Aerosol and Air Quality Research, 14: 981990, 2014

Copyright Taiwan Association for Aerosol Research

ISSN: 1680-8584 print / 2071-1409 online
doi: 10.4209/aaqr.2013.04.0135

Characterization and Evaluation of Prepared Fe2O3/Al2O3 Oxygen Carriers for

Chemical Looping Process

Ping-Chin Chiu1, Young Ku1*, You-Lin Wu1, Hsuan-Chih Wu1, Yu-Lin Kuo2,
Yao-Hsuan Tseng1
1
Department of Chemical Engineering, National Taiwan University of Science and Technology, No. 43, Sec. 4, Keelung
Rd., Daan Dist., Taipei 106, Taiwan
2
Department of Mechanical Engineering, National Taiwan University of Science and Technology, No. 43, Sec. 4, Keelung
Rd., Daan Dist., Taipei 106, Taiwan

ABSTRACT

Alumina supported Fe2O3 was prepared to evaluate its feasibility as an oxygen carrier for chemical looping using a
thermogravimetric analyzer (TGA) and fixed bed reactor. Fe2O3/Al2O3 particles containing 60 wt% Fe2O3 and sintered at
1300C demonstrated reasonable oxygen conversion. The reduction mechanism of Fe2O3/Al2O3 oxygen carriers was
proposed based on the thermogravimetric analysis and XRD characterization. FeAl2O4 is formed and can serve as a
supporting material as well as oxygen carrier in practical operations by using a moving bed reactor. The prepared
Fe2O3/Al2O3 oxygen carriers demonstrated high CO2 yields in relation to syngas and methane combustion in the fixed bed
reactor operated at temperatures higher than 500 and 850C, respectively. Moreover, hydrogen generation was demonstrated
to be feasible by steam oxidation with reduced Fe2O3/Al2O3 oxygen carriers for experiments conducted at temperatures
above 800C. The crush strength and TGA of Fe2O3/Al2O3 were examined, and the results showed that they had an
appropriate crush strength and reasonable reactivity as oxygen carriers for use in a chemical looping process.

Keywords: Chemical looping process; Fe2O3/Al2O3 Oxygen carrier; TGA; Fixed bed reactor.

INTRODUCTION of additional units to obtain high purity CO2; in addition,

Carbon dioxide (CO2) as one of the anthropogenic GHGs
has been rapidly grown by 39% above pre-industrial levels
at the end of 2010 (IPCC, 2011). For satisfying the energy
demand, fossil fuel supported around 80% of primary
energy through combustion, and became the major CO2
emission point sources from industry and energy sectors,
presently (IEA, 2010). For reduction of CO2 emissions, use
of renewable energies such as solar, wind, biomass is
considered a long-term destination in place of fossil fuel to
generate energy. In order to reduce CO2 emissions in the
near future, CO 2 capture for utilization and storage
(CCUS) is currently developed for mitigating CO2 emitted
into atmosphere (Olajire, 2010; MacDowell et al., 2010).
The CO2 capture technologies are typically including pre-
combustion, post-combustion and oxyfuel-combustion.
However, the efficiency loss was estimated from 6 to 14%
for the above CO2 capture technologies due to the operation
for economical point of view, the cost for CO2 capture,
transportation and sequestration were estimated as 30 to 60
/tCO2 (Notz et al., 2011), which is much higher than the
price of CO2 emission rights in European Energy Exchange
(EEX) approximately 2.5 to 5.0 /tCO2 in 2013. Hence, the
CO2 capture technologies should be substantially increased
their energy efficiency to meet the economical requirement.
Chemical looping technology is proposed and considered as
a combustion technology with high potential to substantially
cut down the cost of CO2 capture (Figureoa et al., 2008).
Chemical looping process is typically consisted of a fuel
reactor and an air reactor, as illustrated in Fig. 1, and utilizes
the oxygen present in metal oxides as oxygen carriers
circulating between the reactors for fuel combustion (Ishida
et al., 1987). In the fuel reactor, combustion between
oxygen carriers and carbonaceous fuels yields CO2 and
H2O as described by Eq. (1). In the air reactor, reduced
oxygen carriers are oxidized as described by Eq. (2) to
generate heat for applications (Chiu and Ku, 2012).

