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Oxygen carrier materials and their role in chemical
looping reactions for fuel conversion
Vidya S Batra1 and Hung-Pin Li2
Oxygen carrier materials offer an attractive means of providing
oxygen for fuel oxidation without contact between fuel and air
thus facilitating CO2 capture and storage. Materials such as
metal oxides, perovskites on different supports have been
examined. The efforts are to achieve high activity, durability
over multiple cycles, mechanical strength to handle fluidized
bed conditions and low toxicity. Studies on use of economical
natural and waste materials have also been reported. The
preparation methods include ones like spray drying that are
suitable for scale up.
Addresses
1
The Energy and Resources Institute, India Habitat Centre, Lodi Road,
New Delhi 110003, India
2
Jinwen University of Science & Technology, New Taipei City 23154,
Taiwan
Corresponding author: Batra, Vidya S (vidyasb@teri.res.in)
Current Opinion in Chemical Engineering 2017, 15:44–48
This review comes from a themed issue on Material engineering
Edited by Thein Kyu and Jai A Sekhar
For a complete overview see the Issue and the Editorial
Available online 26th December 2016
http://dx.doi.org/10.1016/j.coche.2016.11.006
2211-3398/# 2016 Elsevier Ltd. All rights reserved.
Introduction
Reaction of fuel with oxygen is necessary for its combus-
tion. When air is used, dilution with nitrogen takes place.
Also, the CO2 formed has to be separated from the other
flue gases for its sequestration. Therefore it is attractive to
have the fuel react with pure oxygen so that only CO2 and
H2O are formed from which CO2 can be easily separated.
In view of increasing interest in carbon sequestration and
storage, such an option is being increasingly examined
using oxygen carrier materials (OCM).
Oxygen carrier materials are typically single or mixed
metal oxides used in chemical looping combustion
(CLC) or reforming (CLR). On the basis of the composi-
tion, these materials are also catalytically active (e.g. NiO)
and in some cases, the OCM is combined with an active
catalyst. In combustion complete oxidation of fuel to CO2
and H2O takes place while in reforming syngas comprising
CO and H2 is produced. The lattice oxygen in the OCM
Current Opinion in Chemical Engineering 2017, 15:44–48
takes place in the reaction with the fuel either in the solid
form from its surface or by releasing gaseous oxygen in the
reduction cycle (chemical looping with oxygen uncou-
pling). The reduced material can then be regenerated
in an oxidizing cycle. Equations 1 and 2 below show the
two cycles for complete combustion or partial oxidation.
Fuel=tar þ Mex Oy ! Mex Oy1 þ CO2 =CO þ H2 O=H2
reducingcycle (1)
Mex Oy1 þ 12O2 ! Mex Oy oxidizingcycle (2)
The OCM is typically in the form of powdered material
and is recirculated between the reducing and oxidizing
reactors. In some instances, the OCM is used in the form
of dense membrane in a membrane reactor where the
oxygen is consumed at the reduction side where the fuel
is passed and is replenished by the oxygen from the
oxidizing side where air is passed (Figure 1).
The properties expected in OCMs are high activity,
durability over multiple cycles, mechanical strength to
handle fluidized bed conditions and lack of toxicity
related to its eventual disposal. From the reaction point
of view, the key properties are reactivity at temperatures
well below the melting point; no agglomeration or sinter-
ing at operating temperature; thermodynamic properties
which will determine the theoretical limitations; compo-
sition, size, porosity and surface area which effects the
oxygen mobility from bulk to surface, diffusion of reac-
tant and hence the kinetics of the reaction. Transition
metal oxides are commonly used as OCMs. To achieve
the combination of properties, the metal oxides are often
supported on inert oxides such as SiO2, TiO2, ZrO2,
Al2O3. To achieve higher activity, mixed oxides and
perovskites are also commonly used. While many re-
search activities are underway, there are also commercial
and pilot systems being tested such as 200 hours opera-
tion of 25 kWth coal CLC using iron based oxygen carrier
(http://oee.osu.edu/successful-200-hour-continuous-
operation-of-coal-direct-chemical-looping-combustion-
technology.html, accessed 16 November 2016) and auto-
thermal CLC of coal in a 1 MWth pilot plant using
ilmenite as oxygen carrier [1]. In this paper, the recent
trends in the development of OCMs and their applica-
tions are discussed.
Transition metal based single and mixed
oxides
Oxides of nickel, copper, iron, manganese, cobalt have
been commonly used. Nickel oxide has been widely
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 Oxygen carrier materials for energy applications Batra and Li 45
Figure 1
N2 CO2
O2 H2O
MexOy
Air Fuel
reactor reactor
MexOy-I
Air Fuel
(a) Chemical looping combustion with
oxygen carrier material
Illustration of oxygen carrier material and oxygen transport membrane.
studied due to its high activity, ability to withstand high
temperatures and low volatility; however, due to concerns
of cost and toxicity, alternate materials are being exam-
ined.
Co modified Ni-Al2O3 has been studied. The presence of
Co decreased the activation energy for hydrogen desorp-
tion and Co–Ni/Al2O3 reduction. This was attributed to
reduced metal-support interaction which increased the
activity of the material [2]. The material also showed
stability over multiple CLC cycles [3].
