31
2.51
3.25
4.45
5.35
6.15

20 wt.% Ethanol + 80 wt.% [EMIM][Tf2N] ionic liquid

1.27
0.101
313.2
2.20
0.176
313.2
313.2
3.29
0.252
4.10
0.317
313.2
313.2
5.32
0.396
5.96
0.425
313.2
6.20
0.441
313.2

0.100
0.176
0.243
0.304
0.396
0.432
0.439

333.2
333.2
333.2
333.2
333.2
333.2
333.2

0.61
1.83
2.35
3.34
4.50
4.91
5.64

0.053
0.120
0.155
0.220
0.278
0.295
0.322

0.63
1.80
2.33
3.37
4.50
4.90
5.64

0.00 wt.% Ethanol + 100 wt.% [EMIM][Tf2N] ionic liquid

313.2
1.21
0.221
313.2
2.84
0.443
313.2
3.50
0.524
313.2
4.73
0.667
313.2
6.20
0.715

0.221
0.460
0.543
0.668
0.715

333.2
333.2
333.2
333.2
333.2
333.2

0.95
1.37
2.61
3.87
4.32
5.42

0.137
0.193
0.348
0.473
0.500
0.565

0.136
0.196
0.348
0.468
0.500
0.564

T (K)

P (MPa)

x (mole fraction)a

Estimated uncertainty of the measured mole fractions is 0.003.

Table 2
Values of Tc , Pc and for components.

3. Thermodynamic modeling
In this study, PengRobinson thermodynamic model is used to
correlate the solubility data of CO2 in ethanol, [EMIM][Tf2 N] ionic
liquid and their mixtures. The model is given as follows [38,39],
P=

RT
a

Vm b
Vm 2 + 2bVm b2

 2
0.45724(RTc )2
[1 + k(1 Tr )]
Pc

Tc [ C]

Pc [bar]

CO2
Ethanol
[EMIM][Tf2 N]

241.61
31.04
633.76

61.4
72.8
29.16

0.644
0.239
0.4223

(4)

where P is the pressure, T is the temperature, V is molar volume,

R is the gas constant (8.314 J mol1 K1 ), parameters a, b and are
dened as,
a=

Components

Compressibility factor is calculated as follows,(8)Z 3 + (1

B)Z 2 + (A 3B2 2B)Z + (AB + B2 + B3 ) = 0where
A=

n
n 


xi xj Aij

(9)

i=1 j=1

(5)

Aij = (Ai Aj )0.5 (1 kij )

T
Tr =
Tc

(6)

B=

k = 0.37464 + 1.54226 0.269922

(7)

n


xi Bi

(10)
(11)

i=i

where Tc and Pc are critical properties, Tr is reduced temperature

and is the acentric factor of the species. Table 2 shows Tc , Pc and
values for components used in this work.

Ai = 0.45724ai
Bi = 0.07780

Pri
Tr2i

Pri
Tri

(12)

(13)

10

M. Mirarab et al. / Fluid Phase Equilibria 371 (2014) 614

Fig. 3. ANN architecture developed for prediction of CO2 capture rate.

where Pri (Pri = P/Pci ) is reduced pressure and kij is the binary
interaction parameter. In this work, kij value for CO2 and ethanol
binary system was assumed to be zero. Binary interaction parameter between CO2 and [EMIM][Tf2 N] was obtained by tting the
experimental data in a wide range of temperature and pressure.

4. Neural networks
Neural networks are useful mathematical techniques inspired
by the study of the human brain. Neural networks are also computational structures consisting of large numbers of primitive process
units connected on a massively parallel scale. These units (neurons)
are relatively simple devices by themselves, and it is only through
the collective behavior of these nodes that neural networks can
realize their powerful ability to form generalized representations
of complex relationships and data structures.
Each neuron consists of a processing element with a set of input
connections, as well as a single output connection. The interaction
between the nodes is characterized by weight values (wi ) associated with the strength of the connections between the neurons.
The output of the neuron can be expressed as follows:

z=f

 i=N



wi xi

or z = f (wT x)

(14)

i=1

The function f (wT x) is referred to as the activation function,

where w is the weight vector of the neural, dened as:
w = [w1 , w2 , w3 , ..., wN ]

(15)

And x is the input vector, dened as:

Fig. 4. GA ow chart for optimization process.

x = [x1 , x2 , x3 , ..., xN ].

(16)

M. Mirarab et al. / Fluid Phase Equilibria 371 (2014) 614

11

0.004

Mean square error (MSE)

0.0035
0.003
0.0025
0.002
0.0015
0.001
0.0005
0

10 11 12 13 14 15 16 17 18 19 20

Number of neurons
Fig. 7. A schematic of variation of mean squared error (MSE) vs. epoch numbers for
training, validation, and test data sets of CO2 capture rate.