CnH2m + (2n + m)MexOy nCO2 + mH2O + (2n + M)

*
Corresponding author. MexOy1 (1)
Tel.: +886-2-2378-5535; Fax: +886-2-2737-6644
E-mail address: ku508@mail.ntust.edu.tw O2 + 2MexOy1 2MexOy (2)
982 Chiu et al., Aerosol and Air Quality Research, 14: 981990, 2014
Fig. 1. Schematic diagram of chemical looping process.
The CO2 yields were estimated to be higher than 90%
for fuel combustion by chemical looping process with
various metal oxides, such as Fe2O3, NiO, CuO, Mn2O3
and Co3O4, based on thermodynamic analysis (Cao and
Pan, 2006; Gupta et al., 2007; Fan and Li, 2010). Chemical
looping is considered a promising technology with high
energy efficiency as well as inherent CO2 concentration for
possible carbon reuse or storage (Figueroa et al., 2008).
The efficiency of electricity generation for syngas (CO/H2)
combustion by chemical looping process was estimated to
be 43.2% with 99% CO2 yield (Xiang and Wang, 2008),
much higher than those for pulverized coal power plants
with amine absorption for CO2 capture (Li and Fan, 2008).
Iron-based oxygen carriers are commonly applied for
chemical looping process due to a number of advantages,
including higher melting point, better mechanical strength,
less impact on environment and health, and lower cost than
most other oxygen carriers (Mattisson et al., 2001; Johansson
et al., 2004; Berguerand and Lyngfelt, 2009; Li et al., 2009;
Kuo et al., 2013; Tseng et al., 2013). However, sintering
and attrition of oxygen carriers during continuous, high-
temperature chemical looping operation would decrease
the reactivity of oxygen carriers. Therefore, support materials,
such as Al2O3, MgAl2O4, ZrO2, TiO2 and bentonite, are
combined with hematite (Fe2O3) to retard the sintering of
oxygen carriers and to enhance their mechanical strength
for chemical looping operation (Johansson et al., 2004;
Mattisson et al., 2004; Son et al., 2006; Abad et al., 2007;
Mattisson et al., 2007; Azis et al., 2010). Among the support
materials, Al2O3 is frequently used for iron-based oxygen
carriers to improve their reactivity and recyclability (Ishida
et al., 2005). The reactors proposed for chemical looping
process including circulating fluidized bed, bubbling fluidized
bed, spouted bed, rotating bed and moving bed reactors
(Lyngfelt, 2011; Sridhar et al., 2012). The design of moving
bed fuel reactor with counter-flow pattern was proposed to
increase the available oxygen for combustion with iron-
based oxygen carriers (Gupta et al., 2007; Ku et al., 2014).
Hydrogen generation is one of the applications of
chemical looping process using iron-based oxygen carriers
(Gupta et al., 2007). The Fe2O3 is reduced to Fe and FeO
in a counter-flow moving bed fuel reactor, and moving to an
oxidizer for hydrogen generation through steam oxidation
as described reactions (Li et al., 2010):
3Fe + 4H2O Fe3O4 + 4H2 (3)
3FeO + 3H2O Fe3O4 + 3H2 (4)
For practical H2 generation by chemical looping process,
a 25 kW moving bed system demonstrated continuous
generating 94.4 to 98.4% of H2 (Sridhar et al., 2012). The
high purity of H2 can be used as raw material for chemicals
production, such as methanol, ammonia and dimethyl ether
(DME).
Preparation of Fe2O3/Al2O3 oxygen carriers was
investigated by thermogravimetric analyzer (TGA) in this
study. Experiments on the reduction of Fe2O3/Al2O3 oxygen
carriers was conducted by TGA and characterized by X-ray
diffraction (XRD). The performance of prepared Fe2O3/Al2O3
oxygen carriers on CO2 yield with syngas and methane
combustions, and on H2 generation by H2O oxidation were
determined in a fixed bed reactor. The mechanical strength
of Fe2O3/Al2O3 pellets was evaluated by texture analyzer;
and the reactivity and recyclability of Fe2O3/Al2O3 pellets
were evaluated by TGA with continuous 50 redox cycles.
EXPERIMENTAL
Preparation of Fe2O3/Al2O3 Oxygen Carriers
Alumina-supported Fe2O3 oxygen carriers (Fe2O3/Al2O3)
with various Fe2O3 fractions (20, 40, 50, 60 or 80wt%) were
prepared by mixing Fe2O3 and Al2O3 powders (approximately
1 m in particle size) with a ball miller operated at 380 rpm
for 5 minutes. The Fe2O3/Al2O3 powders were then sintered
in a muffle furnace at 900, 1000, 1100, 1200 or 1300C for
2 hours. The prepared oxygen carriers were examined for
