i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1

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Sustainable iron-based oxygen carriers for

Chemical Looping for Hydrogen Generation

Yoran De Vos a,b,c,d, Marijke Jacobs a, Pascal Van Der Voort b,

Isabel Van Driessche c, Frans Snijkers a, An Verberckmoes d,*
a
Sustainable Materials Management, Flemish Institute for Technological Research (VITO), Boeretang 200, 2400, Mol,
Belgium
b
Department of Chemistry, Center for Ordered Materials, Organometallics and Catalysis (COMOC), Faculty of
Sciences, Ghent University, Krijgslaan 281 (S3), 9000, Ghent, Belgium
c
Department of Chemistry, Sol-gel Centre for Research on Inorganic Powders and Thin Films Synthesis (SCRiPTS),
Faculty of Sciences, Ghent University, Krijgslaan 281 (S3), 9000, Ghent, Belgium
d
Department of Materials, Textiles and Chemical Engineering, Industrial Catalysis and Adsorption Technology
(INCAT), Ghent University, Valentin Vaerwyckweg 1, 9000, Ghent, Belgium

article info abstract

Article history: We report a detailed reactor study of two sustainable Fe-based oxygen carriers (OC) pre-
Received 1 October 2018 pared by spray drying. We compare Fe2O3 supported on Al2O3 and MgFeAlOx in isothermal
Received in revised form Chemical Looping for Hydrogen Generation. In this process, CH4 is converted into syngas
8 November 2018 (H2 þ CO) and H2O is used as the oxidant that reduces to pure H2. We noticed that the Al2O3
Accepted 12 November 2018 supported OC deactivates quickly while the MgFeAlOx supported OC withstands >60 cycles.
Available online 7 December 2018 We will show that the irreversible formation of an inactive FeAl2O4 phase is responsible for
the deactivation of the alumina supported OC. We show detailed information on all the
Keywords: transient stages of the process and the different crystalline forms that are created, and
Chemical looping combine this information into a full chemical looping cycle for both OC. Moreover, we
Hydrogen evaluate the crushing strength of the oxygen carriers within a full chemical looping cycle
Oxygen carriers and during long-term operation and we investigated the conversion of H2O and the
Supported materials selectivity to H2-production during long-term oxygen carrier regeneration. The MgFeAlOx
Water splitting support with an extra Fe-based active phase is a promising material to replace the typical
Ni-based oxygen carriers, as it forms a sustainable non-toxic, stable and green alternative
for hydrogen generation by chemical looping.
© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

and above all for the production of methanol and ammonia.

Introduction Additionally, it is a clean energy source which can be used in
fuel cells when it has high enough purity [1]. Currently, the
Hydrogen is one of the most important base materials in the most economical and widely used method for producing
chemical industry as it is used in the Fisher-Tropsch synthesis

