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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].
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
nCO2 =
Vgc
RTgc
P
Zi
Pf
Zf
(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
(3)
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
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
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
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
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
0.221
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
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)
Components
n
n
xi xj Aij
(9)
i=1 j=1
(5)
T
Tr =
Tc
(6)
B=
(7)
n
xi Bi
(10)
(11)
i=i
Ai = 0.45724ai
Bi = 0.07780
Pri
Tr2i
Pri
Tri
(12)
(13)
10
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
(15)
x = [x1 , x2 , x3 , ..., xN ].
(16)
11
0.004
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.
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
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)
12
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
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
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.
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
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