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Available at www.sciencedirect.com

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

Sequential simulation of dense oxygen permeation

membrane reactor for hydrogen production from oxidative
steam reforming of ethanol with ASPEN PLUS
Yun Jin a, Zebao Rui a, Ye Tian a, Yuesheng Lin b, Yongdan Li a,*
a
b

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:

Hydrogen production via oxidative steam reforming of ethanol in a dense tubular

Received 25 January 2010

membrane reactor (DMR) is sequentially simulated with ASPEN PLUS. The DMR is divided

Received in revised form

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-

Accepted 10 April 2010

reactors. A FORTRAN sub-routine is integrated into ASPEN PLUS to simulate the oxygen

Available online 18 May 2010

permeation through membranes in the sub-separators. The simulation result indicates

that there is an optimal length of the tubular membrane reactor at the operating

Keywords:

temperature and steam-to-ethanol (H2O/EtOH) ratio, under which hydrogen and carbon

Dense tubular membrane reactor

monoxide formation reach their maxima.

Sequential simulation

2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

Oxidative steam reforming of ethanol

Oxygen permeation

1.

Introduction

The potential benefits of a hydrogen economy coming from

renewable energy sources are creating a large consensus [1,2].
Hydrogen production from fossil fuels has been investigated
for many years. Among various liquid fuels, either for direct
feeding or indirect via conversion to hydrogen rich mixtures,
methanol has been thoroughly studied [3e6], since methanol is
available as an abundant feedstock already largely distributed.
However, the main drawback of methanol, besides its relatively high toxicity, is that its production is essentially based on
reforming of non-renewable fossil fuels (mostly natural gas).
Ethanol which can be produced in large quantities from
renewable bio-resources appears as an attractive alternative to
methanol since it is much less toxic, almost CO2 neutral and
now more and more available as industrial feedstock.

Hydrogen may be generated from ethanol by different

technologies, including steam reforming (SR) (Eq. (1)), partial
oxidation (POX) (Eq. (2)) and oxidative steam reforming (OSR)
(Eq. (3)) [7].
CH3 CH2 OH l 3H2 O l42CO2 g 6H2 g;

DH298

347:4 kJ=mol
CH3 CH2 OH l 1:5O2 g42CO2 g 3H2 g;

(1)
DH298

554:0 kJ=mol

(2)

CH3 CH2 OHl1:8H2 Ol0:6O2 g42CO2 g4:8H2 ; DH298

2:4kJ=mol

(3)

SR generates a high H2/CO ratio product but has the disadvantage of high endothermicity and catalyst deactivation due

* Corresponding author. Tel.: 86 22 27405613; fax: 86 22 27405243.

E-mail address: ydli@tju.edu.cn (Y. Li).
0360-3199/$ e see front matter 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.04.042

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Nomenclature
aik
Cep
Ci
Da

d1
d2
b
fi
fi0
F
G
Gi
0

Gi

nG

numbers of the kth atom in molecule i

permeation capacity of membrane surface area/
thickness, cm
density of oxygen ions, mol cm3
ambipolar diffusion coefficient (the diffusion
coefficient of oxygen ion-electron hole pairs),
cm2 s1
outer diameter of the membrane tube, cm
inner diameter of the membrane tube, cm
fugacity of species i in the gas mixture, Pa
fugacity of species i at its standard state, Pa
inlet flow rate, mol s1
molar Gibbs free energy, J mol1
partial molar Gibbs free energy of species i in the
gas mixture, J mol1
Gibbs free energy of species i at its standard state,
J mol1
total Gibbs free energy of the system, J