reactivity by a thermogravimetric analyzer (TGA).
For preparation of Fe2O3/Al2O3 pellets for fixed bed
experiments, Fe2O3 and Al2O3 powders were mixed in the
de-ionized water in a stirring tank equipped for 30 minutes
at room temperature. The well-mixed Fe2O3/Al2O3 slurry
solution was dried at 80C for 6 hours, and then pulverized
and screened their particle sizes from 1.2 to 1.4 mm.
Fe2O3/Al2O3 particles were sintered in a muffle furnace at
1300C for 2 hours.
The Fe2O3/Al2O3 particles were pelletized by a bead
machine to be pellets of 3 mm both in diameter and height,
and then sintered in a muffle furnace at 1300C for 2 hours.
The Fe2O3/Al2O3 pellets were employed to 50 redox cycles
test by TGA and crush strength test by texture analyzer.
Reactivity Tests by Thermogravimetric Analyzer (TGA)
The reactivity and recyclability of Fe2O3 and Fe2O3/Al2O3
oxygen carriers were analyzed by a Netzsch STA 449F3
TGA. 200 mg oxygen carriers were loaded in an alumina
crucible, the temperature of TGA chamber was increased
with a ramping rate of 20C/min in N2 atmosphere, and
eventually kept at 900C. 200 mL/min reducing gas
composed of 20% H2 and 80% N2 was introduced into TGA
chamber for 15 minutes to reduce oxygen carriers. After the
reduction process, 200 mL/min N2 was introduced for 5
minutes for sweeping reducing gas contained in the TGA
chamber. 200 mL/min air was then introduced for 10 minutes
to oxidize the reduced oxygen carriers. The procedure of
redox cycling was replicated for 50 times with Fe2O3 and
Fe2O3/Al2O3 pellets to evaluate the reactivity and recyclability
with respect to practical moving bed operation of chemical
 Chiu et al., Aerosol and Air Quality Research, 14: 981990, 2014
looping process. The redox cycling for oxygen carriers was
carried out by repeating the procedure described above,
while the reducing time was 20 minutes. The oxygen
conversion for reduction of oxygen carriers is described by
Eq. (5):
mo m(t )
X OC (5)
mo mr
where mo is weight of fully oxidized oxygen carrier; mr is
weight of fully reduced oxygen carrier; m(t) is weight of
oxygen carrier after reduction period of t.
Characterization of Oxygen Carriers
The phase transformation of prepared Fe2O3/Al2O3
during redox cycle was characterized by X-ray diffraction
(XRD, Bruker D2 Phaser), the incident beam was Cu K
characteristic X-ray at 30 kV and 10 mA scanning with
rate of 0.05 deg/s in the 2 range from 10 to 80. Surface
morphology and interfacial behaviors of Fe2O3/Al2O3
oxygen carrier were examined by a field emission scanning
electron microscope (FESEM, JOEL JSM-6500F). The
crush strength of prepared Fe2O3/Al2O3 oxygen carriers
were analyzed by a texture machine (TA.XT plus).
Fixed Bed Reactor
Fixed bed reactor system employed in this study is shown
Fig. 2. Schematic diagram of fixed bed reactor system.
983
in Fig. 2, and is composed of a 25.4 mm ID stainless steel
(SS310) reactor and a PID-controlled heating element
covering 200 mm of reactor height. A plate with sixteen
0.25 mm apertures was located in the lower part of the
reactor for supporting Fe2O3/Al2O3 oxygen carriers. For
reduction of Fe2O3/Al2O3 oxygen carriers with methane
and syngas, 1.5 L/min reducing gas was introducing into
the fixed bed reactor at various temperatures, ranging from
100 to 900C. The reducing gases were composed of 20%
of CH4 and 80% of N2 for methane combustion and 10%
of CO, 10% of H2 and 80% of N2 for syngas combustion,
respectively. For H2 generation by steam oxidation of reduced
Fe2O3/Al2O3 oxygen carriers, 50 mmol/min of steam was
introduced into the fixed bed reactor at various temperatures,
ranging from 500 to 900C. The outlet stream from the fixed
bed reactor was passed through a cold trap to condense
steam, and 200 mL/min of spent gas was consequently
analyzed by a non-dispersive infrared analyzer (Molecular
Analysis 6000i) to detect CO, CH4 and CO2 separately by
specific light beams, respectively. A gas chromatography
analyzer equipped with thermal conductivity detector (Agilent
7890) was employed for measuring H2 concentration. The
CO2 yield (YCO2) is defined as:
FCO2
YCO2 100% (6)
FCO2 FCO FCH 4 FH 2
984 Chiu et al., Aerosol and Air Quality Research, 14: 981990, 2014

