international journal of hydrogen energy 34 (2009) 1301–1309

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Hydrogen production from two-step steam methane

reforming in a fluidized bed reactor

Kang Seok Goa, Sung Real Sona, Sang Done Kima,*, Kyoung Soo Kangb, Chu Sik Parkb
a
Department of Chemical and Biomolecular Engineering, Energy and Environment Research Center, Korea Advanced Institute of Science
and Technology (KAIST), 335 Gwahangno, 373-1 Guseong-dong, Yuseong-gu, Daejeon 305-701, Republic of Korea
b
Hydrogen Energy Research Center, Korea Institute of Energy Research, 71-2 Jang-dong, Yuseong-gu, Daejeon, 305-343, Republic of Korea

article info abstracts

Article history: Based on the chemical looping (CL) concept, two-step steam methane reforming (SMR)
Received 27 August 2008 system with a reduction/oxidation (redox) reaction of iron oxides to produce pure
Received in revised form hydrogen is proposed. This system consists of fuel reactor (FR) and steam reactor (SR). The
24 November 2008 feasibility of producing pure hydrogen without any purifying steps in SR and the synthetic
Accepted 25 November 2008 gas (syngas, CO þ H2) to the Fisher–Tropsch reaction in FR was evaluated. The effect of
Available online 30 December 2008 reaction temperature on the redox reactivity of iron oxides was determined in thermo-
gravimetric analyzer (TGA) and the effects of gas velocity and reactant concentration on
Keywords: the reactivity at the isothermal condition in a fluidized bed reactor were determined. The
Hydrogen production conversion range of the optimum reaction (FeO / Fe3O4) in the two-step SMR system is
Steam methane reforming found to be from 0 to 0.5 based on the iron oxides. In this condition, hydrogen (H2) with CO-
Chemical looping free and synthetic gas (syngas) having the H2/(2CO þ 3CO2) molar ratio of 0.65 can be
Iron oxides obtained in SR and FR, respectively. The solid inventory ratio of FR to SR to compensate the
Fluidization difference of reaction rates in the redox system of FeO/Fe3O4 is determined to be 2.9.
ª 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
reserved.

1. Introduction CH4 þ H2 O/CO þ 3H2 ; DH+298 K ¼ þ241 kJ=mol (1)

Exothermic reaction of CO with H2O (water–gas shift reaction)

Research activities on H2 production increase rapidly since it
is an environmental friendly fuel that does not emit carbon
dioxide which is known as one of the global warming gases [1].
In particular, H2 as a fuel for the mobile and stationary power
generation by using fuel cell has a great potential to increase
H2 demand in the near future [2–4].
Steam reforming of natural gas (i.e., mainly methane) is the
most common and well developed technology used for H2
production at large scales [5,6]. This process mainly has three
parts and the simplified flow diagram of this process is shown
in Fig. 1. Desulfurized methane is catalytically reformed at the
temperature range of 970–1100 K and pressure up to 3.5 Mpa to
produce synthetic gas (syngas) mixture of CO and H2 [6]:
is then carried out to produce H2 at 470–820 K [7–10].
CO þ H2 O/CO2 þ H2 ; DH+298 K ¼ 41:1 kJ=mol (2)
As a final stage, pressure swing adsorption (PSA) is commonly
used to remove CO2 (mainly), water, methane, and CO from
the offgas. In this manner, production of H2 from conventional
SMR process has many complex reaction steps to purify H2 so
that the capital investment would be high and the process
efficiency is reduced [11,12]. Cost of WGS and PSA practically
accounts for about 30% of the total cost for producing H2 as
reported by Myers et al [13]. In this respect, many researches
are underway to produce syngas and H2 by chemical looping

