Front. Chem. Sci. Eng.

https://doi.org/10.1007/s11705-017-1698-z

VIEWS & COMMENTS

Mature versus emerging technologies for CO2 capture in

power plants: Key open issues in post-combustion amine
scrubbing and in chemical looping combustion

Giorgia De Guido (✉)1, Matteo Compagnoni2, Laura A. Pellegrini1, Ilenia Rossetti2

1 Department of Chemistry, Materials and Chemical Engineering “Giulio Natta”, Politecnico di Milano,
Piazza Leonardo da Vinci 32, 20133 Milan,Italy
2 Department of Chemistry, Università degli Studi di Milano, INSTM Unit Milano-Università and CNR-ISTM,
Via Camillo Golgi 19, 20133 Milan, Italy

© Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract Carbon capture and storage (CCS) have 1 Introduction

acquired an increasing importance in the debate on global
warming as a mean to decrease the environmental impact
of energy conversion technologies, by capturing the CO2
produced from the use of fossil fuels in electricity
generation and industrial processes. In this respect, post-
combustion systems have received great attention as a
possible near-term CO2 capture technology that can be
retrofitted to existing power plants. This capture technol-
ogy is, however, energy-intensive and results in large
equipment sizes because of the large volumes of the flue
gas to be treated. To cope with the demerits of other CCS
technologies, the chemical looping combustion (CLC)
process has been recently considered as a solution for CO2
separation. It is typically referred to as a technology
without energy penalty. Indeed, in CLC the fuel and the
combustion air are never mixed and the gases from the
oxidation of the fuel (i.e., CO2 and H2O) leave the system
as a separate stream and can be separated by condensation
of H2O without any loss of energy. The key issue for the
CLC process is to find a suitable oxygen carrier, which
provides the fuel with the activated oxygen needed for
combustion. The aim of this work is to explore the
feasibility of using perovskites as oxygen carriers in CLC
and to consider the possible advantages with respect to the
scrubbing process with amines, a mature post-combustion
technology for CO2 separation.
Keywords CO2 capture, monoethanolamine, chemical
looping combustion, oxygen carrier, perovskites
Received September 21, 2017; accepted October 21, 2017
E-mail: giorgia.deguido@polimi.it
In the last decade, the scientific community has worked a
lot to reach a better understanding of the world climate and
of the long-term impact of climate change, which is related
to the emission of greenhouse gases (e.g., CO2, NOx, SOx,
CH4), of which CO2 is the prevalent one. At the Paris
climate conference (COP21), held in December 2015, 195
countries adopted the first-ever universal, legally binding
global climate agreement that is due to enter into force in
2020. The Parties to the United Nations Framework
Convention on Climate Change have agreed on strength-
ening the global response to the threat of climate change. In
particular, they have decided to “hold the increase in the
global average temperature to well below 2 °C above pre-
industrial levels and to pursue efforts to limit the
temperature increase to 1.5 °C above pre-industrial levels,
recognizing that this would significantly reduce the risks
and impacts of climate change”. In addition to this, they
have agreed on increasing the ability to foster low
greenhouse gas emissions development, in a manner that
does not threaten food production. In this context, all
parties have been asked to formulate and implement
programmes containing measures to mitigate climate
change [1]. Mitigation actions used by developed country
Parties mostly focused on the large emitting sectors. In this
respect, it is estimated that fossil fuel-based power
generation contributes to about one-third of the total
carbon dioxide released from fuel combustion [2]. An
example of mitigation actions include the switch from a
fossil fuel-based economy to an economy that relies on the
use of renewable energy resources, such as biomass, solar
and wind energies. However, given their current state of
development, these alternative energy sources cannot fully
2 Front. Chem. Sci. Eng.
replace fossil fuels in the electricity production. Therefore,
in order to limit CO2 emissions into the atmosphere the
adoption of other mitigation actions becomes crucial. In
this respect, the carbon capture and storage (CCS)
technology, which involves the capture of CO2 and its
disposal into geological formations, has been considered as
a technically feasible option for the reduction of these
emissions. In order to capture CO2, a number of processes
is currently available, which can be categorized as follows:
(i) pre-combustion, (ii) post combustion, and (iii) oxy-fuel
combustion.
A pre-combustion system consists in CO2 capture before
the combustion step [3]. The first stage of reaction this
system comprises produces a mixture of hydrogen and
carbon monoxide (syngas) from a primary fuel. This can be
accomplished by one of the two following routes: by
adding steam (in which case the process is called ‘steam
reforming’) or by adding under-stoichiometric oxygen (in
which case the process is called ‘partial oxidation’ when
applied to gaseous and liquid fuels, and ‘gasification’ when
applied to a solid fuel). CO is then converted into CO2 by
the addition of steam (via the ‘water gas shift’ reaction) and
CO2 is finally removed from the CO2/H2 mixture by PSA
or by physical absorption processes [4]. A post-combus-
tion system consists in removing CO2 from flue gases after
the combustion of fossil fuels in air has taken place. In this
type of systems, the flue gas is passed through equipment,
which separates most of the CO2, before being discharged
to the atmosphere. In oxy-fuel combustion, nearly pure
oxygen is used for combustion instead of air, resulting in a
Table 1 Comparison among existing CO2 separation technologies
Technology Advantages
Absorption Well established process
High operational confidence
Adsorption Lower regeneration energy relative to solvent-based processes
Membranes Low energy requirements relative to solvent-based processes
Small foot-print
Possible modular designc)
Cryogenics Mature technology already adopted for CO2 recovery
Viable for very high CO2 concentrations
Hydrate-based Small energy penaltyd)
a) This implies a parasitic load on the net output of a power plant of ca. 30% and an increase of the cost of electricity by 60%‒90% [5]; b) amine emissions have been
reported to possibly degrade into nitrosamines and nitramines, which are potentially harmful to the human health and the environment [6]; c) this may allow for flexible
operation; d) 6%‒8%, according to Elwell and Grant [7].
flue gas that mainly consists of CO2 and H2O. This would
allow using simpler post-combustion separation techni-
ques (e.g., condensation) with significantly lower energy
and capital costs.
The available CO2 separation technologies for separa-