where FCO2, FCO, FH2 and FCH4 are the molar flow rates of
CO2, CO, H2 and CH4 in the outlet stream, respectively.
RESULTS AND DISCUSSION
Thermogravimetric Analysis of Fe2O3/Al2O3 Oxygen
Carriers
The conversion of oxygen present in oxygen carriers for
prepared Fe2O3/Al2O3 with various Fe2O3 fractions was
conducted at 900C by TGA, and is shown in Fig. 3. The
conversion of oxygen was increased with the fraction of
Fe2O3 for Fe2O3/Al2O3 oxygen carriers containing 20 to
60wt% Fe2O3, whereas decreased for Fe2O3/Al2O3 oxygen
carriers containing 80wt% Fe2O3 possibly because of the
sintering of oxygen carriers during reduction and oxidation
reactions.
The effect of sintering temperature for preparation of
Fe2O3/Al2O3 on the conversion of oxygen present in oxygen
carriers is shown in Fig. 4. For experiments conducted with
Fe2O3/Al2O3 oxygen carriers sintered at temperature lower
than 1000C, the conversions of oxygen were independent
on sintering temperature. For experiments conducted with
Fe2O3/Al2O3 oxygen carriers sintered at temperature higher
than 1100C, the conversion was increased with increasing
sintering temperature. Based on the experience of ceramic
sintering, solid state sintering between ceramic materials
would be started as sintering temperature higher than 2/3 of
its melting point for uniformly dispersion of multiple ceramic

100
Effect of Fe2O3 Fraction in Fe2O3/Al2O3 Oxygen Carrier

90 Reaction temperature: 900C

Reducing gas: 20% H2
Gas flow rate: 200 mL/min
80

70
XOC (%)

60

50

40

30
20 40 60 80
Fe2O3 Fraction (wt%)
Fig. 3. Oxygen conversion of Fe2O3/Al2O3 oxygen carriers for 20, 40, 60 and 80wt% of Fe2O3 fractions by using H2 as
reducing gas conducted by TGA at 900C.

