Materials Today Sustainability 1-2 (2018) 1e27

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Materials Today Sustainability

journal homepage: https://www.journals.elsevier.com/
materials-today-sustainability

Progress in the development and application of CaO-based adsorbents

for CO2 captureda review
H. Sun a, C. Wu a, b, c, **, B. Shen b, ***, X. Zhang b, Y. Zhang d, J. Huang e, *
a
School of Engineering and Computer Science, University of Hull, Hull, HU6 7RX, UK
b
School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin, China
c
School of Chemistry and Chemical Engineering, Queen's University Belfast, Belfast, BT7 1NN, UK
d
School of Science, China University of Petroleum (East China), Qingdao, China
e
School of Chemical and Biomolecular Engineering, The University of Sydney, Sydney, NSW 2037, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Carbon dioxide (CO2) capture using CaO-based adsorbents has recently attracted intense attention from
Available online 27 August 2018 both academic and industrial sectors in the last decade due to the high theoretical capacity of CO2
capture, low cost, and potential use in large scale. However, the successful development of CaO-based
Keywords: adsorbents is limited by significant sintering of adsorbent particles over a number of cycles of CaO
Sintering-resistant carbonation/calcination. In this work, a systematic understanding of fundamental aspects of the cyclic
Kinetic and mechanism
carbonation/calcination of CaO-based materials is reviewed. A number of efforts have been discussed to
Reactivation
improve the sintering-resistant properties of CaO-based adsorbents, such as decreasing the particle size
Pilot scale
Economic assessment
and increasing the surface area, dispersing CaO on inert support, as well as surface modification. In
particular, severe process conditions such as carrying out material calcination under pure CO2 atmo-
sphere were considered for the development of CaO-based materials. In addition, important process
parameters for CaO-based carbon capture such as CO2 partial pressure, carbonation temperature,
carbonation time and the presence of contaminants have been reviewed, as well as the reactivation of
spent sorbents. Synthetic CaO-based adsorbents have better performance than natural adsorbents due to
the improved porosity and the presence of nanosized particles. The promising capacity and stability of
CO2 capture can be obtained when the synthetic adsorbents have high surface area and mesopores and/
or CaO particles are stabilized using inert materials such as Ca12Al14O33. With an increase of steam
concentration in the process, the decay of CO2 capture capacity was mitigated due to the formation of a
stable pore structure. The calcium looping technology has been demonstrated in pilot scale combining
with catalytic reforming or gasification process. However, the reduction of sorbent costs and the opti-
mization of process conditions (e.g. carbonation and calcination time) still need to be tested in larger
scale to reduce the overall costs and enhance the overall energy efficiency. Material attrition is a key
challenge in large-scale demonstration of calcium looping process. Novel technology could be developed
to avoid the transportation of solid sorbents. For example, by integrating with CO2 conversion to
methane, the capture of CO2 and the regeneration of bifunctional sorbents can be carried out at the same
temperature in a fixed bed reactor. This can be fulfilled by introducing hydrogen to the stage of sorbent
regeneration. However, much more fundamental understanding is required in this area, such as the
exploration of synergies between sorbent regeneration and catalytic conversion of CO2.
© 2018 Published by Elsevier Ltd.

1. Introduction

CO2 is one of the major anthropogenic greenhouse gases in the

* Corresponding author. atmosphere. The accumulation of CO2 leads to serious climate
** Corresponding author. changes [1,2]. In the last half century, the concentration of CO2 has
*** Corresponding author. exhibited a dramatic growth from about 310 to over 401 ppm
E-mail addresses: c.wu@qub.ac.uk (C. Wu), shenbx@hebut.edu.cn (B. Shen), jun.
owing to the large-scale utilization of fossil fuels and various
huang@sydney.edu.au (J. Huang).

https://doi.org/10.1016/j.mtsust.2018.08.001
2589-2347/© 2018 Published by Elsevier Ltd.
2 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27
chemical refinery processes [3e5]. With the growth of global eco-
nomics, more fossil fuels will be consumed to feed the global ac-
tivity, especially in developing countries. Thus, worldwide efforts
have been devoted to developing new technologies for reducing
CO2 emissions, and most of the United Nations members have
approved Paris Climate Agreements for greenhouse gas reduction
[6e9]. CO2 capture and storage (CCS) technology is one of the most
promising solutions and has been commercially demonstrated. CCS
consists of three main steps including CO2 capture, transportation,
and storage. Among these steps, CO2 capture is the most critical
technology as it takes more than 70% of the whole operating costs
of CCS [10]. Several methods based on various sorbents have been
developed for CO2 capture such as liquid absorption, solid
adsorption, and membrane absorption. Among them, liquid ab-
sorption and membrane absorption have challenges in large-scale
operation such as solvent degradation, high cost, and the corro-
sive nature of sorbents [11e14].
Recently, CO2 capture using solid adsorbents attracts a great
attention due to the technology that it can be operated at a wide
range of temperature window (from ambient temperature to
700
C). In addition, the spent solid sorbents can be disposed with
less environmental precautions [15]. According to the range of re-
action temperature, solid CO2 adsorbents can be classified into
three types: low-temperature (<200
C) [16], intermediate-
temperature (200e400
C) [17], and high-temperature (>400
C)
adsorbents [18]. High-temperature CaO-based materials have been
largely applied for CO2 capture because of the high reactivity with
CO2 (theoretical capture capacity of CaO is 17.8 mmol g1) and the
availability of low cost natural CaO precursors [19e23]. Recent
studies showed that the cost of using CaO-based adsorbents for
carbon capture was $ 16e44 per ton CO2 [24,25], which is very
competitive than the current amine scrubbing technologies costing
about $ 32e80 per ton CO2.
There are several review articles focusing on developing CaO-
based sorbents. For example, Kierzkouska et al. [26] discussed
fundamental aspects of the carbonation of CaO including the
associated changes in the material’s morphology and kinetic pa-
rameters. Erans et al. [27] reviewed the decay of adsorbent reac-
tivity and the attrition of sorbents in fluidized bed reactors. The
authors also discussed the progress on the modification of sorbents
over extended numbers of cycles of CO2 capture. System integration
and pilot-scale testing of calcium looping technology have also
been reported [22,28]. In this review work, we extensively
reviewed the fundamental aspects of carbon capture using CaO-
based material. The improvement of CaO-based adsorbents for
CO2 capture (e.g. surface modification and dispersing on inert
supports) has also been discussed in detail. In particular, severe
process conditions such as generating CaO-based sorbents under
100% CO2 were discussed for CO2 capture. A systematic explanation
was conducted to study the effects of operation conditions (e.g. CO2
partial pressure, carbonation temperature, carbonation time, and
contaminants) on the cyclic performance of carbonation and
calcination. The comprehensiveness of this review work extends to
the discussion of the applications of calcium looping technology in
steam-reforming and gasification process, as well as the recent
studies in large-scale demonstration. The attrition problem of CaO-
based materials in real applications was further addressed, fol-
lowed by an economic analysis of the carbon capture technology
using CaO-based sorbents.
2. Fundamental understanding of the adsorbent reactivity
CaO reacts with CO2 in a temperature range of 600e800
C and
is regenerated at a temperature higher than 800
C [26]. The
carbonation and calcination reactions with CO2 are as follows:
Carbonation:
CaO ðsÞ þ CO2 ðgÞ/CaCO3 ðsÞ; DHr;298K ¼ 178 kJ mol1 (1)
Calcination:
CaCO3 ðsÞ/CaOðsÞ þ CO2 ðgÞ; DHr;298K ¼ þ178 kJ mol1 (2)
The carbonation of CO2 is an exothermic reaction that consists of
an initial fast reaction stage followed by a substantially slower
second reaction stage [29]. The two-stage mechanisms for the
carbonation reaction are shown in Fig. 1a, which gives the adsor-
bent conversion as a function of reaction time [30], where XN is the
molar conversion of CaO in each cycle, XK is the molar conversion
under fast reaction regime, and XD is the molar conversion under
diffusion-controlled regime. As shown in Fig. 1a, at the fast reaction
stage of carbonation, reaction took place on the surface of CaO via
the nucleation and growth of CaCO3. When CaCO3 collapsed to form
a continuous layer over the unreacted adsorbent, the fast stage of
CaO carbonation finished.
2.1. Fast stage of CaO carbonation
2.1.1. Modeling of fast stage of CaO carbonation
Several models have been used to describe the carbonation
reaction between CaO and CO2, including random pore model
(RPM) [33e36], grain model (GM) [37e40], apparent model
[41,42], shrinking core model [43,44], ion reaction mechanism
model [45], and rate equation theory model [46]. The RPM and
GM are of particular interest to researchers because the RPM
correlates the carbonation behavior with the internal pore struc-
ture by three structural parameters. In addition, the GM assumes
that the adsorbent is composed of small grains that are dispersed
in gas phase, and each grain is converted according to the
shrinking core model. Bhatia and Perlmutter [35] studied the ki-
netics via the RPM to fit the early stage of their experimental data.
The experiments were carried out in an atmospheric themogra-
vimetric analyser (ATGA) with 0e10 vol% CO2. Zero activation
energy was suggested. This was consistent with the equilibrium
analysis carried out by Dennis and Hayhurst [47]. Sun et al. [48]
conducted a systematic study regarding the intrinsic kinetics of
CaO carbonation under a wide range of CO2 partial pressures. The
GM was used to determine the rate-controlling steps of CaO
carbonation. It was found that the activation energies of the
carbonation of limestone and dolomite were 29 ± 4 and
24 ± 6 kJ mol1, respectively.
Although the two models (RPM and GM) are widely used to
study the carbonation reaction, few researchers have compared
them probably because of the limitations in the early GM; for
example, the structural change of sorbent occurred during
carbonation was normally ignored. However, the GM has been
intensively developed in recent years and is quite different from its
original form. For example, an overlapping grain model (OGM)
developed by Liu et al. [39] who considered not only the grain size
distribution and the overlapping effect of grains but also the
structure change during the carbonation process. Therefore, it is
interesting to compare the RPM with the OGM, especially the ki-
netic and diffusion parameters obtained from using the two
models. Zhou et al. compared the RPM model and OGM in relation
to the carbonation behaviors of CaO-based adsorbents. It was found
that both models described the carbonation of the adsorbents very
well, and the estimated activation energy by the RPM for the
kinetically limited reaction stage was 28.4 kJ mol1, which was
comparable with 32.3 kJ mol1 obtained by the OGM. The average
value of intrinsic rate constant obtained by the OGM was
 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27 3

Fig. 1. Fundamental understanding of the adsorbent reactivity: (a) Schematic representation of the adsorbent conversion during carbonation [30]; Relative conversion rate as a
function of carbonation reaction time by (b) RPM/DFM and (c) three-stage model [31]; (d) Schematic description of the transformation of a CaO adsorbent in recarbonation/
decomposition cycles [32]. RPM, random pore model; DFM, dual function material.