tion of CO2 from the fuel/flue gas stream can be classified
as follows: absorption, adsorption, membrane separation,
cryogenic separation, hydrate-based separation. The
advantages and disadvantages each of them poses are
summarized in Table 1.
CO2 is removed by absorption in a liquid solvent, either
by exploiting solubility differences (physical absorption)
or by chemical interaction with the solvent (chemical
absorption). In particular, chemical absorption by alkano-
lamines (e.g., monoethanolamine, MEA) is the most
mature method for CO2 separation. Indeed, a big attraction
of the absorption approach is that it is already in use
commercially, albeit on a very small scale relative to what
would be required by a power station producing hundreds
or thousands of megawatts of electricity [8]. The main
drawback is the energy penalty associated with the
regeneration. According to the literature, the CO2 capture
by MEA absorption will reduce the electrical efficiency by
8%–10% points [9]. In addition to this, there are problems
resulting from the corrosive nature of the solvent,
particularly in the presence of residual oxygen in flue
gas, which can attack carbon steel and result in amine loss.
Also, stable solvent by-products (salts) can accumulate as a
result of reaction with acid gas impurities (SOx and NOx)
during operation.
Disadvantages
Energy penalty for solvent regenerationa)
Equipment corrosion in presence of O2
Pre-absorption treatment required to remove solvent-detri-
mental components (e.g., SOx and NOx)
Possible environmental impact and safety problems due to
solvent degradationb)
Particle attrition
Large volumes of solid sorbents
Thermal management of large scale adsorber vessels
Currently not suitable for processing very high gas flows
containing many impurities
Strongly affected by flue gas conditions (e.g., low CO2
concentration and pressure)
Potential fouling of membrane surfaces
Uncertainty about the possibility of integration into a power
plant
Not a mature technology
Low operating temperatures
At the R&D stage
 Giorgia De Guido et al. Amine scrubbing and chemical looping combustion for CO2 capture
Therefore, despite the huge interest in developing
effective CO2 capture processes, pros and cons coexist
for every technology, so that “the solution” is hardly
attainable. Hence, this paper contributes to the current
discussion about CO2 capture technologies developing a
comparison between a conventional technology, like
chemical absorption into an aqueous MEA solution, and
a novel one, like chemical looping combustion (CLC).
After a brief analysis of the existing CO2 capture methods
(i.e., pre-combustion, post-combustion and oxy-fuel com-
bustion), it focuses on post-combustion amine scrubbing
(currently the most mature CO2 capture technology) and
on CLC that has recently received great attention as a
combustion process with inherent separation of CO2. In
this respect, the use of perovskites as oxygen carrier is
investigated, addressing one of the issues related to CLC, i.
e., the choice of a suitable (efficient, stable and poorly
expensive) oxygen carrier.
2 Comparison among existing CO2 capture
methods
Among the three CO2 capture technologies previously
described, pre-combustion is mainly applied to coal-
gasification plants, where it has turned out to have the
lowest cost per tonne of CO2 avoided [6]. Despite that,
Hoffmann et al. [10] have conducted a performance and
cost analysis on advanced combined cycle gas turbine
plants operated by natural gas with pre-combustion CO2
capture system and have obtained a CO2 capture efficiency
of 80% with the cost of CO2 avoided reaching $29/t CO2
for an advanced design concept.
As for natural gas fired-power plants, post-combustion
can be preferably applied with an efficiency of 50%
compared to 60% without capture [11]. Post-combustion
systems have received great attention as a possible near-
term CO2 capture technology for retrofitting existing
power plants, either gas-fired or coal-fired, and as an
“end-of-pipe” solution. The energy penalty and associated
costs for post-combustion CO2 capture are typically
elevated due to the low CO2 level in combustion flue
gases (i.e., 7%–14% for coal-fired and 4% for gas-fired)
[6], which requires a high effort to reach the concentration
(typically greater than 95.5%) needed for transport and
storage. A recent study has reported that the cost of
electricity for post-combustion in gas- and coal-fired
power plants would increase by, respectively, 32% and
65% [11]. Hossain and de Lasa have estimated that, for a
500 MW plant integrated with a MEA-based separation
unit, about 79% of the cost is associated with the capture
and compression, while 8% and 13% of the cost are,
respectively, assigned to the transportation and storage
[12]. Moreover, the chemical solvent-based capture
technology has some drawbacks when used in applications
3
different from the sweetening of natural gas, in which it has
been used for over 70 years: indeed, unlike natural gas
sweetening in which gas streams are typically under high
pressure and contain little or no oxygen, flue gases from a
combustion plant are closer to ambient pressure, so the
operating conditions for the absorber are very different,
meaning that equipment sizes are much larger (absorber
columns with diameters of 12 m can be found in industrial
applications) [13,14], and the presence of O2 leads to the
degradation of traditional CO2 absorbents, such as MEA,
as well as to corrosion problems. This suggests the
importance of finding a capture method that allows to cope
with the demerits of post-combustion technologies and is
more energy efficient and, thus, less expensive.
One of the issues related to the oxy-fuel combustion
concerns the temperatures that are reached. Possible
solutions to this issue proposed in the literature consist in
recycling flue gases or injecting water. Thus, the main
drawback is due to the production of the needed oxygen,
which is made by cryogenic air separation: the oxygen
separation plant would consume about 23% to 37% of the
total plant output [15], and the energy penalty may reach
over 7% compared with a plant without CCS [6].
To overcome the problems encountered when adopting
the existing CO2 capture technologies, novel ones have
been considered, including CLC. CLC has been identified
as having inherent advantages for CO2 separation with
minimum energy losses. This may be seen as a very special
case for oxy-fuel combustion, in which oxygen is
selectively adsorbed and activated by an oxygen carrier,
and made available to the fuel. In this way, the refill of
oxygen in air is separated from the combustion step,
avoiding the dilution of the products stream with nitrogen
and leading to carbon dioxide and water as only products
of the combustion steps. This latter mixture is very easily
separated through condensation of water, leading to
roughly pure CO2 ready for storage or use, avoiding the
energetic penalty present in other competing technologies.