Fig. 5. Variations of MSE vs. number of neuron in the hidden layer.

5. Statistical analysis
6. Results and discussion
To check the accuracy of the ANN model and also compare
the predicted results with the actual data, the following statistical
parameters were used, Mean square error (MSE),
1
(yi xi )2
n
i=n

MSE =

(17)

i=1

where n is the number of data points, xi is value of actual data sets,

and yi is value of predicted data sets.
Average absolute deviation (AAD),(18)AAD% =

1
n

i=n

(x y )
i

xi

i=1

100
Least square (R2 ),

i=n
R2 =

i=1

(xi x )2

i=1
i=n

i=1

(xi yi )2

i=n
2

(xi x )

(19)

where x the arithmetic mean of actual data sets and y is the

arithmetic mean of predicted data sets.

To start developing the neural network, the experimental data

of CO2 capture rate must be collected and provided. In our work,
a total of 70 data sets obtained from experimental setup for solubility of CO2 in ethanol[EMIM][Tf2 N] ionic liquid mixtures were
utilized to assess the prediction performance of the ANN model.
Temperature, pressure, wt.% of ethanol and [EMIM][Tf2 N] ionic liquid were set as input variables to the ANN, while the CO2 capture
rate assigned as output variable. Fig. 3 provides architecture of ANN
model developed in this work.
Data selection plays a key role to successfully train data sets and
subsequently increase the ANN performance. Hence, in this study,
experimental data of CO2 capture rate were randomly divided into
three distinct groups: 70% of data sets (50 data) for training, 15%
(10 data) for validation and 15% (10 data) for test ANN model.
In this study, a multilayer feed-forward ANN with backpropagation algorithm was developed due to its capability of
representing non-linear functional mappings between inputs
and outputs. Moreover, Levenberg-Marquardt back-propagation
method, which is the fastest training function, was used for training neural network due to its better performance on function tting
and nonlinear regression problems. Log sigmoid transfer function

Fig. 6. ANN structure designed on the basis of GA for prediction of target.

12

M. Mirarab et al. / Fluid Phase Equilibria 371 (2014) 614

Fig. 8. Comparison of predicted results of the ANN and PengRobinson models and
experimental data of CO2 capture rate.

was used in the hidden layer and a linear transfer function was
employed for the output layer in the architecture of ANN model.
A crucial task to develop the multilayer feed-forward ANN is to
nd the number of neurons in the hidden layer. It highly affects performance of the network. In this work, genetic algorithm was used
to determine the optimum neuron numbers in the hidden layer.
Flow chart of GA used in this study has been presented in Fig. 4.
The stop criteria were on the basis of mean square error (MSE) as a
network performance function for the training data sets. The total
number of neurons in the hidden layer varied from 1 to 20 to select
the best ANN architecture with optimum neuron numbers on the
basis of genetic algorithm. Variation of MSE as a function of number of neurons in the hidden layer has been presented in Fig. 5. A
network with the lower values of MSE results the best ANN architecture. It can be observed from Fig. 5 that the optimum neuron
numbers in the hidden layer was found to be 15. Too many hidden
neurons may lead to overlearning of the neural network. On the
other hand, fewer hidden neurons will not give sufcient freedom
to the neural network to accurately learn the problem behavior.
Therefore, a MLP neural network with four variables (temperature, pressure, wt. % of ethanol and [EMIM][Tf2 N] ionic liquid) as
inputs and one variable (CO2 capture rate) as output, 15 neurons in
the hidden layer, log-sigmoid transfer function in the hidden layer
and linear transfer function in the output layer, designed for prediction of target value. The ANN structure developed in this work
to estimate solubility of CO2 in ethanol[EMIM][Tf2 N] ionic liquid
mixtures has been shown in Fig. 6.
Fig. 7 presents a schematic of MSE variations during training,
validation, and test data sets to determine the best neural network
conguration for estimation of CO2 capture capacity. It can be seen

Fig. 10. Mole fraction vs. equilibrium pressure for CO2 capture rate of
ethanol[EMIM][Tf2 N] ionic liquid mixture (5050 wt.%).

Fig. 11. Mole fraction vs. equilibrium pressure for CO2 capture rate of [EMIM][Tf2 N]
ionic liquid.

from Fig. 7 that the MSE error begins with a higher value at the
rst epoch then it decreases as epoch increases. This is because the
weights become update after each epoch.
Fig. 8 compares experimental data of CO2 capture rate with
predicted results of the developed ANN model for the training, validation and test data sets. In this work, a 45 straight line between
the predicted values versus experimental data points was drawn
on the cross plot to evaluate the performance of the developed
ANN model. As it is observed, the least deviation from the 45 line
Exp.