100
Effect of Sintering Temperature
90 Reaction temperature: 900C
Reducing gas: 20% H2
Gas flow rate: 200 mL/min
80

70
XOC (%)

60

50

40

30
900 1000 1100 1200 1300
Sintering Temperature (C)
Fig. 4. Oxygen conversion of Fe2O3/Al2O3 oxygen carriers for 900, 1000, 1100, 1200 and 1300C of sintering temperature
by using H2 as reducing gas conducted by TGA at 900C.
 Chiu et al., Aerosol and Air Quality Research, 14: 981990, 2014
materials (Rahaman, 2008). Therefore, solid state sintering
was suggested beginning at 1100C which was exactly
higher than 2/3 of melting point of Fe2O3 (1560C), for well
dispersion of Fe2O3 in Fe2O3/Al2O3 oxygen carriers. Thus,
the reaction between Fe2O3 and reducing gas was increased
as Fe2O3 was more uniformly dispersed in Fe2O3/Al2O3
oxygen carriers by increasing sintering temperature. It was
reported that 60wt% of Fe2O3 supported by 40wt% of
Al2O3 sintered at 1300C demonstrated better reactivity
(Mattisson et al., 2004), which is corresponded to the results
in this study.
Experimental results for Fe2O3/Al2O3 oxygen carrier
reduced by syngas for 60 minutes and oxidized by air for
10 minutes in TGA are depicted in Fig. 5. Approximately
70% of oxygen was reduced by syngas combustion within
about 21 minutes of reaction time; furthermore, roughly
20wt% of oxygen was reduced from 21 to 60 minutes. The
oxygen carrier was sampled at the reduction time at 0, 4,
21 and 60 minutes, and characterized by XRD for phase
identification as shown in Fig. 6. Prior to starting reduction
process, Fe2O3 and Al2O3 were the major crystalline phase
of oxygen carriers. After 4 minutes of reduction, Fe3O4 was
found to be the major crystalline phase. The conversion of
oxygen for Fe2O3/Al2O3 oxygen carriers was around 10%
for 4 minutes of reduction that corresponded to the amount
of oxygen utilization from Fe2O3 to Fe3O4. FeO and FeAl2O4
were formed at the end of first stage, indicating that Fe3O4
was further reduced to FeO, and part of FeO reacted with
Al2O3 to form FeAl2O4. The formation of FeAl2O4 was
corresponded to the previous research reported by Ishida et
al. (2005) using Al2O3 supported Fe2O3 in the reduction
process. Therefore, reduction of Fe2O3/Al2O3 oxygen
carrier in the first stage less than 4 minutes of reaction time,
as illustrated in Fig. 5 is suggested by following reactions:
100 Fe2O3+Al2O3
First stage
80 Fe3O4/FeO/FeAl2O4
Weight (%)
60
Second stage
40
20 Third stage
Fe/FeAl2O4
0
0 10 20 30
Time (min)
Fig. 5. Oxygen conversion of Fe2O3/Al2O3 oxygen carriers for 900, 1000, 1100, 1200 and 1300C of sintering temperature
by using H2 as reducing gas conducted by TGA at 900C.
985
6Fe2O3 + 2CO/H2 4Fe3O4 + 2CO2/H2O (7)
Fe3O4 + CO/H2 3FeO + CO2/H2O (8)
FeO + Al2O3 FeAl2O4 (9)
For oxygen carriers sampled at 21 minutes of reduction,
Fe and FeAl2O4 were observed to be the major crystalline
phases, while FeO and Fe3O4 were absence in the XRD
pattern. The reduction of Fe2O3/Al2O3 oxygen carrier in the
second stage (4 to 21 minutes of reaction time) is suggested
by the following reactions:
FeO + CO/H2 Fe + CO2/H2O (10)
FeAl2O4 + CO/H2 Fe + Al2O3 + CO2/H2O (11)
The XRD intensity of Fe was enhanced at 60 minutes of
reduction indicating that FeAl2O4 was continuously reduced
to Fe. Hence, reduction of FeAl2O4 was much slower than
Fe2O3 and Fe3O4 resulted in the slow reduction rate in the
third stage (21 to 60 minutes of reaction time). The counter-
flow moving bed reactor might promote the utilization of
oxygen in iron-based oxygen carriers up to 50%, which
was much higher than that by the fluidized bed reactors (Li
and Fan, 2008). Accordingly, FeAl2O4 and Fe are suggested
the major crystalline phases as using Fe2O3/Al2O3 oxygen
carriers for a counter-flow moving bed reactor as illustrated
in Fig. 6. Hence, the reduction mechanism of Fe2O3/Al2O3
oxygen carriers was proposed in accordance with
thermogravimetric analysis and XRD characterization. In
addition, the intermediate crystalline phase, FeAl2O4, would
serve as the supporting material as well as oxygen carrier in
practical operation by moving bed reactor.
TG Analysis of Reduction of Fe2O3/Al2O3
Weight of Fe2O3/Al2O3: 200 mg
Reaction temperature: 900C
Reducing gas: 10% CO+10% H2
Oxidizing gas: air
Gas flow rate: 200 mL/min
Fe/FeAl2O4
40 50 60 70 80
986 Chiu et al., Aerosol and Air Quality Research, 14: 981990, 2014