* Corresponding author. Tel.: þ82 42 350 3953; fax: þ82 42 350 3910.
E-mail address: kimsd@kaist.ac.kr (S.D. Kim).
0360-3199/$ – see front matter ª 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2008.11.062
1302 international journal of hydrogen energy 34 (2009) 1301–1309
Nomenclature
AR Air reactor
CL Chemical looping
CLC Chemical looping combustion
Ci Concentration of component i, %
FR Fuel reactor
MFR Solid mass weight in the fuel reactor, kg
MSR Solid mass weight in the steam reactor, kg
n_ i Molar rate of component i, mol/s
ns Theoretical mole of oxygen corresponds to the
oxidation from FeO to Fe3O4, mol
PSA Pressure swing adsorption
SR Steam reactor
SMR Steam methane reforming
(CL) system to improve conventional SMR process [14–23].
Chemical looping concept is similar to the chemical looping
combustion (CLC) where oxygen needed to combust the fuel
can be taken from the metal oxides in a fuel reactor (FR) and
then the reduced metal oxides can be regenerated by air in air
reactor (AR). Therefore, the metal oxides in this reaction are
used as an oxygen carrier between FR and AR. As a result, CO2
can be inherently separated when the fuel is combusted
[24,25].
For production of syngas or H2 from the CL system, the
reported main studies can be summarized as: (A) partial
oxidation of methane with oxygen carrier in FR and the
recovery of heat from the product gases in AR to generate the
electric power and steam or transfer of heat from AR to FR
thorough the oxygen carrier [14–18], (B) carbonation and
calcination with carbon carrier such as dolomite to improve
the selectivity of H2 among the offgas in FR as well as the
syngas production with the oxygen carriers in (A) [14,18–20],
(C) generation of the reduced oxygen carrier from complete
oxidation of methane with the inherent separation of CO2 in
FR and the reduced oxygen carrier then reacts with steam to
produce pure H2 in SR and regeneration of itself [21]. These
reported studies on SMR with CL concept are summarized in
Table 1.
Among the above three cases, (C) has rather simple
concept for the process design since homogeneous solid
material is circulating inside the reactor. With this concept,
conventional SMR process for the production of purified
hydrogen is divided into methane oxidation and steam
reduction steps with oxygen carriers. If carbon deposition
does not take place on the surface of the solids, production of
steam
800K
Natural gas Steam
HDS/ZnO Pre-refomer
feedstock reformer
Fig. 1 – Simplified flow diagram of conventional SMR process.
WGS Water–gas shift reaction
TGA Thermo-gravimetric analyzer
T Temperature, K
t time, min
Ug Superficial gas velocity, m/s
Umf Minimum fluidizing gas velocity, m/s
W Weight of the measured sample, mg
wox Weight of the fully oxidized sample, mg
wred Weight of the fully reduced sample, mg
X Fractional conversion of metal oxides
xox Fractional oxidation conversion of metal oxides
xred Fractional reduction conversion of metal oxides
Greek symbols
6H+298 K Enthalpy of reaction at 298 K, kJ/mol
purified H2 from the steam reduction is possible without any
post-process such as WGS and PSA. Therefore, it can reduce
the purification cost significantly compared to conventional
processes.
However, researches of this concept have been sparse
based on the experimental studies but only for the conceptual
consideration [21]. Also, studies on mass transfer between gas
and solid for the mass production of H2 have not been con-
ducted. Therefore, in the present study, iron oxide was
selected as an oxygen carrier since it is environmental friendly
having relatively low cost [26] and proposed the two-step SMR
with concept (C) for production of pure H2 in SR without post-
process. In addition, gaseous products in FR can be changed
into two ways which are full or partial oxidation of methane
by iron oxides and these reactions are presented in Eqs. (3)–(5).
Complete methane oxidation
4Fe3 O4 þ CH4 /12FeO þ CO2 þ 2H2 O; DH+298 K ¼ 463:7 kJ=mol (3)
Partial methane oxidation
Fe3 O4 þ CH4 /3FeO þ CO þ 2H2 ; DH+298 K ¼ 280:9 kJ=mol (4)
Steam reduction
3FeO þ H2 O/Fe3 O4 þ H2 ; DH+298 K ¼ 74:7 kJ=mol (5)
In the partial oxidation of methane (Eq. (4)), it is noticed that
the produced syngas (CO þ H2) can be utilized as a feedstock to
the Fisher–Tropsch reaction. Although the product gas
contains some CO2, all the product gases (H2, CO, CO2) can be
converted to FT products with a H2/(2CO þ 3CO2) ratio equal to
about 1.05 [27]. In that case, the two-step SMR process can
reduce CO2 emission and produce high purity hydrogen and
HTS (620-820K)
LTS (470-520K)
H2 product
1100K
Heat Heat
Shift reactors PSA
exchanger exchanger
 international journal of hydrogen energy 34 (2009) 1301–1309 1303

Table 1 – Chemical looping researches for the improvement of SMR.