This rather new option is compared with MEA
scrubbing, the most popular option available for the
separation of CO2. In order to properly assess the reference
MEA scrubbing case it is essential to underline the
importance of using proper tools in modelling this type of
system. As for the emerging CLC technology, different
issues are important. A particular focus is set on the
materials used as oxygen carriers, which is the key for
process productivity. This work investigates the possibility
to use for this purpose a set of perovskite-type mixed
oxides with general formula LaBO3 (B = Fe, Mn, Co, Ni),
possibly doped at A-position with Sr2+ or Ce4+ or added
with 0.5 wt-% Pt or Pd. The oxygen release properties of
the materials play a key role in understanding their
suitability for application to CLC. Some parameters have
been here identified to quantify the oxygen release,
together with experimental methods for their correct
4 Front. Chem. Sci. Eng.
quantification, allowing the modelling of the phenomenon.
These parameters have been also related to experimental
data of methane oxidation.
3 Post-combustion by MEA scrubbing
Nowadays, the most popular option available for the
removal of CO2 from flue gas streams is absorption by
chemical solvents. This technology is also widely used in
the gas processing industry and, in particular, for refinery
gas treating and for natural gas sweetening. Among the
several chemical solvents that can be used for this purpose,
alkanolamines have received great attention. MEA, in
particular, has been widely studied for the removal of CO2
from flue gases. Indeed, it is considered as the best solvent
to accomplish that, mainly because of the highest rate of
reaction that generally also implies a greater mass transfer
rate [16]. Veawab et al. have found that MEA is the most
efficient aqueous alkanolamine for CO2 absorption with
efficiency over 90% [17]. The drawback is that more heat
is required to regenerate the MEA solvent, which accounts
for as much as 80% of the total energy in a chemical
solvent-based CO2 separation process. Some strategies
have been proposed in the literature for reducing the
energy consumption in this type of processes. Chakma
[16], for instance, has presented a slightly modified version
of a MEA unit, which differs from a typical one because of
the presence of a pre-contactor and of two steam injection
lines in the stripper. This allows to increase the cyclic
capacity (i.e., the difference in the acid gas loading of the
lean and of the rich solvent) of MEA from the standard
design value of 0.2 mole of CO2/mole of MEA to 0.3 mole
of CO2/ mole of MEA, which represents a reduction of the
solvent circulation rate. In order to reduce the high energy
requirement of the regeneration unit, some of the authors
have also studied different configurations, namely the
double column and the multipressure column configura-
tions [18].
However, a key point often neglected in the literature,
that may lead to a wrong assessment of plant efficiency,
performance and, consequently, cost estimations, is related
to the correct modelling of the reacting system. The model
of the absorption-regeneration system for the chemical
solvent-based capture process has to take into account the
role of thermodynamics, kinetics and mass transfer, which
influence the chemical absorption process. CO2 and MEA
are weak electrolytes, which partially dissociate in the
aqueous phase: The high non-ideality of the liquid phase
must be properly taken into account when dealing with
vapor-liquid equilibria and a γ/φ approach is often used by
commercial process simulators (e.g., Aspen HYSYS®,
Aspen Plus®) [19,20]. The thermodynamic model exerts an
influence also over the determination of the overall heat of
absorption of the acid gas in the solvent, being the heat
released at chemical equilibrium related to the extent of
reactions. Its estimation is of paramount importance, since
it is directly related to the energy requirement at the
reboiler and determines the temperature increase of the
absorber. In Aspen Plus® the “rate-based” model can be
used to avoid the approximation of stage efficiency by
analysing mass and heat transfer phenomena. In this
simulation software, the prediction of mass transfer
coefficients is based on the film theory by Lewis and
Whitman [21], while other theories can more conveniently
be used, i.e., the Eddy diffusivity theory [22]. Due to the
suitability of Aspen Plus® to be user-customized, the
simulator has been chosen as framework with integration
of an in-house kinetic/mass transfer subroutine in Fortran
developed by some of the authors and currently available
[23]. The developed model has been previously validated
by comparing the absorber simulation results with
experimental data of a pilot plant for the purification of
exhaust gases from a coal-fired power plant [24]. The pilot
plant facility included two carbon steel columns, one
functioning as an absorber and the other one acting as a
stripper for solvent regeneration. It also included a lean
solvent storage tank, a heater and a cooler in place of the
cross exchanger used industrially, a pump for the
regenerated solvent, a liquid accumulator for water
condensed out of the gas exiting the condenser of the
stripper, and an accumulation tank for CO2 obtained from
the top of the partial condenser (the reader can refer to the
work by Dugas [24] for further details about it). Of the
available 48 tests, only some have been chosen for model
validation, taking into account that the results of the first
runs (in which the structured packing Flexypack 1Y was
used) are inconsistent with the remaining ones (in which
the random metal packing IMTP #40 was used) and that,
even among the latter ones, there exist some for which the
total material balance is not fulfilled. For these reasons,
cases 29, 30, 43, 44, 47, 48 have been simulated. Table 2
summarizes the operating conditions and the energy
contributions of each selected run: it is possible to observe
that the highest heat duties were required with higher liquid
flow rates, which typically entered the stripper at cooler
temperatures because of an inadequate pre-heat [24].
Results in Table 3 show that, in comparison with the
default model implemented in Aspen Plus® [20], the
improved model allows to achieve better performances as
regards the prediction of the concentration of carbon
dioxide in the purified gas leaving the absorber [25],
obtaining a lower percentage average absolute deviation
(AAD%).
This can be explained by the fact that with the proposed
model the absorption process tends to be slower, so that the
concentration of CO2 in the purified outlet stream is higher
with respect to that obtained by the default Aspen Plus®
model (as shown in the parity plot in Fig. 1) [20], being
thus closer to the experimental values.
 Giorgia De Guido et al. Amine scrubbing and chemical looping combustion for CO2 capture 5

