Journal of Natural Gas Science and Engineering 2 (2010) 105e113

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Journal of Natural Gas Science and Engineering

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3D Simulation of bubbling fluidized bed reactors for sorption enhanced steam

methane reforming processes
Yuefa Wang, Zhongxi Chao, Hugo A. Jakobsen*
Department of Chemical Engineering, Norwegian University of Science and Technology, NTNU, Sem Sælands vei 4, NO-7491 Trondheim, Norway

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

Article history: Hydrogen production by the Sorption Enhanced Steam Methane Reforming (SE-SMR) process was
Received 18 February 2010 studied with a numerical two-fluid model. The process was simulated in a three dimensional bubbling
Received in revised form fluidized bed reactor. The effects of pressure, steam-to-carbon ratio and inlet gas flow rate on the
19 April 2010
reactions are studied. High pressure and low steam-to-carbon ratio will decrease the conversion of
Accepted 19 April 2010
methane. But the high pressure makes the adsorption of CO2 faster. Compared to the standard SMR
Available online 14 May 2010
process, the methane conversion and heat utility are enhanced by CO2 adsorption. The CO2 produced in
the methane reforming process is adsorbed almost totally in a relative long period of time in the
Keywords:
Methane reforming
bubbling fluidized bed. It means that the adsorption rate of CO2 is fast enough compared with the SMR
Carbon dioxide capture rate. In a certain range of gas flow rates, the mass transfer and reaction kinetics can reach the equilib-
SE-SMR rium, and the reaction efficiency is independent of gas flow rate. The temperature distribution is almost
CaO sorbent uniform over the whole reactor.
3D simulation Ó 2010 Elsevier Ltd. All rights reserved.
Fluidized bed

1. Introduction CH4 þ H2 O5CO þ 3H2 DH298 ¼ 206 kJ=mol (1)

Natural gas is both an important source of energy and an

important precursor for chemical materials. Compared to other
fossil fuels, natural gas is a clean energy which produces negligible
emissions of carcinogen mutagenic hydrocarbon species in
combustion (Barros Zárante and Sodré, 2009). The carbon dioxide is
the main product in the natural gas combustion. However, with the
increasing impact of global warming caused mostly by increasing
concentrations of greenhouse gases, the emission control of CO2 as
the most important anthropogenic greenhouse gas was concerned
by many researchers. Hydrogen is considered to be a potential clean
energy source. As a raw material of chemical industry, natural gas
can be converted to hydrogen and synthesis gas by the steam
methane reforming (SMR) process (Al-Qahtani, 1997; Pedernera
et al., 2007).
Actually, there are several ways of catalytic reforming of
methane to produce hydrogen, i.e. steam reforming, dry reforming,
oxidative reforming, and autothermal reforming, by using Ni-based
catalyst. The steam reforming of methane is the main industrial
route (Ávila-Neto et al., 2009). It usually includes the following
three reactions:
* Corresponding author.
E-mail address: jakobsen@chemeng.ntnu.no (H.A. Jakobsen).
CO þ H2 O5CO2 þ H2 DH298 ¼ 41 kJ=mol (2)
CH4 þ 2H2 O5CO2 þ 4H2 DH298 ¼ 165 kJ=mol (3)
Xu and Froment (1989) developed a model for the SMR reaction
kinetics considering all the three reactions as independent,
although at equilibrium the third reaction is dependent as it is the
sum of the first two reactions. It is an endothermic process usually
carried out at high temperature of 1000e1200 K and pressure of
20e35 bar (Rusten et al., 2007a).
Recently the process of sorption enhanced steam methane
reforming (SE-SMR) is becoming an important topic due to its
integration of hydrogen production and CO2 separation. In this
process, carbon dioxide is captured by an on-line sorbent, and the
chemical equilibrium is shifted to the product side of the SMR
reaction. Therefore, the product obtained may be almost pure
hydrogen (Han and Harrison, 1994). The carbon dioxide adsorbed
by the sorbent can be separated from sorbent by desorption later
for storage or other treatment. The SE-SMR reactions can proceed at
temperatures of about 200 C lower than that for standard SMR
process (Hufton et al., 1999). The integration of heat between the
exothermic sorption reaction and the endothermic reforming
reactions improves the energy efficiency of the SE-SMR process.
The regeneration of the sorbent requires the largest energy supply