XRD Analysis of Fe2O3/Al2O3 Oxygen Carrier Reduction
Weight of Fe2O3/Al2O3: 200 mg
Reaction temperature: 900 C
Reducing Gas: syngas
Intensity (a.u.)
20 30 40
2
Fig. 6. XRD patterns of Fe2O3/Al2O3 oxygen carriers sampled at each time level of reduction at 0, 4, 21 and 60 minutes
conducted by TGA at 900C (: Fe2O3, : Al2O3, : Fe, : FeAl2O4, : Fe3O4, : FeO).
Fixed Bed Experiments with Fe2O3/Al2O3 Oxygen Carriers
The combustions of methane and syngas with Fe2O3/Al2O3
oxygen carriers were employed in a fixed bed reactor at
temperatures ranging from 100 to 900C. As shown in Fig. 7,
the YCO2 of syngas combustion was noticeable for experiment
conducted at 300C, and reached 100% for experiments
conducted at temperatures higher than 500C. Based on the
thermodynamic analysis by previous researchers (Li et al.,
2010), CO and H2 can be completely converted to CO2 and
H2O through the reduction from Fe2O3 to Fe3O4 at
temperatures ranging from 200 to 1200C. However, as
illustrated in Fig. 7, the equilibrium was not achieved because
the reaction rates were too slow to reach complete conversion
at temperatures ranging lower than 400C. The CO2 yields
of methane combustion were observed for experiment
conducted at 600C and reached 100% for experiments
conducted at temperatures higher than 850C, as shown in
Fig. 7. Therefore, methane combustion with Fe2O3/Al2O3
oxygen carriers was suggested to carry out at temperatures
higher than 850C for chemical looping process, which
corresponded to the previous study that natural gas (over
90% of CH4) combustion with iron-based oxygen carriers
to achieve complete conversion at 950C (Abad et al.,
2007). Hence, the prepared Fe2O3/Al2O3 oxygen carriers
demonstrated high CO2 yields regarding to syngas and
methane combustion in the fixed bed reactor.
Experiments with regards to steam oxidation with
completely reduced oxygen carriers for H2 generation in a
fixed-bed reactor were conducted at temperature varied
from 500 to 900C. As shown in Fig. 8, the flow rate of H2
in the outlet stream was significantly increased with reaction
temperature and reached a steady value for experiments
conducted at temperature above 800C. Based on the mole
balance calculation, the conversion of H2O to H2 reached
Fe2O3/Al2O3 reduction for 60 min
Fe2O3/Al2O3 reduction for 21 min
Fe2O3/Al2O3 reduction for 4 min
Fresh Fe2O3/Al2O3
50 60 70 80
roughly 75% for experiments conducted at temperature
above 800C. The results of conversions were corresponded
to the thermodynamic analysis of oxidation of Fe by H2O
reported by previous study (Li et al., 2010) that 60 to 70%
of H2O would be reduced to form H2 using reduced Fe2O3
oxygen carriers at temperature ranging from 600 to 1000C.
Hence, the prepared Fe2O3/Al2O3 oxygen carriers could be
feasible for H2 generation by chemical looping process.
Performance Evaluation of Fe2O3/Al2O3 Oxygen Carriers
for Chemical Looping Process
For applications of Fe2O3/Al2O3 oxygen carriers in
moving bed reactors, the Fe2O3/Al2O3 oxygen carriers are
usually pelletized to provide stronger mechanical strength
to sustain the bumping in the reactor system. The crush
strength of Fe2O3 is examined to be 33 and 60 N for 1.2 to
1.4 mm and 1.4 to 2.0 mm of particles size, respectively,
as listed in Table 1. The crush strength of Fe2O3/Al2O3
particles were lower than Fe2O3 examined to be 22 and 28
N for 1.2 to 1.4 mm and 1.4 to 2.0 mm of particles size,
respectively. The interspace between Fe2O3 and Al2O3
particles is possibly greater than Fe2O3 particles because
the crystallite size of Fe2O3 is different with Al2O3 particles,
which generated more space in the prepared Fe2O3/Al2O3
particles. The comparatively loose packed Fe2O3/Al2O3
particles resulted in lower crush strength than Fe2O3 particles.
Pelletizing of Fe2O3 and Fe2O3/Al2O3 particles effectively
enhanced their crush strength to be 251 and 230 N,
respectively. The interspace of the pelletized particles would
be substantially reduced for more compact packing in the
pellet. Therefore, the crush strength is greatly enhanced by
pelletizing process. The pelletized Fe2O3 and Fe2O3/Al2O3
oxygen carriers were used for experiments in TGA to
evaluate their reactivity and recyclability.
 Chiu et al., Aerosol and Air Quality Research, 14: 981990, 2014 987