to coke deposition. On the other hand, POX is exothermic but

it generates a low H2/CO ratio than SR. OSR is a combination of
POX and SR and can produce suitable H2/CO ratio without
external energy consumption. OSR seems to be a reasonably
good alternative whose salient features are reduced rate of
carbon deposition and more favorable thermal equilibrium
that can be varied as a function of the oxygen feed [8].
Within the category of dense membranes, ionic oxygen
conducting membranes (IOCM) offer the unique advantage to
provide activated oxygen at its surface while preventing
hydrocarbon losses to the opposite side [9]. Intensive studies
on the IOCM process in the membrane reactors have been
performed taking into account: the catalytic properties of
perovskite-type [10,11], tubular membrane [12e15], packed
catalyst in the tubular membrane reactor [15], the effects of
oxygen flux, temperature and feed composition [16] and the
comparison of the membrane reactor with a co-feed reactor
[17,18].
Modeling of membrane reactor presents interesting challenges because of the coupling of selective diffusion through
the permeable membrane with chemical reactions and mass
transfer on the both sides of reactor. Rui et al. [19,20] considered the differences of partial oxidation of methane in
a conventional fixed-bed reactor and a dense oxygen permeation membrane reactor (DMR) caused by the different oxygen
feed method, and set up a more reasonable one-dimensional
DMR model considering the oxidation of the products, i.e., H2
and CO. Akin [21] and Rui et al. [22] recently simulated the
oxygen permeation through oxygen ionic or mixed-conducting ceramic membranes under reaction conditions with
a model taking into account of different electrical transport
mechanisms (p-type and n-type transports), and found that
the effect of downstream conditions, especially the rate of
chemical reactions involving oxygen, have strong effects on
the oxygen permeation.
However, except for Sarvar-Amini et al. [23] and Ye et al.
[24], all other models were solved by FORTRAN, MATLAB or

DG0fi
DH298
JO2
L
m
ni
P
P1
P2
S
T
yi

standard Gibbs free energy of formation of

compound i, J mol1
heat of the reaction at 298 K, kJ mol1
oxygen permeation flux through membrane,
mol s1 m2
length of a tubular dense membrane reactor, cm
number of sub-separators used in the model
yield of compound i, mol
total pressure in the tube membrane reactor, Pa
oxygen partial pressure at oxygen-lean side, Pa
oxygen partial pressure at oxygen-rich side, Pa
effective oxygen permeation area of the
membrane tube, cm2
operating temperature, K
molar fraction of compound I in the gas mixture

Greek letters
Lagrange multiplier
lk
bi
Fugacity coefficient of species i in the gas mixture
4

other computer programs, which are not easily accessible to

design engineers in industry. Various process simulators,
such as ASPEN PLUS and HYSYS, are employed widely for
industrial process simulations. ASPEN PLUS includes standard
and ideal unit operations, such as Gibbs reaction models. This
course of action is useful when the kinetic models of reactions
are unknown or are high in number due to many components
participating in the reactions. A FORTRAN sub-routine was
integrated into ASPEN PLUS to simulate oxygen permeation
through membrane in the sub-separator. A DMR model based
on such popular process simulators can facilitate the application of such models, and help chemical engineers to design
such reactors and to simulate alternative hydrogen production processes.
There is few paper reported work of sequential simulation of
DMR for hydrogen production from oxidative steam reforming
of ethanol with ASPEN PLUS. This work performs such a simulation and provides some useful guidance on the design of a DMR
configuration for the reaction. The DMR used in this work is
composed of a perovskite-type oxide Ba0.5Sr0.5Co0.8Fe0.2O3d
(BSCF5582) tubular membrane.

2.

Modeling and simulation

2.1.

Simulation with ASPEN PLUS

ASPEN PLUS 11.1 (Aspen Technology, Inc., MA, USA), one of

the most important process simulators in the chemical
industry and oil refining processes, is utilized. As there is no
separation model based on the oxygen permeation flux in
ASPEN PLUS and the DMR operation does not exist in the
simulator. To simulate the DMR process with ASPEN PLUS
11.1, a sequential modular approach was implemented and
a FORTRAN sub-routine was built and integrated into ASPEN
PLUS to simulate the permeation of oxygen through the
membrane.

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In the simulation, the DMR is modeled using the sequential

modular approach by dividing the reactor into multi-subreactors. At each sub-reactor, the Gibbs reactor model in
ASPEN PLUS is employed to simulate the production process
with an assumption that the OSR reaction reach thermodynamic equilibrium locally. In the Gibbs reactor model, Gibbs
free energy minimization is performed to determine the
product composition. The equilibrium computation brings in
temperature dependence, without requiring detailed information regarding the specific reaction or catalyst performance. The total Gibbs function for the system is given by
nG

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)

Moreover, in the gas phase b

f i can be written as b
f i yi Pb
4i .
With the restraints of the material balances, the minimum
Gibbs free energy of the system then is expressed as
X
lk aik 0

(7)

where yi is replaced by ni/Sni.

In this simulation, the product species of CH3CH2OH, H2O,
O2, H2, CO, CO2 CH4, C2H4 and CH3CHO are considered to exist
in the equilibrium system.