* Corresponding author.
E-mail addresses: Yoran.DeVos@vito.be (Y. De Vos), Marijke.Jacobs@vito.be (M. Jacobs), Pascal.VanDerVoort@UGent.be (P. Van Der
Voort), Isabel.VanDriessche@UGent.be (I. Van Driessche), Frans.Snijkers@vito.be (F. Snijkers), An.Verberckmoes@UGent.be
(A. Verberckmoes).
https://doi.org/10.1016/j.ijhydene.2018.11.099
0360-3199/© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1
hydrogen is the steam methane reforming (SMR) process in
which syngas is produced (CH4 þ H2O / CO þ 3H2), followed
by a water-gas shift reaction (CO þ H2O / CO2 þ H2) where
this syngas is transformed to pure hydrogen [2]. To fulfil the
large energy demands of SMR, vast amounts of non-
renewable feedstock are burned outside of the reactor tubes
leading to large emissions of CO2, which contribute to the
greenhouse gas effect [3,4]. Additionally, SMR makes use of Ni-
based catalysts [4] that can pose harm to environment and
health [5].
A major trend in the chemical industry is the development
and use of more sustainable technologies with reduced
impact on the environment [6]. These technologies are pref-
erably less energy intensive and exploit renewable feedstock
(e.g. biomass and water) and renewable energy sources for the
production of various chemicals while limiting greenhouse
gas emissions and attaining an optimal atom economy. They
preferably make use of materials and chemicals which pose
minimum harm to environment and health and which have
the required properties for achieving long-term operation [6].
Recently, novel and renewable ways of producing hydrogen
have received significant attention from the research com-
munity, such as electrolysis [7e11], the use of biomass [12e14]
and the use of solar energy [15e19].
Chemical Looping Hydrogen Generation (CLHG) is a novel
and promising approach for producing hydrogen from both
conventional or renewable feedstock and steam [20,21]. By
splitting the process into alternating steps, a pure H2-stream is
inherently separated from a COx stream without additional
separation costs [20,21]. These alternating steps are enabled
by use of metal oxides that ‘carry’ oxygen from an oxygen rich
stream (such as air or steam) to the fuel. These materials,
hence called oxygen carriers, consist most frequently of metal
oxides based on Ni, Cu, Co, Mn and/or Fe combined with
suitable support materials. During each step in the CLHG
process, the oxygen carrier is first reduced while transforming
fuel to syngas or to the total oxidation products, CO2 and H2O.
Afterwards their lattice oxygen is replenished by reacting with
steam with the production of pure hydrogen [22,23]. Chemical
looping processes are usually operated in fluidized-bed sys-
tems [24], where the use of particles with defined densities,
shapes and sizes are necessary for optimal transport and
mixing in the reactor system. The most frequently used
methods for synthesizing such oxygen carrier materials in a
possible cost-effective way at industrial scale are spray drying
and impregnation [25,26].
The development of appropriate oxygen carriers is a key
challenge for optimizing the chemical looping process and
enabling it to compete with the current standard. The syn-
thesis of the oxygen carrier should be economically viable and
the OC should possess a sufficiently high oxygen transport
capacity, good thermal properties and a high reactivity and
sufficient mechanical and chemical stability under reducing
and oxidizing conditions. While developing oxygen carriers
for a sustainable chemical looping process, their toxicity and
impact on the environment are also crucially important [26].
During the past two decades, researchers gave much
attention to the development of Ni-based oxygen carriers due
to their good reactivity, conversion and mechanical stability.
However, their high cost and susceptibility towards S-
1375
containing impurities and the fact that they pose significant
harm to health and environment are key drivers for devel-
oping Ni-free materials [27,28]. Fe-based oxygen carriers are
promising candidates to replace Ni-based oxygen carriers due
to their low cost and diminished impact on health and envi-
ronment. They are used for both syngas generation as total
oxidation and they show high activity in the water splitting
reaction [27,29,30], which is an essential property for succes-
fully producing pure hydrogen in the CLHG process.
The suitability of these pure metal oxides as oxygen car-
riers and their utilization in the process are limited due to the
possibility of (i) agglomeration, which will lead to defluidiza-
tion [31], (ii) limited mechanical properties, which will lead to
attrition and decrease their lifetime [32] and (iii) sintering,
which can cause material deactivation and reduced mixing in
the fluidized-bed [33]. Therefore, these active materials are
usually combined with an inert support such as TiO2, SiO2,
Al2O3, Zr-based, kaolin and more recently ceria [21,34e36] and
perovskites [37e39]. In spite of the increased interest in new
supports such as ceria or perovskites, Al2O3 is still widely used
because of its low cost and its advantageous properties. Also
MgO-modified Al2O3 supports are widely in use for OC devel-
opment. From 2003 onwards, MgAl2O4-supports were already
selected several times for Ni-based OC for their improved
resistance against sintering and agglomeration during
fluidized-bed operation [40e42]. When utilizing spray-dried
MgAl2O4-supported OC's, long term operation was achieved
in CLC and the OC showed an improved performance
compared to spray-dried Al2O3-supported OC [43], even at
high temperatures due to the chemical stability of MgAl2O4
which inhibits NiAl2O4-formation [42,44]. This support stabi-
lizes NiII in the cubic (NiO) phase [45] for multiple cycles [40,46]
and improves their regenerability [40,46] even at temperatures
above 1300  C [24]. Additionally, the MgAl2O4-supported oxy-
gen carriers displayed several other advantages compared to
Al2O3-supported oxygen carriers such as higher methane
conversion because of more active phase at the surface of the
oxygen carrier [47,48], a higher selectivity to reforming [43]
and a lower tendency for carbon formation. On the other
hand, it was also noted that higher sintering temperatures are
necessary for obtaining similar crushing strengths as Al2O3-
supported oxygen carriers, while the porosity of the material
decreased, indicating a lower mechanical performance [49,50].
Their attrition resistance, which is a better measure for their
mechanical performance in the fluidized-bed reactors of the
process is, however, shown to be sufficient [42,49].
Besides Ni-based OC's, also for Cu-based oxygen carriers
the addition of MgO to an Al2O3-support is shown to be ad-
vantageous. The reaction between support and active phase to
CuAl2O4 or CuAlO2 was avoided, resulting in a better reactivity
as the kinetics for CuAlO2-oxidation are slow [51,52]. These
slow kinetics resulted in a not fully reversible CuAl2O4-
decomposition which has also a negative influence on the
actual oxygen transfer capacity for the oxygen carrier in the
process [53,54]. Additionally agglomeration problems which
were sometimes observed when testing Cu-based oxygen
carriers supported on Al2O3 were prevented by utilizing the
MgAl2O4-support [51], even up to 1000  C [52] and in oxygen
carriers containing up to 80 wt% CuO [53]. They also showed
sufficient stability and attrition resistance [53]. For Co- or Mn-
1376 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1
based OC's no MgAl2O4-supports were used until now, as far as
the authors are aware. When utilizing these supports for Fe-
based oxygen carriers a better reactivity with both methane
[38,55] and the gasification products (CO and H2) was obtained
[56e58] and an improved agglomeration resistance was
observed [56].
The authors of this paper displayed recently that the re-
actions between iron-oxides and an Al2O3-support can be
detrimental to chemical looping operation. This is especially
the case when utilizing only steam during oxygen carrier
oxidation as used in CLHG [59] due to the active
phaseesupport interactions leading to FeAl2O4-formation [60]
which results into OC deactivation. When utilizing MgAl2O4 as
a support for these oxygen carriers no presence of FeAl2O4 was
observed [24,30,60]. However, Fe-ions are still taken up in the
spinel lattice of the support, potentially influencing their
properties [59] and their long-term performance.
In the present work, the authors want to elucidate the long-
term chemical looping performance of a spray-dried Fe-based
oxygen carrier with an in-situ generated MgFeAlOx-support
and compare it with a previously optimized Al2O3-supported
oxygen carrier in isothermal Chemical Looping Hydrogen
Generation with methane and steam. In order to verify the
long-term chemical and mechanical stability of the oxygen
carriers and their performance during each cycle, the mate-
rials were used in numerous reactor tests in a lab-scale batch-
fluidized-bed reactor coupled with the appropriate analysis
and characterization techniques (MS, ex situ XRD, SEM, SEM-
EDS and crushing tests). During the first cycle, the Fe-
incorporation and release in and from the support were
investigated in detail, together with the complex reactions
and phase transitions which occur during the sequence of
reduction and oxidation reactions, in order to assess the
magnitude of take up of Fe-into the support and its influence
on the long term stability of the oxygen carriers. The chemical
performance of the MgFeAlOx-supported oxygen carrier for
syngas and hydrogen generation by Chemical Looping for