Table 2 Operating conditions and energy contributions for the experimental tests performed by Dugas [24] that have been chosen in this work for
model validation (packing for the absorber: IMTP #40)
LL Mole inlet CO2 Gas rate Liquid rate CO2 removal Actual reboiler duty
Test run [24]
/(molCO2$molMEA–1) /mol-% /(m3$min–1) /(L$min–1) /% /(MJ$h–1)
29 0.28 16.6 11.00 54.9 70 918
30 0.28 16.6 11.00 54.9 70 918
43 0.23 17.0 11.00 39.4 72 756
44 0.23 17.0 11.00 39.4 72 754
47 0.28 18.0 8.23 30.1 69 738
48 0.28 18.0 8.23 30.1 69 775

Table 3 CO2 mole fraction in the purified gas stream leaving the absorber in the test runs [24] considered in this work
Exp. Aspen Plus® default [20] Proposed model [25]
Test run [24]
y CO2,out y CO2,out Abs. err. /% y CO2,out Abs. err. /%
29 0.0532 0.04619 13.18 0.05156 3.08
30 0.0591 0.05022 15.03 0.05558 5.96
43 0.0558 0.04698 15.81 0.05238 6.13
44 0.0540 0.04655 13.80 0.05203 3.65
47 0.0638 0.06682 4.73 0.06753 5.85
48 0.0619 0.06339 2.41 0.06374 2.97
AAD% 10.82 AAD% 4.61

patent named “Production of pure carbon dioxide” [27]. It

Fig. 1 Parity plot for the concentration (mole fraction) of CO2 in
the purified gas stream leaving the absorber for the test runs
reported in Table 3
4 CLC
Preliminary economic assessments in the literature have
suggested that the CLC technology has the potential for
achieving very efficient and low-cost CO2 capture [12]. It
is considered to be a promising technology for fossil fuel
combustion as it prevents CO2 dilution with flue gases,
mainly nitrogen. The beginning of this technology dates
back to 1954 [26], when Gilliland and Lewis presented a
was further developed when Ritcher and Knoche
suggested a fuel oxidation reaction scheme involving two
intermediate reactions with a metal oxide as an oxygen
carrier [28]. The term was coined later by Ishida et al. in the
second half of the 1980s [29]. Some years later in the mid
90s, Ishida along with Jin proposed a CLC process for CO2
capture using Fe-based and Ni-based oxygen carriers [30].
Since then, the CLC process has gained an increasing
importance.
The CLC process has also been called “unmixed
combustion” since direct contact between fuel and
combustion air is avoided by the use of an oxygen carrier
that brings oxygen from air to the fuel. In this way, oxygen
for fuel combustion is provided without nitrogen, leading
to a nitrogen-free mixture and also allowing a reduced NOx
formation. Thus, in CLC systems the conventional
combustion reaction is replaced by two successive
reactions forming a chemical loop. The first reaction,
which occurs in the so-called fuel reactor consists in the
oxidation of the fuel to CO2 and H2O accompanied by the
reduction of the solid oxygen carrier. The second reaction,
which takes place in the so-called air reactor, consists in the
oxidation of the reduced oxygen carrier by air. A schematic
representation of this two-step combustion process is
shown in Fig. 2.
The recent interest in CCS systems has brought about an
intense research activity on CLC. Despite that, at the
present time it is not a fully established technology and
research activities have been carried out to address the
6 Front. Chem. Sci. Eng.