1875-5100/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jngse.2010.04.004
106 Y. Wang et al. / Journal of Natural Gas Science and Engineering 2 (2010) 105e113

considering both the SE-SMR and regeneration processes. However,
considering the SE-SMR reactor unit solely, the energy supply by
the sorption reaction and by the circulating hot solid particles from
the regeneration vessel is important to avoid considerable addi-
tional energy supply requirements for the SE-SMR reactor unit. The
overall heat integration including regeneration must be considered
in future investigations. In the SE-SMR process, the performances of
the sorbents and the reactors are the main factors studied in the
current investigations. Ca-based sorbents are more widely studied
and used because of their high CO2 capacity and rapid reaction, as
well as lower cost (Balasubramanian et al., 1999; Lopez Ortiz and
Harrison, 2001; Yi and Harrison, 2005; Grasa and Abanades,
2006; Sun et al., 2008). Lithium-containing materials were inves-
tigated recently as CO2 sorbent due to its promising stability and
high adsorption capacity (Xiong et al., 2003; Kato et al., 2004;
Kimura et al., 2005; Lindborg and Jakobsen, 2009). However,
kinetic limitations and high cost are the main drawback of Lithium-
based sorbents (Ochoa-Fernandez et al., 2005). A CaO-based CO2
sorbent is used in this study. The adsorption reaction is:
This paper is focused on the performances of the SE-SMR
process with CaO sorbent conducted in a bubbling fluidized bed
reactor. A 3D numerical two-fluid model was developed to imple-
ment our work. The bubbling regime in the beds provided a rela-
tively long residence time and low rates of attrition for sorbent
because of the low gas and particle velocities.
2. Models
2.1. Hydrodynamic model
The two-fluid model is a popular approach for dense gas-solid
systems. Kinetic theory of granular flow (KTGF) is applied to obtain
the governing equations and closures of the particle phase while
retaining the standard Eulerian formulation for the continuous
phase. The mass balance, species mass balance and momentum
balance equations of the particle phase have a similar form as those
of the gas phase, as shown in Eqs. (5)e(7):

v
CaO þ CO2 5CaCO3 DH298 ¼ 178 kJ=mol (4) ða r Þ þ V$ðak rk vk Þ ¼ Gk k ¼ c; d (5)
vt k k

v



It is an exothermic reaction being able to provide a large part of the
energy required by the steam reforming reactions. ar6 þ V$ ak rk vk 6k;j ¼ V$ ak rk Deff
k;j V6k;j
vt k k k;j
The fixed bed reactors have been used since 1930s and are
currently widespread for tranditional SMR process. At the early þ Mj Rij k ¼ c; d ð6Þ
stages of the SE-SMR research, most studies on the reactor
performance for the SE-SMR process were focused on fixed bed v
ða r v Þ þ V$ðak rk vk vk Þ ¼  ak Vp þ V$sk þ ak rk g
reactors both in experiments (Hufton et al., 1999; Balasubramanian vt k k k
et al., 1999; Lopez Ortiz and Harrison, 2001; Yi and Harrison, 2005; þ Mk k ¼ c; d ð7Þ
Li et al., 2006) and in numerical simulations (Ding and Alpay, 2000;
Xiu and Rodrigues, 2002; Lee et al., 2004; Ochoa-Fernández et al., The KTGF postulates that the dispersed particulate phase (granular
2005; Rusten et al., 2007a,b; Li and Cai, 2007). material) can be represented by a collection of identical, smooth,
In view of the adsorption/regeneration cycles of sorbents rigid spheres with similarities to gas molecules (Jakobsen, 2008).
needed in SE-SMR process, the fixed bed reactors must be switched The granular temperature was difined as the mean kinetic energy of
periodically between two operating conditions, and the heat inte- the particle fluctuations to describe the random motion of the
gration is not sufficient to avoid cold spots at the inlet area. Such granular particles. The governing equation for the granular
operation is not preferable for industrial purpose. The solid parti- temperature is:
cles can be circulated between two reactors continuously in the  
3 v
fluidized bed reactors. Thus fluidized bed reactors are favorable for ðad rd QÞ þ V$ðad rd vd QÞ ¼ sd : Vvd þ V$ðkd VQÞ
SE-SMR process thanks to the continuous operation, as well as 2 vt
D E 3
effective heat transfer, thereby temperature uniformity, and low  g  3bQ þ b v ~ 0c $Cd þ Gk Q ð8Þ
mass transfer resistance (Lindborg and Jakobsen, 2009). 2
The experimental results of CaO carbonation in a pilot-scale Molecular temperature equations for gas and particle phase are
fluidized-bed reactor by Abanades et al. (2004) showed that high as follows:
CO2 capture efficiencies from combustion flue gas are obtained in
a fluidized bed. Hughes et al. (2004) investigated cyclic carbonation DTc