Hydrogen Generation was investigated for 60 cycles and the
reaction-induced changes in crushing strength, in surface
morphology and in oxygen carrier microstructure were also
evaluated for up to 60 cycles.
Materials and methods
Materials preparation
The oxygen carrier for this paper was synthesized by a spray
drying method according to our previous work [59,61]. Briefly,
for the MgFeAl OC, 60 wt% a-Fe2O3 (Alfa Aesar, 98% (metals
basis), 325 mesh powder), 11.3 wt% MgO (MAF Magnesite,
MagChem 30) and 28.7 wt% a-Al2O3 (Almatis, CT3000SG) par-
ticles (molar ratio MgO/Al2O3 is 1/1) were dispersed in de-
ionized water with the necessary dispersants. These suspen-
sions were homogenized by milling in a planetary ball mill
(Retsch, Pulverisette 5, Germany). After adding a suitable
polymeric binder, the suspension was spray-dried. The
chamber fraction collected underneath the cone was then
sieved to obtain particles of suitable dimensions for an in-
dustrial CL-process inside an interconnected fluidized bed
process. For the FeAl oxygen carrier, 60 wt% a-Fe2O3 and 40 wt
% a-Al2O3, was used.
These particles were then calcined at 500  C for 1 h in air
and afterwards a sintering procedure was performed in air at
1175  C for MgFeAl and at 1225  C for FeAl using a high tem-
perature furnace (Bouvier, Belgium) to obtain oxygen-carrier
particles with sufficient mechanical properties (strength and
attrition resistance).
The development of the OC's, the selection of their sinter-
ing temperature in order to achieve solid state reactions be-
tween Al2O3 and MgO, their resulting composition and
physical properties were already discussed in previous work
[59]. The most important parameters such as crushing
strength, Hg-intrusion porosity, as well as their composition
after sintering determined by Rietveld refinement are
included in Table 1. The observations of Baek et al. that Ni-
based OC supported on MgAl2O4 needed higher sintering
temperatures compared to Al2O3-supported OC for achieving
similar strengths [49,50] were also confirmed in our previous
paper [59]. We however, selected a lower sintering tempera-
ture for the MgFeAl OC as a sintering temperature of 1225  C
leads to particles with a decreased porosity.
Materials characterization
The microstructure of the oxygen carriers was investigated by
optical microscopy (SteREO Imager, ZEISS) and by scanning
electron microscopy using a FEI NOVA NanoSEM 450 with an
energy dispersive spectroscopy (EDS) system on polished
cross-sections of embedded particles inside an epoxy resin.
The cross sections were analyzed utilizing the Circular Back-
scatter (CBS) detector and an acceleration voltage of 20 kV.
The particle surface and morphology was also characterized
by scanning electron microscopy utilizing the same device in
SE mode on the fresh particles with the acceleration voltage
limited to 5 kV in order to only check the surface morphology
of the particles.
The crushing strength or compressive strength of the heat-
treated particles was measured using an Instron 5582 appa-
ratus with a 10 N load cell using a movement speed of 0.5 mm/
min. This crushing strength refers to the maximum obtained
strength before the particle starts to break. The analyzed
particles have a size in the range of 100e200 mm and at least 40
particles were individually measured per sample.
To characterize the phase composition of the oxygen car-
riers (ex-situ) during reaction powder X-ray diffraction (XRD)
experiments were done using a Philips X'Pert diffractometer
with PANalytical X'Pert Pro software with CuKa (l ¼ 1.5405 Å)
at 40 kV. The identification of the crystalline phases was done
by comparison of the peaks and the profile data in the dif-
fractograms with the database. For the ease of comparison
between diffractograms and to eliminate errors leading to the
displacement of the diffraction data, a TiO2-standard (around
20 wt%) was mixed and grinded together with the oxygen
carrier before the XRD measurement.
In order to separate the effects of (i) the change in cationic
distribution across the tetrahedral and octahedral positions in
the spinel lattice and (ii) the amount of MgFeAlOx or FeA-
l2O4-spinel, the relative intensities related to the (022), (113),
(115) and (044) planes of the FeAl2O4 spinel were compared as
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1
Table 1 e Resulting physical properties of spray-dried oxygen carriers FeAl sintered for 4 h at 1225  C and MgFeAl sintered
for 4 h at 1175  C, collected from previous work [59].
Crushing Porosity <5 mma [%] Porosity 5e50 mmb [%] a-Fe2O3 [%] a-Al2O3 [%] MgFe2O4 [%] Mg1-xAl2-yFexþyO4 [%]
Strength [N]
FeAl 3.1 23.1 10.7
MgFeAl 1.2 39.5 5.4
a
Calculated from Hg-porosity measurements of pore with sizes <5 mm in order to exclude interparticle porosity.
b
Calculated from Hg-porosity measurements of accessible pores in the range of 5 and 50 mm in order to include the cavity of the hollow
particles and a fraction of the interparticle porosity.
well as the relative intensities related to the (022), (004), (224),
(115) and (444) planes of the MgFeAlOx-spinel. As these in-
tensities did not change systematically during reaction, and as
the reactions took place at 900  C, a random cationic distri-
bution is most likely to be found in the material. It is thus not
possible to distinguish between take-up of Fe-cations in
octahedral or tetrahedral positions in the spinel lattice. For
sample FeAl, increase in intensities can thus be related to an
increase in the amount of spinel in the OC. For the MgFeAl OC,
an increase in intensity is the result of the take-up of Fe-
cations in the spinel, as on one hand Mg and Al have nearly
the same atomic scattering factor and on the other hand no
MgO and Al2O3 was detected during reaction.
The disadvantage of using (room temperature) ex-situ XRD
experiments for these reactions is that the oxygen carrier
material could be slightly modified during cooling down after
reaction. In this regard, in-situ XRD can offer a few advantages
for investigating such complex solid-state reactions the
moment they occur. Therefore, this technique has already
been used in oxygen carrier and catalyst development [62],
especially during TPR, TPO and isothermal cycling [63]. In-situ
XRD, however, is not suitable for measurements during op-
erations in a fluidized-bed setup with actual large, porous
particles as used in the process. Because this study especially
tries to evaluate the long term stability, combined with the
reactions which occur during one cycle, the use of ex-situ XRD
should be appropriate.
Reactor tests
Fig. 1 shows the small lab-scale fluidized bed reactor at VITO
used for investigating the reduction and oxidation reactions of
the oxygen carriers. Calibrated mass flow controllers intro-
duced a total flow of 100 sccm of inert and reacting gases in
the reactor resulting in a bubbling fluidized bed regime in the
quartz reactor tube of 6 mm internal diameter. During the
methane step, the oxygen carriers were reduced by 20 sccm
methane. During the oxidation phase, steam was generated in
a heated vaporizer from where inert gases such as nitrogen
and helium transport 0.020 ml/min vaporized water which
was introduced in the vaporizer by a HPLC pump. The exper-
iments were conducted at a temperature of 900  C to attain
sufficient reaction between CH4 and the oxygen carrier ma-
terial. The reactor temperature was measured by a thermo-
couple outside but in close contact with the reactor tube. The
composition of the gases exiting the reactor was measured
using mass spectrometry. During the oxidation step steam
was introduced for 20 min to make sure that complete
1377
55.8 44.2
34.9 0.7 0.9 63.5
oxidation with steam is achieved. The reaction with methane
was executed until the stoichiometry of the exiting gases in-
dicates the formation of cokes inside the reactor due to
methane decomposition. This cokes formation was deter-
mined by the mass spectrometer when the fraction of H2 and
H2O on CO and CO2 exceeds 3 (a safety margin of 50% was
deemed necessary for avoiding an early stop of the reduction
step due to momentarily fluctuations in the gas composition).
After the oxidation and reduction phases pure helium was
introduced for respectively 23 and 15 min of flushing before
moving on to the next step. When it was time to determine the
composition of the oxygen carrier by ex-situ XRD 100 sccm He
was introduced in the fluidized bed and the reactor was
cooled. Afterwards the OC was moved to a closed vessel before
analysis by XRD. For each reactor test new OC material was
introduced and subjected to the reacting gases. A list of all
reactor tests used in this paper is included in Table S1 in the
supporting information.
Results and discussion
Gas composition during reaction
Fig. 2 shows the composition of the gases that leave the
reactor during the first cycle of a representative reactor
experiment with both oxygen carrier FeAl and oxygen carrier
MgFeAl. An extensive amount of reactor experiments was
executed in order to investigate the composition of the oxygen
carrier by ex-situ XRD. The experiments were stopped at
different times during reaction, denoted by arrows in Fig. 2
and included in Table S1 in the supporting information. In
this paper, these changes within the oxygen carrier compo-
sition and the interactions between support and active phase
are discussed. The methane conversion and the H2 and CO
selectivity, calculated from the gas compositions are also
included in Fig. 2. These values are calculated by equations
(1)e(3) and their derivation is included in the supporting
information.