carrier represents one of the main challenges still to be

Fig. 2 Schematic representation of the CLC technology (MexOy
denotes the generic metal oxide acting as oxygen carrier, MexOy –δ
the reduced material sent to the regeneration step)
issues for large-scale implementation of this technology.
Among them, the following issues can be mentioned: (1)
selection of the oxygen carrier; (2) representation of the
kinetics of reduction and oxidation of oxygen carriers; (3)
development of suitable reaction schemes, also taking into
account the metal-support interactions and coke formation;
(4) reactor design.
As for the design of the reactor, the configuration of two
interconnected fluidized bed reactors (air and fuel reactors)
has been reported to appear as a preferred best option
[2,31–34]1). A different possible configuration that may be
applied to gas-fired power plants may consist of multiple
fixed bed reactors, which alternate a combustion and a
regeneration step. This latter option may be simpler to
implement and does not require to use materials very
resistant to abrasion, but its efficiency depends on the
amount of oxygen made available by the material.
Reaction schemes have been proposed, but more compli-
cated ones could be developed in order to also account for
the formation of complex compounds that can occur
because of the metal-support interactions.
Regarding reaction kinetics, two general types of models
have been considered to represent the kinetics of reduction
and oxidation of metal-supported oxygen carriers: the
nucleation and nuclei growth model and the unreacted
shrinking core model [35–40]. In this respect, it has been
found that the former one provides a better description of
both the reduction and the oxidation steps.
Among the previously reported issues, the first one
concerning the selection of a reactive and stable oxygen
faced for a large-scale implementation of CLC systems.
This requires to use a suitable oxygen carrier, which must
have the following characteristics [12]: (1) reactivity in
both reduction and oxidation cycles; (2) ability to
completely combust the fuel; (3) stability under repeated
oxidation/reduction cycles at high temperatures (typically
in the range 600–1200 °C) [41]; (4) fluidizability;
(5) resistance to agglomeration; (6) resistance to the
friction stress associated with high circulation of particles;
(7) environmental compatibility; (8) economical feasibil-
ity.
Up to 2010, more than 700 different materials were
compiled [41]. Previous literature on CLC presented
transition metal oxides such as nickel, copper, cobalt,
iron and manganese as good candidates given their
favorable reductive/oxidative thermodynamic properties.
Moreover, in addition to bulk metal oxide materials, also
supported ones have been considered in order to increase
reactivity, durability and fluidizability of the oxygen
carrier. In the case of a supported metal oxide oxygen
carrier, the active metal is deposited on an inert support,
such as Al2O3, MgAl2O4, SiO2, TiO2, ZrO2, YSZ and
bentonite. Since every type of oxygen carrier material has
its own merits and demerits, also supported mixed metallic
materials have been studied, resulting to have a better
reactivity when compared with their monometallic coun-
terparts. In this respect, the bimetallic Co-Ni/Al2O3 can be
mentioned [42,43]: it has been demonstrated that the
synergistic effect of NiO and CoO ensures a stable
conversion during repeated CLC cycles and that the
addition of Co can also favorably modify metal-support
interactions, reducing the Ni/support contact and, thus,
reducing the possible formation of nickel aluminate
(NiAl2O4) during the oxidation step. Nickel aluminate is
much less reducible than Ni oxide, thus depressing activity
in the fuel reactor. Among mixed oxides, perovskite-based
oxygen carriers have been also tested for CLC applica-
tions. Perovskites are mixed oxides with general formula
ABO3, where A is an alkali, alkaline earth or rare earth
metal and B is an element in the transition series or in the
main groups III, IV or V [26]. As reported by Readman et
al. [44], perovskites are well-known combustion catalysts
in the presence of oxygen or air and, as a result of the high
oxygen mobility in the bulk, they are believed to permit the
achievement of good kinetics in an oxidation process in the
absence of additional oxygen added. Perovskite-type
oxides can lead to good results thanks to their stability in
widely different oxygen stoichiometries and easy oxygen
release/recovery cycles. Examples are CaMn1 – xBxO3 – δ (B

