Energy 147 (2018) 884e895

Contents lists available at ScienceDirect

Energy
journal homepage: www.elsevier.com/locate/energy

Computational fluid dynamic simulation of a sorption-enhanced

palladium membrane reactor for enhancing hydrogen production
from methane steam reforming
Guozhao Ji a, Ming Zhao a, *, Geoff Wang b
a
School of Environment, Tsinghua University, Beijing, 100084, China
b
School of Chemical Engineering, The University of Queensland, Brisbane, Qld, 4072, Australia

a r t i c l e i n f o a b s t r a c t

Article history: To understand the reaction process of methane steam reforming in a sorption enhanced membrane
Available online 19 January 2018 reactor (SEMR), a computational fluid dynamic (CFD) model was developed to simulate the methane
(CH4) steam reforming in a palladium-based membrane reactor using a Ni-based catalyst and Na2ZrO3
Keywords: CO2 sorbent. The CFD model gained the insight of details in the reactor which could not be obtained by
CFD simulation experiment. With the detailed information, this model detected the difference of reaction kinetics and
Sorption-enhanced membrane reactor
fluid dynamic conditions in a SEMR and a traditional membrane reactor (MR). The comparison suggests
Methane steam reforming
that sorption-enhanced membrane reactor not only decreases CO2 fraction, but also improves hydrogen
Hydrogen production
Ni catalyst
(H2) production by increasing reaction rates, CH4 conversion and H2 yield. The poisoning effect of carbon
Na2ZrO3 sorbent monoxide (CO) on the palladium membrane can also be minimized by reduced CO fraction as a result of
in-situ CO2 capture.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction further convert CO into H2 and a by-product CO2 (Eqn. R2).

Currently, fossil fuels are still the primary source for satisfying
the growing energy demand of our contemporary society. However,
the growing level of CO2 from the emission of fossil fuel combustion
is increasing the concern of global warming. In the case of low
carbon emission technologies, H2 becomes an attractive alternative,
mainly due to its high calorific value and non-polluting emission
[1]. H2 can be produced via thermo-chemical processes from a
variety of sources including biomass [2,3], natural gas [4,5], coal
[6,7], water [8,9], and some industrial waste chemicals [10]. For
most of these H2 production technologies, methane steam
reforming (MSR), referring to Eqn. R1 below, is a necessary step to
convert CH4 and water to H2 [11].
CH4 þ H2O # CO þ 3H2 DH298 ¼ 206.1 kJ mol1
However the H2 yield through reaction (R1) is accompanied
with approximately 25 vol% toxic gas CO. To avoid producing the
toxic gas, water-gas shift (WGS) reaction is usually implemented to
* Corresponding author.
E-mail address: ming.zhao@tsinghua.edu.cn (M. Zhao).
CO þ H2O # CO2 þ H2 DH298 ¼ 41.15 kJ mol1 (R2)
It should be noted that reaction (R1) is endothermic and reac-
tion (R2) is exothermic, which prevents them achieving high con-
version simultaneously in a single reactor where they are in the
same temperature range. It is generally required to control MSR at
temperatures higher than 700  C. However WGS reacts efficiently
only below 450  C. For ordinary MSR hydrogen production, the hot
gas mixture has to be delivered from MSR reactor to WGS reactor,
which resulted in a large energy penalty due to the cooling down
between reactors. In order to minimize this impact, a membrane
reactor was invented to allow these two reactions to proceed
simultaneously in a single reactor with better CH4 conversion and
(R1) improved H2 production. The membrane is designed to be H2 se-
lective, thus that H2 could be partially removed continuously from
the reactor by membrane permeation, meanwhile sustaining other
gas components in the reactor. In turn, the equilibriums of MSR and
WGS are shifted towards the H2 side owing to the H2 removal.
Therefore, separating H2 at high temperatures becomes attractive
due to the reduction of energy penalties associated with the cooling
encountered in traditional MSR.
Among potential gas separation technologies, inorganic

https://doi.org/10.1016/j.energy.2018.01.092
0360-5442/© 2018 Elsevier Ltd. All rights reserved.
 G. Ji et al. / Energy 147 (2018) 884e895 885