2.2.

dFO2
Air

O2
dl

l=0

l=L

Fig. 1 e Schematic of a dense membrane reactor.

Therefore, based on Eq. (8), the local oxygen flow rate in
a differential element across the membrane is given as Eq. (9).
As there is no separation model based on Eq. (9) in ASPEN
PLUS, a FORTRAN sub-routine was built and integrated into
ASPEN PLUS to simulate the permeated oxygen flow rate
through the membrane as described by Eq. (9). After the user
model (sub-routine) was built, it was compiled using the
aspcomp procedure in ASPEN PLUS.

The membrane reactor model

A one-dimensional dense membrane reactor assumed in DMR

for pure hydrogen production by OSR of ethanol is shown
schematically in Fig. 1. The tubular BSCF82 membrane has an
outer diameter of 8 mm, an inner diameter of 5 mm, and length
up to 30 cm. According to the cross-flow pattern, the feed of
steam and ethanol is a plug flow in the tube side while permeated oxygen are perfectly mixed in the tube side, where the OSR
takes place, closely approaching thermodynamic equilibrium.
To illuminate the simulation of OSR of ethanol, the domain
sketched in Fig. 1 is considered for model development. To
represent the characteristics of dense oxygen permeation
tubular membrane reactor, following assumptions have been
adopted:

Oxygen permeation equations

For the oxygen permeation through tubular BSCF5582

membrane, the oxygen flux equation (8), which was developed
by Kim et al. [25], can be used to predict the permeation flux
when bulk diffusion is the controlling step for oxygen
permeation [26]. Lu et al. [27] deduced the ambipolar diffusion
coefficients Da for the BSCF5582 material based on the bulk
oxygen ionic diffusion current model. Table 1 presents the
ambipolar diffusion coefficients Da of the oxygen permeation
fluxes of the BSCF5582 membrane at 973e1123 K.
JO2

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)

There is a distribution of oxygen in the tube side along the

dense membrane, the oxygen flow rate built up from zero.

1. The separator is under steady-state isothermal operation.

2. The radial diffusion of gases in DMR is negligible.
3. Ideal gas law can be applied to describe the gas behavior of
a single component or gas mixture.
4. The gas-phase mass-transfer resistances are negligible.
Thus, the oxygen partial pressures on both membrane
surfaces are the same as that in the shell side or tube side,
respectively.
5. The total pressure in both sides is kept at constant.
To develop a sequential modular the dense tubular
membrane reactor is axially divided into multi-sub-reactor, as
illustrated in Fig. 2, where sub-reactor consists of an oxygen
permeation tubular membrane sub-separator and a Gibbs
sub-reactor. At each section, the flow of gas is considered as
a plug flow with axial dispersion on both the tube and shell
sides. Overall, the OSR process is represented by m subseparators and m Gibbs sub-reactors, where in each sub-

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)

Moles of H2 per mole of ethanol

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.

Results and discussion

3.1.

Number of sub-reactors

Fig. 3 shows the influence of m on the predicted hydrogen

production rate for a typical case: reactor pressure P 0.1 MPa,
operating temperature T 973 K, steam-to-ethanol ratio (H2O/
EtOH) is 0.5, the oxygen partial pressure gradient term Ln(P1/
P2) 2, and the axial length of membrane reactor is 30 cm. It
can be seen that for m > 55, the influence of m on hydrogen
yield is negligible. So m can be taken as 55 for the simulation.
In the following simulations for various length values
(<30 cm) of the reactor, the m value is set as 55, and it is
considered in each case that its influence on the hydrogen
production rate is negligible.

3.2.

Influence of temperature

Figs. 4 and 5 show the four major products at different

temperature along DMR with different length for a restraint

3.5

Moles of H2 per mole of ethanol

(moles/mole)

separator it has a membrane permeation capacity of Cep/m.

The separator oxygen from the mth sub-separator is fed to
the mth Gibbs sub-reactor. For example, at m 1, the model
represents a case with one sub-separator and a regular
Gibbs sub-reactor, so that the oxygen separation process is
ahead of OSR process. m 2 represents a case with two
sub-separators and two Gibbs sub-reactors, where in each
sub-separator has a membrane permeation capacity of Cep/
2. The greater the number of the sub-separators employed
in the model, the more closely the sequential modular
approach method should represent the real reaction
process. In practice, m should be high enough to ensure
that the predicted hydrogen production rate from the
model is virtually independent of m.

that H2O/EtOH ratio is 0.5. The conversion of ethanol is almost

100% over the whole temperature range (973e1123 K). As
described in Fig. 4(a) that hydrogen yield increases with the
length of the reactor at 973 K, while at the other temperatures,
hydrogen yield increases with the length of the reactor and

3.0

2.5

2.0

Temperature
973 K
1023 K
1073 K
1098 K
1123 K

1.5

1.0

0.5

Moles of CO2 per mole of ethanol

(moles/mole)

Fig. 2 e Sequential modular simulation diagram of DMR

with ASPEN PLUS.