nCH4 ;ðconvertedÞ 1
nH2 þ nH2 O
Conversion ¼ ¼ 2
(1)
nCH4 ;ðintroducedÞ nCH4 þ 12 nH2 þ nH2 O
nH2 ;ðtotÞ
SelectivityH2 ¼ (2)
nH2 þ nH2 O
nCO
SelectivityCO ¼ 1
(3)
2
nH2 þ nH2 O
1378 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1

Fig. 1 e Schematic overview of the small scale fluidized bed batch reactor setup at VITO.

Fig. 2 e The composition of the gases leaving the reactor during the first cycle with both the FeAl (top) and MgFeAl (middle)
oxygen carriers. Also included are conversion of methane and selectivity towards hydrogen and CO of both materials during
the first reduction step (bottom). Arrows indicate the times at which the various reactor experiments were stopped for
collecting powder XRD.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1
where ni stands for moles of i in the gas of the outlet of the
reactor.
When investigating the gas compositions of both OC's
during one reactor test, a similar gas evolution is observed
during the reduction. This gas evolution can be broken down
into three different phases: (i) total oxidation of the fuel, (ii)
partial oxidation of the fuel and (iii) methane splitting. Fig. 3
schematically shows the underlying reactions with the oxy-
gen carrier in the Chemical Looping for Hydrogen Generation
process. Both partial oxidation products (CO and H2 from re-
action (a)) and their respective total oxidation products (CO2
from (b) and H2 from (c)) are observed in the gases exiting the
reactor. After sufficient reduction of the oxygen carrier also
methane splitting with carbon deposition is observed (d).
During H2O-oxidation in the regeneration step, the previously
deposited carbon is oxidized with the formation of CO and H2
(e) while the introduced steam regenerates the oxygen carrier
material with the formation of H2 (f).
During the first phase of the reduction (i.e. the first 5e8 min
in Fig. 2), the oxygen carrier transforms CH4 to CO2 and H2O.
This total oxidation is favored when the active phase of the Fe-
based oxygen carrier is present in its fully oxidized state
(Fe2O3). Almost no partial oxidation products are present in
the reactor and the selectivity to H2 and CO is lower than 20%
for both materials.
During the second phase of the reduction step, until 47 and
60 min in Fig. 2 respectively for the MgFeAl and FeAl oxygen
carriers, the reaction rate decreases significantly. More than
90% of the introduced CH4 remains in the gas stream after
contact with the OC in the fluidized-bed. CH4 reacts to a
mixture of total and partial oxidation products, although only
low amounts of CO2 are produced. CO selectivity is thus high
(>70%). The selectivity for H2 increases as the production of
H2O shifts towards H2-production at the end of this phase.
Fig. 3 e Chemical looping for hydrogen generation,
different reactions which may occur with and at the
surface of the oxygen carrier.
1379
During the third and final phase of the reduction step, until
62 and 90 min in Fig. 2, respectively for the MgFeAl and FeAl
oxygen carriers, the reaction rate increases significantly. The
MgFeAlOx- and Al2O3-supported oxygen carriers convert both
above 90% of the introduced methane. In this phase the
selectivity to CO drops as more CO2 forms and as, at the end of
the reduction step, cokes are deposited on the oxygen carrier
material due to metallic Fe-catalyzed methane splitting when
the lattice oxygen of the active material is depleted. At the end
of this phase, pure hydrogen is produced and less CO pro-
duction occurs.
After flushing with He, H2O is introduced in the reactor
during the oxidation step for regenerating the oxygen carrier.
Initially, this H2O oxidizes the previously deposited cokes into
CO. Afterwards, pure H2 is formed when the lattice oxygen of
the OC is replenished by reacting with H2O. The Fe-based
active phase shows very good performance in the hydrogen
production step as only limited time is needed for completely
regenerating both oxygen carriers and as significant hydrogen
production is observed. After the regeneration of the OC, H2O
is moving through the reactor bed unchanged and the oxygen
carrier is ready to react with methane. At 900  C H2O is not
suitable for regenerating the active phase in the OC to Fe2O3
due to thermodynamic limitations, but instead Fe3O4 is
formed after the oxidation step. During the second cycle, the
first phase of the reduction step as observed in the first cycle
will thus not occur and no significant total oxidation of CH4
will be found. It should also be noted that it is possible to stay
in the more reactive part of step 3 during continuous cycling
by limiting the amount of introduced H2O in the preceding
oxidation step. However, because we want to investigate the
deactivation pathway of the current OC and relate this to the
phases present in the material, we always fully oxidize the
oxygen carrier by H2O until no H2 is present in the gas stream.
Phase transformation during reaction within one cycle -
reactions with active phase
Included in Fig. 4 are the ex-situ XRD-maps that show the
evolution of the composition of the oxygen carriers during
both the reduction by methane/He and the oxidation by H2O/
He. The times at which each reactor experiment was stopped
for collecting the ex-situ XRD diffractograms were already
included in Fig. 2. Arrows indicate the transformations of the
active phases and these transformations can be associated
with the formation of certain reaction products in Fig. 2. It
appears that the transformations of the Fe-based active phase
under reacting conditions occur sequentially during both the
reduction and oxidation steps. This means that the mixing of
the particles in the fluidized-bed and the size of the pores in
the oxygen carriers were sufficient for achieving homoge-
neous reaction throughout the reactor bed. A figure with the
evolution of integrated peak values is included in the sup-
porting information (Figure S1).
The transformation of Fe2O3 to Fe3O4 occurs during the first
minutes of the reduction step for both materials as no Fe2O3-
peaks are detected in the XRD diffractograms collected from
oxygen carrier MgFeAl and FeAl after 5 and 10 min, respec-
tively. At the same time, methane is converted to total
oxidation products by the lattice oxygen of Fe2O3 (see Fig. 2).
1380 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1

Fig. 4 e XRD-map of oxygen carrier materials recovered from the lab-scale fluidized-bed reactor. The maps are built up from
ex-situ XRD diffractograms collected after stopping the experiment of oxygen carrier FeAl and MgFeAl at several times
during the reaction. (a) and (b) were collected from OC FeAl, and (c) and (d) from OC MgFeAl during reduction and oxidation,
respectively. Arrows indicate transformations of the active phase.