1.67  105 m s1 at 500e700
C, which was slightly higher than morphology of natural materials, Mess et al. [52] carried out long-
that obtained by the RPM (5.44106 m s1). duration carbonation tests on non-porous CaO particles with the
size range of 15e20 mm. It was found that the product layer
thickness was homogeneous up to 2 mm at very intense carbonation
2.1.2. Critical thickness of CaCO3 layer
conditions (11.74 atm of CO2 and 2000 min at 850
C). In consid-
Barker attributed the reduced rate of CaO carbonation at the
eration of a porous CaO, Alvarez and Abanades [53] refined the
second reaction stage to the diffusion of CO2 through the formed
model proposed by Barker [49] and reported that the small pores in
CaCO3 [49]. During the carbonation reaction, the ratio of reaction
the calcined material were filled completely before the maximum
rate between the first and second reaction stages was 100. It was in
product thickness was reached. In the reported model, a product
good agreement with the ratio of diffusion coefficient of CO2
layer of CaCO3 was formed on the surface of the CaO during the
through CaCO3 and CaO which was 0.3 cm2 s1 and 0.003 cm2 s1,
carbonation process. An average value of 49 nm (19% standard
respectively [50]. Thus, Barker proposed that a critical layer of the
deviation) has been obtained combining the pore model with the
CaCO3 product was formed after which the reaction rate was
experimentally determined pore size distribution and the CaO
controlled by the diffusion of CO2 [49]. At the fast stage, the
conversion at the onset of the second reaction stage. Wang et al.
carbonation reaction took place on the surface of CaO via the
[54] numerically simulated CaO carbonation with CO2 and the
nucleation and growth of CaCO3. When the formed CaCO3 collapsed
product layer thickness of CaCO3. It showed a continuous increase
to form a continuous layer over the unreacted adsorbent, the fast
of the overall product layer thickness up to 65.5 nm at the kineti-
stage of CaO carbonation ended abruptly [30]. Therefore, the fast
cally limited reaction stage. But afterward, the thickness of CaCO3
reaction stage and substantially slower reaction stage were re-
layer was only increased less than 4 nm at the diffusion-controlled
ported to be controlled by the kinetics and CO2 diffusion through
stage. However, there was no direct measurement or observation of
the CaCO3 layer, respectively [49,51].
the thickness of the critical CaCO3 layer except for calculation using
To have a better understanding of the fast reaction stage of the
numeric models.
carbonation process, the studies focused on the critical thickness of
product layers are discussed in the following section. Barker [49]
proposed a ‘critical carbonate layer thickness’ of 22 nm at which 2.2. Slow stage of CaO carbonation
the reaction rate became controlled by diffusive limitation. How-
ever, the estimating equation used in the study had large number of 2.2.1. Kinetics of slow stage of CaO carbonation
uncertainties, and it required a detailed knowledge of the pore An early study concerning the kinetics of the second stage of
model and the carbonation pattern across the particles of sorbent. carbonation reaction was carried out by Dedman and Owen [51]. It
To exclude the effects caused by the complex and unquantifiable was reported that the activation energy of CO2 diffusion was
4 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27
39.8 ± 8.3 kJ mol1 in a temperature range from 200 to 600
C. This
value was significantly lower than the activation energy for ion
diffusion in crystals (84 kJ mol1) and fell into the typical range of
gas diffusion. Thus, Dedman and Owen hypothesized that the
second stage of CaO carbonation reaction was governed by the
diffusion of CO2, which probably occurred along grain boundaries.
In addition, Oakeson and Cutler [55] studied the kinetics of CO2
capture using non-porous CaO particles (around 40 mm in diam-
eter), and it was found that the partial pressure of CO2 had a major
effect on the rate of initial carbonation. Scanning electron micro-
scopy (SEM) images of the particles showed a coherent interface
between CaO and CaCO3, indicating that CaO did not diffuse
through the carbonate layer. Thus, it was concluded that either CO2
diffused through CaCO3 product layer or counter-diffusion of CO2 3
and O2 occurred. Oakeson and Cutler [55] determined an activa-
tion energy of 121 ± 25 kJ mol1 for CaO carbonation, which was
higher than the values reported by Dedman and Owen [51].
Mess et al. [52] demonstrated that there were two independent
parallel processes taking place during the carbonation of non-
porous CaO. The first process was grain boundary diffusion that
was directly proportional to the length of grain boundary (de-
creases with reaction time) and independent of partial pressure of
CO2. The second process was bulk diffusion through the CaCO3
crystal to the unreacted CaO. This process was linearly proportional
to CO2 partial pressure and became dominant with the increase of
reaction time.
2.2.2. Diffusion mechanisms of CO2
Bhatia and Perlmutter [35] recognized that the diffusion
mechanism may be influenced by reaction temperature. When the
temperature was below 515
C, carbonation reaction took place on
the surface of CaO pores and controlled by the diffusion of CO2. The
activation energy was 88.9 kJ mol1, and CaCO3 had good pore
channels and grain boundaries; thus, the diffusion of CO2 was not a
problem. However, when the temperature was above 515
C, the
carbonation reaction took place on the interface of CaOeCaCO3, and
CO2
3 was the diffusion specie. The calculated activation energy was
179.2 kJ mol1. A more compact layer was formed; thus, the
diffusion of CO2 became a problem. Bhatia and Perlmutter [35]
proposed the following reaction mechanisms for the carbonation
of CaO:
At the interface of CaOeCaCO3
CO2
3 þ CaO4CaCO3 þ O
2
(3)
At the pore surface
CO2 ðgÞ4ðCO2 Þads (4)
ðCO2 Þads þ O2 4CO2
3 (5)
The two-stage model is usually used to investigate the kinetics
of CaO carbonation using CaO-based adsorbents [41,56]. However,
there was no distinct boundary between the two stages of kinetics.
A transition stage of CO2 capture could exist in the process of CaO
carbonation. As shown in Fig. 1b, neither chemical
reactionecontrolled stage (RPM) nor diffusion-controlled stage
(dual function material [DFM]) was applicable between 25 s and
750 s reaction time [31]. Thus, the authors concluded that a satis-
fying result could hardly be obtained by applying one of the com-
mon two-stage models.
Therefore, a more precise kinetic model had been taken into
consideration about the existence of a transition stage in carbon-
ation reaction. Jiang et al. [31] developed a new three-stage model
including the transition stage that can be expressed as
8
>
>
> 1  eð1þkjt=4Þkt t  t1
>
> Zt
>
<
Xr ðtÞ ¼ X ðt
r 1 Þ þ rdt t1 < t < t2 (6)
>
>
>
>  1 .
t
>
>
: 1  eatþb 0:8 t  t2
The calculated results as shown in Fig. 1c fitted well to the
experimental results [31].
2.3. Deactivation mechanisms of CaO for long-term applications
The main challenge for CO2 capture using CaO-based adsorbents
at high temperature is the poor reversibility during the regenera-
tion of sorbents owing to the sintering of adsorbent particles
[32,57,58]. As shown in Fig. 1d, CaCO3 was indicated by dark grey,
and CaO was shown by light grey. When CaCO3 was initially
decomposed, highly dispersed reactive CaO particles were pro-
duced. However, the incomplete carbonation happened during the
next cycle of carbon capture. The amount of unreacted CaO was
increased after each cycle of CO2 capture until a rigid inter-
connected CaO skeleton was formed, preventing further sintering
of the adsorbent [32].
There are three major factors causing the sintering of CaO par-
ticles: (1) highly exothermic reaction of sorbent carbonation, (2)
dramatic volume increase during the transformation from CaO to
CaCO3 (16.9e34.1 cm3 mol1), and (3) comparatively lower Tam-
man temperature of CaCO3 (only 533
C) than normal carbonation
temperature [59,60]. The Tamman temperature is the temperature
at which the mobility and reactivity of the molecules in a solid
become appreciable. Thus, the low Tamman temperature of CaO
sorbents could result in the sintering of CaO particles during the
cycle of carbonation/calcination. Therefore, extensive efforts have
been devoted to enhancing the capacity of CO2 capture and the
sintering-resistant properties of CaO-based adsorbents. As sum-
marized in Fig. 2, the main improvement methods are (1) devel-
oping synthetic CaO with high surface area, (2) dispersing CaO on
inert support such as Al, Ti, Mg, Ce, Zr etc., and (3) surface
modification.
3. Improvements of CaO-based adsorbents
The deactivation of CaO-based materials for CO2 capture is well
known and represents one of the key challenges for the deploy-
ment of the technology. In addition, developing novel CaO mate-
rials with high CO2 capture capacity and fast conversion is a
promise for industrial applications. CaO-based materials'
improvement is reviewed in this section, while the capacity of CO2
capture (Eq. (7)) and the conversion of CaO carbonation (Eq. (8)) as
well as carbonation rate (Eq. (9)) are used to facilitate the
discussion.
 
Capature capacity mmol g1 ¼ mmol of CO2 =g of
(7)
calcined adsorbent
mN  m1 MCaO
Carbonation conversion XN ð%Þ ¼ $ $100% (8)
m0 $b MCO2

Carbonation rate ¼ dXN dt (9)
where XN is the carbonation conversion of sample, N is the number
of cycles, m0 is the initial mass of sample, b is the content of CaO in
the initial sample, mN is the mass of the carbonated sample after N
 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27 5

Fig. 2. A brief summary of main methods for improving the capacity of CO2 capture using CaO-based adsorbents. FSP, flame spray pyrolysis.

cycles, m1 is the mass of sample after calcination (mass of sample
after each calcination is the same), and MCaO and MCO2 are the mole
masses of CaO and CO2, respectively.
3.1. Developing synthetic CaO with high surface area
Introducing various CaO precursors and improving synthesized
methods are two important technologies to enhance the perfor-
mance of CO2 capture using CaO-based adsorbents due to the
improved high surface area and porosity. The detailed perfor-
mances of various synthetic CaO-based adsorbents are summarized
in Table 1.
3.1.1. Introduction of various CaO precursors
Nanosized CaO precursors have been used to produce efficient
CaO adsorbents with exceptionally high surface area, which pro-
vide many reactive sites for CO2 capture. For example, Florin and
Harris [18] prepared a pure CaO derived from nanosized CaCO3, and
the sorbent was used for CO2 capture. The conversion of CO2 cap-
ture was doubled compared to that of a regular limestone. In
addition, the residual conversion of CaO calcined from nanosized
CaCO3 was 21% after 100 cycles, which was higher than that in a
previous report using commercial CaCO3, which was 11% after 40
cycles of carbon capture [32]. Another attempt to use nanosized
CaCO3 as the precursor of CaO was investigated by Wu et al. [61] It
was confirmed that the nano-CaCO3 was better than Ca(OH)2 and
micro CaCO3 in relation to the uptake of CO2, and the decomposi-
tion of nano-CaCO3 had low activation energy due to its higher
surface area.
Lu et al. [62] prepared a series of CaO adsorbents using different
precursors, including Ca(NO3)2$4H2O, CaO, Ca(OH)2, CaCO3, and
Ca(CH3COO)2$H2O. Among all the obtained CaO adsorbents, the
material derived from the Ca(CH3COO)2$H2O (CC-CaO) maintained
a higher conversion of 62 % at 700
C in a 27-cycle (carbonation/
calcination) operation due to the presence of higher Brunauer-
Emmett-Teller (BET) surface area and larger pore volume.
Furthermore, Liu et al. [63] further investigated the influence of
other CaO precursors. It was found that CaO adsorbent derived from
calcium D-gluconate monohydrate (CG-CaO) exhibited the best
performance of CO2 capture and the lowest temperature of sorbent
regeneration compared with the CaO sorbents derived from
Ca(CH3COO)2$H2O and other precursors (e.g. calcium acetate hy-
drate, calcium L-lactate hydrate, and calcium D-gluconate mono-
hydrate (CG-CaO)). This phenomenon was attributed to the less
diffusional effects caused by the apparently porous structure of CG-
CaO.
3.1.2. Improvement of synthesis methods
Precipitation method is effective to enhance CO2 uptake of CaO-
based adsorbents because it affects the size and porosity of CaO
particles. Gupta and Fan [64] tailored a wet precipitation process to
synthesize precipitated calcium carbonate (PCC) with high surface
area (Fig. 3a). A porous frit at the bottom provided a good distri-
bution of CO2 through the slurry. A K-type thermocouple inserted in
the slurry continuously recorded the slurry temperature. A pH
probe monitored the pH of the slurry as the reaction medium
changed from a basic to an acidic solution as the reaction pro-
ceeded. The PCC had a highly porous structure with pore size
ranging from 5 to 20 nm. The CaO adsorbent derived from the PCC
(PCC-CaO) was less susceptible to pore blockage, and more than
90% conversion to CaCO3 was obtained for carbonation reaction.
Yang et al. [65] synthesized a novel CaO adsorbent consisting of

Table 1
CO2 capture using synthetic CaO adsorbents with high surface area.

Methods Calcination conditions Carbonation conditions Reactor CO2 uptake (mmol g1) Ref.

T (
C) Atmosphere t (min) T (
C) Atmosphere t (min)

Calcination method 850 100% N2 10 650 15% CO2 in N2 10 TGA (100 cycles) 3.75 [18]
Calcination method 800 100% N2 5 650 33% CO2 in N2 40 TGA (50 cycles) 4.0 [61]
Calcination method 700 100% He 30 700 30% CO2 in He 300 TGA (27 cycles) 11.1 [62]
Calcination method 900 100% N2 10 650 15% CO2 in N2 30 TGA (9 cycles) 15.0 [63]
Precipitation method 700 100% N2 10 650 100% CO2 60 TGA (3 cycles) 14.5 [64]
Precipitation method 700 100% N2 10 600 60% CO2 in N2 20 TGA (50 cycles) 9.1 [65]
Precipitation method 850 100% N2 10 700 35% CO2 in N2 60 TGA (17 cycles) 12.5 [66]
Solgel method 800 100% N2 13 700 15% CO2 in N2 50 TGA (70 cycles) 5.5 [67]
FSP method 700 100% He 30 700 30% CO2 in He 300 TGA (60 cycles) 8.9 [77]

FSP, flame spray pyrolysis; TGA, themogravimetric analyser.

6 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27
Fig. 3. Schematic diagrams of the various techniques employed for the improvement of CaO-based adsorbents: (a) coprecipitation method [64]; (b) carbon gel template method
[71]; (c) hydrolysis method [72]; (d) flame spray pyrolysis (FSP) method [73]; (e) one-pot method [74]; (f) standard sol-gel combustion process [68].
nanosized platelets with approximately 200 nm in diameter and up
to 600 nm in length. The CaCO3 precursor was prepared by
bubbling CO2 through a Ca(OH)2 slurry in the presence of poly-
ethylene oxide-polypropylene oxide-polyethylene oxide (P123).
CaO derived from precipitated CaCO3 without the P123 displayed a
significant drop-off in absorption capacity. In contrast, the CaO
derived from the CaCO3 nanopods displayed a steady and much
slower rate of sorbent decay, maintaining an absorption ratio of
about 51% at the 50th cycle. Karami and Mahinpey [66] prepared
CaO-based adsorbents via the precipitation of different chemical
solutions including CaCl2 and Ca(NO3)2. The obtained adsorbent
using CaCl2 as a precursor exhibited a relatively high conversion
(70%) of CaO due to the formation of fine particles of CaO, which
helps to recover the activity for CO2 capture. The high capacity of
CO2 uptake and the good ability of the regeneration of spent sor-
bent were attributed to the formation of fine CaO particles with
enhanced BET surface area and porous structure.
Recently, solgel method has attracted more attention to produce
reactive CaO-based adsorbents because it can produce the mate-
rials with uniformly dispersed particles [67e69]. Santos et al. [67]
synthesized a highly reactive CaO-based adsorbent by the solgel
method to prohibit CaO sintering during the process of CO2 capture.
Compared to a pure CaO, the solgel-derived adsorbent had a larger
surface area (45 m2 g1), smaller grain size (100e200 nm), and
highly interconnected pore network. The obtained adsorbent
possessed a CO2 capture capacity of 5.5 mmol g1 after 70 cycles of
carbonation/calcination when the carbonation and calcination
conditions were 700
C at 15% CO2 balanced with N2 for 50 min and
800
C at 100% N2 for 13 min, respectively. The capacity of CO2
capture using the CaO produced from the solgel method was much
higher than that derived from a limestone (1.8 mmol g1) [70].
An alternative method for decreasing the particle size and
increasing the surface area of CaO is flame spray pyrolysis (FSP)
method, in which precursor droplets are converted into solid
nanoparticles in flames. FSP technology has been proposed as a
promising large-scale method for producing various types of
reactive powders because it is a fast, cost-effective, and versatile
process (several tons per hour) with no liquid by-products [75,76].
In addition, by FSP technique, different adsorbents could be pro-
duced by doping with silica, titanium, chromium oxide, cobalt ox-
ide, zirconia, and ceria [59]. Better performance of CO2 capture
using a nano-CaO prepared by the FSP method was reported than
an adsorbent produced with normal wet impregnation. For
example, Lu et al. [77] prepared CaO-based adsorbents consisting of
nanostructured CaO and CaCO3 with high specific surface area
(40e60 m2 g1) by the FSP method. It was found that the nano-
structured FSP-made adsorbents (30e50 nm) demonstrated a sta-
ble, reversible, and high capacity of CO2 uptake, sustaining a
maximum CaO conversion around 50% even after 60 cycles of
carbonation/calcination. The excellent performance of CO2 capture
using the FSP-derived CaO was attributed to the formation of
nanostructure, maximizing CO2 capture to happen in the reaction-
controlled carbonation regime rather than the diffusion-controlled
regime.
3.2. Dispersing CaO on inert supports
Incorporating CaO particles into inert materials such as Al
[78e82], Ti [83,84], Mg [60,82], Ce [85], and Zr [86] is another
promising method to improve the capacity of CO2 capture and the
stability of adsorbents. The inert material has a relatively higher
Tamman temperature than CaO. It provides physical barriers to
prevent or delay the sintering and aggregation of CaO particles in
the process of CO2 capture. Based on the final forms of supports,
these inert materials can be divided into two groups. Group A is the
calcium-support metal oxide formed through the reaction between
CaO and support metal oxide, including Ca12Al14O33, Ca9Al6O18,
CaTiO3, and CaZrO3. The calcium-support metal oxide is inert as it
 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27 7