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

Axial length of reactor (cm)

Fig. 4 e Influence of operating temperature at different
length of membrane reactor on the H2 and CO2 yields, P
[ 0.1 MPa, Ln(P2/P1) [ 2, H2O/EtOH [ 0.5.

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Moles of CO per mole of ethanol

(moles/mole)

1.8

1.5

1.2

Temperature
973 K
1023 K
1073 K
1098 K
1123 K

0.9

0.6

Moles of CH4 per mole of ethanol

(moles/mole)

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

Axial length of reactor (cm)

Fig. 5 e Influence of operating temperature at different

length of membrane reactor on the CH4 and CO yields, P
[ 0.1 MPa, Ln(P2/P1) [ 2, H2O/EtOH [ 0.5.

reaches maximum and then decreases with the increase of

the length of the reactor. For example, the maximal yield of
hydrogen is 2.942 with 10 cm at 1023 K, 3.184 with 6 cm at
1073 K, 3.248 with 4 cm at 1098 K, and 3.296 with 4 cm at
1123 K.
The OSR process in a DMR consists of SR reaction (1) and
POX reaction (2). Both of these two reactions consume ethanol
and produce hydrogen. Since the supply of oxygen in DMR is
distributed along the axial length of the membrane tube and
a fixed oxygen partial pressure ratio between the two sides is
assumed during the calculation, the oxygen feeding amount
increases with the increase of the length of the membrane
tube. When the membrane length is short, the permeated
oxygen will react with the excess ethanol by reaction (2) along
with reaction (1) to produce more hydrogen. As a consequence,
the hydrogen yield increases with an increase of the length of
the membrane tube for this case. When the permeated oxygen
reaches the stoichiometric amount of reaction (2) with the
excess ethanol, the hydrogen yield reaches maximum. Beyond
this point, the permeated oxygen may react with the product
hydrogen by the following reaction [19,20,28].
2H2 g O2 g42H2 O g;

DH298 483:63 kJ=mol

(10)

As a result, the hydrogen yield decreases with the further

increase of the length of the membrane after reaching the
maximum point for the temperatures 1023 K, 1073 K, 1098 K
and 1123 K, respectively, as shown in Fig. 4(a).

The change of temperature has two main effects. Firstly,

the oxygen permeation flux, as expressed by Eq. (8), increases
with the increase of temperature when the oxygen partial
pressure ratio between the two sides is fixed. Therefore, the
effect of the permeated oxygen is more significant at a higher
temperature for the same length of the membrane tube. As
indicated in Fig. 4(a), the length for the maximum hydrogen
yield decreases with the increase of temperature. For the
temperature 973 K, the hydrogen yield cannot yet reach the
maximum point at the length of 30 cm. On the other hand, the
change of temperature affects the equilibrium states of reactions (1), (2) and (10). Since reaction (1) is endothermic and
reactions (2) and (10) are exothermic, increasing temperature
favors reaction (1), while shifts reactions (2) and (10) to the left
side. The final hydrogen yield depends on the relative dominances of these two effects. For example, when the length of
the membrane tube is shorter than 4 cm (the maximum
hydrogen yield point at 1123 K), the hydrogen yield increases
with the increase of temperature due to both the favorable
effect of improved oxygen permeation amount and the equilibrium shift of reaction (1), as shown in Fig. 4(a).
Fig. 4(b) reveals the trend of carbon dioxide yield which
increases with the increase of the operating temperature and
the length of the reactor. When the membrane length is short,
the permeated oxygen reacts with the excess ethanol by
reaction (2) along with reaction (1) to produce more carbon
dioxide. Therefore, the carbon dioxide yield increases with the
length of the membrane tube for this case. When the
membrane length is long, the permeated oxygen moles in
DMR is more than the stoichiometric amount of reaction (2)
for the excess ethanol, the excess permeated oxygen leads to
the combustion of other products to produce more carbon
dioxide [29e31,36], for instance, CO, CH4, C2H4 and CH3CHO,
which are considered in the equilibrium system. Therefore, in
the excess presence of oxygen, the following reactions (11)e
(14) can also occur.
2CO g O2 g42CO2 g;