Research Class/ Process concept Process characteristics
group Research type

Wolf and A, B Extended CLC: oxygen carrier circulates along with Inherent H production
2
Yan [14] Conceptual a CO2 acceptor between three fluidized bed reactor Addition of CO acceptor (CaO) in FR
2
(Fuel / CO2 desorption / Air reactor)

Zafar et al. [15] A Integrated hydrogen and power production with Inherent CO separation
2
Experimental CO2 capture Necessary for additional processes: WGS, PSA
Ryden and A Energy for the endothermic reforming reactions The offgas from the PSA unit is used as fuel
Lyngfelt [16] Conceptual is provided by indirect combustion that takes place in the fuel reactor.
in two separate reactors: one for air and one for fuel The tubes located inside the CL fuel reactor.
Improved selectivity towards H and higher
2
reformer efficiency with CO2 capture

Ryden A Two interconnected fluidized beds for CL reforming Complete conversion of natural gas
et al. [17] Experimental High selectivity towards H and CO
2
Implementation of the continuous reaction
Duponta A, B Unmixed steam reforming: steam reforming that 90% Selectivity of H in FR using dolomite
2
et al. [18] Experimental uses separate air and fuel–steam feeds

Johnsen B Ni-based catalyst and dolomite circulate between 98–99 Vol.% hydrogen after 4 cycles at 873 K
et al. [20] Experimental reformer and regenerator Loss of CO up-take capacity of the dolomite
2

Chiesa C Three-reactors CL system, where iron oxide particles Direct production of the H and CO from
2 2
et al. [21] Conceptual are circulated to: (i) oxidize natural gas (ii) reduce steam, natural gas, by means of a process that simpler
to produce hydrogen as the final product of the process, than the conventional technologies with CO2
(iii) consume oxygen from an air stream capture capabilities

the feedstock to the FT synthesis. Simplified flow diagram of thermo-gravimetric analyzer (TGA) and the effects of gas
two-step SMR system is shown in Fig. 2. velocity and reactant concentration on the reactivity at the
For two-step SMR system, the effect of reaction tempera- isothermal condition in a fluidized bed reactor were deter-
ture on the redox reactivity of iron oxides was determined in mined. Based on composition of the product gases at the

CO2
sequestration

Heat
Eq(3)
exchanger

Syngas
product 470-520K

Heat
Natural gas exchanger FT process
HDS HDS/ZnO FR
feedstock Eq(4)
preheater
Iron oxides circulation

1070-1170 K

Some H2 moves to FR
to utilize in FT process

H2 product
Heat
Steam exchanger Purification
SR

Eq(5)

Fig. 2 – Simplified flow diagram of two-step SMR process.