membranes such as palladium-based membranes [12,13] and

silica-based membranes [14,15] have performed well at high tem-
peratures. These membranes have been deployed in membrane
reactor configurations for H2 production via MSR [16,17], WGS re-
actions [18,19], as well as dehydrogenation reactions [20]. The CH4
conversion enhancement mainly depends on the H2 permeation. As
is known that increasing the sweep flow could improve H2
permeation. Anzelmo et al. enhanced the CH4 conversion from
about 50% to 84% by varying the sweep flow 0e100 ml min1 [21].
Based on open literature in membrane reactor design,
palladium-based membranes showed superior popularity over
silica-based membranes for its infinite H2 selectivity and higher
permeability [22,23], though its capital cost is 2 orders of magni-
tudes higher than the silica counterpart. However, CO, which is an
inevitable gas component in MSR, is an inhibitor for the palladium
membrane because it affects the H2 dissociation path [24]. The
presence of CO is attributed to the faster reaction of MSR than that
of WGS. The net gain of CO accumulates in the reactor. Enhancing
the CO conversion is a feasible solution to reduce the CO concen-
tration and resultantly minimize its inhibition effect to palladium.
Sufficiently removing H2 could possibly achieve this goal in some
situations. But once the membrane reactor needs to process large
quantity of gases, the high space velocity doesn't give sufficient Fig. 1. The schematic of methane steam reforming in a membrane reactor with in-situ
CO2 capture.
retention time for reactants to react and for H2 to permeate.
Membrane reactors still suffer from low conversions with high
space velocities [25,26]. concentration, pressure and temperature. In turn, these processes
Apart from H2 removal by membrane, capturing the other will also affect the fluid dynamic conditions. All the processes and
product gas (CO2), may further shift the WGS reaction equilibrium fluid dynamic conditions are inter-correlated and spatially
towards H2þCO2 side and in turn enhance the CO conversion. distributed in a reactor. It is extremely difficult, if not impossible, to
Furthermore, the CO depletion resulted from CO2 capture would measure all the concerned parameters inside the reactor experi-
also enhance the MSR reaction towards the H2 side because CO is mentally. In order to better understand the reaction processes,
one of the products of MSR. Regarding the in-situ CO2 capture, detailed information (e.g. gas concentration distribution) inside a
various materials such as CaO, Na2ZrO3, and hydrotalcite have been reactor should be studied. To address this problem, computational
used as sorbents and some of them was successfully deployed to fluid dynamics (CFD) simulation can be used to correlate fluid dy-
enhance MSR [27e31] and WGS [32]. If these sorbent materials namics with space coordinate and time [38], thus providing
were integrated with membrane separation, a further enhance- detailed gas flow characteristics and the distributed reaction ki-
ment of ‘shift effect’ could be expected for MSR. This type of netics in a membrane reactor with CO2 sorption for MSR. The
configuration is called sorption enhanced membrane reactor source term in CFD allowed the reactions and permeation to be
(SEMR). However, the number of publications with this idea is very written in the CFD governing equations to couple the microscopic
limited [33,34]. Only Li et al. [33] and Madeira et al. [34] had used model (reactions, permeation) with macroscopic model (fluid dy-
hydrotalcite as CO2 sorbent in palladium membrane for WGS. Other namics). As a result, the CFD simulation can become a feasible tool
sorbent materials could also be applied in membrane reactors for to improve the design of given membrane reactor and improve the
MSR. The limited number of studies using both membrane and operation of methane steam reforming in the membrane reactor.
sorbents was owing to the complexity of synergistic effects among Therefore, we will carry out a CFD simulation of SEMR. The simu-
MSR, WGS, membrane permeation and CO2 capture. Moreover, lation with distributed information such as reaction rates and gas
these synergistic effects were difficult to be studied experimentally. concentrations would assist the analysis and improvement of the
Zhang et al. [35] and Chen et al. [36] deployed one dimensional reactor performance, especially the CH4 conversion and CO
‘plug flow’ model to calculate the sorption enhanced membrane concentration.
reactor performance. However, plug flow model was criticized by
Koukou et al. [37] due to the inadequacy in considering radial 2. Model description
profile. CFD simulation which gives the distributed three-
dimensional information is needed to get an insight of reaction The design of the membrane reactor investigated in this work is
details in a reactor. There hasn't been a CFD model study to inter- depicted in Fig. 2. The reactant gases, CH4þH2O, were fed from the
pret and analyze the MSR performance in a SEMR. This study for the
first time will deploy CFD simulation to fill this knowledge gap and
fulfill the need of investigating the coupled processes and assist the
analysis of the shift effect.
This work is aimed to investigate the enhancement of MSR
process by applying membrane separation and in-situ CO2 sorption
together in one reactor as described in Fig. 1. The processes in this
reactor include MSR, WGS, H2 permeation and CO2 sorption. H2
permeation and CO2 capture reduce the product concentration and
shift the reactions towards products side on basis of Le Chatelier's
principle. The dynamics and the equilibria of these processes
depend on the fluid dynamic conditions such as gas component Fig. 2. The structure of a membrane reactor for methane steam reforming.
886 G. Ji et al. / Energy 147 (2018) 884e895

inlet of the reactor. As the gases flowed in the catalyst packed bed,
MSR and WGS proceeded. The generated H2 that permeated across vuz vuz uq vuz vuz
þ ur þ þ uz
the membrane was collected with sweep N2 via the outlet. The vt vr r vq vz
"   # (4)
unpermeated gas exited the reactor from the right outlet. For the 1 vp h 1 v vuz 1 v2 uz v2 uz
case with in-situ CO2 sorption, the catalyst would mix with CO2 ¼ þ r þ 2 þ 2  Sz
r vz r r vr vr r vq2 vz
sorbents and some generated CO2 may be captured by the sorbents.
The MSR, WGS, H2 permeation and CO2 sorption only occur
where Sr , Sq and Sz represent the momentum source (or mo-
between the feed inlet and the outlet of the unpermeated gas. For
mentum loss) in radial and axial direction caused by the packed
simplicity, the CFD model only simulated the processes in the zone
catalyst and sorbent.
between the membrane and the reactor shell, which is made from a
Further for a multi-component system, the continuity equation
hollow cylinder. In view of the axial symmetry of the reactor, a 15
of each component is described as
portion of the reacting zone with symmetry planes on both side
was simulated to save the computational time (Fig. 3). The
vci 1 v 1 v v
boundary condition of inlet was mass flowrate with fixed compo- þ ðr$ci $ur Þ þ ðc $u Þ þ ðci $uz Þ
vt r vr r vq i q vz
sition of CH4 and H2O vapor. The outlet was a pressure opening. The       (5)
reactor shell was set as wall. The membrane was also set as wall, 1 v vc 1 v vc v vc
¼ r$D i þ D i þ D i þ Si
but with negative H2 mass source to represent the H2 permeation. r vr vr r vq vq vz vz
At the two symmetries, there was no tangential gradient for any
variables. The structured mesh was created from inlet to outlet by where Si is the source term of each component which is depleted or
sweep method to facilitate the computation speed. generated by chemical reactions as well as selective permeation. In
The CFD model is mathematically expressed by the governing this study for methane steam reforming, i ¼ CH4, CO2, CO, H2, H2O.
equations consisting of continuity equations and momentum Apart from reactions (R1) and (R2), there are some other
equations. The continuity equation governs the mass balance, possible reactions together with MSR listed as follows
giving
CH4 þ 2H2O # CO2 þ 4H2 DH298 ¼ 165.0 kJ mol1 (R3)

vc 1 v 1 v v CH4 þ CO2 # 2 CO þ 2H2 DH298 ¼ 247.3 kJ mol1 (R4)

