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abstract
Article history:
An equilibrium model of steam methane reforming coupled with in-situ membrane sepa-
ration for hydrogen production was developed. The model employed Sieverts Law for
membrane separation and minimum Gibbs energy model for reactions. The reforming and
25 August 2010
separation processes were coupled by the mass balance. The model assumed a continu-
ously stirred tank reactor for the fluidized bed hydrodynamics. The model predictions for
a typical case were compared with those from the model of Ye et al. [15] which assumed
a plug flow for bed hydrodynamics. The model predictions show satisfactory agreement
Keywords:
with experimental data in the literatures. The influences of reactor pressure, temperature,
Hydrogen
steam to carbon ratio, and permeate side hydrogen partial pressure on solid carbon, NHx
Fluidized bed
Reforming
2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
Membrane
Modeling
1.
Introduction
effectiveness, low heat transfer rates, large temperature gradients within the bed and thermodynamic equilibrium constraint
on chemical reaction [3e6]. To overcome these problems,
Fluidized Bed Membrane Reactors (FBMR) have been proposed
and developed by several research groups [1,4e7].
The principal reactions involved in catalytic steam
methane reforming are [8]:Steam methane reforming (SMR):
CH4 H2O CO 3H2,
(R1)
(R2)
(R3)
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 ) 1 1 7 9 8 e1 1 8 0 9
proceeds. Equilibrium conversions of both reforming reactions benefit from high temperatures and low pressures,
whereas the wateregas shift reaction (R3), being exothermic
and having no change in the number of molars, benefits
thermodynamically from lower temperatures and is independent of pressure.
To sustain the above endothermic reactions (R1) and (R2),
oxygen or air can be introduced into the system with the
following oxidation reactions taking place [9]:
11799
C H2O CO H2,
C 0.5O2 CO,
(R10)
C CO2 2CO,
(R11)
N2 3H2 2NH3
(R12)
N2 2H2 N2H4
(R13)
N2 2O2 2NO2
DHo298 68 kJ/mol
(R14)
N2 O2 2NO
(R15)
N2 2O2 N2O4
DHo298 10 kJ/mol
(R16)
N2O2 2N2O
(R17)
(R4)
(R5)
(R6)
(R7)
(R8)
(R9)
2.
Model development
2.1.
Primary assumptions
A fluidized bed membrane reactor for pure hydrogen production by steam methane reforming is shown schematically in
Fig. 1. Preheated high-temperature (usually 500e800 C) and
high-pressure (usually 1e3 MPa) natural gas and steam are
premixed and fed into the reactor. The reactor contains Nickel
based catalyst and palladium (or its alloy) membrane modules
11800
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 ) 1 1 7 9 8 e1 1 8 0 9
EP
M
RT
QH h k Cep PRH PM
MH e
(1)
2.2.
9. Hydrogen permeation through the membrane follows Sieverts Law [16], i.e.:
Governing equations
Membranes module
vGt
0;
vni
Sweep gas
Air
i 1e15
(2)
ni aik Ak ;
k 1; 2; 3
(3)
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 ) 1 1 7 9 8 e1 1 8 0 9
ni ai;H 2QH AH
(4)
i1
14
X
ni Gi nC Gc
(5)
i1
(6)
where
yi
ni
14
X
(7)
ni
i1
For solid carbon, its Gibbs free energy is related to the system
pressure by
GC VC P P0
(8)
2.3.
11801
2.4.
YH2
nCO nCO2
FCH4
QH
FCH4
(9)
(10)
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 ) 1 1 7 9 8 e1 1 8 0 9
1.2
4.0
1.1
3.5
1.0
3.0
0.9
2.5
0.8
2.0
0.7
1.5
0.6
1.0
H2 yield PFR
0.5
0.4
CH4 conversion ( - )
11802
0.5
20
40
60
80
100
120
140
160
0.0
180
3.
Comparison of model predictions with
experimental data
The FBMR process has been intensively studied by researchers
in recent years. Some experimental data are available from
the literature for model validations. Experimental results by
Adris et al. [12], Roy [39], and Mahecha-Botero et al. [5] are used
to validate the current model performances.