1) (a) Ryu H-J, Jin G-T, Yi C-K. Chemical-looping combustion process with inherent CO2 separation; Reaction kinetics of oxygen carrier particles and 50kWth
reactor design. Proceedings of the World Congress of Korean and Korean Ethnic Scientists and Engineers. Seoul, Korea, 2002; (b) Ryu H-J, Jin G-T, Yi C-
K. Demonstration of inherent CO2 separation and no NOx emission in a 50 kW chemical-looping combustor: Continuous reduction and oxidation
th
experiment. Proceedings of the 7 International Conference on Greenhouse Gas Control Technologies. Vancouver, 2004; (c) Johansson E, Lyngfelt A,
Mattisson T, Johnsson F. A circulating fluidized bed combustor system with inherent CO2 separation-application of chemical looping combustion.
th
Proceedings of the 7 International Conference on Circulating Fluidized Beds. Niagara Falls, Ontario, 2002
 Giorgia De Guido et al. Amine scrubbing and chemical looping combustion for CO2 capture
= Al, V, Fe, Co, and Ni) [45], La1 – xSrxFeO3 – δ [46], and
CaMg0.1Ti0.125Mn0.775O2.9 – aδ [47]. A key parameter to
assess the suitability of the material for this application is
the rate of oxygen transport across the lattice, which is in
turn related to the reducibility of the B-site ion and to the
microstructure and defectivity of the material.
The use of perovskites can be of interest considering
CLC applied to natural gas, which allows using fixed beds
rather than fluidized beds as reactors, thus requiring less
strict characteristics to the oxygen carrier. To the authors’
knowledge, very few studies in the literature deal with the
use of these materials in CLC. In this respect, Brandvoll
has reported the possible use of perovskites as oxygen
carriers in CLC [4], pointing out the low-temperature
stability (e.g., perovskites of the general type LanConO3n – 1
have been reported to undergo decomposition at tempera-
tures above 650 °C) [48], which can be increased by
adding elements such as Sr and Fe, resulting in compounds
with the general formula La1 – xSrxCoyFe1 – yO3 – δ. Read-
man et al. [44] have investigated the structural properties of
various members of this series under both oxidative and
reductive atmosphere in order to find a potential material
for use in a chemical looping type reactor. Their results
have led to conclude that the high cobalt content samples
are not suitable as oxygen carrier if no phase segregation is
desired (in order to avoid particle break up by internal
stress). On the contrary, the low cobalt content sample
La0.8Sr0.2Co0.2Fe0.8O3 – δ maintained the cationic lattice
upon reduction, only exhibiting a hexagonal/orthorhombic
to cubic phase transition, but it turned out not to have the
redox properties required for chemical looping due to fast
reduction and re-oxidation of the perovskite under the
conditions used by Readman et al. [44]. Linderholm has
reported that the perovskite CaMn0.875Ti0.125O3 shows
promise as a CLOU-carrier, where CLOU stands for
“chemical looping with oxygen uncoupling”, which differs
from classical CLC because of the release of gaseous
oxygen by the oxygen carrier in the fuel reactor [49].
Quite simpler compositions of perovskitic materials
have been used in this work. Indeed, the present study is an
evaluation of a set of perovskite-type mixed oxides with
general formula LaBO3 (B = Fe, Mn, Co, Ni) as potential
oxygen carriers for CLC, possibly doped at A-position
with Sr2+ or Ce4+ or added with 0.5 wt-% Pt or Pd. The
native perovskite structure (CaTiO3) has a well defined,
regular lattice, where all the oxygen positions are, in
principle, occupied. The mechanism of oxygen transfer
across the lattice is based on oxygen hopping through
vacant sites. Therefore, the availability of oxygen “holes”
(or vacancies) in the lattice would decrease the activation
energy for oxygen transport. Vacancies can naturally occur
in some distorted lattices, due to irregularly occupied
framework positions, ultimately depending on the compo-
sition of the material, i.e., the relative sizes of the two
cations arranging in the structure. On the other hand,
additional vacancies can be formed by partial isomorphous
7
substitution of one or both the cations with ions of different
valence, leading to a general formula AA’BB’O3
δ. The
different ionic radius of the here selected ions and their
different affinity with oxygen affect the transport rate due
to both lattice distortion and metal-oxygen interaction
strength. The effect of doping at A position was instead
focused on modifying the amount of available oxygen in
the structure and the oxygen vacancies concentration. In
particular, Sr2+ would increase the amount of oxygen
vacancies, thus favouring oxygen mobility, whereas Ce4+
induced a surplus of oxygen in interstitial (extraframe-
work) position.
The oxygen release properties of the materials play a key
role in understanding their suitability for application to
CLC. We have identified and quantified some parameters
to check the oxygen release properties of each oxygen
carrier, together with experimental methods for their
correct quantification allowing the modelling of the
phenomenon. These parameters have been related to
experimental data of methane oxidation.
4.1 Perovskite oxides performance
4.1.1 Experimental
The detailed description of the experimental methods set
up for the quantification of the oxygen release properties of
mixed oxides and the relative modelling algorithms are
comprehensively described elsewhere [50–52], referring to
laboratory experiments. The latter allowed to establish
kinetic parameters for oxygen transport across the oxide
lattice and to quantify the amount of available oxygen in
the material.
The oxygen release properties of the materials were
determined by temperature programmed desorption (TPD)
and reduction (TPR). The experiments were carried out on
ca. 0.15 g of catalyst, loaded into a continuous, tubular
quartz microreactor, heated by an electric furnace and
controlled by an Eurotherm 2408 TRC. The composition
of the outlet gas was continuously monitored by means of a
quadrupolar mass spectrometer (MKS, PPT Residual Gas
Analyser). Examples of TPD and TPR patterns are
reported in Fig. 3.
TPD of pre-adsorbed O2 was carried out in 30 Ncm3/min
flowing He (purity≥99.9999 vol-%), after pre-treatment at
800 °C in He for 1 h, saturation at 750 °C for 1 h in 20
Ncm3/min flowing air (purity≥99.9995 vol-%) and cool-
ing down to 50 °C, in flowing air as well. Prior to
desorption, the sample was equilibrated in 30 Ncm3/min
flowing He at 50 °C and, then, heated (10 °C/min) up to
800 °C. After the same pre-treatment previously described,
the TPR experiments were carried out by continuously
feeding 30 Ncm3/min of a 10 vol-% H2 in He gas mixture,
while heating (10 °C/min) from 50 up to 800 °C.
TGA analysis was carried out using a Perkin Elmer
TGA7 instrument on ca. 20–35 mg of the sample
8 Front. Chem. Sci. Eng.