The presence of Fe2O3 thus delivers only limited selectivity
towards syngas production.
The next transformation from Fe3O4 to FeO proceeds much
slower. No Fe3O4-peaks are observed from 65 to 33 min on-
wards for the FeAl and MgFeAl oxygen carriers. It should be
mentioned that only 22% of the total theoretical amount of
transferrable oxygen from the active phase is released during
this transformation. This slow reaction step can be associated
with the step where limited reaction takes place in Fig. 2,
which indicates the limited reactivity of Fe3O4 with CH4.
The transformation of FeO to Fe proceeds much faster,
although three times more oxygen is released compared to the
previous transformation. This is due to the presence of
metallic Fe in the OC as this has a catalytic effect on the
methane decomposition reaction. This methane decomposi-
tion into C and H2 leads to CO-formation as the lattice oxygen
of the active phase in the OC is simultaneously oxidizing the
deposited C. When the FeO in the OC is gradually getting
reduced completely to Fe, more C is remaining in the OC and
eventually even the formation of Fe3C can be observed [64].
This Fe3C and the remaining C deposited on the OC pref-
erentially react with the H2O in the oxidation step, as CO-
formation can be observed at this time in Fig. 2. These side
reactions slightly increase the time where Fe is present in the
OC during the H2O introduction. Simultaneously Fe trans-
forms to FeO up to 8.25 and 5.7 min for OC FeAl and MgFeAl,
respectively. The further oxidation of FeO to Fe3O4 proceeds
very fast, which indicates the high reactivity of FeO with H2O.
After condensation of H2O, pure H2 is produced in the reactor.
As mentioned before, Fe3O4 will not be oxidized further to
Fe2O3 by H2O at reactor conditions due to thermodynamic
limitations, and no further transformations of the active
phase were observed when the H2-production from Fig. 2 was
stopped.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1
Both oxidation and reduction steps with sample MgFeAl
are finished earlier compared to sample FeAl (60 min
compared to 90 min for the reduction step and 8.25 compared
to 12 min for the oxidation step). It should be noted however,
that the total amount of active phase in the MgFeAl oxygen
carrier is lower compared to the FeAl-oxygen carrier (34,9%
compared to 55,8%) due to the take-up of Fe into the support
during the heat treatment after the synthesis. Additionally,
the porosity of sample MgFeAl is also higher (44.9% compared
to 33.8%) which should facilitate diffusion through the
material.
Phase transformation during reaction within one cycle -
interaction with support
Irreversible interactions that occur between the active phase
and the oxygen carrier support most often limit the longevity
of the OC under reacting conditions. These interactions can be
investigated by following the evolution of the composition of
the oxygen carrier during reaction, e.g. by ex-situ XRD as
shown in Fig. 4. Especially the relation between these in-
teractions and the oxidation state of the active phase is
important.
Fig. 5 shows the schematic representation of the first
chemical looping cycle with both oxygen carriers. By
comparing the intensities of the XRD-peaks from the
different reactor tests, a visualization of the trans-
formations of the active phases and of the interactions be-
tween active phase and support is created. The top and
bottom parts of Fig. 5 shows the transformations which
occur inside the FeAl and MgFeAl oxygen carriers, respec-
tively, during both reduction (left) and oxidation (right) steps
in the first cycle. The inside part shows the transformations
of the active phase, while the outside part shows the
transformations of the support. Some colored arrows denote
interactions between support and active phase, which result
in changes in intensity of respective peaks in the ex-situ
XRD diffractograms. The thickness of each arrow is related
to this change in intensity and thus the actual amounts of
material inside the oxygen carriers. Especially the in-
teractions between the support and active phase are
observed to be important for both materials. Colors are thus
used for indicating take-up (red) and release (green) of active
material into the support.
The top part in Fig. 5 essentially shows the deactivation
pathway of the FeAl oxygen carrier throughout one cycle, as
FeAl2O4 (hercynite) gradually accumulates during reaction.
The MgFeAlOx-support also interacts with the active phase, as
shown in the bottom part of Fig. 5, but at a much lower
magnitude. The active phase of this material regenerates after
each oxidation, which is an important factor leading to long
term chemical stability.
Hercynite formation is vital for the stability of the FeAl
oxygen carrier as it leads to its deactivation. This hercynite
formation occurs especially when phases that contain FeII are
present in the sample. Especially during the transformation
from Fe3O4 to FeO, the amount of FeAl2O4-spinel increases
significantly, as indicated by the large red arrow in Fig. 5. In
the meantime, the intensities of the Al2O3-peaks slightly
decrease.
1381
During the subsequent reduction of FeII, present in the FeO,
to Fe0, a significant amount of the recently formed FeAl2O4-
phase regenerates back to Fe0 and Al2O3. This is denoted by
the green arrow in Fig. 5. However, some hercynite remains in
the oxygen carrier as indicated by the peaks in the XRD-
diffractograms (see Fig. 4).
During the oxidation of Fe to FeO with steam, the amount
of FeAl2O4 is increased again to earlier levels. Even when
oxidizing the active phase to Fe3O4, the active phase further
reacts with the support, leading to the accumulation of
FeAl2O4. During the complete oxidation step with H2O, no
hercynite reacts with H2O and no regeneration is observed as
denoted by the red arrows and red shade at the center of the
FeAl-part of the figure.
The amount of Fe3O4 present after the oxidation of the
oxygen carrier is lower compared to during the reduction step
due to the take-up of Fe into the support. This could lead
eventually to the deactivation of the oxygen carrier when the
amount of active phase decreases further after each cycle.
This is especially true if the release of active phase from the
hercynite during the last phase of the reduction step is
insufficient, when compared to the total take-up of active
phase into the support during one cycle.
During the reduction of the MgFeAl OC, similar interactions
between active phase and support occur. However, the
changes in intensity are much smaller and the take-up of Fe
into the support occurs at much lower magnitudes, which is
denoted by the much finer lines in Fig. 5. During the initial
transformation of the active phase from Fe2O3 to Fe3O4, the
area of the support peaks stays nearly constant. However, the
XRD-peaks related to the MgFeAlOx-support shift to lower
two-theta values, which corresponds to an increase in the
lattice parameter from a ¼ 8.157 to 8.186 (see arrow in
Figure S2 in supporting information). This increase in lattice
parameter can be explained by a reduction of at least part of
the FeIII-cations in the spinel lattice, as FeII ions are larger than
FeIII-ions. This partial reduction from FeIII to FeII in the
MgFeAlOx-support was also observed during similar reaction
conditions in a recent paper of Dharanipragada et al. [63].
During the following transformation of the active phase to
FeO, the XRD-peaks of the MgFeAlOx-phase increase slightly
in intensity, which means that more Fe-ions are being incor-
porated into the support. This is denoted by the small red
arrow in Fig. 5. During the reduction of FeO to Fe and Fe3C, the
intensities of the XRD-peaks drop again, similarly to the OC
with the Al2O3-support, while they slightly shift to a higher
two theta value. Both the peak shift and the change in in-
tensity indicate that Fe is getting released from the support
when the active phase is completely transformed to metallic
Fe. (i) The peak shift indicates a slightly smaller unit cell
(a ¼ 8.178) after reduction, which can be achieved after a
partial release of Fe from the support, as MgII and AlIII have
smaller ionic diameters compared to Fe-cations. (ii) The
decrease in intensity of the XRD-peaks indicates a smaller
structure factor while both Mg and Al have lower atomic
scattering factors when compared to Fe. Additionally, no for-
mation of MgO or Al2O3 is detected during the reduction of the
active phase.
During the initial oxidation of the MgFeAl oxygen carrier,
similar behavior as for sample FeAl is observed. Some active
1382 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1

Fig. 5 e Chemical transformations in FeAl (top) and MgFeAl (bottom) oxygen carriers during the first chemical looping cycle.
Red arrows denote incorporation of active phase into support, while green arrows denote release of Fe from the support.
The thickness of the arrow is an indication of the amount of phase that reacts or transforms. The transformations inside the
circle are those related to the active phase and the transformations of the outside layer are those related to the support
material. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this
article.)