In order to improve performance of NiO (which also has
a high catalytic activity) supported on Y-Al2O3, Ca and
Mg aluminates were used or a-Al2O3 was used. These
were found to have better reactivity and selectivity in
the chemical looping combustion of methane since
there was less interaction between catalyst and support
[4]. NiO on g-Al2O3 and a-Al2O3 has been tested for
chemical-looping auto-thermal reforming (CLR) of
methane for syngas production. Both catalysts showed
good conversion but a-Al2O3 support had higher reac-
tivity [5]. Ni based oxygen carriers on a-Al2O3 support
have been tested for CLC of methane in the presence
of sulphur (H2S). Formation of nickel sulphide and
catalyst deactivation took place. However, the catalyst
regained its activity when H2S in the feed was stopped
and it was concluded that fuel with less than 100 ppm
H2S can be used in CLC [6]. The same group tested
presence of light hydrocarbons C2H6 and C3H8 in the
fuel stream and found that above 9008C, complete
conversion took place [7].
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Methane Syngas
CH4 + O2– → CO + 2H2 + 2e–
O2–↑ ↓e–
oxygen
Air depletion
CH4 CO N2 O2 H2
(b) Methane reforming with oxygen
transport membrane
Current Opinion in Chemical Engineering
Solgel method combined with solution combustion
synthesis was used to prepare Fe2O3/Al2O3 where
Fe2O3 was the active material and Al2O3 the support.
Nitrate salts and urea were dissolved in water and aged
to form a sol which was dried to obtain the gel. The gel
was ignited at 6008C and calcined at 9508C. The
ignited gel had a mixture of Fe2O3 and FeAl2O4 and
after calcination a mixture of Fe2O3 and
Al2O3. Hydrogen TPR showed a single step reduction
from Fe2O3 to Fe and this was attributed to high
transfer rate of lattice oxygen. The material showed
stable mass loss and mass loss rate over four reduction–
oxidation cycles [8]. Methods such as combustion
synthesis and carbon combustion synthesis also offer
an economic way to obtain ceramic oxides powders, also
in a nano form [9,10].
Complex oxide of Ce and Fe was prepared using
coprecipitation method by preparing solution of the
respective nitrates in an equimolar ratio of Ce and
Fe, followed by precipitation by adding NaOH and
ammonia. The precipitate was dried and calcined at
8008C. The calcined sample mainly showed phase of
CeO2 which implied that iron oxide was present in too
small a size to be detected and/or was in solid solution
with CeO2. From the O2-temperature programmed
desorption (TPD) and H2-temperature programmed
reduction (TPR), it was concluded that the sample
had adsorbed oxygen as well as bulk lattice oxygen.
With successive cycling of methane oxidation and re-
generation, the lattice oxygen played a more active role
and selectivity improved [11].
Current Opinion in Chemical Engineering 2017, 15:44–48
46 Material engineering
Oxygen carrier based on CeO2–Fe2O3 has been used in
two step steam reforming of methane. In the first step,
methane reaction with OCM is carried out to obtain
syngas. In the second step the regeneration of metal is
done in steam instead of oxygen, thereby generating
hydrogen. The CeO2–Fe2O3 was prepared by co precipi-
tation using nitrates and was stable over successive cycles.
CuFeO3 formation took place over successive redox
cycles which contributed to good durability and activity
[12].
Commercially procured CuO was tested as oxygen carrier
for chemical looping combustion of solid coal fuel. It was
observed that it reduced completely to Cu in the reduc-
tion cycle without any carbon deposits. The reduction
started at temperatures of around 5008C [13].
Perovskites
In an attempt to find a substitute for Ni based OCM for
CLC which has the disadvantage of high cost and envi-
ronmental concerns, the INNOCUOUS project short-
listed CaMn0.9Mg0.1O3d and CaMn0.775Mg0.1Ti0.125d
as suitable alternatives. These were prepared using spray
drying since it is cost effective and easy to scale up [14].
BaCoxFeyZrzO3d (BCFZ) perovskite has been prepared
by modified citrate method. The nitrate salts of the
metals were dissolved in EDTA (ethylenediaminetetraa-
cetic acid)–NH3H2O solution and citric acid was added.
Gel was obtained from the solution which was then dried
and calcined. The powders were used to prepare hollow
fiber form and combined with Ni catalyst for partial
oxidation of methane. Good activity was obtained for
conversion of methane to syngas. The reaction pathway
was attributed to oxidation of methane to CO2 and H2O
and subsequent reforming of remaining methane with
CO2 and H2O to form syngas [15].
CSFM (Ca0.5Sr0.5Fe0.5Mn0.5O3d) perovskite has been
prepared with starting oxides in the required ratios and
solid state reaction between them. These powders have
been used to prepare honeycomb which was further
coated with NiO catalyst slurry for tar partial oxidation
[16].