þ ðr$c$ur Þ þ ðc$uq Þ þ ðc$uz Þ ¼ Sct (1)
vt r vr r vq vz
CH4 þ 3 CO2 # 4 CO þ 2H2O DH298 ¼ 330.0 kJ mol1 (R5)
where Sct is the source term caused by the processes which break
the total mass balance such as H2 permeation and CO2 sorption. The
Reaction (R3) can be considered as a superposition of (R1) and
momentum balance can be expressed by the Navier-Stokes equa-
(R2). However, it has been proved that (R4) and (R5) don't occur in
tion as follows
methane steam reforming [39,40]. Thus these two reactions were
not taken account in this model.
vur vur uq vur u2q vur Ni-based catalyst was the most widely utilized catalyst in
þ ur þ  þ uz
vt vr r vq r vz palladium MSR reactors due to the low cost and high CH4 conver-
"   # sion [41]. The MSR reaction rate under the catalysis (Ni/Al2O3) was
1 vp h 1 v vur 1 v2 u r v2 u r u r 2 vuq assumed to follow Langmuir-Hinshelwood-Hougen-Watson
¼ þ r þ 2 þ    Sr
r vr r r vr vr r vq2 vz2 r 2 r 2 vq (LHHW) model [40,42].
(2)  
p3H pCO
pCH4 pH2 O  2
KMSR
kMSR
rMSR ¼ (6)
vuq vu u vuq ur uq vu p2:5 DEN 2
þ ur q þ q  þ uz q H2
vt vr r vq r vz
"   #
1 vp h 1 v vuq 1 v2 uq v2 uq uq 2 vur where KMSR is the equilibrium constant for MSR. kMSR is the rate
¼ þ r þ 2 þ 2  2 2  Sq coefficient of MSR. These values are functions of temperature and
r vq r r vr vr r vq2 vz r r vq
generally follow the Arrhenius correlation, giving
(3)
 
Ek;MSR
kMSR ¼ kMSR;r exp  (7)
RT

 
EK;MSR
KMSR ¼ KMSR;r exp  (8)
RT

where Ek;MSR and EK;MSR are the activation energies for rate coef-
ficient and equilibrium constant, respectively, R is the gas constant
and T is absolute temperature.
!
p3H pCO
The term in the bracket pCH4 pH2 O  2
KMSR can be seen as the

reaction driving force. When all the gas compositions reach equi-
librium, this term equals zero. H2 removal or CO depletion would
break the equilibrium and increase the value of this term, thus
increasing the reaction rate.
Fig. 3. The reaction domain and boundary conditions in CFD model. Similarly, for WGS reaction, the rate is
 G. Ji et al. / Energy 147 (2018) 884e895 887

 pH2 pCO2

k pCO pH2 O KWGS
rWGS ¼ WGS (9)
pH2 DEN2
The rate coefficient and equilibrium constant of WGS are
 
Ek;WGS
kWGS ¼ kWGS;r exp  (10)
RT

 
EK;WGS
KWGS ¼ KWGS;r exp  (11)
RT
Since MSR is endothermic, EK;MSR is positive and KMSR increases
with temperature. But EK;WGS is negative due to the exothermic
characteristic of WGS reaction. The reaction driving force term
 
pH pCO
pCO pH2 O  K2WGS 2 mathematically implied the removal of both H2
Fig. 4. CO2 sorption kinetics in Na2ZrO3 under various CO2 partial pressures with CO2-
and CO2 from the reactor would result in a higher driving force than N2 mixture at 500  C ( ).10 vol% of CO2 in N2; ( ) 30 vol% of CO2 in N2; ( ) 50 vol% of
the case with removal of either of them. CO2 in N2; ( ) 70 vol% of CO2 in N2;
The adsorption factor in Eqns. (6) and (9) is defined as

pH2 O
DEN ¼ 1 þ KCO pCO þ KH2 pH2 þ KCH4 pCH4 þ KH2 O
pH2
Eqns. (6) and (9) reflect the mechanism of the reaction
enhancement by H2 permeation. In the case of membrane reactor,
H2 partial pressure (pH2 ) decreases when the H2 permeation occurs.
Reaction rates of MSR (rMSR ) and WGS (rWGS ) increase by
decreasing H2 partial pressure (pH2 ). Eqn. (9) also indicates that
lowering CO2 partial pressure (pCO2 ) could directly favor the WGS
(rWGS ). WGS reduces CO partial pressure (pCO ), then MSR is
enhanced in the meantime.
The H2 permeation across palladium membrane has been well
modeled by Sieverts law [41,43,44].
dp0:5
H2
JH2 ¼ Q
dl
where JH2 is the H2 permeation flux across palladium membrane
and Q is the H2 permeability. l is the coordinate in the membrane
thickness direction.
Na2ZrO3, which showed decent CO2 capacity (volume based),
fast sorption kinetic and excellent cyclic stability [45e51], could be
mixed with Ni/Al2O3 catalyst as the sorbent for in-situ CO2 sorption.
To obtain CO2 sorption kinetics data, a TGA (Thermo-gravimetric
analysis) test was carried out using Na2ZrO3 powder at 500  C
under various CO2 partial pressures (0.1, 0.3, 0.5 and 0.7 bar). The
measured CO2 uptakes shown in Fig. 4 suggested that the sorption
kinetic is a function of sorbent conversion and CO2 partial pressure.
A polynomial fitting was applied to develop a correlation between
the sorption kinetics with sorbent conversion and CO2 partial
pressure. The sorption rate is expressed as
In addition to CO2 capture, Na2ZrO3 was also reported for some
(12)
catalytic effect in reforming and WGS reactions [52]. However, the
catalytic effect from alkali catalyst occurs only when the temper-
ature is greater than 800  C [53], thus this model assumed that the
catalytic effect of Na2ZrO3 is minor compared to that of Ni and the
catalytic effect of Na2ZrO3 was not taken into account in the model.
3. Mesh and time-step independence study
The flow diagram for the entire CFD model was illustrated in
Fig. 5. The model was solved by the commercial CFD code CFX
(ANSYS Inc., US) in double precision mode.
The partial differential equations (PDE) from (1) to (5) are
continuous in space and time. However, discretization must be
(13) adopted by mesh size and time step whereby the equations are
replaced by the approximations using finite element method. Nu-
merical error is inevitable in finite element method, especially
when the mesh size and time step are large. Smaller mesh size and
time step can deliver more precise result but prolong the compu-
tational time. To ensure the precision of results from this model,
mesh and time-step independence study was performed by grad-
ually reducing mesh and time-step from a larger value until the
results did not change with mesh and time-step.
Under several mesh sizes and time-steps, the CH4 mass fraction