phase also incorporates into the support when oxidizing Fe to for Fe-based oxygen carriers, shows a partial regeneration and
FeO. However, when the active phase oxidizes further to release of active phase during oxidation by steam. This is very
Fe3O4, the intensities of the MgFeAlOx-peaks decrease again. different when compared to utilizing Al2O3-supports or for
This indicates that the MgFeAlOx-spinel, as support material example Fe-based-perovskites supports [65]. After oxidation
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1
by steam, the XRD-peaks of the support material have reduced
areas in intensities when compared to the original intensities
before reduction. Because the active phase of the oxygen
carrier is still regenerated completely to Fe3O4 as similar in-
tensities are observed as during the reduction step, it is shown
that the take-up of the Fe-ions in the support does not sys-
tematically decrease the amount of active phase throughout
the cycle. This shows that the utilization of the MgFeAlOx-
support combined with a pure Fe-based active phase leads to
an oxygen carrier which can be regenerated by steam.
Long term stability of oxygen carriers
Composition, microstructure and surface morphology of oxygen
carriers
After investigating the reactions, transformations and in-
teractions that occur throughout one chemical looping cycle,
it is interesting to investigate the long-term stability and
performance of the oxygen carrier materials. Therefore, the
oxygen carriers underwent several experiments with multi-
cycle chemical looping operation with ex-situ XRD after
multiple reduction or oxidation steps. In this way, the
composition of the oxygen carriers was followed for up to 11
oxidations for the FeAl oxygen carrier and for up to 60 oxi-
dations for the MgFeAl oxygen carrier. These ex-situ XRD-
diffractograms are included in Figs. 6 and 7 for the FeAl and
MgFeAl oxygen carriers, respectively.
In Fig. 6, which shows the ex-situ XRD map of diffracto-
grams collected after the oxidation step for the FeAl oxygen
carrier for up to 11 cycles, it is shown that hercynite is accu-
mulating throughout this period. The area of the peak at a 2q-
value around 30.2, related to the Fe3O4-phase, is decreasing by
about 85%, indicating a deactivation of the active phase in the
oxygen carrier.
This systematic deactivation can be explained by the
transformations that were discussed in section 3.3, together
with Fig. 5. Essentially, the inability of steam to regenerate
FeAl2O4 decreases the amount of active phase present in the
Fig. 6 e XRD-map of sample FeAl, determined by ex-situ
XRD after up to 11 oxidation cycles.
1383
OC after each cycle, and thus limits the ability of the OC to
transform methane to syngas.
In Fig. 7, the composition of the MgFeAl OC is followed for
up to 60 cycles. In the left part, ex-situ XRD-diffractograms are
combined for up to 20 reduction steps, while the right part
includes ex-situ XRD-diffractograms for up to 60 oxidation
steps.
After each oxidation step, full oxidation of the active phase to
Fe3O4 occurs as no peaks around a 2q-value of 60.9, related to a
FeO phase, are detected. In the meantime, a very slight decrease
in active phase for about 10% after 60 oxidation cycles is
observed from the peak areas of the Fe3O4-peaks. This decrease
in active phase is already appearing after 11 cycles, and after-
wards no lower peak areas are observed for the other samples,
indicating a stable performance without significant deactiva-
tion. This is significantly lower compared to the 85% decrease in
amount of active phase inside the FeAl OC after 11 cycles.
After 11 and 20 reduction cycles an increased amount of
metallic Fe is present. This can be explained by the change in
microstructure as shown by the SEM-EDS data from the cross
sections of the OC displayed in Fig. 8, which shows SEM-EDS
images for both the FeAl (left) and MgFeAl (right) oxygen
carriers.
Fig. 8 (a) and (b) show the microstructure before reaction
indicating a slightly larger grain size of Fe2O3 in the MgFeAl
oxygen carrier. (c) and (d) show the microstructure after 1
oxidation cycle, where already differences can be observed
between both oxygen carriers, such as a noticeable change in
intensity which is due to the take-up of Fe into the support in
the FeAl oxygen carrier. (e) and (f) show the microstructure
after deactivation (9 cycles) for the FeAl oxygen carrier and
after 60 cycles for the MgFeAl oxygen carrier, respectively.
For the SEM images of the MgFeAl oxygen carrier, after 1
and 60 oxidation cycles, the observed microstructure in-
dicates an enhanced Fe-dispersion and the generation of finer
grains of active phase and support, accompanied with an in-
crease in observed porosity and thus an absence of significant
sintering during chemical looping. This decreases the dis-
tance by which the Fe-cations and O2--anions need to diffuse
during the various chemical transformations of the active
phase and the support thus possibly enabling faster attain-
ment of a situation where equilibrium is achieved and where a
maximum amount of Fe can be incorporated and released
from the support during one cycle. The enhancement of the
dispersion of active metal oxides in the materials when uti-
lizing MgAl2O4-supports has also previously been reported for
Ni-based materials [66].
The SEM images of the FeAl oxygen carrier cross sections
clearly show the deactivation of the material as Fe is taken op
into the support when the active phase reacts with the Al2O3
to FeAl2O4. The images also indicate a decrease in porosity
during multiple chemical looping cycles.
Fig. 9 displays the surface morphology of the oxygen carrier
particles (a) before reaction, (b) after an almost complete
reduction, (c) after the first oxidation and (d) after the oxida-
tion in cycle 60. More SEM images are included in the sup-
porting information (Figure S8 e S11). By SEM-EDS, the darker
particles were determined to be systematically Fe-rich (Fe2O3,
the active phase of the oxygen carrier) and the lighter particles
were determined to be Mg- and Al-rich (corresponding to the
1384 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1

Fig. 7 e XRD-map of sample MgFeAl, determined by ex-situ XRD after several reduction (left) and oxidation (right) cycles.

Fig. 8 e SEM and SEM-EDS images from cross sections of sample FeAl after sintering, 1 and 9 oxidation cycles (left) and from
MgFeAl after sintering, 1 and 60 oxidation cycles (right). Lighter parts are locations with more Fe (red in EDS), while Mg- and
Al- rich parts are darker (respectively green and blue in EDS). The white scale bar represents 20 mm. (For interpretation of the
references to color in this figure legend, the reader is referred to the Web version of this article.)

MgFeAlOx-support). While the support particles remain
largely unchanged in size and morphology, the particles of the
active phase change in morphology and size during the take
up and release of lattice oxygen in the chemical looping
process.
In the sample before reaction, two different types of par-
ticles can be clearly distinguished: (i) large Fe2O3-particles
with a clearly defined crystal structure and crystal facets and
(ii) smaller MgFeAlOx particles. After 52 min of methane
introduction, the active phase is reduced to FeO and a-Fe (see
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1 1385

Fig. 9 e SEM and SEM-EDS images from the surface of sample MgFeAl (a) before reaction, (b) after 52 min of reduction in the
first cycle, (c) after oxidation during the first cycle and (d) after oxidation during the 60th cycle. Darker parts are locations
with more Fe (red in EDS), while Mg- and Al- rich parts are lighter (respectively green and blue in EDS). The white scale bar
represents 2 mm. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version
of this article.)