1304 international journal of hydrogen energy 34 (2009) 1301–1309
optimum condition in the redox reaction, the concept and the
chemical reactions for the production of pure H2 from SR and
syngas from FR were analyzed with variation of iron oxide
conversion and the guideline for designing the continuous
process of two-step SMR system is presented.
2. Experimental
2.1. Reaction characteristics of iron oxides in
thermo-gravimetric analyzer
The redox reactions of Fe/Fe2O3 (Bayer Co.) were carried out
in thermo-gravimetric analyzer (TGA, SETARAM 92). The
sample weight of 7–8 mg (0.1–2.5 micron) and the gas velocity
of 0.08 m/s were selected to eliminate the diffusion effect on
the reaction. The maximum experimental temperature was
limited up to 1173 K which is similar to the operating
condition of conventional SMR reaction. Air was injected into
the analyzer to prevent the pre-reduction before attaining
the isothermal condition. When the desired temperature was
reached, methane with 10 Vol.% nitrogen gas was supplied
into TGA and then variation of sample weight was measured
with time. For oxidation of Fe, a sample was prepared in
advance by using hydrogen having the same conversion.
Inert gas was injected to prevent pre-oxidation before
attaining the isothermal condition. Saturated steam was
then supplied into the analyzer through a steam bubbler
at 333 K.
2.2. Experimental apparatus
A fluidized bed reactor (83 mm-ID  1350 mm-high) made of
inconel 600 pipe is schematically shown in Fig. 3. The reactor
was heated with an electric kantal wire and insulated with
ceramic fiber wool to prevent heat loss to surroundings. The
Fig. 3 – Schematic diagram of the fluidized bed reactor system.
fluidizing gas was injected into the bed via a plenum chamber
to a sintered plate distributor having 40% opening area. Before
entering the gas into the bed, a pre-heater was used in heating
the reducing gas and generating steam from water supplied by
a water pump. To measure the bed pressure, two pressure
taps were mounted flush with the wall of the reactor at 35 mm
and 145 mm above the distributor plate and pressure trans-
mitters (Sensys) were used.
2.3. Experimental procedure
To obtain stable fluidization, zirconia–silica beads (Saint-
Gobain Co. Ltd.) were added as an inert solid medium in the
fluidized bed reactor. Initially, 10 wt.% hematite (total bed
weight: 3.415 kg) was premixed with zirconia–silica beads and
then it was loaded into the bed to make a static bed height
having an aspect ratio (length/diameter) of 4. To maintain the
initial oxidation state of iron oxides to Fe3O4, first redox cycle
was carried out. To prevent the carbon deposition from the
catalytic cracking of methane [28], the reaction in this study is
limited from FeO to Fe3O4. For the reduction of iron oxides,
methane with dilution by nitrogen gas was supplied through
a mass flow controller (MKS Co. Ltd.). After finishing the
reduction step, the residue gases were purged by nitrogen gas
and then the oxidation reaction was conducted. In the
oxidation step, the injected water was evaporated in a pre-
heater at 573 K and then steam was supplied by nitrogen gas
into the reactor. Physical properties of the particles used in
this study are presented in Table 2.
2.4. Analysis of product gases and solids
The fractional conversion by the weight change in TGA is
defined as:
Fractional reduction conversion from Fe2O3 to Fe is
 international journal of hydrogen energy 34 (2009) 1301–1309 1305

Table 2 – Physical properties of iron oxides and inert

thermal medium.
Properties Symbol Dimension Fe2O3 Zirconia–
(hematite) silica bead

Particle size dp mm 0.1–2.5/0.63 63–125/90

range/mean
size
Density of r kg/m3 5180 3850
particle
Minimum Umf m/s N/A 0.0067
fluidizing
gas velocity

xred ¼ ðwox  wÞ=ðwox  wred Þ (6)

Fractional oxidation conversion from Fe to Fe2O3 is

xox ¼ ðw  wred Þ=ðwox  wred Þ (7)

where x is the fractional conversion, w is the weight of sample

at any time and wox, wred are the weights of the sample after
fully oxidized and reduced, respectively.
Concentrations of product gases from the redox reaction in
the fluidized bed was measured by infrared gas analyzer (Fuji
Co., Ltd.) to detect CH4, CO, CO2, by thermal conductivity
analyzer (Fuji Co., Ltd.) to detect H2 and H2O was calculated
from the mass balance. Composition of product gases was
also confirmed by gas chromatograph (HP 5890 series II
equipped with a Molsieve 5A and PoraPak Q column).
The fractional conversion of the product gases is defined as:
R t1  
t0
n_ CO þ 2n_ CO2 þ n_ H2 O dt
xred ¼ (8)
ns
R t1  
t0
n_ H2 dt
xox ¼ (9)
ns
where the fractional conversions of reduction and oxidation
are determined by integrating the molar evolution rate of each
components (n_ i ) with time from t0 to t1 and ns is the theoretical
oxygen mole corresponds to oxidation from FeO to Fe3O4.
The phase of iron oxides before and after reaction was
analyzed by X-ray diffractometer (XRD, D/MAX-IIIC (3 kW), Fig. 4 – Fractional (a) reduction conversion of Fe2O3 and (b)
RIGAKU). oxidation conversion of Fe at a given temperature in TGA.