da
rCO2 ¼ rmol Mmax (14)
dt

where rmol is the apparent molar density of the sorbent and Mmax is
the maximum CO2 molar capacity. The fitted correlation from the
experimental sorption test was included in the CFD model to ac-
count for CO2 depletion in the reactor.
The sorbent conversion is a function to time based on Eqn. (15),
giving

da
atþDt ¼ at þ Dt (15)
dt
Fig. 5. The Program flow chart of CFD model.
888 G. Ji et al. / Energy 147 (2018) 884e895
at a point which locates 1 cm from the inlet was recorded with
simulation time. The reason to select this monitoring point is that
reactants are rich in this region and reactions are more severe. It is
more sensitive to detect the difference of result from different mesh
system. Meanwhile this point would give a quick response to the
inlet flow to save the simulation time. As shown in Fig. 6, the
comparison of different time-step Dt showed that reducing Dt from
0.001 s to 0.0005 s present no difference in the result, suggesting
that Dt has little effect on the precision of results. As such, the
Dt¼0.001 s was used throughout this work. When the minimum
mesh size was reduced from 2 mm to 0.5 mm, the monitored re-
sults were different, which implied that 2 mm mesh size is too
rough in this situation. Reducing the mesh size further to 0.3 and
0.1 mm delivered same results to 0.5 mm mesh, which means
0.5 mm mesh size is already sufficiently small to be used in
approximating the PDE equations of the CFD model. Finally the
mesh system used in this study is 5632 hexahedra (number of
nodes: 7965) with max edge length ratio of 1.4634 and volume of
5.19955  107 m3.
4. Model validation and results
To validate this model, the model geometry and boundary
conditions were set the same as the experiment reported by Tong
et al. [54] who carried out comprehensive tests by using different
palladium membrane reactors (Membrane_L and Membrane_H) to
produce H2 from MSR with varied space velocities (1120, 2240 and
3360 h1). The reactor configuration was demonstrated in Fig. 2
and the detailed boundary conditions were listed in Table 1. The
experiment was conducted in a membrane reactor without in-situ
CO2 capture. So in the first step, the CFD model for membrane
reactor (MR) only included MSR, WGS and H2 permeation, but CO2
sorption was not considered in this model. The results from this
Fig. 6. The comparison of monitored CH4 mass fraction in varying mesh and time-step combinations (Monitored location is 1 cm away from inlet).
model was denoted as MR. This model was run for validation
purpose. In the second step, it is assumed 20% volume were occu-
pied by Na2ZrO3 sorbent, thus the in-situ CO2 sorption was included
in the CFD model for sorption enhanced membrane reactor (SEMR).
The results from the model taking account of the CO2 sorption was
denoted as SEMR. The convergence criteria for all the simulations
was set as 1  105 which means all the errors of continuity
equation, and each component (CH4, CO2, H2, CO, H2O) continuity
equation have to be less than 1  105.
CH4 conversion measured by experiment and computed from
the CFD model under identical operating conditions were
compared for model validation (Fig. 7) for two membrane reactors.
It can be seen that the simulated CH4 conversion shown in Fig. 7 fits
very well with the experimental CH4 conversion reported by Tong
et al. [54]. Based on this good agreement, this model is considered
accurate permitting its utilization for further simulations into un-
derstanding and analysis of the processes in the reactor.
The further comparison was made between MR model and
SEMR model (Fig. 8). The addition of CO2 sorbents in SEMR model
dramatically promoted the CH4 conversion with the greatest
enhancement of 37% for 3360 h1 space velocity. For the case of
3360 h1, the advantage of SEMR over MR prevailed from around
the 1st sec until 300th sec. Prior to the 1st sec, the CO2 sorption had
not commenced yet. This is because the sorption rate is slow when
the sorbent conversion a is low (Fig. 4). Therefore, during this initial
period, the SEMR showed little difference from MR. Once the sor-
bents started to capture CO2 efficiently, CH4 conversion increased
due to the equilibrium shifting caused by CO2 sorption. As the
sorbent conversion approached to saturation (a/1) when the
sorbents were used for longer time, the CO2 sorption kinetic
decreased to almost zero as presented in Fig. 4. Thus the MSR and
WGS enhancement by sorption would vanish. Therefore, the CH4
conversion in SEMR dropped to the level of that in MR.
 G. Ji et al. / Energy 147 (2018) 884e895 889

Table 1
Boundary conditions of the CFD model.

Parameters Value Parameters Value

Membrane diameter (m) 9.5  103 H2 permeance (mol m2 s1 Pa0.5) Membrane_L: 9.38  104
Reactor diameter (m) 1.7  102 Membrane_H: 1.88  103
Membrane length (m) 7.0  102 Space velocity (h1) 1120 (Re y 2.8)
Temperature 500  C 2240 (Re y 5.6)
CH4/H2O molar ratio 1/3 3360 (Re y 8.4)
Outlet pressure (MPa) 0.3 Turbulence Laminar