Fig. 4). The morphology of the Fe-oxide particles also greatly
changes during this reduction step, due to the release of lat-
tice oxygen and the accompanied phase transformations
which occur. The particle morphology of the active phase does
not show distinct features at this moment. In Figure S9 in the
supporting information, however, some crystal facets can still
be observed with higher magnification. After the first oxida-
tion, the active phase is oxidized completely to Fe3O4 which
again clearly changes the crystal morphology due to the take-
up of lattice oxygen on preferential sites leading to a specific
grain growth resulting in defined and characteristic crystal
morphology. A similar, but lightly less distinguishable crystal
morphology is observed after the oxidation after 60 cycles.
In all SEM-images the MgFeAlOx-particles have approxi-
mately the same size and no distinct crystallographic features
are observed. The active Fe-based phase clearly changes in
crystal structure due to the oxidation-reduction reactions. The
crystal facets change during take-up and release of oxygen
and the size of the grains seems to decrease over time (this is
also observed in Fig. 8), which indicates that the use of the
MgFeAlOx-support limits sintering of the active phase.
Evolution of the mechanical properties
The SEM images in Fig. 8 indicate that the porosity of the ox-
ygen carrier material changes over time. Because this change
in porosity accompanied with a change in oxygen carrier
composition might affect the mechanical properties of the
material, it is important to check if the oxygen carrier still
possesses enough strength to withstand industrial scale
chemical looping operation. In order to provide some insight
into the effect of the chemical transformations of the oxygen
carrier material on the mechanical performance, Fig. 10 in-
cludes crushing strength data from OC-samples of both
MgFeAl and FeAl oxygen carriers. For these crushing strength
measurements OC-samples were removed from the reactor
during the reduction and oxidation in the first cycle and after
oxidation after multiple cycles. SEM images from cross sec-
tions of these oxygen carriers and the indication of the
porosity of these cross sections are included in supporting
information (Fig S4 e S7).
During the first cycle, similar trends were observed for both
oxygen carriers. When the active phase of the oxygen carrier
is reduced by methane, a decrease in crushing strength is
observed. During the subsequent reaction with H2O, the
crushing strength increases again. This trend can be
explained by the effect of the change in molar volume of the
active phase present in the oxygen carrier, as this will affect
the porosity of the OC materials. The changes in molar volume
of the active iron-based phases inside the oxygen carrier,
recalculated per mole Fe for comparison purposes, are
included in Table 2. It is shown that the active phase shrinks
significantly when FeO and Fe are formed. Due to the presence
of the support, a large shrinkage of the total particle is
inhibited and its porosity will increase. The totally reduced
samples, which have a maximum increase in porosity, then
possess the worst mechanical properties. After complete
reduction, the FeAl and MgFeAl oxygen carriers possess
respective crushing strengths of 1.5 ± 0.2 N and 0.60 ± 0.09 N.
After oxidation the reverse effect happens and the crushing
strength increases again to approximately the original values.
During long term operation it can be noted that the
crushing strength of the MgFeAl oxygen carrier drops
1386 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1
Fig. 10 e Crushing strength evolution of MgFeAl and FeAl oxygen carriers during the first cycle and during long-term
chemical looping operation.
gradually up to 10 cycles from 1.09 ± 0.17 N to 0.80 ± 0.08 N
after oxidation (by 27%). Afterwards, only a slight additional
drop of 0.04 N (3.7%) could be measured during operation for
up to 60 cycles. This indicates that the material reaches stable
operation after a few cycles. The crushing strength of
0.76 ± 0.09 N is low compared to the broadly accepted limit of 1
and 1.5 N, however it should be noted that no significant
degradation or breakage of the particles was observed after
prolonged operation in the lab-scale fluidized-bed system (see
Figure S8 in the supporting information for a SEM overview of
both fresh and used particles). Furthermore, the authors want
to stress the fact that crushing strength results are signifi-
cantly influenced by the size of the investigated particles.
These relations between degradation during operation, the
size of the investigated particles, their attrition resistance and
their crushing strength are important aspects for further
investigation.
During the deactivation of the FeAl oxygen carrier, no real
trend in the change of the crushing strength is observed.
During the first cycle, however, the crushing strength clearly
decreases during the reduction and increases afterwards
when the oxygen carrier is regenerated, similarly to the
MgFeAl oxygen carrier.
Long-term chemical performance
This change in microstructure also affects the chemical
performance of the oxygen carrier during its reaction with
CH4. Fig. 11 shows the conversion of methane and the
selectivity to H2 and to CO production during several reduc-
tion steps of the MgFeAl oxygen carrier. In the top part, the
conversion and selectivity are plotted against the actual time
in minutes. The time needed for complete reduction of the
Table 2 e Molar volumes for active iron phases (corrected
to 1 mol of Fe).
Density [g cm3] V’M [ml/mol Fe]
Fe2O3 5.28 0.0661
Fe3O4 5.20 0.0674
FeO 5.87 0.0816
Fe 7.66 0.1407
active phase in the MgFeAl OC is systematically reduced
from 34 min on stream for cycle 2 to around 19 min on stream
for cycle 60, although the total amount of methane converted
during the reduction step stays nearly the same for all cycles.
Because no systematic observations can be made from the
selectivity data when all cycles are compared in this way, the
conversion and selectivity are plotted against the relative
times of each cycle in the bottom part of Fig. 11. In this way
the unreactive and reactive parts of the reduction step can be
compared with each other more easily. The vertical dotted
line in Fig. 11 indicates the border between the unreactive
and reactive parts during the reduction step (around 60e70%
of the time when methane is introduced in the oxygen carrier
bed). During the unreactive state, the selectivity to CO and H2
generally increases during the reduction of the oxygen car-
rier, as was also observed in the first cycle. It can, however,
be observed that the length of the unreactive part decreases
from 70% of the total time to around 62% of the total time
accompanied by a slight increase in reactivity (from 5% to 8%)
and a major change in selectivity to CO (from 80% at cycle
2e45% at cycle 60, denoted by the arrow). The selectivity to
H2 stays nearly constant. These changes in selectivity and
reactivity can also be explained by the improved dispersion
of the active phase and increase in porosity, visible from SEM
in Fig. 8. This change in microstructure improves the contact
between the active material and the reactive gases, thus
enabling the further conversion of syngas towards total
oxidation products. The selectivity for both CO and H2 is
however always high (>70%) during the time-step where the
largest amount of CH4 was converted, especially before sig-
nificant cokes deposition due to methane splitting is
observed (indicated by the drop in CO selectivity denoted by
the dotted orange and black lines in Fig. 11). Therefore, it can
be stated that long-term operation does not significantly
impact the syngas production, and overall high syngas yields
are obtained.