does not react with CO2; however, it reacts with CaO. The perfor-
mance of CaO-based adsorbents (Group A inert supports) is sum-
marized in Table 2. Group B support is the metal oxide formed
through the calcination of corresponding support precursors,
including MgO, Y2O3, SiO2, and CeO2. The Group B metal oxide
support is inert to both CO2 and CaO. The performance of CaO-based
adsorbents (Group B inert supports) is summarized in Table 3.
3.2.1. Bimetallic metal oxide as support
3.2.1.1. Al-doped CaO-based adsorbent. Aluminum-derived mate-
rials have attracted much attention due to the low cost and good
thermal stability. It has been proposed that the formation of Ca-Al
mixed oxides during the calcination of adsorbents resulted in a
uniform distribution of (Ca:Al)Ox throughout the adsorbent, which
efficiently stabilized CaO particles and retarded sintering in the
process of carbon capture. For example, Li et al. [87] synthesized a
novel CaO-based adsorbent via hydrolysis method using CaO and
Ca12Al14O33 as a solid reactant and binder, respectively. The ob-
tained adsorbent exhibited a high capacity of CO2 capture about
10.2 mmol g1 over 13 cycles of carbonation and calcination which
were carried out at 690
C and 950
C, respectively.
High surface area and porous structure of support are beneficial
to the capture of CO2. Thus, solgel method has been used to disperse
CaO into inert materials to obtain a nanoporous structure. Broda
et al. [88] developed a CaO-based adsorbent composed of 17.84 wt%
Ca12Al14O33 through solgel method, and the produced adsorbent
possessed a stable CO2 uptake of 7.0 mmol g1 after 30 cycles of
carbonation/calcination conducted in a fluidized bed. The capacity
of CO2 capture was approximately 60% higher than that obtained
from a regular limestone. The higher CO2 uptake was attributed to
the nanostructure of the synthetic material produced by the solgel
technique, which ensured that Ca2þ and Al3þ were homogenously
mixed (mostly in the form of the mixed oxide mayenite). The for-
mation of fine and homogeneously dispersed support with high
Tamman temperature stabilized the morphology of the support
over multiple cycles of CaO carbonation/calcination. However, the
nanostructured morphology of limestone could be rapidly lost
owing to its intrinsic lack of supporting component. The authors
also adapted carbon gel as a template to synthesize highly efficient
Ca-based and Al2O3-stabilized adsorbents. Excellent CO2 capture
performance (12.7 mmol g1) was obtained. It was suggested that
the homogeneous dispersion of CaO particles and the high melting
point network were key to the good performance of CO2 capture
(Fig. 3b) [71]. Xu et al. [89] synthesized a series of CaO-based ad-
sorbents that consist of active CaO and inert Ca9Al6O18 support
matrix by solgel method. In comparison with a pure CaO, the solgel-
derived adsorbent had smaller grains (less than 1 mm) and highly
interconnected pore networks as well as uniformly distributed CaO
and Ca9Al6O18 particles. Therefore, the adsorbent with a CaO con-
tent of 90 wt % derived from the solgel method exhibited a superior
performance of CO2 capture during a long-term cyclic operation,
and the capacity of CO2 capture remained as high as 13.4 mmol g1
after 35 cycles of carbonation/calcination. This was attributed to the
formation of interconnected pore networks in the adsorbent. In
addition, Jing et al. [90] found that the thermally pretreated tem-
perature played an overwhelming role in the CO2 capture capacity
and stability of the CaO/Ca3Al2O6 sorbents.
3.2.1.2. Ti-doped CaO-based adsorbent. Coating the surface of
CaCO3 with a nano-TiO2 using a solution containing Ti4þ can
generate CaTiO3. It is regarded as a promising method to enhance
the stability of sorbent framework and reduce the sintering of ad-
sorbents due to the higher melting point of the newly formed
CaTiO3. Aihara et al. [83] prepared novel adsorbents composed of
CaO as the reactant and CaTiO3 as the inert framework via a con-
ventional powder method and a metal alkoxide method, respec-
tively. Compared to the powder method, the alkoxide method
resulted in a faster carbonation rate for the first carbonation and
calcination of the adsorbents (1.8 and 2.4 times, respectively). Be-
sides, the solid adsorbent with the inert CaTiO3 framework
exhibited a stable reversibility than those without the inert
framework when the carbonation and calcination remained at
750
C. It was suggested that the inert CaTiO3 framework retained
the reactant with its initial size, and the created voids buffered the
volume changes during the process of CO2 capture. Wu and Zhu
[84] coated the surface of nano-CaCO3 with a nano-TiO2 film (less
than 10 nm) via tetrabutyl titanate (Ti(OC4H9)4) hydrolysis. A layer
of CaTiO3 was formed by calcination at a temperature up to 850
C,
thus preventing the nano-CaO particles from migrating at high
temperatures. It was found that the CaTiO3/nano-CaO adsorbent
had a capacity of CO2 uptake of 5.3 mmol g1, which was much
higher than that of the uncoated nano-CaCO3 adsorbent

Table 2
The performance of CaO-based adsorbents using bimetallic metal oxide acting as the inert material.

Supports (wt%) Methods Calcination conditions Carbonation conditions Reactor CO2 uptake Ref.



(mmol g1)
T ( C) Atmosphere t (min) T ( C) Atmosphere t (min)

Ca12Al14O33 (25%) Hydrolysis method 950 100% N2 10 690 14% CO2 in N2 30 TGA (13 cycles) 10.2 [87]
Ca12Al14O33 (17.84%) Solgel technology 750 100% N2 15 750 50% CO2 in N2 6 Fluidized bed 7.0 [88]
(30 cycles)
Ca12Al14O33 (17.84%) Solgel technology 750 100% N2 20 750 40% CO2 in N2 20 TGA (30 cycles) 12.7 [71]
Ca9Al6O18 (10%) Solgel technology 800 100% N2 10 650 15% CO2 in N2 30 TGA (35 cycles) 13.4 [89]
CaTiO3 (70.8%) Metal alkoxide method 750 100% N2 60 750 20% CO2 in N2 60 TGA (10 cycles) 3.2 [83]
CaTiO3 (28.15%) Coating method 750 100% N2 10 600 20% CO2 in N2 10 TGA (40 cycles) 5.3 [84]
CaZrO3 (57.8%) FSP method 700 100% He 30 700 30% CO2þ 10% H2O in He 30 TGA (100 cycles) 4.8 [59]
CaZrO3 (76.17%) FSP method 700 100% He 30 700 99.95% CO2 30 TGA (1200 cycles) 2.5 [73]
CaZrO3 (58%) Surfactant 750 100% Ar 30 700 100% CO2 30 TGA (15 cycles) 3.3 [91]
template-ultrasound
synthesis method
CaZrO3 (26.2%) Solgel method 800 100% N2 15 800 50% CO2 in N2 5 TGA (90 cycles) 7.7 [92]
SiO2 (34.9%) Solgel method 700 100% N2 5 600 66.7% CO2 60 TGA (50 cycles) 7.5 [94]
SiO2 (51.7%) Hydrolysis method 850 100% N2 20 700 15% CO2 in N2 15 The twin fixed bed 3.6 [95]
reactor (50 cycles)
SiO2 (15%) Dry physical mixture 850 100% air 5 650 15% CO2 in air 5 TGA (100 cycles) 2.7 [97]
SiO2 (90%) Dry physical mixture 850 100% air 5 650 15% CO2 in air 5 TGA (25 cycles) 1.1 [98]
SiO2 (10%) Dry physical mixing 900 100% N2 3 700 100% CO2 5 TGA (30 cycles) 7.3 [103]
SBA-15(32%) Wet impregnation 910 100% N2 30 700 100% CO2 60 TGA (40 cycles) 9.7 [99]

FSP, flame spray pyrolysis; TGA, themogravimetric analyser.

8 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27

Table 3
The performance of CaO-based adsorbents using calcium-support metal oxide acting as an inert material.

Supports (wt%) Methods Calcination conditions Carbonation conditions Reactor CO2 uptake (mmol g1) Ref.

T (
C) Atmosphere t (min) T (
C) Atmosphere t (min)

MgO (20%) Doping method 750 100% N2 30 750 25% CO2 in N2 20 TGA (1250 cycles) 4.0 [102]
MgO (26%) Physical mixing 758 100% He 30 758 100% CO2 30 TGA (50 cycles) 9.5 [60]
MgO (6.7%) Wet mixing technique 750 100% Ar 30 650 15% CO2 in Ar 30 TGA (25 cycles) 7.0 [107]
MgO (25%) Sol-gel method 850 100% N2 6 650 20% CO2 in N2 10 TGA (50 cycles) 8.1 [109]
MgO (8%) ‘One-pot’ recrystallization 750 100% N2 10 750 100% CO2 20 TGA (10 cycles) 10.7 [105]
MgO (25%) Wet mixing method 900 100% N2 10 650 15% CO2 in N2 30 TGA (24 cycles) 12.7 [82]
Y2O3 (80.1%) Calcination method 740 100% Ar 10 740 25% CO2 in Ar 10 TGA (190 cycles) 1.8 [106]
Y2O3 (20%) Solgel combustion method 850 100% N2 5 650 20% CO2 in N2 30 TGA (10 cycles) 13.0 [110]
Yb2O3 (10%) Wet mixing technique 800 100% N2 5 650 30% CO2 in N2 25 TGA (15 cycles) 12.0 [111]
CeO2 (15%) Solgel method 700 100% N2 20 600 50% CO2 in N2 45 TGA (18 cycles) 13.4 [85]
CaO/mSiO2 (5.6%) ‘One-pot’ 850 100% N2 35 650 100% CO2 40 TGA (50 cycles) 6.2 [74]
CaO/mTiO2 Wet coating process 850 100% N2 10 675 100% CO2 10 TGA (30 cycles) 5.1 [108]
combined with solgel method

FSP, flame spray pyrolysis; TGA, themogravimetric analyser.