In order to reveal the reason of the different performance in MR

Fig. 7. The comparison of CH4 conversion resulted from experiment and CFD model.
⋄
(,) Low performance membrane at 773 K with space velocity 1120 h1; ( ) Low
performance membrane at 773 K with space velocity 2240 h1; (△) Low performance
membrane at 773 K with space velocity 3360 h1; (-) High performance membrane at
773 K with space velocity 1120 h1; (A) High performance membrane at 773 K with
space velocity 2240 h1; (:) High performance membrane at 773 K with space ve-
locity 3360 h1; Experimental data was reproduced from Ref. [54].
and SEMR, the map of CO2 molar fractions on the symmetry plane
(refer to Fig. 3) at the 100th sec in MR and SEMR were compared in
Fig. 9. In the MR, CO2 fraction was increasing with the flow (from
inlet to outlet) due to the accumulation of generated CO2 from WGS
reaction. In the radial direction (from membrane to reactor shell),
CO2 fraction slightly decreased. This is because the H2 permeation
promoted WGS, thus WGS produced more CO2 at the vicinity of the
membrane. On the contrary, in the sorption enhanced membrane
reactor, CO2 fraction decreased with the flow, which indicated that
the CO2 sorption rate is close to the CO2 generation rate from WGS.
The level of CO2 fraction is 2 orders of magnitudes lower in the
SEMR than in the simple MR.
Since WGS reaction could be enhanced directly by the in-situ
CO2 sorption, the map of WGS reaction rate (rWGS ) in each reactor
was then graphed in Fig. 10. In MR, the WGS reaction rate decreased
in the radial direction (from membrane surface to the reactor shell),
confirming the enhancement by H2 permeation as the effect was
greater near the membrane. The decrement of WGS reaction rate in
the axial direction from the inlet to the outlet is due to the CO2
fraction increment, which reduced the WGS driving force based on
Eqn. (9). Since the overall CO2 fraction in SEMR is much lower than
that MR (Fig. 9), around 1 order of magnitude higher reaction rate
was observed for the SEMR owing to the CO2 sorption (Fig. 10).
As mentioned above for palladium-based membrane, the

Fig. 8. CH4 conversion of membrane reactor and sorption enhanced membrane reactor under different space velocities ( ). Sorption enhanced membrane reactor under 1120 h1;
( ) Simple membrane reactor under 1120 h1; ( ) Sorption enhanced membrane reactor under 2240 h1; ( ) Simple membrane reactor under 2240 h1; ( ) Sorption enhanced
membrane reactor under 3360 h1; ( ) Simple membrane reactor under 3360 h1.
890 G. Ji et al. / Energy 147 (2018) 884e895

Fig. 9. The distribution of CO2 molar fraction in membrane reactor and sorption-enhanced membrane reactor at the 100th sec.

Fig. 10. The distribution of water gas shift reaction rate in membrane reactor and sorption enhanced membrane reactor at the 100th sec.

presence of CO inhibits H2 dissociation and permeation, so the CO which is below 0.2% throughout the entire membrane length. But in
concentration level in a palladium membrane reactor is of special the simple MR reactor, the CO fraction reached up to 1.3%. Conse-
importance. Fig. 11 showed the CO molar fraction distribution in the quently, the palladium membrane suffers a higher risk of perfor-
two reactors. Significant reduction of CO fraction was seen in SEMR, mance decay.

Fig. 11. The distribution of CO molar fraction in membrane reactor and sorption enhanced membrane reactor at the 100th sec.
 G. Ji et al. / Energy 147 (2018) 884e895 891

With higher WGS reaction rates, according to Eqn. (6) the rate of
methane steam reforming would be further enhanced as a conse-
quence of lower CO fraction. This prediction was confirmed by the
methane steam reforming rate (rMSR ) in Fig. 12, which showed that
SEMR reformed methane at a faster rate than MR. If the methane
steam reforming rate at any location in SEMR is faster than that in
MR, the overall CH4 converted must be more for SEMR. This map of
methane steam reforming rate (Fig. 12) explained why SEMR
improved CH4 conversion by 37% (Fig. 8).
The main target of the whole process is to produce H2, therefore,
H2 production is of the greatest interest in methane steam
reforming. On basis of reactions (R1) and (R2), H2 yield is directly
related to the MSR and WGS rate. Figs. 12 and 10 had demonstrated
the improvement of MSR and WGS for SEMR, thus higher H2 frac-
tion could be certainly expected from SEMR. Fig. 13 displayed the
H2 fraction map of MR and SEMR. The comparison demonstrated
evident enhancement of H2 concentration in SEMR. The generated
H2 would eventually be collected in the permeate stream as pure H2
and the outlet stream as H2 rich gas. The remarkable enrichment of
H2 in the reactor would provide a higher driving force for the
membrane permeation. The calculated H2 permeation of SEMR
being 2.87  104 mol s1 was 29% higher than that of MR being
2.23  104 mol s1. In addition to the pure H2 production in the
permeate stream, the unpermeated H2 was also collected in the
meantime at the outlet stream. The H2 flow at the outlet was
8.42  105 mol s1 for SEMR and 5.67  105 mol s1 for MR. H2
dry base fraction at the outlet was 80.79 mol.% for SEMR and
34.47 mol.% for MR. Beside the pure H2 in permeate stream, the
SEMR configuration can also produce high purity H2 in the outlet
stream owing to the decline of CO, CO2 (Fig. 14b, d) and more
complete conversion of CH4.
The variations of CO2 fraction, WGS rate, CO fraction, MSR rate
and H2 fraction are plotted as curves along a line from inlet to outlet
in Fig. 14. The location of the line to extract those values is shown in
Fig. 14a. The reductions of outlet CO2 and CO were more than 95%
by deploying SEMR. The reduced CO2 and CO concentration in the
SEMR almost doubled the WGS rate and MSR rate, which made the
reactor rich in H2. The SEMR showed superior performance over
simple MR in terms of CH4 conversion, CO reduction and H2 yield.
Sensitivity analysis of operating parameters in this SEMR CFD
model is a pathway to identify how the output changes with these
operating conditions, and provides an instructive direction for
improving the reactor performance. A key operating parameter to
inspect in this study is the space velocity as it affects the CH4 re-
action time and the quantity of CH4 that the reactor processes in
unit time. Reactor pressure is another interesting parameter worth
investigating, because increasing pressure can accelerate both for-
ward reaction and reverse reaction of R1. Owning to the higher

Fig. 12. The distribution of methane steam reforming rate in membrane reactor and sorption enhanced membrane reactor at the 100th sec.