Stable chemical looping operation is thus observed for at
least 60 cycles with the MgFeAl OC, while the microstructure
gradually changed towards a more porous OC with a more
dispersed active phase. The increase in porosity during multi
cycle CLHG experiments for an Fe-based MgFeAlOx-supported
oxygen carrier was also observed by Ma et al. [67].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1
During repeated isothermal cycling for sample FeAl, a
microstructure with one region of FeAl2O4 and reduced
porosity forms (see Fig. 8). As the active phase gradually in-
corporates into the support, sintering occurs. After 9 cycles,
only a small amount of active phase remains and is present at
the outside layer of the OC. This amount of OC is insufficient
for significant chemical looping operation and sample FeAl
deactivates after 9 cycles.
In the CLHG process, the oxygen carrier should also be able
to selectively produce hydrogen gas during the regeneration
step with H2O. It is important that the hydrogen production
remains stable and reproducible, cycle after cycle, and that a
minimum amount of CO is produced, especially during long
term operation. The primary focus should be avoiding the
cokes deposition on the surface of the oxygen carrier, but
sometimes the carbon can be stripped from the oxygen carrier
in a separate step [68]. Especially during long term operation
stable H2-production is very important.
From Fig. 2 and from Figure S3 in the supporting informa-
tion three different stages can be distinguished during oxygen
carrier regeneration. In a first stage, only CO production due to
the oxidation of the cokes deposited on the oxygen carrier (or
conversion of Fe3C to Fe þ CO) is observed. In a second stage, a
plateau with high H2O-conversion to H2 is observed with
limited CO production. In a third stage, a plateau with lower
H2O-conversion to H2 is observed. The diffraction data from
Fig. 11 e Methane conversion and selectivity to CO and H2 of different cycles during long-term experiments of the MgFeAl
oxygen carrier, plotted against absolute (top) and relative time (bottom).
1387
Fig. 5 shows that the high plateau is obtained during the
oxidation of the reduced active phase to FeO. Correspond-
ingly, the low plateau is obtained during additional oxidation
of the active phase to Fe3O4.
Fig. 12 shows the H2O-conversion, the selectivity to
hydrogen production and the actual moles of H2 produced in
each cycle as well as the amount of cokes removed from the
oxygen carrier. Similarly to the previous paragraph, the H2-
production is split into different parts. Part 1 corresponds to
the high plateau, part 2 corresponds to the low plateau and the
total is from the beginning of the oxidation step to the end of
the low plateau (initial C-oxidation included). Also the C-
oxidation is split up in two parts: The cokes before actual H2-
production is observed (which could be removed in a C-
stripper without a drop in H2-production) and the cokes which
are removed during the actual H2-production process.
In Fig. 12 it is shown that high conversion (around 60%) of
H2O to H2 can be obtained, especially when Fe is converted to
FeO (part 1). When looking at the whole oxidation step, around
50% conversion of H2O to H2 occurs. A high selectivity for H2-
production is observed. During the two plateaus, a reproduc-
ible selectivity of more than 95% is obtained. When the
deposited carbon would not be stripped before H2-production,
the selectivity to H2 still exceeds 75%. Accordingly, large
amounts of hydrogen are produced in each cycle compared to
the cokes that are present and removed from the sample by
1388 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1
Fig. 12 e Oxygen carrier performance (H2O conversion, selectivity to H2) and cokes formation during H2-production during
long-term chemical looping.
H2O-oxidation. In average during one steam-regeneration
step, 5.1 mmol of H2 is produced, 1 mmol of C is removed
before H2-production and 0.1 mmol of C is removed during H2-
production. As shown in Fig. 12, these values remain relatively
stable throughout the long term experiment. Additionally it is
interesting to note that the obtained value of the first cycle is
in good agreement with the oxygen transfer capacity calcu-
lated from the composition of the initial oxygen carrier (34.9%
Fe2O3 (from Table 1) completely reduced to Fe would be able to
generate 5.8 mmol H2 during the oxidation to Fe3O4).
Conclusions
Two different spray-dried Fe-based oxygen carriers (OC), sup-
ported on a-Al2O3 and MgFeAlOx, were extensively investigated
by numerous reactor tests coupled with ex-situ XRD for the
Chemical Looping for Hydrogen Generation (CLHG) process.
The pathway by which the Al2O3-supported OC deactivated was
elucidated. Also their long term performance for reactions with
methane and steam their and chemical stability for up to 60
cycles were investigated, and related with their mechanical
strength and microstructure as observed by SEM-EDS.
Both supports partially showed similar behavior. (i) When
oxidizing or reducing the active Fe-based phase to wustite
(FeO), FeII-cations incorporate into both the supports. (ii)
During the complete reduction of the active phase by CH4,
both hercynite (FeAl2O4) as the MgFeAlOx-support release part
of the active phase. While FeAl2O4 transforms into Al2O3 and
Fe, the stoichiometry of the MgFeAlOx-support slightly
changed, and no MgO or Al2O3 was formed.
While the MgFeAlOx-supported OC was chemically stable
for up to 60 cycles due to its regenerability by H2O, the Al2O3-
supported OC deactivated after 9e11 cycles because H2O did
not regenerate the FeAl2O4 phase.
The microstructure of both materials also changed during
the multi-cycle experiments. While the accumulation of
FeAl2O4 leads to a decrease in porosity and a reduced disper-
sion of the active phase, prolonged cycling showed a favorable
change in microstructure for the MgFeAl OC. An enhanced Fe-
dispersion, increased porosity and the generation of finer
grains activated the MgFeAl OC, as slightly higher reactivity
and a lower time for completely converting the active phase
was observed after multiple cycles. The crushing strength of
the MgFeAl OC decreased gradually by 27% after cycle 11 but
then remained stable until at least 60 cycles.
With these isothermal lab scale experiments for up to 60 cy-
cles, the first step has been made towards an industrial imple-
mentation of these Fe-based OC in a CLHG-process. The Fe-based
active phase displayed a conversion of H2O of at least 50% and H2-
selectivity of at least 75% during the subsequent hydrogen gen-
eration steps (selectivity higher than 95% during actual hydrogen
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 3 7 4 e1 3 9 1
production after initial cokes oxidation). An optimization of
reactor conditions combined with the presence of the reactive
oxidation states by a proper coupling of both the reduction and
oxidation reactors will also enable sufficient syngas generation
while limiting cokes formation. And especially the partly
regenerable MgFeAlOx-support seemed suitable in combination
with the Fe-based active phase for the CLHG-process as it
enabled a large oxygen transfer capacity without sintering of the
grains and without long term deactivation. The next step to-
wards industrial implementation would be a demonstration of
the performance of these sustainable, non-toxic and cost effec-
tive particles in a larger scale coupled fluidized-bed reactor.
Acknowledgements
This work was supported by the FWO-Vlaanderen (Fund for
Scientific Research) [grant number 1S16516N].
Y. De Vos also thanks R. Kemps, M. Mertens, A.M. De Wilde,
M. Gysen, D. Vanhoyweghen, and P. Lens at VITO for their
technical support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2018.11.099.
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