140
Fixed Bed Experiments
Oxygen carrier: 100 g
120 1.5 L/min of syngas (10 % CO+10 % H2)
1.5 L/min of CH4 (10 % CH4)
100

YCO2 (%) 80

60

40

20

0
100 200 300 400 500 600 700 800 900
Reaction Temperature (C)
Fig. 7. CO2 yields for syngas and methane combustions varied with reaction temperatures in the fixed bed reactor packed
with 100 g of Fe2O3/Al2O3 particles.

50 100
H2 Generation in Fixed Bed Reactor
Fe2O3/Al2O3 oxygen carriers: 10 g
40 Steam flow rate: 50 mmol/min 80

H2O Conversion (%)

H2 (mmol/min)

30 60

20 40

10 20

0 0
500 600 700 800 900

Reaction Temperature (C)

Fig. 8. H2 generation by steam oxidation of reduced Fe2O3/Al2O3 particles in the fixed bed reactor at 500, 600, 700, 800
and 900C.

Table 1. Crush strength of Fe2O3 and Fe2O3/Al2O3 particles and pellets examined by texture analyzer.
Oxygen Carriers Oxygen Content (wt%) Particle Size (mm) Crush Strength (N)
1.21.4 33
Fe2O3 30 1.42.0 60
3.0 (pellet) 251
1.21.4 22
Fe2O3/Al2O3 18 1.42.0 28
3.0 (pellet) 230

The reactivity and recyclability of Fe2O3 and Fe2O3/Al2O3 of Fe2O3 oxygen carriers was decayed rapidly after the
pellets using syngas as reducing gas were evaluated in TGA second redox cycle. However, the conversion of Fe2O3/Al2O3
for 50 redox cycles. As depicted in Fig. 9, the conversion pellet was maintained at above 70% during continuous
988 Chiu et al., Aerosol and Air Quality Research, 14: 981990, 2014