3. Results and discussion more sensitive to temperature in the reduction of Fe3O4. In

3.1. Effect of the temperature on the redox reactivity of
iron oxides in TGA
The effect of temperature on the reactivity of reduction and
oxidation of iron oxides in two-step SMR process was deter-
mined in TGA as shown in Fig. 4. As can be seen, the
conversions of both reduction and oxidation increase with
increasing temperature. Also, it is found that the effect of
temperature on the reduction reactivity of iron oxides is more
pronounced than that of the oxidation due to the large
endothermic reduction reaction of Eqs. (3) and (4). The reac-
tion rate is shown to be slow in the range of 0.2–0.4 and it is
that region, the reduction rate decreases with increasing FeO
(xred ¼ 0.33) phase since FeO reduction by H2 and CO is unfa-
vorable in thermodynamic aspects [28,29]. As can be seen in
Fig. 4(a), the initial stage of reaction, Fe2O3 (at xred ¼ 0) / Fe3O4
(at xred ¼ 0.11), is very fast regardless of the reaction temper-
ature. However, the reduction temperature should be limited
above 1073 K since oxidation of iron oxides by water vapor can
reach up to Fe3O4 [30,31]. After almost complete consumption
of oxygen at 1148 K and 1173 K, carbon deposition is presented
by the catalytic methane decomposition with increasing the
sample weight as report by Cho et al. [32].
For oxidation of Fe in Fig. 4(b), the conversion increases
with increasing temperature and the reaction occurs
1306 international journal of hydrogen energy 34 (2009) 1301–1309

comparatively at lower temperatures compared to the

reduction. However, the oxidation rate is lower than the
reduction rate. At 1173 K, the reaction rate in the initial
stage is fast and levels off at the later stage. Based on the
data from TGA, the optimum working temperature in this
study is determined to be 1173 K based on the reaction
kinetics and similar operating temperature in conventional
process.

3.2. Reduction characteristics of iron oxides in the

fluidized bed reactor (FR)

Chemical looping system can be achieved in a two-step SMR

system in the fluidized bed reactor. The effect of gas velocity
on the reduction of Fe3O4 in the bed is shown in Fig. 5. The
reactivity exhibits its maximum value at gas velocity of
0.0287 m/s (4.28 Umf) where gas–solid mixing would be highest
due to the gross solids circulation caused by drift and wake
transport of bubbles and small scale local-mixing in bubble
wakes [33,34]. At the optimum gas velocity, the effect of
methane concentration on reactivity of the reduction is Fig. 6 – Effect of methane concentration on the reduction
shown in Fig. 6. As can be seen, the maximum conversion of conversion of iron oxides (Ug [ 0.0287 m/s; T [ 1173 K;
around 0.32 can be attained at methane concentration above t [ 20 min).
25%. The reactivity in TGA is higher than that in the fluidized
bed reactor because the gas–solid contacting or mixing is
limited due to the reactant gas encapsulated in bubbles in the
reactor. FR. This difference of the optimum gas velocity can be
attributed to gas volume change from the reduction of Fe3O4
3.3. Oxidation characteristics of iron oxides in the by methane accompanied by volume expansion in the reac-
fluidized bed reactor (SR) tion Eq. (3) but oxidation of FeO has no volume change in the
reaction Eq. (4).
The performance of oxygen carrier in terms of the maximum The effect of steam concentration on the maximum
H2 evolution rate in SR with 50% steam injection as a function evolution rate of H2 is shown in Fig. 8 where the evolution rate
of gas velocity is shown in Fig. 7. As can be seen, the of H2 is improved with increasing steam concentration while
maximum evolution rate of H2 can be obtained at gas velocity the increasing rate becomes lower over 50% steam.
of 0.0402 m/s (6 Umf) that is a little higher velocity than that in

Fig. 7 – Hydrogen evolution rate as a function of gas

Fig. 5 – Effect of gas velocity on the reduction conversion of velocity in oxidation of iron oxides (CH2 O [ 50%;
iron oxides (CCH4 [ 25%; T [ 1173 K; t [ 20 min). T [ 1173 K).
 international journal of hydrogen energy 34 (2009) 1301–1309 1307

Fig. 8 – Hydrogen evolution rate in oxidation of iron oxides

as a function of steam concentration (Ug [ 0.0402 m/s;
T [ 1173 K).