Adris et al. [12] reported experimental results from a pilotscale fluidized bed membrane reactor for reaction temperatures from 447 to 640 C and steam to carbon molar ratio (SC)
of 2.4. The reactor has a diameter of 97 mm and length of
1.143 m. Twelve thin-walled (nominal wall thickness of
Table 1 e Comparison of equilibrium model predictions with experimental data of Adris et al. [12]. (FCH4 [ 74.2 mol/h,
SC [ 2.4, OC [ 0, Fs [ 80 mol/h, Cep [ 0.4 Km, P [ 0.98 MPa, PM [ 0.4 MPa, h [ 0.39).
Bed temperature ( C)
447
494
542
594
640
Experimental data
CSTR prediction
PFR prediction
0.12
0.11
0.11
0.17
0.16
0.16
0.24
0.22
0.22
0.33
0.32
0.34
0.43
0.41
0.42
H2 production (mol/h)
Experimental data
CSTR prediction
PFR prediction
1.70
1.73
1.77
2.50
2.51
2.55
3.57
3.50
3.61
4.81
4.77
4.95
6.23
6.23
6.30
Experimental data
CSTR prediction
PFR prediction
Experimental data
CSTR prediction
PFR prediction
Experimental data
CSTR prediction
PFR prediction
Experimental data
CSTR prediction
PFR prediction
61.7
62.1
62.7
0.10
0.19
0.30
9.5
7.8
7.6
28.7
29.4
29.4
49.6
51.9
52.3
0.40
0.52
0.50
11.5
9.6
9.5
38.5
38.0
37.6
37.6
41.8
42.3
1.20
1.25
1.24
13.0
11.2
10.8
48.2
45.8
45.9
27.3
31.8
32.1
3.20
2.73
2.60
13.5
12.1
11.7
56.0
53.4
55.3
19.5
23.9
24.0
5.60
4.80
4.70
13.3
12.0
11.7
61.6
59.3
59.5
CO
CO2
H2
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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 ) 1 1 7 9 8 e1 1 8 0 9
Table 2 e Comparison of model predictions with experimental data of Roy [39]. (FH2 O [ 138.33 mol/h, FS [ 45 mol/h,
Cep [ 8.16 Km, P [ 0.68 MPa, PM [ 0.14 MPa, k [ 7.85 3 10L9 mol/(m.s Pa0.72), Ep [ 11.5 KJ/mol, M [ 0.72).
Bed P (MPa)
0.68
0.68
0.68
0.68
0.68
0.68
0.68
0.68
0.99
0.99
0.99
0.68
0.68
0.68
0.68
0.68
0.78
0.88
0.99
Bed T ( C)
650
650
650
650
650
650
650
650
600
625
650
576
600
625
649
600
600
600
600
SC
4.1
4.1
4.1
4.1
4.1
4.1
3.1
2.4
3.1
3.1
3.1
4.1
4.1
4.1
4.1
4.1
4.1
4.1
4.1
OC
0.44
0.45
0.5
0.56
0.62
0.35
0.35
0.35
0.40
0.40
0.40
0.45
0.45
0.45
0.45
0.45
0.45
0.45
0.45
Experimental
Predicted
h 0.3
Predicted
h 0.1
Experimental
Predicted
h 0.3
Predicted
h 0.1
0.76
0.77
0.79
0.81
0.82
0.74
0.66
0.59
0.52
0.56
0.6
0.62
0.67
0.73
0.77
0.68
0.67
0.63
0.62
0.92
0.93
0.94
0.95
0.96
0.91
0.85
0.77
0.74
0.80
0.86
0.78
0.84
0.89
0.93
0.84
0.84
0.83
0.85
0.87
0.86
0.88
0.90
0.92
0.85
0.77
0.70
0.63
0.69
0.75
0.70
0.76
0.82
0.87
0.76
0.86
0.85
0.85
18.6
18.6
18.5
17.6
17.1
19.1
20.5
21.4
19.0
21.0
23.2
14.6
15.9
17.5
18.6
14.8
16.0
16.3
17
43.0
42.6
41.4
39.8
38.1
45.1
50.9
54.8
40.2
45.2
49.9
32.3
36.1
39.7
42.5
36.1
39.2
42.1
44.9
21.7
21.6
21.2
20.6
19.9
22.5
24.1
25.1
23.5
26.6
29.7
15.8
17.8
19.8
21.5
17.8
23.5
25.2
27.06
4.
Effects of operation conditions on carbon
formation
Coke formation is a serious operational problem in conventional steam reforming. The presence of the solid carbon can
4.1.