Fig. 13. The distribution of H2 molar fraction in membrane reactor and sorption enhanced membrane reactor at the 100th sec.
892
Fig. 14. The variations of CO2 fraction, WGS rate, CO fraction, MSR rate and H2 fraction along a line from inlet to outlet. (a) the location of the line to extract these variables, from
(6.625  103 m, 0 rad, 0 m) to (6.625  103 m, 0 rad, 8  102 m) in cylindrical coordinate; (b) CO2 molar fraction; (c) water gas shift reaction rate; (d) CO molar fraction; (e)
methane steam reforming reaction rate; (f) H2 molar fraction.
stoichiometric number of product gases in R1, higher pressure fa-
vors the reverse reaction. However, elevated pressure facilitates H2
membrane permeation as well as CO2 capture, hence it also favors
forward reaction of R1 by removing more H2 and CO2. Fig. 15
predicated the performance of CH4 conversion, H2 generation rate
and total H2 yield within the initial 3 min with varied space velocity
and pressure. Increasing the space velocity led to declined CH4
conversion due to the shortened reaction time. But H2 generation
rate and H2 total yield increased with space velocity as the reactor
processed more CH4 per time. Higher pressure resulted in higher
CH4 conversion which indicated that the total effect of enhanced
pressure is positive for the forward reaction. The effect of pressure
on the H2 generation rate seems more complicated (Fig. 15e). In the
initial period of around 1 s, the H2 generation rate is favored at
lower pressure, in agreement with the intrinsic nature of R1. But
after 1 s, the shift effect from the removal of H2 and CO2 started to
dominate and higher pressure provided more severe shift effect, as
a result H2 was produced at a faster rate at higher pressures. The
overall H2 yield within 3 min was enhanced gradually by elevated
pressure.
However, the advantage of SEMR only presented in limited
period. With longer time operation, the sorbents will reach to the
saturation and thus the SEMR will eventually become a simple MR.
More capital cost is required to construct a SEMR than a MR due to
the addition of sorbents. But the sorbents only occupy the space
and become functionless when they are saturated. To reuse the
sorbents, regeneration is needed, as such the reactor has to be
operated in batch system. The idea of sorption enhancement for
membrane reactor could be further improved by using moving bed
G. Ji et al. / Energy 147 (2018) 884e895
or circulating fluidized bed which could be operated in continuous
system. Therefore, the greater performance of SEMR over MR is
sustained all the time. Another issue associated with SEMR is the
sorbent regeneration is generally operated at high temperature
(>850  C) which makes the process energy intensive. Furthermore,
the possible interaction between catalyst and sorbent may affect
the performance of catalytic reaction and CO2 capture. This issue is
worth investigating in future studies.
5. Conclusions
A computational fluid dynamic (CFD) model, which allows the
access of dynamic and distributed information of reactants and
products in a sorption-enhanced membrane reactor, was developed
in this study. The model was validated by comparing the simulated
results with experimental results obtained from a membrane
reactor without CO2 sorbents. Further employment of this model
was implemented to explain the difference of reaction process
between a SEMR and the traditional MR. The results show that the
SEMR not only reduced the CO2 fraction, but also increased the
rates of MSR and WGS as well as the yield of H2. The CO fraction
level decreased by 1 order of magnitude in the sorption-enhanced
membrane reactor than the traditional membrane reactor, which
minimized the possibility of H2 permeation decay. With the
detailed information inside a reactor which is blind to experimental
measurements, this model could be used as a general tool to
analyze the reaction process and interpret reactor performance.
 G. Ji et al. / Energy 147 (2018) 884e895 893

Fig. 15. Predicted performance of SEMR at different conditions. (a) CH4 conversion at different space velocities (S/C ¼ 3; P ¼ 3 Bar); (b) H2 generation rate at different space velocities
(S/C ¼ 3; P ¼ 3 Bar); (c) H2 yield within 3 min at different space velocities (S/C ¼ 3; P ¼ 3 Bar); (d) CH4 conversion at different pressures (S/C ¼ 3; SV ¼ 3360 s1); (e) H2 generation
rate at different pressures (S/C ¼ 3; SV ¼ 3360 s1) and (f) H2 yield within 3 min at different pressures (S/C ¼ 3; SV ¼ 3360 s1).

Acknowledgement kMSR Rate coefficient of MSR, mol Pa0.5 m3 s1

kMSR;r Rate coefficient of MSR at reference temperature, mol
M. Zhao thank for the support by the National Recruitment Pa0.5 m3 s1
Program of Global Youth Experts (The National Youth 1000 e Talent kWGS Rate coefficient of WGS, mol Pa1 m3 s1
Program) of China (grant number: 20151710227) and the Tsinghua kWGS;r Rate coefficient of WGS at reference temperature, mol
University Initiative Scientific Research Program (grant number: Pa1 m3 s1
20161080094). G. Ji is grateful for the support by China Postdoctoral KCH4 Sorption coefficient for CH4, Pa1
Science Foundation (grant number: 2017M610910). KCO Sorption coefficient for CO, Pa1
KH2 Sorption coefficient for H2, Pa1
KH2 O Sorption coefficient for H2O
Nomenclature
KMSR Equilibrium constant for MSR, Pa2
KMSR;r Equilibrium constant for MSR at reference temperature,
c Gas concentration, mol m3
Pa2
ci Gas concentration of component i, mol m3
KWGS Equilibrium constant for WGS
D Diffusion coefficient, m2 s1
KWGS;r Equilibrium constant for WGS at reference temperature
DEN Adsorption factor
Ek;MSR Activation energy of rate coefficient for MSR, J mol1 l Space coordinate in membrane thickness direction, m
Mmax Maximum CO2 molar capacity
EK;MSR Activation energy of equilibrium constant for MSR, J
pCH4 CH4 partial pressure, Pa
mol1
pCO CO partial pressure, Pa
Ek;WGS Activation energy of rate coefficient for WGS, J mol1
pCO2 CO2 partial pressure, Pa
EK;WGS Activation energy of equilibrium constant for WGS, J
pH2 H2 partial pressure, Pa
mol1
pH2 O H2O partial pressure, Pa
JH2 H2 permeation flux across membrane, mol m2 s1
894 G. Ji et al. / Energy 147 (2018) 884e895