redox cycling indicating that the recyclability of Fe2O3 was
considerably improved with Al2O3 support. The SEM images
of Fe2O3 and Fe2O3/Al2O3 pellets are shown in Fig. 10. The
grain size of fresh Fe2O3/Al2O3 was observed to be larger
than fresh Fe2O3 because Fe2O3/Al2O3 pellets were sintered
at 1300C for 2 hours during preparation. The agglomeration
of Fe2O3/Al2O3 sintered at 1300C was also observed in
previous literature (Mattisson et al., 2004). As demonstrated
in Fig. 10(c), the Fe2O3 oxygen carriers were obviously
agglomerated after 5 redox cycles to decrease the surface
area and reactivity of Fe2O3 pellets. For Fe2O3/Al2O3 pellets
after 50 redox cycles, no obvious agglomeration was
observed comparing with fresh Fe2O3/Al2O3 pellets, as
shown in Fig. 10(d). Fe2O3/Al2O3 pellet was illustrated to
provide better reactivity owing to the inhibition of
agglomeration as observed by SEM image. Formation of
FeAl2O4 by reduced FeO and Al2O3 was characterized by
XRD in Fig. 6, and the melting point of FeAl2O4 is
1780C, which is higher than that of FeO, thus mitigated
agglomeration of pellets. Hence, Fe2O3/Al2O3 pellets that
examined by crush strength and TGA demonstrated proper
crush strength and reasonable reactivity, indicating
Fe2O3/Al2O3 pellets are preliminary validated as oxygen
carrier for chemical looping process.

100

90

80

70

60 Redox Cycling by TGA

Reaction Temperature: 900C
XOC (%)

50 Reducing gas: 10% CO+10% H2

40 Gas flow rate: 200 mL/min

Reducing time: 20 min
30 3 mm Fe2O3 pellet
3 mm Fe2O3/Al2O3 pellet
20

10

0
0 10 20 30 40 50
Redox Cycle
Fig. 9. Oxygen conversion of Fe2O3 and Fe2O3/Al2O3 pellets using syngas as reducing gas conducted by TGA at 900C.

(a) Fresh Fe2O3 (c) Fe2O3 after 5 redox cycles

(b) Fresh Fe2O3/Al2O3 (d) Fe2O3/Al2O3 after 50 redox

Fig. 10. SEM images of (a) fresh Fe2O3, (b) fresh Fe2O3/Al2O3, (c) Fe2O3 after 5 redox cycles and (d) Fe2O3/Al2O3 after 50
redox cycles conducted by TGA at 900C.
 Chiu et al., Aerosol and Air Quality Research, 14: 981990, 2014
CONCLUSIONS
Fe2O3/Al2O3 particles containing 60wt% Fe2O3 and
sintered at 1300C is a suitable preparation parameter to
demonstrate reasonable oxygen conversion. The reduction
mechanism of Fe2O3/Al2O3 oxygen carriers was proposed
in accordance with thermogravimetric analysis and XRD
characterization. In addition, the intermediate crystalline
phase, FeAl2O4, would serve as the supporting material as
well as oxygen carrier in practical operation by moving
bed reactor. The prepared Fe2O3/Al2O3 oxygen carriers
demonstrated high CO2 yields regarding to syngas and
methane combustion in the fixed bed reactor, operated at
temperatures higher than 500 and 850C, respectively.
Moreover, hydrogen generation was demonstrated to be
feasible by steam oxidation with reduced Fe2O3/Al2O3 oxygen
carriers for experiments conducted at temperature above
800C. Fe2O3/Al2O3 pellets that examined by crush strength
and TGA demonstrated proper crush strength and reasonable
reactivity, indicating Fe2O3/Al2O3 pellets are preliminary
validated as oxygen carrier for chemical looping process.
ACKNOWNLEDGEMENT
This research was supported by grant NSC-98-3114-E-
007-013, NSC- 100-3113-E-007-005 and NSC-101-3113-
E-007-005 from the National Science and Technology
Program-Energy in Taiwan. The authors appreciate China
Steel Corp. to provide hematite powders for preparation of
oxygen carriers.
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Received for review, April 24, 2013
Accepted, August 27, 2013