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Tianjin Key Laboratory of Catalysis Science and Technology, School of Chemical Engineering, Tianjin University, Tianjin 300072, China
Department of Chemical Engineering, Arizona State University, Tempe, AZ 85287-6006, USA
article info
abstract
Article history:
membrane reactor (DMR) is sequentially simulated with ASPEN PLUS. The DMR is divided
into multi-sub-reactors, and the Gibbs free energy minimization sub-model in ASPEN PLUS
8 April 2010
is employed to simulate the oxidative steam reforming of ethanol process in the sub-
reactors. A FORTRAN sub-routine is integrated into ASPEN PLUS to simulate the oxygen
Keywords:
temperature and steam-to-ethanol (H2O/EtOH) ratio, under which hydrogen and carbon
Sequential simulation
2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
1.
Introduction
DH298
347:4 kJ=mol
CH3 CH2 OH l 1:5O2 g42CO2 g 3H2 g;
(1)
DH298
554:0 kJ=mol
(2)
(3)
SR generates a high H2/CO ratio product but has the disadvantage of high endothermicity and catalyst deactivation due
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Nomenclature
aik
Cep
Ci
Da
d1
d2
b
fi
fi0
F
G
Gi
0
Gi
nG
DG0fi
DH298
JO2
L
m
ni
P
P1
P2
S
T
yi
Greek letters
Lagrange multiplier
lk
bi
Fugacity coefficient of species i in the gas mixture
4
2.
2.1.
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N
X
ni Gi
(4)
i1
If Gi is substituted by
b
f
Gi G0i RTln 0i
fi
(5)
then
nG
X
b
X
f
ni G0i RT
ni ln 0i
fi
(6)
(7)
2.2.
dFO2
Air
O2
dl
l=0
l=L
O2
CH3CH2OH+H2O
2.3.
bi
DG0fi RTln P RTln yi RTln 4
Air
pLCi Da
P1
ln
2Slnd1 =d2
P2
dFO2
(8)
pLCi Da
P1
dl
ln
2lnd1 =d2
P2
(9)
Table 1 e The ambipolar diffusion coefficients (Da) at different temperatures (973e1123 K) [26].
T(K)
Da (cm2 s1)
973
1.62 106
1023
2.24 106
1073
2.98 106
1098
3.47 106
1123
4.12 106
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2.60
2.55
(moles/mole)
2.65
2.50
2.45
2.40
2.35
2.30
2.25
10
20
30
40
50
60
m = number of sub-reactors
Fig. 3 e Influence of the number of sub-reactors on the
predicted yield of H2 per mole of ethanol, P [ 0.1 MPa, T
[ 973 K, H2O/EtOH [ 0.5, Ln(P2/P1) [ 2, L [ 30 cm.
3.
3.1.
Number of sub-reactors
3.2.
Influence of temperature
3.5
3.0
2.5
2.0
Temperature
973 K
1023 K
1073 K
1098 K
1123 K
1.5
1.0
0.5
1.5
Temperature
973 K
1023 K
1073 K
1098 K
1123 K
1.2
0.9
0.6
0.3
0.0
0
10
15
20
25
30
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1.8
1.5
1.2
Temperature
973 K
1023 K
1073 K
1098 K
1123 K
0.9
0.6
0.3
Temperature
973 K
1023 K
1073 K
1098 K
1123 K
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0
10
15
20
25
30
(10)
DH298
890:29 kJ=mol
C2 H4 g 3O2 g42CO2 g 2H2 O l;
(12)
DH298
1411:14 kJ=mol
2CH3 CHO g 5O2 g44CO2 g 4H2 O l;
2384:63 kJ=mol
(11)
(13)
DH298
(14)
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 6 6 9 1 e6 6 9 8
(15)
DH298 41:2 kJ=mol
(16)
DH298
341:73 kJ=mol
CO g H2 O g4H2 g CO2 g;
DH298
(17)
3.3.
C2 H5 OH l H2 O l44H2 g 2CO g;
C2 H5 OH l4H2 g CH4 g CO g;
H2O/EtOH
0
0.5
1
2
5
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b
1.4
1.2
1.0
0.8
0.6
H2O/EtOH
0
0.5
1
2
5
0.4
0.2
0.0
0
10
15
20
25
30
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2.0
a
1.5
1.0
H2O/EtOH
0
0.5
1
2
5
0.5
0.0
1.0
0.8
H2O/EtOH
0
0.5
1
2
5
0.6
0.4
0.2
0.0
0
10
15
20
25
30
4.
moles of the excess ethanol, which can react with the
permeated oxygen by POX reaction (2) and affects the change
of hydrogen yield with the membrane tube length. In addition,
for the fixed length of DMR, the hydrogen yield increases with
the increase of H2O/EtOH ratio due to its favorable effect on
the SR reaction (1), as depicted in Fig. 6(a).
It can be found from Fig. 6(b) that carbon dioxide yield
increases both monotonically with the increase of the H2O/
EtOH ratio and the length of the reactor. According to the SR
reaction (1), the increase of H2O/EtOH ratio favors the carbon
dioxide yield by shifts reaction (1) to the right. Furthermore,
the oxygen feeding amount, which increases with the length
of the membrane tube, favors reaction (2) to produce more
carbon dioxide. Reactions (11)e(14) can also occur in the
excess presence of oxygen, which produces more carbon
dioxide. As a result, carbon dioxide yield increases with the
increase of the H2O/EtOH ratio and the length of the DMR, as
shown in Fig. 6(b).
Fig. 7(a) provides the trend of carbon monoxide yield
changes with the H2O/EtOH ratio and the length of membrane
tube. It can be seen that carbon monoxide yield at a lower H2O/
EtOH ratio is higher than that at a higher H2O/EtOH ratio for
the fixed length of the DMR. Moreover, carbon monoxide yield
shows the volcano shaped curves and reaches the maxima for
the H2O/EtOH ratios of 0, 0.5 and 1, respectively. For example,
the maximal yield of carbon monoxide is 1.824 with 10 cm at
H2O/EtOH 0, 1.821 with 6 cm at H2O/EtOH 0.5 and 1.815
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Conclusion
Acknowledgements
This work has been supported by the Natural Science Foundation of China under contract number 20425619 and
20736007. The work has been also supported by the Program of
Introducing Talents to the University Disciplines under file
number B06006, and the Program for Changjiang Scholars and
Innovative Research Teams in Universities under file number
IRT 0641.
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references