DH298 565:93 kJ=mol

CH4 g 2O2 g4CO2 g 2H2 O l;

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)

The carbon dioxide yield increases with the increase of the

operating temperature due to two positive behaviors of OSR in
DMR. The first, the oxygen permeation flux increases with the
increase of temperature as explained in the previous paragraph,
which leads to the production of more carbon dioxide. Meanwhile, the increase of temperature affects the equilibrium state
of reactions (1)e(2) and (11)e(14). Since reaction (1) is endothermic, and reactions (2) and (11)e(14) are exothermic,
increasing temperature favors reaction (1), while shifts reactions (2) and (11)e(14) to the left side. However, the final carbon
dioxide yield depends on the dominant reaction (1) at high

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temperatures. As a consequence, the increase of the operating

temperature favors more carbon dioxide as indicated in Fig. 4(b).
Fig. 5(a) shows the carbon monoxide yield increases with
the length of the DMR at 973 K, while it increases with the
length of the DMR and reaches maxima and then decreases
with the increase of the length at the other temperatures. For
example, the maximal yield of carbon monoxide is 1.669 with
10 cm at 1023 K, 1.818 with 6 cm at 1073 K, 1.867 with 4 cm at
1098 K, and 1.894 with 4 cm at 1123 K, respectively.
The SR reaction (1) can be well represented by the following
reactions (15) and (16) [32,33].

CH4 g H2 O g4CO g 3H2 g;

DH298 206:16 kJ=mol

(19)

(15)
DH298 41:2 kJ=mol
(16)

The permeated oxygen, which is distributed along the axial

length of DMR, oxidizes excess ethanol along with reaction
(15) to produce more carbon monoxide by the following
reaction (17) when the length of membrane tube is short.
2CH3 CH2 OH l O2 g44CO g 6H2 g;
111:80 kJ=mol

Since the permeated oxygen reacts with the formed

methane by reaction (12), the equilibrium methane yield
decreases with the increase of the length of the membrane
tube as shown in Fig. 5(b). Increase the temperature cannot
only improve the oxygen permeation through the membrane
and also favor the endothermic methane steam reforming
reaction (19) [35], which in turn decrease the methane yield.

DH298

341:73 kJ=mol
CO g H2 O g4H2 g CO2 g;

DH298 91:57 kJ=mol

(18)

DH298
(17)

As a result, the carbon monoxide yield increases with the

increase of the length of the DMR. When the permeated
oxygen reaches the stoichiometric amount of reaction (17) for
the excess ethanol, the carbon monoxide yield reaches
maximum. Beyond this point, the excess permeated oxygen
reacts with carbon monoxide according to the reaction (11),
therefore, the carbon monoxide yield decreases with the
further increase of the length of the reactor after reaching the
maximum point for the temperatures 1023 K, 1073 K, 1098 K
and 1123 K, respectively, as shown in Fig. 5(a).
As described in the previous paragraph, an increase of
temperature leads to more oxygen permeated into DMR, so the
effect of the permeated oxygen is more significant at a higher
temperature for the same length of the membrane tube. As
indicated in Fig. 5(a), the length for the maximum carbon
monoxide yield decreases with the increase of the temperature.
For the temperature 973 K, the carbon monoxide yield cannot
reach the maximum point at the length of 30 cm. On the other
hand, the change of temperature affects the equilibrium states
of reactions (11) and (15)e(17). Since reactions (15) and (17) are
endothermic, and reactions (11) and (16) are exothermic,
increasing temperature favors reaction (15) and (17), while
shifts reactions (11) and (16) to the left side. The final carbon
monoxide yield depends on the relative dominances of these
two effects. For example, when the length of the membrane
tube is shorter than 10 cm (the maximum carbon monoxide
yield point at 1023 K), the carbon monoxide yield increases with
the increase of the temperature due to both the favorable effect
of improved oxygen permeation amount and the equilibrium
shift of reactions (15) and (17), as shown in Fig. 5(a).
Fig. 5(b) gives the trend of methane yield with the change of
operating temperature and the length of the DMR. The
production of methane at high temperature was suggested to
follow the ethanol decomposition reaction according to (18) [34].