and calcination reactions for CO2 capture from combustion and
ac rc Cp;c ¼ V$ ac keff i
c VTc þ Qc (9)
Dt
gasification processes. Their approach may reduce the CO2 emis-
sions from coal- and petroleum coke-fired fluidized bed combus- DTd
 X

tors by up to 85%.
ad rd Cp;d ¼ V$ ad keff
d VTd þ DHiR RR;i
i
 Qci (10)
Dt i
Several papers have reported studies on the performance of the SE-
SMR process in fluidized bed reactors. Prasad and Elnashaie (2004) The standard ke3 turbulence models are used to describe the gas
proposed a circulating fluidized-bed membrane reactor for steam phase turbulence quantities (Pfleger et al., 1999). The drag corre-
methane reforming with CO2 sequestration using the CO2-lime reac- lation of Benyahia et al. (2006) is used in this work to account for
tion, and studied the reactor performance with a one-dimensional the gas-solid interactions.
model. Johnsen et al. (2006a) conducted an experimental investiga- Constitutive equations for internal momentum transfer are
tion on reforming and sorbent calcination in cyclic operation in given in Table 1.
a bubbling fluidized bed reactor. Johnsen et al. (2006b) studied the SE- The KTGF model only accounts for particle streaming and short
SMR and sorbent regeneration processes conducted continuously in term particle-particle contacts. However, in dense flows of particles
two coupled bubbling beds with a homogeneous model. Lindborg and as in the bubbling fluidized bed, the frictional stresses have
Jakobsen (2009) studied the process performance and analyzed the significant effects on the hydrodynamic properties of the two
reactor design for SE-SMR in a bubbling fluidized bed reactor by using phases (Boemer et al., 1997; Lu et al., 2004; Patil et al., 2005). In this
a two-dimensional model, and pointed out that investigations of SE- paper the kinetic-frictional stress model was used for particle
SMR process using a three-dimensional multifluid model are needed. phase. This effective particulate stress tensor is assumed equal to
 Y. Wang et al. / Journal of Natural Gas Science and Engineering 2 (2010) 105e113 107

Table 1 Table 2
Constitutive equations for internal momentum transfer. Constitutive equations for internal heat and mass transfer.

Gas phase stress: Effective conductivity:

sc ¼ 2ac mc Sc (11) mtk
keff m
k ¼ kk þ (28)
Solid phase stress: rk Prt

sd ¼ ð  pd þ ad zd V$vk ÞI þ 2ad md Sd (12) Molecular conductivity (Bauer and Schlünder, 1978):

Deformation rate: k0c pffiffiffiffiffiffi

km
c ¼ ð1  ad Þ (29)
1
 1 ac
Sk ¼ Vvk þ ðVvk ÞT  ðV$vk ÞI (13)
2 3 k0c
Solid phase bulk viscosity (Lun et al., 1984): d ¼ pffiffiffiffiffiffiðfA þ ð1  fLÞÞ
km
ad
(30)
rffiffiffiffi
4 Q " #
zd ¼ ad rd dd g0 ð1 þ eÞ (14) 2 A1 B A B1 1
3 p L ¼ ln   ðB þ 1Þ
1  B=A ð1  B=AÞ2 A B 1  B=A 2
Conductivity of the granular temperature:
10=9
rffiffiffiffi k0 a
 2 A ¼ d0 ; B ¼ 1:25 d ; f ¼ 7:26  103 ð31Þ
15 mdilute 6 Q kc ac
kd ¼ d
1 þ ad g0 ð1 þ eÞ þ2a2d rd dd g0 ð1 þ eÞ (15)
2 g0 ð1 þ eÞ 5 p
Effective diffusivity:
Collisional energy dissipation (Jenkins and Savage, 1983):
rffiffiffiffi ! mtk