Exp.

ANN

ANN

0.8

CO2 capture rate [mole fraction]

0.7
0.6
T=313.2 C
P=6.2 MPa

0.5
0.4
0.3

T=333.2 C
P=6.2 MPa

0.2
0.1
0

Fig. 9. Mole fraction vs. equilibrium pressure for CO2 capture rate of ethanol.

0.1

0.2

0.3

0.4
0.5
0.6
Wt.% [EMIM][TF2N]

0.7

0.8

0.9

Fig. 12. The plot of mole fraction as a function of [EMIM][Tf2 N] concentration at

pressure of 6.2 MPa.

M. Mirarab et al. / Fluid Phase Equilibria 371 (2014) 614

13

Fig. 13. 3D diagram of CO2 capture rate as a function of pressure and [EMIM][Tf2 N] concentration for ANN model at temperature of 313.2 C.

occurred, which indicates low error of ANN model for prediction

of target value. It shows that predicted values of the ANN model
for training data sets coincide very well with experimental data of
CO2 capture rate giving AAD of 0.88 and R2 of 0.999, indicating that
the ANN model was successfully capable of learning the relationships among the input and output variables for training data sets.
In addition, statistical results obtained for validation and test data
sets, giving AAD of 8.67 and 4.09, R2 of 0.992 and 0.994, respectively,

proved that the predictions are as good as with the training data
sets.
As mentioned earlier, 70 data sets were used to evaluate the
predictive capability of the present ANN model and compare its performance against the PengRobinson (PR) thermodynamic model.
According to Fig. 8, it can be concluded that the developed ANN
model outperforms the PengRobinson model on the basis of statistical parameters.

Fig. 14. 3D diagram of CO2 capture rate as a function of pressure and [EMIM][Tf2 N] concentration for ANN model at temperature of 333.2 C.

14

M. Mirarab et al. / Fluid Phase Equilibria 371 (2014) 614

Figs. 911 present variations of mole fraction as a function

of equilibrium pressure at 0, 50 and 100 wt.% of [EMIM][Tf2 N]
ionic liquid. It is apparent from these gures that CO2 capture rate increases as [EMIM][Tf2 N] concentration increases.
As can be seen from gures, there is a satisfactory agreement between predicted and experimental data of CO2 capture
rate estimated by the ANN model for the whole pressure
range.
The variation of CO2 solubility with [EMIM][TF2 N] concentration at different temperatures and a xed pressure (6.2 MPa) for
both experimental data and ANN predictions has been shown in
Fig. 12. As it shown, there is a continuous increase in the solubility with increasing IL concentration up to 80 wt.% [EMIM][TF2 N]
for both temperatures, while it increases sharply up to 100 wt.%.
As it is observed from Fig. 14, at a constant wt.% [EMIM][TF2 N],
solubility of CO2 decreases as temperature increases from 313.2 to
333.2 C.
3D diagram of CO2 solubility as a function of IL concentration and pressure for different temperatures has been presented
in Figs. 13 and 14. According to the gures, the goodness of ANN
approach to predict solubility of CO2 in ethanolIL mixtures is
acceptable for the whole range of pressure and ionic liquid concentration.
Therefore, the current study found that ANN technique on the
basis of genetic algorithm is an effective way to predict solubility of CO2 in ethanolEMIM][Tf2 N] ionic liquid mixtures. This is
possible because of the high capability of the ANN technique in
driving complex and non-linear relationships.
7. Conclusion
This study presents a new articial neural network (ANN) model
for the prediction of solubility of CO2 in ethanol[EMIM][Tf2 N] ionic
liquid mixtures. Experimental values of CO2 capture rate were measured at 0, 20, 50 and 80 and 100 wt.% mixture of [EMIM][Tf2 N]
ionic liquid, temperatures of 313.2 and 333.2 C, and pressure range
of 07 MPa. A three layer feed-forward ANN with 15 neurons in
the hidden layer, log-sigmoid transfer function in the hidden layer,
and linear transfer function in the output later was developed on
the basis of optimization procedure performed by genetic algorithm. Very little difference between the prediction results of the
developed ANN and experimental data of the CO2 capture rate
conrmed great performance of ANN technique. Moreover, statistical analysis proved that ANN technique with the high least
square close to one and low mean average absolute deviation
(AAD) near zero had the highest capability of predicting output
variables.

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