Q H2 permeability through palladium membrane, mol steam reforming in high flux membrane reactor: experimental validation,
m1 s1 Pa0.5 model predictions and membrane inhibition. Chem Eng J 2015;262:862e74.
[17] Tong J, Matsumura Y. Effect of catalytic activity on methane steam reforming
r Radial coordinate, m in hydrogen-permeable membrane reactor. Appl Catal A-Gen 2005;286:
rCO2 CO2 sorption rate, mol m3 s1 226e31.
rMSR MSR reaction rate, mol m3 s1 [18] Chen W-H, Hsieh T-C, Jiang TL. An experimental study on carbon monoxide
conversion and hydrogen generation from water gas shift reaction. Energy
rWGS WGS reaction rate, mol m3 s1 Convers Manag 2008;49:2801e8.
R Gas constant, 8.314 J mol1 K1 [19] Battersby S, Smart S, Ladewig B, Liu S, Duke MC, Rudolph V. J.C.D.d. Costa.
Hydrothermal stability of cobalt silica membranes in a water gas shift
Sct Source term for continuity equation
membrane reactor. Sep Purif Technol 2009;66:299e305.
Si Source term for component balance equation [20] Battersby S, Teixeira PW, Beltramini J, Duke MC, Rudolph V, Diniz da Costa JC.
Sr Source term in radial direction for Navier-Stokes An analysis of the Peclet and Damkohler numbers for dehydrogenation re-
equation actions using molecular sieve silica (MSS) membrane reactors. Catal Today
2006;116:12e7.
Sz Source term in axial direction for Navier-Stokes [21] Anzelmo B, Wilcox J, Liguori S. Natural gas steam reforming reaction at low
equation temperature and pressure conditions for hydrogen production via Pd/PSS
t Time, s membrane reactor. J Membr Sci 2017;522:343e50.
[22] Boon J, Pieterse JAZ, van Berkel FPF, van Delft YC, van Sint Annaland M.
T Temperature, K Hydrogen permeation through palladium membranes and inhibition by car-
ur Radial velocity, m s1 bon monoxide, carbon dioxide, and steam. J Membr Sci 2015;496:344e58.
uq Tangential velocity, m s1 [23] Chen W-H, Hsu P-C. Hydrogen permeation measurements of Pd and PdeCu
membranes using dynamic pressure difference method. Int J Hydrogen En-
uz Axial velocity, m s1 ergy 2011;36:9355e66.
z Axial coordinate, m [24] Coroneo M, Montante G, Catalano J, Paglianti A. Modelling the effect of
a Sorbent conversion operating conditions on hydrodynamics and mass transfer in a PdeAg
membrane module for H2 purification. J Membr Sci 2009;343:34e41.
q Tangential coordinate [25] Tong J, Matsumura Y, Suda H, Haraya K. Experimental study of steam
r Density, kg m3 reforming of methane in a thin (6 mm) pd-based membrane reactor. Ind Eng
rmol Molar density of sorbent in the reactor, mol m3 Chem Res 2005;44:1454e65.
[26] Battersby S, Duke MC, Liu S, Rudolph V, Costa JCDd. Metal doped silica
membrane reactor: operational effects of reaction and permeation for the
Abbreviations water gas shift reaction. J Membr Sci 2008;316:46e52.
CFD Computational fluid dynamics [27] Shokrollahi Yancheshmeh M, Radfarnia HR, Iliuta MC. High temperature CO2
sorbents and their application for hydrogen production by sorption enhanced
MR Membrane reactor steam reforming process. Chem Eng J 2016;283:420e44.
MSR Methane steam reforming [28] Zhao M, Yang X, Church TL, Harris AT. Interaction between a bimetallic NieCo
PDE Partial differential equation catalyst and micrometer-sized CaO for enhanced H2 production during cel-
lulose decomposition. Int J Hydrogen Energy 2011;36:421e31.
SEMR Sorption-enhanced membrane reactor [29] Barelli L, Bidini G, Gallorini F, Servili S. Hydrogen production through
WGS Water gas shift sorption-enhanced steam methane reforming and membrane technology: a
review. Energy 2008;33:554e70.
[30] Ochoa-Ferna ndez E, Lacalle-Vila
 C, Zhao T, Rønning M, Chen D. Experimental
References demonstration of H2 production by CO2 sorption enhanced steam methane
reforming using ceramic acceptors. In: Fa bio Bellot Noronha MS, Eduardo
[1] Saxena RC, Seal D, Kumar S, Goyal HB. Thermo-chemical routes for hydrogen Falabella S-A, editors. Studies in surface science and catalysis. Elsevier; 2007.
rich gas from biomass: a review. Renew Sust Energ Rev 2008;12:1909e27. p. 159e64.
[2] Ji P, Feng W, Chen B. Production of ultrapure hydrogen from biomass gasifi- [31] Ochoa-Fernandez E, Haugen G, Zhao T, Ronning M, Aartun I, Borresen B,
cation with air. Chem Eng Sci 2009;64:582e92. Rytter E, Ronnekleiv M, Chen D. Process design simulation of H2 production by
[3] Khonde R, Chaurasia A. Rice husk gasification in a two-stage fixed-bed sorption enhanced steam methane reforming: evaluation of potential CO2
gasifier: production of hydrogen rich syngas and kinetics. Int J Hydrogen acceptors. Green Chem 2007;9:654e62.
Energy 2016;41:8793e802. [32] van Selow ER, Cobden PD, Verbraeken PA, Hufton JR, van den Brink RW.
[4] Lee SHD, Applegate DV, Ahmed S, Calderone SG, Harvey TL. Hydrogen from Carbon capture by sorption-enhanced watergas shift reaction process using
natural gas: part Idautothermal reforming in an integrated fuel processor. Int hydrotalcite-based material. Ind Eng Chem Res 2009;48:4184e93.
J Hydrogen Energy 2005;30:829e42. [33] García-García FR, Leo n M, Ordo n~ ez S, Li K. Studies on wateregas-shift
[5] Ross JRH. Natural gas reforming and CO2 mitigation. Catal Today 2005;100: enhanced by adsorption and membrane permeation. Catal Today
151e8. 2014;236(Part A):57e63.
