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Simulation of Methanol Synthesis From Synthesis Gas in Fixed Bed
Simulation of Methanol Synthesis From Synthesis Gas in Fixed Bed
ISSN 2229-5518
1 INTRODUCTION
2 METHANOL SYNTHESES
Methanol is very commonly used as a feedstock in the
chemical industries. It is also used as a fuel and as a solvent. It
is produced commercially from synthesis gas (CO/CO 2/H2)
under high pressure and temperature. The used catalyst is
mainly the copper/zinc based oxide catalyst. Used oxide additives include, for example, Al2O3, Cr2O3 and ZrO2 [4,5] . Methanol is used when producing for example formaldehyde,
acetic acid, and methyl tertiary butyl ether (MTBE) [1]. The
use of CO2 as a feedstock in methanol synthesis has gained a
lot of attention and nowadays is widely studied. The research
has focused mainly on the search for the most suitable catalyst, as the performance of the process is highly dependent on
used catalyst. In methanol synthesis, either CO or CO2 or both
hydrogenate to methanol. The reactions together with the water-gas shift reaction are[6,7].
CO + 2H2 CH3OH
H298= - 90.55 kJ.mol-1
CO2 + 3H2 CH3OH + H2O H298= - 49.43 kJ.mol-1
CO2 + H2 CO + H2O
H298= 41.12 kJ.mol-1
(1)
(2)
(3)
rCH 3OH
PCH 3OH PH 2 O
k1 PCO 2 PH 2
3
1 K eq P
2
CO 2 PH 2
k 3 PH 2 O
k 4 PH 2 k 5 PH 2 O
1
Parvaneh Nakhostin Panahi is a PhD student of Applied Chemistry in UniPH 2
PH 2 O PCO
k 2 PCO 2 1 K 3eq
Iran,
P
CO 2 PH 2
k 3 PH 2 O
k 4 PH 2 k 5 PH 2 O
Dariush salari is a prof of Applied Chemistry in University of Tabriz, Tabriz,
1 P
H2
Iran,
Ali Farzi is a prof of Chemical Engineering in University of Tabriz, Tabriz,
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(4)
(5)
ISSN 2229-5518
All the constants (kj) in the above equation follow the general
Arrhenius equation and equilibrium constants were obtained
from analyses that are listed in table 1 [8].
kj Aj exp Bj
RT
(6)
TABLE 1
Frequency Factors of Kinetic Equation[8]
k1
A
1.07
B
36696
A
3453.38
k3
B
A
0.499
k4
B
17197
A
6.62*10 -11
k5
B
124119
A
1.22*1010
k2
B
-94765
K2 eq
10 3066/ T-10.592
K3 eq
10 -2073/ T + 2.029
dFi
dl
c ri A
(7)
dT
dl
A ri
Fi C
i
(8)
Pi
Where Hi is heat of reaction, c density of catalyst, A crosssectional area of reactor, r i the rate of reaction i, Fij the molar
flow rate of component i and Cpi is molar heat capacity of i.
Relationship of partial pressure and molar flow of components
the assuming ideal gas is given by equation 9.
Pi P
Fi
Ft
Ft i Fi
(9)
CP
(10)
H H
298
C P dT
(11)
298
CP CP products CP reactonts
(12)
TABLE 3
Frequency Factors of Enthalpy Equaction
Chemical
A
103 B
106 C
10 -5 D
species
CH3 OH
2.211
12.216
-3.450
---
H2 O
H2
CO2
CO
3.47
3.249
5.457
3.376
1.45
0.472
1.045
0.557
---------
0.121
0.081
-1.157
-0.031
ISSN 2229-5518
FCO
2
CO 2
X H 2 FH 2 FH 2
Yield CH 3OH H 2
Yield CH 3OH C
(14)
FH 2
FCH 3OH
FCH 3OH
FH 2
CO
100
FCO
2
(15)
100
(16)
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50
45
(a)
2500
X: 10
Y: 49.15
(b)
40
X: 10
Y: 2674
35
Conversion of CO2
3000
2000
1500
30
25
20
15
1000
10
500
5
0
5
6
Length(m)
10
5
6
Length(m)
10
16
7
(c)
14
(d)
X: 10
Y: 15.17
X: 10
Y: 7.052
6
Yield CH3OH(H2)
Conversion of H2
12
10
8
5
4
3
6
2
4
1
2
0
5
6
Length(m)
5
6
Length(m)
10
10
530
(f)
80
525
(e)
70
X: 10
Y: 73.17
X: 10
Y: 528.2
520
Temperature(K)
Yield CH3OH(C)
60
50
40
515
510
30
505
20
500
10
0
495
0
5
6
Length(m)
5
6
Length(m)
10
10
Fig. 1. a) Molar flow rate of methanol, b) H2 conversion, c) CO2 conversion, d) Yield CH3OH(H2), e) Yield CH3OH(C) and f) temperature profiles
along the length of the reactor
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1100
2.00E-05
1.80E-05
1.60E-05
1.40E-05
1.20E-05
1.00E-05
8.00E-06
6.00E-06
4.00E-06
2.00E-06
0.00E+00
1050
1000
MSE
(a)
950
900
850
800
2
0
6
H2/CO2
10
12
10.5
(b)
In the second step, an ANN with four neurons in hidden layer
was considered for the variation of training algorithms. Fig.4
shows the performance (MSE for training sets) of designed
network with different training algorithms. It was found that a
network with the Levenberg-Marquardt backpropagation algorithm has MSE less than other trained networks. The MSE
was 3.48e-10 for training set and 4.63e-8 for test set.
Yield CH3OH(H2)
10
9.5
8.5
7.5
6
H2/CO2
10
3.50E-04
12
3.00E-04
MSE
2.50E-04
2.00E-04
different number of neurons in the hidden layer and then, the
best design of the ANN was considered for the variation of
training algorithms such as gradient descent backpropagation
(gd), gradient descent with adaptive learning rule backpropagation (gda), gradient descent with momentum backpropagation (gdm) and Levenberg-Marquardt backpropagation (lm).
The mean squared error (MSE) for test set was used as the error function.
In first step, many networks with different neurons in hidden
layer were trained with Levenberg-Marquardt backpropagation algorithm. Fig.3 shows the performance (MSE for training
sets) of designed network with different neurons in hidden
layer. It was found that the network with four neurons in hidden layer has MSE less than other trained networks. The MSE
was 3.48e-10 for training set and 4.63e-8 for test set.
1.50E-04
1.00E-04
5.00E-05
0.00E+00
gd
gda
gdm
lm
Training Algorithm
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4 Conclusions
1100
1050
1000
950
900
850
800
10
6
H2/CO2
10
12
y=x
train data
test data
Predicted Values
7
6
5
4
3
2
1
0
4
5
6
Measured Values
10
References
[1]
10.5
Mathematical model results
ANN model results
Yield CH3OH(H2)
10
[2]
9.5
[3]
9
8.5
[4]
8
7.5
6
H2/CO2
10
12
[5]
[8]
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[9]
[10]
[11]
[12]
[13]
[14]
[15]
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