3.4. Feasibility study of two-step SMR system

At the optimum condition (Ug: 0.0287 m/s, CCH4 : 25%) compo-

sition of the product gases from FR with time and the
conversion was determined. The reactivity is changed at
40 min (xFe3 O4 /FeO y0:55) after reaction started as can be seen
in Fig. 9(a). In the former part, it is shown that concentrations
of H2O and CO2 of the product gases are relatively high due to
oxygen in Fe3O4 were consumed. On the other hand, it can be
Fig. 9 – Gas concentration from the fluidized bed reactor (a)
seen that concentration of H2 and CO increases after the
reducing with methane (CCH4 [ 25%; Ug [ 0.0287 m/s), (b)
conversion of 0.55. This result can be elucidated by the reac-
oxidizing with steam (CH2 O [ 50%; Ug [ 0.0402 m/s) of iron
tion of catalytic decomposition of methane with phase change
of iron oxides and this mechanism is shown in Fig. 10. As can

oxides at 1173 K, 6: CO, : CO2, -: CH4, ,: H2, ;: H2O.

be seen, methane is slowly decomposed at the initial reaction

(in the absence of catalyst [32]) of Fe3O4 with methane to
produce solid carbons and H2 which are fully oxidized to H2O
and CO2 by reduction of Fe3O4. Also CO gas can be generated
through the further reaction of CO2 with solid carbons (Bou-
douard reverse reaction [32]). However, the rate of catalytic
methane decomposition increases with increasing FeO phase
in the middle of the reaction so that production rates of solid
carbon and H2 rapidly increase [32,35]. After all, direction of
the reaction is favorable to the partial oxidation of methane
under the fixed amount of oxygen carriers in the batch reac-
tion system. In particular, the reason why the reduction rate
of iron oxides is not improved despite the fast increase of
methane consumption in the latter stage is also explained by
the partial oxidation of methane. From the data in the figure,
the average molar ratio of H2/(2CO þ 3CO2) in the latter part is
found to be about 0.65. The phases of Fe3O4 (magnetite) and
FeO (wuestite) can be confirmed from the XRD patterns of
sampling solids after the reduction (Fig. 11b).
The carbon deposition can be confirmed by the mass
balance of carbon at a fixed methane supply (25%) in the batch
reaction. From the gas composition obtained with time in
Fig. 9(a), carbon deposition is mainly caused by the partial
oxidation of methane (i.e., after 40 min). However, any carbon
component was not observed on the surface of the sampling
particles after the reduction (Fig. 11b) because the deposited
carbon is small and almost emitted in the form of CO2. After
finishing the reduction reaction, residual gases were purged
by nitrogen gas for 20 min, where small amount of CO2 is still
detected in the reactor. Subsequently, composition of the
product gases with time and the oxidation conversion of FeO
Fig. 10 – Mechanism of the methane oxidation with iron
oxides.
1308 international journal of hydrogen energy 34 (2009) 1301–1309
Fig. 11 – XRD patterns of solid particles: (a) raw material, (b)
sample after reduction (c) sample after oxidation.
were determined with 50% steam introduced in the reactor as
shown in Fig. 9(b). With steam injection to the reactor, FeO is
oxidized fast to produce H2 under the excess oxygen present.
About 10 min after starting reaction (xox: 0.45–0.5), the abrupt
change of the reaction rate occur and this point is similar with
the result in FR based on the conversion from FeO to Fe3O4. At
the oxidation conversion of FeO over 0.9, the oxidation rate
sharply decreases. Meanwhile, it has been expected that solid
carbon deposited on particles in FR can appear to be in the
form of CO, CO2, and CH4 in SR. However, it is shown that CO
and CH4 are not present in the product gases except small
amount of CO2 because the equilibrium composition is
favorable to the direction of CO2 production. Based on XRD
patterns of the sampling solids after the oxidation (Fig. 11c), it