Fig. 3 Examples of (a) TPD analysis of sample La0.9Ce0.1MnO3 (blu, solid line) and LaMnO3 (red, dotted line); (b) TPR pattern relative
to sample LaCoO3

(sensitivity 10–5 g), either in step or ramp mode. The step Arrhenius form of the kinetic constant for oxygen
mode analysis was performed after pre-treating and pre- desorption. The oxygen release rate was calculated from
saturating the sample as reported above. The temperature the TPD data as:
was, then, set at 570 °C in N2 flow for 4 h. Further steps of  
FHe Pi
50 °C each followed up to 750 °C. In ramp mode, a heating ri ¼ –1 : (2)
rate of 10 °C/min was used in N2 flow from room Vsample P0
temperature up to 800 °C.
In Eq. (2), FHe is the molar flow rate of the carrier gas, Pi
Methane oxidation activity under anaerobic conditions
the oxygen partial pressure detected by the spectrometer at
(first step of the chemical looping cycle) was tested on the
Ti, and P0 the background oxygen partial pressure.
same testing grid by continuously feeding 20 Ncm3/min of
The selected model for oxygen desorption was the
1.04 vol-% CH4 in He gas mixture, after pre-saturation of
Polanyi-Wigner equation [53–55]:
the sample in air. The temperature was raised by 10 °C/min
up to 800 °C. The results have been compared with its rdes ¼ kn Θn , (3)
oxidation under aerobic conditions while co-feeding 20
Ncm3/min of air. where Θ represents the oxygen surface coverage, as a
measure of available oxygen concentration. Combining all
the equations above one can obtain:
4.1.2 Results and discussion      
FHe Pi 1 Pi
Different methods have been compared to assess the ri ¼ –1 ¼ –1
oxygen release properties of perovskite mixed oxides, Vcat P0 τ P0
depending primarily on the nature of the B-site ion and on  
n Ea
possible dopants in A-position. TPD and TGA experiments ¼  n Θ exp – , (4)
have been used to determine qualitatively the onset RT
temperature of oxygen release. Two possible peaks, called or the analogous logarithmic form, used for data regression
α (max 500 °C) and β (onset temperature higher than (Eq. (5)).
550 °C), were possibly present (Fig. 3(a)). For CLC the β
peak is more significant, since it is related to the release of Ea E
lnri ¼ ln n þ nlnΘ – ¼ lnA0 ð n ,ΘÞ – a : (5)
bulk oxygen due to the reduction of the B-site ion RT RT
(reversible during the second step of the process, i.e., Based on the kinetic modelling of the oxygen release for
regeneration in air). The TPD data were elaborated as different perovskites as defined by TPD and TGA
follows (the interested reader can find all the details in ref. experiments, different kinetic regimes have been identified
[52] and in the literature cited therein). The reaction rate as detailed elsewhere [52]. At low temperature the process
was expressed as: is kinetically limited by oxygen transport through the
 
Ea lattice, with decreasing activation energy upon increasing
ri ¼ A⋅exp ⋅f ð½O2 ,nÞ, (1) concentration of structural defects. Doping with an ion
RTi
(Sr2+) of valence lower than that of La3+ induces a decrease
where ri was the desorption rate at Ti,f([O2],n) a given of the activation energy for oxygen transfer. A further rate-
expression for the dependence on oxygen concentration determining mechanism is surface recombination of
and on the reaction order n, A was the pre-exponential oxygen, becoming predominant only at very high
factor and Ea (kJ$mol–1) the activation energy of the temperatures, when oxygen mobility is sufficiently fast.
 Giorgia De Guido et al. Amine scrubbing and chemical looping combustion for CO2 capture 9