 4 Q Deff m
k;j ¼ Dk;j þ (32)
g ¼ 3a2d rd g0 Q 1  e2  V$vd (16) rk Sct
dd p
Molecular diffusion coefficient (Wilke, 1950):
Radial distribution function (Ma and Ahmadi, 1986):
16
Dm
c;j ¼ P 6j (33)
1 þ 2:5ad þ 4:5904a2d þ 4:515439a3d Mm
g0 ¼ h
3 i0:67802 (17) Mj Dij
jsi
1  aamax
d
d
Binary diffusion coefficient (Fuller et al., 1966):
Dilute viscosity (Gidaspow, 1994): qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
pffiffiffiffiffiffiffi Tc1:75 1=Mj þ 1=Mi
5 Dij ¼
mdilute ¼ r d Qp (18) h P P 1=3 i2
(34)
d 96 d d 1=3
101:325P ð VÞj þ ð VÞi
Dissipation of granular energy due to fluid turbulence (Lindborg et al., 2007):
D E b2 dp jvd  hvc ij2 Rs
b v~0c $Cd ¼ pffiffiffiffiffiffiffi (19)
4a4c ad rd pQ
1
Rs ¼  pffiffiffiffiffiffi  (20) The internal heat and mass transfer equations can be found in Table 2.
g0 1 þ 3:5 ad þ 5:9ad
The constitutive equations concerning the interfacial momentum
and heat coupling are given in Table 3. More detailed descriptions
of the model and solution methods can be found in Lindborg et al.
the sum of the kinetic stress tensor and the frictional stress tensor
(2007) and Lindborg and Jakobsen (2009).
(Srivastava and Sundaresan, 2003):

sd ¼ sk;c
d
þ sd
f
(21) 2.2. Chemical model

Thus the solid pressure and viscosity were calculated by the Steam methane reforming on nickel-based catalysts is the main
following equations: process for industrial production of hydrogen or synthesis gas.
Numerous studies have been reported on the kinetics of these
pd ¼ pk;c
d
þ pfd (22) reactions (Akers and Camp, 1955; Allen et al., 1975; Hou and
Hughes, 2001). Xu and Froment (1989) investigated a large
md ¼ mk;c
d
þ mfd (23) number of detailed mechanisms and derived the intrinsic rate
equations for the steam reforming of methane on nickel-alumina
The kinetic and collisional pressure (Lun et al., 1984) and the
viscosity (Gidaspow, 1994) are:
Table 3
d ¼ ad rd Q½1 þ 2ð1  eÞad g0 
pkc (24) Interfacial momentum and heat transfer equations.

 2 rffiffiffiffi Interfacial force:

2mdilute 4 4 Q Mc [  Md ¼ FD ¼ bðvd  vc Þ
mkc ¼ d
1 þ ad g0 ð1 þ eÞ þ ad rd g0 ð1 þ eÞ (25) (35)
d ad g0 ð1 þ eÞ 5 5 p Interfacial heat transfer (spherical particles):
Frictional pressure (Johnson et al., 1990) and viscosity (Ocone 6ad
Qc ¼ h ðT -Tc Þ (36)
et al., 1993) are: dd cd d

8 r
Interfacial heat transfer coefficient (Gunn, 1978):
< F ðad amin
d Þ
if ad > amin kc h


pfd
s
¼ ðamax ad Þ d (26) hcd ¼ 7  10ac þ 5a2c
1 þ 0:7Re0:2
p Pr
1=3
: d
ad
0 if ad  amin d

 i
þ 1:33  2:4ac þ 1:2a2c Re0:7
p Pr
1=3
ð37Þ

f pffiffiffi Particle Reynolds number and Prandtl number:

pd 2sinf
mfd ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi (27) ac rc jvd  vc jdd m Cp;c
Rep ¼ ; Prp ¼ c (38)
2ad Sd : Sd þ Q=d2p mc kc
108 Y. Wang et al. / Journal of Natural Gas Science and Engineering 2 (2010) 105e113

catalysts which have been widely used. Their rate equations were
also used in our simulations:
" #
3
k1 pCH4 pH2 O  pH2 pCO =K1
R1 ¼ 2:5 (39)
p H2 DEN2