(3.7 mmol g1) under the same test conditions after 10 cycles of
carbonation/calcination. Similar results were obtained by Wang
et al. [72]. The authors achieved a controlled coating layer of
4.5e11.6 nm by increasing the content of TiO2 through microscale
hydrolysis of Ti(OC4H9)4. The coating of TiO2 can prevent the sin-
tering of nano-CaCO3 particles during multiple cycles of carbon-
ation/calcination. The mechanism of coating TiO2 on the surface of
nano-CaCO3 is shown in Fig. 3c. The nano-CaCO3 was dehydrated
using zeolite in the presence of water, and only a thin layer of water
on the round surface of the nano-CaCO3 particle was maintained.
When an ethanol solution of Ti(OC4H9)4 was added drop wise into
the dehydrated suspension, the Ti(OC4H9)4 spread to the water
layer and quickly hydrolyzed.
3.2.1.3. Zr-doped CaO-based adsorbent. A CaO adsorbent with Zr/Ca
atomic ratio of 3/10 was reported to have a better performance in
terms of the capacity and the stability of CO2 capture after 100
cycles of carbonation/calcination than adsorbents doped with other
elements such as Si, Ti, Cr, Co, and Ce [59]. Koirala et al. [73]
extended the previous work to prepare a Zr/Ca adsorbent with a
molar ratio of 5/10 prepared by FSP method. An excellent perfor-
mance of CO2 capture and remarkable stability of sorbent were
obtained after up to 1200 cycles of carbonation/calcination, as
shown in Fig. 3d. It was attributed to the formation of a well-
dispersed CaZrO3 support with a high Tamman temperature
(1036
C) [59].
A surfactant template/ultrasound-assisted synthesis method
was reported by Radfarnia and Iliuta to prepare Zr-doped CaO ad-
sorbents [91]. The method was found to be efficient to generate
nanoparticles compared to conventional methods, e.g. hydrolysis
method. The developed Zr-stabilized CaO with a Zr/Ca molar ratio
of 0.303 showed the most favorable stability and the highest ca-
pacity of CO2 uptake during 15 carbonation/calcination cycles. It
was proposed that the incorporation of Zr inhibited the agglom-
eration of CaO particles. Furthermore, a self-reactivation phenom-
enon was observed for the Zr-CaO adsorbent when the capture of
CO2 was carried out at carbonation of 700
C in pure CO2 and at
calcination temperature of 750
C in pure argon, respectively. The
self-reactivation of the adsorbent at a temperature higher than
600
C might be attributed to the structural rearrangement of the
adsorbent and the highly dispersed CaZrO3, which prevented
structural collapse and particle sintering and enabled better access
of CO2 molecules to the active CaO sites.
ZrO2-stabilized CaO-based adsorbents were also prepared by
the solgel method by Broda et al. [92] The capacity of CO2 reached
7.7 mmol g1 after 90 cycles of carbonation/calcination because
Ca2þ and Zr4þ were uniformly mixed via the formation of CaZrO3.
The nanoporous structure of the CaO-based adsorbents was
maintained by the formed CaZrO3. Guo et al. [93] developed a (Ce-
Mn)-doped CaO-based adsorbent and investigated the effect of Ce
and Mn incorporation on CO2 capture. It was found that the
improvement of CO2 capture capacity was attributed to the electron
donation from Ca atom to surface oxygen atoms promoted by the
interaction between Ce and Mn. In addition, CeO2 and Ca2MnO4
retarded the crystallite growth and agglomeration of CaO phase.
Thus, the (Ce-Mn)-doped adsorbents exhibited excellent long-term
durability with capture capacity of 13.9 mmol g1 after 40 cycles.
3.2.1.4. SiO2 as support. Silica dioxide is a cost-effective and widely
available inert material in nature. It has been widely used as a
support for the development of CaO-based adsorbents. Zhao et al.
[94] prepared porous SiO2esupported CaO adsorbents (CaO-SiO2)
by solgel method. The uptake of CO2 of the developed adsorbent
(nCa/nSi ¼ 2:1) reached 7.5 mmol g1 after 50 cycles of carbonation
and calcination due to the presence of Ca-O-Si interactions and the
ordered porous structure. Li et al. [95] and Chen et al. [96] devel-
oped rice husk ash (93 wt% SiO2)ebased CaO adsorbent by hydro-
lysis method under atmospheric and pressurized conditions. An
improvement of the capacity of cyclic CO2 capture was observed.
This was attributed to the formation of dicalcium silicates (Ca2SiO4)
by the reaction between SiO2 and Ca(OH)2. Valverde et al. [97] and
Sanchez-Jimenez et al. [98] suggested that nanostructured silica
could accelerate carbonation rate and improved mechanical
strength of synthetic adsorbents, resulting in the enhancement of
the capacity of CO2 capture compared to an original adsorbent in a
short carbonation time (5 min). In addition, Huang et al. [99]
developed a modified CaO-based mesoporous CO2 adsorbent us-
ing calcium acetate (Ca(AC)2) as a precursor and highly ordered
mesoporous SBA-15 as a support via an impregnation method. The
obtained adsorbents exhibited high capacity of CO2 uptake (about
9.7 mmol g1) and long-term durability (remained at 80% after 40
cycles) because the SBA-15 provided a stable framework, inhibiting
the deactivation of CaO.
Al, Ti, Zr, and Si are widely used as a support to provide a stable
framework and enhance carbon capture capacity of CaO-based
adsorbents. However, the presence of Ca-O-Al, Ca-O-Ti, Ca-O-Zr,
and Ca-O-Si interactions consumes active sites of CaO during the
preparation of adsorbents. Therefore, it is important to consider the
problem from two perspectives: the stable framework and active
sites.
3.2.2. Metal oxide as support
3.2.2.1. MgO as support. MgO is a promising support to enhance
the sintering resistance of CaO particles during the process of CO2
 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27
capture. For example, a mixture of CaO and MgO was obtained by
the decomposition of dolomite [100]. The produced MgO-support
adsorbent showed a stable capacity of CO2 capture compared to
CaO derived from limestones [101]. However, it is impractical to
incorporate a large amount of inert material in an industrial
adsorbent due to increasing capital and operating costs. Thus, the
use of smaller concentrations of MgO by a doping method has
attracted more attention. For example, Albrecht et al. [102] intro-
duced 20 wt% MgO into a CaO-based adsorbent. The added MgO
particles were finely dispersed within the adsorbent and served as
an ‘inert’ material. It is assumed that the reaction between CO2 and
MgO was ignored as the temperature of CaO carbonation is too high
for MgO to react with CO2. The obtained adsorbent exhibited a
significant enhancement of the stability for CO2 capture. For
example, at the end of a 1200-cycle test, the capacity of CO2 capture
of the MgO-CaO adsorbents was 45% greater than that of the un-
treated adsorbents. Li et al. [60] prepared a series of CaO-based
absorbents by physically mixing Ca(AC)2 with small MgO parti-
cles. And, it was found that with 26 wt% MgO, the CaO-MgO
adsorbent exhibited a CO2 capacity about 9.5 mmol g1 after 50
cycles of carbonation/calcination probably as a result of providing
stable segregations for small CaO particles. Without the addition of
MgO, the capacity of CO2 capture of a pure CaO decreased from
11.8 mmol g1 for the first cycle to 4.6 mmol g1 for the 50th cycle of
carbonation/calcination.
In addition, Mabry and Mondal [104] demonstrated that the
maximum capacity of CO2 capture retained 86% after 50 cycles of
carbonation/calcination using a MgO/CaO sorbent. ‘One-pot’
recrystallization technique was applied in the synthesis of the
efficient MgO-CaO adsorbent. It was found that the obtained ma-
terial possessed excellent performance of CO2 capture
(10.7 mmol g1 after 10 cycles of CO2 capture) exceeding the CO2
uptake (10th cycle) of limestone by 200%. The excellent perfor-
mance of the MgO/CaO for CO2 capture was attributed to the mix of
the active component CaO and support MgO on the nano-scale
level [105]. In this technique, CaO acted as the active site, and
MgO was regarded as the support because only CaO exhibited CO2
capture performance at 750
C. In addition, no evidence of new
active Mg-O-Ca sites was observed during the process of carbon
capture in the aforementioned work.
Liu et al. [82] produced sintering-resistant adsorbents from
calcium D-gluconate monohydrate and magnesium D-gluconate
hydrate by a wet mixing method. It was found that CaO particles
were well distributed in the MgO support. MgO nanoparticles
formed on the surface of the CaO-based adsorbents acted as
physical barriers of CaO in the process of carbon capture. The ca-
pacity of CO2 capture of the adsorbents was 12.7 mmol g1 after 24
cycles of carbonation/calcination, which was close to its theoretical
maximum capacity (13.4 mmol g1). In comparison, the capacity of
CO2 capture of the reference CaO decreased to 4.3 mmol g1 after
24 cycles of carbon capture, which was much lower than its theo-
retical maximum capacity (17.8 mmol g1). To explore the viability
of the wet mixing process, the authors prepared a range of adsor-
bents with different combinations of precursors. All adsorbents
showed a high capacity of CO2 capture which was close to the
theoretical value and also the capacity of CO2 capture retained over
cycles of carbonation/calcination. However, all the experiments of
CO2 capture were performed less than 10 cycles. More cycles of
carbon capture are necessary to study the feasibility of novel sor-
bents in practical application.
3.2.2.2. Y2O3 as support. Owing to the high Tamman temperature
of 2145
C, Y2O3 is widely used as an inert support to retard CaO
from agglomeration under high temperature. Derevschikov et al.
[106] incorporated CaO into Y2O3 through a wet impregnation
9
method. An adsorbent having the same elemental composition was
prepared for comparison by the calcination of mixed salt pre-
cursors. The capacity of cyclic CO2 capture using the developed
sorbents was tested isothermally at 740
C. It was found that the
preparation method had little influence on the performance of the
CaO-based absorbents in relation to the capacity of CO2 capture.
The capacities of CO2 capture were 1.78 mmol g1 and
1.75 mmol g1 after 100 cycles of carbonation/calcination for the
sorbents obtained from wet impregnation and the calcination of
mixed salt precursors, respectively. Radfarnia and Iliuta [107]
incorporated Y2O3 into limestones via a wet mixing technique.
During the test of CO2 capture, Y2O3 showed almost no advantages
in relation to the capacity and stability of CO2 capture compared
with other metal oxide stabilizers, e.g. Al, Zr, and Mg. This was
attributed to the insoluble nature of yttrium oxide, which restricted
the effective dispersion of Y2O3 among CaO particles.
3.2.2.3. Other metal oxide supports. Wang et al. [85] incorporated
Ce into CaO-based adsorbents through a solgel method and studied
different amounts of doping metals. It was found that the adsorbent
with a Ca/Ce molar ratio of 15/1 exhibited an excellent performance
(13.4 mmol g1) of CO2 capture and a remarkable stability after up
to 18 cycles of carbonation and calcination because the well-
dispersed CeO2 acting as a barrier effectively prevented the sin-
tering of CaO particles. Thus, the adsorbent exhibited outstanding
stability for cyclic CO2 capture.
In addition to dispersing CaO on inert supports, preparing
CaO@porous metal oxide adsorbents, which indicates CaO and
porous metal oxide acting as core and shell, respectively, is an
effective scheme to minimize the loss of activity for CO2 capture
and enhance the life cycle performance of CO2 capture. Li et al. [74]
reported a cost-effective one-pot method to synthesize a
CaCO3@mesoporous silica material with a core-shell structure
(Fig. 3e). The obtained adsorbent denoted as CaCO3@5.6 wt% mSiO2
possessed an improved carbonation conversion (around 25%) after
50 cycles of carbonation/calcination, which was higher than that of
the CaCO3-based adsorbent (13%). It was indicated that the meso-
porous silica can serve as a stable framework structure to improve
the reversibility of the adsorbent in the cycle of CO2 capture and
release. Mahinpey et al. [108] prepared core/shell adsorbents with
protective porous shell and mesoporous silica and titania layers.
Among all the obtained adsorbents, the CaO@mTiO2 pellet showed
the best performance in relation to CO2 uptake (5.1 mmol g1) over
30 cycles of carbonation/calcination. The carbonation was carried
out at 675
C in 100% CO2 for 10 min, and the calcination was
performed at 850
C in N2 for 10 min. It was attributed to the for-
mation of a protective layer of thermally stable mesoporous TiO2,
which prevented the aggregation of CaO crystals and the sintering
of the adsorbent.
3.3. Surface modification of CaO
The other important method to enhance the capacity and the
stability of CaO adsorbent for CO2 capture is to modify the surface of
the precursors during the preparation of adsorbents. Owing to low
cost and wide availability in nature, limestone and dolomite
attracted extensive attention as CaO precursors in the field of CO2
capture. The main challenge for limestone and dolomite to be
practically used is the sintering of the adsorbent particles. By
modifying limestone and dolomite with organic acids (acetic acid,
formic acid, and oxalic acid) or mineral acids (HCl, HBr, and HI), the
porosity of the modified adsorbent could be improved to enhance
the capacity of CO2 capture. The performance of CO2 capture using
limestone and dolomite via surface modification is summarized in
Table 4.
10 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27

Table 4
The performance of limestone and dolomite via surface modification for carbon capture.

Concentration of acid Calcination conditions Carbonation conditions Reactor CO2 uptake (mmol g1) Ref.

T (
C) Atmosphere t (min) T (
C) Atmosphere t (min)

Oxalic acid (10 vol.%) 850 100% N2 5 650 15% CO2 in N2 20 TGA (20 cycles) 5.7 [112]
Formic acid (10 vol.%) 850 100% N2 5 650 15% CO2 in N2 20 TGA (20 cycles) 5.0 [113]
L-(þ)-tartaric acid 900 100% N2 10 650 15% CO2 in N2 30 The twin fixed bed (26 cycles) 6.4 [114]
Citric acid 750 100% Ar 10 700 15% CO2 in Ar 30 TGA (18 cycles) 10.2 [115]
Pyroligneous acid 850 100% N2 15 700 15% CO2 in N2 30 The twin fixed bed (103 cycles) 3.1 [116]
Propionic acid (80 vol.%) 850 100% N2 10 700 15% CO2 in N2 20 The twin fixed bed (100 cycles) 3.0 [117]
Propionic acid (80 vol.%) 850 100% N2 15 700 15% CO2 in N2 30 The twin fixed bed (20 cycles) 6.5 [118]

TGA, themogravimetric analyser.

Ridha et al. [112] carried out a comprehensive assessment of the
treatment of limestones with various organic acids. After 20 cycles
of carbonation/calcination, the capacity of CO2 capture using the
limestones treated with acetic acid, vinegar, formic acid, and oxalic
acid was 5.2 mmol g1, 3.4 mmol g1, 5.0 mmol g1, and
5.7 mmol g1, respectively, when the untreated limestone had a
CO2 uptake of only 3.0 mmol g1.
To reduce the cost of CO2 capture, the authors investigated the
impact the treatment of vapor and liquid-phase formic acid on CO2
capture using CaO-based adsorbents [113]. It was found that the
treatment of limestones with aqueous solutions containing 10 or 30
vol% formic acid affected the growth of CaO. Smaller particle size of
CaO was produced when higher acid concentration was used.
Despite the low surface area and pore volume of the natural
limestone, the treated sorbent with 10% formic acid solution could
capture 67.4% more CO2 than the natural adsorbent after 20 cycles
of carbon capture due to the enlarged pore size. However, acid
vapor treatment was less efficient than the modification with a
relatively low concentration of acid solution in relation to the ca-
pacity of CO2 capture of CaO-based adsorbents.
Hu et al. [114] compared the performance of limestones modi-
fied by eight different organic acids under the same test conditions
for CO2 capture. The results showed that the adsorbent modified by
L-(þ)-tartaric acid exhibited the best cyclic performance with a
high carbonation conversion of 36% after the 26th cycle of carbon-
ation/calcination. The conversion rate of carbonation using the
modified limestone was almost twice that of the unmodified
adsorbent. It was proposed that the modified adsorbent exhibited
micromorphology with more pores and less aggregation of grains
than the unmodified one, mitigating the sintering of CaO particles
and the loss of specific surface area. Radfarnia and Iliuta [115]
investigated the acidification of natural limestones using citric
acid to produce porous CaO adsorbent. It was found that the CaO
derived from citric acid acidification exhibited a superior CO2
capture behavior and stability, particularly at an operating tem-
perature of 700
C. The development of finger-shaped morphology
corresponding to an adequate porous structure provided a higher
active area for CO2 capture. The generation of this kind of
morphology was due to the heat treatment of the adsorbent in two
steps (argon followed by air). The decomposition of calcium citrate
in an argon atmosphere during the temperature ramp programmed
from ambient to 850
C was accompanied by the in situ formation
of carbon, which can effectively cover the CaO particles and inhibit
their growth. The burning off of carbon in the last step was reported
to promote the dispersion of the CaO agglomerates during the
thermal treatment.
In addition, pyroligneous acid (PA) is a renewable product
generated in the flash pyrolysis of biomass and has been studied for
surface modification of CO2 adsorbent. Li et al. [116] investigated the
cyclic CO2 capture behavior of a limestone modified by PA in a TGA
and a dual fixed bed reactor. The carbonation conversion of the PA-
modified limestone achieved 0.33 after 103 cycles of carbon
capture, which was 4.2 times higher than that of an original lime-
stone at the same capture conditions. It was attributed that the
calcined form of the modified limestone had more pores in the
ranges of 1.8e4.6 and 18e155 nm, enabling the fast diffusion of CO2
inside the adsorbent. Similar results were reported by Sun et al.
[117] showing that the surface area and pore volume were increased
followed by the surface modification of limestone using propionic
acid, resulting in a higher carbonation conversion of CaO. In addi-
tion, the improved performance with acid surface modification was
reported when an industrial waste (carbide slag) was modified by
propionic acid for CO2 capture [118]. Therefore, the microstructure
of modified adsorbent is important to enhance the capacity of CO2
capture in the multiple cycles of carbonation/calcination.
3.4. Enhancement of carbon capture in severe calcination
conditions
Most of the mentioned improvements for CO2 capture using
CaO-based materials are prepared by calcination in pure inert gas.
However, CO2 or O2 is always present in severe calcination condi-
tions. In addition, the released CO2 is mixed with inert gas and
makes it difficult to be used in practical applications. If the adsor-
bents are calcined in pure CO2 atmosphere, it is more convenient
for the downstream utilization of the captured CO2, e.g. methana-
tion and hydrogenation. However, CO2 capture tests using CaO-
based materials conducted in severe calcination conditions are
rarely reviewed and discussed. In this section, we give a detailed
introduction of the efforts (Table 5) devoted to the enhancement of
CO2 capture of CaO-based adsorbents in severe calcination
conditions.
For example, Lo
pez-Periago et al. [119] studied carbon capture
using CaO-based adsorbents prepared by a supercritical method
under both mild calcination condition (750
C under N2) and severe
calcination condition (900
C under CO2). It was found that at the
supercritical conditions, a micrometric adsorbent was produced
resulting in an enhanced reversibility of the carbonization/calci-
nation process. After 25 cycles of carbonization/calcination, the
micrometric sample reached the highest CO2 uptake at 11.6 and
5.4 mmol g1 when the sorbent was calcined in 100% N2 and CO2,
respectively. In addition, it was found that the ultrasound played a
decisive role in increasing the carbonation rate during the prepa-
ration of calcium carbonate by the supercritical precipitation.
Compared with the mechanical stirring and non-agitated systems,
the ultrasonic agitation can stimulate the removal of the covering
CaCO3 layer around the starting Ca(OH)2 particles, which enabled
the further dissolution of Ca(OH)2 and speeded the formation of
precipitated calcium carbonate [120].
Luo et al. [68] adopted a solgel method (as shown in Fig. 3f) to
synthesize CaO-based adsorbents using citric acid as a chelation
agent, and the obtained adsorbent achieved a high CO2 capture
capacity of 11.6 and 4.5 mmol g1 at calcination in 100% N2 and CO2,
respectively. Interestingly, it was found that the obtained adsorbent
 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27 11

Table 5
Improvements of CO2 capture performance for CaO-based adsorbents conducted in severe calcination conditions.