Influence of steam to carbon ratio and membrane
permeation capacity
Fig. 3 shows the influence of steam to carbon ratio and
membrane permeation capacity on carbon formation under
the operation conditions of FCH4 1000 mol/h, FS 0, OC 0.2,
P 2.0 MPa, T 650 C, PM 0.1 MPa. It can be seen that carbon
formation is suppressed by higher steam to carbon ratio. The
in-situ removal of hydrogen through membranes enhanced
the carbon formation. The coking boundary moves toward
higher SC values as the reactor Cep is raised. For example, for
the operation conditions investigated, when Cep increased
from 1.0 Km to 10.0 Km, the coking boundary increased from
an SC value of 0.8e1.0. With higher membrane permeation
capacities per unit feed of methane and steam, more
hydrogen is removed from the reactor, and reaction (R8) is
pushed forward to produce more solid carbon.
4.2.
Influence of temperature and membrane permeation
capacity
Fig. 4 shows the influence of temperature and membrane
permeation capacity on carbon formation for the operation
conditions of FCH4 1000 mol/h, FS 0, OC 0.2, P 2.0 MPa,
T 650 C, PM 0.1 MPa. The range of the temperature
investigated is between 450 and 850 C. It should be pointed
out that when palladium alloy membrane is installed, the
reactor temperature is usually maintained below 700 C for
the protection of membrane. It can be seen that temperature
is a strong factor for the formation of solid carbon. The
11804
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 ) 1 1 7 9 8 e1 1 8 0 9
21.3
47.7
54.3
40.6
45.3
29.4
72.2
74.2
50.9
37.5
47.6
N/A
N/A
N/A
13.8
39.3
42.0
41.5
41.1
N/A
49.6
48.2
36.6
32.6
39.7
Prediction
Expt
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0 Km
Cep=10.0 Km
0.35
0.30
0.25
0.20
0.15
0.10
Prediction
53.7
51.0
31.4
49.2
43.5
39.2
35.6
30.8
26.8
19.9
19.9
14.2
11.2
15.5
Expt
43.5
33.3
22.2
40.1
41.1
33.3
29.4
20.6
22.0
17.5
16.2
11.9
8.7
8.7
0.00
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
4.3.
Influence of reactor pressure and membrane
permeation capacity
Reactions (R8eR11) are related to solid carbon formation in the
reforming process. In these reactions, reaction (R8) should be
0.30
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0 Km
Cep=10.0 Km
0.25
a In bed gas sampling not performed. The methane conversion was calculated from reactor off gas composition analysis.
0.30
0.27
0.45
0.39
0.50
0.51
0.66
0.69
0.58
0.78
0.78
0.92
0.96
0.95
0.29
0.22
0.40
0.25a
0.66
0.66
0.43a
0.67
0.46a
0.73
0.69
0.81
0.76a
0.73
1
2
3
4
5
6
7
8
9
10
11
12
13
14
0
0
0
0.09
0.09
0.09
0.09
0.09
0.18
0.18
0.18
0.18
0.18
0.18
0
0
0.35
0
0
0
0
0
0.35
0.35
0.35
0.35
0.35
0
40
40
40
40
40
40
20
20
40
40
40
20
13.3
13.3
0.75
1.00
1.00
0.75
0.75
1.00
0.75
1.00
1.00
1.00
1.00
1.00
1.00
1.00
N/A
N/A
N/A
0.10
0.03
0.03
0.03
0.03
0.10
0.03
0.03
0.03
0.03
0.03
Prediction
Expt
Membrane
area (m2)
OC
Natural gas
feed
(mol/h)
Reactor
pressure
(MPa)
Permeate
pressure
(MPa)
0.05
Expt
Table 3 e Comparison of model predictions with experimental data of Mahecha-Botero et al. [5]. (Fs [ 0, SC [ 3.0, Cep [ 0.4 Km, P [ 0.98 MPa, k [ 1.37 3 10L3 mol/
(m$h$Pa0.5), Ep [ 20.5 KJ/mol, M [ 0.5, h [ 0.6).
0.40
0.20
0.15
0.10
0.05
0.00
450
500
550
600
650
700
750
800
850
Temperature ( C )
11805
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 ) 1 1 7 9 8 e1 1 8 0 9
250
0.15
0.10
200
0.0008
150
0.0006
100
50
0
400
0.5
1.0
1.5
2.0
2.5
3.0
500
550
600
650
700
750
800
0.0000
850
0.30
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0 Km
Cep=10.0 Km
Cep=20.0 Km
0.25
0.20
Temperature ( C )
3.5
4.4.