3.3.

Influence of steam-to-ethanol ratio

Figs. 6 and 7 plot the relationship between the four major

product yields and the H2O/EtOH ratio and the length of the
DMR at 1023 K. It can be seen from Fig. 6(a) that the hydrogen
yield is significantly influenced by the H2O/EtOH ratio. For the
H2O/EtOH ratio of 0, 0.5 and 1, hydrogen yield shows the
volcano shape and reaches the maxima with different lengths
of reactor, respectively. For example, the maximal yield of
hydrogen is 2.723 with 10 cm at H2O/EtOH 0, 3.183 with 6 cm
at H2O/EtOH 0.5 and 3.645 with 2 cm at H2O/EtOH 1,
respectively. However, for H2O/EtOH ratio of 2 and 5, hydrogen
yield decreases with the length of the DMR monotonically.
Additionally, for the fixed length of DMR, moles of hydrogen
are higher at a higher H2O/EtOH ratio than at a lower H2O/
EtOH ratio. This is because the amount of the H2O affects the

Moles of H2 per mole of ethanol

(moles/mole)

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

Moles of CO2 per mole of ethanol

(moles/mole)

6696

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

Axial length of reactor (cm)

Fig. 6 e Influence of steam-to-ethanol ratio at different

length of membrane reactor on the H2 and CO2 yields, T
[ 1073 K, P [ 0.1 MPa, Ln(P2/P1) [ 2.

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Moles of CO per mole of ethanol

(moles/mole)

2.0

a
1.5

1.0

H2O/EtOH
0
0.5
1
2
5

0.5

0.0

Moles of CH4 per mole ethanol

(moles/mole)

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

Axial length of reactor (cm)

Fig. 7 e Influence of steam-to-ethanol ratio at different

length of membrane reactor on the CH4 and CO yields, T
[ 1073 K, P [ 0.1 MPa, Ln(P2/P1) [ 2.

with 2 cm at H2O/EtOH 1, respectively. However, for the

H2O/EtOH ratio of 2 and 5, the carbon monoxide yield
decreases monotonically with the length of the DMR.
The H2O amount in the reactant affects the equilibrium
state of the water gas shift reaction (16) and the H2 yield, as
depicted in Fig. 7(a). For the effect of the membrane length,
when it is short, the permeated oxygen reacts with the excess
ethanol to produce more carbon monoxide by reaction (17).
Therefore, the carbon monoxide yield increases with the
increase of the length of the membrane tube for the H2O/EtOH
ratio of 0, 0.5 and 1. When the permeated oxygen reaches the
stoichiometric amount of reaction (17), carbon monoxide
yield reaches maximum. Beyond this point, the permeated
oxygen reacts with the producced carbon monoxide by reaction (10) [29], as a result, the carbon monoxide yield decreases
with the further increase of the length of the membrane, as
shown in Fig. 7(a). However, for the H2O/EtOH ratios of 2 and
5, there is no excess ethanol to consume the permeated
oxygen, which will react directly with the product carbon
monoxide by reaction (10). The carbon monoxide yield
decreases with the length of the DMR, as shown in Fig. 7(a).
Fig. 7(b) shows the trend of methane yield changes with the
H2O/EtOH ratio and the length of membrane tube. The
methane yield decreases with the increase of H2O/EtOH ratio
and the length of DMR both monotonically and approaches
zero along with the tube length with different slope for the
different H2O/EtOH ratio. This is because both H2O and O2 can
affect the methane yield by reacting with CH4 according to the
steam reforming reaction (19) [36] and reaction (12).

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

6697

Conclusion

Hydrogen production via oxidative steam reforming of

ethanol with a dense tubular membrane reactor (DMR) has
been sequentially simulated with ASPEN PLUS. Simulation
result on DMR performance shows that there exists an
optimal length of the tubular membrane reactor at an operating temperature and a fixed steam-to-ethanol ratio. Under
this condition, the carbon monoxide and hydrogen formation
reaches its maximum. For example, at the fixed ratio H2O/
EtOH 0.5, the maximum hydrogen yield occurred at
a temperature of 1123 K with the length of tubular DMR of
4 cm. For the temperature of 1073 K, the maximum hydrogen
yield appears at H2O/EtOH 5 with the length of tubular DMR
of 0 cm. Using the approach proposed in this work, the
prediction of the DMRs behavior under different operating
conditions becomes meaningful.

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.

6698

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

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