Consistent results have been obtained by combining Table 4 Quantitative titration of oxygen (as mol/kgcat) by TPR analysis
independent analytical methods that make use of dynamic (experimental data from ref. [51])
oxygen release, such as TPD or TGA under non-isothermal Sample Titrated oxygen Oxygen ratio,
conditions. In contrast to this, the isothermal TGA analysis /(mol$kgcat–1) RO
correctly indicates a diffusion-limited process and the LaCoO3 6.88 0.110
effect of doping on the activation energy for oxygen
La0.9Sr0.1 CoO3 6.10 0.098
release, though the estimation of the activation energy for
La0.9Ce0.1 CoO3 6.45 0.103
oxygen diffusion was in poor accordance with the results
obtained through dynamic methods. 0.5wt-% Pt- LaCoO3 5.60 0.090
The measured activation energy for the spontaneous 0.5wt-% Pd- LaCoO3 6.67 0.107
oxygen release from samples saturated with oxygen has LaMnO3 6.21 0.099
been tightly correlated to their composition. In particular,
La0.9Sr0.1 MnO3 7.55 0.121
for the series of manganites, oxygen release started at ca.
600 °C, with an activation energy of 172
2 kJ/mol for La0.9Ce0.1 MnO3 6.82 0.109
LaMnO3, of 147
2 kJ/mol for the sample doped with Sr, 0.5wt-% Pt- LaMnO3 3.65 0.058
of 96
2 kJ/mol for the sample doped with Ce. Thus, 0.5wt-% Pd- LaMnO3 4.91 0.079
doping increased effectively the rate of oxygen release Fe2O3 a)
9.37 b)
0.30
[52].
NiOa) 6.56b) 0.21
By looking at the methane oxidation activity, higher
reducibility of the B3+ ion was beneficial to the decrease of a) from Lyngfelt et al. [2]; b) calculated as maximum available oxygen amount
based on the nominal oxygen ratio reported in Lyngfelt et al. [2]
the light-off temperature for methane oxidation, but if its
subsequent re-oxidation was not sufficiently fast, this can than that reported for Fe2O3. It should be underlined that
be detrimental for the overall catalyst performance. the oxygen ratio reported in the cited reference is a nominal
A quantitative TPR analysis has allowed to quantify the value, i.e., the maximum mass fraction of oxygen available
oxygen non-stoichiometry and to determine the content of assuming the full reduction of the metal. That value is
available oxygen. This is an important parameter in reactor usually coupled with conversion, which represents the
sizing for the first stage of a CLC process and has been evolution of oxygen release across the reactor or during
related to catalytic activity showing that the higher the time (0.98 in the cited examples for both nickel and iron
titrated oxygen amount (referring, in particular, to the low- oxides).
temperature reduction feature), the higher the catalytic An advantage for the use of a perovskite-based mixed
activity for methane oxidation. An exception is represented oxide is the elastic structure of the oxide if compared with a
by Pt-doped samples, which show very high activity single oxide. Indeed, perovskites can exchange a relative
though their oxygen release properties are lower than other high amount of oxygen maintaining the overall crystal
samples. structure almost unaltered (except for some distortion).
The amount of available oxygen (as mol/kgcat) has been This prevents major modifications of the oxide lattice, thus
obtained from quantitative TPR data, which are reported in a longer material life is expected with respect to single
Table 4 for some representative samples. From these data it oxides, which are subject to cyclic major modifications that
appears that the material which makes available the higher may cause embrittlement in their particles.
amount of oxygen is La0.9Sr0.1 MnO3. As reported above, Finally, when testing methane conversion under anae-
this sample is also characterised by a relatively low robic conditions, a relation has been found between
activation energy for oxygen release. activity and oxygen release as measured by TPD of pre-
The oxygen ratio in Table 4 has been calculated as: RO = adsorbed oxygen [50]. The lower the oxygen desorption
(mox – mred)/mox, that is the normalised difference between temperature, the higher and faster the methane combustion
the solid carrier mass in oxidised and reduced form, as a activity. For instance, La2NiO4 began to be active at
measure of the oxygen availability. Basically, the values of 400 °C and achieved 100% methane conversion at 750 °C.
titrated oxygen and of oxygen ratio can be used as an This sample showed very low temperature oxygen release
estimate of d reported in Fig. 2. The RO values here during TPD, with an intense α peak at 300–400 °C and β
obtained (Table 4) range between 0.06 and 0.11, lower than peak onset at ca. 550 °C. By contrast, LaFeO3 did not
what reported for the Fe2O3 and NiO single oxide carriers release O2 up to 800 °C during TPD and, consequently, it
(see, for example, the data reported by Lyngfelt et al. [2], did not reach full methane conversion, with the slowest
recalled in Table 4 for the sake of clarity). This is expected reaction rate of this samples set.
due to the presence of heavy ions (such as La and Sr) in the
formulation of the material. However, the overall oxygen
availability (‘Titrated oxygen’ in Table 4) is higher for the 5 Conclusions
present materials with respect to the nominal oxygen ratio
for NiO samples reported in the literature, though lower This paper contributes to the current discussion about CCS
10 Front. Chem. Sci. Eng.
technologies, focusing on a very well assessed process
(MEA scrubbing), yet needing careful modelling, and a
promising newly developed technology CLC. The latter is
here addressed as a promising combustion system with
inherent separation of CO2. As for MEA absorption, in
spite of its wide spread application, we have evidenced
critical modelling issues, to assess more credibly plant
performance and costing. In particular, the simulation
approach has been carefully revised and the reliability of
the here proposed tool (i.e., an in-house kinetic/mass
transfer routine) has been proved by comparison with the
experimental data available in the literature for an existing
pilot plant.
On the other hand, CLC has been analysed revising the
numerous open questions of this new process. They spread
from materials choice to kinetics and reactor design issues.
In particular, it is compulsory to find out a suitable oxygen
carrier that provides oxygen for combustion of the fuel.
The possible use of perovskites has been, therefore,
investigated for this purpose. Combined experimental
techniques and appropriate kinetic modelling have been
used to quantify the oxygen storage capacity of the
perovskite mixed oxides here exemplified. Furthermore,
the same experimental methods have been effectively used
to predict the reactivity of the selected materials. This
analysis is key to the appropriate sizing of the first stage of
the process (anaerobic methane oxidation). According to
the results presented in this work, perovskite mixed oxides
are promising candidates for the CLC of natural gas in
particular, for which both fluidized bed and fixed bed
reactors can be employed.
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