Supports (wt%) Methods Calcination conditions Carbonation conditions Reactor CO2 uptake Ref.
(mmol g1)
T (
C) Atmosphere t (min) T (
C) Atmosphere t (min)

N.A Precipitation method 900 100% CO2 15 750 15% CO2 in N2 15 Microbalance 5.4 [119]
(25 cycles)
N.A Solgel method 950 100% CO2 10 650 15% CO2 in N2 15 TGA (20 cycles) 4.5 [68]
Ca12Al14O33 (15%) Precipitation 900 50% CO2 in N2 5 650 50% CO2 in N2 10 TGA (15 cycles) 5.2 [121]
and He and He
Ca12Al14O33 (41.65%) FSP method 950 30% CO2 in He 10 850 100% CO2 10 TGA (45 cycles) 5.7 [128]
Ca9Al6O18 (22.1%) Wet mixing technique 930 50% CO2 in Ar 10 650 15% CO2 in Ar 30 TGA (25 cycles) 5.2 [107]
Ca9Al6O18 (20%) Solgel technology 930 100% CO2 5 650 100% CO2 30 TGA (31 cycles) 7.5 [129]
SiO2 (21.1%) Hydrolysis method 950 100% CO2 10 700 15% CO2 in N2 25 The twin fixed bed 10.6 [96]
reactor (10 cycles)
SiO2 (10%) Dry physical mixing 920 100% CO2 3 700 100% CO2 5 TGA (30 cycles) 5.2 [103]
MgO (25%) Solgel method 850 50% CO2 in N2 6 650 20% CO2 in N2 10 TGA (46 cycles) 6.1 [109]
Y2O3 (20%) Solgel combustion method 950 100% CO2 5 650 20% CO2 in N2 30 TGA (10 cycles) 11.1 [110]
N.A Acetic acid (50 vol.%) 920 80% CO2 in O2 15 650 15% CO2 in N2 20 The twin fixed bed 4.9 [122]
(20 cycles)
N.A Acetic acid (50 vol.%) 950 100% CO2 10 700 (0.5) Mpa) 15% CO2 in N2 25 The twin fixed bed 4.9 [123]
(50 cycles)
N.A Ethanol-water solution 920 80% CO2 in O2 15 700 15% CO2 in N2 20 The twin fixed bed 5.0 [130]
(90 vol.%) (15 cycles)
N.A HBr 900 15% CO2 in N2 10 700 15% CO2 in N2 10 The fluidized-bed 5.9 [124]
reactor (13 cycles)
N.A. HBr þ 10% Steam 900 15% CO2 in N2 10 650 15% CO2 in N2 10 The fluidized-bed 5.9 [126]
reactor (13 cycles)
Al2O3 (10.8%) Template-assisted 900 100% CO2 10 650 12% CO2 in N2 20 TGA (30 cycles) 12.5 [127]
hydrothermal approach

TGA, themogravimetric analyser.

had a very rapid carbonation rate at the initial stage, achieving a
calcium conversion ratio of 60% within 20 s due to the enhanced
porous structure. In comparison, the carbonation conversion of
microsized CaCO3 (around 2 mm) was about 40% within 2 min, and
the adsorbent required a much longer time for sufficient
carbonation.
In addition, numerous supported CaO-based adsorbents
attracted intensive attention in the utilization of severe calcination
conditions. Florin et al. [121] synthesized a CaO-based adsorbent
with a mixed calcium-aluminum binder via precipitation method
and investigated the influence of calcination conditions on the
carrying capacity. The best adsorbent possessed a weight ratio of
CaO to Ca12Al14O33 of 85:15, and the uptakes of CO2 at 6.6 and
5.2 mmol g1 were reported after 15 cycles of carbonation/calci-
nation at 100% N2 and 50% CO2, respectively. However, when the
corresponding CO2 capture experiments were performed in a flu-
idized bed reactor, a dramatic decrease of CO2 uptake occurred,
reaching only 3.0 mmol g1 after 15 cycles of carbonation/calci-
nation. It was suggested that the structure of adsorbent changed
due to the superior heat transfer characteristics of the fluidized bed
reactor.
Yan et al. [103] firstly reported an environmental benign and
cost-effective strategy to reduce the sintering of CaO by introducing
waste-derived nano-SiO2 from photovoltaic waste (SiCl4) into CaO-
based adsorbents through a simple dry mixing method. The uptake
of CO2 using the optimum adsorbent (10 wt% SiO2) reached 7.3 and
5.2 mmol g1 when the sorbent was calcined in 100% N2 and CO2,
respectively. In addition, the capture of CO2 reached 90% of the total
capacity in the fast carbonation stage (20 s), which was of great
interest for real applications that require fast material conversion.
This phenomenon was attributed to the formation of stable and
refractory larnite (Ca2SiO4) particles during the preparation of the
adsorbent.
In addition, Li et al. [122] investigated the CO2 capture perfor-
mance of limestone modified by acetic acid under severe calcination
condition in a twin fixed bed reactor system. The results showed
that the capacity of CO2 capture of the modified limestone achieved
as high as 4.9 mmol g1 after 20 carbonation/calcination cycles
when the material was calcined at 80% CO2 balanced with O2,
whereas the unmodified limestone exhibited a maximum CO2
capture capacity of only 1.5 mmol g1 after 20 cycles of carbonation/
calcination. The antisintering performance of the modified lime-
stone was significantly improved due to the formation of smaller
size CaO particles after the acidification of limestone. Chen et al.
[123] enhanced CO2 uptake by modifying the limestone with ace-
tate solution under a pressurized carbonation condition. Compared
to a natural adsorbent (3.4 mmol g1), the acetified adsorbent
showed a great enhancement of CO2 uptake (4.9 mmol g1) when
calcinated at 100% CO2 and 0.5 MPa after 50 cycles of carbonation/
calcination due to the alternation of porous structure.
Incorporating halogen ions into CaO crystalline matrix is also a
promising method to improve the performance of CaO-based ad-
sorbents in severe calcination conditions. It can enhance the ionic
diffusion and mobility of carbonate ions through CaCO3 by straining
the crystalline matrix and encouraging the formation of additional
vacancies [124]. Al-Jeboori et al. [124] carried out a systematic
study of CO2 capture on limestones (Havelock, Longcliffe, and
Purbeck) doped with a range of mineral acids (HCl, HBr, HI, and
HNO3). It was found that the highest conversion was obtained for
the Havelock and Longcliffe limestones when HBr or HCl was used
as dopants with a 0.167 mol % concentration. It might be because
the apparent ionic radius of Br (1.89 nm), Cl (1.81 nm), and car-
bonate anion (1.85 nm) are very close [125]. However, the Purbeck
limestone was not significantly improved in relation to the capture
of CO2 by all dopants because the original Purbeck limestone had a
relatively higher long-term reactivity than other types of lime-
stones. The enhanced capacity of CO2 capture by doping acid was
attributed to the significant changes of pore size distribution. For
example, after doping with 0.167 mol % HCl or HBr, pores with size
of less than 20 nm were mainly closed. The pores with diameters
greater than 30 nm appeared to be enlarged in diameter while
conserving the overall pore volume. It seems that the introduction
of chemicals, e.g. steam, into calcination and carbonation of
adsorbent was beneficial to the capture of CO2. Gonza
lez et al. [126]
12 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27
investigated the effects of steam and HBr on five natural lime-
stones. CO2 uptake of the HBr-doped limestone was found to be up
to three times higher than that of the natural limestone in the
presence of 10% steam after 13 cycles of carbonation/calcination.
Recently, a template-assisted hydrothermal approach was used
to develop CaO-based sorbents exhibiting a very high and cyclically
stable CO2 uptake [127]. These sorbents exhibited a porous shell
comprised of CaO nanoparticles coated by a thin layer of Al2O3
(<3 nm) as shown in Fig. 4b, which provided minimal diffusion
limitations and the space to accompany the substantial volumetric
changes during CO2 capture and release. In addition, a minimal
quantity of Al2O3 for structural stabilization will maximize the
fraction of CO2-capture active CaO. The obtained sample yielded a
remarkably high CO2 uptake of 12.5 mmol g1 (80.5% capacity
retention), exceeding the benchmark limestone (2.5 mmol g1) by
almost 500% at a severe calcination condition. This is attributed to
the pores that were regenerated in the shell during calcination even
after 30 cycles, allowing for the rapid transport of CO2 to the inte-
rior and thus minimizing diffusive limitations during carbonation
(Fig. 4c).
4. Process optimizations
4.1. Influence of CO2 partial pressure
4.1.1. Influence of CO2 partial pressure on carbonation rate
The partial pressure of CO2 in the process of CaO-based carbon
capture dynamically affects the efficiency of the process [123]. For
Fig. 4. Structural design with atomic level control to enhance the performance of CaO-based CO2 sorbents: (a) relatively large CaO particles (dp > 500 nm); (b) hollow and porous
spherical architecture (dp < 100 nm) and high-resolution transmission electron microscopy (HR-TEM) ; (c) foucused ion beam (FIB) cross sections of Al2O3-stabilized sorbents [127].
example, Grasa et al. [131] carried out the carbonation of CaO at
650
C for 20 min by varying CO2 partial pressure from 2 kPa to
100 kPa and found that the carbonation reaction was strongly
affected by the partial pressure of CO2 during the multiple cycles of
CO2 capture as shown in Fig. 5a and b. The first-order reaction of
CaO with respect to CO2 capture was verified, and the results were
consistent with the report from Bhatia and Perlmutter [35]. Thus, a
higher CO2 partial pressure was proposed to enhance the diffusion
of CO2 in both the interparticles and intraparticles of the adsorbent,
resulting in an improved carbonation reaction rate. However, Sun
et al. [48] found that the intrinsic rate of carbonation changed from
first order to zero order with the increase of CO2 partial pressure to
10 kPa, when limestone and dolomite were tested using an ATGA
and a pressurized thermogravimetric analyser (PTGA). The
enhancement of carbonation rate was not observed with the
further increase of CO2 partial pressure to 100 kPa, indicating that
there might be a critical point of CO2 partial pressure affecting the
rate of CaO carbonation. When the CO2 partial pressure was higher
than 10 kPa, Fernandez et al. [132] also found that it had almost no
influence on the capture of CO2 using a Ca(OH)2/MCM-41
adsorbent.
4.1.2. Influence of CO2 partial pressure on the maximum
carbonation conversion
During the process of CO2 capture using CaO-based adsorbents,
the maximum carbon conversion is regarded as the overall CO2
uptake capacity during the CO2 capture process. It seems that
 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27
Fig. 5. Influence of CO2 partial pressure (a: conversion; b: relative reaction rate [131], and c: synthetic adsorbent [133]).
natural and synthetic CaO-based adsorbents have different re-
sponses with the change of CO2 partial pressure.
Natural limestone was less affected by the partial pressure of
CO2 as reported by Grasa and Abanades [70]. When the partial
pressure of CO2 was increased from 0.05 to 0.1 MPa, the capture of
CO2 using a natural limestone adsorbent was slightly reduced for
the first 10 cycles of carbonation/calcination due to the blockage of
pores. With the further increase of the cycle of carbon capture, the
capacity of CO2 capture using the limestone was almost the same at
different values of CO2 partial pressure. Therefore, the maximum
carbonation conversion of CaO derived from natural limestones
was less sensitive to the partial pressure of CO2. Furthermore, Sal-
vador et al. [134] and Lysikov et al. [32] also found that the final CO2
uptake capacity of CaO derived from the natural limestone was
independent on the CO2 partial pressure during carbon capture.
However, the maximum carbon conversion of synthetic CaO-
based adsorbents was significantly affected by the CO2 partial
pressure, as reported by Pacciani et al. [133]. It was found that the
maximum carbon conversion of synthetic CaO-based adsorbents
was increased by increasing the partial pressure of CO2, which was
subsequently confirmed by Broda et al [88]. The capacity of CO2
capture was increased largely when the CO2 partial pressure was
13
increased (CO2 concentration was increased from 14 to 27%) [133].
When the CO2 concentration was reduced to 14%, the uptake of CO2
was decreased; however, it was still higher than the initial capacity
of CO2 capture (Fig. 5c).
The difference between synthetic and natural sorbents in rela-
tion to the effect of CO2 partial pressure on carbon capture could be
related to the mechanical characteristics of the CaCO3 product
layers formed in the process of CO2 carbonation. Dennis and Pac-
ciani [135] argued that the natural adsorbent formed a layer of
CaCO3 with a high cohesion to the unreacted CaO; thus, the layer of
formed CaCO3 had a higher yield stress. Based on their model
predictions, natural adsorbents required a much higher yield stress
than synthetic adsorbents in relation to the formed CaCO3. Thus,
owing to the higher yield stress of the CaCO3 layer on the surface of
CaO formed during the CO2 capture, CO2 partial pressure has little
influence on the maximum conversion of natural CaO adsorbents
[135].
4.1.3. Influence of CO2 partial pressure in the presence of SO2
In contrast, with the increase of CO2 partial pressure, the sul-
fation of CO2 adsorbent was inhibited, resulting in less SO2 absor-
bed during carbonation/calcination [136,137]. Therefore, a higher
14 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27
efficiency of CO2 capture in relation to the conversion of adsorbent
was expected with the increase of CO2 partial pressure due to the
mitigation of the influence of SO2. However, Chen and Zhao [138]
investigated the influence of CO2 partial pressure on CO2 capture
using limestone and dolomite in the presence of SO2 and found that
some of the available pores in the adsorbents were lost and that the
pores were easily blocked by CaSO4 formed in the presence of SO2
during the successive calcinations. Thus, the accessibility of the
active CaO site was reduced even at a relatively higher CO2 partial
pressure. In this case, increasing CO2 partial pressure had little in-
fluence on CO2 uptake.
4.2. Influence of carbonation temperature
From a macroscopic point of view, the reaction temperature is
well known to have a great effect on the reaction kinetics and solid
conversion for gas-solid reactions. With increasing temperature,
the apparent carbonation rate and the reaction of CaO with CO2 are
expected to be enhanced. The effect of reaction temperature on the
gas-solid reaction can be understood according to the collision
theory or activated complex theory.
Recent studies confirmed the positive influence of reaction
temperature on the carbonation of CaO-based adsorbents. For
example, Li et al. [139] studied the influence of temperature on the
reaction rate of carbonation (Fig. 6a). It was found that the size and
height of the formed CaCO3 produced from CaO carbonation were
increased and that the density of the formed CaCO3 was reduced
when the carbonation temperature was increased from 500 to
600
C, resulting in an enhancement of CO2 capture.
Wu et al. [140] investigated the influence of temperature on the
performance of CO2 capture using carbon-supported nanocrystal-
line calcium oxides (Fig. 6b). When the temperature increased from
25 to 150
C, a gradual decrease of the capacity of CO2 capture was
observed due to the purge of the adsorbed CO2 at higher temper-
ature. With the further increase of temperature to 400
C, chemi-
sorption reaction was dominant. However, the increase of CO2
uptake was slow, indicating that both reaction- and diffusion-
controlled mechanisms were presented. Finally, when the tem-
perature rose to 450
C, the capacity of CO2 capture dramatically
increased, indicating a carbonation temperature higher than 450
C
was essential for the capture of CO2 using the studied sorbent.
However, when the temperature of carbonation is higher
enough, calcination of adsorbent might be favored. For example,
Huang et al. [99] studied the influence of carbonation temperature
on the capture of CO2 using CaO-based mesoporous silica. A
maximum carbonation rate was observed at 700
C. When the
temperature was higher than 700
C, the CO2 carbonation rate
slowed down due to a competition between the carbonation and
calcination of CaO. In the regime of adsorbent calcination, it was
clearly decomposed to CaO and CO2 when the temperature was
above 900
C.
4.3. Influence of carbonation time
Carbonation time was important in the process of CO2 capture
using CaO [142]. A marginal increase of carbonation time had a
positive influence on the capacity of CO2 capture over several cycles
of carbonation/calcination. Chen et al. [141] found that it was
capable to restore the capacity of CO2 capture of adsorbents to their
original behavior if the duration of carbonation in one cycle was
greatly extended (Fig. 6c). Sun et al. [118] also found that a pro-
longed carbonation treatment was beneficial to CO2 capture using
raw and modified carbide slags. The prolonged carbonation of 9 h in
the 21st cycle of carbonation/calcination increased the capacity of
CO2 capture in the next cycle of CO2 capture. Furthermore, it is
demonstrated that CaO conversion was increased with the increase
of carbonation time. Barker [49] also demonstrated that increasing
carbonation time enhanced the performance of carbon capture
using CaO-based adsorbents due to the closed small pores of the
adsorbents which may be reopened at a longer carbonation time.
Furthermore, German and Munir [143] proposed that the comple-
tion of the slow diffusion stage of carbonation would result in an
increase of porosity and surface area of the adsorbent. Thus, longer
carbonation time in the slow diffusion stage of carbonation is
beneficial to the capture of CO2 due to the generation of porous
structure. However, with the increase of carbonation time, the
energy consumption will also be significantly increased. Thus, a
balanced consideration is required between capture efficiency and
energy input when the carbonation time is prolonged in the pro-
cess of CO2 capture.
4.4. Influence of contaminants on CO2 capture
4.4.1. Influence of steam
Arias et al. [144] studied the effect of steam in the flue gas on the
carbonation reaction over a short reaction time (typically less than
1 min) using two different types of limestone. The carbonation
reaction happened under the kinetic-controlled regime. It was
found that steam had no influence on the initial fast reaction of
adsorbent carbonation. In contrast, Manovic and Anthony [145]
reported that the carbonation of seven types of limestone as well
as one synthetic calcium aluminate pellet was enhanced by steam
addition, especially at temperature lower than 600
C. However, the
enhancement of carbonation became negligible because the con-
version reached a plateau (75e80% for samples calcined in N2) even
without steam at a relatively higher temperature and longer
carbonation time. Besides, it was observed that steam can improve
the diffusion of CO2 through the adsorbent, resulting in an
enhancement of the carbonation rate. Steam-enhanced carbonation
had also been observed in a dual fluidized bed reactor system using
two natural limestones by Symonds et al. [146]. In addition, Donat
et al. [147] investigated the influence of steam in both flue and fuel
gases on the conversion of CaO adsorbent. A schematic diagram is
shown in Fig. 7a. It was found that the addition of steam during
carbonation can reduce the diffusion resistance of CO2 molecule in
the process of carbonation. When steam was present during calci-
nation only, larger pores (~50 nm) were formed due to steam-
enhanced sintering. These larger pores were less susceptible to
pore blockage and thus resulted in a higher conversion.
Recently, Champagne et al. [148] investigated the effect of steam
concentration including 0 vol.%, 15 vol.%, and 65 vol.% on CO2
capture in a calcium looping process. The decay of the adsorbent in
relation to CO2 capture was slowed down when more steam was
injected into the calcium looping (CaL). They suggested that a stable
pore structure of the adsorbent was maintained resulting from the
increasing steam concentration and the corresponding reduction of
CO2 concentration in the process. In addition, the reduced CO2-
induced sintering resulted in an increased surface area and pore
volume which were stable over many cycles of carbonation/
calcination.
4.4.2. Influence of SO2
SO2 has shown a crucial influence on CO2 capture using CaO-
based adsorbents as carbon capture is largely applied for the flue
gas produced from the power plant, where SO2 is normally present.
Iyer et al. [149] studied a simultaneous carbonation and sulfation of
CaO in a flue gas (10% CO2, 3000 ppm of SO2, 4% O2 in N2). It was
found that CaO reacted with SO2 to form thermally stable CaSO4,
which led to a reduction in the capacity of CO2 capture. Ryu et al.
[150] investigated the simultaneous CO2 and SO2 capture of three
 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27 15