 
k2 pCO pH2 O  pH2 pCO2 =K2
R2 ¼ 2
(40)
p H2 DEN
" 2 4
#
k1 pCH4 pH2 O  pH2 pCO2 =K3
R3 ¼ 3:5 (41)
p H2 DEN2

where

DEN ¼ 1 þ KCO pCO þ KH2 pH2 þ KCH4 pCH4 þ KH2 O pH2 O =pH2 (42)
R1, R2 and R3 correspond to the reactions (1), (2) and (3) respectively.
The rate equation for CO2 adsorption by the CaO sorbent is taken
from Sun et al. (2008):

dX
n
Ra ¼ ¼ 56ka ð1  XÞ pCO2  pCO2;eq S (43) Fig. 1. Instantaneous contour of voidage (a) and solid velocity vector profiles (b) in
dt a vertical plane in the bubbling fluidized bed (u0 ¼ 0.3 m/s, T ¼ 848 K, rsc ¼ 5:1,
where n is the reaction order with the following values: p ¼ 1 bar).

n ¼ 1 when pCO2  pCO2 ;eq  10 KPa

n ¼ 0 when pCO2  pCO2 ;eq > 10 KPa of solids hence the solid circulation flux is zero. The gas phase
consisting of CH4 and steam flows into the reactor from the bottom
uniformly and flows out of the reactor from the top of the reactor.
Figs. 2 and 3 give the dry concentration profiles of the components
3. Results
along the axis for SMR and SE-SMR respectively. The temperature
and pressure are 848 K and 1 bar. The superfacial inlet gas velocity
The catalytic steam methane reforming reactions and the CO2
is 0.3 m/s, and the steam-to-carbon ratio is 5.
adsorption by sorbent are performed simultaneously in the
In the SMR results, the outlet concentration of H2 is only 76%,
bubbling flow regime to provide sufficient residence time for the
and a lot of CO2 is emitted out of the reactor. However in the
solid phase processes. The solid phase consists of the identical
simulations of SE-SMR process, both the conversion of methane
particles. The catalyst and the sorbent are assumed to be mixed
and the adsorption of CO2 are larger than 99% even after 210 s. In
uniformly in the particles with the same mass ratio. Table 4 lists the
this case the amount of CO2 produced in methane reforming
simulation parameters.
reactions can be considered to be adsorbed totally by the sorbent,
the methane reforming and hydrogen production are greatly
3.1. Hydrodynamics of the bubbling fluidized bed
enhanced. The sorbent capacity is large enough for the simulated
conditions.
The model is built up and solved in three-dimensional cylin-
drical coordinates. Fig. 1 presents the contour of the voidage and
the solid velocity vector profiles in an vertical plane. The simulation
results revealed the heterogeneous structure of the bed and the
non axial symmetric behavior of the solid flow.

3.2. Comparison between SE-SMR and standard SMR

The CO2 adsorption by CaO was carried out in a bubbling

fluidized bed. The solid particles are restrained in a constant
amount in the bubbling fluidized bed reactor. There is no exchange

Table 4
Simulation parameters.