Influence of oxygen to carbon ratio and membrane
permeation capacity
Obviously, oxygen input can reduce the amount of solid
carbon formation through reaction (R10). Again, the in-situ
removal of product hydrogen could enhance the carbon
formation. Fig. 6 shows the influence of OC and membrane
permeation capacity on carbon formation at the operation
condition of FCH4 1000 mol/h, FS 0, SC 0.8, T 650 C,
P 2.0 MPa, PM 0.1 MPa. It can be seen that with increasing
the oxygen to carbon ratio, the mole of carbon formed is
decreasing for all Cep values. The coking boundary moves
toward higher OC ratio as the reactor Cep is raised. For the
operation conditions investigated, when Cep increased from
180
160
0.15
0.10
0.05
0.1
0.2
0.3
0.4
0.5
450
0.0002
Pressure (MPa)
0.00
0.0
0.0004
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0 Km
Cep=10.0 Km
0.05
0.00
0.0
0.0010
0.20
0.0012
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0 Km
Cep=10.0 Km
140
0.0009
0.0008
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0 Km
Cep=10.0 Km
0.0007
0.0006
120
0.0005
0.0004
100
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0 Km
Cep=10.0 Km
80
60
40
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0.0003
0.0002
0.25
300
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0 Km
Cep=10.0 Km
Cep=20.0 Km
0.30
0.0001
0.0000
3.5
Pressure (MPa)
11806
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 ) 1 1 7 9 8 e1 1 8 0 9
0.0010
120
0.0006
110
0.0005
0.0004
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0 Km
Cep=10.0 Km
90
0
120
0.0008
0.0007
100
0.0011
0.0009
130
0.0012
130
0.0010
0.0009
110
0.0008
100
0.0007
0.0006
90
0.0003
70
4
0.0002
0.0
0.1
5.
Effects of operation conditions on NH3
formation
0.26
0.20
0.18
0.16
0.14
0.12
0.20
0.16
0.12
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0 Km
Cep=10.0 Km
0.08
0.04
0.10
1.0
1.5
2.0
2.5
3.0
3.5
4.0
0.0002
0.24
0.22
0.5
0.5
0.28
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0Km
Cep=10.0 Km
0.24
0.08
0.0
0.4
0.0003
0.28
0.3
0.0004
5.1.
Influence of temperature and membrane permeation
capacity
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0 Km
Cep=10.0 Km
0.2
0.0005
0.30
Cep=0.4 Km
Cep= 1.0 Km
Cep= 5.0 Km
Cep=10.0 Km
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0 Km
Cep=10.0 Km
80
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0 Km
Cep=10.0 Km
140
4.5
5.0
5.5
0.0
0.1
0.2
0.3
Cep=0.4 Km
Cep=1.0 Km
Cep=5.0 Km
Cep=10.0 Km
0.4
0.5
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 ) 1 1 7 9 8 e1 1 8 0 9
11807
with increasing the oxygen to carbon ratio, the N2 concentration increases and H2 concentration decreases. The overall
tendency of NH3 formation by the influence of oxygen to
carbon ratio then behaves as illustrated in Fig. 11.
5.2.
Influence of pressure and membrane permeation
capacity
Fig. 8 shows the influence of pressure and membrane
permeation capacity on the NH3 formation. It can be seen that
the NH3 concentration increases with increasing the operation pressure. This can be explained by LeChateliers principle
that NH3 formation is favored by high pressure as the product
moles are less than the reactants in reaction (R12). Again
membrane helps to reduce the formation of NH3.
5.3.
5.4.
6.
Conclusions
11808
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 ) 1 1 7 9 8 e1 1 8 0 9
Acknowledgement
Financial support from the National High Technology Research
and Development Program of China (2009AA05Z102) and the
Fundamental Research Funds for the Central Universities
(project # 2009ZZ0013) are gratefully acknowledged.
Notation
aik
Ak
Cep
EP
FCH4
Fs
Gt
Goi
Gi
GC
QH
k
m
ni
M
OC
P
P0
PRH
PMH
PM
R
SC
T
VC
XCH4
YH2
yi
h
references
[1] Xie D, Grace JR, Lim CJ. Experimental study of gas and solid
circulation in an internally circulating fluidized bed
membrane reactor cold model. Chem Eng Sci 2009;64:
2599e606.
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 ) 1 1 7 9 8 e1 1 8 0 9
11809