Fig. 6. (a) Mechanism of temperature effect [139]; (b) temperature-dependent CO2 sorption curves at 25e500
C of the mesoporous CaO/C-4-700 composites with a CaO content of
18.5 wt% [140]; (c) results of a long-term carbonation/calcination cycling with Strassburg limestone [141].

Fig. 7. Influence of (a) steam (i: no steam present; ii: steam present during carbonation only; iii: steam during calcination on; and iv: steam present for carbonation and calcination
[147]); and (b) SO2 [150].
16 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27
limestones in a pilot-scale fluidized bed reactor and observed that
the capacity of CO2 capture was decreased with the increase of the
concentration of SO2. Furthermore, the reaction with SO2 was
enhanced with the increase of the concentration of SO2, promoting
the deactivation of the adsorbent. Two types of sulfation of the
adsorbent in the process of CO2 capture are shown in Fig. 7b. One
type is unreacted coreetype sulfation. The reaction between CaO
and SO2 happened mainly on the outer layers of the limestone
particle, forming a dense and nearly non-porous CaSO4 layer or
shell. Another type is uniform-type sulfation. CaSO4 was formed on
the outer layers of individual CaO grain inside the adsorbent par-
ticles [150e152].
Furthermore, a negative effect of SO2 on CO2 capture using CaO-
based adsorbent was also reported by Sun et al. [153]. The authors
investigated the influence of SO2 during simultaneous capture of
CO2 and SO2 using both an atmospheric thermogravimetric reactor
and a PTGA. It was found that SO2 had an impeditive effect on cyclic
CO2 capture due to pore blockage by sulfated products. However, the
reduction of the capacity of CO2 capture due to the presence of SO2
was mitigated when a higher CO2 partial pressure was used [153].
The introduction of SO2 into carbon capture process using CaO-
based adsorbents might also be due to the competition between
carbonation and sulfation reactions [154]. Lu and Smirniotis [154]
introduced different dopants to reduce the negative effect of SO2
on CO2 capture using CaO adsorbents. It was found that the Ce-
doped Ca adsorbent exhibited the best performance for CO2 cap-
ture due to the weak affinity between SO2 and CaO-based adsor-
bents, indicating that Ce was promising to reduce the influence of
SO2 on CO2 capture. However, doping Mn into CaO showed the
poorest performance of CO2 capture due to the prepared Mn-CaO
adsorbent that had the strongest affinity for SO2.
Furthermore, the influence of SO2 on carbon capture using CaO-
based adsorbent was affected by other process conditions such as
carbonation temperature, carbonation pressure, SO2 concentration,
and CO2 concentration. As reported by Chen and Zhao [138], SO2
showed a significant negative influence on the capture of CO2 when
the carbonation temperature was higher than 700
C, whereas the
pressure of carbonation showed a larger negative effect on CO2
uptake than the temperature. The competition of the reaction with
SO2 over CO2 using CaO-based material was also reported by Ridha
et al. [155] and Luo et al. [156]. Therefore, in a process of CO2
capture from flue gas, the presence of SO2 needs be largely reduced.
5. Reactivation of spent CaO adsorbent
The rapid degradation of the capacity of CO2 capture using CaO-
based materials during the cycles of carbonation/calcination is a big
challenge for practical applications of the technology [157,158].
Reactivating the degraded adsorbents has been proposed as a good
solution. Besides, the requirement of low-cost adsorbents promotes
the development of reactivation technology [159].
5.1. Hydration
Hydration not only can be used as a pretreatment method to
activate CaO precursor (limestone) but also is an effective technique
for spent adsorbent reactivation. Hydration is beneficial for CO2
capture due to the formation of cracks in the CaO particles and the
creation of channels extending to the interior of the particles
[160e162]. Another positive effect of hydration is the formation of
larger pores, which make the particles less susceptible to pore
blockage [163].
Reactivation can be achieved using water [161,164,165] and
steam [166e168]. Among them, water hydration of spent adsorbent
is the most effective method. Spent natural adsorbent reactivated
with water for 1 min could reach 70% of its initial capacity of
adsorbent conversion [165]. Wang et al. [164] proposed to partially
reactivate sulfated adsorbent by hydration. The results showed that
temperature played a dominated role in improving the rate of hy-
dration of the partially sulfated adsorbent. However, a low effi-
ciency of hydration was followed due to the limitation of the
penetration of water through the product layer. The hydration of
partially sulfated adsorbent was enhanced by using ultrasonic and
wet grinding due the increase of water transfer rate [164]. In
contrast, Yin et al. [165] reported a periodic water hydration
method to reactivate a limestone and a synthetic CaO/cement
adsorbent. They discovered that the water hydration of the calcined
limestone was independent on the factors including particle size,
hydration duration, hydration temperature, and precalcination
temperature. However, the synthetic CaO/cement adsorbent
showed a strong dependence on those factors. A clear difference
between the natural limestone and the synthetic CaO/cement
adsorbent lies in the presence of cement in the synthetic sorbent.
During the water hydration of the synthetic CaO/cement, there was
a competition between Ca2þ and (Ca12Al14O32)2þ ions toward hy-
droxyl ions, resulting in a poor hydration of CaO and Ca12Al14O34;
therefore, the final conversion of the synthetic adsorbents was
reduced [169]. Recently, Coppola et al. [161] investigated the
property changes of adsorbents after hydration, and the adsorbents
were investigated in a double looping process as shown in Fig. 8a.
The double looping process combined the basic Ca looping for CO2
capture with a second loop in which the spent adsorbent was
continuously regenerated by water hydration. The result showed
that hydration was effective to reactivate the spent adsorbent: the
capacity of CO2 uptake was increased from 0.9 mmol g1 (last
carbonation before hydration) to 7.3e8.4 mmol g1 after hydration.
However, direct water hydration of the spent adsorbent is far
from practical application due to the energy penalty caused by
drying humid hydrated lime. Hence, steam hydration attracted
more attention due to its effective enhancement of CO2 capture for
spent adsorbent and the relative low process cost [148,166,167]. For
example, Manovic and Anthony [167] conducted steam reactivation
of the spent adsorbent to improve the reversibility of multiple cy-
cles of CaO-CO2 capture in a pressurized reactor. After reactivation,
the adsorbent exhibited even better performance for CO2 capture
than the natural adsorbent. The carbonation conversion over 10
cycles of CO2 capture for the reactivated adsorbent approached 70%,
which was significantly higher than the original adsorbent
(35e40%) due to the increase of surface area. Furthermore, the
process conditions such as hydration temperature have clear in-
fluence on the reactivation of spend adsorbent. For example, Rong
et al. [168] investigated the effect of hydration temperature, steam
concentration, and hydration frequency on the adsorbent (reagent-
grade CaCO3) reactivity during 10 cycles of carbonation/calcination
using a pressurized TGA. The results revealed that the reactivity and
durability of the spent adsorbent were significantly enhanced at
lower hydration temperature (~300
C) and higher steam concen-
tration (~80 vol%). In addition, frequent steam reactivation
enhanced the capture of CO2 as shown in Fig. 8b. However, the
steam consumption under these conditions was very high (esti-
mated over 1.2 mol of steam per mol of captured CO2) [173].
A major drawback of steam hydration to reactivate adsorbents is
the dramatic reduction of mechanical strength of the regenerated
material [173e175]. The mechanical properties of CaO-based
adsorbent will be discussed in detail in the following section.
5.2. Repelletization technique
The repelletization process uses water to rebind the pellets of
the adsorbent. Therefore, the porosity of the particles of the
 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27
Fig. 8. Reactivation of spent CaO adsorbent: (a) the double looping process [161]; (b) effect of hydration frequency [168]; (c) conversions of pellets (1 mm) [170]; (d) SEM images of
(i, iii) original carbon-templated CO2 adsorbent and (ii, iv) pellets [171]; (e) influence of recarbonation (black dots: after 15 cycles; white dots: after 100 cycles) [172].
adsorbent is improved, and some unreacted CaO particles become
accessible to CO2. Furthermore, the addition of water enables the
hydration of the adsorbent during the process of CO2 capture to
further enhance the reactivity of the spent adsorbent.
This technique was first proposed by Jia et al. [176] in the field of
sulfur capture from flue gas, and the authors found that wet
grinding was beneficial for the repelletization of spent material
compared to dry grinding because wet grinding achieved a high
conversion of CaO to Ca(OH)2. Recently, this technique of wet
repelletization was applied in the area of CO2 capture using CaO-
based adsorbents. For example, the repelletization of CaO-based
adsorbents showed that the mechanical strength of the adsor-
bents was significantly enhanced by the addition of binders
[177,178]. Manovic and Anthony [177] mixed calcined limestone
with calcium aluminate cement to obtain pellets and conducted a
long-term CO2 capture with 1000 cycles of carbonation/calcination.
The results showed that an excellent capacity of CO2 capture was
obtained after the life time test of the repelletized adsorbent. This
superior performance was attributed to the existence of a large
number of nanosized pores generated by the formation of mayenite
(Ca12Al14O33) from the repelletization. The crushing tests showed
that the pellets lost mechanical strength after 300 cycles of
carbonation/calcination due to the formation of cracks in the
pellets.
Furthermore, Manovic and Anthony [170] investigated
remaking (reshaping) of pellets as an option for both the reac-
tivation of adsorbent and the reuse of the spent adsorbent (lime-
stone). Cyclic carbonation/calcination of the pellet adsorbent was
performed under severe CO2 capture conditions with calcination in
100% CO2 at temperature up to 950
C. It was found that the con-
version of the pellets was recovered using hydration after 210 cy-
cles of carbonation/calcination due to the reopening of pores as
shown in Fig. 8c. It is demonstrated that, with periodic hydration/
remaking steps, pellets can be used for extended times in CO2
capture cycles, regardless of capture/regeneration conditions.
17
Besides, Manovic et al. [179] prepared CaO-based pellets in a
pilot scale using a mechanical pelletizer. During this process, a
water spray was used to promote granulation of the hydrated
adsorbent. The authors made three types of granules (without
binder; with 10% calcium aluminate cement; and with a core-in-
shell structure). A small beneficial effect of cement addition on
adsorbent conversion was observed after 30 cycles of carbonation/
calcination. It was attributed to the formation of mayenite
(Ca12Al14O33). Although the reactivity of CO2 capture was increased,
the pellets exhibited a lower level of conversion rate than the fresh
limestone due to material sulfation. Recently, Broda et al. [171]
illustrated the effect of pelletization on the performance of CaO-
based adsorbents for CO2 capture, and the morphologies of the
adsorbents are shown in Fig. 8d. The repelletization with and
without steam was studied for CO2 capture using a fluidized bed. It
was found that the CO2 uptake of the pellets after 30 cycles of
carbonation/calcination conducted was 6.6 mmol g1, which was
45% higher than that of a reference limestone adsorbent.
Therefore, repelletization seems to be a promising technique to
reactivate spent adsorbents because it is a relatively low-cost pro-
cess. Most importantly, it combines the hydration and pelletization,
enabling the adsorbent to be less sensitive to adsorbent attrition
[27].
5.3. Recarbonation
Introducing a recarbonation stage between carbonation and
calcination has been proposed as a practically feasible procedure to
retard the deactivation and increase the residual conversion of the
adsorbent without affecting its efficiency of CO2 capture and
without the need for additional reagents [172,180]. It was achieved
by placing a small regeneration reactor between the carbonator and
the calciner. The adsorbent will be partially carbonized in practical/
experimental conditions (e.g. 15% CO2), followed by an extra step of
carbonation under high concentration of CO2 at high temperature
18 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27
(around 800
C). On the calcination of the recarbonated adsorbent,
CO2 escaping from the solid inward skeleton would produce a re-
generated CaO-based adsorbent with enhanced porosity and sur-
face area. For example, Arias et al. carried out two series of
experiments over 100 cycles of carbonation/calcination in a TGA
[172]. The results showed that the addition of a recarbonation step
greatly improved the capacity of CO2 capture which was almost two
times higher than the case without recarbonation after 100 cycles
of CO2 capture (Fig. 8e). Besides, Grasa et al. [180] confirmed that
the introduction of a short recarbonation stage (100e200 s) pro-
moted the stabilization of the adsorbent. High recarbonation
temperature (750e800
C), high partial pressures of CO2 (above
60 kPa), and the presence of steam can enhance the rate of CO2
diffusion and therefore strongly favor the recarbonation of CaO
because the recarbonation mainly happened in the slow diffusion
reaction regime. In contrast, Valverde et al. [181] proposed a novel
calcium looping concept using a recarbonator operated at high
temperature and high CO2 concentration. It was shown that at
these conditions, CaO conversion showed a drastic drop to a very
small residual value in only a few cycles of carbonation/calcination.
This was because CaO sintering was greatly accelerated by the
presence of CO2 at high concentration during limestone calcination.
Moreover, the introduction of a recarbonation stage had actually an
adverse effect on CO2 capture, further accelerating the decay of CaO
conversion. This was because the diffusion-controlled carbonation
was intensified, causing the defects of the adsorbent due to the
increased bulk stresses [181,182]. Thus, further studies need to be
carried out regarding the potential of this technology for the
reactivation of spent adsorbents.
6. Applications of calcium looping
6.1. Calcium looping for precombustion carbon capture
A typical process diagram for the application of calcium looping
for precombustion carbon capture is shown in Fig. 9a. The CaL cycle
provides a number of benefits when it is coupled with reforming or
gasification as precombustion capture process. Carbonation of the
limestone is an exothermic process and provides heat for endo-
thermic in situ steam reforming or gasification reactions, leading to
an overall autothermic reaction. Another benefit derived from the
presence of CaO is to shift the equilibrium to hydrogen production.
In addition, CaO and CaCO3 catalytically enhance the destruction of
tars [183], which cause a severe problem for syngas applications. In
this review, we mainly focus on the applications of CaL in sorption-
enhanced steam reforming (SESR) and gasification. CO2 capture is
feasible in these cases because the concentration of CO2 ranges
between 15 and 60%.
6.1.1. Sorption-enhanced steam reforming
Among the available techniques for hydrogen production, the
SESR is an emerging technology consisting of the integration of
reforming reaction (H2 production) and the separation of CO2 in a
single step. Thus, the reforming reaction is shifted toward the
hydrogen production.
Fig. 10a illustrates the formation of CaCO3 during the carbon-
ation of CaO in the presence of steam. The involved H2O molecule
dissociates to Hþ and OH. With a very small radius, Hþ easily
diffuses through the CaCO3 product layer to the CaCO3-CaO inter-
face and interacts with O2 to form OH. Then, OH diffuses
outwardly to the CaCO3 gas interface to react with CO2. Broda et al.
[185] successfully synthesized a bifunctional catalyst for sorbent-
enhanced steam methane reforming from a hydrotalcite-based
precursor via a coprecipitation technique. The material contained
both Ni-reforming catalyst and Ca-based CO2 adsorbent. After
approximately seven cycles of reforming and regeneration, the
decay of CO2 capture almost stabilized, resulting in an average
decay rate of only 0.3% per cycle over the last three cycles. The
bifunctional material produced a larger amount of high-purity H2
than limestone mixed with Ni-SiO2 or a Ca-free nickel hydrotalcite-
derived catalyst, making the new material an interesting candidate
for the sorbent-enhanced steam methane reforming (SE-SMR)
process. Xie et al. [186] used CaO-Ca9Al6O18 as the sorbent and
Ni0.50/Mg2.50Al as the catalyst to study sorption-enhanced steam
methane reforming. The distribution of gases produced from five
cycles of experiment is shown in Fig. 10b. The results showed that
the breakthrough time decreased with increasing cycle number
and with the increase of reaction time. In real applications, the
sorbents should be regenerated before breakthrough occurs.
However, the process of sorbent calcination (regeneration) is
suggested to be carried out at about 850
C from the thermody-
namic perspective [187]. To develop efficient CaO-based sorbents
for CO2 removal at high-temperatureesteam reforming reaction,
there is much work to be done such as (1) understanding the
carbonation mechanism of CO2 on different types of materials and
conditions; (2) studying the kinetics of carbonation and calcination
of CO2 in the presence of catalytic sites; and (3) exploring the
synergies between CO2 carbonation/calcination and catalytic
reforming.
6.1.2. Sorption-enhanced gasification
Coupling solid fuel gasification with CaL process for increasing
hydrogen content in the syngas has been largely reported. C. M.
Tessie
Du Motay [189] patented a method using the CaL with
limestone to promote gasification of carbon as early as 1880. The
key reactions in the process are shown in Eq. (1) and the following
reactions:
CðSÞ þ H2 OðgÞ ¼ COðgÞ þ H2ðgÞ DHr;298K ¼ þ131kJ mol1 (10)
2CðSÞ þ H2ðgÞ þ H2 OðgÞ ¼ CH4ðgÞ þ COðgÞ DHr;298K ¼ þ57kJ mol1
(11)
COðgÞ þ H2 OðgÞ ¼ CO2ðgÞ þ H2ðgÞ DHr;298K ¼ 41kJ mol1
(12)
CH4ðgÞ þ H2 OðgÞ ¼ 3H2ðgÞ þ COðgÞ DHr;298K ¼ þ206 kJ mol1
(13)
COðgÞ þ H2 OðgÞ þ CaOðsÞ ¼ CaCO3ðsÞ þ H2ðgÞ DHr;298K
¼ 219 kJ mol1 (14)
The desired overall reaction in the gasifier is Eq. (14). The
removal of CO2 shifts the equilibrium of Eq. (12) toward the product
side, enhancing the conversion of CO to hydrogen. The carbonation
reaction is exothermic, and the released heat (178 kJ mol1) is
close to the required heat for the endothermic reaction (13)
(206 kJ mol1). Thus, the carbonation reaction provides heat for
the gasifier. Ramkumar and Fan conducted thermodynamic anal-
ysis to determine the equilibrium CO conversion and H2 purity
obtained in CaL for syngas production from various gasifiers [190].
The results revealed that CaO-based adsorbents showed a positive
effect on water gas shift (WGS) reaction in relation to the purity of
hydrogen (over 99%). However, Curran et al. [191] found that melts
forming in the CaO-Ca(OH)2-CaCO3 system became a problem in
the gasifier operating at temperature between 815 and 870
C
when the partial pressure of steam exceeded 1.3 MPa. A more
 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27 19