Particle diameter 500 mm

Particle density 1500 kg/m3
Initial bed height 1.2 m
Initial solid fraction 0.58
Reactor size R ¼ 0.1 m, z ¼ 4 m
Grid cell number 10  12  80 (BFB)
Time step 1  104s
Convergence criterion krm k < 3kbk 3 ¼ 1010
Sorbent capacity 0.25 g(CO2)/g (CaO)
Fig. 2. Axial distributions of components concentration in gas phase in the bubbling
Sorbent-to-catalyst mass ratio 4
fluidized bed for the standard SMR process at time 49 s.
 Y. Wang et al. / Journal of Natural Gas Science and Engineering 2 (2010) 105e113
Fig. 3. Axial distributions of components concentration in gas phase and CO2 concentration in solid phase in the bubbling fluidized bed for SE-SMR process at time 210 s.
3.3. Influence of pressure
Figs. 4e7 show the different effects of the reaction pressure on
the SMR and SE-SMR process. The concentrations of methane and
hydrogen are increased and decreased respectively with increasing
the pressure in both processes. However the change in SMR is much
larger than that in SE-SMR (Figs. 4 and 6). The smaller effects of
pressure in the SE-SMR process may be owing to the CO2 adsorp-
tion by the sorbents. CO2 adsorption can make the conversion of
methane almost complete and counteract the influence of the
higher pressure. The CO2 concentrations in the gas phase decreased
with increasing pressure in both the SMR and SE-SMR processes,
but to a less degree (Fig. 5). This trend is due to the combined effects
of lower methane conversion and higher CO2 adsorption rate by
sorbents at higher pressure. Fig. 7 shows that the adsorption rate of
carbon dioxide by sorbents is higher at higher pressure. It is
a natural result of the adsorption process.
Fig. 4. Average outlet concentration of methane for SMR and SE-SMR at different
pressures (u0 ¼ 0.3 m/s, T ¼ 848 K, rsc ¼ 5:1).
109
3.4. Influence of steam-to-carbon ratio
Steam-to-carbon ratio is an important factor for the steam
methane reforming reactions because it may influence the equi-
librium of these reactions.
For the SE-SMR process, the outlet methane concentration is
increased a little (from 0.3% to 0.7%) when the steam-to-carbon
ratio is decreased from 5 to 4, but increased much more (from 0.7%
to 3%) when the steam-to-carbon ratio is decreased from 4 to 3
(Fig. 8(a)). A similar effect was obtained for the hydrogen concen-
tration, the variation is about the same but the changes are in the
opposite direction (Fig. 8(b)). However, the outlet concentration of
carbon dioxide was less influenced by the steam-to-carbon ratio as
shown in Fig. 9(a). The CO2 concentration within the sorbents
decreased with the increasing steam-to-carbon ratio (Fig. 9(b)).
For the standard SMR process, the effects of steam-to-carbon
ratio on the reactions are much larger than that in SE-SMR process.
Fig. 5. Average outlet concentration of carbon dioxide for SMR and SE-SMR at different
pressures (u0 ¼ 0.3 m/s, T ¼ 848 K, rsc ¼ 5:1).
110 Y. Wang et al. / Journal of Natural Gas Science and Engineering 2 (2010) 105e113

Fig. 6. Average outlet concentration of hydrogen for SMR and SE-SMR at different
pressures (u0 ¼ 0.3 m/s, T ¼ 848 K, rsc ¼ 5:1).
Fig. 8. Average outlet concentrations of methane (a) and hydrogen (b) for both
SMR and SE-SMR at different steam-to-carbon ratios (p ¼ 1 bar, u0 ¼ 0.3 m/s, T ¼ 848 K,
All concentrations of methane, hydrogen and carbon dioxide in gas t ¼ 49 s).
phase changed clearly with the variation of steam-to-carbon ratio.
The reason may be that the integration of CO2 adsorption to SMR
promoted the conversion of methane largely. This effect and the in
situ removal of CO2 weaken the influence of steam-to-carbon ratio
to the reforming reactions in the SE-SMR process.

3.5. Influence of inlet gas flow rate

In order to simulate the bubbling flow at higher gas flow rates,

the particles of higher density 2400 kg/m3 was used in this part.
The diameter of particles is still 500 mm. Fig. 10 shows that the
components concentrations in the gas phase are almost the same
for different gas flow rates after the initial unstable period (about
10s). Actually, the concentrations of methane and CO2 are close to
zero (0.6% and 0.3% respectively), and that of hydrogen is near 99%.
In this case the methane reforming, the CO2 adsorption can be
considered completed for all gas flow rates investigated. It indicates
the mass transfer and reaction kinetics are fast enough to reach
equilibrium under the simulated conditions.
The CO2 adsorption rate is increased as the gas flow rate
increased (Fig. 11). This trend occurs because the reaction rate of
Fig. 9. Average outlet concentration of carbon dioxide for SMR and SE-SMR (a) and
CO2 adsorption depends on the partial pressure of CO2 and the carbon dioxide fractionin sorbents for SE-SMR (b) at different steam-to-carbon ratios
specific surface area of sorbent. At the reactor startup and at lower (p ¼ 1bar, u0 ¼ 0.3 m/s, T ¼ 848 K, t ¼ 49 s).
gas flow rates, the SMR CO2 production rate is relatively low, thus

Fig. 7. Average concentration of carbon dioxide in sorbents for SE-SMR at different Fig. 10. Average outlet concentration of hydrogen (a) and carbon dioxide (b) for SE-
pressures (u0 ¼ 0.3 m/s, T ¼ 848 K, rsc ¼ 5:1). SMR at different inlet gas flow rates (p ¼ 1 bar, T ¼ 848 K, rsc ¼ 5:1).
 Y. Wang et al. / Journal of Natural Gas Science and Engineering 2 (2010) 105e113 111

process in the fluidized bed is quite uniform since the released heat
by CO2 adsorprion is close to the absorbed heat by methane
reforming, and the gas and solid phases in the bubbling bed are
well-mixed.