[6] Jin H, Lu Y, Liao B, Guo L, Zhang X. Hydrogen production by coal gasification in [34] Soria MA, Tosti S, Mendes A, Madeira LM. Enhancing the low temperature
supercritical water with a fluidized bed reactor. Int J Hydrogen Energy wateregas shift reaction through a hybrid sorption-enhanced membrane
2010;35:7151e60. reactor for high-purity hydrogen production. Fuel 2015;159:854e63.
[7] Stiegel GJ, Ramezan M. Hydrogen from coal gasification: an economical [35] Chen Y, Mahechabotero A, Lim CJ, Grace JR, Zhang J, Zhao Y, Zheng C.
pathway to a sustainable energy future. Int J Coal Geol 2006;65:173e90. Hydrogen production in a sorption-enhanced fluidized-bed membrane
[8] Woodbridge TC, Woodbridge DD. Ocean hydrogen for launch operations. Int J reactor: operating parameter investigation. Ind Eng Chem Res 2014;53:
Hydrogen Energy 1996;21:81e6. 6230e42.
[9] Martinez-Frias J, Pham A-Q, Aceves SM. A natural gas-assisted steam elec- [36] Chen Z, Po F, Grace JR, Jim Lim C, Elnashaie S, Mahecha-Botero A, Rakib M,
trolyzer for high-efficiency production of hydrogen. Int J Hydrogen Energy Shirasaki Y, Yasuda I. Sorbent-enhanced/membrane-assisted steam-methane
2003;28:483e90. reforming. Chem Eng Sci 2008;63:170e82.
[10] McLellan B, Shoko E, Dicks AL, Diniz da Costa JC. Hydrogen production and [37] Koukou MK, Papayannakos N, Markatos NC. On the importance of non-ideal
utilisation opportunities for Australia. Int J Hydrogen Energy 2005;30: flow effects in the operation of industrial-scale adiabatic membrane re-
669e79. actors. Chem Eng J 2001;83:95e105.
[11] Adanez J, Abad A, Garcia-Labiano F, Gayan P, de Diego LF. Progress in [38] Ji G, Wang G, Hooman K, Bhatia S, Diniz da Costa J. Computational fluid dy-
chemical-looping combustion and reforming technologies. Prog Energy namics applied to high temperature hydrogen separation membranes. Front
Combust Sci 2012;38:215e82. Chem Sci Eng 2012;6:3e12.
[12] Fernandez E, Coenen K, Helmi A, Melendez J, Zun ~ iga J, Pacheco Tanaka DA, van [39] Xu J, Froment GF. Methane steam reforming, methanation and water-gas
Sint Annaland M, Gallucci F. Preparation and characterization of thin-film shift: I. Int. kinetics. AlChE J 1989;35:88e96.
PdeAg supported membranes for high-temperature applications. Int J [40] Hou K, Hughes R. The kinetics of methane steam reforming over a Ni/a-Al2O
Hydrogen Energy 2015;40:13463e78. catalyst. Chem Eng J 2001;82:311e28.
[13] Yun S, Ted Oyama S. Correlations in palladium membranes for hydrogen [41] Iulianelli A, Liguori S, Wilcox J, Basile A. Advances on methane steam
separation: a review. J Membr Sci 2011;375:28e45. reforming to produce hydrogen through membrane reactors technology: a
[14] Ballinger B, Motuzas J, Smart S, Diniz da Costa JC. Palladium cobalt binary review. Catal Rev 2016;58:1e35.
doping of molecular sieving silica membranes. J Membr Sci 2014;451:185e91. [42] Xu J, Froment GF. Methane steam reforming: II. Diffusional limitations and
[15] Ji G, Smart S, Bhatia SK, Diniz da Costa JC. Improved pore connectivity by the reactor simulation. AlChE J 1989;35:97e103.
reduction of cobalt oxide silica membranes. Sep Purif Technol 2015;154: [43] Holleck GL. Diffusion and solubility of hydrogen in palladium and
338e44. palladiumesilver alloys. J Phys Chem 2002:74.
[16] Patrascu M, Sheintuch M. On-site pure hydrogen production by methane [44] Ward TL, Dao T. Model of hydrogen permeation behavior in palladium
 G. Ji et al. / Energy 147 (2018) 884e895
membranes. J Membr Sci 1999;153:211e31.
[45] Radfarnia HR, Iliuta MC. Application of surfactant-template technique for
preparation of sodium zirconate as high temperature CO2 sorbent. Sep Purif
Technol 2012;93:98e106.
[46] Zhao T, Ochoa-Ferna ndez E, Rønning M, Chen D. Preparation and high-
temperature CO2 capture properties of nanocrystalline Na2ZrO3. Chem
Mater 2007;19:3294e301.
rreca-Corte I, Fregoso-Israel E, Pfeiffer H. CO2 absorption on Na2ZrO3: A
[47] Alce
kinetic analysis of the chemisorption and diffusion processes. J Phys Chem C
2008;112:6520e5.
[48] Martínez-dlCruz L, Pfeiffer H. Cyclic CO2 chemisorptionedesorption behavior
of Na2ZrO3: structural, microstructural and kinetic variations produced as a
function of temperature. J Solid State Chem 2013;204:298e304.
[49] Zhao T, Rønning M, Chen D. Preparation of nanocrystalline Na2ZrO3 for high-
temperature CO2 acceptors: chemistry and mechanism. J Energy Chem
895
2013;22:387e93.
[50] Martínez-dlCruz L, Pfeiffer H. Microstructural thermal evolution of the Na2CO3
phase produced during a Na2ZrO3eCO2 chemisorption process. J Phys Chem C
2012;116:9675e80.
[51] Santill
an-Reyes GG, Pfeiffer H. Analysis of the CO2 capture in sodium zirconate
(Na2ZrO3). Effect of the water vapor addition. Int J Green Gas Con 2011;5:
1624e9.
[52] Memon MZ, Zhao X, Sikarwar VS, Vuppaladadiyam AK, Milne SJ, Brown AP,
Li J, Zhao M. Alkali metal CO2 sorbents and the resulting metal carbonates:
potential for process intensification of sorption-enhanced steam reforming.
Environ Sci Technol 2017;51:12e27.
[53] Sutton D, Kelleher B, Ross JRH. Review of literature on catalysts for biomass
gasification. Fuel Process Technol 2001;73:155e73.
[54] Tong J, Matsumura Y. Pure hydrogen production by methane steam reforming
with hydrogen-permeable membrane reactor. Catal Today 2006;111:147e52.