can be claimed that most of iron oxides are re-oxidized to the
solid phase of Fe3O4 (magnetite) by steam.
In the present study, H2 without CO can be generated from
the two-step SMR reaction with the redox of FeO/Fe3O4. The
CO-free gas in SR [36,37] can directly feed to the polymer
electrolyte membrane (PEM) fuel cell. The results from FR are
divided into following two cases: the full oxidation of methane
is favorable below 50% conversion of Fe3O4 / FeO at oxygen
carrier rich condition while the syngas production for the
feedstock to the Fischer–Tropsch reaction and the reduction
of Fe3O4 prevail over 50% conversion of Fe3O4 / FeO at oxygen
carrier lean condition. In particular, the production of both
purified H2 and syngas mixture for Fischer–Tropsch reaction
can be obtained from H2 generated from SR that supplied to FR
to satisfy the proper ratio of product gas composition as
shown in Fig. 2.
3.5. Consideration of designing a continuous two-step
SMR system with redox of FeO/Fe3O4
Based on the present study, the design base for the continuous
process of two-step SMR with the redox of FeO/Fe3O4 could be
obtained. The reaction conversion range could be 0–0.5 from
FeO to Fe3O4 since H2 evolution rate in SR is fast at the lower
oxidation state between FeO and Fe3O4 (Fig. 9b) and the syngas
production and reactivity of solids in FR is also favorable at the
lower oxidation state of FeO (Fig. 9a). To compensate the
difference of the redox reaction rates, the solid inventory ratio
of two-reaction regions should be determined from the
present experimental data. This is defined as the ratio of solid
mass weight (MFR/MSR) that corresponds to an average resi-
dence time of solids in each reactor. Based on the data in Fig. 9,
the solid inventory ratio can be determined to be about 2.9. As
maintaining the mass balances of the reaction, the amount of
H2 production depends on the contact time between gas and
solids since the increase of contact time improves the
conversion of methane and steam. In this respect, bubbling
fluidized bed reactors would be a best choice since it has long
reaction time with good solid mixing. Therefore, two bubbling
fluidized beds system which has the double pressure loops as
a driving force for solid circulation with two gas streams (fuel
and steam) [38] is proposed for two-step SMR reaction. In
addition, a pneumatic transfer line for upward solids trans-
port and non-mechanical valves for the control of solid flow
are also needed for the continuous reaction system.
4. Conclusions
The two-step steam methane reforming system with the
redox of FeO/Fe3O4 for H2 production using the chemical
looping process is confirmed in the present study and the
guideline for the construction of continuous process is
proposed. In TGA, the range of reaction temperature is found
to be over 1073 K for FR and the reaction rate increases with
increasing temperature in both FR and SR. The optimum
operating conditions (Ug ¼ 0.0287 m/s and CCH4 > 25% in FR
and Ug ¼ 0.0402 m/s and CH2 O > 50% in SR) were determined
for the mass transfer between gas and solid in the fluidized
bed. It is found that pure hydrogen except for CO2 can be
obtained from the reaction of FeO / Fe3O4 in SR at 1173 K.
With respect to the syngas production for the Fischer–Tropsch
reaction and the oxidation reactivity of FeO, the conversion
range of the redox reaction is found to be 0–0.5 from FeO to
Fe3O4. Based on the present experimental data, the design
basis for the continuous two-step SMR is proposed as the
double-loop solids circulation system with fuel and steam
streams. The solid inventory ratio of FR to SR to compensating
the reaction rate is determined to be 2.9.
Acknowledgements
This Research (Paper) was performed for the Hydrogen Energy
R&D Center, one of the 21st Century Frontier R&D Program,
funded by the Ministry of Education, Science and Technology
of Korea.
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