4. Conclusion

The temperature distribution is quite uniform in the bubbling

fluidized bed reactors for the SE-SMR reactions due to the heat
integration of the SMR and the CO2 capture processes. The Higher
pressure is favorable for adsorption of CO2, but unfavorable for
methane reforming.
The steam-to-carbon ratio is important to the conversion of
methane in the reactor. Sufficient steam concentration in the feed is
a necessary condition for complete conversion of methane. When
the ratio is lower than 4, the conversion of methane is reduced
markedly.
Fig. 11. Average concentration of carbon dioxide in sorbents for SE-SMR at different Under the investigated conditions, the reaction efficiency is
inlet gas flow rates (p ¼ 1 bar, T ¼ 848 K, rsc ¼ 5:1). independent of the inlet gas flow rate. This trend occurs because
the mass transfer and reaction kinetics are fast enough to reach the
the partial pressure of CO2 in the gas phase is low and only a frac- chemical equilibrium. The production time will decrease with
tion of the surface area of the sorbent is occupied by CO2. Under increasing gas flow rates.
these SMR conditions the adsorption rate is low and far from its The simulation results show that the integration of CO2 sorption
equilibrium. As a result, the adsorption rate will increase with the into the SMR process can increase the methane conversion to about
increase of partial pressure of CO2 at the higher gas flow rates. A 100% and allows more effective energy utility. The adsorption rate
higher adsorption rate will reduce the time to reach the equilibrium of CO2 is fast enough compared with the SMR rate to completely
of the adsorption, thus decrease the total production time for the adsorb the CO2 produced in the bubbling fluidized bed investigated.
same amount of sorbents. Similar conclusions were drawn by
Johnsen et al. (2006a) evaluating experimentally the effects of Acknowledgement
variations in the superficial gas velocity.
The PhD fellowship (Chao, Z.) financed through the GASSMAKS
program (Advanced Reactor Modeling and Simulation) and the Post
3.6. Temperature distribution
doc fellowship (Wang, Y.) financed through the RENERGI program
(Hydrogen Production by Sorbent Enhanced Reforming) of the
Fig. 12 presents the temperature distributions in SE-SMR
Norwegian Research Council are gratefully appreciated.
process. The temperature of the inlet gas was set to 848 K. As the
gas goes through the bed, the SMR and adsorption reactions take
Nomenclature
place, the temperature decreased gradually to about 845.5 K. It
means that the CO2 adsorption can supply some of the heat
required by the SMR reactions, but still not enough under the Latin letters
simulated conditions. After a peak value in the bed at about 0.2 m CD drag coefficient for a particle
above the inlet, the temperature increased to about 847.5 K at the Cp,k heat capacity of phase k
upper surface, which is possibly a result of a reduction of the SMR s
CCO CO2 fraction in sorbent
reaction rates. As a whole, the temperature distribution for SE-SMR 2
dd, dp particle diameter
Dji binary diffusion coefficient
Dk,j diffusion coefficient for component j in phase k
e coefficient of restitution
F constant
g gravity
g0 radial distribution function
hcd interfacial heat transfer coefficient
HiR reaction enthalpy for reaction i
k rate coefficient
kk thermal conductivity of phase k
K1, K2, K3 equilibrium constant
KY adsorption constants for component Y (Y ¼ CH4, CO2, H2,
H2O)
M mole mass
Qki interfacial heat transfer to phase k
n reaction order of CO2 adsorption
p pressure
pd particle pressure
Fig. 12. (a) Temperature distribution in a vertical cross section, (b) average axial
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112 Y. Wang et al. / Journal of Natural Gas Science and Engineering 2 (2010) 105e113

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