Fig. 9. Applications of calcium looping: (a) precombustion process [183]; (b) postcombustion process [184].

Fig. 10. (a) Mechanism of CaO carbonation in the presence of water vapor [185]; (b) gas product purities obtained from the sorption-enhanced reaction (SER) process [186]; (c) CO2
capture and recycle as synthetic natural gas (CH4) back to an industrial facility [188].

ambitious configuration (CO2 acceptor process) has been developed
in Japan, entitled HyPr-RING (Hydrogen Production by Reaction
Integrated Novel Gasification). The challenge was to carry out the in
situ CO2 capture in a coal gasifier reactor in which coal, steam, and
CaO-based adsorbents were present. CO2 in the produced syngas
directly reacts with CaO, thus enhancing the amount of H2 pro-
duced via WGS reaction. In the regenerator, the oxyfuel combustion
of non-reacted coal provided sufficient energy to regenerate the
sorbent. An intermediate stage of hydration was included to pre-
vent sorbent degradation. The gasifier/carbonator operated at
600e700
C and 3 MPa resulted in more than 50% carbon conver-
sion and around 90% H2 in the syngas corresponding to cold gas
efficiency above 77%. The regenerator was operated at 800
C and
0.1 MPa. Similar proposals for in situ gasification with CaL CO2
removal have also been reported by Florin and Harris using biomass
and low-grade fuels [192]. This second concept (in situ gasification
and CO2 capture with CaO) has been demonstrated by Abanades
et al. in a pilot plant called INCAR [193].
6.2. Calcium looping for postcombustion carbon capture
CO2 can also be captured from flue gas released after combus-
tion. A typical process diagram for CaL used in the postcombustion
carbon capture is shown in Fig. 9b as originally proposed by
Shimizu et al. [184]. In their proposal, limestone-derived sorbent
was used to capture CO2 from the flue gas produced from a power
plant. The carbonation was carried out with a circulating fluidized
bed operating at temperature between 600
C and 650
C. The
reacted sorbent was passed to a second fluidized bed operating at
temperature between 900
C and 950
C, the calciner, in which the
sorbent was regenerated, before being returned to the carbonator.
Coal was burnt in the calciner in an atmosphere of CO2/O2 to pro-
duce the heat required for calcination.
A number of technologies can be used for this approach because
no modification is required to the existing combustion facilities.
The main disadvantage of this approach is that the produced CO2
has a relative low concentration, which ranges from ~4 vol % for a
natural gas combined cycle process to 13e15 vol % for a coal-fired
combustion plant [194,195]. A higher energy penalty of the CaL
process will be resulted from a lower concentration of CO2 in the
€hle et al. [196] indicated that the
flue gas. The calculations from Stro
calcium looping cycle could be applied to the exhaust of a power
station and imposed 3% efficiency drop, which was used to
compress CO2. Abanades et al. [197] have calculated an efficiency
penalty between 6 and 8% for a CaL system integrated with a power
station (46% initial efficiency).
However, the great challenge of CaL process lies in the logistics
and energy penalties of managing the concentrated CO2, which
20 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27
must be transported to an underground injection facility (CCS) or a
processing plant for conversion to useful products (CCU) [188,198].
Compared to CCS, which can present negative economics as well as
environmental impacts [199], CCU seems to be more attractive and
promising due to CO2 that can be used as a chemical reagent. Thus,
there is a growing interest in exploring the possibility of using the
captured CO2 as a carbon feedstock and converting it to fuels or
value-added chemicals [200e202].
Recently, Robert J. Farrauto group developed a novel technology
combining two separate process steps (CO2 capture and utilization)
in the same reactor and at the same temperature via DFMs as
shown in Fig. 10c [188,200,201,203,204]. The DFM consisted of Ru
as the methanation catalyst and nano-dispersed CaO as CO2
adsorbent, both supported on a porous Al2O3 carrier. In the pres-
ence of Ru active sites, the captured CO2 inside the sorbent reacts
with H2 produced from renewable power. This approach uses the
sensible heat inside the flue gas and eliminates the energy for
sorbent regeneration. No transportation of sorbent material and
additional external heat were required in this process [188]. In
addition, the kinetics of CO2 hydrogenation over a 10% Ru/Al2O3
catalyst were investigated using thermogravimetric analysis and a
differential reactor approach at atmospheric pressure and
230e245
C. It was found that H2 gas reacts with adsorbed CO2
species, and methane was the only hydrocarbon product observed
during CO2 hydrogenation. The rate of methanation of CO2 showed
a significant dependence on H2 partial pressure with a reaction
order of 0.88. In addition, CO2 partial pressure had little influence
on CO2 methanation with a reaction order of 0.34 [204].
6.3. Large pilot scale for the calcium looping cycles
Demonstration of the CaL technology in pilot scale is necessary
for the deployment of the technology. To date, these facilities have
demonstrated a high efficiency of CO2 capture around 80%. For
example, an SER process (1.7 MWth) has been performed at the
Vienna University of Technology, Austria. The pilot plant consisted
of two interconnected circulating fluidized bed (CFB) reactors
operating at gas velocities of 3e5 m s1, with a gasifier/carbonator
operating at 600e715
C at atmospheric pressure and a combustor/
calciner operating at 820e950
C [205]. High efficiency of CO2
capture (>90%) was demonstrated with satisfactory balances of
carbon and sulfur during steady-state runs.
The reactivity of sorbent plays an important role in pilot-scale
CaL demonstration [206,207]. By introducing a stage of recarbo-
nation, the high capacity of CO2 capture has reported to be main-
tained in CaL postcombustion systems. For example, the capacity of
CO2 capture was enhanced by 10% with the addition of a recarbo-
nation stage [208]. Recently, Diego et al. [209] demonstrated a
continuous large-scale CaL pilot plant and investigated the influ-
ence of calcination time on the average maximum CO2-carrying
capacity of CaO particles (Xave). These parameters are key variables
in designing the CO2 capture carbonator and for optimizing the
performance of the CaL system. The process has been modeled
[210] and used in much larger trials in an 8 MWth fuel input
combined heat and power (CHP) unit in Guessing, Austria [211]. The
trials at Guessing were reported successful as the feasibility of the
SER process was demonstrated on an industrial scale. And, future
work was proposed to focus on varying process parameters to in-
crease hydrogen production.
In Germany, a 10 kWth pilot-scale testing facility and a 200
kWth pilot plant were constructed by the University of Stuttgart
[212,213]. The operating stability of research facilities was investi-
gated, and the scale-up design for achieving 90% CO2 capture effi-
ciency was reported. In addition, the CO2 capture efficiency was
found to decrease with decreasing CaO looping ratio (CaO looping
rate between beds/CO2 flow to carbonator) and space time (number
of moles of CaO in carbonator/CO2 flow to carbonator) [212]. The
larger facility (200 kWth) was intended to run 24 h a day for 7 days
at a time to obtain information for future scale-up and economic
evaluation of CaL technology.
In Canada, a 75 kWth pilot plant was built by the CANMET En-
ergy Technology Centre [146,214]. Characteristics of the sorbent
were tested, and the efficiency of CO2 capture was studied in a fully
stable and continuous mode for more than 50 h. The authors
concluded that the attrition of the sorbent made a significant
contribution to the decay of reactivity of the sorbent and was
therefore an important consideration in Ca looping process. A 120
kWth subpilot system was built by the Ohio State University in the
USA [215], and 90% CO2 and 100% SO2 removals from the flue gas
were achieved. In addition, a hydrator was installed to the CaL
process to improve the capacity of CO2 uptake [157].
One 1 MWth pilot plant consisting of two interconnected CFB
reactors was designed in Technische Universita €t Darmstadt [216].
The pilot plant has been operated for >1500 h in fluidized bed
mode, with >400 h CO2 capture. High CO2 absorption efficiency up
to 88% in the carbonator was achieved. Following that, Hilz et al.
[217,218] tested a 1 MWth scale CaL process under severe condi-
tions, i.e. using coal-originated flue gas for decarbonation and
oxyfuel conditions for calcination. The feasibility of the CaL process
was successfully proven by running the steady-state process for
more than 1200 h, while the absorption rate in the carbonator was
higher than 90% and the overall capture rate was higher than 95%
under a wide range of operating parameters, e.g. type of fuel, flue
gas composition, or reactor temperature. The Industrial Technology
Research Institute in Taiwan has developed a 1.9 MWth CaL process.
It was integrated into a cement plant that was able to remove a
tonne of CO2 per hour. The system contained a bubbling fluidized
bed reactor, a gas distributor, and a moving bed calciner. The
temperature in the carbonator was controlled by water-cooled steel
jackets, and the heat for calcination was obtained by oxy-
combustion of diesel [219]. The integration of CaL and cement
plant was reported to reduce the cost of adsorbent and the energy
required for calcination process.
6.4. Attrition problems of CaO-based materials
In practical application, an interconnected fluidized bed is nor-
mally used in the process of carbon capture. The adsorbents are
carbonized in one reactor and transferred into another reactor for
the regeneration/calcination. Therefore, the attrition of adsorbents
normally happens, which is a big challenge for the development of
adsorbents for carbon capture [173,220,221]. The attrition of ad-
sorbents leads to the generation of fine particles that tend to
elutriate from the reactor, causing the loss of adsorbent and the
blockage of downstream equipment/pipes. The attrition behavior of
the adsorbent in the process of carbon capture mainly relates to (1)
the cyclically repeated thermal shocks as the adsorbent switches
between carbonation (600e850
C) and calcination (850e950
C)
reactor, (2) the mechanical stresses from abrasion between adsor-
bents and reactor wall, and (3) the internal excess pressures asso-
ciated with CO2 released from the adsorbents. Materic et al. [222]
reported that impact-based mechanical stress was the main cause
of attrition. It was supported by the fact that attrition occurred at a
higher rate at the stage of calcination than at the stage of carbon-
ation [214,223].
It is widely accepted that the attrition of adsorbents was sig-
nificant in early cycles of carbonation/calcination. For example,
Gonza
lez et al. [224] observed a rapid attrition of adsorbents during
the initial cycles of CO2 capture, and then the rate of attrition was
drastically dropped in the following cycles and then stabilized for
 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27
up to 140 h. Ghadiri and Zhang [225] and Jia et al.[226] proposed
two aspects affecting adsorbent attrition including the properties
of sorbents and experimental conditions during carbon capture.
The physical properties of sorbents such as initial sizes, surface,
porosity, hardness, cracks, density, shape, and particle strength
strongly affect the attrition of sorbent in cycles of carbonation/
calcination. Operating conditions such as fluidized velocity, tem-
perature, and attrition time also play important roles in attrition
performance. Besides, different methods of feeding (batch and
continuous injection) adsorbent to the system influence the
behavior of sorbent attrition [227].
To maintain a desirable CO2 capture performance, fresh adsor-
bents need to be added into the process, and the elutriated adsor-
bents need to be disposed. It results in a significant increase of the
cost of CO2 capture using CaO-based materials [228]. Therefore,
specific efforts have been devoted to enhance the attrition resis-
tance of CaO-based adsorbents in the process of carbon capture.
6.4.1. The selection of CaO adsorbent
Natural CaO-based adsorbents are attractive because they are
cheap, efficient for CO2 capture, and are readily available for
industrial-scale applications [2]. Limestone is one of the most
promising natural CaO-based adsorbents, exhibiting better attrition
resistance than other natural adsorbents such as dolomite [229].
The origin of limestone also shows influence on the attrition during
the process of CO2 capture. For example, an Italian limestone
(Massicci) was found to have excellent prohibition of attrition
compared to a Swedish limestone (Ignaberga) [230]. In an earlier
research, CaO-based pellets manufactured by an extrusion method
exhibited no apparent change of the distribution of particle size
before and after cyclic carbonation/calcination, indicating that a
desirable antiattrition property was obtained by an extrusion
method [231]. However, the test was carried out in static condi-
tions, which did not reflect fluidization conditions. In addition, it
has been proved that spherical particles were better than cylin-
drical particles in relation to resisting attrition during carbon cap-
ture process [232]. Recently, Cai et al. [233] found that for cement-
based sorbents, extending hydration time plays a positive role in