Manganese and copper based oxides have been exam-
ined. To overcome thermodynamic and kinetic limita-
tions in the conversion of Mn3O4 to Mn2O3,
CaMn(1x)MgxO3d perovskite has been studied. The
precursors Ca(OH)2, Mn3O4, and MgO were formed into
a slurry and spray dried followed by sintering in the
temperature range 1100–13008C. The prepared samples
showed presence of CaMnO2.95 and MgO. The low ionic
radius of Mg was the possible reason for Mg not being
incorporated in the perovskite. The improvement in
performance in the presence of MgO was attributed to
its role in the oxidation reaction possibly as a catalyst.
Current Opinion in Chemical Engineering 2017, 15:44–48
CaMn(1x)MgxO3d perovskite gave more than 97% con-
version for methane combustion and complete conversion
for syngas conversion in the temperature range 900–
10508C; good stability was obtained for 50 cycles [17].
SrCo1xFexO3d has been prepared using citrate method.
The nitrate salts in the required ratio were dissolved in
dilute nitric acid with citric acid. The gel obtained after
heating the solution was dried and ignited followed by
sintering at 8508C and grinding to obtain fine powders. In
another set of procedure, the nitric acid was substituted
with NH3–EDTA. The EDTA method showed better
oxygen production which was attributed to smaller parti-
cle size and larger surface area [18].
Several OCMs were evaluated for chemical looping appli-
cations. LaxSr1xFeO3d perovskite was found to be
suitable for chemical looping reforming, Fe2O3/MgAl2O4
was suitable for both combustion and reforming and
Mn3O4/MgZrO2 was suitable for chemical looping com-
bustion [19]. CaMn0.9Mg0.1O3d perovskite prepared by
spray drying has been evaluated in a 10 kW continuous
reactor for CLC of natural gas. It was observed that the
material could release gaseous oxygen above 7008C lead-
ing to chemical looping with oxygen uncoupling. After
more than 350 hours of fluidization, there was no agglom-
eration or attrition [20].
High surface area (26–45 m2/g) La1xCexBO3 (B = Co,
Mn) was prepared by reactive grinding and nanocasting
and tested for methane CLC. At high methane pressure,
better reactivity was obtained while at low methane
pressure better selectivity to CO2 was obtained [21].
Waste and naturally occurring materials
Many studies have examined the use of waste materials
and naturally occurring materials to take advantage of the
low cost and easy availability.
Iron and manganese ores were modified by impregnation
with nitrate salt and used as oxygen carriers. The iron ore
was impregnated to obtain 33% Mn2O3 and the manga-
nese ore was impregnated to obtain 33% Fe2O3. The
main phases were (Fe,Mn)2O3 and Fe2O3 and the im-
pregnated samples had higher attrition resistance and
surface area compared to the corresponding ore sample.
However, only the manganese impregnated iron ore
showed good results for chemical looping combustion
of syngas. The poor performance of impregnated manga-
nese ore sample was attributed to presence of non-active
MnFe2O4 phase [22].
Another natural material that has been tested is ilmenite
(FeTiO3). Granules were prepared using inorganic bin-
ders by extrusion followed by drying and sintering; the
properties were characterized in detail [23]. Ilmenite was
also used as oxygen carrier material along with NiO as
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 Oxygen carrier materials for energy applications Batra and Li 47
catalyst for tar partial oxidation. Ilmenite was extruded as
mini honeycomb and sintered at 13008C. Catalyst coating
was done by dipping in slurry followed by drying and
sintering at 10008C. The catalyst was found to have
penetrated the pores of the honeycomb and was evenly
distributed17.
Natural Australian hematite has been examined for CLC
of coal. A carbon conversion efficiency of 81.2% was
achieved and Fe2O3 was mostly reduced to Fe3O4 with
good activity for the 10 hours of tests that were done [24].
Iron rich residue from Bayer’s process has been tested for
CLC of coal and combustion efficiencies up to 90% was
obtained. The material was considered suitable alterna-
tive for ilmenite due to its lower oxygen demand and
higher oxygen transfer rate [25]. Iron oxide scale from
the rolling of steel has been tested in the chemical looping
combustion of syngas. The material showed 99% com-
bustion efficiency at 9008C but disintegration of the
particles took place. The performance and stability of
ilmenite tested under the same conditions was better
[26].
Inexpensive raw materials such as manganese ore and
commercial Ca(OH)2 were used to prepare
CaMnO3. Methane conversion in the range 40–75%
was obtained based on type of manganese ore obtained
[27]. Iron ore was also tested in the chemical looping
combustion of syngas and methane. Complete conversion
was obtained for syngas but not for methane [28].
Summary
The use of oxygen carrier materials in chemical looping
combustion is attractive due to the ability to obtain pure
CO2 stream that can be sequestrated. In case of reform-
ing, it prevents nitrogen dilution without the need for
oxygen separation devices. The current trend is to look
for materials that have the required properties while at
the same time are economical without any negative
environmental impact. Use of mixed oxides, suitable
supports, ores and wastes are being reported. The prepa-
ration of these materials using techniques that are easy to
scale up is also being examined.
References and recommended reading
Papers of particular interest, published within the period of review,
have been highlighted as:
 of special interest
 of outstanding interest
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