improving the attrition resistance and maintaining initial specific
surface area in the fluidized bed system.
6.4.2. Additives in CaO-based adsorbent
Adding biomass templates into adsorbents is an effective and
economic method to prevent the sintering of adsorbent and to
increase the CO2 uptake performance by increasing the porosity of
CaO-based adsorbents. However, it is generally accepted that the
addition of biomass makes the adsorbent more prone to frag-
mentation at early stages of high-temperature calcination. Thus,
the addition of biomass reduces the attrition resistance for the
adsorbents. Sun et al. [234] investigated the variation of anti-
attrition ability of CaO-based pellets with the addition of different
types and amounts of biomass materials. It was found that
different biomass templates led to different degrees of abrasion in
the process of CO2 capture. Among microcrystalline cellulose, corn
starch, rice husk, sesbania powder, and lycopodium powder, the
rice husk template adsorbent exhibited the best performance
against attrition after 1000 and 3000 cycles of carbonation/
calcination.
Besides, adding binders into adsorbent can remarkably improve
antiattrition property of the adsorbent. It is because when the
binders were heated with limestone, the formation of local eutectic
melts improved the mechanical strength of adsorbent [235]. Erans
et al. [236] found that the addition of calcium aluminate cement
binder had a positive effect on making the particles less susceptible
21
to fragmentation than adding biomass-onlyetemplated material.
The attrition rate of the adsorbent was 7.4% when cement was
added. However, without the addition of cement, the attrition rate
of the adsorbent was significantly increased to 24.6% [31].
The selection of an appropriate binder also helps enhance the
attrition resistance of adsorbents. Manovic and Anthony [235]
screened six binders including two types of bentonite and four
types of commercial calcium aluminate cements for CaO-based
adsorbent in a calcium looping process. The results showed that
the use of bentonite binder led to a significant poor performance for
CO2 capture, resulting from the formation of low-melting-point
compounds that could be easily sintered. However, pelletization
using calcium aluminate cement binder showed very promising
results with good attrition property and less sintering problems.
Yin et al. [237] studied the relationship between the attrition
property and the content of aluminum in a cement binder. The
adsorbent with a high aluminate cement as the binder showed a
great improvement on both CO2 capture performance and the
antiattrition property. Furthermore, Wu and Jiang [238] observed
that when the ratio of Ca/Al molar was between 2.3 and 3.5 in the
CaO-based adsorbents, the generation of a super stable Ca12Al14O33
reduced the abrasion and fragmentation of the adsorbent in carbon
capture.
Therefore, it seems that a higher content of the binder in the
adsorbent improves the antiattrition during CO2 capture. However,
the overall capacity of CO2 capture per unit of adsorbent is reduced
due to the dilution of active sites. Thus, a balanced ratio between
binder and CaO precursor needs to be considered.
6.4.3. Synthetic methods
Using a new synthetic method is another alternative to improve
the attrition resistance of CaO-based adsorbents. Core-
shellecoating strategy is one of the effective ways to enhance the
attrition property of adsorbents. Through a repeated wet impreg-
nation coating process, core-shell structured adsorbents could be
synthesized using CaO-based pellets as cores and metal oxides as
shells. Alumina, zirconia, titanium, or silicon had been used as a
protective shell on improving the stability of adsorbents [108,239].
Sun et al. [239] synthesized CaO-based adsorbents with thermally
stable zirconia species as shell. And, a significant enhancement of
attrition resistance of the adsorbent was observed. Wu and Jiang
[238] carried out the coating of CaCO3 nanoparticles with Al2O3 by
spray-drying process. After calcination, CaO nanospheres were
obtained. A hard nanoscale calcium aluminate layer on the surface
of CaO was formed from the reaction between CaO and the sur-
rounding Al2O3 (Ca12Al14O33 layer), which largely reduced the
attrition of CaO nanoparticles during the process of CO2 capture.
Xu et al. [240] developed a new modeling approach with bamboo,
a pore-creating agent templating, to enhance the CO2 capture and
attrition resistance performance of the calcium-based sorbents
simultaneously. This method is beneficial to prepare sorbents with
favorable mechanical strength, and the optimum mass ratio of the
template is 2 wt% (lost a minority of 0.166 wt% during 20,000
turns, which was almost negligible comparing to 3.64 wt% of
limestone).
7. Economic assessment of the calcium looping process
The economics of calcium looping process used in post-
combustion system has been investigated by Abanades et al. [24].
The authors studied a system consisting of three main components:
a combustion power plant, an oxy-fired fluidized bed calciner, and a
fluidized bed carbonator. They estimated a capture cost around 15
USD/tCO2 for the proposed system in comparison to 23.8 USD/tCO2
22 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27
for a standard oxyfuel circulating fluidized bed combustion process
(2007 estimate). It was explained that despite a slight increase in
capital costs to construct the carbonator, the plant could capture
CO2 not only from the oxy-fired combustion in the calciner but also
from a neighboring power plant.
A detailed economic analysis of a similar process by MacKenzie
et al. [25] gave favorable economic results in comparison with
postcombustion capture using amine scrubbing. The authors re-
ported that the cost for CO2 capture using calcium looping process
(19.75 USD/t) was much lower than the cost for amine scrubbing
(2005 estimate) ranging from 32.5 to 80 USD/t. The sensitivity
analysis revealed that the overall costs of the process were signif-
icantly affected by the feedstock of limestone and the Ca/C ratio.
Romeo et al. [228] examined the impact of Ca/C molar ratio and
make-up flow (purge) of solids on the cost of CO2 capture system. A
purge is necessary to reduce the sorbent deactivation and to
compensate the formation of CaSO4 from the SOx content in the
flue gas. It is reported that the impact of make-up flow on the cost
of carbon capture was more significant at higher Ca/C ratios (Ca/
C > 4). Because at higher Ca/C ratios, increasing the make-up flow
led to no increase of CO2 capture capacity while the overall cost
rose monotonically.
The techno-economic analysis of calcium looping process (using
CaO-based material for CO2 capture) by Epple and Stro €hle [241]
showed that compared to a reference plant without CO2 capture,
energy efficiency in a plant using CaO-based adsorbents for CO2
capture was only reduced by 2.75%. However, Zhao et al. [242]
compared the economics of four promising technologies
including chilled ammonia, alkali metal carbonates, membranes,
and calcium looping for the postcombustion CO2 capture retrofitted
to a conventional pulverized-coal power plant. It was found that
the calcium looping technology resulted in the lowest efficiency
penalty (4.6%) and the lowest cost of postcombustion CO2 capture
(36.3% increase in levelised cost of electricity). In addition, the cost
of CO2 capture system by using calcium looping for postcombustion
CO2 capture can be as low as 29 USD2010/tCO2. On these three
criteria, the calcium looping technology performed much better
than the benchmark CO2 capture process using monoethanol-
amine. In addition, Diego et al. [243] carried out an analysis of a
double calcium looping process for CO2 capture in cement plants.
This novel scheme uses a number of advanced cyclonic preheaters.
In the carbonator reactor, the solids were overheated by being
directly contacted with high-temperature gas streams before
entering into the calciner. A preliminary economic analysis indi-
cated that the calculated cost was 27 USD/tCO2 avoided when a
double calcium looping process configuration was used, which is
much lower compared to 42 USD/tCO2 avoided without this
configuration. Hanak and Manovic [244] studied the economics of
calcium looping combustion for high-efficiency low-emission po-
wer generation. Depending on whether the concentrated CO2
stream was used elsewhere or permanently stored, the cost of CO2
avoided for calcium looping combustion was estimated to be 10.0
V/tCO2 and 33.9 V/tCO2, respectively.
It is important to note that the capture of CO2 by CaO-based
looping cycles cannot reach 100% due to the constraint of reac-
tion equilibrium. Depending on the plant size, an efficiency of less
than 90% CO2 capture may be more cost-effective [245]. In addition,
the overall cost of carbon capture will be decreased if CaL system is
integrated with existing facilities (e.g. carbonator) [246].
However, there are few studies that compared the economic
benefit of synthesized CaO-based sorbents to the limestone in a
long-term operation as these materials are just in the preliminary
stage and have not been put into a large-scale application. In the
further study, we need to take economic benefit of synthesized
CaO-based sorbents into more consideration including the capacity
of CO2 capture per unit of sorbent, reaction time, cost of sorbent,
carbonation/calcination temperature, regeneration cycles, and
addition of new sorbent.
8. Summary and outlook
In this article, the most recent research progress in the devel-
opment of CaO-based adsorbents for high-temperature CO2 capture
has been reviewed and discussed. Despite the simplicity of the
reaction, it still lacks a systemic fundamental understanding of the
adsorbent reactivity for CO2 capture. A two-stage model is usually
used to investigate the kinetics of CaO carbonation including a fast
stage limited by kinetics and a substantially slow stage controlled
by the diffusion of CO2. However, there was no distinct boundary
between the two stages of kinetics of CaO carbonation. A transition
stage of CO2 capture could exist in the process of carbonation of
CaO. Therefore, a more precise kinetic model should be taken into
consideration about the existence of the transition stage in the
carbonation reaction.
In addition, CaO has a high theoretical capacity, low cost, and
potential use in large scale, but suffers severely from the sintering
of adsorbent particles during the regeneration stage. Extensive ef-
forts have been devoted to enhancing the sintering resistance
properties of CaO-based adsorbents. First, coprecipitation, solgel,
FSP, and supercritical methods are effective to improve the uptake
of CO2 due to the decrease of particle size or the increase of surface
area. Second, dispersing CaO on an inert support such as Al, Ti, Mg,
Ce, Zr, etc. via hydration preparation, physical mixing, or ‘one-pot’
recrystallization is also an effective alternative to improve the
sintering resistance performance during carbonation/calcination
cycles. The inert support acts as a physical barrier to preventing or
delaying the sintering and aggregation of CaO particles. Third,
surface modification via organic acids and mineral acids is applied
to minimize the loss of activity and enhance the life cycle perfor-
mance during CO2 capture.
Besides, some other important parameters for CO2 carbonation
such as CO2 partial pressure, carbonation temperature, carbonation
time, and contaminants are considered in this article. It seems that
natural and synthetic CaO-based adsorbents showed a different
response with the change of CO2 partial pressure due to the for-
mation of CaCO3 product layers with different physical properties.
Both reaction temperature and carbonation time had a positive
influence on the capacity of CO2 capture over several cycles of
carbonation/calcination. Moreover, with an increase of steam
concentration in the process, a decreased decay of adsorbent ca-
pacity occurred due to the formation of a stable pore structure.
In conclusion, nanoparticles with stable framework and porous
structure are essential to the development of CaO-based adsorbents
in relation to the stability of materials. However, novel adsorbents
are rarely tested under severe conditions such as regeneration
under 100% CO2, and the attrition problem has rarely been
addressed for the novel synthetic adsorbents. A further aspect is
whether the synthesis of CaO-based adsorbents is economic and
environmental benign. Therefore, for future work, these aspects
need to be fully considered for the development of new carbon
capture adsorbents. In addition, to improve the efficiency of carbon
capture using CaO-based adsorbents, the first-stage carbonation
(fast stage) is preferred. Thus, fabricating nano-CaO adsorbents that
can generate a thin layer of CaCO3 (smaller than the critical thick-
ness of CaCO3 layer) during carbonation stage is of great signifi-
cance. These nano-CaO materials could be of nanowire or nanofilm
structure. Furthermore, developing novel integrated calcium
looping technology is preferred to reduce the cost and enhance the
overall energy efficiency. For example, the conversion of captured
 H. Sun et al. / Materials Today Sustainability 1-2 (2018) 1e27
CO2 can be integrated with carbon capture and energy and power
generation from renewables.
Declaration of interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
The financial supports from National Natural Science Founda-
tion of China (no. 201706050) and the China Scholarship Council
(no. 201606450016) are greatly acknowledged.
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